WorldWideScience

Sample records for interfacial electrochemical electron

  1. Interfacial Electrochemical Electron Transfer Processes in Bacterial Biofilm Environments on Au(111)

    DEFF Research Database (Denmark)

    Hu, Yifan; Zhang, Jingdong; Ulstrup, Jens

    2010-01-01

    We have studied Streptococcus mutans (S. mutans) biolilm growth and growth inhibition on Au(111)-surfaces using atomic force microscopy (AFM) and interfacial electrochemistry of a number of redox probe molecules. AFM of the biofilm growth and growth inhibition on both mica and Au(111)-surfaces wa...

  2. Single-Molecule Interfacial Electron Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Lu, H. Peter [Bowling Green State Univ., Bowling Green, OH (United States). Dept. of Chemistry and Center for Photochemical Sciences

    2017-11-28

    This project is focused on the use of single-molecule high spatial and temporal resolved techniques to study molecular dynamics in condensed phase and at interfaces, especially, the complex reaction dynamics associated with electron and energy transfer rate processes. The complexity and inhomogeneity of the interfacial ET dynamics often present a major challenge for a molecular level comprehension of the intrinsically complex systems, which calls for both higher spatial and temporal resolutions at ultimate single-molecule and single-particle sensitivities. Combined single-molecule spectroscopy and electrochemical atomic force microscopy approaches are unique for heterogeneous and complex interfacial electron transfer systems because the static and dynamic inhomogeneities can be identified and characterized by studying one molecule at a specific nanoscale surface site at a time. The goal of our project is to integrate and apply these spectroscopic imaging and topographic scanning techniques to measure the energy flow and electron flow between molecules and substrate surfaces as a function of surface site geometry and molecular structure. We have been primarily focusing on studying interfacial electron transfer under ambient condition and electrolyte solution involving both single crystal and colloidal TiO2 and related substrates. The resulting molecular level understanding of the fundamental interfacial electron transfer processes will be important for developing efficient light harvesting systems and broadly applicable to problems in fundamental chemistry and physics. We have made significant advancement on deciphering the underlying mechanism of the complex and inhomogeneous interfacial electron transfer dynamics in dyesensitized TiO2 nanoparticle systems that strongly involves with and regulated by molecule-surface interactions. We have studied interfacial electron transfer on TiO2 nanoparticle surfaces by using ultrafast single

  3. Facile Interfacial Electron Transfer of Hemoglobin

    Directory of Open Access Journals (Sweden)

    Chunhai Fan

    2005-12-01

    Full Text Available Abstract: We herein describe a method of depositing hemoglobin (Hb and sulfonated polyaniline (SPAN on GC electrodes that facilitate interfacial protein electron transfer. Well-defined, reproducible, chemically reversible peaks of Hb and SPAN can be obtained in our experiments. We also observed enhanced peroxidase activity of Hb in SPAN films. These results clearly showed that SPAN worked as molecular wires and effectively exchanged electrons between Hb and electrodes.Mediated by Conjugated Polymers

  4. Electrochemically modulated liquid chromatography: Theoretical investigations and applications from the perspectives of chromatography and interfacial electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Keller, David W. [Iowa State Univ., Ames, IA (United States)

    2005-01-01

    Electrochemically modulated liquid chromatography (EMLC) employs a conductive material as both a stationary phase for chromatographic separations and as a working electrode for performing electrochemistry experiments. This dual functionality gives EMLC the capacity to manipulate chromatographic separations by changing the potential applied (Eapp) to the stationary phase with respect to an external reference. The ability to monitor retention as a function of Eapp provides a means to chromatographically monitor electrosorption processes at solid-liquid interfaces. In this dissertation, the retention mechanism for EMLC is examined from the perspective of electrical double layer theory and interfacial thermodynamics. From the chromatographic data, it is possible to determine the interfacial excess (Λ) of a solute and changes in interfacial tension (dγ) as a function of both Eapp and the supporting electrolyte concentration. Taken together, these two experimentally manipulated parameters can be examined within the context of the Gibbs adsorption equation to delineate the contribution of a variety of interfacial properties, including the charge of solute on the stationary phase and the potential of zero charge (PZC), to the mechanism behind EMLC-based retention. The chromatographic probing of interfacial phenomena is complemented by electroanalytical experiments that exploit the ability to monitor the electronic current flowing through an EMLC column. Cyclic voltammetry and chronoamperometry of an EMLC column are used to determine the electronic performance characteristics of an EMLC column. An electrochemical flow injection analysis of a column is provided in which the current required to maintain a constant Eapp is monitored and provides a way to examine the influence that acetonitrile and supporting electrolyte composition, flow rate, column backpressure, and ionic strength have on the structure of electrified interfaces.

  5. Single-Molecule Interfacial Electron Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Ho, Wilson [Univ. of California, Irvine, CA (United States)

    2018-02-03

    Interfacial electron transfer (ET) plays an important role in many chemical and biological processes. Specifically, interfacial ET in TiO2-based systems is important to solar energy technology, catalysis, and environmental remediation technology. However, the microscopic mechanism of interfacial ET is not well understood with regard to atomic surface structure, molecular structure, bonding, orientation, and motion. In this project, we used two complementary methodologies; single-molecule fluorescence spectroscopy, and scanning-tunneling microscopy and spectroscopy (STM and STS) to address this scientific need. The goal of this project was to integrate these techniques and measure the molecular dependence of ET between adsorbed molecules and TiO2 semiconductor surfaces and the ET induced reactions such as the splitting of water. The scanning probe techniques, STM and STS, are capable of providing the highest spatial resolution but not easily time-resolved data. Single-molecule fluorescence spectroscopy is capable of good time resolution but requires further development to match the spatial resolution of the STM. The integrated approach involving Peter Lu at Bowling Green State University (BGSU) and Wilson Ho at the University of California, Irvine (UC Irvine) produced methods for time and spatially resolved chemical imaging of interfacial electron transfer dynamics and photocatalytic reactions. An integral aspect of the joint research was a significant exchange of graduate students to work at the two institutions. This project bridged complementary approaches to investigate a set of common problems by working with the same molecules on a variety of solid surfaces, but using appropriate techniques to probe under ambient (BGSU) and ultrahigh vacuum (UCI) conditions. The molecular level understanding of the fundamental interfacial electron transfer processes obtained in this joint project will be important for developing efficient light harvesting

  6. Chitosan/graphene oxide nanocomposite films with enhanced interfacial interaction and their electrochemical applications

    International Nuclear Information System (INIS)

    He, Linghao; Wang, Hongfang; Xia, Guangmei; Sun, Jing; Song, Rui

    2014-01-01

    Graphical abstract: Nanocomposites by introducing graphene oxide (GO) into chitosan (CS) matrix were prepared and the effect of GO on the crystallization, thermal stability and mechanical properties of the films were investigated. In addition, the electrochemical behavior of the CS/GO modified electrode was comparatively studied with that of the neat CS-modified electrode. - Highlights: • Graphene oxide (GO) with well dispersion in the biopolymer chitosan (CS) matrix. • Detectable interactions do exist between the GO nanosheets and CS segments. • The addition of minor GO can improve the electrochemical activity of the neat CS. - Abstract: A series of chitosan (CS) nanocomposites incorporated with graphene oxide (GO) nanosheets were facilely prepared by sonochemical method. Characterized by scanning electron microscopy, the obtained nanocomposites showed fine dispersion of GO in the CS matrix. Meanwhile, a marked interfacial interaction was also revealed as the values of glass transition temperature, the decomposition temperature and the storage modulus were significantly increased with the addition of GO. Furthermore, the well dispersed GO nanosheets could significantly improve the electrochemical activity of the CS as demonstrated by the electrochemical behaviors of pure CS and the GO/CS composite electrodes. Hence, the GO/CS nanocomposites film could be a promising candidate in the fabrication of electrochemical biosensors

  7. Water/ionic liquid/organic three-phase interfacial synthesis of coral-like polypyrrole toward enhanced electrochemical capacitance

    International Nuclear Information System (INIS)

    Hou Linrui; Yuan Changzhou; Li Diankai; Yang Long; Shen Laifa; Zhang Fang; Zhang Xiaogang

    2011-01-01

    Highlights: → Interfacial synthesis strategies are proposed to synthesize PPy samples. → Water/ionic liquid /organic three-phase interface for preparing coral-like PPy. → Coral-like PPy with more ordered structure and better electronic conductivity. → Coral-like PPy owns higher rate performance and better electrochemical stability. - Abstract: Two interfacial synthesis strategies are proposed to synthesize polypyrrole samples for electrochemical capacitors (ECs). In contrast to water/organic two-phase route, unique water/ionic liquid (IL)/organic three-phase interface strategy is first performed to prepare coral-like polypyrrole with even better electrochemical capacitance, where 1-Ethyl-3-methylimidazolium tetrafluoroborate IL, as a 'buffering zone', is set between the water and organic phases to control the morphology and micro-structure of the polypyrrole phase during polymerization. The polypyrrole synthesized by three-phase interfacial route owns more ordered structure, less charge transfer resistance and better electronic conductivity, compared with two-phase method, and delivers larger specific capacitance, higher rate performance and better electrochemical stability at large current densities in 3 M KCl aqueous electrolyte.

  8. Biomimetic Interfacial Electron-Induced Electrochemiluminesence.

    Science.gov (United States)

    Pu, Guiqiang; Zhang, Dongxu; Mao, Xiang; Zhang, Zhen; Wang, Huan; Ning, Xingming; Lu, Xiaoquan

    2018-04-17

    We provide here, for the first time, a new interfacial electron-induced electrochemiluminescence (IEIECL) system, realizing bionic construction of bioluminescence (BL) by exploiting electrochemiluminescence (ECL) and ITIES (the interface between two immiscible electrolyte solutions). Significantly, the superiority of the IEIECL system is embodied with the solution of the two bottlenecks encountered in the conventional ECL innovation: that are (a) the applications of hydrophobic luminophores in more commonly used aqueous solution are inhibited tremendously due to the poor inherent solubility and the instability of radicals and (b) the analytes, insoluble in water, are hard to be discovered in an aqueous system because of too little content. More productive IEIECL radiation, analogous to BL, originates from the triplet excited state porphyrin in comparison to the homogeneous ECL. The mechanism of IEIECL, as well as the interaction mechanism between IEIECL and charge transfer (comprising electron transfer (ET), ion transfer (IT), and facilitated ion transfer (FIT)) at the ITIES, are explored in detail. Finally, we emphasize the actual application potential of the IEIECL system with the detection of cytochrome c (Cyt c); it is a key biomolecule in the electron transport chain in the process of biological oxidation and is also an intermediate species in apoptosis. Potentially, the IEIECL system permits ones to explore the lifetime and diffusion path of free radicals, as well as imparting a possibility for the construction of a bionic sensor.

  9. Electrodeposition of enzymes-integrated mesoporous composite films by interfacial templating: A paradigm for electrochemical biosensors

    International Nuclear Information System (INIS)

    Wang, Dongming; Tan, Yiwei

    2014-01-01

    The development of nanostructured electrodes for electrochemical biosensors is of significant interest for modern detection, portable devices, and enhanced performance. However, development of such sensors still remains challenging due to the time-consuming, detriment-to-nature, and costly modifications of both electrodes and enzymes. In this work, we report a simple one-step approach to fabricating high-performance, direct electron transfer (DET) based nanoporous enzyme-embedded electrodes by electrodeposition coupled with recent progress in potential-controlled interfacial surfactant assemblies. In contrast to those previously electrodeposited mesoporous materials that are not bioactive, we imparted the biofunctionality to electrodeposited mesoporous thin films by means of the amphiphilic phospholipid templates strongly interacting with enzymes. Thus, phospholipid-templated mesoporous ZnO films covalently inlaid with the pristine enzymes were prepared by simple one-step electrodeposition. We further demonstrate two examples of such hybrid film electrodes embedded with alcohol dehydrogenase (ADH) and glucose oxidase (GOx), which are effectively employed as electrochemical biosensors for amperometric sensing of ethanol and glucose without using any electron relays. The favorable mass transport and large contact surface area provided by nanopores play an important role in improving the performance of these two biosensors, such as excellent sensitivities, low detection limits, and fast response. The matrix mesoporous films acting as effective electronic bridges are responsible for DET between enzyme molecules and metal electrode

  10. Modeling Insight into Battery Electrolyte Electrochemical Stability and Interfacial Structure.

    Science.gov (United States)

    Borodin, Oleg; Ren, Xiaoming; Vatamanu, Jenel; von Wald Cresce, Arthur; Knap, Jaroslaw; Xu, Kang

    2017-12-19

    Electroactive interfaces distinguish electrochemistry from chemistry and enable electrochemical energy devices like batteries, fuel cells, and electric double layer capacitors. In batteries, electrolytes should be either thermodynamically stable at the electrode interfaces or kinetically stable by forming an electronically insulating but ionically conducting interphase. In addition to a traditional optimization of electrolytes by adding cosolvents and sacrificial additives to preferentially reduce or oxidize at the electrode surfaces, knowledge of the local electrolyte composition and structure within the double layer as a function of voltage constitutes the basis of manipulating an interphase and expanding the operating windows of electrochemical devices. In this work, we focus on how the molecular-scale insight into the solvent and ion partitioning in the electrolyte double layer as a function of applied potential could predict changes in electrolyte stability and its initial oxidation and reduction reactions. In molecular dynamics (MD) simulations, highly concentrated lithium aqueous and nonaqueous electrolytes were found to exclude the solvent molecules from directly interacting with the positive electrode surface, which provides an additional mechanism for extending the electrolyte oxidation stability in addition to the well-established simple elimination of "free" solvent at high salt concentrations. We demonstrate that depending on their chemical structures, the anions could be designed to preferentially adsorb or desorb from the positive electrode with increasing electrode potential. This provides additional leverage to dictate the order of anion oxidation and to effectively select a sacrificial anion for decomposition. The opposite electrosorption behaviors of bis(trifluoromethane)sulfonimide (TFSI) and trifluoromethanesulfonate (OTF) as predicted by MD simulation in highly concentrated aqueous electrolytes were confirmed by surface enhanced infrared

  11. Interfacial compatibility of polymer-based structures in electronics

    OpenAIRE

    Turunen, Markus P. K.

    2004-01-01

    Interfacial compatibility of dissimilar materials was investigated to achieve a better understanding of interfacial adhesion in metal/polymer/metal systems. Surface modifications of polymers were applied to improve the adhesion. The modified surfaces were characterised by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contact angle measurements accompanied by surface free energy evaluations. The pull-off test was employed to asses...

  12. Nanoscale and single-molecule interfacial electron transfer

    DEFF Research Database (Denmark)

    Hansen, Allan Glargaard; Wackerbarth, Hainer; Nielsen, Jens Ulrik

    2003-01-01

    for comprehensive later theoretical work and data interpretation in many areas of chemistry, electrochemistry, and biology. We discuss here some new areas of theoretical electrochemical ET science, with focus on nanoscale electrochemical and bioelectrochemical sciences. Particular attention is given to in situ...... scanning tunneling microscopy (STM) and single-electron tunneling (SET, or Coulomb blockade) in electrochemical. systems directly in aqueous electrolyte solution and at room temperature. We illustrate the new theoretical formalism and its perspectives by recent cases of electrochemical SET, negative...... differential resistance patterns, and by ET dynamics of organized assemblies of biological macromolecules, such as redox metalloproteins and oligonucleotides on single-crystal Au(III)-electrode surfaces....

  13. The Au-S bond in biomolecular adsorption and electrochemical electron transfer

    DEFF Research Database (Denmark)

    Ford, M. J.; Hush, N. S.; Marcuccio, S.

    Interfacial electrochemical electron transfer (ET) of redox metalloproteins is long established. For the proteins to retain full ET or enzyme activity, modification of the electrode surfaces, such as goldsurfaces by self-assembled molecular monolayers (SAMs), is nearly always required, where pure...

  14. Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

    Directory of Open Access Journals (Sweden)

    Sanju Gupta

    2015-10-01

    Full Text Available Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO1, (PPy/ErGO1, (PAni/GO1 and (PPy/GO1. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, Cs, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent Cs of ≥350 F g−1 as compared with constituents (∼70 F g−1 at discharge current density of 0.3 A g−1 that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting and conducting polymers (semiconducting backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (reactivity of surface ion

  15. Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Sanju, E-mail: sanju.gupta@wku.edu; Price, Carson [Department of Physics and Astronomy, Western Kentucky University, 1906 College Heights Blvd., Bowling Green, KY 42101-3576 (United States)

    2015-10-15

    Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO){sub 1}, (PPy/ErGO){sub 1}, (PAni/GO){sub 1} and (PPy/GO){sub 1}. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, C{sub s}, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent C{sub s} of ≥350 F g{sup −1} as compared with constituents (∼70 F g{sup −1}) at discharge current density of 0.3 A g{sup −1} that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine

  16. Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

    Science.gov (United States)

    Gupta, Sanju; Price, Carson

    2015-10-01

    Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO)1, (PPy/ErGO)1, (PAni/GO)1 and (PPy/GO)1. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, Cs, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent Cs of ≥350 F g-1 as compared with constituents (˜70 F g-1) at discharge current density of 0.3 A g-1 that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (re)activity of surface ion adsorption sites

  17. Interfacial characterization of flexible hybrid electronics

    Science.gov (United States)

    Najafian, Sara; Amirkhizi, Alireza V.; Stapleton, Scott

    2018-03-01

    Flexible Hybrid Electronics (FHEs) are the new generation of electronics combining flexible plastic film substrates with electronic devices. Besides the electrical features, design improvements of FHEs depend on the prediction of their mechanical and failure behavior. Debonding of electronic components from the flexible substrate is one of the most common and critical failures of these devices, therefore, the experimental determination of material and interface properties is of great importance in the prediction of failure mechanisms. Traditional interface characterization involves isolated shear and normal mode tests such as the double cantilever beam (DCB) and end notch flexure (ENF) tests. However, due to the thin, flexible nature of the materials and manufacturing restrictions, tests mirroring traditional interface characterization experiments may not always be possible. The ideal goal of this research is to design experiments such that each mode of fracture is isolated. However, due to the complex nonlinear nature of the response and small geometries of FHEs, design of the proper tests to characterize the interface properties can be significantly time and cost consuming. Hence numerical modeling has been implemented to design these novel characterization experiments. This research involves loading case and specimen geometry parametric studies using numerical modeling to design future experiments where either shear or normal fracture modes are dominant. These virtual experiments will provide a foundation for designing similar tests for many different types of flexible electronics and predicting the failure mechanism independent of the specific FHE materials.

  18. Quantification of interfacial segregation by analytical electron microscopy

    CERN Document Server

    Muellejans, H

    2003-01-01

    The quantification of interfacial segregation by spatial difference and one-dimensional profiling is presented in general where special attention is given to the random and systematic uncertainties. The method is demonstrated for an example of Al-Al sub 2 O sub 3 interfaces in a metal-ceramic composite material investigated by energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy in a dedicated scanning transmission electron microscope. The variation of segregation measured at different interfaces by both methods is within the uncertainties, indicating a constant segregation level and interfacial phase formation. The most important random uncertainty is the counting statistics of the impurity signal whereas the specimen thickness introduces systematic uncertainties (via k factor and effective scan width). The latter could be significantly reduced when the specimen thickness is determined explicitly. (orig.)

  19. Diagnosis of schistosomiasis japonica with interfacial co-assembly-based multi-channel electrochemical immunosensor arrays

    Science.gov (United States)

    Deng, Wangping; Xu, Bin; Hu, Haiyan; Li, Jianyong; Hu, Wei; Song, Shiping; Feng, Zheng; Fan, Chunhai

    2013-05-01

    Schistosomiasis control remains to be an important and challenging task in the world. However, lack of quick, simple, sensitive and specific sero-diagnostic test is still a hurdle in the control practice. The commonly employed enzyme-linked immuno-sorbent assay (ELISA) relies on the native soluble egg antigen (SEA) that is limited in supply. Here we developed an electrochemical immunosensor array (ECISA) assay with an interfacial co-assembly strategy. A recombinant Schistosoma japonicum (Sj) calcium-binding protein (SjE16) was used as a principal antigen, while the SEA as a minor, co-assembling agent, with a ratio of 8:1 (SjE16: SEA, Sj16EA), which was co-immobilized on a disposable 16-channel screen-printed carbon electrode array. A portable electrochemical detector was employed to detect antibodies in serum samples. The sensitivity of ECISA reached 100% with minimal cross-reactions. Therefore, we have demonstrated that this rapid, sensitive and specific ECISA technique has the potential to perform large-scale on-site screening of Sj infection.

  20. Electrode Cultivation and Interfacial Electron Transport in Subsurface Microorganisms

    Science.gov (United States)

    Karbelkar, A. A.; Jangir, Y.; Reese, B. K.; Wanger, G.; Anderson, C.; El-Naggar, M.; Amend, J.

    2016-12-01

    Continental subsurface environments can present significant energetic challenges to the resident microorganisms. While these environments are geologically diverse, potentially allowing energy harvesting by microorganisms that catalyze redox reactions, many of the abundant electron donors and acceptors are insoluble and therefore not directly bioavailable. Microbes can use extracellular electron transfer (EET) as a metabolic strategy to interact with redox active surfaces. This process can be mimicked on electrode surfaces and hence can lead to enrichment and quantification of subsurface microorganisms A primary bioelectrochemical enrichment with different oxidizing and reducing potentials set up in a single bioreactor was applied in situ to subsurface microorganisms residing in iron oxide rich deposits in the Sanford Underground Research Facility. Secondary enrichment revealed a plethora of classified and unclassified subsurface microbiota on both oxidizing and reducing potentials. From this enrichment, we have isolated a Gram-positive Bacillus along with Gram-negative Cupriavidus and Anaerospora strains (as electrode reducers) and Comamonas (as an electrode oxidizer). The Bacillus and Comamonas isolates were subjected to a detailed electrochemical characterization in half-reactors at anodic and cathodic potentials, respectively. An increase in cathodic current upon inoculation and cyclic voltammetry measurements confirm the hypothesis that Comamonas is capable of electron uptake from electrodes. In addition, measurements of Bacillus on anodes hint towards novel mechanisms that allow EET from Gram-positive bacteria. This study suggests that electrochemical approaches are well positioned to dissect such extracellular interactions that may be prevalent in the subsurface, while using physical electrodes to emulate the microhabitats, redox and geochemical gradients, and the spatially dependent interspecies interactions encountered in the subsurface. Electrochemical

  1. Electronic structures of interfacial states formed at polymeric semiconductor heterojunctions

    Science.gov (United States)

    Huang, Ya-Shih; Westenhoff, Sebastian; Avilov, Igor; Sreearunothai, Paiboon; Hodgkiss, Justin M.; Deleener, Caroline; Friend, Richard H.; Beljonne, David

    2008-06-01

    Heterojunctions between organic semiconductors are central to the operation of light-emitting and photovoltaic diodes, providing respectively for electron-hole capture and separation. However, relatively little is known about the character of electronic excitations stable at the heterojunction. We have developed molecular models to study such interfacial excited electronic excitations that form at the heterojunction between model polymer donor and polymer acceptor systems: poly(9,9-dioctylfluorene-co-bis-N,N-(4-butylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine) (PFB) with poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT), and poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) with F8BT. We find that for stable ground-state geometries the excited state has a strong charge-transfer character. Furthermore, when partly covalent, modelled radiative lifetimes (~10-7s) and off-chain axis polarization (30∘) match observed `exciplex' emission. Additionally for the PFB:F8BT blend, geometries with fully ionic character are also found, thus accounting for the low electroluminescence efficiency of this system.

  2. Long-range interfacial electron transfer and electrocatalysis of molecular scale Prussian Blue nanoparticles linked to Au(111)-electrode surfaces by different chemical contacting groups

    DEFF Research Database (Denmark)

    Zhu, Nan; Ulstrup, Jens; Chi, Qijin

    2017-01-01

    We have explored interfacial electrochemical electron transfer (ET) and electrocatalysis of 5–6 nm Prussian Blue nanoparticles (PBNPs) immobilized on Au(111)-electrode surfaces via molecular wiring with variable-length, and differently functionalized thiol-based self-assembled molecular monolayers...... (SAMs). The SAMs contain positively (−NH3+) or negatively charged (–COO–) terminal group, as well an electrostatically neutral hydrophobic terminal group (–CH3). The surface microscopic structures of the immobilized PBNPs were characterized by high-resolution atomic force microscopy (AFM) directly...... in aqueous electrolyte solution under the same conditions as for electrochemical measurements. The PBNPs displayed fast and reversible interfacial ET on all the surfaces, notably in multi-ET steps as reflected in narrow voltammetric peaks. The ET kinetics can be controlled by adjusting the length of the SAM...

  3. Engineering Pt/Pd Interfacial Electronic Structures for Highly Efficient Hydrogen Evolution and Alcohol Oxidation.

    Science.gov (United States)

    Fan, Jinchang; Qi, Kun; Zhang, Lei; Zhang, Haiyan; Yu, Shansheng; Cui, Xiaoqiang

    2017-05-31

    Tailoring the interfacial structure of Pt-based catalysts has emerged as an effective strategy to improve catalytic activity. However, little attention has been focused on investigating the relationship between the interfacial facets and their catalytic activity. Here, we design and implement Pd-Pt interfaces with controlled heterostructure features by epitaxially growing Pt nanoparticles on Pd nanosheets. On the basis of both density functional theory calculation and experimental results, we demonstrate that charge transfer from Pd to Pt is highly dependent on the interfacial facets of Pd substrates. Therefore, the Pd-Pt heterostructure with Pd(100)-Pt interface exhibits excellent activity and long-term stability for hydrogen evolution and methanol/ethanol oxidation reactions in alkaline medium, much better than that with Pd (111)-Pt interface or commercial Pt/C. Interfacial crystal facet-dependent electronic structural modulation sheds a light on the design and investigation of new heterostructures for high-activity catalysts.

  4. Pulsed Electrochemical Mass Spectrometry for Operando Tracking of Interfacial Processes in Small-Time-Constant Electrochemical Devices such as Supercapacitors.

    Science.gov (United States)

    Batisse, Nicolas; Raymundo-Piñero, Encarnación

    2017-11-29

    A more detailed understanding of the electrode/electrolyte interface degradation during the charging cycle in supercapacitors is of great interest for exploring the voltage stability range and therefore the extractable energy. The evaluation of the gas evolution during the charging, discharging, and aging processes is a powerful tool toward determining the stability and energy capacity of supercapacitors. Here, we attempt to fit the gas analysis resolution to the time response of a low-gas-generation power device by adopting a modified pulsed electrochemical mass spectrometry (PEMS) method. The pertinence of the method is shown using a symmetric carbon/carbon supercapacitor operating in different aqueous electrolytes. The differences observed in the gas levels and compositions as a function of the cell voltage correlate to the evolution of the physicochemical characteristics of the carbon electrodes and to the electrochemical performance, giving a complete picture of the processes taking place at the electrode/electrolyte interface.

  5. A solution-processed binary cathode interfacial layer facilitates electron extraction for inverted polymer solar cells.

    Science.gov (United States)

    Zhang, Xinyuan; Li, Zhiqi; Liu, Chunyu; Guo, Jiaxin; Shen, Liang; Guo, Wenbin

    2018-03-15

    The charge transfer and separation are significantly affected by the electron properties of the interface between the electron-donor layer and the carrier-transporting layer in polymer solar cells (PSCs). In this study, we investigate the electron extraction mechanism of PSCs with a low temperature solution-processed ZnO/PEI as electron transport layer. The incorporation of PEI layer can decrease the work function of ZnO and reduce interfacial barrier, which facilitates electron extraction and suppresses bimolecular recombination, leading to a significant performance enhancement. Furthermore, PEI layer can induce phase separation and passivite inorganic surface trap states as well as shift the interfacial energy offset between metal oxide and organic materials. This work offers a simple and effective way to improve the charge transporting property of organic photovoltaic devices. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Patterned electrochemical deposition of copper using an electron beam

    Directory of Open Access Journals (Sweden)

    Mark den Heijer

    2014-02-01

    Full Text Available We describe a technique for patterning clusters of metal using electrochemical deposition. By operating an electrochemical cell in the transmission electron microscope, we deposit Cu on Au under potentiostatic conditions. For acidified copper sulphate electrolytes, nucleation occurs uniformly over the electrode. However, when chloride ions are added there is a range of applied potentials over which nucleation occurs only in areas irradiated by the electron beam. By scanning the beam we control nucleation to form patterns of deposited copper. We discuss the mechanism for this effect in terms of electron beam-induced reactions with copper chloride, and consider possible applications.

  7. On the electrochemical migration mechanism of tin in electronics

    DEFF Research Database (Denmark)

    Minzari, Daniel; Jellesen, Morten Stendahl; Møller, Per

    2011-01-01

    Electrochemical migration (ECM) of tin can result in the growth of a metal deposit with a dendritic structure from cathode to anode. In electronics, such growth can lead to short circuit of biased electrodes, potentially leading to intermittent or complete failure of an electronic device...

  8. Adsorption and Interfacial Electron Transfer of Saccharomyces Cerevisiae

    DEFF Research Database (Denmark)

    Hansen, Allan Glargaard; Boisen, Anja; Nielsen, Jens Ulrik

    2003-01-01

    We have studied the adsorption and electron-transfer dynamics of Saccharomyces cerevisiae (yeast) iso-l-cytochrome c adsorbed on Au(lll) electrodes in aqueous phosphate buffer media. This cytochrome possesses a thiol group dos e to the protein surface (Cysl02) suitable for linking the protein...

  9. Physico-Chemical Characterization and Interfacial Electrochemical Properties of Nanoparticles of Anatase-TiO2 Prepared by the Sol-Gel Method

    Directory of Open Access Journals (Sweden)

    Ikram Daou

    2013-07-01

    Full Text Available In this work, we prepared by the sol-gel method titanium dioxide nanoparticles having a large specific area (SBET = 218 m2/g. The isotherm of N2 adsorption-desorption at 77K revealed that it concerns a mesoporous solid with a maximum pore diameter of 43 Å. The X-ray diffraction showed that the solid is constituted of the anatase phase. The transmission electron microscopy revealed us that the synthesized grains of TiO2 are of nanometric sizes (diameter between 8 and 20 nm and manifest under agglomerated shape. The study of its solubility in dispersing phase, by conductometric titrations, showed that the prepared solid is totally insoluble in all the domain of the studied pH. The measured inter-facial electrochemical properties, based on the isotherms of ionic adsorption and the conductometric titrations, are: the point of zero charge found equal to 6,2±0,1, the total number of sites of surface found equal to 5,8 OH/nm2 and the nature of action of the dispersed phase on the dispersing phase which is found organizer of the structure of water. Besides, the difference of the ionizationconstants pK is found superior to 4 for all the adsorbed ions and the constants of surface complexation are independent from the nature of the adsorbed ion.

  10. Interfacial and Thin Film Chemistry in Electron Device Fabrication

    Science.gov (United States)

    1992-01-01

    Chemistry During Electronic Processing" by Professor Richard Osgood, Jr.; "In Situ Optical Diagnostics of Semiconductors Prepared by Laser Chemical Processing...N(Igde Area Code) 22c OFF ft SYMBO. Professors Georee Flynn and Richard Os~ood I MSL DD Form 1473, JUN 86 Previous edotions are obsolete SECURITY...and D. L. Smith, Phys.I Rev. Lett. 62, 649 (1989). 19. E. A. Caridi, T. Y. Chang, K. W. Goossen and L. F. Eastman, AOLi Phvs. Tett. 56, 659 (1990). 1

  11. Chemically controlled interfacial nanoparticle assembly into nanoporous gold films for electrochemical applications

    DEFF Research Database (Denmark)

    Christiansen, Mikkel U. -B.; Seselj, Nedjeljko; Engelbrekt, Christian

    2018-01-01

    at the liquid/air interface starting from gold nanoparticles (AuNPs) in an aqueous solution, providing silver-free gold films. Chloroauric acid is reduced to AuNP building blocks by 2-(N-morpholino)ethanesulfonic acid, which also acts as a protecting agent and pH buffer. By adding potassium chloride before Au......, they can be controlled by varying the temperature, chloride concentration, ionic strength, and protonation of the buffer. cNPGF formation is attributed to the destabilization of AuNPs at the air–liquid interface. The developed method generates electrochemically stable cNPGFs up to 20 cm2 in size...

  12. Interfacial electronic charge transfer and density of states in short period Cu/Cr multilayers; TOPICAL

    International Nuclear Information System (INIS)

    Barbee, T W; Bello, A F; Klepeis, J E; Van Buuren, T

    1999-01-01

    Nanometer period metallic multilayers are ideal structures to investigate electronic phenomena at interfaces between metal films since interfacial atoms comprise a large atomic fraction of the samples. The Cu/Cr binary pair is especially suited to study the interfaces in metals since these elements are mutually insoluble, thus eliminating mixing effects and compound formation and the lattice mismatch is very small. This allows the fabrication of high structural quality Cu/Cr multilayers that have a structure which can be approximated in calculations based on idealized atomic arrangements. The electronic structure of the Cu and the Cr layers in several samples of thin Cu/Cr multilayers were studied using x-ray absorption spectroscopy (XAS). Total electron yield was measured and used to study the white lines at the Cu L(sub 2) and L(sub 3) absorption edges. The white lines at the Cu absorption edges are strongly related to the unoccupied d-orbitals and are used to calculate the amount of charge transfer between the Cr and Cu atoms in interfaces. Analysis of the Cu white lines show a charge transfer of 0.026 electrons/interfacial Cu atom to the interfacial Cr atoms. In the Cu XAS spectra we also observe a van Hove singularity between the L(sub 2) and L(sub 3) absorption edges as expected from the structural analysis. The absorption spectra are compared to partial density of states obtained from a full-potential linear muffin-tin orbital calculation. The calculations support the presence of charge transfer and indicate that it is localized to the first two interfacial layers in both Cu and Cr

  13. Electrochemical and spectroscopic study of interfacial interactions between chalcopyrite and typical flotation process reagents

    Science.gov (United States)

    Urbano, Gustavo; Lázaro, Isabel; Rodríguez, Israel; Reyes, Juan Luis; Larios, Roxana; Cruz, Roel

    2016-02-01

    Comparative voltammetry and differential double-layer capacitance studies were performed to evaluate interfacial interactions between chalcopyrite (CuFeS2) and n-isopropyl xanthate (X) in the presence of ammonium bisulfite/39wt% SO2 and caustic starch at different pH values. Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, contact angle measurements, and microflotation tests were used to establish the type and extent of xanthate adsorption as well as the species involved under different mineral surface conditions in this study. The results demonstrate that the species that favor a greater hydrophobicity of chalcopyrite are primarily CuX and S0, whereas oxides and hydroxides of Cu and Fe as well as an excess of starch decrease the hydrophobicity. A conditioning of the mineral surface with ammonium bisulfite/39wt% SO2 at pH 6 promotes the activation of surface and enhances the xanthate adsorption. However, this effect is diminished at pH ≥ 8, when an excess of starch is added during the preconditioning step.

  14. Defect-driven interfacial electronic structures at an organic/metal-oxide semiconductor heterojunction.

    Science.gov (United States)

    Winget, Paul; Schirra, Laura K; Cornil, David; Li, Hong; Coropceanu, Veaceslav; Ndione, Paul F; Sigdel, Ajaya K; Ginley, David S; Berry, Joseph J; Shim, Jaewon; Kim, Hyungchui; Kippelen, Bernard; Brédas, Jean-Luc; Monti, Oliver L A

    2014-07-16

    The electronic structure of the hybrid interface between ZnO and the prototypical organic semiconductor PTCDI is investigated via a combination of ultraviolet and X-ray photoelectron spectroscopy (UPS/XPS) and density functional theory (DFT) calculations. The interfacial electronic interactions lead to a large interface dipole due to substantial charge transfer from ZnO to 3,4,9,10-perylenetetracarboxylicdiimide (PTCDI), which can be properly described only when accounting for surface defects that confer ZnO its n-type properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Electrochemical, interfacial, and surface studies of the conversion of carbon dioxide to liquid fuels on tin electrodes

    Science.gov (United States)

    Wu, Jingjie

    The electrochemical reduction of carbon dioxide (CO2) into liquid fuels especially coupling with the intermittent renewable electricity offers a promising means of storing electricity in chemical form, which reduces the dependence on fossil fuels and mitigates the negative impact of anthropogenic CO2 emissions on the planet. Although converting CO2 to fuels is not in itself a new concept, the field has not substantially advanced in the last 30 years primarily because of the challenge of discovery of structural electrocatalysts and the development of membrane architectures for efficient collection of reactants and separation of products. An efficient catalyst for the electrochemical conversion of CO2 to fuels must be capable of mediating a proton-coupled electron transfer reaction at low overpotentials, reducing CO2 in the presence of water, selectively converting CO 2 to desirable chemicals, and sustaining long-term operations (Chapter 1). My Ph.D. research was an investigation of the electroreduction of CO2 on tin-based electrodes and development of an electrochemical cell to convert CO2 to liquid fuels. The initial study focused on understanding the CO2 reduction reaction chemistry in the electrical double layer with an emphasis on the effects of electrostatic adsorption of cations, specific adsorption of anion and electrolyte concentration on the potential and proton concentration at outer Helmholtz plane at which reduction reaction occurs. The variation of potential and proton concentration at outer Helmholtz plane accounts for the difference in activity and selectivity towards CO2 reduction when using different electrolytes (Chapter 2). Central to the highly efficient CO2 reduction is an optimum microstructure of catalyst layer in the Sn gas diffusion electrode (GDE) consisting of 100 nm Sn nanoparticles to facilitate gas diffusion and charge transfer. This microstructure in terms of the proton conductor fraction and catalyst layer thickness was optimized to

  16. Destructive electronics from electrochemical-mechanically triggered chemical dissolution

    International Nuclear Information System (INIS)

    Sim, Kyoseung; Wang, Xu; Yu, Cunjiang; Li, Yuhang; Linghu, Changhong; Song, Jizhou; Gao, Yang

    2017-01-01

    The considerable need to enhance data and hardware security suggest one possible future for electronics where it is possible to destroy them and even make them disappear physically. This paper reports a type of destructive electronics which features fast transience from chemical dissolution on-demand triggered in an electrochemical-mechanical manner. The detailed materials, mechanics, and device construction of the destructive electronics are presented. Experiment and analysis of the triggered releasing and transience study of electronic materials, resistors and metal-oxide-semiconductor field effect transistors illustrate the key aspects of the destructive electronics. The reported destructive electronics is useful in a wide range of areas from security and defense, to medical applications (paper)

  17. Activating "Invisible" Glue: Using Electron Beam for Enhancement of Interfacial Properties of Graphene-Metal Contact.

    Science.gov (United States)

    Kim, Songkil; Russell, Michael; Kulkarni, Dhaval D; Henry, Mathias; Kim, Steve; Naik, Rajesh R; Voevodin, Andrey A; Jang, Seung Soon; Tsukruk, Vladimir V; Fedorov, Andrei G

    2016-01-26

    Interfacial contact of two-dimensional graphene with three-dimensional metal electrodes is crucial to engineering high-performance graphene-based nanodevices with superior performance. Here, we report on the development of a rapid "nanowelding" method for enhancing properties of interface to graphene buried under metal electrodes using a focused electron beam induced deposition (FEBID). High energy electron irradiation activates two-dimensional graphene structure by generation of structural defects at the interface to metal contacts with subsequent strong bonding via FEBID of an atomically thin graphitic interlayer formed by low energy secondary electron-assisted dissociation of entrapped hydrocarbon contaminants. Comprehensive investigation is conducted to demonstrate formation of the FEBID graphitic interlayer and its impact on contact properties of graphene devices achieved via strong electromechanical coupling at graphene-metal interfaces. Reduction of the device electrical resistance by ∼50% at a Dirac point and by ∼30% at the gate voltage far from the Dirac point is obtained with concurrent improvement in thermomechanical reliability of the contact interface. Importantly, the process is rapid and has an excellent insertion potential into a conventional fabrication workflow of graphene-based nanodevices through single-step postprocessing modification of interfacial properties at the buried heterogeneous contact.

  18. Molecular monolayers and interfacial electron transfer of pseudomonas aeruginosa azurin on Au(111)

    DEFF Research Database (Denmark)

    Chi, Qijin; Zhang, Jingdong; Nielsen, Jens Ulrik

    2000-01-01

    disulfide group to form a monolayer. The adsorption of this protein on Au(111) via a gold-sulfur binding mode is further supported by XPS measurements. In situ STM images with molecular resolution have been recorded and show a dense monolayer organization of adsorbed azurin molecules. Direct electron......We provide a comprehensive approach to the formation and characterization of molecular monolayers of the blue copper protein Pseudomonas aeruginosa azurin on Au(111) in aqueous ammonium acetate solution. Main issues are adsorption patterns, reductive desorption, properties of the double layer......, and long-range electrochemical electron transfer between the electrode and the copper center. Voltammetry, electrochemical impedance spectroscopy (EIS), in situ scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS) have been employed to disclose features of these issues. Zn...

  19. Effects of interfacial Fe electronic structures on magnetic and electronic transport properties in oxide/NiFe/oxide heterostructures

    International Nuclear Information System (INIS)

    Liu, Qianqian; Chen, Xi; Zhang, Jing-Yan; Yang, Meiyin; Li, Xu-Jing; Jiang, Shao-Long; Liu, Yi-Wei; Cao, Yi; Wu, Zheng-Long; Feng, Chun; Ding, Lei; Yu, Guang-Hua

    2015-01-01

    Highlights: • The magnetic and transport properties of oxide/NiFe/oxide films were studied. • The oxide (SiO 2 , MgO and HfO 2 ) has different elemental electronegativity. • Redox reaction at different NiFe/oxide interface is dependent on the oxide layer. • Different interfacial electronic structures shown by XPS influence the properties. - Abstract: We report that the magnetic and electronic transport properties in oxide/NiFe(2 nm)/oxide film (oxide = SiO 2 , MgO or HfO 2 ) are strongly influenced by the electronic structure of NiFe/oxide interface. Magnetic measurements show that there exist magnetic dead layers in the SiO 2 sandwiched film and MgO sandwiched film, whereas there is no magnetic dead layer in the HfO 2 sandwiched film. Furthermore, in the ultrathin SiO 2 sandwiched film no magnetoresistance (MR) is detected, while in the ultrathin MgO sandwiched film and HfO 2 sandwiched film the MR ratios reach 0.35% and 0.88%, respectively. The investigation by X-ray photoelectron spectroscopy reveals that the distinct interfacial redox reactions, which are dependent on the oxide layers, lead to the variation of magnetic and transport properties in different oxide/NiFe/oxide heterostructures

  20. Application of Degenerately Doped Metal Oxides in the Study of Photoinduced Interfacial Electron Transfer.

    Science.gov (United States)

    Farnum, Byron H; Morseth, Zachary A; Brennaman, M Kyle; Papanikolas, John M; Meyer, Thomas J

    2015-06-18

    Degenerately doped In2O3:Sn semiconductor nanoparticles (nanoITO) have been used to study the photoinduced interfacial electron-transfer reactivity of surface-bound [Ru(II)(bpy)2(4,4'-(PO3H2)2-bpy)](2+) (RuP(2+)) molecules as a function of driving force over a range of 1.8 eV. The metallic properties of the ITO nanoparticles, present within an interconnected mesoporous film, allowed for the driving force to be tuned by controlling their Fermi level with an external bias while their optical transparency allowed for transient absorption spectroscopy to be used to monitor electron-transfer kinetics. Photoinduced electron transfer from excited-state -RuP(2+*) molecules to nanoITO was found to be dependent on applied bias and competitive with nonradiative energy transfer to nanoITO. Back electron transfer from nanoITO to oxidized -RuP(3+) was also dependent on the applied bias but without complication from inter- or intraparticle electron diffusion in the oxide nanoparticles. Analysis of the electron injection kinetics as a function of driving force using Marcus-Gerischer theory resulted in an experimental estimate of the reorganization energy for the excited-state -RuP(3+/2+*) redox couple of λ* = 0.83 eV and an electronic coupling matrix element, arising from electronic wave function overlap between the donor orbital in the molecule and the acceptor orbital(s) in the nanoITO electrode, of Hab = 20-45 cm(-1). Similar analysis of the back electron-transfer kinetics yielded λ = 0.56 eV for the ground-state -RuP(3+/2+) redox couple and Hab = 2-4 cm(-1). The use of these wide band gap, degenerately doped materials provides a unique experimental approach for investigating single-site electron transfer at the surface of oxide nanoparticles.

  1. Electrochemical fabrication and electronic behavior of polypyrrole nano-fiber array devices

    International Nuclear Information System (INIS)

    Liu Ling; Zhao Yaomin; Jia Nengqin; Zhou Qin; Zhao Chongjun; Yan Manming; Jiang Zhiyu

    2006-01-01

    Electrochemically active Polypyrrole (PPy) nano-fiber array device was fabricated via electrochemical deposition method using aluminum anodic oxide (AAO) membrane as template. After alkaline treatment electrochemically active PPy nano-fiber lost electrochemical activity, and became electrochemically inactive PPy. The electronic properties of PPy nano-fiber array devices were measured by means of a simple method. It was found that for an indium-tin oxide/electrochemically inactive PPy nano-fiber device, the conductivity of nano-fiber increased with the increase of voltage applied on the two terminals of nano-fiber. The electrochemical inactive PPy nano-fiber might be used as a nano-fiber switching diode. Both Au/electrochemically active PPy and Au/electrochemically inactive PPy nano-fiber devices demonstrate rectifying behavior, and might have been used for further application as nano-rectifiers

  2. Electrochemical fabrication and electronic behavior of polypyrrole nano-fiber array devices

    Energy Technology Data Exchange (ETDEWEB)

    Ling, Liu [Department of Chemistry, and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433 (China); Yaomin, Zhao [Department of Chemistry, and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433 (China); Nengqin, Jia [Department of Chemistry, and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433 (China); Qin, Zhou [Department of Chemistry, and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433 (China); Chongjun, Zhao [Photon Craft Project, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences and Japan Science and Technology Agency, Shanghai 201800 (China); Manming, Yan [Department of Chemistry, and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433 (China); Zhiyu, Jiang [Department of Chemistry, and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433 (China)

    2006-05-01

    Electrochemically active Polypyrrole (PPy) nano-fiber array device was fabricated via electrochemical deposition method using aluminum anodic oxide (AAO) membrane as template. After alkaline treatment electrochemically active PPy nano-fiber lost electrochemical activity, and became electrochemically inactive PPy. The electronic properties of PPy nano-fiber array devices were measured by means of a simple method. It was found that for an indium-tin oxide/electrochemically inactive PPy nano-fiber device, the conductivity of nano-fiber increased with the increase of voltage applied on the two terminals of nano-fiber. The electrochemical inactive PPy nano-fiber might be used as a nano-fiber switching diode. Both Au/electrochemically active PPy and Au/electrochemically inactive PPy nano-fiber devices demonstrate rectifying behavior, and might have been used for further application as nano-rectifiers.

  3. Interfacial bonding and electronic structure of GaN/GaAs interface: A first-principles study

    International Nuclear Information System (INIS)

    Cao, Ruyue; Zhang, Zhaofu; Wang, Changhong; Li, Haobo; Dong, Hong; Liu, Hui; Wang, Weichao; Xie, Xinjian

    2015-01-01

    Understanding of GaN interfacing with GaAs is crucial for GaN to be an effective interfacial layer between high-k oxides and III-V materials with the application in high-mobility metal-oxide-semiconductor field effect transistor (MOSFET) devices. Utilizing first principles calculations, here, we investigate the structural and electronic properties of the GaN/GaAs interface with respect to the interfacial nitrogen contents. The decrease of interfacial N contents leads to more Ga dangling bonds and As-As dimers. At the N-rich limit, the interface with N concentration of 87.5% shows the most stability. Furthermore, a strong band offsets dependence on the interfacial N concentration is also observed. The valance band offset of N7 with hybrid functional calculation is 0.51 eV. The electronic structure analysis shows that significant interface states exist in all the GaN/GaAs models with various N contents, which originate from the interfacial dangling bonds and some unsaturated Ga and N atoms. These large amounts of gap states result in Fermi level pinning and essentially degrade the device performance

  4. Unravelling surface and interfacial structures of a metal-organic framework by transmission electron microscopy.

    Science.gov (United States)

    Zhu, Yihan; Ciston, Jim; Zheng, Bin; Miao, Xiaohe; Czarnik, Cory; Pan, Yichang; Sougrat, Rachid; Lai, Zhiping; Hsiung, Chia-En; Yao, Kexin; Pinnau, Ingo; Pan, Ming; Han, Yu

    2017-05-01

    Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

  5. Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy

    KAUST Repository

    Zhu, Yihan

    2017-02-21

    Metal–organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis1, 2, 3. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation4, 5, 6, 7. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

  6. Ultrafast Interfacial Electron and Hole Transfer from CsPbBr3 Perovskite Quantum Dots.

    Science.gov (United States)

    Wu, Kaifeng; Liang, Guijie; Shang, Qiongyi; Ren, Yueping; Kong, Degui; Lian, Tianquan

    2015-10-14

    Recently reported colloidal lead halide perovskite quantum dots (QDs) with tunable photoluminescence (PL) wavelengths covering the whole visible spectrum and exceptionally high PL quantum yields (QYs, 50-90%) constitute a new family of functional materials with potential applications in light-harvesting and -emitting devices. By transient absorption spectroscopy, we show that the high PL QYs (∼79%) can be attributed to negligible electron or hole trapping pathways in CsPbBr3 QDs: ∼94% of lowest excitonic states decayed with a single-exponential time constant of 4.5 ± 0.2 ns. Furthermore, excitons in CsPbBr3 QDs can be efficiently dissociated in the presence of electron or hole acceptors. The half-lives of electron transfer (ET) to benzoquinone and subsequent charge recombination are 65 ± 5 ps and 2.6 ± 0.4 ns, respectively. The half-lives for hole transfer (HT) to phenothiazine and the subsequent charge recombination are 49 ± 6 ps and 1.0 ± 0.2 ns, respectively. The lack of electron and hole traps and fast interfacial ET and HT rates are key properties that may enable the development of efficient lead halide perovskite QDs-based light-harvesting and -emitting devices.

  7. Quantifying Chemical and Electrochemical Reactions in Liquids by in situ Electron Microscopy

    DEFF Research Database (Denmark)

    Canepa, Silvia

    and developing a robust imaging analysis method for quantitatively understand chemical and electrochemical process during in situ liquid electron microscopy. By using two custom-made liquid cells (an electrochemical scanning electron microscopy (EC-SEM) platform and Liquid Flow S/TEM holder) beam...... of electrochemical deposition of copper (Cu) by electrochemical liquid scanning electron microscopy (EC-SEM) was done in order to direct observe the formation of dendritic structures. Finally the shape evolution from solid to hollow structures through galvanic replacement reactions were observed for different silver...

  8. Decoupling electron and ion storage and the path from interfacial storage to artificial electrodes

    Science.gov (United States)

    Chen, Chia-Chin; Maier, Joachim

    2018-02-01

    The requirements for rechargeable batteries place high demands on the electrodes. Efficient storage means accommodating both ions and electrons, not only in substantial amounts, but also with substantial velocities. The materials' space could be largely extended by decoupling the roles of ions and electrons such that transport and accommodation of ions take place in one phase of a composite, and transport and accommodation of electrons in the other phase. Here we discuss this synergistic concept being equally applicable for positive and negative electrodes along with examples from the literature for Li-based and Ag-based cells. Not only does the concept have the potential to mitigate the trade-off between power density and energy density, it also enables a generalized view of bulk and interfacial storage as necessary for nanocrystals. It furthermore allows for testable predictions of heterogeneous storage in passivation layers, dependence of transfer resistance on the state of charge, or heterogeneous storage of hydrogen at appropriate contacts. We also present an outlook on constructing artificial mixed-conductor electrodes that have the potential to achieve both high energy density and high power density.

  9. Minimizing performance degradation induced by interfacial recombination in perovskite solar cells through tailoring of the transport layer electronic properties

    Directory of Open Access Journals (Sweden)

    Liang Xu

    2018-03-01

    Full Text Available The performance of hybrid organic-inorganic metal halide perovskite solar cells is investigated using one-dimensional drift-diffusion device simulations. We study the effects of interfacial defect density, doping concentration, and electronic level positions of the charge transport layer (CTL. Choosing CTLs with a favorable band alignment, rather than passivating CTL-perovskite interfacial defects, is shown to be beneficial for maintaining high power-conversion efficiency, due to reduced minority carrier density arising from a favorable local electric field profile. Insights from this study provide theoretical guidance on practical selection of CTL materials for achieving high-performance perovskite solar cells.

  10. Interfacial reaction in SiC_f/Ti-6Al-4V composite by using transmission electron microscopy

    International Nuclear Information System (INIS)

    Huang, Bin; Li, Maohua; Chen, Yanxia; Luo, Xian; Yang, Yanqing

    2015-01-01

    The interfacial reactions of continuous SiC fiber reinforced Ti-6Al-4V matrix composite (SiC_f/Ti-6Al-4V composite) and continuous SiC fiber coated by C reinforced Ti-6Al-4V matrix composite (SiC_f/C/Ti-6Al-4V composite) were investigated by using micro-beam electron diffraction (MBED) and energy disperse spectroscopy (EDS) on transmission electron microscopy (TEM). The sequence of the interfacial reactions in the as-processed and exposed at 900°C for 50h SiC_f/Ti-6Al-4V composites can be described as SiC||TiC||Ti_5Si_3 + TiC||Ti-6Al-4V and SiC||TiC||Ti_5Si_3||TiC||Ti_5Si_3||TiC||Ti_5Si_3||Ti-6Al-4V, respectively. Additionally, both in as-processed and exposed composites, Ti_3SiC_2 and Ti_3Si are absent at the interfaces. For the SiC_f/C/Ti-6Al-4V composite exposed at 900 °C for 50 h, the sequence of the interfacial reaction can be described as SiC||C||TiC_F||TiC_C||Ti-6Al-4V before C coating is completely consumed by interfacial reaction. When interfacial reaction consumes C coating completely, the sequence of the interfacial reaction can be described as SiC||TiC||Ti_5Si_3||TiC||Ti-6Al-4V. Furthermore, in SiC_f/C/Ti-6Al-4V composite, C coating can absolutely prevent Si diffusion from SiC fiber to matrix. Basing on these results, the model of formation process of the interfacial reaction products in the composites was proposed. - Highlights: • We obtained the sequence of the interfacial reactions in the as-processed and exposed at 900 °C for 50 h SiC_f/Ti-6Al-4 V composites as well as in the SiC_f/C/Ti-6Al-4 V composite exposed at 900 °C for 50 h. • We verified that both in as-processed and exposed SiC_f/Ti-6Al-4 V composites, Ti_3SiC_2 and Ti_3Si are absent at the interfaces. • Carbon coating can absolutely prevent silicon diffusion from SiC fiber to matrix. • Basing on these results, the model of formation process of the interfacial reaction products in the composites was proposed.

  11. Gold nanoparticle assisted assembly of a heme protein for enhancement of long-range interfacial electron transfer

    DEFF Research Database (Denmark)

    Jensen, Palle Skovhus; Chi, Qijin; Grumsen, Flemming Bjerg

    2007-01-01

    and characterization of water-soluble gold nanoparticles (AuNPs) with core diameter 3-4 nm and their application for the enhancement of long-range interfacial ET of a heme protein. Gold nanoparticles were electrostatically conjugated with cyt c to form nanoparticle-protein hybrid ET systems with well...... and the protein molecule. When the nanoparticle-protein conjugates are assembled on Au(111) surfaces, long-range interfacial ET across a physical distance of over 50 A via the nanoparticle becomes feasible. Moreover, significant enhancement of the interfacial ET rate by more than an order of magnitude compared...... with that of cyt c in the absence of AuNPs is observed. AuNPs appear to serve as excellent ET relays, most likely by facilitating the electronic coupling between the protein redox center and the electrode surface....

  12. Electronic Coupling Dependence of Ultrafast Interfacial Electron Transfer on Nanocrystalline Thin Films and Single Crystal

    Energy Technology Data Exchange (ETDEWEB)

    Lian, Tianquan

    2014-04-22

    The long-term goal of the proposed research is to understand electron transfer dynamics in nanoparticle/liquid interface. This knowledge is essential to many semiconductor nanoparticle based devices, including photocatalytic waste degradation and dye sensitized solar cells.

  13. Influence of enzymatic reactions on the electrochemical behavior of EN X2CrNiMo17-11-2 (AISI 316L) stainless steel in bio-corrosion: role of interfacial processes on the modification of the passive layer

    International Nuclear Information System (INIS)

    Landoulsi, J.

    2008-01-01

    The outstanding corrosion behavior of stainless steels (SS) results from the presence of thin oxide layer (some nanometers). In non sterile aqueous media, stainless steels may exhibit a non stable behavior resulting from interactions between microbial species and passive film. In fact, microorganisms can be deeply involved in the corrosion processes usually reported as Microbial Influenced Corrosion (MIC). They can induce the initiation or the acceleration of this phenomenon and they do so when organized in bio-films. From the electrochemical point of view, stainless steels showed an increase of the free corrosion potential (Ecorr) attributed to the bio-film settlement. The Eco' ennoblement was broadly reported in seawater and seems to be confirmed in fresh water according to recent findings. A considerable progress in the comprehension of MIC processes was related to the role of extracellular species, essentially enzymes. Many enzymatic reactions occurring in bio-films consist on using oxygen as electron acceptor to generate hydrogen peroxide and related species. The aim of this work is to understand the mechanisms involved in the electrochemical behavior of stainless steel according to an enzymatic approach in medium simulating fresh water. To this end, glucose oxidase was chosen to globalize aerobic activities of bio-films. Electrochemical measurements in situ and surface analysis allow the comprehension of the role and the nature of interfacial processes. Surface characterization was performed with the help of a new quantitative utilization of XPS analysis and AFM. Results show a significant evolution in term of morphology (surface organization), (ii) chemical composition (passive layer, adsorbed organic species) and (iii) chemical reaction (oxidation, dissolution, effect of enzyme). Finally, a new enzymatic system is proposed to mimic specific physicochemical conditions at the SS / bio-film interface, in particular enzymatic generation of oxidant species in

  14. Observation of Dynamic Interfacial Layers in Li-Ion and Li-O_2 Batteries by Scanning Electrochemical Microscopy

    International Nuclear Information System (INIS)

    Bülter, Heinz; Schwager, Patrick; Fenske, Daniela; Wittstock, Gunther

    2016-01-01

    Highlights: • Imaging changes of solid electrolyte interphases on rinsed lithiated graphite. • Strongly non-uniform changes of SEI passivation properties. • In situ imaging of clogged gas diffusion electrodes of Li/O_2 batteries. - Abstract: The requirements of high energy density in modern batteries dictate the use of very high (oxidizing) or very low (reducing) potential for negative and positive electrode materials. These extreme potentials can cause molecular compounds to undergo electron transfer reactions at the interfaces. This is well documented for lithium-ion batteries, where a solid electrolyte interphase (SEI) between the lithiated graphite electrode and the electrolyte is formed by the decomposition of electrolyte components mainly during the first charging process. Characterization of the SEI is a challenge because of the variety of chemically similar components and enclosed electrolyte species. Furthermore, ex situ analysis of the SEI requires separation and isolation of the SEI, which may change the content and the structure of the SEI. Scanning electrochemical microscopy (SECM) provides in situ analysis of passivating layers formed at battery electrodes. Such approaches must deal with continuous changes of the studied interfaces. This is illustrated for the in situ investigation of the electron transport at SEI-covered lithiated graphite using 2,5-di-tert-butyl-1,4-dimethoxy benzene as SECM mediator in an inert atmosphere. With this setup, the influence of rinsing protocols on the passivating properties of the SEI was studied. An extensive rinsing compared to our previous studies [DOI 10.1002/anie.201403935] leads to much higher local variation of the SEI passivation properties which continue over the entire observation time of 54 h. The second example uses a SECM generation-collection experiment to detect gas permeation through a gas-diffusion electrode (GDE) of a Li-O_2 cell into a Li"+-containing organic electrolyte. The passivation of the

  15. Amorphous oxide alloys as interfacial layers with broadly tunable electronic structures for organic photovoltaic cells.

    Science.gov (United States)

    Zhou, Nanjia; Kim, Myung-Gil; Loser, Stephen; Smith, Jeremy; Yoshida, Hiroyuki; Guo, Xugang; Song, Charles; Jin, Hosub; Chen, Zhihua; Yoon, Seok Min; Freeman, Arthur J; Chang, Robert P H; Facchetti, Antonio; Marks, Tobin J

    2015-06-30

    In diverse classes of organic optoelectronic devices, controlling charge injection, extraction, and blocking across organic semiconductor-inorganic electrode interfaces is crucial for enhancing quantum efficiency and output voltage. To this end, the strategy of inserting engineered interfacial layers (IFLs) between electrical contacts and organic semiconductors has significantly advanced organic light-emitting diode and organic thin film transistor performance. For organic photovoltaic (OPV) devices, an electronically flexible IFL design strategy to incrementally tune energy level matching between the inorganic electrode system and the organic photoactive components without varying the surface chemistry would permit OPV cells to adapt to ever-changing generations of photoactive materials. Here we report the implementation of chemically/environmentally robust, low-temperature solution-processed amorphous transparent semiconducting oxide alloys, In-Ga-O and Ga-Zn-Sn-O, as IFLs for inverted OPVs. Continuous variation of the IFL compositions tunes the conduction band minima over a broad range, affording optimized OPV power conversion efficiencies for multiple classes of organic active layer materials and establishing clear correlations between IFL/photoactive layer energetics and device performance.

  16. Electronic band structures and optical properties of type-II superlattice photodetectors with interfacial effect.

    Science.gov (United States)

    Qiao, Peng-Fei; Mou, Shin; Chuang, Shun Lien

    2012-01-30

    The electronic band structures and optical properties of type-II superlattice (T2SL) photodetectors in the mid-infrared (IR) range are investigated. We formulate a rigorous band structure model using the 8-band k · p method to include the conduction and valence band mixing. After solving the 8 × 8 Hamiltonian and deriving explicitly the new momentum matrix elements in terms of envelope functions, optical transition rates are obtained through the Fermi's golden rule under various doping and injection conditions. Optical measurements on T2SL photodetectors are compared with our model and show good agreement. Our modeling results of quantum structures connect directly to the device-level design and simulation. The predicted doping effect is readily applicable to the optimization of photodetectors. We further include interfacial (IF) layers to study the significance of their effect. Optical properties of T2SLs are expected to have a large tunable range by controlling the thickness and material composition of the IF layers. Our model provides an efficient tool for the designs of novel photodetectors.

  17. Hydrogen storage material, electrochemically active material, electrochemical cell and electronic equipment

    NARCIS (Netherlands)

    2008-01-01

    The invention relates to a hydrogen storage material comprising an alloy of magnesium. The invention further relates to an electrochemically active material and an electrochemical cell provided with at least one electrode comprising such a hydrogen storage material. Also, the invention relates to

  18. A layer-by-layer ZnO nanoparticle-PbS quantum dot self-assembly platform for ultrafast interfacial electron injection

    KAUST Repository

    Eita, Mohamed Samir; Usman, Anwar; El-Ballouli, AlA'A O.; Alarousu, Erkki Antero; Bakr, Osman; Mohammed, Omar F.

    2014-01-01

    solar cell. To achieve sufficient electron transfer and subsequently high conversion efficiency in these solar cells, however, energy-level alignment and interfacial contact between the donor and the acceptor units are needed. Here, the layer-by

  19. Long-Range Interfacial Electrochemical Electron Transfer of Pseudomonas aeruginosa Azurin-Gold Nanoparticle Hybrid Systems

    DEFF Research Database (Denmark)

    Jensen, Palle Skovhus; Chi, Qijin; Zhang, Jingdong

    2009-01-01

    We have prepared a "hybrid" of the blue copper protein azurin (Pseudomonas aeruginosa) and a 3 nm gold nanoparticle (AuNP). The AuNP/azurin hybrid was assembled on a Au(111)-electrode surface in a two-step process. The AuNP was first attached to the Au(111) electrode via Au-S chemisorption of a 4...

  20. Interfacial electrochemical electron transfer in biology – Towards the level of the single molecule

    DEFF Research Database (Denmark)

    Zhang, Jingdong; Chi, Qijin; Hansen, Allan Glargaard

    2012-01-01

    Physical electrochemistry has undergone a remarkable evolution over the last few decades, integrating advanced techniques and theory from solid state and surface physics. Single-crystal electrode surfaces have been a core notion, opening for scanning tunnelling microscopy directly in aqueous elec...

  1. Computational micromechanics analysis of electron hopping and interfacial damage induced piezoresistive response in carbon nanotube-polymer nanocomposites

    International Nuclear Information System (INIS)

    Chaurasia, A K; Seidel, G D; Ren, X

    2014-01-01

    Carbon nanotube (CNT)-polymer nanocomposites have been observed to exhibit an effective macroscale piezoresistive response, i.e., change in macroscale resistivity when subjected to applied deformation. The macroscale piezoresistive response of CNT-polymer nanocomposites leads to deformation/strain sensing capabilities. It is believed that the nanoscale phenomenon of electron hopping is the major driving force behind the observed macroscale piezoresistivity of such nanocomposites. Additionally, CNT-polymer nanocomposites provide damage sensing capabilities because of local changes in electron hopping pathways at the nanoscale because of initiation/evolution of damage. The primary focus of the current work is to explore the effect of interfacial separation and damage at the nanoscale CNT-polymer interface on the effective macroscale piezoresistive response. Interfacial separation and damage are allowed to evolve at the CNT-polymer interface through coupled electromechanical cohesive zones, within a finite element based computational micromechanics framework, resulting in electron hopping based current density across the separated CNT-polymer interface. The macroscale effective material properties and gauge factors are evaluated using micromechanics techniques based on electrostatic energy equivalence. The impact of the electron hopping mechanism, nanoscale interface separation and damage evolution on the effective nanocomposite electrostatic and piezoresistive response is studied in comparison with the perfectly bonded interface. The effective electrostatic/piezoresistive response for the perfectly bonded interface is obtained based on a computational micromechanics model developed in the authors’ earlier work. It is observed that the macroscale effective gauge factors are highly sensitive to strain induced formation/disruption of electron hopping pathways, interface separation and the initiation/evolution of interfacial damage. (paper)

  2. Interfacial engineering of electron transport layer using Caesium Iodide for efficient and stable organic solar cells

    Science.gov (United States)

    Upama, Mushfika Baishakhi; Elumalai, Naveen Kumar; Mahmud, Md Arafat; Wright, Matthew; Wang, Dian; Xu, Cheng; Haque, Faiazul; Chan, Kah Howe; Uddin, Ashraf

    2017-09-01

    Polymer solar cells (PSCs) have gained immense research interest in the recent years predominantly due to low-cost, solution process-ability, and facile device fabrication. However, achieving high stability without compromising the power conversion efficiency (PCE) serves to be an important trade-off for commercialization. In line with this, we demonstrate the significance of incorporating a CsI/ZnO bilayer as electron transport layer (ETL) in the bulk heterojunction PSCs employing low band gap polymer (PTB7) and fullerene (PC71BM) as the photo-active layer. The devices with CsI/ZnO interlayer exhibited substantial enhancement of 800% and 12% in PCE when compared to the devices with pristine CsI and pristine ZnO as ETL, respectively. Furthermore, the UV and UV-ozone induced degradation studies revealed that the devices incorporating CsI/ZnO bilayer possess excellent decomposition stability (∼23% higher) over the devices with pristine ZnO counterparts. The incorporation of CsI between ITO and ZnO was found to favorably modify the energy-level alignment at the interface, contributing to the charge collection efficiency as well as protecting the adjacent light absorbing polymer layers from degradation. The mechanism behind the improvement in PCE and stability is analyzed using the electrochemical impedance spectroscopy and dark I-V characteristics.

  3. Overpotential-induced lability of the electronic overlap factor in long-range electrochemical electron transfer: charge and distance dependence

    DEFF Research Database (Denmark)

    Kornyshev, A. A.; Kuznetsov, A. M.; Nielsen, Jens Ulrik

    2000-01-01

    Long-distance electrochemical electron transfer exhibits approximately exponential dependence on the electron transfer distance. On the basis of a jellium model of the metal surface we show that the slope of the logarithm of the current vs. the transfer distance also depends strongly...

  4. Enzyme-immobilized SiO2-Si electrode: Fast interfacial electron transfer with preserved enzymatic activity

    Science.gov (United States)

    Wang, Gang; Yau, Siu-Tung

    2005-12-01

    The enzyme, glucose oxidase (GOx), is immobilized using electrostatic interaction on the native oxide of heavily doped n-type silicon. Voltammetric measurement shows that the immobilized GOx gives rise to a very fast enzyme-silicon interfacial electron transfer rate constant of 7.9s-1. The measurement also suggests that the enzyme retains its native conformation when immobilized on the silicon surface. The preserved native conformation of GOx is further confirmed by testing the enzymatic activity of the immobilized GOx using glucose. The GOx-immobilized silicon is shown to behave as a glucose sensor that detects glucose with concentrations as low as 50μM.

  5. Carbon nanotubes--electronic/electrochemical properties and application for nanoelectronics and photonics.

    Science.gov (United States)

    Sgobba, Vito; Guldi, Dirk M

    2009-01-01

    The fundamental chemical, redox, electrochemical, photoelectrochemical, optical and optoelectronic features of carbon nanotubes are surveyed with particular emphasis on the most relevant applications as electron donor/electron acceptor or as electron conductor/hole conductor materials, in solutions and in the solid state. Methods that aim at p- and n-doping as a means to favor hole or electron injection/transport are covered as well (critical review, 208 references).

  6. Electrochemical migration of tin in electronics and microstructure of the dendrites

    DEFF Research Database (Denmark)

    Minzari, Daniel; Grumsen, Flemming Bjerg; Jellesen, Morten Stendahl

    2011-01-01

    The macro-, micro-, and nano-scale morphology and structure of tin dendrites, formed by electrochemical migration on a surface mount ceramic chip resistor having electrodes consisting of tin with small amounts of Pb (∼2wt.%) was investigated by scanning electron microscopy and transmission electr...... by the dehydration of the hydrated oxide originally formed in solution ex-situ in ambient air.......The macro-, micro-, and nano-scale morphology and structure of tin dendrites, formed by electrochemical migration on a surface mount ceramic chip resistor having electrodes consisting of tin with small amounts of Pb (∼2wt.%) was investigated by scanning electron microscopy and transmission electron...... microscopy including Energy dispersive X-ray spectroscopy and electron diffraction. The tin dendrites were formed under 5 or 12V potential bias in 10ppm by weight NaCl electrolyte as a micro-droplet on the resistor during electrochemical migration experiments. The dendrites formed were found to have...

  7. Interfacial electron and phonon scattering processes in high-powered nanoscale applications.

    Energy Technology Data Exchange (ETDEWEB)

    Hopkins, Patrick E.

    2011-10-01

    The overarching goal of this Truman LDRD project was to explore mechanisms of thermal transport at interfaces of nanomaterials, specifically linking the thermal conductivity and thermal boundary conductance to the structures and geometries of interfaces and boundaries. Deposition, fabrication, and post possessing procedures of nanocomposites and devices can give rise to interatomic mixing around interfaces of materials leading to stresses and imperfections that could affect heat transfer. An understanding of the physics of energy carrier scattering processes and their response to interfacial disorder will elucidate the potentials of applying these novel materials to next-generation high powered nanodevices and energy conversion applications. An additional goal of this project was to use the knowledge gained from linking interfacial structure to thermal transport in order to develop avenues to control, or 'tune' the thermal transport in nanosystems.

  8. Many-electron electrochemical processes. Reactions in molten salts, room-temperature ionic liquids and ionic solutions

    Energy Technology Data Exchange (ETDEWEB)

    Andriiko, Aleksandr A. [National Technical Univ. Ukraine, Kyiv (Ukraine). Kyiv Polytechnic Inst.; Andriyko, Yuriy O. [CEST Centre of Electrochemical Surface Technology, Wiener Neustadt (Austria); Nauer, Gerhard E. [Vienna Univ. (Austria). Inst. of Physical Chemistry

    2013-02-01

    The authors provide a unified concept for understanding multi-electron processes in electrochemical systems such as molten salts, ionic liquids, or ionic solutions. A major advantage of this concept is its independence of assumptions like one-step many-electron transfers or 'discrete' discharge of complex species. This book contains the following main topics: 1. Many-electron electrochemical systems: Concepts and definitions. 2. Many-electron systems at equilibrium. 3. Phenomenology of electrochemical kinetics. 4. Electrode film systems: experimental evidences. 5. Dynamics of a non-equilibrium electrochemical system. 6. Electrochemistry of Ti(IV) in ionic liquids.

  9. A layer-by-layer ZnO nanoparticle-PbS quantum dot self-assembly platform for ultrafast interfacial electron injection

    KAUST Repository

    Eita, Mohamed Samir

    2014-08-28

    Absorbent layers of semiconductor quantum dots (QDs) are now used as material platforms for low-cost, high-performance solar cells. The semiconductor metal oxide nanoparticles as an acceptor layer have become an integral part of the next generation solar cell. To achieve sufficient electron transfer and subsequently high conversion efficiency in these solar cells, however, energy-level alignment and interfacial contact between the donor and the acceptor units are needed. Here, the layer-by-layer (LbL) technique is used to assemble ZnO nanoparticles (NPs), providing adequate PbS QD uptake to achieve greater interfacial contact compared with traditional sputtering methods. Electron injection at the PbS QD and ZnO NP interface is investigated using broadband transient absorption spectroscopy with 120 femtosecond temporal resolution. The results indicate that electron injection from photoexcited PbS QDs to ZnO NPs occurs on a time scale of a few hundred femtoseconds. This observation is supported by the interfacial electronic-energy alignment between the donor and acceptor moieties. Finally, due to the combination of large interfacial contact and ultrafast electron injection, this proposed platform of assembled thin films holds promise for a variety of solar cell architectures and other settings that principally rely on interfacial contact, such as photocatalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Direct electron transfer: an approach for electrochemical biosensors with higher selectivity and sensitivity

    Directory of Open Access Journals (Sweden)

    Freire Renato S.

    2003-01-01

    Full Text Available The most promising approach for the development of electrochemical biosensors is to establish a direct electrical communication between the biomolecules and the electrode surface. This review focuses on advances, directions and strategies in the development of third generation electrochemical biosensors. Subjects covered include a brief description of the fundamentals of the electron transfer phenomenon and amperometric biosensor development (different types and new oriented enzyme immobilization techniques. Special attention is given to different redox enzymes and proteins capable of electrocatalyzing reactions via direct electron transfer. The analytical applications and future trends for third generation biosensors are also presented and discussed.

  11. Electrochemical Migration on Electronic Chip Resistors in Chloride Environments

    DEFF Research Database (Denmark)

    Minzari, Daniel; Jellesen, Morten Stendahl; Møller, Per

    2009-01-01

    Electrochemical migration behavior of end terminals on ceramic chip resistors (CCRs) was studied using a novel experimental setup in varying sodium chloride concentrations from 0 to 1000 ppm. The chip resistor used for the investigation was 10-kΩ CCR size 0805 with end terminals made of 97Sn3Pb...... rate of the Sn and stability of Sn ions in the solution layer play a significant role in the formation of dendrites, which is controlled by chloride concentration and potential bias. Morphology, composition, and resistance of the dendrites were dependent on chloride concentration and potential....

  12. Engineering Electrochemical Setups for Electron Microscopy of Liquid Processes

    DEFF Research Database (Denmark)

    Jensen, Eric; Burrows, Andrew

    This work focuses on creating tools for imaging liquid samples at atmospheric pressure and room temperature in two different electron microscopes; the scanning electron microscope (SEM) and the transmission electron microscope (TEM). The main focus of the project was the fabrication of the two sy...

  13. Electrochemically oxidized electronic and ionic conducting nanostructured block copolymers for lithium battery electrodes.

    Science.gov (United States)

    Patel, Shrayesh N; Javier, Anna E; Balsara, Nitash P

    2013-07-23

    Block copolymers that can simultaneously conduct electronic and ionic charges on the nanometer length scale can serve as innovative conductive binder material for solid-state battery electrodes. The purpose of this work is to study the electronic charge transport of poly(3-hexylthiophene)-b-poly(ethylene oxide) (P3HT-PEO) copolymers electrochemically oxidized with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt in the context of a lithium battery charge/discharge cycle. We use a solid-state three-terminal electrochemical cell that enables simultaneous conductivity measurements and control over electrochemical doping of P3HT. At low oxidation levels (ratio of moles of electrons removed to moles of 3-hexylthiophene moieties in the electrode), the electronic conductivity (σe,ox) increases from 10(-7) S/cm to 10(-4) S/cm. At high oxidation levels, σe,ox approaches 10(-2) S/cm. When P3HT-PEO is used as a conductive binder in a positive electrode with LiFePO4 active material, P3HT is electrochemically active within the voltage window of a charge/discharge cycle. The electronic conductivity of the P3HT-PEO binder is in the 10(-4) to 10(-2) S/cm range over most of the potential window of the charge/discharge cycle. This allows for efficient electronic conduction, and observed charge/discharge capacities approach the theoretical limit of LiFePO4. However, at the end of the discharge cycle, the electronic conductivity decreases sharply to 10(-7) S/cm, which means the "conductive" binder is now electronically insulating. The ability of our conductive binder to switch between electronically conducting and insulating states in the positive electrode provides an unprecedented route for automatic overdischarge protection in rechargeable batteries.

  14. Electrochemical migration in electronics: effect of contamination and bias conditions

    DEFF Research Database (Denmark)

    Verdingovas, Vadimas; Jellesen, Morten Stendahl; Ambat, Rajan

    A number of reliability issues are caused by mechanisms different from the conventional corrosion due to specific aspects of the printed circuit board assembly (PCBA). The size of the components and the distance between them, combinations of dissimilar metals, voltage and temperature gradients...... – all together influence susceptibility of electronic PCBA to corrosion. When electronics is operating under humid conditions, the cleanliness of the PCBA becomes essential, since corrosion related failures in electronics can occur at extremely low levels of moisture and contamination. A synergetic...... effect of the aspects mentioned above makes it challenging to predict the lifetime of electronic device. The aim of this work is to investigate corrosion influencing factors, which at a later stage improve capabilities of predicting the functioning and herewith reliability of electronics under certain...

  15. Pulse radiolytic and electrochemical investigations of intramolecular electron transfer in carotenoporphyrins and carotenoporphyrin-quinone triads

    International Nuclear Information System (INIS)

    Land, E.J.; Lexa, D.; Bensasson, R.V.; Gust, D.; Moore, T.A.; Moore, A.L.; Liddell, P.A.; Nemeth, G.A.

    1987-01-01

    Thermodynamic and kinetic aspects of intramolecular electron-transfer reactions in carotenoporphyrin dyads and carotenoid-porphyrin-quinone triads have been studied by using pulse radiolysis and cyclic voltammetry. Rapid (<1 μs) electron transfer from carotenoid radical anions to attached porphyrins has been inferred. Carotenoid cations, on the other hand, do not readily accept electrons from attached porphyrins or pyropheophorbides. Electrochemical studies provide the thermodynamic basis for these observations and also allow estimation of the energetics of photoinitiated two-step electron transfer and two-step charge recombination in triad models for photosynthetic charge separation

  16. Exploring the kinetic and thermodynamic aspects of four-electron electrochemical reactions: electrocatalysis of oxygen evolution by metal oxides and biological systems.

    Science.gov (United States)

    Wang, Vincent C-C

    2016-08-10

    Finding fundamental and general mechanisms for electrochemical reactions, such as the oxygen evolution reaction (OER) from water and reduction of CO2, plays vital roles in developing the desired electrocatalysts for facilitating solar fuel production. Recently, density functional theory (DFT) calculations have shown that there is a universal scaling relation of adsorption energy between key intermediate species, HO(ad) and HOO(ad), on the surface of metal oxides as OER electrocatalysts. In this paper, a kinetic and thermodynamic model for the four-electron electrochemical reaction based on previous OER mechanisms proposed by DFT calculations is developed to further investigate the electrocatalytic properties over a wide range of metal oxides and photosystem II. The OER activity of metal oxides (i.e. electrocatalytic current) calculated from the DFT-calculated equilibrium potentials with kinetic properties, such as the rate constants for interfacial electron transfer and catalytic turnover, can lead to a volcano-shaped trend that agrees with the results observed in experiments. In addition, the kinetic aspects of the impact on the electrocatalysts are evaluated. Finally, comparing the results of metal oxides and photosystem II, and fitting experimental voltammograms give further insights into kinetic and thermodynamic roles. Here, the general guidelines for designing OER electrocatalysts with unified kinetic and thermodynamic properties are presented.

  17. Multi-target electrochemical biosensing enabled by integrated CMOS electronics

    International Nuclear Information System (INIS)

    Rothe, J; Lewandowska, M K; Heer, F; Frey, O; Hierlemann, A

    2011-01-01

    An integrated electrochemical measurement system, based on CMOS technology, is presented, which allows the detection of several analytes in parallel (multi-analyte) and enables simultaneous monitoring at different locations (multi-site). The system comprises a 576-electrode CMOS sensor chip, an FPGA module for chip control and data processing, and the measurement laptop. The advantages of the highly versatile system are demonstrated by two applications. First, a label-free, hybridization-based DNA sensor is enabled by the possibility of large-scale integration in CMOS technology. Second, the detection of the neurotransmitter choline is presented by assembling the chip with biosensor microprobe arrays. The low noise level enables a limit of detection of, e.g., 0.3 µM choline. The fully integrated system is self-contained: it features cleaning, functionalization and measurement functions without the need for additional electrical equipment. With the power supplied by the laptop, the system is very suitable for on-site measurements

  18. Interfacial electron transfer of glucose oxidase on poly(glutamic acid)-modified glassy carbon electrode and glucose sensing.

    Science.gov (United States)

    Zhou, Xuechou; Tan, Bingcan; Zheng, Xinyu; Kong, Dexian; Li, Qinglu

    2015-11-15

    The interfacial electron transfer of glucose oxidase (GOx) on a poly(glutamic acid)-modified glassy carbon electrode (PGA/GCE) was investigated. The redox peaks measured for GOx and flavin adenine dinucleotide (FAD) are similar, and the anodic peak of GOx does not increase in the presence of glucose in a mediator-free solution. These indicate that the electroactivity of GOx is not the direct electron transfer (DET) between GOx and PGA/GCE and that the observed electroactivity of GOx is ascribed to free FAD that is released from GOx. However, efficient electron transfer occurred if an appropriate mediator was placed in solution, suggesting that GOx is active. The PGA/GCE-based biosensor showed wide linear response in the range of 0.5-5.5 mM with a low detection limit of 0.12 mM and high sensitivity and selectivity for measuring glucose. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Electrochemical migration of tin in electronics and microstructure of the dendrites

    Energy Technology Data Exchange (ETDEWEB)

    Minzari, Daniel, E-mail: dmin@mek.dtu.d [Section for Materials and Surface Technology, Department for Mechanical Engineering, Technical University of Denmark (Denmark); Grumsen, Flemming Bjerg; Jellesen, Morten S.; Moller, Per; Ambat, Rajan [Section for Materials and Surface Technology, Department for Mechanical Engineering, Technical University of Denmark (Denmark)

    2011-05-15

    Graphical abstract: The electrochemical migration of tin in electronics forms dendritic structures, consisting of a metallic tin core, which is surrounded by oxide layers having various thickness. Display Omitted Research highlights: Electrochemical migration occurs if two conductors are connected by condensed moisture. Metallic ions are dissolved and grow in a dendritic structure that short circuit the electrodes. The dendrite consists of a metallic tin core with oxide layers of various thickness surrounding. Detailed microstructure of dendrites is investigated using electron microscopy. The dendrite microstructure is heterogeneous along the growth direction. - Abstract: The macro-, micro-, and nano-scale morphology and structure of tin dendrites, formed by electrochemical migration on a surface mount ceramic chip resistor having electrodes consisting of tin with small amounts of Pb ({approx}2 wt.%) was investigated by scanning electron microscopy and transmission electron microscopy including Energy dispersive X-ray spectroscopy and electron diffraction. The tin dendrites were formed under 5 or 12 V potential bias in 10 ppm by weight NaCl electrolyte as a micro-droplet on the resistor during electrochemical migration experiments. The dendrites formed were found to have heterogeneous microstructure along the growth direction, which is attributed to unstable growth conditions inside the micro-volume of electrolyte. Selected area electron diffraction showed that the dendrites are metallic tin having sections of single crystal orientation and lead containing intermetallic particles embedded in the structure. At certain areas, the dendrite structure was found to be surrounded by an oxide crust, which is believed to be due to unstable growth conditions during the dendrite formation. The oxide layer was found to be of nanocrystalline structure, which is expected to be formed by the dehydration of the hydrated oxide originally formed in solution ex-situ in ambient air.

  20. Electron transport determines the electrochemical properties of tetrahedral amorphous carbon (ta-C) thin films

    International Nuclear Information System (INIS)

    Palomäki, Tommi; Wester, Niklas; Caro, Miguel A.; Sainio, Sami; Protopopova, Vera; Koskinen, Jari; Laurila, Tomi

    2017-01-01

    Amorphous carbon based electrodes are very promising for electrochemical sensing applications. In order to better understand their structure-function relationship, the effect of film thickness on the electrochemical properties of tetrahedral amorphous carbon (ta-C) electrodes was investigated. ta-C thin films of 7, 15, 30, 50 and 100 nm were characterized in detail with Raman spectroscopy, transmission electron microscopy (TEM), conductive atomic force microscopy (c-AFM), scanning tunneling spectroscopy (STS) and X-ray absorption spectroscopy (XAS) to assess (i) the surface properties of the films, (ii) the effect of film thickness on their structure and electrical properties and (iii) the subsequent correlation with their electrochemistry. The electrochemical properties were investigated by cyclic voltammetry (CV) using two different outer-sphere redox probes, Ru(NH 3 ) 6 3+/2+ and FcMeOH, and by electrochemical impedance spectroscopy (EIS). Computational simulations using density functional theory (DFT) were carried out to rationalize the experimental findings. The characterization results showed that the sp 2 /sp 3 ratio increased with decreasing ta-C film thickness. This correlated with a decrease in mobility gap value and an increase in the average current through the films, which was also consistent with the computational results. XAS indicated that the surface of the ta-C films was always identical and composed of a sp 2 -rich layer. The CV measurements indicated reversible reaction kinetics for both outer-sphere redox probes at 7 and 15 nm ta-C films with a change to quasi-reversible behavior at a thickness of around 30 nm. The charge transfer resistance, obtained from EIS measurements, decreased with decreasing film thickness in accordance with the CV results. Based on the characterization and electrochemical results, we conclude that the reaction kinetics in the case of outer-sphere redox systems is determined mainly by the electron transport through the

  1. Effect of an Interfacial Layer on Electron Tunneling through Atomically Thin Al2O3 Tunnel Barriers.

    Science.gov (United States)

    Wilt, Jamie; Sakidja, Ridwan; Goul, Ryan; Wu, Judy Z

    2017-10-25

    Electron tunneling through high-quality, atomically thin dielectric films can provide a critical enabling technology for future microelectronics, bringing enhanced quantum coherent transport, fast speed, small size, and high energy efficiency. A fundamental challenge is in controlling the interface between the dielectric and device electrodes. An interfacial layer (IL) will contain defects and introduce defects in the dielectric film grown atop, preventing electron tunneling through the formation of shorts. In this work, we present the first systematic investigation of the IL in Al 2 O 3 dielectric films of 1-6 Å's in thickness on an Al electrode. We integrated several advanced approaches: molecular dynamics to simulate IL formation, in situ high vacuum sputtering atomic layer deposition (ALD) to synthesize Al 2 O 3 on Al films, and in situ ultrahigh vacuum scanning tunneling spectroscopy to probe the electron tunneling through the Al 2 O 3 . The IL had a profound effect on electron tunneling. We observed a reduced tunnel barrier height and soft-type dielectric breakdown which indicate that defects are present in both the IL and in the Al 2 O 3 . The IL forms primarily due to exposure of the Al to trace O 2 and/or H 2 O during the pre-ALD heating step of fabrication. As the IL was systematically reduced, by controlling the pre-ALD sample heating, we observed an increase of the ALD Al 2 O 3 barrier height from 0.9 to 1.5 eV along with a transition from soft to hard dielectric breakdown. This work represents a key step toward the realization of high-quality, atomically thin dielectrics with electron tunneling for the next generation of microelectronics.

  2. Metal/dielectric thermal interfacial transport considering cross-interface electron-phonon coupling: Theory, two-temperature molecular dynamics, and thermal circuit

    Science.gov (United States)

    Lu, Zexi; Wang, Yan; Ruan, Xiulin

    2016-02-01

    The standard two-temperature equations for electron-phonon coupled thermal transport across metal/nonmetal interfaces are modified to include the possible coupling between metal electrons with substrate phonons. The previous two-temperature molecular dynamics (TT-MD) approach is then extended to solve these equations numerically at the atomic scale, and the method is demonstrated using Cu/Si interface as an example. A key parameter in TT-MD is the nonlocal coupling distance of metal electrons and nonmetal phonons, and here we use two different approximations. The first is based on Overhauser's "joint-modes" concept, while we use an interfacial reconstruction region as the length scale of joint region rather than the phonon mean-free path as in Overhauser's original model. In this region, the metal electrons can couple to the joint phonon modes. The second approximation is the "phonon wavelength" concept where electrons couple to phonons nonlocally within the range of one phonon wavelength. Compared with the original TT-MD, including the cross-interface electron-phonon coupling can slightly reduce the total thermal boundary resistance. Whether the electron-phonon coupling within the metal block is nonlocal or not does not make an obvious difference in the heat transfer process. Based on the temperature profiles from TT-MD, we construct a new mixed series-parallel thermal circuit. We show that such a thermal circuit is essential for understanding metal/nonmetal interfacial transport, while calculating a single resistance without solving temperature profiles as done in most previous studies is generally incomplete. As a comparison, the simple series circuit that neglects the cross-interface electron-phonon coupling could overestimate the interfacial resistance, while the simple parallel circuit in the original Overhauser's model underestimates the total interfacial resistance.

  3. Surface plasmon enhanced interfacial electron transfer and resonance Raman, surface-enhanced resonance Raman studies of cytochrome C mutants

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Junwei [Iowa State Univ., Ames, IA (United States)

    1999-11-08

    Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO2 were studied on electrochemically roughened silver electrode surfaces. The dependence of the photocurrent on photon energy, applied potential and concentration of nitrite demonstrates that the photoelectrochemical reduction proceeds via photoemission process followed by the capture of hydrated electrons. The excitation of plasmon resonances in nanosized metal structures resulted in the enhancement of the photoemission process. In the case of photoelectrocatalytic reduction of CO2, large photoelectrocatalytic effect for the reduction of CO2 was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO2 in solution. Photoinduced reduction of microperoxidase-11 adsorbed on roughened silver electrode was also observed and attributed to the direct photoejection of free electrons of silver metal. Surface plasmon assisted electron transfer at nanostructured silver particle surfaces was further determined by EPR method.

  4. Electronically type-sorted carbon nanotube-based electrochemical biosensors with glucose oxidase and dehydrogenase.

    Science.gov (United States)

    Muguruma, Hitoshi; Hoshino, Tatsuya; Nowaki, Kohei

    2015-01-14

    An electrochemical enzyme biosensor with electronically type-sorted (metallic and semiconducting) single-walled carbon nanotubes (SWNTs) for use in aqueous media is presented. This research investigates how the electronic types of SWNTs influence the amperometric response of enzyme biosensors. To conduct a clear evaluation, a simple layer-by-layer process based on a plasma-polymerized nano thin film (PPF) was adopted because a PPF is an inactive matrix that can form a well-defined nanostructure composed of SWNTs and enzyme. For a biosensor with the glucose oxidase (GOx) enzyme in the presence of oxygen, the response of a metallic SWNT-GOx electrode was 2 times larger than that of a semiconducting SWNT-GOx electrode. In contrast, in the absence of oxygen, the response of the semiconducting SWNT-GOx electrode was retained, whereas that of the metallic SWNT-GOx electrode was significantly reduced. This indicates that direct electron transfer occurred with the semiconducting SWNT-GOx electrode, whereas the metallic SWNT-GOx electrode was dominated by a hydrogen peroxide pathway caused by an enzymatic reaction. For a biosensor with the glucose dehydrogenase (GDH; oxygen-independent catalysis) enzyme, the response of the semiconducting SWNT-GDH electrode was 4 times larger than that of the metallic SWNT-GDH electrode. Electrochemical impedance spectroscopy was used to show that the semiconducting SWNT network has less resistance for electron transfer than the metallic SWNT network. Therefore, it was concluded that semiconducting SWNTs are more suitable than metallic SWNTs for electrochemical enzyme biosensors in terms of direct electron transfer as a detection mechanism. This study makes a valuable contribution toward the development of electrochemical biosensors that employ sorted SWNTs and various enzymes.

  5. Simultaneous electrochemical-electron spin resonance studies of carotenoid cation radicals and dications

    International Nuclear Information System (INIS)

    Khaled, M.; Hadjipetrou, A.; Xinhai Chen; Kispert, L.

    1989-01-01

    Carotenoids are present in the chloroplasts of photosynthetic green plants and serve as photoprotect devices and antenna pigments, and active role in the photosynthetic electron-transport chain with the carotenoid cation radical as an integral part of the electron-transfer process. The research reported herein has confirmed that carotenoid cation radicals have a lifetime that is sensitive to solvent, being longest in CH 2 Cl 2 and are best prepared electrochemically. Semiempirical AM1 and INDO calculations of the trans and cis isomers of β-carotene, canthaxanthin and β-apo-8'-carotenal cation radicals predicted the unresolved EPR line whose linewidth varies to a measurable degree with carotenoid, which subsequent experimental observations affirmed. Simultaneous electrochemical - electron spin resonance studies of carotenoid cation radicals and dications have shown the radicals detected by EPR are formed by the one electron oxidation of the carotenoid, that dimers are not formed upon decay of the radical cations and an estimate of the rate of comproportionation as a function of carotenoid can be given. The formal rate constant K' for heterogenous electron transfer rate at the electrode surface has been deduced from rotating disc experiments. Upon deuteration, and in the presence of excess β-carotene, the half-life for decay of the carotenoid radical cation increased an order of magnitude due to the reaction between diffusion carotenoid dications and carotenoids to form additional radical cations. The carotenoid diffusion coefficients deduced by chronocoulometry substantiates this measurement. The produces formed upon electrochemical studies are being studied by HPLC and the isomers formed thermally are being separated. Additional radical reactions are currently being studied by EPR and electrochemical methods

  6. Interfacial electronic structure of C{sub 60}/ZnPc/AZO on photoemission spectroscopy for organic photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Heo, Nari; Kim, Yoonsu; Jung, Yunwoo; Cheon, Suyoung; Cho, Soohaeng [Department of Physics, Yonsei University, Wonju 220-710 (Korea, Republic of); Cho, Sang Wan, E-mail: dio8027@yonsei.ac.kr [Department of Physics, Yonsei University, Wonju 220-710 (Korea, Republic of); Park, Soohyung; Yi, Yeonjin [Institute of Physics and Applied Physics, Yonsei University, Seoul 120-749 (Korea, Republic of); Smith, Kevin E. [Department of Physics, Boston University, 590 Commonwealth Ave, Boston, MA 02215 (United States)

    2016-10-20

    Highlights: • The electronic structure of a bilayer on AZO has been evaluated by UPS and XPS. • The energy difference between the ZnPc HOMO and the C{sub 60} LUMO was determined. • The result is discussed in terms of the work function and resistivity of each TCO. - Abstract: The interfacial electronic structure of a bilayer of fullerene (C{sub 60}) and zinc phthalocyanine (ZnPc) grown on aluminum-doped zinc oxide (AZO) substrates has been evaluated by X-ray and ultraviolet photoemission spectroscopy. The energy difference between the highest occupied molecular orbital (HOMO) level of the ZnPc layer and the lowest unoccupied molecular orbital (LUMO) level of the C{sub 60} layer (E{sup D}{sub HOMO} − E{sup A}{sub LUMO}) was determined and compared to that grown on an indium tin oxide (ITO) substrate. The E{sup D}{sub HOMO} − E{sup A}{sub LUMO} value of the heterojunction on AZO was 1.4 eV, while that on ITO was 1.1 eV. This result is discussed in terms of the differences of the work function and resistivity of each transparent conductive oxide. We also obtained complete energy level diagrams of C{sub 60}/ZnPc/AZO and C{sub 60}/ZnPc/ITO.

  7. Structural and interfacial characteristics of thin (2 films grown by electron cyclotron resonance plasma oxidation on [100] Si substrates

    International Nuclear Information System (INIS)

    Nguyen, T.D.; Carl, D.A.; Hess, D.W.; Lieberman, M.A.; Gronsky, R.

    1991-04-01

    The feasibility of fabricating ultra-thin SiO 2 films on the order of a few nanometer thickness has been demonstrated. SiO 2 thin films of approximately 7 nm thickness have been produced by ion flux-controlled Electron Cyclotron Resonance plasma oxidation at low temperature on [100] Si substrates, in reproducible fashion. Electrical measurements of these films indicate that they have characteristics comparable to those of thermally grown oxides. The thickness of the films was determined by ellipsometry, and further confirmed by cross-sectional High-Resolution Transmission Electron Microscopy. Comparison between the ECR and the thermal oxide films shows that the ECR films are uniform and continuous over at least a few microns in lateral direction, similar to the thermal oxide films grown at comparable thickness. In addition, HRTEM images reveal a thin (1--1.5 nm) crystalline interfacial layer between the ECR film and the [100] substrate. Thinner oxide films of approximately 5 nm thickness have also been attempted, but so far have resulted in nonuniform coverage. Reproducibility at this thickness is difficult to achieve

  8. Effect of morphology and defect density on electron transfer of electrochemically reduced graphene oxide

    International Nuclear Information System (INIS)

    Zhang, Yan; Hao, Huilian; Wang, Linlin

    2016-01-01

    Highlights: • Different morphologies of ERGO on the surface of GCE were prepared via different methods. • The defect densities of ERGO were controlled by tuning the mass or concentration of GO. • A higher defect density of ERGO accelerates electron transfer rate. • ERGO with more exposed edge planes shows significantly higher electron transfer kinetics. • Both edge planes and defect density contribute to electron transfer of ERGO. - Abstract: Electrochemically reduced graphene oxide (ERGO) is widely used to construct electrochemical sensors. Understanding the electron transfer behavior of ERGO is essential for its electrode material applications. In this paper, different morphologies of ERGO were prepared via two different methods. Compared to ERGO/GCEs prepared by electrochemical reduction of pre-deposited GO, more exposed edge planes of ERGO are observed on the surface of ERGO-GCE that was constructed by electrophoretic deposition of GO. The defect densities of ERGO were controlled by tuning the mass or concentration of GO. The electron transfer kinetics (k"0) of GCE with different ERGOs was comparatively investigated. Owing to increased surface areas and decreased defect density, the k"0 values of ERGO/GCE initially increase and then decrease with incrementing of GO mass. When the morphology and surface real areas of ERGO-GCE are the same, an increased defect density induces an accelerated electron transfer rate. k"0 valuesof ERGO-GCEs are about 1 order of magnitude higher than those of ERGO/GCEs due to the difference in the amount of edge planes. This work demonstrates that both defect densities and edge planes of ERGO play crucial roles in electron transfer kinetics.

  9. Effect of morphology and defect density on electron transfer of electrochemically reduced graphene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan, E-mail: yanzhang@sues.edu.cn [School of Material Engineering, Shanghai University of Engineering Science, Shanghai 201620 (China); Hao, Huilian, E-mail: huilian.hao@sues.edu.cn [School of Material Engineering, Shanghai University of Engineering Science, Shanghai 201620 (China); Wang, Linlin, E-mail: wlinlin@mail.ustc.edu.cn [College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620 (China)

    2016-12-30

    Highlights: • Different morphologies of ERGO on the surface of GCE were prepared via different methods. • The defect densities of ERGO were controlled by tuning the mass or concentration of GO. • A higher defect density of ERGO accelerates electron transfer rate. • ERGO with more exposed edge planes shows significantly higher electron transfer kinetics. • Both edge planes and defect density contribute to electron transfer of ERGO. - Abstract: Electrochemically reduced graphene oxide (ERGO) is widely used to construct electrochemical sensors. Understanding the electron transfer behavior of ERGO is essential for its electrode material applications. In this paper, different morphologies of ERGO were prepared via two different methods. Compared to ERGO/GCEs prepared by electrochemical reduction of pre-deposited GO, more exposed edge planes of ERGO are observed on the surface of ERGO-GCE that was constructed by electrophoretic deposition of GO. The defect densities of ERGO were controlled by tuning the mass or concentration of GO. The electron transfer kinetics (k{sup 0}) of GCE with different ERGOs was comparatively investigated. Owing to increased surface areas and decreased defect density, the k{sup 0} values of ERGO/GCE initially increase and then decrease with incrementing of GO mass. When the morphology and surface real areas of ERGO-GCE are the same, an increased defect density induces an accelerated electron transfer rate. k{sup 0} valuesof ERGO-GCEs are about 1 order of magnitude higher than those of ERGO/GCEs due to the difference in the amount of edge planes. This work demonstrates that both defect densities and edge planes of ERGO play crucial roles in electron transfer kinetics.

  10. Effect of Electron Beam Irradiation of the Characteristics of Jute Fibers and the Interfacial Properties of Jute/PLA Green Composites

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Sang Gyu; Cho, Dong Hwan [Kumoh National Institute of Technology, Gumi (Korea, Republic of); Lee, Byung Cheol [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2010-07-01

    Cellulose-based natural fibers such as jute, knife and hemp have promising potential as a replacement for glass fibers in a polymer composite system because of their many advantages like natural abundance, low cost, light weight, biodegradability, carbon dioxide reduction in nature and acceptable mechanical properties. However, natural fibers need an appropriate surface treatment modifying their surface characteristics in order to effectively improve the interfacial properties as well as the mechanical and thermal properties. Electron beam irradiation technique is particularly interesting as it may offer the possibility to modify the surfaces and to enhance the properties of polymer materials such as fibers, films and composites. In addition, electron beam processing has a merit because it is a dry, solvent free and eco-friendly method with a fast throughput rate. In the present study, Jute fibers were irradiated at different dosages of electron beam from 10 to 100 kGy. The result was compared with raw jute fibers un-irradiated, showing the effect on the interfacial shear strength between jute fibers and PLA in terms of single fiber tensile property, fiber surface topology, and chemical composition occurring in jute fibers upon irradiation. It has been found that the surface topology and chemical characteristics of jute fibers significantly depended on the electron beam dosage irradiated, directly influencing the interfacial shear strength and interlaminar shear strength of jute-PLA green composites. It was concluded that electron beam irradiation played a contributing role not only in physically modifying the jute fiber surfaces but also in improving the interfacial properties between jute fibers and poly in the green composite, exhibiting the most effectiveness at a low electron beam energy of 10 kGy.

  11. Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy

    KAUST Repository

    Zhu, Yihan; Ciston, Jim; Zheng, Bin; Miao, Xiaohe; Czarnik, Cory; Pan, Yichang; Sougrat, Rachid; Lai, Zhiping; Hsiung, Chia-En; Yao, Kexin; Pinnau, Ingo; Pan, Ming; Han, Yu

    2017-01-01

    .1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM

  12. Studies of Interfacial Regions by Sum-Frequency Generation with a Free-Electron Laser

    NARCIS (Netherlands)

    Eliel, E. R.; van der Ham, E. W. M.; Vrehen, Q. H. F.; Thooft, G. W.; Barmentlo, M.; Auerhammer, J. M.; van der Meer, A. F. G.; van Amersfoort, P. W.

    1995-01-01

    The use of a Free-Electron Laser (FEL) allows the study of (non)linear optical properties of materials over unsurpassed large spectral intervals. As an example, we report on the use of a FEL as the infrared source in spectroscopic infrared-visible Sum-Frequency Generation (SFG). Employing the

  13. Van der Waals Epitaxy of GaSe/Graphene Heterostructure: Electronic and Interfacial Properties.

    Science.gov (United States)

    Ben Aziza, Zeineb; Henck, Hugo; Pierucci, Debora; Silly, Mathieu G; Lhuillier, Emmanuel; Patriarche, Gilles; Sirotti, Fausto; Eddrief, Mahmoud; Ouerghi, Abdelkarim

    2016-10-07

    Stacking two-dimensional materials in so-called van der Waals (vdW) heterostructures, like the combination of GaSe and graphene, provides the ability to obtain hybrid systems which are suitable to design optoelectronic devices. Here, we report the structural and electronic properties of the direct growth of multilayered GaSe by Molecular beam Epitaxy (MBE) on graphene. Reflection high-energy electron diffraction (RHEED) images exhibited sharp streaky features indicative of high quality GaSe layer produced via a vdW epitaxy. Micro-Raman spectroscopy showed that, after the vdW hetero-interface formation, the Raman signature of pristine graphene is preserved. However, the GaSe film tuned the charge density of graphene layer by shifting the Dirac point by about 80 meV toward lower binding energies, attesting an electron transfer from graphene to GaSe. Angle-resolved photoemission spectroscopy (ARPES) measurements showed that the maximum of the valence band of few layers of GaSe are located at the Γ point at a binding energy of about -0.73 eV relatively to the Fermi level (p-type doping). From the ARPES measurements, a hole effective mass defined along the ΓM direction and equal to about m*/m0 = -1.1 was determined. By coupling the ARPES data with high resolution X-ray photoemission spectroscopy (HR-XPS) measurements, the Schottky interface barrier height was estimated to be 1.2 eV. These findings allow deeper understanding of the interlayer interactions and the electronic structure of GaSe/graphene vdW heterostructure.

  14. Probing interfacial electronic properties of graphene/CH3NH3PbI3 heterojunctions: A theoretical study

    Science.gov (United States)

    Hu, Jisong; Ji, Gepeng; Ma, Xinguo; He, Hua; Huang, Chuyun

    2018-05-01

    Interfacial interactions and electronic properties of graphene/CH3NH3PbI3 heterojunctions were investigated by first-principles calculations incorporating semiempirical dispersion-correction scheme to describe van der Waals interactions. Two lattice match configurations between graphene and CH3NH3PbI3(0 0 1) slab were constructed in parallel contact and both of them were verified to form remarkable van der Waals heterojunctions with similar work functions. Our calculated energy band structures show that the Dirac-cone of graphene and the direct band gap of CH3NH3PbI3 are still preserved in the heterojunctions, thus graphene can be a promising candidate either as a capping or supporting layer for encapsulating CH3NH3PbI3 layer. It is identified that the Schottky barrier of graphene/CH3NH3PbI3 heterojunctions can be controlled by the interlayer distance and affected by the stacking pattern of graphene and CH3NH3PbI3. The 3D charge density differences present the build-in internal electric field from graphene to CH3NH3PbI3 after interface equilibrium and thus, a low n-type Schottky barrier is needed for high efficient charge transferring in the interface. The possible mechanism of the band edge modulations in the heterojunctions and corresponding photoinduced charge transfer processes are also described.

  15. Thermal analysis of epidermal electronic devices integrated with human skin considering the effects of interfacial thermal resistance

    Science.gov (United States)

    Li, Yuhang; Zhang, Jianpeng; Xing, Yufeng; Song, Jizhou

    2018-05-01

    Epidermal electronic devices (EEDs) have similar mechanical properties as those of human skin such that they can be integrated with human skin for potential applications in monitoring of human vital signs for diagnostic, therapeutic or surgical functions. Thermal management is critical for EEDs in these applications since excessive heating may cause discomfort. Comprehensive analytical studies, finite element analysis and experiments are carried out to study the effects of interfacial thermal resistance between EEDs and human skin on thermal properties of the EED/skin system in this paper. The coupling between the Fourier heat transfer in EEDs and the bio-heat transfer in human skin is accounted in the analytical model based on the transfer matrix method to give accurate predictions on temperatures, which agree well with finite element analysis and experimental measurements. It is shown that the maximum temperature increase of the EED for the case of imperfect bonding between EED and skin is much higher than that of perfect bonding. These results may help the design of EEDs in bi-integrated applications and suggest a valuable route to evaluate the bonding condition between EEDs and biological tissues.

  16. CRADA Final Report for CRADA No. ORNL99-0544, Interfacial Properties of Electron Beam Cured Composites

    Energy Technology Data Exchange (ETDEWEB)

    Janke, C.J.

    2005-10-17

    Electron beam (EB) curing is a technology that promises, in certain applications, to deliver lower cost and higher performance polymer matrix composite (PMC) structures compared to conventional thermal curing processes. PMCs enhance performance by making products lighter, stronger, more durable, and less energy demanding. They are essential in weight- and performance-dominated applications. Affordable PMCs can enhance US economic prosperity and national security. US industry expects rapid implementation of electron beam cured composites in aircraft and aerospace applications as satisfactory properties are demonstrated, and implementation in lower performance applications will likely follow thereafter. In fact, at this time and partly because of discoveries made in this project, field demonstrations are underway that may result in the first fielded applications of electron beam cured composites. Serious obstacles preventing the widespread use of electron beam cured PMCs in many applications are their relatively poor interfacial properties and resin toughness. The composite shear strength and resin toughness of electron beam cured carbon fiber reinforced epoxy composites were about 25% and 50% lower, respectively, than those of thermally cured composites of similar formulations. The essential purpose of this project was to improve the mechanical properties of electron beam cured, carbon fiber reinforced epoxy composites, with a specific focus on composite shear properties for high performance aerospace applications. Many partners, sponsors, and subcontractors participated in this project. There were four government sponsors from three federal agencies, with the US Department of Energy (DOE) being the principal sponsor. The project was executed by Oak Ridge National Laboratory (ORNL), NASA and Department of Defense (DOD) participants, eleven private CRADA partners, and two subcontractors. A list of key project contacts is provided in Appendix A. In order to properly

  17. A study on the electronic and interfacial structures of monolayer ReS2-metal contacts.

    Science.gov (United States)

    Wang, Jin; Yang, Guofeng; Sun, Rui; Yan, Pengfei; Lu, Yanan; Xue, Junjun; Chen, Guoqing

    2017-10-11

    In this paper, we perform a systematic and rigorous study to evaluate the Ohmic nature of the top-contact formed by the monolayer ReS 2 (mReS 2 ) and metals (gold, silver, platinum, nickel, titanium, and scandium) by means of first-principles density functional theory calculations. We investigate the potential barrier, charge transfer and atomic orbital overlap at the mReS 2 -metal interface in consideration of van der Waals forces to understand how efficiently carriers could be injected from the metal contact to the mReS 2 channel. ReS 2 is physisorbed on Au and Ag, which leads to little perturbation of its electronic structures and forms a larger Schottky contact and a higher tunnel barrier at the interface. ReS 2 is chemisorbed on Ti and Sc, where the bonding strongly perturbs the electronic structures and is found to be purely Ohmic. The bonding of ReS 2 on Pt and Ni lies between these two extreme cases, demonstrating an intermediate behavior. These findings not only provide an insight into the mReS 2 -metal interfaces but may also prove to be instrumental in the future design of ReS 2 -based devices with good performance.

  18. Endocrine disruptive estrogens role in electron transfer: bio-electrochemical remediation with microbial mediated electrogenesis.

    Science.gov (United States)

    Kumar, A Kiran; Reddy, M Venkateswar; Chandrasekhar, K; Srikanth, S; Mohan, S Venkata

    2012-01-01

    Bioremediation of selected endocrine disrupting compounds (EDCs)/estrogens viz. estriol (E3) and ethynylestradiol (EE2) was evaluated in bio-electrochemical treatment (BET) system with simultaneous power generation. Estrogens supplementation along with wastewater documented enhanced electrogenic activity indicating their function in electron transfer between biocatalyst and anode as electron shuttler. EE2 addition showed more positive impact on the electrogenic activity compared to E3 supplementation. Higher estrogen concentration showed inhibitory effect on the BET performance. Poising potential during start up phase showed a marginal influence on the power output. The electrons generated during substrate degradation might have been utilized for the EDCs break down. Fuel cell behavior and anodic oxidation potential supported the observed electrogenic activity with the function of estrogens removal. Voltammetric profiles, dehydrogenase and phosphatase enzyme activities were also found to be in agreement with the power generation, electron discharge and estrogens removal. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. The study of optimal conditions of electrochemical etching of tunnel electron microscopy tungsten tips

    International Nuclear Information System (INIS)

    Anguiano, E.; Aguilar, M.; Olivar, A.I.

    1996-01-01

    We present the experimental results obtained during the study made in the electrochemical etching of tunneling electron microscopy tungsten tips. The experiments was made using DC and two usual electrolytes: KOH and NaOH. For the tip preparation we used a electrochemical cell with stainless steel cathode and the tungsten wire as anode. the electrodes was introduced in a glass recipient containing the electrolytic solution. We study the effects of applied voltage, polish time, tip length and electrolyte concentration as process relevant parameters. The best condition for tip preparation was obtained with a metallurgical microscope and with a SEM.EDX and Auger analysis was made. The results shown the better tips was made with KOH as electrolyte with a limited concentration range (2-4 normal) and applied voltage (2-6 volts) (Author) 20 refs

  20. Organic/inorganic electrochromic nanocomposites with various interfacial interactions: A review

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Shanxin, E-mail: xiongsx@xust.edu.cn; Yin, Siyuan; Wang, Yuyun; Kong, Zhenzhen; Lan, Jinpeng; Zhang, Runlan; Gong, Ming; Wu, Bohua; Chu, Jia; Wang, Xiaoqin

    2017-07-15

    Highlights: • We review the effects of interfacial interactions in electrochromic nanocomposites. • Interfacial interactions are useful for film fabrication and property-enhancement. • The strong interaction can enhance the electron conduction and structural strength. • The weak interactions exist widely between organic and inorganic phases. • Multiple weak interactions can provide various performance-adjusting approaches. - Abstract: Electrochromic properties of organic or inorganic materials can be improved through preparing organic/inorganic electrochromic nanocomposites. In electrochromic nanocomposites, the interfacial interactions between the organic and inorganic phases play three important roles in preparation and application of the nanocomposites. Firstly, the interfacial interactions result in stable molecular structures. Secondly, they also improve the electron conduction and ion transport process in the nanocomposites. Thirdly, they enhance the electrochemical and electrochromic properties of the nanocomposites. In this paper, we review the common interfacial interactions including covalent bond, coordination bond, electrostatic interaction, hydrogen bond and π-π stacking interaction between the organic and inorganic phases in the electrochromic nanocomposites. The preparation method, the relationship between the structure and properties, and the mechanism of modulation of electrochromic effect in the nanocomposites with various interfacial interactions are surveyed. The strong interfacial interaction, e.g., covalent bond, is helpful for obtaining electrochromic nanocomposites with high electron conduction and high structural strength. However it is very complicated to construct covalent bond between the organic and inorganic phases. Another strong interfacial interaction, the coordination bond is mainly confined to preparation of electrochromic complex of metal ion and pyridine derivative. While, the weak interfacial interactions, e

  1. Organic/inorganic electrochromic nanocomposites with various interfacial interactions: A review

    International Nuclear Information System (INIS)

    Xiong, Shanxin; Yin, Siyuan; Wang, Yuyun; Kong, Zhenzhen; Lan, Jinpeng; Zhang, Runlan; Gong, Ming; Wu, Bohua; Chu, Jia; Wang, Xiaoqin

    2017-01-01

    Highlights: • We review the effects of interfacial interactions in electrochromic nanocomposites. • Interfacial interactions are useful for film fabrication and property-enhancement. • The strong interaction can enhance the electron conduction and structural strength. • The weak interactions exist widely between organic and inorganic phases. • Multiple weak interactions can provide various performance-adjusting approaches. - Abstract: Electrochromic properties of organic or inorganic materials can be improved through preparing organic/inorganic electrochromic nanocomposites. In electrochromic nanocomposites, the interfacial interactions between the organic and inorganic phases play three important roles in preparation and application of the nanocomposites. Firstly, the interfacial interactions result in stable molecular structures. Secondly, they also improve the electron conduction and ion transport process in the nanocomposites. Thirdly, they enhance the electrochemical and electrochromic properties of the nanocomposites. In this paper, we review the common interfacial interactions including covalent bond, coordination bond, electrostatic interaction, hydrogen bond and π-π stacking interaction between the organic and inorganic phases in the electrochromic nanocomposites. The preparation method, the relationship between the structure and properties, and the mechanism of modulation of electrochromic effect in the nanocomposites with various interfacial interactions are surveyed. The strong interfacial interaction, e.g., covalent bond, is helpful for obtaining electrochromic nanocomposites with high electron conduction and high structural strength. However it is very complicated to construct covalent bond between the organic and inorganic phases. Another strong interfacial interaction, the coordination bond is mainly confined to preparation of electrochromic complex of metal ion and pyridine derivative. While, the weak interfacial interactions, e

  2. Electrochemical Detection of Circadian Redox Rhythm in Cyanobacterial Cells via Extracellular Electron Transfer.

    Science.gov (United States)

    Nishio, Koichi; Pornpitra, Tunanunkul; Izawa, Seiichiro; Nishiwaki-Ohkawa, Taeko; Kato, Souichiro; Hashimoto, Kazuhito; Nakanishi, Shuji

    2015-06-01

    Recent research on cellular circadian rhythms suggests that the coupling of transcription-translation feedback loops and intracellular redox oscillations is essential for robust circadian timekeeping. For clarification of the molecular mechanism underlying the circadian rhythm, methods that allow for the dynamic and simultaneous detection of transcription/translation and redox oscillations in living cells are needed. Herein, we report that the cyanobacterial circadian redox rhythm can be electrochemically detected based on extracellular electron transfer (EET), a process in which intracellular electrons are exchanged with an extracellular electrode. As the EET-based method is non-destructive, concurrent detection with transcription/translation rhythm using bioluminescent reporter strains becomes possible. An EET pathway that electrochemically connected the intracellular region of cyanobacterial cells with an extracellular electrode was constructed via a newly synthesized electron mediator with cell membrane permeability. In the presence of the mediator, the open circuit potential of the culture medium exhibited temperature-compensated rhythm with approximately 24 h periodicity. Importantly, such circadian rhythm of the open circuit potential was not observed in the absence of the electron mediator, indicating that the EET process conveys the dynamic information regarding the intracellular redox state to the extracellular electrode. These findings represent the first direct demonstration of the intracellular circadian redox rhythm of cyanobacterial cells. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  3. Interfacial electronic structure of Na deposited on rubrene thin film studied by synchrotron radiation photoemission

    International Nuclear Information System (INIS)

    Wei, Ching-Hsuan; Cheng, Chiu-Ping; Lin, Hong-Cheu; Pi, Tun-Wen

    2015-01-01

    Graphical abstract: - Highlights: • Na deposited on rubrene had undergone three-stage development process via (1) atomic diffusion, (2) atomic incorporation in the surface region, (3) formation of a metallic film. • High resolution core-level photoemission was used to determine the location of the doped Na atoms, which is affiliated at the end position of the tetracene-like backbone. • Na metal was formed on the rubrene thin film. • Ionization potential of the organic molecule regulated with different Na doping concentration could be controllable and favorable in practical applications. - Abstract: The electronic structure of rubrene doped with various concentrations of Na was studied by synchrotron-radiation photoemission. Three stages of development were found with increasing Na concentration; Na penetrating deep into the organic film, followed by development of gap states, and ended with a metallic Na film. The charge transfer from Na to rubrene resulted in a vacuum-level shift. By doping Na into rubrene, we could control the IP of the organic molecule, which is favorable for application in organic semiconductor devices.

  4. Transmission electron microscopy characterization of the interfacial structure of a galvanized dual-phase steel

    Energy Technology Data Exchange (ETDEWEB)

    Aslam, I., E-mail: ia31@msstate.edu [Center for Advanced Vehicular Systems, Mississippi State University, MS 39759 (United States); Department of Mechanical Engineering, Mississippi State University, MS 39762 (United States); Li, B. [Center for Advanced Vehicular Systems, Mississippi State University, MS 39759 (United States); Department of Chemical and Materials Engineering, University of Nevada, Reno, NV 89557 (United States); Martens, R.L.; Goodwin, J.R. [Central Analytical Facility, the University of Alabama, Tuscaloosa, AL 35487 (United States); Rhee, H.J. [Center for Advanced Vehicular Systems, Mississippi State University, MS 39759 (United States); Department of Mechanical Engineering, Mississippi State University, MS 39762 (United States); Goodwin, F. [International Zinc Association, Durham, NC 27713 (United States)

    2016-10-15

    Site-specific studies were carried out to characterize the interface of a galvanized dual-phase (DP) steel. Focused ion beam (FIB) was used to prepare specimens in the interface region (~ 100 nm thick) between the coating and the substrate. Transmission electron microscopy (TEM), scanning TEM (STEM), and high resolution TEM (HRTEM) were performed to resolve the phases and the structures at the interface between the zinc (Zn) coating and the steel substrate. The STEM and TEM results showed that a continuous manganese oxide (MnO) film with a thickness of ~ 20 nm was present on the surface of the substrate while no silicon (Si) oxides were resolved. Internal oxide particles were observed as well in the sub-surface region. Despite the presence of the continuous oxide film, a well-developed inhibition layer was observed right on top of the oxide film. The inhibition layer has a thickness of ~ 100 nm. Possible mechanisms for the growth of the inhibition layer were discussed. - Highlights: •Site-specific examinations were performed on the Zn/steel interface. •Continuous external MnO oxides (20 nm) were observed at the interface. •No Si oxides were observed at the interface. •Internal oxide particles were distributed in the subsurface. •A continuous inhibition layer grew on top of the external oxides.

  5. Synthesis, electronic structure, elastic properties, and interfacial behavior of icosahedral boron-rich solids

    Energy Technology Data Exchange (ETDEWEB)

    Hunold, Oliver

    2017-08-01

    solids a dense B network, characterized by icosahedra-like bonding, provides the required electronic structure. Young's modulus values of amorphous T{sup '}{sub 0.75}Y{sub 0.75}B{sub 14} (a- T{sup '}{sub 0.75}Y{sub 0.75}B{sub 14}, T{sup '} = Sc, Ti, V, Y, Zr, Nb) reach up to 393 GPa for a-Nb{sub 0.75}Y{sub 0.75}B{sub 14}. To critically appraise these predicted data experimentally, a-TiYB{sub 14} and a-ZrYB{sub 14} thin films were synthesized. Chemical composition analysis revealed the presence of high oxygen impurities. The measured Young's modulus values for a-TiYB{sub 14} (301±8 GPa) and a-ZrYB{sub 14} (306±9 GPa) were more than 20% smaller than the predicted ones but still comparable to other hard coatings. These deviations can be rationalized based on theoretical data revealing that the presence of oxygen impurities disrupts the dense 8 network causing a concomitant decrease in molar density and Young's modulus. This in turn highlights the possible usage of amorphous transition metal borides, which can even be synthesized at room temperature, exhibiting stiffness values of up to 82% compared to TiB{sub 2}. Therefore, as a first step towards applications, the suitability of a-AlYB{sub 14} as a coating for polymer forming was investigated. The influence of surface oxidation on the interaction between CH{sub 4} and a-AlYB{sub 14} has been studied theoretically by using OFT and experimentally by ultra-high vacuum - atomic force microscopy. Theory and experiments show the same trend as interaction increases for the oxidized scenario. Oxygen chemisorption induces changes in surface bonding leading to the higher interaction for the latter case. The data serve as proof of concept for the here implemented research strategy for exploring polymer - hard coating interactions in varying atmospheres based on cerrelative experimental and theoretical methods. The results of this work contribute to the understanding of the electronic structure

  6. Hybrid electronic tongue based on optical and electrochemical microsensors for quality control of wine.

    Science.gov (United States)

    Gutiérrez, Manuel; Llobera, Andreu; Vila-Planas, Jordi; Capdevila, Fina; Demming, Stefanie; Büttgenbach, Stephanus; Mínguez, Santiago; Jiménez-Jorquera, Cecilia

    2010-07-01

    A multiparametric system able to classify red and white wines according to the grape varieties and for analysing some specific parameters is presented. The system, known as hybrid electronic tongue, consists of an array of electrochemical microsensors and a colorimetric optofluidic system. The array of electrochemical sensors is composed of six ISFETs based sensors, a conductivity sensor, a redox potential sensor and two amperometric electrodes, an Au microelectrode and a microelectrode for sensing electrochemical oxygen demand. The optofluidic system is entirely fabricated in polymer technology and comprises a hollow structure, air mirrors, microlenses and self-alignment structures. The data obtained from these sensors has been treated with multivariate advanced tools; Principal Component Analysis (PCA), for the patterning recognition and classification of wine samples, and Partial-Least Squares (PLS) regression, for quantification of several chemical and optical parameters of interest in wine quality. The results have demonstrated the utility of this system for distinguishing the samples according to the grape variety and year vintage and for quantifying several sample parameters of interest in wine quality control.

  7. Electrochemical gate-controlled electron transport of redox-active single perylene bisimide molecular junctions

    International Nuclear Information System (INIS)

    Li, C; Mishchenko, A; Li, Z; Pobelov, I; Wandlowski, Th; Li, X Q; Wuerthner, F; Bagrets, A; Evers, F

    2008-01-01

    We report a scanning tunneling microscopy (STM) experiment in an electrochemical environment which studies a prototype molecular switch. The target molecules were perylene tetracarboxylic acid bisimides modified with pyridine (P-PBI) and methylthiol (T-PBI) linker groups and with bulky tert-butyl-phenoxy substituents in the bay area. At a fixed bias voltage, we can control the transport current through a symmetric molecular wire Au|P-PBI(T-PBI)|Au by variation of the electrochemical 'gate' potential. The current increases by up to two orders of magnitude. The conductances of the P-PBI junctions are typically a factor 3 larger than those of T-PBI. A theoretical analysis explains this effect as a consequence of shifting the lowest unoccupied perylene level (LUMO) in or out of the bias window when tuning the electrochemical gate potential VG. The difference in on/off ratios reflects the variation of hybridization of the LUMO with the electrode states with the anchor groups. I T -E S(T) curves of asymmetric molecular junctions formed between a bare Au STM tip and a T-PBI (P-PBI) modified Au(111) electrode in an aqueous electrolyte exhibit a pronounced maximum in the tunneling current at -0.740, which is close to the formal potential of the surface-confined molecules. The experimental data were explained by a sequential two-step electron transfer process

  8. Real-time studies of battery electrochemical reactions inside a transmission electron microscope.

    Energy Technology Data Exchange (ETDEWEB)

    Leung, Kevin; Hudak, Nicholas S.; Liu, Yang; Liu, Xiaohua H.; Fan, Hongyou; Subramanian, Arunkumar; Shaw, Michael J.; Sullivan, John Patrick; Huang, Jian Yu

    2012-01-01

    We report the development of new experimental capabilities and ab initio modeling for real-time studies of Li-ion battery electrochemical reactions. We developed three capabilities for in-situ transmission electron microscopy (TEM) studies: a capability that uses a nanomanipulator inside the TEM to assemble electrochemical cells with ionic liquid or solid state electrolytes, a capability that uses on-chip assembly of battery components on to TEM-compatible multi-electrode arrays, and a capability that uses a TEM-compatible sealed electrochemical cell that we developed for performing in-situ TEM using volatile battery electrolytes. These capabilities were used to understand lithiation mechanisms in nanoscale battery materials, including SnO{sub 2}, Si, Ge, Al, ZnO, and MnO{sub 2}. The modeling approaches used ab initio molecular dynamics to understand early stages of ethylene carbonate reduction on lithiated-graphite and lithium surfaces and constrained density functional theory to understand ethylene carbonate reduction on passivated electrode surfaces.

  9. Unobstructed electron transfer on porous polyelectrolyte nanostructures and its characterization by electrochemical surface plasmon resonance

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Bryce W.; Linman, Matthew J.; Linley, Kamara S.; Hare, Christopher D. [Department of Chemistry, University of California, Riverside, CA 92521 (United States); Cheng Quan, E-mail: quan.cheng@ucr.ed [Department of Chemistry, University of California, Riverside, CA 92521 (United States)

    2010-06-01

    Thin organic films with desirable redox properties have long been sought in biosensor research. We report here the development of a polymer thin film interface with well-defined hierarchical nanostructure and electrochemical behavior, and its characterization by electrochemical surface plasmon resonance (ESPR) spectroscopy. The nano-architecture build-up is monitored in real time with SPR, while the redox response is characterized by cyclic voltammetry in the same flow cell. The multilayer assembly is built on a self-assembled monolayer (SAM) of 1:1 (molar ratio) 11-ferrocenyl-1-undecanethiolate (FUT) and mercaptoundecanoic acid (MUA), and constructed using a layer-by-layer deposition of cationic poly(allylamine hydrochloride) (PAH) and anionic poly(sodium 4-styrenesulfonate) (PSS). Electron transfer (ET) on the mixed surface and the effect of the layer structures on ET are systematically studied. Under careful control, multiple layers can be deposited onto the 1:1 FUT/MUA SAM that presents unobstructed redox chemistry, indicating a highly ordered, extensively porous structure obtained under this condition. The use of SPR to trace the minute change during the electrochemical process offers neat characterization of local environment at the interface, in particular double layer region, allowing for better control over the redox functionality of the multilayers. The 1:1 SAM has a surface coverage of 4.1 +- 0.3 x 10{sup -10} mol cm{sup -2} for ferrocene molecules and demonstrates unperturbed electrochemistry activity even in the presence of a 13 nm polymer film adhered to the electrode surface. This thin layer possesses some desirable properties similar to those on a SAM while presenting approx15 nm exceedingly porous structure for high loading capacity. The high porosity allows perchlorate to freely partition into the film, leading to high current density that is useful for sensitive electrochemical measurements.

  10. Electrochemical Measurement of Electron Transfer Kinetics by Shewanella oneidensis MR-1*

    Science.gov (United States)

    Baron, Daniel; LaBelle, Edward; Coursolle, Dan; Gralnick, Jeffrey A.; Bond, Daniel R.

    2009-01-01

    Shewanella oneidensis strain MR-1 can respire using carbon electrodes and metal oxyhydroxides as electron acceptors, requiring mechanisms for transferring electrons from the cell interior to surfaces located beyond the cell. Although purified outer membrane cytochromes will reduce both electrodes and metals, S. oneidensis also secretes flavins, which accelerate electron transfer to metals and electrodes. We developed techniques for detecting direct electron transfer by intact cells, using turnover and single turnover voltammetry. Metabolically active cells attached to graphite electrodes produced thin (submonolayer) films that demonstrated both catalytic and reversible electron transfer in the presence and absence of flavins. In the absence of soluble flavins, electron transfer occurred in a broad potential window centered at ∼0 V (versus standard hydrogen electrode), and was altered in single (ΔomcA, ΔmtrC) and double deletion (ΔomcA/ΔmtrC) mutants of outer membrane cytochromes. The addition of soluble flavins at physiological concentrations significantly accelerated electron transfer and allowed catalytic electron transfer to occur at lower applied potentials (−0.2 V). Scan rate analysis indicated that rate constants for direct electron transfer were slower than those reported for pure cytochromes (∼1 s−1). These observations indicated that anodic current in the higher (>0 V) window is due to activation of a direct transfer mechanism, whereas electron transfer at lower potentials is enabled by flavins. The electrochemical dissection of these activities in living cells into two systems with characteristic midpoint potentials and kinetic behaviors explains prior observations and demonstrates the complementary nature of S. oneidensis electron transfer strategies. PMID:19661057

  11. Interfacial chemical and electronic structure of cobalt deposition on 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene (C8-BTBT)

    International Nuclear Information System (INIS)

    Zhu, Menglong; Lyu, Lu; Niu, Dongmei; Zhang, Hong; Zhang, Yuhe; Liu, Peng; Gao, Yongli

    2017-01-01

    Highlights: • Chemical reaction and band bending at the interface are confirmed by the UPS and XPS. • Co atoms mostly accumulate at or near the interface and penetration into sublayer is weak. • The electron and hole barriers are too high and interfacial buffer layer is needed for device design. - Abstract: Interfacial chemical and electronic structure of Co deposition on 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene(C8-BTBT) was investigated by ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). Chemical reaction of cobalt with C8-BTBT at the interface is confirmed by a new component of S 2s peak which is electron-rich compared to the original one of C8-BTBT molecules. Intensity evolution of the core level in XPS indicates that the adsorption of Co atoms is mainly at the surface without deeper diffusion into C8-BTBT layer. Initial deposition of Co atoms downward shifts the core levels of C8-BTBT by electron transfer from isolated Co atoms or clusters to the C8-BTBT. Further deposition of Co upward shifts the core levels of C8-BTBT because of the neutralization of the thicker metal Co film. Our investigation suggests an inert buffer layer inserted to protect organic layer from reaction or decomposition and to lower the carrier barriers for both the electron and hole to improve the performance of Co/C8-BTBT-based OFETs.

  12. Interfacial chemical and electronic structure of cobalt deposition on 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene (C8-BTBT)

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Menglong; Lyu, Lu [Institute of Super-Microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Hunan Key Laboratory for Super-Microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Niu, Dongmei, E-mail: mayee@csu.edu.cn [Institute of Super-Microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Hunan Key Laboratory for Super-Microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Zhang, Hong; Zhang, Yuhe; Liu, Peng [Institute of Super-Microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Hunan Key Laboratory for Super-Microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Gao, Yongli, E-mail: ygao@pas.rochester.edu [Institute of Super-Microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Hunan Key Laboratory for Super-Microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Department of Physics and Astronomy, University of Rochester, Rochester NY14627 (United States)

    2017-04-30

    Highlights: • Chemical reaction and band bending at the interface are confirmed by the UPS and XPS. • Co atoms mostly accumulate at or near the interface and penetration into sublayer is weak. • The electron and hole barriers are too high and interfacial buffer layer is needed for device design. - Abstract: Interfacial chemical and electronic structure of Co deposition on 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene(C8-BTBT) was investigated by ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). Chemical reaction of cobalt with C8-BTBT at the interface is confirmed by a new component of S 2s peak which is electron-rich compared to the original one of C8-BTBT molecules. Intensity evolution of the core level in XPS indicates that the adsorption of Co atoms is mainly at the surface without deeper diffusion into C8-BTBT layer. Initial deposition of Co atoms downward shifts the core levels of C8-BTBT by electron transfer from isolated Co atoms or clusters to the C8-BTBT. Further deposition of Co upward shifts the core levels of C8-BTBT because of the neutralization of the thicker metal Co film. Our investigation suggests an inert buffer layer inserted to protect organic layer from reaction or decomposition and to lower the carrier barriers for both the electron and hole to improve the performance of Co/C8-BTBT-based OFETs.

  13. Energy resolved electrochemical impedance spectroscopy for electronic structure mapping in organic semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Nádaždy, V., E-mail: nadazdy@savba.sk; Gmucová, K. [Institute of Physics SAS, Dúbravská cesta 9, 845 11 Bratislava (Slovakia); Schauer, F. [Faculty of Education, Trnava University in Trnava, 918 43 Trnava (Slovakia); Faculty of Applied Informatics, Tomas Bata University in Zlin, 760 05 Zlin (Czech Republic)

    2014-10-06

    We introduce an energy resolved electrochemical impedance spectroscopy method to map the electronic density of states (DOS) in organic semiconductor materials. The method consists in measurement of the charge transfer resistance of a semiconductor/electrolyte interface at a frequency where the redox reactions determine the real component of the impedance. The charge transfer resistance value provides direct information about the electronic DOS at the energy given by the electrochemical potential of the electrolyte, which can be adjusted using an external voltage. A simple theory for experimental data evaluation is proposed, along with an explanation of the corresponding experimental conditions. The method allows mapping over unprecedentedly wide energy and DOS ranges. Also, important DOS parameters can be determined directly from the raw experimental data without the lengthy analysis required in other techniques. The potential of the proposed method is illustrated by tracing weak bond defect states induced by ultraviolet treatment above the highest occupied molecular orbital in a prototypical σ-conjugated polymer, poly[methyl(phenyl)silylene]. The results agree well with those of our previous DOS reconstruction by post-transient space-charge-limited-current spectroscopy, which was, however, limited to a narrow energy range. In addition, good agreement of the DOS values measured on two common π-conjugated organic polymer semiconductors, polyphenylene vinylene and poly(3-hexylthiophene), with the rather rare previously published data demonstrate the accuracy of the proposed method.

  14. Electrochemically grafted polypyrrole changes photoluminescence of electronic states inside nanocrystalline diamond

    Energy Technology Data Exchange (ETDEWEB)

    Galář, P., E-mail: pavel.galar@mff.cuni.cz; Malý, P. [Faculty of Mathematics and Physics, Charles University in Prague, Ke Karlovu 3, Prague 121 16 (Czech Republic); Čermák, J.; Kromka, A.; Rezek, B. [Institute of Physics ASCR v.v.i., Cukrovarnická 10, Prague 160 00 (Czech Republic)

    2014-12-14

    Hybrid diamond-organic interfaces are considered attractive for diverse applications ranging from electronics and energy conversion to medicine. Here we use time-resolved and time-integrated photoluminescence spectroscopy in visible spectral range (380–700 nm) to study electronic processes in H-terminated nanocrystalline diamond films (NCD) with 150 nm thin, electrochemically deposited polypyrrole (PPy) layer. We observe changes in dynamics of NCD photoluminescence as well as in its time-integrated spectra after polymer deposition. The effect is reversible. We propose a model where the PPy layer on the NCD surface promotes spatial separation of photo-generated charge carriers both in non-diamond carbon phase and in bulk diamond. By comparing different NCD thicknesses we show that the effect goes as much as 200 nm deep inside the NCD film.

  15. Theoretical Analysis of Proton Relays in Electrochemical Proton-Coupled Electron Transfer

    International Nuclear Information System (INIS)

    Auer, Benjamin; Fernandez, Laura; Hammes-Schiffer, Sharon

    2011-01-01

    The coupling of long-range electron transfer to proton transport over multiple sites plays a vital role in many biological and chemical processes. Recently a molecule with a hydrogen-bond relay inserted between the proton donor and acceptor sites in a proton-coupled electron transfer (PCET) system was studied electrochemically. The standard rate constants and kinetic isotope effects (KIEs) were measured experimentally for this system and a related single proton transfer system. In the present paper, these systems are studied theoretically using vibronically nonadiabatic rate constant expressions for electrochemical PCET. Application of this approach to proton relays requires the calculation of multidimensional proton vibrational wavefunctions and incorporation of multiple proton donor-acceptor motions. The calculated KIEs and relative standard rate constants for the single and double proton transfer systems are in agreement with the experimental data. The calculations indicate that the standard rate constant is lower for the double proton transfer system because of the smaller overlap integral between the ground state reduced and oxidized proton vibrational wavefunctions for this system, resulting in greater contributions from excited electron-proton vibronic states with higher free energy barriers. The decrease in proton donor-acceptor distances due to thermal fluctuations and the contributions from excited electron-proton vibronic states play important roles in proton relay systems. The theory suggests that the PCET rate constant may be increased by decreasing the equilibrium proton donor-acceptor distances or modifying the thermal motions of the molecule to facilitate the concurrent decrease of these distances. The submission of this journal article in ERIA is a requirement of the EFRC subcontract with Pennsylvania State University collaborators to get publications to OSTI.

  16. The Electrochemical Behavior of SnSb as an Anode for Li-ion Batteries Studied by Electrochemical Impedance Spectroscopy and Electron Microscopy

    International Nuclear Information System (INIS)

    Tesfaye, Alexander T.; Yücel, Yasemin D.; Barr, Maïssa K.S.; Santinacci, Lionel; Vacandio, Florence; Dumur, Frédéric; Maria, Sébastien; Monconduit, Laure; Djenizian, Thierry

    2017-01-01

    Highlights: •Electrochemical behavior of SnSb is investigated by EIS, SEM and TEM. •Formation of SEI and cracks occurs during cycling experiments. •The capacity fading as a result of the electrode modifications is discussed. -- Abstract: Evolution of the electrical and morphological properties of micron-sized SnSb has been investigated to understand the electrochemical behavior observed during cycling experiments. Electron microscopy techniques (scanning electron microscopy and transmission electron microscopy) and electrochemical impedance spectroscopy have been combined to evidence the electrode modifications and particularly the formation of a solid electrolyte interphase (SEI) layer. Evolution of the SEI resistance and the charge transfer resistance with the cell voltage can be explained by the electrolyte degradation and expansion/contraction of the electrode. Furthermore, we show that the SEI formation is not limited at the first discharge/charge of the battery. The continuous growth of the SEI layer up to 50 cycles associated to the electrode pulverization caused by the large volume variations are responsible for the capacity fading.

  17. Interfacial Energy Alignment at the ITO/Ultra-Thin Electron Selective Dielectric Layer Interface and Its Effect on the Efficiency of Bulk-Heterojunction Organic Solar Cells.

    Science.gov (United States)

    Itoh, Eiji; Goto, Yoshinori; Saka, Yusuke; Fukuda, Katsutoshi

    2016-04-01

    We have investigated the photovoltaic properties of an inverted bulk heterojunction (BHJ) cell in a device with an indium-tin-oxide (ITO)/electron selective layer (ESL)/P3HT:PCBM active layer/MoOx/Ag multilayered structure. The insertion of only single layer of poly(diallyl-dimethyl-ammonium chloride) (PDDA) cationic polymer film (or poly(ethyleneimine) (PEI) polymeric interfacial dipole layer) and titanium oxide nanosheet (TN) films as an ESL effectively improved cell performance. Abnormal S-shaped curves were observed in the inverted BHJ cells owing to the contact resistance across the ITO/active layer interface and the ITO/PDDA/TN/active layer interface. The series resistance across the ITO/ESL interface in the inverted BHJ cell was successfully reduced using an interfacial layer with a positively charged surface potential with respect to ITO base electrode. The positive dipole in PEI and the electronic charge phenomena at the electrophoretic deposited TN (ED-TN) films on ITO contributed to the reduction of the contact resistance at the electrode interface. The surface potential measurement revealed that the energy alignment by the transfer of electronic charges from the ED-TN to the base electrodes. The insertion of the ESL with a large positive surface potential reduced the potential barrier for the electron injection at ITO/TN interface and it improved the photovoltaic properties of the inverted cell with an ITO/TN/active layer/MoOx/Ag structure.

  18. Electrochemomechanics with flexoelectricity and modelling of electrochemical strain microscopy in mixed ionic-electronic conductors

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Pengfei; Hu, Shuling; Shen, Shengping, E-mail: sshen@mail.xjtu.edu.cn [State Key Laboratory for Strength and Vibration of Mechanical Structures, School of Aerospace, Xi' an Jiaotong University, Xi' an 710049 (China)

    2016-08-14

    Recently, a new scanning probe microscopy approach, referred to as electrochemical strain microscopy (ESM), for probing local ionic flows and electrochemical reactions in solids based on the bias-strain coupling was proposed by Morozovska et al. Then, a series of theoretical papers for analyzing the image formation and spectroscopic mechanism of ESM were published within the framework of Fermi-Dirac statistics, the Vegard law, the direct flexoelectric coupling effect, the electrostriction effect, and so on. However, most of the models in these papers are limited to the partial coupling or particular process, and numerically solved by using decoupling approximation. In this paper, to model the ESM measurement with the coupling electrical-chemical-mechanical process, the chemical Gibbs function variational principle for the thermal electrical chemical mechanical fully coupling problem is proposed. The fully coupling governing equations are derived from the variational principle. When the tip concentrates the electric field within a small volume of the material, the inhomogeneous electric field is induced. So, both direct and inverse flexoelectric effects should be taken into account. Here, the bulk defect electrochemical reactions are also taken into account, which are usually omitted in the existing works. This theory can be used to deal with coupling problems in solids, including conductors, semiconductors, and piezoelectric and non-piezoelectric dielectrics. As an application of this work, a developed initial-boundary value problem is solved numerically in a mixed ion-electronic conductor. Numerical results show that it is meaningful and necessary to consider the bulk defect chemical reaction. Besides, the chemical reaction and the flexoelectric effect have an interactive influence on each other. This work can provide theoretical basis for the ESM as well as investigating the bulk chemical reaction process in solids.

  19. Exogenous electron shuttle-mediated extracellular electron transfer of Shewanella putrefaciens 200: electrochemical parameters and thermodynamics.

    Science.gov (United States)

    Wu, Yundang; Liu, Tongxu; Li, Xiaomin; Li, Fangbai

    2014-08-19

    Despite the importance of exogenous electron shuttles (ESs) in extracellular electron transfer (EET), a lack of understanding of the key properties of ESs is a concern given their different influences on EET processes. Here, the ES-mediated EET capacity of Shewanella putrefaciens 200 (SP200) was evaluated by examining the electricity generated in a microbial fuel cell. The results indicated that all the ESs substantially accelerated the current generation compared to only SP200. The current and polarization parameters were linearly correlated with both the standard redox potential (E(ES)(0)) and the electron accepting capacity (EAC) of the ESs. A thermodynamic analysis of the electron transfer from the electron donor to the electrode suggested that the EET from c-type cytochromes (c-Cyts) to ESs is a crucial step causing the differences in EET capacities among various ESs. Based on the derived equations, both E(ES)(0) and EAC can quantitatively determine potential losses (ΔE) that reflect the potential loss of the ES-mediated EET. In situ spectral kinetic analysis of ES reduction by c-Cyts in a living SP200 suspension was first investigated with the E(ES), E(c-Cyt), and ΔE values being calculated. This study can provide a comprehensive understanding of the role of ESs in EET.

  20. Electrochemical Testing of Gas Tungsten Arc Welded and Reduced Pressure Electron Beam Welded Alloy 22

    International Nuclear Information System (INIS)

    Day, S D; Wong, F G; Gordon, S R; Wong, L L; Rebak, R B

    2006-01-01

    Alloy 22 (N06022) is the material selected for the fabrication of the outer shell of the nuclear waste containers for the Yucca Mountain high-level nuclear waste repository site. A key technical issue in the waste package program has been the integrity of the container weld joints. The currently selected welding process for fabricating and sealing the containers is the traditional gas tungsten arc welding (GTAW) or TIG method. An appealing faster alternative technique is reduced pressure electron beam (RPEB) welding. It was of interest to compare the corrosion properties of specimens prepared using both types of welding techniques. Standard electrochemical tests were carried on GTAW and RPEB welds as well as on base metal (non-welded) to determine their relative corrosion behavior in simulated concentrated water (SCW) at 90 C (alkaline), 1 M HCl at 60 C (acidic) and 1 M NaCl at 90 C (neutral) solutions. Results show that for all practical purposes, the three tested materials had the same electrochemical behavior in the three tested electrolytes

  1. A lactate electrochemical biosensor with a titanate nanotube as direct electron transfer promoter

    International Nuclear Information System (INIS)

    Yang Mingli; Wang Jin; Li Huaqing; Wu Nianqiang Nick; Zheng Jianguo

    2008-01-01

    Hydrogen titanate (H 2 Ti 3 O 7 ) nanotubes (TNTs) have been synthesized by a one-step hydrothermal processing. Lactate oxidase (LOx) enzyme has been immobilized on the three-dimensional porous TNT network to make an electrochemical biosensor for lactate detection. Cyclic voltammetry and amperometry tests reveal that the LOx enzyme, which is supported on TNTs, maintains their substrate-specific catalytic activity. The nanotubes offer the pathway for direct electron transfer between the electrode surface and the active redox centers of LOx, which enables the biosensor to operate at a low working potential and to avoid the influence of the presence of O 2 on the amperometric current response. The biosensor exhibits a sensitivity of 0.24 μA cm -2 mM -1 , a 90% response time of 5 s, and a linear response in the range from 0.5 to 14 mM and the redox center of enzyme obviates the need of redox mediators for electrochemical enzymatic sensors, which is attractive for the development of reagentless biosensors

  2. Electrochemical Testing of Gas Tungsten ARC Welded and Reduced Pressure Electron Beam Welded Alloy 22

    International Nuclear Information System (INIS)

    S. Daniel Day; Frank M.G. Wong; Steven R. Gordon; Lana L. Wong; Raul B. Rebak

    2006-01-01

    Alloy 22 (N06022) is the material selected for the fabrication of the outer shell of the nuclear waste containers for the Yucca Mountain high-level nuclear waste repository site. A key technical issue in the waste package program has been the integrity of the container weld joints. The currently selected welding process for fabricating and sealing the containers is the traditional gas tungsten arc welding (GTAW) or TIC method. An appealing faster alternative technique is reduced pressure electron beam (RPEB) welding. It was of interest to compare the corrosion properties of specimens prepared using both types of welding techniques. Standard electrochemical tests were carried on GTAW and RPEB welds as well as on base metal (non-welded) to determine their relative corrosion behavior in simulated concentrated water (SCW) at 90 C (alkaline), 1 M HCI at 60 C (acidic) and 1 M NaCl at 90 C (neutral) solutions. Results show that for all practical purposes, the three tested materials had the same electrochemical behavior in the three tested electrolytes

  3. A lactate electrochemical biosensor with a titanate nanotube as direct electron transfer promoter

    Science.gov (United States)

    Yang, Mingli; Wang, Jin; Li, Huaqing; Zheng, Jian-Guo; Wu, Nianqiang Nick

    2008-02-01

    Hydrogen titanate (H2Ti3O7) nanotubes (TNTs) have been synthesized by a one-step hydrothermal processing. Lactate oxidase (LOx) enzyme has been immobilized on the three-dimensional porous TNT network to make an electrochemical biosensor for lactate detection. Cyclic voltammetry and amperometry tests reveal that the LOx enzyme, which is supported on TNTs, maintains their substrate-specific catalytic activity. The nanotubes offer the pathway for direct electron transfer between the electrode surface and the active redox centers of LOx, which enables the biosensor to operate at a low working potential and to avoid the influence of the presence of O2 on the amperometric current response. The biosensor exhibits a sensitivity of 0.24 µA cm-2 mM-1, a 90% response time of 5 s, and a linear response in the range from 0.5 to 14 mM and the redox center of enzyme obviates the need of redox mediators for electrochemical enzymatic sensors, which is attractive for the development of reagentless biosensors.

  4. Electrochemical and conversion electron Moessbauer study of corrosion induced by acid rain

    International Nuclear Information System (INIS)

    Vertes, C.; Lakatos-Varsanyi, M.; Vertes, A.; Meisel, W.; Guetlich, P.

    1993-01-01

    The passivation of low carbon steel was studied in aqueous solution of 0.5M Na 2 SO 4 +0.001M NaHSO 3 (pH 3.5, 6.5 and 8.5) which can be considered as a model of acid rain. The used conversion electron Moessbauer spectroscopy (CEMS) with the complementary electrochemical investigations proved that the sulfite ions induce pitting corrosion at pH 3.5 and 6.5, while the measurements showed much weaker pitting at pH 8.5. The compositions and thicknesses of the passive films formed during the electrochemical treatments are determined from the CEM spectra. Only γ-FeOOH was found on the surface of the samples at pH 6.5 and 8.5. Nevertheless, at pH 3.5 the sextet belonging to Fe 3 C appears in the spectra, and also FeSO 4 .H 2 O could be detected in low concentration. (orig.)

  5. Electrochemical Sensing of Neurotoxic Agents Based on Their Electron Transfer Promotion Effect on an Au Electrode.

    Science.gov (United States)

    Shimada, Hiroshi; Noguchi, Shiori; Yamamoto, Masahiro; Nishiyama, Katsuhiko; Kitamura, Yusuke; Ihara, Toshihiro

    2017-06-06

    An electrochemical molecular sensor based on a new principle is reported. Nereistoxin (NRT, 4-N,N-dimethylamino-1,2-dithiolane), a naturally occurring neurotoxin (nicotinic acetylcholine receptor agonist), was adsorbed on an Au electrode via Au-S covalent bonding and accelerated the electron transfer between the electrode and the marker, ferricyanide anion. The contrast between the electrochemical responses obtained with the bare and NRT-modified Au electrodes was more pronounced at a low ionic strength of the supporting electrolyte, KCl. In the presence of 1 mM KCl, almost a 0/1 contrast between the signals was obtained through electrostatic interaction between the protonated tertiary amino group of NRT and the anionic ferricyanide ion. No current was observed with an electrode modified with mercaptopropionic acid. An unusually low ionic strength thickened the electric double layer to the degree where current was not observed with the bare electrode. The effect of the electrostatic concentration of the marker ion becomes obvious under such conditions. Commercially available NRT-related pesticides such as Cartap and Bensultap were also detected using the same format after pretreatments by hydrolysis/reduction. The present sensing method was successfully applied to human serum with satisfactory sensitivity.

  6. Profiling the interfacial electron gas of LaAlO{sub 3}/SrTiO{sub 3}(111) heterointerfaces

    Energy Technology Data Exchange (ETDEWEB)

    Gabel, Judith; Zapf, Michael; Scheiderer, Philipp; Schuetz, Philipp; Kirilmaz, Ozan; Sing, Michael; Claessen, Ralph [Physikalisches Institut and Roentgen Center for Complex Material Systems (RCCM), Universitaet Wuerzburg (Germany); Schlueter, Christoph; Lee, Tien-Lin [Diamond Light Source Ltd., Didcot (United Kingdom); Cancellieri, Claudia [EMPA, Laboratory of Joining Technologies and Corrosion, Duebendorf (Switzerland); Rogalev, Victor [Physikalisches Institut and Roentgen Center for Complex Material Systems (RCCM), Universitaet Wuerzburg (Germany); Swiss Light Source, Paul Scherrer Institute, Villigen (Switzerland); Strocov, Vladimir [Swiss Light Source, Paul Scherrer Institute, Villigen (Switzerland)

    2016-07-01

    Akin to the the well established LaAlO{sub 3}(LAO)/SrTiO{sub 3}(STO) (001) a two-dimensional electron system (2DES) also forms at the interface between LAO and STO in (111) orientation. In contrast to the (001) samples, the (111) oriented structures are predicted to display highly non-trivial topological properties induced by symmetry breaking and the peculiar real space lattice topology. We have investigated the electronic structure of the LAO/STO (111) heterostructure by hard and resonant soft X-ray photoemission. The momentum-resolved electronic structure of the interface Ti 3d states showcases the distinctive symmetry of the (111) orientation. These measurements as well as angular resolved hard X-ray photoemission measurements of the Ti 2p core level furthermore allow conclusions to be drawn about the spatial extent of the interfacial 2DES.

  7. Electrochemical impedance spectroscopy for study of electronic structure in disordered organic semiconductors—Possibilities and limitations

    Science.gov (United States)

    Schauer, F.; Nádaždy, V.; Gmucová, K.

    2018-04-01

    There is potential in applying conjugated polymers in novel organic optoelectronic devices, where a comprehensive understanding of the fundamental processes and energetics involved during transport and recombination is still lacking, limiting further device optimization. The electronic transport modeling and its optimization need the energy distribution of transport and defect states, expressed by the energy distribution of the Density of States (DOS) function, as input/comparative parameters. We present the Energy Resolved-Electrochemical Impedance Spectroscopy (ER-EIS) method for the study of transport and defect electronic states in organic materials. The method allows mapping over unprecedentedly wide energy and DOS ranges. The ER-EIS spectroscopic method is based on the small signal interaction between the surface of the organic film and the liquid electrolyte containing reduction-oxidation (redox) species, which is similar to the extraction of an electron by an acceptor and capture of an electron by a donor at a semiconductor surface. The desired DOS of electronic transport and defect states can be derived directly from the measured redox response signal to the small voltage perturbation at the instantaneous position of the Fermi energy, given by the externally applied voltage. The theory of the ER-EIS method and conditions for its validity for solid polymers are presented in detail. We choose four case studies on poly(3-hexylthiophene-2,5-diyl) and poly[methyl(phenyl)silane] to show the possibilities of the method to investigate the electronic structure expressed by DOS of polymers with a high resolution of about 6 orders of magnitude and in a wide energy range of 6 eV.

  8. Improvement of electron emission characteristics of porous silicon emitter by using cathode reduction and electrochemical oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Li, He; Wenjiang, Wang, E-mail: wwj@mail.xjtu.edu.cn; Xiaoning, Zhang

    2017-03-31

    Highlights: • An electron emitter based on porous silicon having the strong application potential was prepared in the studying. • A new simple and convenient post-treat technique was proposed to improve the electron emission properties of the PS emitter. • It demonstrated that the improving of the PS morphology and the oxygen distribution is very important to the PS emitter. - Abstract: A new simple and convenient post-treat technique combined the cathode reduction (CR) and electrochemical oxidation (ECO) was proposed to improve the electron emission properties of the surface-emitting cold cathodes based on the porous silicon (PS). It is demonstrated here that by introducing this new technique combined CR and ECO, the emission properties of the diode have been significantly improved than those as-prepared samples. The experimental results showed that the emission current densities and efficiencies of sample treated by CR were 62 μA/cm{sup 2} and 12.10‰, respectively, nearly 2 orders of magnitude higher than those of as-prepared sample. Furthermore, the CR-treated PS emitter shows higher repeatability and stability compared with the as-prepared PS emitter. The scanning electron microscope (SEM), atomic force microscope (AFM), energy dispersive spectrometer (EDS), furier transformed infrared (FTIR) spectroscopy results indicated that the improved mechanism is mainly due to the passivation of the PS, which not only improve the PS morphology by the passivation of the H{sup +} but also improve the uniformity of the oxygen content distribution in the whole PS layer. Therefore, the method combined the CR treatment and ECO is expected to be a valuable technique to enhance the electron emission characteristics of the PS emitter.

  9. Improvement of electron emission characteristics of porous silicon emitter by using cathode reduction and electrochemical oxidation

    International Nuclear Information System (INIS)

    Li, He; Wenjiang, Wang; Xiaoning, Zhang

    2017-01-01

    Highlights: • An electron emitter based on porous silicon having the strong application potential was prepared in the studying. • A new simple and convenient post-treat technique was proposed to improve the electron emission properties of the PS emitter. • It demonstrated that the improving of the PS morphology and the oxygen distribution is very important to the PS emitter. - Abstract: A new simple and convenient post-treat technique combined the cathode reduction (CR) and electrochemical oxidation (ECO) was proposed to improve the electron emission properties of the surface-emitting cold cathodes based on the porous silicon (PS). It is demonstrated here that by introducing this new technique combined CR and ECO, the emission properties of the diode have been significantly improved than those as-prepared samples. The experimental results showed that the emission current densities and efficiencies of sample treated by CR were 62 μA/cm"2 and 12.10‰, respectively, nearly 2 orders of magnitude higher than those of as-prepared sample. Furthermore, the CR-treated PS emitter shows higher repeatability and stability compared with the as-prepared PS emitter. The scanning electron microscope (SEM), atomic force microscope (AFM), energy dispersive spectrometer (EDS), furier transformed infrared (FTIR) spectroscopy results indicated that the improved mechanism is mainly due to the passivation of the PS, which not only improve the PS morphology by the passivation of the H"+ but also improve the uniformity of the oxygen content distribution in the whole PS layer. Therefore, the method combined the CR treatment and ECO is expected to be a valuable technique to enhance the electron emission characteristics of the PS emitter.

  10. Tuning the Electronic Structure of Titanium Oxide Support to Enhance the Electrochemical Activity of Platinum Nanoparticles

    KAUST Repository

    Shi, Feifei

    2013-09-11

    Two times higher activity and three times higher stability in methanol oxidation reaction, a 0.12 V negative shift of the CO oxidation peak potential, and a 0.07 V positive shift of the oxygen reaction potential compared to Pt nanoparticles on pristine TiO2 support were achieved by tuning the electronic structure of the titanium oxide support of Pt nanoparticle catalysts. This was accomplished by adding oxygen vacancies or doping with fluorine. Experimental trends are interpreted in the context of an electronic structure model, showing an improvement in electrochemical activity when the Fermi level of the support material in Pt/TiOx systems is close to the Pt Fermi level and the redox potential of the reaction. The present approach provides guidance for the selection of the support material of Pt/TiOx systems and may be applied to other metal-oxide support materials, thus having direct implications in the design and optimization of fuel cell catalyst supports. © 2013 American Chemical Society.

  11. Stability, electrochemical behaviors and electronic structures of iron hydroxyl-phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Wang Zhongli; Sun Shaorui; Li Fan; Chen Ge [College of Environmental and Energy Engineering, Beijing University of Technology, Pingleyuan 100, Chaoyang District, Beijing 100022 (China); Xia Dingguo, E-mail: dgxia@bjut.edu.cn [College of Environmental and Energy Engineering, Beijing University of Technology, Pingleyuan 100, Chaoyang District, Beijing 100022 (China); Zhao Ting; Chu Wangsheng [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); University of Science and Technology of China, Hefei 230026 (China); Wu Ziyu, E-mail: wuzy@ihep.ac.cn [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); University of Science and Technology of China, Hefei 230026 (China)

    2010-09-01

    Iron hydroxyl-phosphate with a uniform spherical particle size of around 1 {mu}m, a compound of the type Fe{sub 2-y}{open_square}{sub y}(PO{sub 4})(OH){sub 3-3y}(H{sub 2}O){sub 3y-2} (where {open_square} represents a vacancy), has been synthesized by hydrothermal methods. The particles are composed of spheres of diameter <100 nm. The compound exhibits good electrochemical performance, with reversible capacities of around 150 mAh g{sup -1} and 120 mAh g{sup -1} at current densities of 170 mA g{sup -1} and 680 mA g{sup -1}, respectively. The stability of crystal structure of this material was studied by TGA and XRD which show that the material remains stable at least up to the temperature 200 deg. C. Investigation of the electronic structure of the iron hydroxyl-phosphate by GGA + U calculation has indicated that it has a better electronic conductivity than LiFePO{sub 4}.

  12. Single Nanostructure Electrochemical Devices for Studying Electronic Properties and Structural Changes in Lithiated Si Nanowires

    KAUST Repository

    McDowell, Matthew T.; Cui, Yi

    2011-01-01

    Nanostructured Si is a promising anode material for the next generation of Li-ion batteries, but few studies have focused on the electrical properties of the Li-Si alloy phase, which are important for determining power capabilities and ensuring sufficient electrical conduction in the electrode structure. Here, we demonstrate an electrochemical device framework suitable for testing the electrical properties of single Si nanowires (NWs) at different lithiation states and correlating these properties with structural changes via transmission electron microscopy (TEM). We fi nd that single Si NWs usually exhibit Ohmic I - V response in the lithiated state, with conductivities two to three orders of magnitude higher than in the delithiated state. After a number of sequential lithiation/delithiation cycles, the single NWs show similar conductivity after each lithiation step but show large variations in conductivity in the delithiated state. Finally, devices with groups of NWs in physical contact were fabricated, and structural changes in the NWs were observed after lithiation to investigate how the electrical resistance of NW junctions and the NWs themselves affect the lithiation behavior. The results suggest that electrical resistance of NW junctions can limit lithiation. Overall, this study shows the importance of investigating the electronic properties of individual components of a battery electrode (single nanostructures in this case) along with studying the nature of interactions within a collection of these component structures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Single Nanostructure Electrochemical Devices for Studying Electronic Properties and Structural Changes in Lithiated Si Nanowires

    KAUST Repository

    McDowell, Matthew T.

    2011-07-19

    Nanostructured Si is a promising anode material for the next generation of Li-ion batteries, but few studies have focused on the electrical properties of the Li-Si alloy phase, which are important for determining power capabilities and ensuring sufficient electrical conduction in the electrode structure. Here, we demonstrate an electrochemical device framework suitable for testing the electrical properties of single Si nanowires (NWs) at different lithiation states and correlating these properties with structural changes via transmission electron microscopy (TEM). We fi nd that single Si NWs usually exhibit Ohmic I - V response in the lithiated state, with conductivities two to three orders of magnitude higher than in the delithiated state. After a number of sequential lithiation/delithiation cycles, the single NWs show similar conductivity after each lithiation step but show large variations in conductivity in the delithiated state. Finally, devices with groups of NWs in physical contact were fabricated, and structural changes in the NWs were observed after lithiation to investigate how the electrical resistance of NW junctions and the NWs themselves affect the lithiation behavior. The results suggest that electrical resistance of NW junctions can limit lithiation. Overall, this study shows the importance of investigating the electronic properties of individual components of a battery electrode (single nanostructures in this case) along with studying the nature of interactions within a collection of these component structures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Interfacial stability and electrochemical behavior of Li/LiFePO4 batteries using novel soft and weakly adhesive photo-ionogel electrolytes

    Science.gov (United States)

    Aidoud, D.; Etiemble, A.; Guy-Bouyssou, D.; Maire, E.; Le Bideau, J.; Guyomard, D.; Lestriez, B.

    2016-10-01

    We have developed flexible polymer-gel electrolytes based on a polyacrylate cross-linked matrix that confines an ionic liquid doped with a lithium salt. Free-standing solid electrolyte membrane is obtained after UV photo-polymerization of acrylic monomers dissolved inside the ionic liquid/lithium salt mixture. The liquid precursor of the photo-ionogel may also be directly deposited onto porous composite electrode, which results in all-solid state electrode/electrolyte stacking after UV illumination. Minor variations in the polymer component of the electrolyte formulation significantly affect the electrochemical behavior in LiFePO4/lithium and lithium/lithium cells. The rate performance increases with an increase of the ionic conductivity, which decreases with the polymer content and decreases with increasing oxygen content in the polyacrylate matrix. Their fairly low modulus endow them weak and beneficial pressure-sensitive-adhesive character. X-Rays Tomography shows that the solid-state photo-ionogel electrolytes keep their integrity upon cycling and that their surface remains smooth. The coulombic efficiency of LiFePO4/lithium cells increases with an increase of the adhesive strength of the photo-ionogel, suggesting a relationship between the contact intimacy at the lithium/photo-ionogel interface and the efficiency of the lithium striping/plating. In lithium/lithium cells, only the photo-ionogels with the higher adhesion strength are able to allow the reversible striping/plating of lithium.

  15. Interfacial reactions between titanium and borate glass

    Energy Technology Data Exchange (ETDEWEB)

    Brow, R.K. [Sandia National Labs., Albuquerque, NM (United States); Saha, S.K.; Goldstein, J.I. [Lehigh Univ., Bethlehem, PA (United States). Dept. of Materials Science

    1992-12-31

    Interfacial reactions between melts of several borate glasses and titanium have been investigated by analytical scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS). A thin titanium boride interfacial layer is detected by XPS after short (30 minutes) thermal treatments. ASEM analyses after longer thermal treatments (8--120 hours) reveal boron-rich interfacial layers and boride precipitates in the Ti side of the interface.

  16. Nb and Ta layer doping effects on the interfacial energetics and electronic properties of LaAlO3/SrTiO3 heterostructure: first-principles analysis.

    Science.gov (United States)

    Nazir, Safdar; Behtash, Maziar; Cheng, Jianli; Luo, Jian; Yang, Kesong

    2016-01-28

    The two-dimensional electron gas (2DEG) formed at the n-type (LaO)(+1)/(TiO2)(0) interface in the polar/nonpolar LaAlO3/SrTiO3 (LAO/STO) heterostructure (HS) has emerged as a prominent research area because of its great potential for nanoelectronic applications. Due to its practical implementation in devices, desired physical properties such as high charge carrier density and mobility are vital. In this respect, 4d and 5d transition metal doping near the interfacial region is expected to tailor electronic properties of the LAO/STO HS system effectively. Herein, we studied Nb and Ta-doping effects on the energetics, electronic structure, interfacial charge carrier density, magnetic moment, and the charge confinements of the 2DEG at the n-type (LaO)(+1)/(TiO2)(0) interface of LAO/STO HS using first-principles density functional theory calculations. We found that the substitutional doping of Nb(Ta) at Ti [Nb(Ta)@Ti] and Al [Nb(Ta)@Al] sites is energetically more favorable than that at La [Nb(Ta)@La] and Sr [Nb(Ta)@Sr] sites, and under appropriate thermodynamic conditions, the changes in the interfacial energy of HS systems upon Nb(Ta)@Ti and Nb(Ta)@Al doping are negative, implying that the formation of these structures is energetically favored. Our calculations also showed that Nb(Ta)@Ti and Nb(Ta)@Al doping significantly improve the interfacial charge carrier density with respect to that of the undoped system, which is because the Nb(Ta) dopant introduces excess free electrons into the system, and these free electrons reside mainly on the Nb(Ta) ions and interfacial Ti ions. Hence, along with the Ti 3d orbitals, the Nb 4d and Ta 5d orbitals also contribute to the interfacial metallic states; accordingly, the magnetic moments on the interfacial Ti ions increase significantly. As expected, the Nb@Al and Ta@Al doped LAO/STO HS systems show higher interfacial charge carrier density than the undoped and other doped systems. In contrast, Nb@Ti and Ta@Ti doped systems may

  17. Interfacial chemical and electronic structure of cobalt deposition on 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene (C8-BTBT)

    Science.gov (United States)

    Zhu, Menglong; Lyu, Lu; Niu, Dongmei; Zhang, Hong; Zhang, Yuhe; Liu, Peng; Gao, Yongli

    2017-04-01

    Interfacial chemical and electronic structure of Co deposition on 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene(C8-BTBT) was investigated by ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). Chemical reaction of cobalt with C8-BTBT at the interface is confirmed by a new component of S 2s peak which is electron-rich compared to the original one of C8-BTBT molecules. Intensity evolution of the core level in XPS indicates that the adsorption of Co atoms is mainly at the surface without deeper diffusion into C8-BTBT layer. Initial deposition of Co atoms downward shifts the core levels of C8-BTBT by electron transfer from isolated Co atoms or clusters to the C8-BTBT. Further deposition of Co upward shifts the core levels of C8-BTBT because of the neutralization of the thicker metal Co film. Our investigation suggests an inert buffer layer inserted to protect organic layer from reaction or decomposition and to lower the carrier barriers for both the electron and hole to improve the performance of Co/C8-BTBT-based OFETs.

  18. Influence of enzymatic reactions on the electrochemical behavior of EN X2CrNiMo17-11-2 (AISI 316L) stainless steel in bio-corrosion: role of interfacial processes on the modification of the passive layer; Influence des reactions enzymatiques sur le comportement electrochimique de l'acier inoxydable ENX2CrNiMo17-11-2 (AISI 316L) en biocorrosion: role des processus interfaciaux sur la modification du film passif

    Energy Technology Data Exchange (ETDEWEB)

    Landoulsi, J

    2008-01-15

    The outstanding corrosion behavior of stainless steels (SS) results from the presence of thin oxide layer (some nanometers). In non sterile aqueous media, stainless steels may exhibit a non stable behavior resulting from interactions between microbial species and passive film. In fact, microorganisms can be deeply involved in the corrosion processes usually reported as Microbial Influenced Corrosion (MIC). They can induce the initiation or the acceleration of this phenomenon and they do so when organized in bio-films. From the electrochemical point of view, stainless steels showed an increase of the free corrosion potential (Ecorr) attributed to the bio-film settlement. The Eco' ennoblement was broadly reported in seawater and seems to be confirmed in fresh water according to recent findings. A considerable progress in the comprehension of MIC processes was related to the role of extracellular species, essentially enzymes. Many enzymatic reactions occurring in bio-films consist on using oxygen as electron acceptor to generate hydrogen peroxide and related species. The aim of this work is to understand the mechanisms involved in the electrochemical behavior of stainless steel according to an enzymatic approach in medium simulating fresh water. To this end, glucose oxidase was chosen to globalize aerobic activities of bio-films. Electrochemical measurements in situ and surface analysis allow the comprehension of the role and the nature of interfacial processes. Surface characterization was performed with the help of a new quantitative utilization of XPS analysis and AFM. Results show a significant evolution in term of morphology (surface organization), (ii) chemical composition (passive layer, adsorbed organic species) and (iii) chemical reaction (oxidation, dissolution, effect of enzyme). Finally, a new enzymatic system is proposed to mimic specific physicochemical conditions at the SS / bio-film interface, in particular enzymatic generation of oxidant species

  19. Electrochemical studies of Pu on prussian blue (PB)-gold nanoparticles (AuNPs) functionalized glassy carbon (GC) electrode

    International Nuclear Information System (INIS)

    Sharma, Manoj K.; Ambolikar, Arvind S.; Aggarwal, Suresh K.

    2011-01-01

    In electrochemical processes, electron transfer across the solid-liquid interface is the elementary step and electron transfer kinetics is significantly influenced by the interfacial properties. Therefore, preparation of well-defined electrochemical interface with highly controllable properties - larger effective surface area, increased mass transport, and better electronic interaction between the analyte and electrode - is significant for both fundamental and applied studies in electrochemistry. In the present work electrochemistry of Pu(IV)/Pu(III) is studied on multilayered AuNPs-PB-AuNPs functionalized electrode

  20. Remote interfacial dipole scattering and electron mobility degradation in Ge field-effect transistors with GeO x /Al2O3 gate dielectrics

    Science.gov (United States)

    Wang, Xiaolei; Xiang, Jinjuan; Wang, Shengkai; Wang, Wenwu; Zhao, Chao; Ye, Tianchun; Xiong, Yuhua; Zhang, Jing

    2016-06-01

    Remote Coulomb scattering (RCS) on electron mobility degradation is investigated experimentally in Ge-based metal-oxide-semiconductor field-effect-transistors (MOSFETs) with GeO x /Al2O3 gate stacks. It is found that the mobility increases with greater GeO x thickness (7.8-20.8 Å). The physical origin of this mobility dependence on GeO x thickness is explored. The following factors are excluded: Coulomb scattering due to interfacial traps at GeO x /Ge, phonon scattering, and surface roughness scattering. Therefore, the RCS from charges in gate stacks is studied. The charge distributions in GeO x /Al2O3 gate stacks are evaluated experimentally. The bulk charges in Al2O3 and GeO x are found to be negligible. The density of the interfacial charge is  +3.2  ×  1012 cm-2 at the GeO x /Ge interface and  -2.3  ×  1012 cm-2 at the Al2O3/GeO x interface. The electric dipole at the Al2O3/GeO x interface is found to be  +0.15 V, which corresponds to an areal charge density of 1.9  ×  1013 cm-2. The origin of this mobility dependence on GeO x thickness is attributed to the RCS due to the electric dipole at the Al2O3/GeO x interface. This remote dipole scattering is found to play a significant role in mobility degradation. The discovery of this new scattering mechanism indicates that the engineering of the Al2O3/GeO x interface is key for mobility enhancement and device performance improvement. These results are helpful for understanding and engineering Ge mobility enhancement.

  1. Interfacial reaction pathways and kinetics during annealing of 111-textured Al/TiN bilayers: A synchrotron x-ray diffraction and transmission electron microscopy study

    International Nuclear Information System (INIS)

    Chun, J.-S.; Desjardins, P.; Lavoie, C.; Petrov, I.; Cabral, C. Jr.; Greene, J. E.

    2001-01-01

    Growth of TiN layers in most diffusion-barrier applications is limited to deposition temperatures T s s =450 deg. C on SiO 2 by ultrahigh vacuum reactive magnetron sputter deposition in pure N 2 . Al overlayers, 160 nm thick with inherited 111 preferred orientation, were then deposited at T s =100 deg. C without breaking vacuum. The as-deposited TiN layer is underdense due to the low deposition temperature (T s /T m ≅0.23 in which T m is the melting point) resulting in kinetically limited adatom mobilities leading to atomic shadowing which, in turn, results in a columnar microstructure with both inter- and intracolumnar voids. The Al overlayer is fully dense. Synchrotron x-ray diffraction was used to follow interfacial reaction kinetics during postdeposition annealing of the 111-textured Al/TiN bilayers as a function of time (t a =12-1200 s) and temperature (T a =440-550 deg. C). Changes in bilayer microstructure and microchemistry were investigated using transmission electron microscopy (TEM) and scanning TEM to obtain compositional maps of plan-view and cross-sectional specimens. Interfacial reaction during annealing is initiated at the Al/TiN interface. Al diffuses rapidly into TiN voids during anneals at temperatures ∼ 3 Ti at the interface. Al 3 Ti exhibits a relatively planar growth front extending toward the Al free surface. Analyses of time-dependent x-ray diffraction peak intensities during isothermal annealing as a function of temperature show that Al 3 Ti growth kinetics are, for the entire temperature range investigated, diffusion limited with an activation energy of 1.5±0.2 eV

  2. Modulation of interfacial electronic properties in PbI{sub 2} and BN van der Waals heterobilayer via external electric field

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Yaqiang [College of Physics and Materials Science, Henan Normal University, Xinxiang 453007 (China); Zhao, Xu, E-mail: zhaoxu@htu.cn [College of Physics and Materials Science, Henan Normal University, Xinxiang 453007 (China); Niu, Mengmeng [College of Physics and Materials Science, Henan Normal University, Xinxiang 453007 (China); Dai, Xianqi, E-mail: xqdai@htu.cn [College of Physics and Materials Science, Henan Normal University, Xinxiang 453007 (China); School of Physics and Electronic Engineering, Zhengzhou Normal University, Zhengzhou, Henan 450044 (China); Li, Wei [College of Physics and Materials Science, Henan Normal University, Xinxiang 453007 (China); Wang, Xiaolong [College of Physics and Materials Science, Henan Normal University, Xinxiang 453007 (China); State Key Laboratory of Information Photonics and Optical Communication, Beijing University Posts and Telecommunications, Beijing 100876 (China); Zhao, Mingyu; Wang, Tianxing [College of Physics and Materials Science, Henan Normal University, Xinxiang 453007 (China); Tang, Yanan [School of Physics and Electronic Engineering, Zhengzhou Normal University, Zhengzhou, Henan 450044 (China)

    2017-07-31

    Highlights: • An atomically type-II heterobilayer which is suitable for optoelectronics and solar cell with wide bandgap was formed. • The charge redistribution is mainly on the surface and the amount of electrons depends on the strength of E{sub field}. • The bandgaps varying with E{sub field} can be divided into three ranges indicating different E{sub field}-sensitive which may possess potential in sensor. • Increasing the E{sub field} upon 0.07 V/Å, the band alignment converts from type-II to type-I heterojunction. - Abstract: The interfacial electronic properties of PbI{sub 2} and BN van der Waals (vdW) heterobilayer are explored by using density functional theory (DFT) method. An intrinsic type-II heterostructure with a wide bandgap is demonstrated. The spatial separation of the lowest energy electron-hole pairs can be actualised and make PbI{sub 2}/BN heterostructure as a good candidate for applications in optoelectronics and solar cell. A simulation of E{sub field} is actualized to modify its electronic properties. Band alignment converts from type-II to type-I heterostructure separated by a forward voltage with the value of about 0.07 V/Å. Three regions implying different E{sub field}-sensitive properties are obtained from the variations of bandgap with E{sub field}. The charge redistribution with an E{sub field} is mainly on the surface of PbI{sub 2} and BN layers as well as the amount of electrons depends on the strength of E{sub field}. In addition, the PbI{sub 2}/BN heterobilayer exhibits more outstanding optical conductivity capability. Our results could bring forward a new perspective on sensor and shed light on the design of novel nano- and optoelectronics based on the PbI{sub 2}/BN vdW heterostructure.

  3. Electrochemically Functionalized Seamless Three-Dimensional Graphene-Carbon Nanotube Hybrid for Direct Electron Transfer of Glucose Oxidase and Bioelectrocatalysis.

    Science.gov (United States)

    Terse-Thakoor, Trupti; Komori, Kikuo; Ramnani, Pankaj; Lee, Ilkeun; Mulchandani, Ashok

    2015-12-01

    Three-dimensional seamless chemical vapor deposition (CVD) grown graphene-carbon nanotubes (G-CNT) hybrid film has been studied for its potential in achieving direct electron transfer (DET) of glucose oxidase (GOx) and its bioelectrocatalytic activity in glucose detection. A two-step CVD method was employed for the synthesis of seamless G-CNT hybrid film where CNTs are grown on already grown graphene film on copper foil using iron as a catalyst. Physical characterization using SEM and TEM show uniform dense coverage of multiwall carbon nanotubes (MWCNT) grown directly on graphene with seamless contacts. The G-CNT hybrid film was electrochemically modified to introduce oxygenated functional groups for DET favorable immobilization of GOx. Pristine and electrochemically functionalized G-CNT film was characterized by electrochemical impedance spectroscopy (EIS), cyclic voltammetry, X-ray photoelectron-spectroscopy, and Raman spectroscopy. The DET between GOx and electrochemically oxidized G-CNT electrode was studied using cyclic voltammetry which showed a pair of well-defined and quasi-reversible redox peaks with a formal potential of -459 mV at pH 7 corresponding to the redox site of GOx. The constructed electrode detected glucose concentration over the clinically relevant range of 2-8 mM with the highest sensitivity of 19.31 μA/mM/cm(2) compared to reported composite hybrid electrodes of graphene oxide and CNTs. Electrochemically functionalized CVD grown seamless G-CNT structure used in this work has potential to be used for development of artificial mediatorless redox enzyme based biosensors and biofuel cells.

  4. Electron transfer kinetics of cytochrome c immobilized on a phenolic terminated thiol self assembled monolayer determined by scanning electrochemical microscopy

    International Nuclear Information System (INIS)

    Alizadeh, Vali; Mousavi, Mir Fazlollah; Mehrgardi, Masoud Ayatollahi; Kazemi, Sayed Habib; Sharghi, Hashem

    2011-01-01

    Highlights: → Preparing a thiolated phenolic self-assembled monolayer surface (SAM). → Application of this SAM to immobilize cytochrome C. → Scanning electrochemical microscopy used for these studies. → Determination of both tunneling electron transfer and bimolecular rate constants between the immobilized protein-substrate and probe. - Abstract: In the present manuscript, the electrochemical behavior of cytochrome c (cyt-c) immobilized onto a phenolic terminated self assembled monolayer (SAM) on a gold electrode is investigated using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The tunneling electron transfer (ET) rate constant between the immobilized protein and the underlying electrode surface, and also the bimolecular ET rate constant between the immobilized protein and a probe has been obtained using approach curves that were obtained by SECM. The approach curves were recorded at different substrate overpotentials in the presence of various concentrations of ferrocyanide as a probe and various surface concentrations of cyt-c; then the standard tunneling ET and bimolecular rate constants are obtained as 3.4 ± 0.3 s -1 and (2.0 ± 0.5) x 10 7 cm 3 mol -1 s -1 , respectively.

  5. Electron transfer kinetics of cytochrome c immobilized on a phenolic terminated thiol self assembled monolayer determined by scanning electrochemical microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Alizadeh, Vali [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mousavi, Mir Fazlollah, E-mail: mousavim@modares.ac.ir [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mehrgardi, Masoud Ayatollahi [Department of Chemistry, University of Isfahan, Isfahan (Iran, Islamic Republic of); Kazemi, Sayed Habib [Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan (Iran, Islamic Republic of); Sharghi, Hashem [Department of Chemistry, Shiraz University, Shiraz (Iran, Islamic Republic of)

    2011-07-01

    Highlights: > Preparing a thiolated phenolic self-assembled monolayer surface (SAM). > Application of this SAM to immobilize cytochrome C. > Scanning electrochemical microscopy used for these studies. > Determination of both tunneling electron transfer and bimolecular rate constants between the immobilized protein-substrate and probe. - Abstract: In the present manuscript, the electrochemical behavior of cytochrome c (cyt-c) immobilized onto a phenolic terminated self assembled monolayer (SAM) on a gold electrode is investigated using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The tunneling electron transfer (ET) rate constant between the immobilized protein and the underlying electrode surface, and also the bimolecular ET rate constant between the immobilized protein and a probe has been obtained using approach curves that were obtained by SECM. The approach curves were recorded at different substrate overpotentials in the presence of various concentrations of ferrocyanide as a probe and various surface concentrations of cyt-c; then the standard tunneling ET and bimolecular rate constants are obtained as 3.4 {+-} 0.3 s{sup -1} and (2.0 {+-} 0.5) x 10{sup 7} cm{sup 3} mol{sup -1} s{sup -1}, respectively.

  6. Electronic states of Ca/PC61BM: Mechanism of low work function metal as interfacial material

    Directory of Open Access Journals (Sweden)

    Ying-Ying Du

    2018-03-01

    Full Text Available We have studied the electronic states at Ca/PC61BM interface using photoemission spectroscopy. It is found that the state of unoccupied molecular orbitals of the top molecular layer (TML becomes occupied by the electrons transferred from the Ca atoms. The work function of the heavily doped TML of PC61BM film is smaller than that of metal Ca, and thus the contact between the TML and metal Ca is Ohmic. A transition layer (TL of several molecular layers forms beneath the TML due to the diffusion of the Ca atoms. The TL is conductive and aligns its Fermi level with the negative integer charge transfer level of the interior PC61BM. The built-in electric field in the TL facilitates the electron transport from the interior of the PC61BM film to the TML.

  7. Auger electron spectroscopy and Rutherford backscattering studies of copper in 2024-T3 aluminum following electrochemical anodization in phosphoric acid

    Science.gov (United States)

    Solomon, J. S.

    1981-05-01

    The effects of the electrochemical anodization of dioxidized 2024-T3 aluminum on copper were characterized by Auger electron spectroscopy and Rutherford backscattering. Anodization was performed in phosphoric acid at constant potential. Data is presented which shows that constant potential anodization of 2024-T3 is more efficient than aluminum in terms of oxide growth rates for short anodization times. However the maximum anodic oxide thickness achievable on the alloy is less than the pure metal. Copper is shown to be enriched at the oxide metal interface because of its diffusion from the bulk during anodization. The presence of copper at the oxide-metal interface is shown to affect oxide morphology.

  8. Electrochemical Tuning of Electronic Structure of Carbon Nanotubes and Fullerene Peapods

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav; Dunsch, L.; Kataura, H.

    2004-01-01

    Roč. 42, - (2004), s. 1011-1019 ISSN 0008-6223 R&D Projects: GA AV ČR IAA4040306; GA MŠk ME 487 Institutional research plan: CEZ:AV0Z4040901 Keywords : electrochemical analysis * carbon nanotubes * Raman spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 3.331, year: 2004

  9. Interfacial phenomenon theory

    International Nuclear Information System (INIS)

    Kim, Jong Deuk

    2000-02-01

    This book is composed of 8 chapters. It tells what interfacial phenomenon is by showing interfacial energy, characteristic of interface and system of interface from chapter 1. It also introduces interfacial energy and structure theory, molecular structure and orientation theory, and interfacial electricity phenomenon theory in the following 3 chapters. It still goes on by introducing super molecule cluster, disequilibrium dispersion, and surface and film through 3 chapters. And the last chapter is about colloid and application of interface.

  10. Remote interfacial dipole scattering and electron mobility degradation in Ge field-effect transistors with GeOx/Al2O3 gate dielectrics

    International Nuclear Information System (INIS)

    Wang, Xiaolei; Xiang, Jinjuan; Wang, Shengkai; Wang, Wenwu; Zhao, Chao; Ye, Tianchun; Xiong, Yuhua; Zhang, Jing

    2016-01-01

    Remote Coulomb scattering (RCS) on electron mobility degradation is investigated experimentally in Ge-based metal–oxide–semiconductor field-effect-transistors (MOSFETs) with GeO x /Al 2 O 3 gate stacks. It is found that the mobility increases with greater GeO x thickness (7.8–20.8 Å). The physical origin of this mobility dependence on GeO x thickness is explored. The following factors are excluded: Coulomb scattering due to interfacial traps at GeO x /Ge, phonon scattering, and surface roughness scattering. Therefore, the RCS from charges in gate stacks is studied. The charge distributions in GeO x /Al 2 O 3 gate stacks are evaluated experimentally. The bulk charges in Al 2 O 3 and GeO x are found to be negligible. The density of the interfacial charge is  +3.2  ×  10 12 cm −2 at the GeO x /Ge interface and  −2.3  ×  10 12 cm −2 at the Al 2 O 3 /GeO x interface. The electric dipole at the Al 2 O 3 /GeO x interface is found to be  +0.15 V, which corresponds to an areal charge density of 1.9  ×  10 13 cm −2 . The origin of this mobility dependence on GeO x thickness is attributed to the RCS due to the electric dipole at the Al 2 O 3 /GeO x interface. This remote dipole scattering is found to play a significant role in mobility degradation. The discovery of this new scattering mechanism indicates that the engineering of the Al 2 O 3 /GeO x interface is key for mobility enhancement and device performance improvement. These results are helpful for understanding and engineering Ge mobility enhancement. (paper)

  11. Electrochemical properties of porous carbon black layer as an electron injector into iodide redox couple

    International Nuclear Information System (INIS)

    Kim, Jung-Min; Rhee, Shi-Woo

    2012-01-01

    Highlights: ► Carbon black (CB) porous layer for triiodide (I 3 − ) ion reduction is coated with spray coating method at 120 °C on the fluorine-doped tin oxide glass. ► The electrochemical impedance spectroscopy is analyzed for a symmetric cell and a new circuit model is applied to identify electrochemical parameters. ► Decreased particle size and increased thickness improve the catalytic activity because of the increase in the surface area and the conductivity of the CB layer. - Abstract: Electrochemical properties of carbon black (CB) porous layer as a counter electrode in dye-sensitized solar cells (DSC) are studied. CB electrode for triiodide (I 3 − ) ion reduction is coated with spray coating method on the fluorine-doped tin oxide glass at 120 °C. The CB particle size is varied from 20 nm to 90 nm and the CB electrode thickness is controlled from 1 μm to 9 μm by controlling the spraying time. The electrochemical impedance spectroscopy is analyzed for a symmetric cell and a new circuit model is applied to identify electrochemical parameters. As the CB particle size is decreased, the catalytic activity is improved because of the increase in the surface area and the conductivity of the CB layer. Increased CB electrode thickness also improves the catalytic activity and leads to the low charge transfer resistance at the electrolyte/CB electrode interface. The CB counter electrode with the particle size of 20 nm and the thickness of 9 μm for DSC shows the energy conversion efficiency of 7.2% with the highest fill factor (FF) of 65.6%, which is similar to the Pt counter electrode with FF of 65.8% and the efficiency of 7.6%.

  12. Interfacial hydration, dynamics and electron transfer: multi-scale ET modeling of the transient [myoglobin, cytochrome b5] complex.

    Science.gov (United States)

    Keinan, Shahar; Nocek, Judith M; Hoffman, Brian M; Beratan, David N

    2012-10-28

    Formation of a transient [myoglobin (Mb), cytochrome b(5) (cyt b(5))] complex is required for the reductive repair of inactive ferri-Mb to its functional ferro-Mb state. The [Mb, cyt b(5)] complex exhibits dynamic docking (DD), with its cyt b(5) partner in rapid exchange at multiple sites on the Mb surface. A triple mutant (Mb(3M)) was designed as part of efforts to shift the electron-transfer process to the simple docking (SD) regime, in which reactive binding occurs at a restricted, reactive region on the Mb surface that dominates the docked ensemble. An electrostatically-guided brownian dynamics (BD) docking protocol was used to generate an initial ensemble of reactive configurations of the complex between unrelaxed partners. This ensemble samples a broad and diverse array of heme-heme distances and orientations. These configurations seeded all-atom constrained molecular dynamics simulations (MD) to generate relaxed complexes for the calculation of electron tunneling matrix elements (T(DA)) through tunneling-pathway analysis. This procedure for generating an ensemble of relaxed complexes combines the ability of BD calculations to sample the large variety of available conformations and interprotein distances, with the ability of MD to generate the atomic level information, especially regarding the structure of water molecules at the protein-protein interface, that defines electron-tunneling pathways. We used the calculated T(DA) values to compute ET rates for the [Mb(wt), cyt b(5)] complex and for the complex with a mutant that has a binding free energy strengthened by three D/E → K charge-reversal mutations, [Mb(3M), cyt b(5)]. The calculated rate constants are in agreement with the measured values, and the mutant complex ensemble has many more geometries with higher T(DA) values than does the wild-type Mb complex. Interestingly, water plays a double role in this electron-transfer system, lowering the tunneling barrier as well as inducing protein interface

  13. In situ transmission electron microscopy investigation of the interfacial reaction between Ni and Al during rapid heating in a nanocalorimeter

    Energy Technology Data Exchange (ETDEWEB)

    Grapes, Michael D., E-mail: mgrapes1@jhu.edu, E-mail: david.lavan@nist.gov, E-mail: weihs@jhu.edu [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Material Measurement Laboratory, Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); LaGrange, Thomas; Reed, Bryan W.; Campbell, Geoffrey H. [Lawrence Livermore National Laboratory, Materials Science and Technology Division, Livermore, California 94550 (United States); Woll, Karsten [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Institute of Applied Materials, Karlsruhe Institute of Technology, 76344 Eggenstein-Leopoldshafen (Germany); LaVan, David A., E-mail: mgrapes1@jhu.edu, E-mail: david.lavan@nist.gov, E-mail: weihs@jhu.edu [Material Measurement Laboratory, Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Weihs, Timothy P., E-mail: mgrapes1@jhu.edu, E-mail: david.lavan@nist.gov, E-mail: weihs@jhu.edu [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States)

    2014-11-01

    The Al/Ni formation reaction is highly exothermic and of both scientific and technological significance. In this report, we study the evolution of intermetallic phases in this reaction at a heating rate of 830 K/s. 100-nm-thick Al/Ni bilayers were deposited onto nanocalorimeter sensors that enable the measurement of temperature and heat flow during rapid heating. Time-resolved transmission electron diffraction patterns captured simultaneously with thermal measurements allow us to identify the intermetallic phases present and reconstruct the phase transformation sequence as a function of time and temperature. The results show a mostly unaltered phase transformation sequence compared to lower heating rates.

  14. Final Report for completed IPP-0110 and 0110A Projects: 'High Energy Ion Technology of Interfacial Thin Film Coatings for Electronic, Optical and Industrial Applications'

    International Nuclear Information System (INIS)

    Brown, Ian

    2009-01-01

    The DOE-supported IPP (Initiatives for Proliferation Prevention) Project, IPP-0110, and its accompanying 'add-on project' IPP-0110A, entitled 'High Energy Ion Technology of Interfacial Thin Film Coatings for Electronic, Optical and Industrial Applications' was a collaborative project involving the Lawrence Berkeley National Laboratory (LBNL) as the U.S. DOE lab; the US surface modification company, Phygen, Inc., as the US private company involved; and the High Current Electronics Institute (HCEI) of the Russian Academy of Sciences, Tomsk, Siberia, Russia, as the NIS Institute involved. Regular scientific research progress meetings were held to which personnel came from all participating partners. The meetings were held mostly at the Phygen facilities in Minneapolis, Minnesota (with Phygen as host) with meetings also held at Tomsk, Russia (HCEI as host), and at Berkeley, California (LBNL as host) In this way, good exposure of all researchers to the various different laboratories involved was attained. This report contains the Final Reports (final deliverables) from the Russian Institute, HCEI. The first part is that for IPP-0110A (the 'main part' of the overall project) and the second part is that for the add-on project IPP-0110A. These reports are detailed, and contain all aspects of all the research carried out. The project was successful in that all deliverables as specified in the proposals were successfully developed, tested, and delivered to Phygen. All of the plasma hardware was designed, made and tested at HCEI, and the performance was excellent. Some of the machine and performance parameters were certainly of 'world class'. The goals and requirements of the IPP Project were well satisfied. I would like to express my gratitude to the DOE IPP program for support of this project throughout its entire duration, and for the unparalleled opportunity thereby provided for all of the diverse participants in the project to join in this collaborative research. The

  15. Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study.

    Science.gov (United States)

    Jovanovič, Primož; Hodnik, Nejc; Ruiz-Zepeda, Francisco; Arčon, Iztok; Jozinović, Barbara; Zorko, Milena; Bele, Marjan; Šala, Martin; Šelih, Vid Simon; Hočevar, Samo; Gaberšček, Miran

    2017-09-13

    Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO 2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

  16. Interfacial electronic structures revealed at the rubrene/CH3NH3PbI3 interface.

    Science.gov (United States)

    Ji, Gengwu; Zheng, Guanhaojie; Zhao, Bin; Song, Fei; Zhang, Xiaonan; Shen, Kongchao; Yang, Yingguo; Xiong, Yimin; Gao, Xingyu; Cao, Liang; Qi, Dong-Chen

    2017-03-01

    The electronic structures of rubrene films deposited on CH 3 NH 3 PbI 3 perovskite have been investigated using in situ ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). It was found that rubrene molecules interacted weakly with the perovskite substrate. Due to charge redistribution at their interface, a downward 'band bending'-like energy shift of ∼0.3 eV and an upward band bending of ∼0.1 eV were identified at the upper rubrene side and the CH 3 NH 3 PbI 3 substrate side, respectively. After the energy level alignment was established at the rubrene/CH 3 NH 3 PbI 3 interface, its highest occupied molecular orbital (HOMO)-valence band maximum (VBM) offset was found to be as low as ∼0.1 eV favoring the hole extraction with its lowest unoccupied molecular orbital (LUMO)-conduction band minimum (CBM) offset as large as ∼1.4 eV effectively blocking the undesired electron transfer from perovskite to rubrene. As a demonstration, simple inverted planar solar cell devices incorporating rubrene and rubrene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTLs) were fabricated in this work and yielded a champion power conversion efficiency of 8.76% and 13.52%, respectively. Thus, the present work suggests that a rubrene thin film could serve as a promising hole transport layer for efficient perovskite-based solar cells.

  17. Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

    Science.gov (United States)

    Varenyk, O. V.; Silibin, M. V.; Kiselev, D. A.; Eliseev, E. A.; Kalinin, S. V.; Morozovska, A. N.

    2015-08-01

    The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. The obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers, which are of potential interest for flexible and high-density non-volatile memory devices.

  18. Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

    Energy Technology Data Exchange (ETDEWEB)

    Varenyk, O. V.; Morozovska, A. N., E-mail: sergei2@ornl.gov, E-mail: anna.n.morozovska@gmail.com [Institute of Physics, National Academy of Sciences of Ukraine, 46, pr. Nauky, 03028 Kyiv (Ukraine); Silibin, M. V. [National Research University of Electronic Technology “MIET,” 124498 Moscow (Russian Federation); Kiselev, D. A. [National University of Science and Technology “MISiS,” 119049 Moscow, Leninskiy pr. 4 (Russian Federation); Eliseev, E. A. [Institute for Problems of Materials Science, NAS of Ukraine, Krjijanovskogo 3, 03142 Kyiv (Ukraine); Kalinin, S. V., E-mail: sergei2@ornl.gov, E-mail: anna.n.morozovska@gmail.com [The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2015-08-21

    The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. The obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers, which are of potential interest for flexible and high-density non-volatile memory devices.

  19. Electrochemical/chemical oxidation of bisphenol A in a four-electron/two-proton process in aprotic organic solvents

    International Nuclear Information System (INIS)

    Chan, Ya Yun; Yue, Yanni; Li, Yongxin; Webster, Richard D.

    2013-01-01

    Graphical abstract: - Highlights: • Bisphenol A undergoes a chemically irreversible voltammetric oxidation process. • Chemical oxidation was performed to overcome adsorption effects that cause electrode fouling. • A new product was isolated from chemical oxidation with 4 mol equiv. of the one-electron oxidant, NO + . • The oxidative mechanism was proposed to be a four-electron/two-proton process. - Abstract: The electrochemical behavior of bisphenol A (BPA) was examined using cyclic voltammetry, bulk electrolysis and chemical oxidation in aprotic organic solvents. It was found that BPA undergoes a chemically irreversible voltammetric oxidation process to form compounds that cannot be electrochemically converted back to the starting materials on the voltammetric timescale. To overcome the effects of electrode fouling during controlled potential electrolysis experiments, NO + was used as a one-electron chemical oxidant. A new product, hydroxylated bisdienone was isolated from the chemical oxidation of BPA with 4 mol equiv of NO + SbF 6 − in low water content CH 3 CN. The structure of the cation intermediate species was deduced and it was proposed that BPA is oxidized in a four-electron/two-proton process to form a relatively unstable dication which reacts quickly in the presence of water in acetonitrile (in a mechanism that is similar to phenols in general). However, as the water content of the solvent increased it was found that the chemical oxidation mechanism produced a nitration product in high yield. The findings from this study provide useful insights into the reactions that can occur during oxidative metabolism of BPA and highlight the possibility of the role of a bisdienone cation as a reactive metabolite in biological systems

  20. Dentin-cement Interfacial Interaction

    Science.gov (United States)

    Atmeh, A.R.; Chong, E.Z.; Richard, G.; Festy, F.; Watson, T.F.

    2012-01-01

    The interfacial properties of a new calcium-silicate-based coronal restorative material (Biodentine™) and a glass-ionomer cement (GIC) with dentin have been studied by confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), micro-Raman spectroscopy, and two-photon auto-fluorescence and second-harmonic-generation (SHG) imaging. Results indicate the formation of tag-like structures alongside an interfacial layer called the “mineral infiltration zone”, where the alkaline caustic effect of the calcium silicate cement’s hydration products degrades the collagenous component of the interfacial dentin. This degradation leads to the formation of a porous structure which facilitates the permeation of high concentrations of Ca2+, OH-, and CO32- ions, leading to increased mineralization in this region. Comparison of the dentin-restorative interfaces shows that there is a dentin-mineral infiltration with the Biodentine, whereas polyacrylic and tartaric acids and their salts characterize the penetration of the GIC. A new type of interfacial interaction, “the mineral infiltration zone”, is suggested for these calcium-silicate-based cements. PMID:22436906

  1. Interfacial Interactions in Monolayer and Few-Layer SnS/CH3 NH3 PbI3 Perovskite van der Waals Heterostructures and Their Effects on Electronic and Optical Properties.

    Science.gov (United States)

    Li, Jian-Cai; Wei, Zeng-Xi; Huang, Wei-Qing; Ma, Li-Li; Hu, Wangyu; Peng, Ping; Huang, Gui-Fang

    2018-02-05

    A high light-absorption coefficient and long-range hot-carrier transport of hybrid organic-inorganic perovskites give huge potential to their composites in solar energy conversion and environmental protection. Understanding interfacial interactions and their effects are paramount for designing perovskite-based heterostructures with desirable properties. Herein, we systematically investigated the interfacial interactions in monolayer and few-layer SnS/CH 3 NH 3 PbI 3 heterostructures and their effects on the electronic and optical properties of these structures by density functional theory. It was found that the interfacial interactions in SnS/CH 3 NH 3 PbI 3 heterostructures were van der Waals (vdW) interactions, and they were found to be insensitive to the layer number of 2D SnS sheets. Interestingly, although their band gap decreased upon increasing the layer number of SnS, the near-gap electronic states and optical absorption spectra of these heterostructures were found to be strikingly similar. This feature was determined to be critical for the design of 2D layered SnS-based heterostructures. Strong absorption in the ultraviolet and visible-light regions, type II staggered band alignment at the interface, and few-layer SnS as an active co-catalyst make 2D SnS/CH 3 NH 3 PbI 3 heterostructures promising candidates for photocatalysis, photodetectors, and solar energy harvesting and conversion. These results provide first insight into the nature of interfacial interactions and are useful for designing hybrid organic-inorganic perovskite-based devices with novel properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. FinalReport for completed IPP-0110 and 0110A Projects:"High Energy Ion Technology of Interfacial Thin Film Coatings for Electronic, Optical and Industrial Applications"

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Ian

    2009-09-01

    The DOE-supported IPP (Initiatives for Proliferation Prevention) Project, IPP-0110, and its accompanying 'add-on project' IPP-0110A, entitled 'High Energy Ion Technology of Interfacial Thin Film Coatings for Electronic, Optical and Industrial Applications' was a collaborative project involving the Lawrence Berkeley National Laboratory (LBNL) as the U.S. DOE lab; the US surface modification company, Phygen, Inc., as the US private company involved; and the High Current Electronics Institute (HCEI) of the Russian Academy of Sciences, Tomsk, Siberia, Russia, as the NIS Institute involved. Regular scientific research progress meetings were held to which personnel came from all participating partners. The meetings were held mostly at the Phygen facilities in Minneapolis, Minnesota (with Phygen as host) with meetings also held at Tomsk, Russia (HCEI as host), and at Berkeley, California (LBNL as host) In this way, good exposure of all researchers to the various different laboratories involved was attained. This report contains the Final Reports (final deliverables) from the Russian Institute, HCEI. The first part is that for IPP-0110A (the 'main part' of the overall project) and the second part is that for the add-on project IPP-0110A. These reports are detailed, and contain all aspects of all the research carried out. The project was successful in that all deliverables as specified in the proposals were successfully developed, tested, and delivered to Phygen. All of the plasma hardware was designed, made and tested at HCEI, and the performance was excellent. Some of the machine and performance parameters were certainly of 'world class'. The goals and requirements of the IPP Project were well satisfied. I would like to express my gratitude to the DOE IPP program for support of this project throughout its entire duration, and for the unparalleled opportunity thereby provided for all of the diverse participants in the project to join

  3. Toward control of the metal-organic interfacial electronic structure in molecular electronics: a first-principles study on self-assembled monolayers of pi-conjugated molecules on noble metals.

    Science.gov (United States)

    Heimel, Georg; Romaner, Lorenz; Zojer, Egbert; Brédas, Jean-Luc

    2007-04-01

    Self-assembled monolayers (SAMs) of organic molecules provide an important tool to tune the work function of electrodes in plastic electronics and significantly improve device performance. Also, the energetic alignment of the frontier molecular orbitals in the SAM with the Fermi energy of a metal electrode dominates charge transport in single-molecule devices. On the basis of first-principles calculations on SAMs of pi-conjugated molecules on noble metals, we provide a detailed description of the mechanisms that give rise to and intrinsically link these interfacial phenomena at the atomic level. The docking chemistry on the metal side of the SAM determines the level alignment, while chemical modifications on the far side provide an additional, independent handle to modify the substrate work function; both aspects can be tuned over several eV. The comprehensive picture established in this work provides valuable guidelines for controlling charge-carrier injection in organic electronics and current-voltage characteristics in single-molecule devices.

  4. Interfacial effects in multilayers

    International Nuclear Information System (INIS)

    Barbee, T.W. Jr.

    1998-01-01

    Interfacial structure and the atomic interactions between atoms at interfaces in multilayers or nano-laminates have significant impact on the physical properties of these materials. A technique for the experimental evaluation of interfacial structure and interfacial structure effects is presented and compared to experiment. In this paper the impact of interfacial structure on the performance of x-ray, soft x-ray and extreme ultra-violet multilayer optic structures is emphasized. The paper is concluded with summary of these results and an assessment of their implications relative to multilayer development and the study of buried interfaces in solids in general

  5. Implications of electronic short circuiting in plasma sprayed solid oxide fuel cells on electrode performance evaluation by electrochemical impedance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    White, B.D. [Department of Mechanical Engineering, The University of British Columbia, 2054-6250 Applied Sciences Lane, Vancouver, British Columbia (Canada); Kesler, O. [Department of Mechanical and Industrial Engineering, University of Toronto, 5 King' s College Road, Toronto, Ontario (Canada)

    2008-02-15

    Electronic short circuiting of the electrolyte in a solid oxide fuel cell (SOFC) arising from flaws in the plasma spray fabrication process has been found to have a significant effect on the perceived performance of the electrodes, as evaluated by electrochemical impedance spectroscopy (EIS). The presence of a short circuit has been found to lead to the underestimation of the electrode polarization resistance (R{sub p}) and hence an overestimation of electrode performance. The effect is particularly noticeable when electrolyte resistance is relatively high, for example during low to intermediate temperature operation, leading to an obvious deviation from the expected Arrhenius-type temperature dependence of R{sub p}. A method is developed for determining the real electrode performance from measurements of various cell properties, and strategies for eliminating the occurrence of short circuiting in plasma sprayed cells are identified. (author)

  6. Implications of electronic short circuiting in plasma sprayed solid oxide fuel cells on electrode performance evaluation by electrochemical impedance spectroscopy

    Science.gov (United States)

    White, B. D.; Kesler, O.

    Electronic short circuiting of the electrolyte in a solid oxide fuel cell (SOFC) arising from flaws in the plasma spray fabrication process has been found to have a significant effect on the perceived performance of the electrodes, as evaluated by electrochemical impedance spectroscopy (EIS). The presence of a short circuit has been found to lead to the underestimation of the electrode polarization resistance (R p) and hence an overestimation of electrode performance. The effect is particularly noticeable when electrolyte resistance is relatively high, for example during low to intermediate temperature operation, leading to an obvious deviation from the expected Arrhenius-type temperature dependence of R p. A method is developed for determining the real electrode performance from measurements of various cell properties, and strategies for eliminating the occurrence of short circuiting in plasma sprayed cells are identified.

  7. Electrochemical Recovery of Gold from Waste Electric and Electronic Equipment Using Circulating Particulate Bed Reactor (CPBE)

    Science.gov (United States)

    Ravinder, T.; Ali, U. F. M.; Ridwan, F. M.; Ibrahim, N.; Azmi, N. H.

    2017-06-01

    The utilization of electrochemical process recovery involving low reactant concentrations of metal requires electrodes with high mass transport rates and specific surface areas. This is essential to increase cross-sectional current densities whilst optimizing the capital and operating costs. Experimental results demonstrated that Circulating Particulate Bed Reactor (CPBE) is suitable for the recovery of low concentrations of gold from aqueous chloride solution containing {{AuCl}}4- and {{AuCl}}2- of less than 0.5 mol m-3(< 102 g m-3). Elemental gold was successfully obtained on 0.5-1 mm gr particles in an electrochemical reactor incorporating a cation- permeable membrane and operated in bath recycle mode. Depletion to concentration < 5 × 10-3 mol m-3 (< 1 g m-3) appeared to be mass transport controlled at an applied potential of +0.20 V (SCE), specific electrical energy consumption (SEEC) of ca. 800-1300 kWh h (tonne Au)-1 for cell voltages (U) of 2.0-3.0 V, and fractional current efficiencies of ca. 0.95. However, atomic absorption and UV spectrophotometry established that as the ([{{AuCl}}4-+[{{AuCl}}2-]) concentration decayed, the [{{AuCl}}4-]:[{{AuCl}}2-] molar ratio changed. A multi-step mechanism for reduction of {{AuCl}}4- ions explained this behavior in terms of changing overpotentials for {{AuCl}}4- and {{AuCl}}2- reduction as total dissolved gold concentration decreased. In addition, SEM images confirmed that adherent and coherent Au deposits were achieved with CPBE for Au deposition under mass transport control at 0.20 V (SCE).

  8. Ferroelectric Polarization-Modulated Interfacial Fine Structures Involving Two-Dimensional Electron Gases in Pb(Zr,Ti)O3/LaAlO3/SrTiO3 Heterostructures.

    Science.gov (United States)

    Wang, Shuangbao; Bai, Yuhang; Xie, Lin; Li, Chen; Key, Julian D; Wu, Di; Wang, Peng; Pan, Xiaoqing

    2018-01-10

    Interfacial fine structures of bare LaAlO 3 /SrTiO 3 (LAO/STO) heterostructures are compared with those of LAO/STO heterostructures capped with upward-polarized Pb(Zr 0.1 ,Ti 0.9 )O 3 (PZT up ) or downward-polarized Pb(Zr 0.5 ,Ti 0.5 )O 3 (PZT down ) overlayers by aberration-corrected scanning transmission electron microscopy experiments. By combining the acquired electron energy-loss spectroscopy mapping, we are able to directly observe electron transfer from Ti 4+ to Ti 3+ and ionic displacements at the interface of bare LAO/STO and PZT down /LAO/STO heterostructure unit cell by unit cell. No evidence of Ti 3+ is observed at the interface of the PZT up /LAO/STO samples. Furthermore, the confinement of the two-dimensional electron gas (2DEG) at the interface is determined by atomic-column spatial resolution. Compared with the bare LAO/STO interface, the 2DEG density at the LAO/STO interface is enhanced or depressed by the PZT down or PZT up overlayer, respectively. Our microscopy studies shed light on the mechanism of ferroelectric modulation of interfacial transport at polar/nonpolar oxide heterointerfaces, which may facilitate applications of these materials as nonvolatile memory.

  9. Simulation of electronic circuit sensitivity towards humidity using electrochemical data on water layer

    DEFF Research Database (Denmark)

    Joshy, Salil; Verdingovas, Vadimas; Jellesen, Morten Stendahl

    2015-01-01

    Climatic conditions like temperature and humidity have direct influence on the operation of electronic circuits. The effects of temperature on the operation of electronic circuits have been widely investigated, while the effect of humidity and solder flux residues are not well understood including...... the effect on circuit and PCBA (printed circuit board assembly) layout design. This paper elucidates a methodology for analyzing the sensitivity of an electronic circuit based on parasitic circuit analysis using data on electrical property of the water layer formed under humid as well as contaminated...

  10. Fundamental Insights into Propionate Oxidation in Microbial Electrolysis Cells Using a Combination of Electrochemical, Molecular biology and Electron Balance Approaches

    KAUST Repository

    Rao, Hari Ananda

    2016-11-01

    Increasing demand for freshwater and energy is pushing towards the development of alternative technologies that are sustainable. One of the realistic solutions to address this is utilization of the renewable resources like wastewater. Conventional wastewater treatment processes can be highly energy demanding and can fails to recover the full potential of useful resources such as energy in the wastewater. As a consequence, there is an urgent necessity for sustainable wastewater treatment technologies that could harness such resources present in wastewaters. Advanced treatment process based on microbial electrochemical technologies (METs) such as microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) have a great potential for the resources recovery through a sustainable wastewater treatment process. METs rely on the abilities of microorganisms that are capable of transferring electrons extracellularly by oxidizing the organic matter in the wastewater and producing electrical current for electricity generation (MFC) or H2 and CH4 production (MEC). Propionate is an important volatile fatty acid (VFA) (24-70%) in some wastewaters and accumulation of this VFA can cause a process failure in a conventional anaerobic digestion (AD) system. To address this issue, MECs were explored as a novel, alternative wastewater treatment technology, with a focus on a better understanding of propionate oxidation in the anode of MECs. Having such knowledge could help in the development of more robust and efficient wastewater treatment systems to recover energy and produce high quality effluents. Several studies were conducted to: 1) determine the paths of electron flow in the anode of propionate fed MECs low (4.5 mM) and high (36 mM) propionate concentrations; 2) examine the effect of different set anode potentials on the electrochemical performance, propionate degradation, electron fluxes, and microbial community structure in MECs fed propionate; and 3) examine the temporal

  11. Suitability of olive oil washing water as an electron donor in a feed batch operating bio-electrochemical system

    Directory of Open Access Journals (Sweden)

    F. G. Fermoso

    2017-06-01

    Full Text Available Olive oil washing water derived from the two-phase manufacturing process was assessed as an electron donor in a bio-electrochemical system (BES operating at 35 ºC. Start-up was carried out by using acetate as a substrate for the BES, reaching a potential of around +680 mV. After day 54, BES was fed with olive oil washing water. The degradation of olive oil washing water in the BES generated a maximum voltage potential of around +520 mV and a Chemical Oxygen Demand (COD removal efficiency of 41%. However, subsequent loads produced a decrease in the COD removal, while current and power density diminished greatly. The deterioration of these parameters could be a consequence of the accumulation of recalcitrant or inhibitory compounds, such as phenols. These results demonstrated that the use of olive oil washing water as an electron donor in a BES is feasible, although it has to be further investigated in order to make it more suitable for a real application.

  12. Suitability of olive oil washing water as an electron donor in a feed batch operating bio-electrochemical system

    International Nuclear Information System (INIS)

    Fermoso, F.G.; Fernández-Rodríguez, M.J.; Jiménez-Rodríguez, A.; Serrano, A.; Borja, R.

    2017-01-01

    Olive oil washing water derived from the two-phase manufacturing process was assessed as an electron donor in a bio-electrochemical system (BES) operating at 35 ºC. Start-up was carried out by using acetate as a substrate for the BES, reaching a potential of around +680 mV. After day 54, BES was fed with olive oil washing water. The degradation of olive oil washing water in the BES generated a maximum voltage potential of around +520 mV and a Chemical Oxygen Demand (COD) removal efficiency of 41%. However, subsequent loads produced a decrease in the COD removal, while current and power density diminished greatly. The deterioration of these parameters could be a consequence of the accumulation of recalcitrant or inhibitory compounds, such as phenols. These results demonstrated that the use of olive oil washing water as an electron donor in a BES is feasible, although it has to be further investigated in order to make it more suitable for a real application. [es

  13. Electrochemically enhanced microbial CO conversion to volatile fatty acids using neutral red as an electron mediator.

    Science.gov (United States)

    Im, Chae Ho; Kim, Changman; Song, Young Eun; Oh, Sang-Eun; Jeon, Byong-Hun; Kim, Jung Rae

    2018-01-01

    Conversion of C1 gas feedstock, including carbon monoxide (CO), into useful platform chemicals has attracted considerable interest in industrial biotechnology. Nevertheless, the low conversion yield and/or growth rate of CO-utilizing microbes make it difficult to develop a C1 gas biorefinery process. The Wood-Ljungdahl pathway which utilize CO is a pathway suffered from insufficient electron supply, in which the conversion can be increased further when an additional electron source like carbohydrate or hydrogen is provided. In this study, electrode-based electron transference using a bioelectrochemical system (BES) was examined to compensate for the insufficient reducing equivalent and increase the production of volatile fatty acids. The BES including neutral red (BES-NR), which facilitated electron transfer between bacteria and electrode, was compared with BES without neutral red and open circuit control. The coulombic efficiency based on the current input to the system and the electrons recovered into VFAs, was significantly higher in BES-NR than the control. These results suggest that the carbon electrode provides a platform to regulate the redox balance for improving the bioconversion of CO, and amending the conventional C1 gas fermentation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Fulleropyrrolidine end-capped molecular wires for molecular electronics--synthesis, spectroscopic, electrochemical, and theoretical characterization

    DEFF Research Database (Denmark)

    Sørensen, Jakob Kryger; Fock, Jeppe; Pedersen, Anders Holmen

    2011-01-01

    In continuation of previous studies showing promising metal-molecule contact properties a variety of C(60) end-capped "molecular wires" for molecular electronics were prepared by variants of the Prato 1,3-dipolar cycloaddition reaction. Either benzene or fluorene was chosen as the central wire...... state. However, the fluorescence of C(60) was quenched by charge transfer from the wire to C(60). Quantum chemical calculations predict and explain the collapse of coherent electronic transmission through one of the fulleropyrrolidine-terminated molecular wires......., and synthetic protocols for derivatives terminated with one or two fullero[c]pyrrolidine "electrode anchoring" groups were developed. An aryl-substituted aziridine could in some cases be employed directly as the azomethine ylide precursor for the Prato reaction without the need of having an electron...

  15. First-principles calculation of electronic energy level alignment at electrochemical interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Azar, Yavar T.; Payami, Mahmoud, E-mail: mpayami@aeoi.org.ir

    2017-08-01

    Highlights: • Using DFT calculation, level shifts of TiO{sub 2} and ZnO at the interfaces with MeCN and DMF are determined. • Level shifts are obtained using potential difference between the surfaces of asymmetric slabs. • Solvent molecules give an up-shift to the levels that varies with coverage. • MD simulations show that at room temperatures the surface is not fully covered by the solvent molecules. - Abstract: Energy level alignment at solid–solvent interfaces is an important step in determining the properties of electrochemical systems. The positions of conduction and valence band edges of a semiconductor are affected by its environment. In this study, using first-principles DFT calculation, we have determined the level shifts of the semiconductors TiO{sub 2} and ZnO at the interfaces with MeCN and DMF solvent molecules. The level shifts of semiconductor are obtained using the potential difference between the clean and exposed surfaces of asymmetric slabs. In this work, neglecting the effects of present ions in the electrolyte solution, we have shown that the solvent molecules give rise to an up-shift for the levels, and the amount of this shift varies with coverage. It is also shown that the shapes of density of states do not change sensibly near the gap. Molecular dynamics simulations of the interface have shown that at room temperatures the semiconductor surface is not fully covered by the solvent molecules, and one must use intermediate values in an static calculations.

  16. Tuning the Electronic Structure of Titanium Oxide Support to Enhance the Electrochemical Activity of Platinum Nanoparticles

    KAUST Repository

    Shi, Feifei; Baker, L. Robert; Hervier, Antoine; Somorjai, Gabor A.; Komvopoulos, Kyriakos

    2013-01-01

    on pristine TiO2 support were achieved by tuning the electronic structure of the titanium oxide support of Pt nanoparticle catalysts. This was accomplished by adding oxygen vacancies or doping with fluorine. Experimental trends are interpreted in the context

  17. Multiple Electron Charge Transfer Chemistries for Electrochemical Energy Storage Systems: The Metal Boride and Metal Air Battery

    Science.gov (United States)

    Stuart, Jessica F.

    performance of nanoscopic anodic materials in addition to the previously developed macroscopic system, as well as the exploration of a high-energy capacity TiB 2/VB2 composite anode. However, the greatest challenge to this room temperature VB2 primary battery is to develop a means to electrochemically recharge the anodic material (how to reinsert the eleven electrons per molecule that are removed during the battery's discharge). Rechargeable batteries, such as the new molten air battery presented in this thesis, offer a high intrinsic capacity mode for energy storage and overcome problems such as the need for higher energy capacity, cost-effective batteries for a range of electronic, transportation, and large-scale power storage devices. Molten air batteries presented and discussed in this work are viable systems that provide a means to electrochemically recharge the VB2-air battery and deliver large-scale energy storage due to their scalability, location flexibility, construction from readily available resources, and offer increased energy storage capacity for the electric grid. One example is the VB2 molten air battery, which discharges according to: VB 2 + 11/4 O2 → 1/ 2 V2O5 + B2O3 (1). Previously, our group has shown that carbon dioxide can be captured from atmospheric air concentrations at solar efficiencies as high as 50%, and that carbon dioxide emissions associated with the production of several commodities can be electrochemically avoided in by the Solar Thermal Electrochemical Process (STEP). Utilizing this process, the carbon molten air battery relies on carbon dioxide directly from the air: Charging: CO2 (g) → C (solid) + O2 (g) (2) Discharging: C (solid) + O2 (g) → CO2 (g) (3). More specifically, in a molten carbonate electrolyte containing added oxide, such as lithium carbonate with lithium oxide, the four-electron charging reaction, Equation 2, approaches 100% faradic efficiency and can be described as the following two equations: O2- (dissolved) + CO2

  18. Stability, electrochemical behaviors and electronic structures of iron hydroxyl-phosphate

    International Nuclear Information System (INIS)

    Wang Zhongli; Sun Shaorui; Li Fan; Chen Ge; Xia Dingguo; Zhao Ting; Chu Wangsheng; Wu Ziyu

    2010-01-01

    Iron hydroxyl-phosphate with a uniform spherical particle size of around 1 μm, a compound of the type Fe 2-y □ y (PO 4 )(OH) 3-3y (H 2 O) 3y-2 (where □ represents a vacancy), has been synthesized by hydrothermal methods. The particles are composed of spheres of diameter -1 and 120 mAh g -1 at current densities of 170 mA g -1 and 680 mA g -1 , respectively. The stability of crystal structure of this material was studied by TGA and XRD which show that the material remains stable at least up to the temperature 200 deg. C. Investigation of the electronic structure of the iron hydroxyl-phosphate by GGA + U calculation has indicated that it has a better electronic conductivity than LiFePO 4 .

  19. Electrochemically grafted polypyrrole changes photoluminescence of electronic states inside nanocrystalline diamond

    Czech Academy of Sciences Publication Activity Database

    Galář, P.; Čermák, Jan; Malý, P.; Kromka, Alexander; Rezek, Bohuslav

    2014-01-01

    Roč. 116, č. 22 (2014), "223103-1"-"223103-6" ISSN 0021-8979 R&D Projects: GA ČR(CZ) GBP108/12/G108; GA MŠk(CZ) LM2011026 Institutional support: RVO:68378271 Keywords : polypyrrole * nanocrystalline diamond * photoluminescence spectroscopy * opto-electronics Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.183, year: 2014

  20. Two-electron electrochemical oxidation of quercetin and kaempferol changes only the flavonoid C-ring

    DEFF Research Database (Denmark)

    Jørgensen, Lars; Cornett, Claus; Justesen, Ulla

    1998-01-01

    Bulk electrolysis of the antioxidant flavonoids quercetin and kaempferol in acetonitrile both yield a single oxidation product in two-electron processes. The oxidation products are more polar than their parent compounds, with an increased molecular weight of 16g/mol, and were identified as 2......-(3,4-dihydroxybenzoyl)-2,4,6-trihydroxy-3 (2H)-benzofuranone and 2-(4-hydroxybenzoyl)-2,4,6-trihydroxy-3(2H)-benzofuranone for quercetin and kaempferol, respectively. Two-electron oxidation of the parent flavonoid is suggested to yield a 3,4-flavandione with unchanged substitution pattern in the A- and B-ring, which...... may rearrange to form the substituted 3(2H)-benzofuranone through the chalcan-trione ring-chain tautomer. The acidity of the 3-OH group is suggested to determine the fate of the flavonoid phenoxyl radical originally formed by one-electron oxidation, as no well-defined oxidation product of luteolin...

  1. Injection of Spin-Polarized Electrons into a AlGaN/GaN Device from an Electrochemical Cell: Evidence for an Extremely Long Spin Lifetime.

    Science.gov (United States)

    Kumar, Anup; Capua, Eyal; Fontanesi, Claudio; Carmieli, Raanan; Naaman, Ron

    2018-04-24

    Spin-polarized electrons are injected from an electrochemical cell through a chiral self-assembled organic monolayer into a AlGaN/GaN device in which a shallow two-dimensional electron gas (2DEG) layer is formed. The injection is monitored by a microwave signal that indicates a coherent spin lifetime that exceeds 10 ms at room temperature. The signal was found to be magnetic field independent; however, it depends on the current of the injected electrons, on the length of the chiral molecules, and on the existence of 2DEG.

  2. Model of interfacial melting

    DEFF Research Database (Denmark)

    Mouritsen, Ole G.; Zuckermann, Martin J.

    1987-01-01

    A two-dimensional model is proposed to describe systems with phase transitions which take place in terms of crystalline as well as internal degrees of freedom. Computer simulation of the model shows that the interplay between the two sets of degrees of freedom permits observation of grain-boundar......-boundary formation and interfacial melting, a nonequilibrium process by which the system melts at the boundaries of a polycrystalline domain structure. Lipid membranes are candidates for systems with pronounced interfacial melting behavior....

  3. Modification of doping front migration in electrochemical devices and application to organic electronics

    International Nuclear Information System (INIS)

    Nolte, Marius; Wan Xianglong; Kopp, Olga; Hermes, Ina; Panz, Jan; Rahmanian, Afsaneh; Knoll, Meinhard

    2011-01-01

    Research highlights: → In this paper we demonstrate several ways of tuning the doping front migration process in polymer electronic multilayer structures for the first time. By altering the migration layer thickness the migration velocity may be controlled and it is possible to switch between migration mechanisms. The mechanism of delamination produces rapid jumps in migration velocity, while the addition of 2-hydroxyethylcellulose (HEC) can inhibit this effect. In case of vapor activation the migration velocity may be influenced by the relative humidity or by varying the concentration of hygroscopic salts added to the migration layer. The migration mechanisms can be explained in terms of diffusion, capillary transport, and delamination. Tuning the migration process may be used to construct polymer electronic structures such as enhancement and depletion type pseudo transistors and electrical switches (ON-OFF and OFF-ON) with an improved switching time of several minutes. The doping front width is determined by microscopic optical absorption spectroscopy and can be controlled by the concentration of the doping solution. In case of low concentrations the electrochromic effect of the double front is observed. - Abstract: We demonstrate several methods of modifying the doping front migration process in multilayer structures, enabling control of migration velocity and switching between different migration mechanisms. Sharp jumps in migration velocity may be induced using a delamination effect. The influence of migration layer thickness and composition is examined. Migration velocity may also be influenced by exposing the system to a defined relative humidity or by varying the concentration of a hygroscopic salt in the migration layer. The migration mechanisms can be explained in terms of diffusion, capillary transport, and delamination. By tailoring the migration process a variety of polymer electronic structures such as pseudo transistors (enhancement and depletion

  4. Quasi-steady-state voltammetry of rapid electron transfer reactions at the macroscopic substrate of the scanning electrochemical microscope.

    Science.gov (United States)

    Nioradze, Nikoloz; Kim, Jiyeon; Amemiya, Shigeru

    2011-02-01

    We report on a novel theory and experiment for scanning electrochemical microscopy (SECM) to enable quasi-steady-state voltammetry of rapid electron transfer (ET) reactions at macroscopic substrates. With this powerful approach, the substrate potential is cycled widely across the formal potential of a redox couple while the reactant or product of a substrate reaction is amperometrically detected at the tip in the feedback or substrate generation/tip collection mode, respectively. The plot of tip current versus substrate potential features the retraceable sigmoidal shape of a quasi-steady-state voltammogram although a transient voltammogram is obtained at the macroscopic substrate. Finite element simulations reveal that a short tip-substrate distance and a reversible substrate reaction (except under the tip) are required for quasi-steady-state voltammetry. Advantageously, a pair of quasi-steady-state voltammograms is obtained by employing both operation modes to reliably determine all transport, thermodynamic, and kinetic parameters as confirmed experimentally for rapid ET reactions of ferrocenemethanol and 7,7,8,8-tetracyanoquinodimethane at a Pt substrate with ∼0.5 μm-radius Pt tips positioned at 90 nm-1 μm distances. Standard ET rate constants of ∼7 cm/s were obtained for the latter mediator as the largest determined for a substrate reaction by SECM. Various potential applications of quasi-steady-state voltammetry are also proposed.

  5. Room Temperature Electrochemical Sintering of Zn Microparticles and Its Use in Printable Conducting Inks for Bioresorbable Electronics.

    Science.gov (United States)

    Lee, Yoon Kyeung; Kim, Jeonghyun; Kim, Yerim; Kwak, Jean Won; Yoon, Younghee; Rogers, John A

    2017-10-01

    This study describes a conductive ink formulation that exploits electrochemical sintering of Zn microparticles in aqueous solutions at room temperature. This material system has relevance to emerging classes of biologically and environmentally degradable electronic devices. The sintering process involves dissolution of a surface passivation layer of zinc oxide in CH 3 COOH/H 2 O and subsequent self-exchange of Zn and Zn 2+ at the Zn/H 2 O interface. The chemical specificity associated with the Zn metal and the CH 3 COOH/H 2 O solution is critically important, as revealed by studies of other material combinations. The resulting electrochemistry establishes the basis for a remarkably simple procedure for printing highly conductive (3 × 10 5 S m -1 ) features in degradable materials at ambient conditions over large areas, with key advantages over strategies based on liquid phase (fusion) sintering that requires both oxide-free metal surfaces and high temperature conditions. Demonstrations include printed magnetic loop antennas for near-field communication devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

    Science.gov (United States)

    Marcus, R. A.

    1962-01-01

    Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

  7. Organic electrochemical transistors

    KAUST Repository

    Rivnay, Jonathan; Inal, Sahika; Salleo, Alberto; Owens, Ró isí n M.; Berggren, Magnus; Malliaras, George G.

    2018-01-01

    Organic electrochemical transistors (OECTs) make effective use of ion injection from an electrolyte to modulate the bulk conductivity of an organic semiconductor channel. The coupling between ionic and electronic charges within the entire volume

  8. Forward-bias diode parameters, electronic noise, and photoresponse of graphene/silicon Schottky junctions with an interfacial native oxide layer

    Science.gov (United States)

    An, Yanbin; Behnam, Ashkan; Pop, Eric; Bosman, Gijs; Ural, Ant

    2015-09-01

    Metal-semiconductor Schottky junction devices composed of chemical vapor deposition grown monolayer graphene on p-type silicon substrates are fabricated and characterized. Important diode parameters, such as the Schottky barrier height, ideality factor, and series resistance, are extracted from forward bias current-voltage characteristics using a previously established method modified to take into account the interfacial native oxide layer present at the graphene/silicon junction. It is found that the ideality factor can be substantially increased by the presence of the interfacial oxide layer. Furthermore, low frequency noise of graphene/silicon Schottky junctions under both forward and reverse bias is characterized. The noise is found to be 1/f dominated and the shot noise contribution is found to be negligible. The dependence of the 1/f noise on the forward and reverse current is also investigated. Finally, the photoresponse of graphene/silicon Schottky junctions is studied. The devices exhibit a peak responsivity of around 0.13 A/W and an external quantum efficiency higher than 25%. From the photoresponse and noise measurements, the bandwidth is extracted to be ˜1 kHz and the normalized detectivity is calculated to be 1.2 ×109 cm Hz1/2 W-1. These results provide important insights for the future integration of graphene with silicon device technology.

  9. A study of intergranular corrosion of austenitic stainless steel by electrochemical potentiodynamic reactivation, electron back-scattering diffraction and cellular automaton

    Energy Technology Data Exchange (ETDEWEB)

    Yu Xiaofei [Department of Chemistry, Shandong University, Jinan 250100 (China); Chen Shenhao [Department of Chemistry, Shandong University, Jinan 250100 (China); State Key Laboratory for Corrosion and Protection, Shenyang 110016 (China)], E-mail: shchen@sdu.edu.cn; Liu Ying; Ren Fengfeng [Department of Chemistry, Shandong University, Jinan 250100 (China)

    2010-06-15

    The impact of solution and sensitization treatments on the intergranular corrosion (IGC) of austenitic stainless steel (316) was studied by electrochemical potentiodynamic reactivation (EPR) test, and the results showed the degree of sensitization (DOS) decreased as solution treatment temperature and time went up, but it increased as sensitization temperature prolonged. Factors that affected IGC were investigated by field emission scanning electron microscope (FE-SEM) and electron back-scattering diffraction (EBSD). Furthermore, the precipitation evolution of Cr-rich carbides and the distribution of chromium concentration were simulated by cellular automaton (CA), clearly showing the effects of solution and sensitization treatments on IGC.

  10. Probing Interfacial Water on Nanodiamonds in Colloidal Dispersion.

    Science.gov (United States)

    Petit, Tristan; Yuzawa, Hayato; Nagasaka, Masanari; Yamanoi, Ryoko; Osawa, Eiji; Kosugi, Nobuhiro; Aziz, Emad F

    2015-08-06

    The structure of interfacial water layers around nanoparticles dispersed in an aqueous environment may have a significant impact on their reactivity and on their interaction with biological species. Using transmission soft X-ray absorption spectroscopy in liquid, we demonstrate that the unoccupied electronic states of oxygen atoms from water molecules in aqueous colloidal dispersions of nanodiamonds have a different signature than bulk water. X-ray absorption spectroscopy can thus probe interfacial water molecules in colloidal dispersions. The impacts of nanodiamond surface chemistry and concentration on interfacial water electronic signature are discussed.

  11. Investigation the effect of porosity on corrosion of macroporous silicon in 1.0 M sodium hydroxide solution using weight loss measurements, electrochemical methods and scanning electron microscope

    International Nuclear Information System (INIS)

    Lai, Chuan; Xiang, Zhen

    2015-01-01

    Highlights: • The dissolution of silicon wafers conforms Faraday’s laws of electrolysis. • The porosity effect on macroporous silicon corrosion was investigated. • The corrosion rate increase linearly with porosity increasing. • The porosity effect on activation parameters was obtained. - Abstract: In this study, the macroporous silicon has been fabricated by electrochemical anodization. The dissolution of n-type silicon wafers in etching solution conforms Faraday’s laws of electrolysis. The fabricated macroporous silicon with different porosity corrosion in 1.0 M NaOH was systemically investigated by weight loss measurements, electrochemical methods and scanning electron microscope. Results show that with the porosity increasing, the corrosion rate of macroporous silicon in 1.0 M NaOH increases linearly. In addition, the increase of corrosion rate of macroporous silicon with relative higher porosity was determined by the pre-exponential factor.

  12. Molecular Level Manipulation of Interfacial Charge Transport

    Science.gov (United States)

    Song, Charles Kiseok

    The bulk-heterojunction organic (BHJ) photovoltaics (OPVs) and lithium ion battery (LiB) have been extensively studied. Power conversion efficiency (PCE) of an OPV greater than 10% and utilizing group 4 elements as the anode to accommodate high capacity for LiBs are the goals of many studies. However, the currently ubiquitous hole-collecting layer of OPVs limit device performance and durability, and group 4 elements are unstable and brittle to be commercially produced. Thus, my thesis has focused on developing functional and durable interfacial layers (IFLs) for OPVs and characterizing flexible artificial solid-electrolyte interphase (SEI) for LiBs. In Chapter 2, a series of robust organosilane-based dipolar self-assembled monolayer (SAM) IFLs on the tin-doped indium oxide (ITO) anodes of OPVs are developed. These hydrophobic and amorphous IFLs modify anode work functions from 4.66 to 5.27 eV. Two series of Glass/ITO/SAM IFL/Active Layer/LiF/Al BHJ OPVs are fabricated, and a strong positive correlation between the electrochemically-derived heterogeneous electron transport rate constants (ks) and OPV PCEs are observed due to enhanced anode carrier extraction. In Chapter 3, a series of unusually denser organosilane-based SAM IFLs on ITO anodes of OPVs are developed. Precursor mixtures having short and long tail groups were simultaneously deposited to minimize sterical encumbrance and denser SAM IFLs are achieved. These heterogeneous supersaturated SAMs (SHSAMs), with PCE (7.62%) exceeding that of PEDOT:PSS IFL, are found to be 17% denser and enhances PCE by 54% versus comparable devices with homogeneous SAM IFLs due to enhanced charge selectivity and collection. In Chapter 4, libraries of electron affinities (EAs) of widely used conductive polymers are constructed by cyclic voltammetry (CV) in conventional and LiB media. The EAs of the conductive polymer films measured via CV in conventional (EAC) and Li+ battery (EAB) media could be linearly correlated by EAB = (1

  13. USING MOLECULAR PROBES TO STUDY INTERFACIAL REDOX REACTION AT FE-BEARING SMECTITES

    Science.gov (United States)

    The interfacial electron transfer of clay-water systems has a wide range of significance in geochemical and biogeochernical environments. However the mechanism of interfacial electron transport is poorly understood. The electron transfer mechanism at the solid-water interfaces of...

  14. An insight into intrinsic interfacial properties between Li metals and Li10GeP2S12 solid electrolytes.

    Science.gov (United States)

    Chen, Bingbing; Ju, Jiangwei; Ma, Jun; Zhang, Jianjun; Xiao, Ruijuan; Cui, Guanglei; Chen, Liquan

    2017-11-29

    Density functional theory simulations and experimental studies were performed to investigate the interfacial properties, including lithium ion migration kinetics, between lithium metal anode and solid electrolyte Li 10 GeP 2 S 12 (LGPS). The LGPS[001] plane was chosen as the studied surface because the easiest Li + migration pathway is along this direction. The electronic structure of the surface states indicated that the electrochemical stability was reduced at both the PS 4 - and GeS 4 -teminated surfaces. For the interface cases, the equilibrium interfacial structures of lithium metal against the PS 4 -terminated LGPS[001] surface (Li/PS 4 -LGPS) and the GeS 4 -terminated LGPS[001] surface (Li/GeS 4 -LGPS) were revealed based on the structural relaxation and adhesion energy analysis. Solid electrolyte interphases were expected to be formed at both Li/PS 4 -LGPS and Li/GeS 4 -LGPS interfaces, resulting in an unstable state of interface and large interfacial resistance, which was verified by the EIS results of the Li/LGPS/Li cell. In addition, the simulations of the migration kinetics show that the energy barriers for Li + crossing the Li/GeS 4 -LGPS interface were relatively low compared with the Li/PS 4 -LGPS interface. This may contribute to the formation of Ge-rich phases at the Li/LGPS interface, which can tune the interfacial structures to improve the ionic conductivity for future all-solid-state batteries. This work will offer a thorough understanding of the Li/LGPS interface, including local structures, electronic states and Li + diffusion behaviors in all-solid-state batteries.

  15. Stiffness, strength and adhesion characterization of electrochemically deposited conjugated polymer films

    Science.gov (United States)

    Qu, Jing; Ouyang, Liangqi; Kuo, Chin-chen; Martin, David C.

    2015-01-01

    Conjugated polymers such as poly(3,4-ethylenedioxythiphene) (PEDOT) are of interest for a variety of applications including interfaces between electronic biomedical devices and living tissue. The mechanical properties, strength, and adhesion of these materials to solid substrates are all vital for long-term applications. We have been developing methods to quantify the mechanical properties of conjugated polymer thin films. In this study the stiffness, strength and the interfacial shear strength (adhesion) of electrochemically deposited PEDOT and PEDOT-co-1,3,5-tri[2-(3,4-ethylene dioxythienyl)]-benzene (EPh) were studied. The estimated Young’s modulus of the PEDOT films was 2.6 ± 1.4 GPa, and the strain to failure was around 2%. The tensile strength was measured to be 56 ± 27 MPa. The effective interfacial shear strength was estimated with a shear-lag model by measuring the crack spacing as a function of film thickness. For PEDOT on gold/palladium-coated hydrocarbon film substrates an interfacial shear strength of 0.7 ± 0.3 MPa was determined. The addition of 5 mole% of a tri-functional EDOT crosslinker (EPh) increased the tensile strength of the films to 283 ± 67 MPa, while the strain to failure remained about the same (2%). The effective interfacial shear strength was increased to 2.4 ± 0.6 MPa. PMID:26607768

  16. Influence of electron delocalization in heterocyclic core systems on the electrochemical communication in 2,5-di- and 2,3,4,5-tetraferrocenyl thiophenes, furans, and pyrroles.

    Science.gov (United States)

    Hildebrandt, Alexander; Schaarschmidt, Dieter; Claus, Ron; Lang, Heinrich

    2011-11-07

    A series of 2,5-di- and 2,3,4,5-tetraferrocenyl-substituted thiophenes, furans, and pyrroles were synthesized using the Negishi C,C cross-coupling protocol. The electronic and electrochemical properties of these compounds were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), and in situ UV-vis/NIR spectroscopy. The molecular structures of 2,5-diferrocenyl furan and 2,3,4,5-tetraferrocenyl-1-methyl-1H-pyrrole in the solid state are discussed. The ferrocenyls could sequentially be oxidized giving two or four reversible responses for the appropriate di- or tetraferrocenyl-substituted heterocyclic molecules. The observed ΔE°' values range between 186 and 450 mV. The NIR measurements confirm electronic communication as intervalence charge transfer (IVCT) absorptions were found in the corresponding mono- and in case of the tetraferrocenyl compounds also in the dicationic species. All compounds, except tetraferrocenyl thiophene (a class I system), were classified as class II systems according to Robin and Day. They show a linear relationship between ΔE°' and the IVCT oscillator strength f which could be shown for the first time in organometallic chemistry. This was possible because the series of molecules exhibit analogous geometries and hence, similar electrostatic properties. This correlation was confirmed by electro- and spectro-electrochemical measurements. Within these studies a new approach for the estimation of the effective electron transfer distances r(ab) is discussed. © 2011 American Chemical Society

  17. Electrochemical gating in scanning electrochemical microscopy

    NARCIS (Netherlands)

    Ahonen, P.; Ruiz, V.; Kontturi, K.; Liljeroth, P.; Quinn, B.M.

    2008-01-01

    We demonstrate that scanning electrochemical microscopy (SECM) can be used to determine the conductivity of nanoparticle assemblies as a function of assembly potential. In contrast to conventional electron transport measurements, this method is unique in that electrical connection to the film is not

  18. Iridium Interfacial Stack (IRIS)

    Science.gov (United States)

    Spry, David James (Inventor)

    2015-01-01

    An iridium interfacial stack ("IrIS") and a method for producing the same are provided. The IrIS may include ordered layers of TaSi.sub.2, platinum, iridium, and platinum, and may be placed on top of a titanium layer and a silicon carbide layer. The IrIS may prevent, reduce, or mitigate against diffusion of elements such as oxygen, platinum, and gold through at least some of its layers.

  19. Amorphous-like interfacial layer between a high-Tc superconducting Tl-1223 film and a Ag substrate examined by high-voltage high-resolution transmission electron microscopy

    International Nuclear Information System (INIS)

    Kim, Bongjun; Kim, Hyuntak; Nagai, Takuro; Matsui, Yoshio; Horiuchi, Shigeo; Jeong, Daeyeong; Deinhofer, Christian; Gritzner, Gerhard; Kim, Youngmin; Kim, Younjoong

    2006-01-01

    The thin amorphous-like layer, formed at the interface between a high-T c superconducting (Tl 0.5 , Pb 0.5 )(Sr 0.8 , Ba 0.2 )Ca 2 Cu 3 O y (Tl-1223) film and a Ag substrate during heating at 910 .deg. C, has been examined by using high-voltage high-resolution transmission electron microscopy. The interfacial layer is less than 10 nm in thickness. It contacts the (001) plane of Tl-1223 and the (113) or (133) planes of Ag in most cases. Its composition is similar to that of Tl-1223, except for the inclusion of a substantial amount of Ag. Its formation proceeds by diffusion of Ag into Tl-1223, during which a structure change first occurs at the layer of CuO 2 + Ca planes. The Tl(Pb)O + the Sr(Ba)O layers are then destroyed to cause the total structure to become amorphous-like. Furthermore, we have found that it is formed under an irradiation of highly energetic electrons.

  20. Amorphous-like interfacial layer between a high-T{sub c} superconducting Tl-1223 film and a Ag substrate examined by high-voltage high-resolution transmission electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Bongjun; Kim, Hyuntak [Electronics and Tele-Communications Research Institute, Daejeon (Korea, Republic of); Nagai, Takuro; Matsui, Yoshio [National Institute for Materials Science, Tsukuba, Ibaraki (Japan); Horiuchi, Shigeo; Jeong, Daeyeong [Electrotechnology Research Institute, Changwon (Korea, Republic of); Deinhofer, Christian; Gritzner, Gerhard [Johannes Kepler University, Linz (Austria); Kim, Youngmin; Kim, Younjoong [Electron Microscopy Team, Korea Basic Science Institute, Daejeon (Korea, Republic of)

    2006-05-15

    The thin amorphous-like layer, formed at the interface between a high-T{sub c} superconducting (Tl{sub 0.5}, Pb{sub 0.5})(Sr{sub 0.8}, Ba{sub 0.2})Ca{sub 2}Cu{sub 3}O{sub y} (Tl-1223) film and a Ag substrate during heating at 910 .deg. C, has been examined by using high-voltage high-resolution transmission electron microscopy. The interfacial layer is less than 10 nm in thickness. It contacts the (001) plane of Tl-1223 and the (113) or (133) planes of Ag in most cases. Its composition is similar to that of Tl-1223, except for the inclusion of a substantial amount of Ag. Its formation proceeds by diffusion of Ag into Tl-1223, during which a structure change first occurs at the layer of CuO{sub 2} + Ca planes. The Tl(Pb)O + the Sr(Ba)O layers are then destroyed to cause the total structure to become amorphous-like. Furthermore, we have found that it is formed under an irradiation of highly energetic electrons.

  1. Understanding supercapacitors based on nano-hybrid materials with interfacial conjugation

    Institute of Scientific and Technical Information of China (English)

    George Z. Chen

    2013-01-01

    The recent fast development of supercapacitors, also known scientifically as electrochemical capacitors, has benefited significantly from synthesis, characterisations and electrochemistry of nanoma-terials. Herein, the principle of supercapacitors is explained in terms of performance characteristics and charge storage mechanisms, i.e. double layer (or interfacial) capacitance and pseudo-capacitance. The semiconductor band model is applied to qualitatively account for the pseudo-capacitance in association with rectangular cyclic voltammograms (CVs) and linear galvanostatic charging and discharging plots (GCDs), aiming to differentiate supercapacitors from rechargeable batteries. The invalidity of using peak shaped CVs and non-linear GCDs for capacitance measurement is highlighted. A selective review is given to the nano-hybrid materials between carbon nanotubes and redox active materials such as electronically conducting polymers and transition metal oxides. A new concept,“interfacial conjugation”, is introduced to reflect the capacitance enhancement resulting from π-π stacking interactions at the interface between two materials with highly conjugated chemical bonds. The prospects of carbon nanotubes and graphenes for supercapacitor applications are briefly compared and discussed. Hopefully, this article can help readers to understand supercapacitors and nano-hybrid materials so that further developments in materials design and synthesis, and device engineering can be more efficient and objective.

  2. Redox properties of structural Fe in clay minerals. 2. Electrochemical and spectroscopic characterization of electron transfer irreversibility in ferruginous smectite, SWa-1.

    Science.gov (United States)

    Gorski, Christopher A; Klüpfel, Laura; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B

    2012-09-04

    Structural Fe in clay minerals is an important, albeit poorly characterized, redox-active phase found in many natural and engineered environments. This work develops an experimental approach to directly assess the redox properties of a natural Fe-bearing smectite (ferruginous smectite, SWa-1, 12.6 wt % Fe) with mediated electrochemical reduction (MER) and oxidation (MEO). By utilizing a suite of one-electron-transfer mediating compounds to facilitate electron transfer between structural Fe in SWa-1 and a working electrode, we show that the Fe2+/Fe3+ couple in SWa-1 is redox-active over a large range of potentials (from E(H) = -0.63 V to +0.61 V vs SHE). Electrochemical and spectroscopic analyses of SWa-1 samples that were subject to reduction and re-oxidation cycling revealed both reversible and irreversible structural Fe rearrangements that altered the observed apparent standard reduction potential (E(H)(ø)) of structural Fe. E(H)(ø)-values vary by as much as 0.56 V between SWa-1 samples with different redox histories. The wide range of E(H)-values over which SWa-1 is redox-active and redox history-dependent E(H)(ø)-values underscore the importance of Fe-bearing clay minerals as redox-active phases in a wide range of redox regimes.

  3. Nanoporous Mo2C functionalized 3D carbon architecture anode for boosting flavins mediated interfacial bioelectrocatalysis in microbial fuel cells

    Science.gov (United States)

    Zou, Long; Lu, Zhisong; Huang, Yunhong; Long, Zhong-er; Qiao, Yan

    2017-08-01

    An efficient microbial electrocatalysis in microbial fuel cells (MFCs) needs both high loading of microbes (biocatalysts) and robust interfacial electron transfer from microbes to electrode. Herein a nanoporous molybdenum carbide (Mo2C) functionalized carbon felt electrode with rich 3D hierarchical porous architecture is applied as MFC anode to achieve superior electrocatalytic performance. The nanoporous Mo2C functionalized anode exhibits strikingly improved microbial electrocatalysis in MFCs with 5-fold higher power density and long-term stability of electricity production. The great enhancement is attributed to the introduction of rough Mo2C nanostructural interface into macroporous carbon architecture for promoting microbial growth with great excretion of endogenous electron shuttles (flavins) and rich available nanopores for enlarging electrochemically active surface area. Importantly, the nanoporous Mo2C functionalized anode is revealed for the first time to have unique electrocatalytic activity towards redox reaction of flavins with more negative redox potential, indicating a more favourable thermodynamic driving force for anodic electron transfer. This work not only provides a promising electrode for high performance MFCs but also brings up a new insight into the effect of nanostructured materials on interfacial bioelectrocatalysis.

  4. Transistor amplifier as an electrochemical transducer with intuitive optical read-out: Improving its performance with simple electronic solutions

    Czech Academy of Sciences Publication Activity Database

    Lacina, K.; Žák, J.; Sopoušek, J.; Szabó, Z.; Václavek, Tomáš; Žeravík, J.; Fiala, P.; Skládal, P.

    2016-01-01

    Roč. 216, OCT (2016), s. 147-151 ISSN 0013-4686 R&D Projects: GA ČR GA13-09086S; GA ČR(CZ) GBP206/12/G014 Institutional support: RVO:68081715 Keywords : electrochemical transducer transistor * operational amplifier * optical read-out * ( bio )sensing Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.798, year: 2016

  5. Transistor amplifier as an electrochemical transducer with intuitive optical read-out: Improving its performance with simple electronic solutions

    Czech Academy of Sciences Publication Activity Database

    Lacina, K.; Žák, J.; Sopoušek, J.; Szabó, Z.; Václavek, Tomáš; Žeravík, J.; Fiala, P.; Skládal, P.

    2016-01-01

    Roč. 216, OCT (2016), s. 147-151 ISSN 0013-4686 R&D Projects: GA ČR GA13-09086S; GA ČR(CZ) GBP206/12/G014 Institutional support: RVO:68081715 Keywords : electrochemical transducer transistor * operational amplifier * optical read-out * (bio)sensing Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.798, year: 2016

  6. Hybrid graphene and graphitic carbon nitride nanocomposite: gap opening, electron-hole puddle, interfacial charge transfer, and enhanced visible light response.

    Science.gov (United States)

    Du, Aijun; Sanvito, Stefano; Li, Zhen; Wang, Dawei; Jiao, Yan; Liao, Ting; Sun, Qiao; Ng, Yun Hau; Zhu, Zhonghua; Amal, Rose; Smith, Sean C

    2012-03-07

    Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long-range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C(3)N(4)) and electronically active graphene. We find an inhomogeneous planar substrate (g-C(3)N(4)) promotes electron-rich and hole-rich regions, i.e., forming a well-defined electron-hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C(3)N(4) substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C(3)N(4) interface opens a 70 meV gap in g-C(3)N(4)-supported graphene, a feature that can potentially allow overcoming the graphene's band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C(3)N(4) is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C(3)N(4) monolayer, the hybrid graphene/g-C(3)N(4) complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications. © 2012 American Chemical Society

  7. Thin films of amorphous nitrogenated carbon a-CN{sub x}: Electron transfer and surface reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Tamiasso-Martinhon, P.; Cachet, H.; Debiemme-Chouvy, C.; Deslouis, C. [Universite Pierre et Marie Curie-Paris 6, Laboratoire Interfaces et Systemes Electrochimiques, CNRS, UPR15-LISE, 4 Place Jussieu, Paris F-75005 (France)

    2008-08-01

    The electrochemical behaviour of thin films of nitrogenated amorphous carbon a-CN{sub x} is similar to that of boron-doped diamond, with a wide potential window in aqueous media. They are elaborated by cathodic sputtering of a graphite target in an Ar-N{sub 2} active plasma for varying nitrogen contents, determined by XPS (0.06 {<=} x {<=} 0.39). Their electrochemical reactivity is sensitive to the surface state. The present study reports on the influence of electrochemical pre treatment on the electronic transfer rate of a fast redox system ferri-ferrocyanide, by focusing on the direction of the potential excursion. On the other hand, the role of both the pH and the potential on the interfacial capacitance in the presence of Na{sub 2}SO{sub 4} without redox species is documented. The results show up the sensitivity of the film surface to the electrochemical conditions. (author)

  8. Interfacial orientation and misorientation relationships in nanolamellar Cu/Nb composites using transmission-electron-microscope-based orientation and phase mapping

    International Nuclear Information System (INIS)

    Liu, X.; Nuhfer, N.T.; Rollett, A.D.; Sinha, S.; Lee, S.-B.; Carpenter, J.S.; LeDonne, J.E.; Darbal, A.; Barmak, K.

    2014-01-01

    A transmission-electron-microscope-based orientation mapping technique that makes use of beam precession to achieve near-kinematical conditions was used to map the phase and crystal orientations in nanolamellar Cu/Nb composites with average layer thicknesses of 86, 30 and 18 nm. Maps of high quality and reliability were obtained by comparing the recorded diffraction patterns with pre-calculated templates. Particular care was taken in optimizing the dewarping parameters and in calibrating the frames of reference. Layers with thicknesses as low as 4 nm were successfully mapped. Heterophase interface plane and character distributions (HIPD and HICD, respectively) of Cu and Nb phases from the samples were determined from the orientation maps. In addition, local orientation relation stereograms of the Cu/Nb interfaces were calculated, and these revealed the detailed layer-to-layer texture information. The results are in agreement with previously reported neutron-diffraction-based and precession-electron-diffraction-based measurements on an accumulated roll bonding (ARB)-fabricated Cu/Nb sample with an average layer thickness of 30 nm as well as scanning-electron-microscope-based electron backscattered diffraction HIPD/HICD plots of ARB-fabricated Cu/Nb samples with layer thicknesses between 200 and 600 nm

  9. Interfacial solvation thermodynamics

    International Nuclear Information System (INIS)

    Ben-Amotz, Dor

    2016-01-01

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air–water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute–solvent) and indirect (solvent–solvent) contributions to adsorption thermodynamics, of relevance to solvation at air–water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. (paper)

  10. Interfacial electron-transfer equilibria and flat-band potentials of α-Fe2O3 and TiO2 colloids studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Dimitrijevic, N.M.; Savic, D.; Micic, O.I.; Nozik, A.J.

    1984-01-01

    The kinetics and equilibria of electron transfer between methylviologen cation radicals and α-Fe 2 O 3 or TiO 2 colloidal particles were studied with the pulse-radiolysis technique. The rates of electron transfer to both colloids are lower than those predicted for a diffusion-controlled reaction. For higher pHs (TiO 2 , pH > 2; α-Fe 2 O 3 , pH > 9) the established equilibrium MV + in equilibrium MV 2+ + (e - )/sub coll/ is strongly influenced by the MV 2+ concentration and pH. The MV + equilibrium concentration can be exploited to derive the flat-band potential of the semiconductor colloids. The method for determining the flat-band potential of the particles is independent of whether the injected electrons are free or trapped, and whether the electrons raise the bulk Fermi level toward the conduction band or just produce a space charge. The flat-band potentials for both colloids appear to be somewhat more negative (-0.1 to -0.2 V) than the corresponding single-crystal electrodes. Also, the flat-band potentials become slightly more negative with increasing radiation dose (initial MV + concentration). The effect of absorbed radiation dose is explained by the corresponding changes in the ratio of oxidized to reduced forms of the redox couple, which in turn changes the adsorbed ionic charge on the semiconductor surface. For colloidal particles of TiO 2 stabilized by poly(vinyl alcohol) (PVA), the flat-band potentials were almost the same as those for PVA-free TiO 2 sols. The decrease of particle diameter from 800 to 70 A does not affect the value of the flat-band potentials for TiO 2 and α-Fe 2 O 3 colloids. 28 references, 9 figures

  11. Functionalized Graphene–Polyoxometalate Nanodots Assembly as “Organic–Inorganic” Hybrid Supercapacitors and Insights into Electrode/Electrolyte Interfacial Processes

    Directory of Open Access Journals (Sweden)

    Sanju Gupta

    2017-07-01

    Full Text Available The stable high-performance electrochemical electrodes consisting of supercapacitive reduced graphene oxide (rGO nanosheets decorated with pseudocapacitive polyoxometalates (phosphomolybdate acid-H3PMo12O40 (POM and phosphotungstic acid-H3PW12O40 (POW nanodots/nanoclusters are hydrothermally synthesized. The interactions between rGO and POM (and POW components create emergent “organic–inorganic” hybrids with desirable physicochemical properties (specific surface area, mechanical strength, diffusion, facile electron and ion transport enabled by molecularly bridged (covalently and electrostatically tailored interfaces for electrical energy storage. The synergistic hybridization between two electrochemical energy storage mechanisms, electrochemical double-layer from rGO and redox activity (faradaic of nanoscale POM (and POW nanodots, and the superior operating voltage due to high overpotential yielded converge yielding a significantly improved electrochemical performance. They include increase in specific capacitance from 70 F·g−1 for rGO to 350 F·g−1 for hybrid material with aqueous electrolyte (0.4 M sodium sulfate, higher current carrying capacity (>10 A·g−1 and excellent retention (94% resulting higher specific energy and specific power density. We performed scanning electrochemical microscopy to gain insights into physicochemical processes and quantitatively determine associated parameters (diffusion coefficient (D and heterogeneous electron transfer rate (kET at electrode/electrolyte interface besides mapping electrochemical (reactivity and electro-active site distribution. The experimental findings are attributed to: (1 mesoporous network and topologically multiplexed conductive pathways; (2 higher density of graphene edge plane sites; and (3 localized pockets of re-hybridized orbital engineered modulated band structure provided by polyoxometalates anchored chemically on functionalized graphene nanosheets, contribute toward

  12. A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced γ-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, A. K. Nanda, E-mail: aknk27@yahoo.com; Subramanian, B. [ECMS Division, Central Electro Chemical Research Institute, Karaikudi (India); Prasanna, S. [Department of Physics, PSG College of Technology, Coimbatore (India); Jayakumar, S. [Department of Physics, PSG Institute of Technology and Applied Research, Coimbatore (India); Rao, G. Mohan [Department of Instrumentation, Indian Institute of Science, Bangalore (India)

    2015-03-28

    Pure α-Al{sub 2}O{sub 3} exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al{sub 2}O{sub 3} thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling γ-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of ≈0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-γ transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source.

  13. A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced γ-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

    Science.gov (United States)

    Kumar, A. K. Nanda; Prasanna, S.; Subramanian, B.; Jayakumar, S.; Rao, G. Mohan

    2015-03-01

    Pure α-Al2O3 exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al2O3 thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling γ-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of ≈0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-γ transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source.

  14. A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced γ-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

    International Nuclear Information System (INIS)

    Kumar, A. K. Nanda; Subramanian, B.; Prasanna, S.; Jayakumar, S.; Rao, G. Mohan

    2015-01-01

    Pure α-Al 2 O 3 exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al 2 O 3 thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling γ-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of ≈0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-γ transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source

  15. Electron transfer study on graphene modified glassy carbon substrate via electrochemical reduction and the application for tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence sensor fabrication.

    Science.gov (United States)

    Xu, Yuanhong; Cao, Mengmei; Liu, Huihui; Zong, Xidan; Kong, Na; Zhang, Jizhen; Liu, Jingquan

    2015-07-01

    In this study, electron transfer behavior of the graphene nanosheets attachment on glassy carbon electrode (GCE) via direct electrochemical reduction of graphene oxide (GO) is investigated for the first time. The graphene modified electrode was achieved by simply dipping the GCE in GO suspension, followed by cyclic voltammetric scanning in the potential window from 0V to -1.5V. Tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)3(2+)] was immobilized on the graphene modified electrode and used as the redox probe to evaluate the electron transfer behavior. The electron transfer rate constant (Ks) was calculated to be 61.9±5.8s(-1), which is much faster than that of tiled graphene modified GCE (7.1±0.6s(-1)). The enhanced electron transfer property observed with the GCE modified by reductively deposited graphene is probably due to its standing configuration, which is beneficial to the electron transfer comparing with the tiled one. Because the abundant oxygen-containing groups are mainly located at the edges of GO, which should be much easier for the reduction to start from, the reduced GO should tend to stand on the electrode surface as evidenced by scanning electron microscopy analysis. In addition, due to the favored electron transfer and standing configuration, the Ru(bpy)3(2+) electrochemiluminescence sensor fabricated with standing graphene modified GCE provided much higher and more stable efficiency than that fabricated with tiled graphene. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn2O4 Spinel Obtained from Polyol-Mediated Synthesis

    Directory of Open Access Journals (Sweden)

    Shuo Yang

    2018-05-01

    Full Text Available LiNi0.5Mn1.5O4 (LNMO spinel has been extensively investigated as one of the most promising high-voltage cathode candidates for lithium-ion batteries. The electrochemical performance of LNMO, especially its rate performance, seems to be governed by its crystallographic structure, which is strongly influenced by the preparation methods. Conventionally, LNMO materials are prepared via solid-state reactions, which typically lead to microscaled particles with only limited control over the particle size and morphology. In this work, we prepared Ni-doped LiMn2O4 (LMO spinel via the polyol method. The cycling stability and rate capability of the synthesized material are found to be comparable to the ones reported in literature. Furthermore, its electronic charge transport properties were investigated by local electrical transport measurements on individual particles by means of a nanorobotics setup in a scanning electron microscope, as well as by performing DFT calculations. We found that the scarcity of Mn3+ in the LNMO leads to a significant decrease in electronic conductivity as compared to undoped LMO, which had no obvious effect on the rate capability of the two materials. Our results suggest that the rate capability of LNMO and LMO materials is not limited by the electronic conductivity of the fully lithiated materials.

  17. Investigation of 3C-SiC/SiO2 interfacial point defects from ab initio g-tensor calculations and electron paramagnetic resonance measurements

    Science.gov (United States)

    Nugraha, T. A.; Rohrmueller, M.; Gerstmann, U.; Greulich-Weber, S.; Stellhorn, A.; Cantin, J. L.; von Bardeleben, J.; Schmidt, W. G.; Wippermann, S.

    SiC is widely used in high-power, high-frequency electronic devices. Recently, it has also been employed as a building block in nanocomposites used as light absorbers in solar energy conversion devices. Analogous to Si, SiC features SiO2 as native oxide that can be used for passivation and insulating layers. However, a significant number of defect states are reported to form at SiC/SiO2 interfaces, limiting mobility and increasing recombination of free charge carriers. We investigated the growth of oxide on different 3C-SiC surfaces from first principles. Carbon antisite Csi defects are found to be strongly stabilized in particular at the interface, because carbon changes its hybridization from sp3 in the SiC-bulk to sp2 at the interface, creating a dangling bond inside a porous region of the SiO2 passivating layer. Combining ab initio g-tensor calculations and electron paramagnetic resonance (EPR) measurements, we show that Csi defects explain the measured EPR signatures, while the hyperfine structure allows to obtain local structural information of the oxide layer. Financial support from BMBF NanoMatFutur Grant 13N12972 and DFG priority program SPP-1601 is gratefully acknowledged.

  18. Enhancement of photocurrent extraction and electron injection in dual-functional CH3NH3PbBr3 perovskite-based optoelectronic devices via interfacial engineering

    Science.gov (United States)

    Tsai, Chia-Lung; Lu, Yi-Chen; Hsiung Chang, Sheng

    2018-07-01

    Photocurrent extraction and electron injection in CH3NH3PbBr3 (MAPbBr3) perovskite-based optoelectronic devices are both significantly increased by improving the contact at the PCBM/MAPbBr3 interface with an extended solvent annealing (ESA) process. Photoluminescence quenching and x-ray diffraction experiments show that the ESA not only improves the contact at the PCBM/MAPbBr3 interface but also increases the crystallinity of the MAPbBr3 thin films. The optimized dual-functional PCBM-MAPbBr3 heterojunction based optoelectronic device has a high power conversion efficiency of 4.08% and a bright visible luminescence of 1509 cd m‑2. In addition, the modulation speed of the MAPbBr3 based light-emitting diodes is larger than 14 MHz, which indicates that the defect density in the MAPbBr3 thin film can be effectively reduced by using the ESA process.

  19. Interfacial effects in organic semiconductor heterojunctions

    International Nuclear Information System (INIS)

    Stadler, P.

    2011-01-01

    The field of organic electronics has systematically gained interest in recent years, technologically and scientifically advances have been made leading to practical applications such as organic light emitting diodes, organic field-effect transistors and organic photo-voltaic cells. In this thesis a fundamental study on organic molecules is presented targeting on interfacial effects at organic heterojunctions. Generally in organic electronic devices interfaces are considered as key parameters for achieving high performance applications. Therefore in this work the emphasis is to investigate layer-by-layer heterojunctions of organic molecules. Defined heterojunctions at inorganic III-V semiconductors form superlattices and quantum-wells, which lead to interfacial effects summarized as quantum confinement and two-dimensional electron gases. Although organic molecules differ in many aspects from their inorganic counterparts, similar effects can be theoretically expected at organic heterojunctions as well. Organic molecules form van-der-Waals type crystals and domains which are macroscopically anisotropic and polycrystalline or amorphous. Organic molecules are intrinsic semiconductors and at interfaces dipoles are formed, which control the energy level alignment. In order to characterize such structures and compare them to inorganic superlattices and quantum-wells it is necessary to induce charge carriers. In this work this is established either by interfacial doping using high-performance dielectrics in a field-effect transistor structure or by photo-doping by exciting a donor-acceptor bilayer. In both cases C 60 was chosen as organic semiconductor exhibiting good acceptor properties and an electron mobility in the range of 0.5 cm 2 V -1 s -1 . The fabrication of well-defined few-molecular layers allows probing directly at the interface. Spectroscopic methods and transport measurements are applied for characterization: Photoemission spectroscopy, absorption and photo

  20. Oxygen effects on the interfacial electronic structure of titanyl phthalocyanine film: p-Type doping, band bending and Fermi level alignment

    International Nuclear Information System (INIS)

    Nishi, Toshio; Kanai, Kaname; Ouchi, Yukio; Willis, Martin R.; Seki, Kazuhiko

    2006-01-01

    The effect of oxygen doping on titanyl phthalocyanine (TiOPc) film was investigated by ultraviolet photoelectron spectroscopy (UPS). The electronic structure of the interface formed between TiOPc films deposited on highly oriented pyrolytic graphite (HOPG) was clearly different between the films prepared in ultrahigh vacuum (UHV) and under O 2 atmosphere (1.3 x 10 -2 Pa). The film deposited in UHV showed downward band bending characteristic of n-type semiconductor, possibly due to residual impurities working as unintentional n-type dopants. On the other hand, the film deposited under O 2 atmosphere showed upward band bending characteristic of p-type semiconductor. Such trends, including the conversion from n- to p-type, are in excellent correspondence with reported field effect transistor characteristics of TiOPc, and clearly demonstrates that bulk TiOPc film was p-doped with oxygen. In order to examine the Fermi level alignment between TiOPc film and the substrate, the energy of the highest occupied molecular orbital (HOMO) of TiOPc relative to the Fermi level of the conductive substrate was determined for various substrates. The alignment between the Fermi level of conductive substrate and Fermi level of TiOPc film at fixed energy in the bandgap was not observed for the TiOPc film prepared in UHV, possibly because of insufficient charge density in the TiOPc film. This situation was drastically changed when the TiOPc film exposed to O 2 , and clear alignment of the Fermi level fixed at 0.6 eV above the HOMO with the Fermi level of the conducting substrate was observed, probably by p-type doping effect of oxygen. These are the first direct and quantitative information about bulk oxygen doping from the viewpoint of the electronic structure. These results suggest that similar band bending with Fermi level alignment may be also achieved for other organic semiconductors under practical device conditions, and also call for caution at the comparison of experimental

  1. Electrochemical biosensors

    CERN Document Server

    Cosnier, Serge

    2015-01-01

    "This is an excellent book on modern electrochemical biosensors, edited by Professor Cosnier and written by leading international experts. It covers state-of-the-art topics of this important field in a clear and timely manner."-Prof. Joseph Wang, UC San Diego, USA  "This book covers, in 13 well-illustrated chapters, the potential of electrochemical methods intimately combined with a biological component for the assay of various analytes of biological and environmental interest. Particular attention is devoted to the description of electrochemical microtools in close contact with a biological cell for exocytosis monitoring and to the use of nanomaterials in the electrochemical biosensor architecture for signal improvement. Interestingly, one chapter describes the concept and design of self-powered biosensors derived from biofuel cells. Each topic is reviewed by experts very active in the field. This timely book is well suited for providing a good overview of current research trends devoted to electrochemical...

  2. Interfacial Studies of Sized Carbon Fiber

    International Nuclear Information System (INIS)

    Shahrul, S. N.; Hartini, M. N.; Hilmi, E. A.; Nizam, A.

    2010-01-01

    This study was performed to investigate the influence of sizing treatment on carbon fiber in respect of interfacial adhesion in composite materials, Epolam registered 2025. Fortafil unsized carbon fiber was used to performed the experiment. The fiber was commercially surface treated and it was a polyacrylonitrile based carbon fiber with 3000 filament per strand. Epicure registered 3370 was used as basic sizing chemical and dissolved in two types of solvent, ethanol and acetone for the comparison purpose. The single pull out test has been used to determine the influence of sizing on carbon fiber. The morphology of carbon fiber was observed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The apparent interfacial strength IFSS values determined by pull out test for the Epicure registered 3370/ethanol sized carbon fiber pointed to a good interfacial behaviour compared to the Epicure registered 3370/acetone sized carbon fiber. The Epicure registered 3370/ethanol sizing agent was found to be effective in promoting adhesion because of the chemical reactions between the sizing and Epolam registered 2025 during the curing process. From this work, it showed that sized carbon fiber using Epicure registered 3370 with addition of ethanol give higher mechanical properties of carbon fiber in terms of shear strength and also provided a good adhesion between fiber and matrix compared to the sizing chemical that contain acetone as a solvent.

  3. The nanostructure of microbially-reduced graphene oxide fosters thick and highly-performing electrochemically-active biofilms

    Science.gov (United States)

    Virdis, Bernardino; Dennis, Paul G.

    2017-07-01

    Biofilms of electrochemically-active organisms are used in microbial electrochemical technologies (METs) to catalyze bioreactions otherwise not possible at bare electrodes. At present, however, achievable current outputs are still below levels considered sufficient for economic viability of large-scale METs implementations. Here, we report three-dimensional, self-aggregating biofilm composites comprising of microbial cells embedded with microbially-reduced graphene oxide (rGO) nanoparticles to form a thick macro-porous network with superior electrochemical properties. In the presence of metabolic substrate, these hybrid biofilms are capable of producing up to five times more catalytic current than the control biofilms. Cyclic voltammetry, linear sweep voltammetry, and electrochemical impedance spectroscopy, show that in spite of the increased thickness, the biofilms amended with GO display lower polarization/charge transfer resistance compared to the controls, which we ascribe to the incorporation of rGO into the biofilms, which (1) promotes fast electron transfer, yet conserving a macroporous structure that allows free diffusion of reactants and products, and (2) enhances the interfacial dynamics by allowing a higher load of microbial cells per electrode surface area. These results suggest an easy-to-apply and cost-effective method to produce high-performing electrochemically-active biofilms in situ.

  4. Effects of magnesium doping on electronic conductivity and electrochemical properties of LiFePO{sub 4} prepared via hydrothermal route

    Energy Technology Data Exchange (ETDEWEB)

    Ou, Xiuqin; Liang, Guangchuan; Wang, Li; Xu, Shengzhao; Zhao, Xia [Institute of Power Source and Ecomaterials Science, Box 1055, Hebei University of Technology, Tianjin 300130 (China)

    2008-10-01

    Carbon free composites Li{sub 1-x}Mg{sub x}FePO{sub 4} (x=0.00,0.02) were synthesized from LiOH, H{sub 3}PO{sub 4}, FeSO{sub 4} and MgSO{sub 4} through hydrothermal route at 180 C for 6h followed by being fired at 750 C for 6 h. The samples were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), flame atomic absorption spectroscopy and electronic conductivity measurement. To investigate their electrochemical properties, the samples were mixed with glucose as carbon precursors, and fired at 750 C for 6 h. The charge-discharge curves and cycle life test were carried out at 23{+-}2 C. The Rietveid refinement results of lattice parameters of the samples indicate that the magnesium ion has been successfully doped into the M1 (Li) site of the phospho-olivine structure. With the same order of magnitude, there is no material difference in terms of the electronic conductivities between the doped and undoped composites. Conductivities of the doped and undoped samples are 10{sup -10}S cm{sup -1} before being fired, 10{sup -9} S cm{sup -1} after being fired at 750 C, and 10{sup -1}S cm{sup -1} after coated with carbon, respectively. Both the doped and undoped composites coated with carbon exhibit comparable specific capacities of 146 mAh g{sup -1} vs. 144 mAh g{sup -1} at 0.2C, 140 mAh g{sup -1} vs. 138 mAh g{sup -1} at 1C, and 124 mAh g{sup -1} vs. 123 mAh g{sup -1} at 5C, respectively. The capacity retention rates of both doped and undoped samples over 50 cycles at 5C are close to 100% (vs. the first-cycle corresponding C-rate capacity). Magnesium doping has little effects on electronic conductivity and electrochemical properties of LiFePO{sub 4} composites prepared via hydrothermal route. (author)

  5. Interfacial Engineered Polyaniline/Sulfur-doped TiO2 Nanotube Arrays for Ultralong Cycle Lifetime Fiber-Shaped, Solid-State Supercapacitors.

    Science.gov (United States)

    Li, Chun; Wang, Zhuanpei; Li, Shengwen; Cheng, Jianli; Zhang, Yanning; Zhou, Jingwen; Yang, Dan; Tong, Dong-Ge; Wang, Bin

    2018-05-04

    Fiber-shaped supercapacitors (FSCs) have great potential in wearable electronics applications. However, the limited specific surface area and inadequate structural stability caused by the weak interfacial interactions of the electrodes result in relatively low specific capacitance and unsatisfactory cycle lifetime. Herein, solid-state FSCs with high energy density and ultralong cycle lifetime based on polyaniline (PANI)/sulfur-doped TiO2 nanotubes array (PANI/S-TiO2) are fabricated by interfacial engineering. The experimental results and ab initio calculations reveal that S doping can effectively promote the conductivity of titania nanotubes and increase the binding energy of PANI anchored on the electrode surface, leading to much stronger binding of PANI on the surface of the electrode and excellent electrode structure stability. As a result, the FSCs using the PANI/S-TiO2 electrodes deliver a high specific capacitance of 91.9 mF cm-2, a capacitance retention of 93.78% after 12,000 charge/discharge cycles, and an areal energy density of 3.2 µWh cm-2, respectively. Meanwhile, the all-solid-state FSC device retains its excellent flexibility and stable electrochemical capacitance even after bending 150 cycles. The enhanced performances of FSCs could be attributed to the large surface area, short ion diffusion path, high electrical conductivity and engineered interfacial interaction of the rationally designed electrodes.

  6. Interfacial forces in aqueous media

    CERN Document Server

    van Oss, Carel J

    2006-01-01

    Thoroughly revised and reorganized, the second edition of Interfacial Forces in Aqueous Media examines the role of polar interfacial and noncovalent interactions among biological and nonbiological macromolecules as well as biopolymers, particles, surfaces, cells, and both polar and apolar polymers. The book encompasses Lifshitz-van der Waals and electrical double layer interactions, as well as Lewis acid-base interactions between colloidal entities in polar liquids such as water. New in this Edition: Four previously unpublished chapters comprising a new section on interfacial propertie

  7. Interfacial Instabilities in Evaporating Drops

    Science.gov (United States)

    Moffat, Ross; Sefiane, Khellil; Matar, Omar

    2007-11-01

    We study the effect of substrate thermal properties on the evaporation of sessile drops of various liquids. An infra-red imaging technique was used to record the interfacial temperature. This technique illustrates the non-uniformity in interfacial temperature distribution that characterises the evaporation process. Our results also demonstrate that the evaporation of methanol droplets is accompanied by the formation of wave-trains in the interfacial temperature field; similar patterns, however, were not observed in the case of water droplets. More complex patterns are observed for FC-72 refrigerant drops. The effect of substrate thermal conductivity on the structure of the complex pattern formation is also elucidated.

  8. Comparison of Interfacial Electron Transfer Efficiency in [Fe(ctpy)2]2+-TiO2 and [Fe(cCNC)2]2+-TiO2 Assemblies: Importance of Conformational Sampling.

    Science.gov (United States)

    Mukherjee, Sriparna; Liu, Chang; Jakubikova, Elena

    2018-02-22

    Fe(II)-polypyridines have limited applications as chromophores in dye-sensitized solar cells due to the short lifetimes (∼100 fs) of their photoactive metal-to-ligand charge transfer (MLCT) states formed upon photoexcitation. Recently, a 100-fold increase in the MLCT lifetime was observed in a [Fe(CNC) 2 ] 2+ complex (CNC = 2,6-bis(3-methylimidazole-1-ylidine)pyridine) which has strong σ-donating N-heterocyclic carbene ligand in comparison to the weaker field parent [Fe(tpy) 2 ] 2+ complex (tpy = 2,2':6',2″-terpyridine). This study utilizes density functional theory (DFT), time-dependent DFT, and quantum dynamics simulations to investigate the interfacial electron transfer (IET) in [Fe(cCNC) 2 ] 2+ (cCNC = 4'-carboxy-2,6-bis(3-methylimidazole-1-ylidine)pyridine) and [Fe(ctpy) 2 ] 2+ (ctpy = 4'-carboxy-2,2':6',2″-terpyridine) sensitized TiO 2 . Our results suggest that the replacement of tpy by CNC ligand does not significantly speed up the IET kinetics in the [Fe(cCNC) 2 ] 2+ -TiO 2 assembly in comparison to the [Fe(ctpy) 2 ] 2+ -TiO 2 analogue. The high IET efficiency in the [Fe(cCNC) 2 ] 2+ -TiO 2 assemblies is therefore due to longer lifetime of [Fe(cCNC) 2 ] 2+ photoactive 3 MLCT states rather than faster electron injection kinetics. It was also found that the inclusion of conformational sampling in the computational model is important for proper description of the IET processes in these systems, as the models relying on the use of only fully optimized structures may yield misleading results. The simulations presented in this work also illustrate various pitfalls of utilizing properties such as electronic coupling, number of available acceptor states, and driving force, as well as calculations based on Fermi's golden rule framework, to reach conclusions on the IET efficiency in dye-semiconductor systems.

  9. Quantitative Determination on Ionic-Liquid-Gating Control of Interfacial Magnetism.

    Science.gov (United States)

    Zhao, Shishun; Zhou, Ziyao; Peng, Bin; Zhu, Mingmin; Feng, Mengmeng; Yang, Qu; Yan, Yuan; Ren, Wei; Ye, Zuo-Guang; Liu, Yaohua; Liu, Ming

    2017-05-01

    Ionic-liquid gating on a functional thin film with a low voltage has drawn a lot of attention due to rich chemical, electronic, and magnetic phenomena at the interface. Here, a key challenge in quantitative determination of voltage-controlled magnetic anisotropy (VCMA) in Au/[DEME] + [TFSI] - /Co field-effect transistor heterostructures is addressed. The magnetic anisotropy change as response to the gating voltage is precisely detected by in situ electron spin resonance measurements. A reversible change of magnetic anisotropy up to 219 Oe is achieved with a low gating voltage of 1.5 V at room temperature, corresponding to a record high VCMA coefficient of ≈146 Oe V -1 . Two gating effects, the electrostatic doping and electrochemical reaction, are distinguished at various gating voltage regions, as confirmed by X-ray photoelectron spectroscopy and atomic force microscopy experiments. This work shows a unique ionic-liquid-gating system for strong interfacial magnetoelectric coupling with many practical advantages, paving the way toward ion-liquid-gating spintronic/electronic devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Influence of electronic and steric effects on stability constants and electrochemical reversibility of divalent ion complexes with glycine and sarcosine

    International Nuclear Information System (INIS)

    Cukrowski, Ignacy; Marques, Helder M.; Mkwizu, Tumaini S.; Magampa, Philemon P.; Serge, Claudette

    2007-01-01

    Cd II complexes with glycine (gly) and sarcosine (sar) were studied by glass electrode potentiometry, direct current polarography, virtual potentiometry, and molecular modelling. The electrochemically reversible Cd II -glycine-OH labile system was best described by a model consisting of M(HL), ML, ML 2 , ML 3 , ML(OH) and ML 2 (OH) (M = Cd II , L = gly) with the overall stability constants, as log β, determined to be 10.30 ± 0.05, 4.21 ± 0.03, 7.30 ± 0.05, 9.84 ± 0.04, 8.9 ± 0.1, and 10.75 ± 0.10, respectively. In case of the electrochemically quasi-reversible Cd II -sarcosine-OH labile system, only ML, ML 2 and ML 3 (M = Cd II , L = sar) were found and their stability constants, as log β, were determined to be 3.80 ± 0.03, 6.91 ± 0.07, and 8.9 ± 0.4, respectively. Stability constants for the ML complexes, the prime focus of this work, were thus established with an uncertainty smaller than 0.05 log units. The observed departure from electrochemical reversibility for the Cd-sarcosine-OH system was attributed mainly to the decrease in the transfer coefficient α. The MM2 force field, supplemented by additional parameters, reproduced the reported crystal structures of diaqua-bis(glycinato-O,N)nickel(II) and fac-tri(glycinato)-nickelate(II) very well. These parameters were used to predict structures of all possible isomers of (i) [Ni(H 2 O) 4 (gly)] + and [Ni(H 2 O) 4 (sar)] + ; and (ii) [Ni(H 2 O) 3 (IDA)] and [Ni(H 2 O) 3 (MIDA)] (IDA = iminodiacetic acid, MIDA = N-methyl iminodiacetic acid) by molecular mechanics/simulated annealing methods. The change in strain energy, ΔU str , that accompanies the substitution of one ligand by another (ML + L' → ML' + L), was computed and a strain energy ΔU str = +0.28 kcal mol -1 for the reaction [Ni(H 2 O) 4 (gly)] + + sar → [Ni(H 2 O) 4 (sar)] + + gly was found. This predicts the monoglycine complex to be marginally more stable. By contrast, for the reaction [Ni(H 2 O) 3 IDA] + MIDA → [Ni(H 2 O) 3 MIDA] + IDA

  11. Interfacial morphologies and growth modes of F.C.C. metallic crystals from liquid alloys

    International Nuclear Information System (INIS)

    Camel, Denis

    1980-01-01

    Equilibrium and growth morphologies of f.c.c. metallic crystals in contact with liquid alloys have been observed in-situ using transmission electron microscopy. These morphologies have been discussed in terms of atomic interfacial structure and growth mechanisms with the help of a statistical thermodynamic model which takes into account the effects of chemical interactions and interfacial adsorption. (author) [fr

  12. The concept of floating electrode for contact-less electrochemical measurements: Application to reinforcing steel-bar corrosion in concrete

    International Nuclear Information System (INIS)

    Keddam, M.; Novoa, X.R.; Vivier, V.

    2009-01-01

    The concept of floating electrode is introduced for defining the common electrochemical behaviour of any non-connected, electronically conducting, body immersed in an electrolytic medium. The emphasis is put on both its own polarisation features and its influence on the d.c. and a.c. current and potential across the cell, hence the feasibility, among others, of contact-less electrochemical measurements on floating electrodes. Application to reinforcing steel bars in concrete is investigated by numerical computation of the a.c. current and potential fields in a broad range of concrete resistivity, interfacial resistance and capacitance. Impedance defined in a 4-electrode configuration, when rationalised against the concrete resistivity, is shown to provide, within a realistic range of parameters, a practical mean to access the properties of the bar-concrete interface.

  13. Interfacial Mechanism in Lithium-Sulfur Batteries: How Salts Mediate the Structure Evolution and Dynamics.

    Science.gov (United States)

    Lang, Shuang-Yan; Xiao, Rui-Juan; Gu, Lin; Guo, Yu-Guo; Wen, Rui; Wan, Li-Jun

    2018-06-08

    Lithium-sulfur batteries possess favorable potential for energy-storage applications due to their high specific capacity and the low cost of sulfur. Intensive understanding of the interfacial mechanism, especially the polysulfide formation and transformation under complex electrochemical environment, is crucial for the build-up of advanced batteries. Here we report the direct visualization of interfacial evolution and dynamic transformation of the sulfides mediated by the lithium salts via real-time atomic force microscopy monitoring inside a working battery. The observations indicate that the lithium salts influence the structures and processes of sulfide deposition/decomposition during discharge/charge. Moreover, the distinct ion interaction and diffusion in electrolytes manipulate the interfacial reactions determining the kinetics of the sulfide transformation. Our findings provide deep insights into surface dynamics of lithium-sulfur reactions revealing the salt-mediated mechanisms at nanoscale, which contribute to the profound understanding of the interfacial processes for the optimized design of lithium-sulfur batteries.

  14. Tunable electronic and magnetism of SrTiO{sub 3}/BiFeO{sub 3} (001) superlattice: For electrochemical applications

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Qiang; Sopiha, Kostiantyn; Sobhan, Mushtaq; Anariba, Franklin; Wu, Ping, E-mail: wuping@sutd.edu.sg [Entropic Interface Group (EIG), Engineering Product Development, Singapore University of Technology and Design (SUTD), 8 Somapah Road, Singapore 487372 (Singapore); Ong, Khuong Phuong; Zheng, Jian Wei [Institute of High Performance Computing (IHPC), Agency for Science, Technology and Research - A*Star, 1 Fusionopolis Way, #16-16 Connexis, Singapore 138632 (Singapore)

    2016-01-04

    Practical strategy in tuning the conductivity and magnetism of SrTiO{sub 3}/BiFeO{sub 3} (STO/BFO) (001) superlattice is investigated using the first-principles method based on density functional theory. Our calculated results show that both the conductivity and magnetism of this superlattice can be tuned via a control of its interface terminations. The STO layers maintain semiconducting, while the BFO layers demonstrate metallic character. Therefore, the conductivity of STO/BFO is controlled by the BFO layers. Furthermore, a magnetic STO/BFO (001) superlattice can be found in n-type TiO{sub 2}/BiO interface but with heavy electron carriers. The thickness of BFO does not change the electronic structure and character of STO/BFO (001) superlattice. This study provides a fundamental understanding of the chemically turned conductivity and magnetism of BFO thin films, which may further advance electrochemical applications like magnetic-field aided chemical gas sensing, solar cells, and photo-catalytic chemical reactions.

  15. Electrochemical Processes

    DEFF Research Database (Denmark)

    Bech-Nielsen, Gregers

    1997-01-01

    The notes describe in detail primary and secondary galvanic cells, fuel cells, electrochemical synthesis and electroplating processes, corrosion: measurments, inhibitors, cathodic and anodic protection, details of metal dissolution reactions, Pourbaix diagrams and purification of waste water from...

  16. Electrochemical analysis

    International Nuclear Information System (INIS)

    Hwang, Hun

    2007-02-01

    This book explains potentiometry, voltametry, amperometry and basic conception of conductometry with eleven chapters. It gives the specific descriptions on electrochemical cell and its mode, basic conception of electrochemical analysis on oxidation-reduction reaction, standard electrode potential, formal potential, faradaic current and faradaic process, mass transfer and overvoltage, potentiometry and indirect potentiometry, polarography with TAST, normal pulse and deferential pulse, voltammetry, conductometry and conductometric titration.

  17. High sulfur content polymer nanoparticles obtained from interfacial polymerization of sodium polysulfide and 1,2,3-trichloropropane in water.

    Science.gov (United States)

    Lim, Jeewoo; Jung, Unho; Joe, Won Tae; Kim, Eui Tae; Pyun, Jeffrey; Char, Kookheon

    2015-06-01

    Sulfur-rich materials have recently attracted keen interest for their potentials in optical, electrochemical, and pesticidal applications as well as their utility in dynamic covalent bond chemistry. Many sulfur-rich polymers, however, are insoluble and processing methods are therefore very limited. The synthesis and characterization of water-dispersible polymer nanoparticles (NPs) with the sulfur content exceeding 75% by weight, obtained from the interfacial polymerization between 1,2,3-trichloropropane and sodium polysulfide in water is reported here. The interfacial polymerization yields well-defined sulfur-rich NPs in the presence of surfactants, which are capable of serving a dual role as a phase transfer catalyst on top of emulsifiers. Such dual role allows for the control of the product NP size by varying its concentration. The surfactants can be easily removed by centrifugation and redispersion in water is also reported here. The resulting sulfur-rich NPs are characterized through elemental analysis, dynamic light scattering, ζ-potential measurements, and scanning electron microscopy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Electrochemical DNA biosensor based on the BDD nanograss array electrode.

    Science.gov (United States)

    Jin, Huali; Wei, Min; Wang, Jinshui

    2013-04-10

    The development of DNA biosensor has attracted considerable attention due to their potential applications, including gene analysis, clinical diagnostics, forensic study and more medical applications. Using electroactive daunomycin as an indicator, the hybridization detection was measured by differential pulse voltammetry in this study. Electrochemical DNA biosensor was developed based on the BDD film electrode (fBDD) and BDD nanograss array electrode (nBDD). In comparison with fBDD and AuNPs/CA/fBDD electrode, the lower semicircle diameter of electrochemical impedance spectroscopy obtained on nBDD and AuNPs/CA/nBDD electrode indicated that the presence of nanograss array improved the reactive site, reduced the interfacial resistance, and made the electron transfer easier. Using electroactive daunomycin as an indicator, the hybridization detection was measured by differential pulse voltammetry. The experimental results demonstrated that the prepared AuNPs/CA/nBDD electrode was suitable for DNA hybridization with favorable performance of faster response, higher sensitivity, lower detection limit and satisfactory selectivity, reproducibility and stability.

  19. Electrochemical One-Electron Oxidation of Low-Generation Polyamidoamine-Type Dendrimers with a 1,4-Phenylenediamine Core

    DEFF Research Database (Denmark)

    Hammerich, Ole; Hansen, Thomas; Thorvildsen, Asbjørn

    2009-01-01

    voltammetry (DPV) in methanol, acetonitrile, dichloromethane, and dimethyl sulfoxide. The dendrimers are more difficult to oxidize than N,N,N',N'-tetramethyl-p-phenylenediamine (TMePD). The oxidation potentials decrease with increasing dendrimer generation up to G0.5, after which the potential is essentially......A series of polyamidoamine (PAMAM)-type dendrimers with a 1,4-phenylenediamine (PD) core is prepared from PD by procedures including Michael addition of methyl acrylate followed by aminolysis with 1,2-ethanediamine. Their one-electron oxidation potentials are determined by differential pulse......,N,N',N'-tetra-n-alkyl-p-phenylenediamines, including a planar arrangement of the atoms linked to the two PD nitrogen atoms. Thus, the effect of chain size on the oxidation potential appears to be caused primarily by a simple electronic effect. The calculations indicate considerable reorientation of the dendrimer side chains on oxidation, presumably...

  20. On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase

    Czech Academy of Sciences Publication Activity Database

    Shleev, S.; Andoralov, V.; Falk, M.; Reimann, C. T.; Ruzgas, T.; Srnec, Martin; Ryde, U.; Rulíšek, Lubomír

    2012-01-01

    Roč. 24, č. 7 (2012), s. 1524-1540 ISSN 1040-0397 Grant - others:7th Framework Program(XE) NMP4-SL-2009-229255 Institutional research plan: CEZ:AV0Z40550506 Keywords : bilirubin oxidase * intramolecular electron transfer * rate-limiting catalytic step * reorganization energy * QM/MM calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.817, year: 2012

  1. Impact of air exposure and surface chemistry on Li-Li7La3Zr2O12 interfacial resistance

    Energy Technology Data Exchange (ETDEWEB)

    Sharafi, Asma [Univ. of Michigan, Ann Arbor, MI (United States); Yu, Seungho [Univ. of Michigan, Ann Arbor, MI (United States); Naguib, Michael [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lee, Marcus [Univ. of Michigan, Ann Arbor, MI (United States); Ma, Cheng [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Meyer, Harry M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Nanda, Jagjit [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Chi, Maiofang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Siegel, Donald J. [Univ. of Michigan, Ann Arbor, MI (United States); Sakamoto, Jeff [Univ. of Michigan, Ann Arbor, MI (United States)

    2017-06-15

    Li7La3Zr2O12 (LLZO) is a promising solid-state electrolyte that could enable solid-state-batteries (SSB) employing metallic Li anodes. For a SSB to be viable, the stability and charge transfer kinetics at the Li–LLZO interface should foster facile plating and stripping of Li. Contrary to these goals, recent studies have reported high Li–LLZO interfacial resistance which was attributed to a contamination layer that forms upon exposure of LLZO to air. This study clarifies the mechanisms and consequences associated with air exposure of LLZO; additionally, strategies to minimize these effects are described. First-principles calculations reveal that LLZO readily reacts with humid air; the most favorable reaction pathway involves protonation of LLZO and formation of Li2CO3. X-ray photoelectron spectroscopy, scanning electron microscopy, Raman spectroscopy, and transmission electron microscopy were used to characterize the surface and subsurface chemistry of LLZO as a function of relative humidity and exposure time. Additionally, electrochemical impedance spectroscopy was used to measure the Li–LLZO interfacial resistance as a function of surface contamination. These data indicate that air exposure-induced contamination impacts the interfacial resistance significantly, when exposure time exceeds 24 h. The results of this study provide valuable insight into the sensitivity of LLZO to air and how the effects of air contamination can be reversed.

  2. Defining the origins of electron transfer at screen-printed graphene-like and graphite electrodes: MoO2 nanowire fabrication on edge plane sites reveals electrochemical insights.

    Science.gov (United States)

    Rowley-Neale, Samuel J; Brownson, Dale A C; Banks, Craig E

    2016-08-18

    Molybdenum (di)oxide (MoO2) nanowires are fabricated onto graphene-like and graphite screen-printed electrodes (SPEs) for the first time, revealing crucial insights into the electrochemical properties of carbon/graphitic based materials. Distinctive patterns observed in the electrochemical process of nanowire decoration show that electron transfer occurs predominantly on edge plane sites when utilising SPEs fabricated/comprised of graphitic materials. Nanowire fabrication along the edge plane sites (and on edge plane like-sites/defects) of graphene/graphite is confirmed with Cyclic Voltammetry, Scanning Electron Microscopy (SEM) and Raman Spectroscopy. Comparison of the heterogeneous electron transfer (HET) rate constants (k°) at unmodified and nanowire coated SPEs show a reduction in the electrochemical reactivity of SPEs when the edge plane sites are effectively blocked/coated with MoO2. Throughout the process, the basal plane sites of the graphene/graphite electrodes remain relatively uncovered; except when the available edge plane sites have been utilised, in which case MoO2 deposition grows from the edge sites covering the entire surface of the electrode. This work clearly illustrates the distinct electron transfer properties of edge and basal plane sites on graphitic materials, indicating favourable electrochemical reactivity at the edge planes in contrast to limited reactivity at the basal plane sites. In addition to providing fundamental insights into the electron transfer properties of graphite and graphene-like SPEs, the reported simple, scalable, and cost effective formation of unique and intriguing MoO2 nanowires realised herein is of significant interest for use in both academic and commercial applications.

  3. Dynamic modeling of interfacial structures via interfacial area transport equation

    International Nuclear Information System (INIS)

    Seungjin, Kim; Mamoru, Ishii

    2004-01-01

    Full text of publication follows:In the current thermal-hydraulic system analysis codes using the two-fluid model, the empirical correlations that are based on the two-phase flow regimes and regime transition criteria are being employed as closure relations for the interfacial transfer terms. Due to its inherent shortcomings, however, such static correlations are inaccurate and present serious problems in the numerical analysis. In view of this, a new dynamic approach employing the interfacial area transport equation has been studied. The interfacial area transport equation dynamically models the two-phase flow regime transitions and predicts continuous change of the interfacial area concentration along the flow field. Hence, when employed in the thermal-hydraulic system analysis codes, it eliminates artificial bifurcations stemming from the use of the static flow regime transition criteria. Therefore, the interfacial area transport equation can make a leapfrog improvement in the current capability of the two-fluid model from both scientific and practical point of view. Accounting for the substantial differences in the transport phenomena of various sizes of bubbles, the two-group interfacial area transport equations have been developed. The group 1 equation describes the transport of small-dispersed bubbles that are either distorted or spherical in shapes, and the group 2 equation describes the transport of large cap, slug or churn-turbulent bubbles. The source and sink terms in the right hand-side of the transport equations have been established by mechanistically modeling the creation and destruction of bubbles due to major bubble interaction mechanisms. The coalescence mechanisms include the random collision driven by turbulence, and the entrainment of trailing bubbles in the wake region of the preceding bubble. The disintegration mechanisms include the break-up by turbulence impact, shearing-off at the rim of large cap bubbles and the break-up of large cap

  4. Electrochemical studies of a reconstituted photosynthetic electron-transfer chain or towards a biomimetic photoproduction of hydrogen

    International Nuclear Information System (INIS)

    Fourmond, V.

    2007-04-01

    The aim of this work is to find an efficient process to convert solar energy into hydrogen. The electrons transfers in reconstituted photosynthetic chains have been particularly studied with the aims 1)in one hand, to better understand the interactions of the different molecules of the photosynthetic chain in order to optimize the changes of the entire organisms for hydrogen production 2)in another hand, to insert the hydrogenases in a photosynthetic chain and then to photo reduce them in order to obtain kinetic data to better understand how it works. (O.M.)

  5. Fractional surface termination of diamond by electrochemical oxidation.

    Science.gov (United States)

    Hoffmann, René; Obloh, Harald; Tokuda, Norio; Yang, Nianjun; Nebel, Christoph E

    2012-01-10

    The crystalline form of sp(3)-hybridized carbon, diamond, offers various electrolyte-stable surface terminations. The H-termination-selective attachment of nitrophenyl diazonium, imaged by AFM, shows that electrochemical oxidation can control the fractional hydrogen/oxygen surface termination of diamond on the nanometer scale. This is of particular interest for all applications relying on interfacial electrochemistry, especially for biointerfaces.

  6. Interfacial trap states in junctions of molecular semiconductors

    International Nuclear Information System (INIS)

    Schlettwein, D.; Oekermann, T.; Jaeger, N.; Armstrong, N.R.; Woehrle, D.

    2002-01-01

    Interfacial states that were established in contacts of molecular semiconductors with aqueous electrolytes or in contacts with another organic semiconductor as a solid film were analyzed by photoelectrochemical experiments and by photoelectron spectroscopy. A crucial role of such states was indicated in the interfacial charge transfer and recombination kinetics of light-induced charge carriers and also in the energetic alignment in the solid contacts. Unsubstituted zinc-phthalocyanine (PcZn) served as model compound. The role of chemical interactions in the establishment of these interfacial states was investigated by use of different reaction partners, i.e., different redox couples in the electrolyte contacts and molecular semiconductors of different ionization potential in the solid contacts. Implications of these results for the use of organic semiconductor thin films in devices of molecular electronics and of dye molecules in dye-sensitized solar cells were also discussed

  7. Electrochemical studies of biocatalytic anode of sulfonated graphene/ferritin/glucose oxidase layer-by-layer biocomposite films for mediated electron transfer.

    Science.gov (United States)

    Inamuddin; Haque, Sufia Ul; Naushad, Mu

    2016-06-01

    In this study, a bioanode was developed by using layer-by-layer (LBL) assembly of sulfonated graphene (SG)/ferritin (Frt)/glucose oxidase (GOx). The SG/Frt biocomposite was used as an electron transfer elevator and mediator, respectively. Glucose oxidase (GOx) from Aspergillus niger was applied as a glucose oxidation biocatalyst. The electrocatalytic oxidation of glucose using GOx modified electrode increases with an increase in the concentration of glucose in the range of 10-50mM. The electrochemical measurements of the electrode was carried out by using cyclic voltammetry (CV) at different scan rates (20-100mVs(-1)) in 30mM of glucose solution prepared in 0.3M potassium ferrocyanide (K4Fe(CN)6) and linear sweep voltammetry (LSV). A saturation current density of 50±2mAcm(-2) at a scan rate of 100mVs(-1) for the oxidation of 30Mm glucose is achieved. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. Scaling of interfacial jump conditions

    International Nuclear Information System (INIS)

    Quezada G, S.; Vazquez R, A.; Espinosa P, G.

    2015-09-01

    To model the behavior of a nuclear reactor accurately is needed to have balance models that take into account the different phenomena occurring in the reactor. These balances have to be coupled together through boundary conditions. The boundary conditions have been studied and different treatments have been given to the interface. In this paper is a brief description of some of the interfacial jump conditions that have been proposed in recent years. Also, the scaling of an interfacial jump condition is proposed, for coupling the different materials that are in contact within a nuclear reactor. (Author)

  9. Dynamic modeling of interfacial structures via interfacial area transport equation

    International Nuclear Information System (INIS)

    Seungjin, Kim; Mamoru, Ishii

    2005-01-01

    The interfacial area transport equation dynamically models the two-phase flow regime transitions and predicts continuous change of the interfacial area concentration along the flow field. Hence, when employed in the numerical thermal-hydraulic system analysis codes, it eliminates artificial bifurcations stemming from the use of the static flow regime transition criteria. Accounting for the substantial differences in the transport phenomena of various sizes of bubbles, the two-group interfacial area transport equations have been developed. The group 1 equation describes the transport of small-dispersed bubbles that are either distorted or spherical in shapes, and the group 2 equation describes the transport of large cap, slug or churn-turbulent bubbles. The source and sink terms in the right-hand-side of the transport equations have been established by mechanistically modeling the creation and destruction of bubbles due to major bubble interaction mechanisms. In the present paper, the interfacial area transport equations currently available are reviewed to address the feasibility and reliability of the model along with extensive experimental results. These include the data from adiabatic upward air-water two-phase flow in round tubes of various sizes, from a rectangular duct, and from adiabatic co-current downward air-water two-phase flow in round pipes of two sizes. (authors)

  10. The Development of Non-Enzymatic Glucose Biosensors Based on Electrochemically Prepared Polypyrrole–Chitosan–Titanium Dioxide Nanocomposite Films

    Directory of Open Access Journals (Sweden)

    Ali M. A. Abdul Amir AL-Mokaram

    2017-05-01

    Full Text Available The performance of a modified electrode of nanocomposite films consisting of polypyrrole–chitosan–titanium dioxide (Ppy-CS-TiO2 has been explored for the developing a non-enzymatic glucose biosensors. The synergy effect of TiO2 nanoparticles (NPs and conducting polymer on the current responses of the electrode resulted in greater sensitivity. The incorporation of TiO2 NPs in the nanocomposite films was confirmed by X-ray photoelectron spectroscopy (XPS spectra. FE-SEM and HR-TEM provided more evidence for the presence of TiO2 in the Ppy-CS structure. Glucose biosensing properties were determined by amperommetry and cyclic voltammetry (CV. The interfacial properties of nanocomposite electrodes were studied by electrochemical impedance spectroscopy (EIS. The developed biosensors showed good sensitivity over a linear range of 1–14 mM with a detection limit of 614 μM for glucose. The modified electrode with Ppy-CS nanocomposite also exhibited good selectivity and long-term stability with no interference effect. The Ppy-CS-TiO2 nanocomposites films presented high electron transfer kinetics. This work shows the role of nanomaterials in electrochemical biosensors and describes the process of their homogeneous distribution in composite films by a one-step electrochemical process, where all components are taken in a single solution in the electrochemical cell.

  11. Electrochemical capacitor

    Science.gov (United States)

    Anderson, Marc A.; Liu, Kuo -Chuan; Mohr, Charles M.

    1999-10-05

    An inexpensive porous metal oxide material having high surface area, good conductivity and high specific capacitance is advantageously used in an electrochemical capacitor. The materials are formed in a sol-gel process which affords control over the properties of the resultant metal oxide materials.

  12. Electrochemical construction

    Science.gov (United States)

    Einstein, Harry; Grimes, Patrick G.

    1983-08-23

    An electrochemical cell construction features a novel co-extruded plastic electrode in an interleaved construction with a novel integral separator-spacer. Also featured is a leak and impact resistant construction for preventing the spill of corrosive materials in the event of rupture.

  13. Electrochemical device

    Science.gov (United States)

    Grimes, Patrick G.; Einstein, Harry; Bellows, Richard J.

    1988-01-12

    A tunnel protected electrochemical device features channels fluidically communicating between manifold, tunnels and cells. The channels are designed to provide the most efficient use of auxiliary power. The channels have a greater hydraulic pressure drop and electrical resistance than the manifold. This will provide a design with the optimum auxiliary energy requirements.

  14. Electrochemical Cell

    DEFF Research Database (Denmark)

    1999-01-01

    The invention relates to a rechargeable electrochemical cell comprising a negative electrode, an electrolyte and a positive electrode in which the positive electrode structure comprises a lithium cobalt manganese oxide of the composition Li¿2?Co¿y?Mn¿2-y?O¿4? where 0 ... for capacity losses in lithium ion cells and lithium-alloy cells....

  15. Interfacial Reaction Dependent Performance of Hollow Carbon Nanosphere – Sulfur Composite as a Cathode for Li-S Battery

    International Nuclear Information System (INIS)

    Zheng, Jianming; Yan, Pengfei; Gu, Meng; Wagner, Michael J.; Hays, Kevin A.; Chen, Junzheng; Li, Xiaohong; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2015-01-01

    Lithium-sulfur (Li-S) battery is a promising energy storage system due to its high energy density, cost effectiveness, and environmental friendliness of sulfur. However, there are still a number of technical challenges, such as low Coulombic efficiency and poor long-term cycle life, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species, which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS) with highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li 2 S 2 /Li 2 S), which limits the reversibility of the interfacial reactions and results in poor electrochemical performances. These findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.

  16. Interfacial Reaction Dependent Performance of Hollow Carbon Nanosphere – Sulfur Composite as a Cathode for Li-S Battery

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jianming; Yan, Pengfei; Gu, Meng [Pacific Northwest National Laboratory, Richland, WA (United States); Wagner, Michael J.; Hays, Kevin A. [The George Washington University, Washington, DC (United States); Chen, Junzheng; Li, Xiaohong; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie, E-mail: jie.xiao@pnnl.gov [Pacific Northwest National Laboratory, Richland, WA (United States)

    2015-05-26

    Lithium-sulfur (Li-S) battery is a promising energy storage system due to its high energy density, cost effectiveness, and environmental friendliness of sulfur. However, there are still a number of technical challenges, such as low Coulombic efficiency and poor long-term cycle life, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species, which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS) with highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li{sub 2}S{sub 2}/Li{sub 2}S), which limits the reversibility of the interfacial reactions and results in poor electrochemical performances. These findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.

  17. Interfacial and Surface Science | Materials Science | NREL

    Science.gov (United States)

    Science group within the Material Science Center. He oversees research studies of surfaces and interfaces Interfacial and Surface Science Interfacial and Surface Science Image of irregular-outlined, light address a broad range of fundamental and applied issues in surface and interfacial science that are

  18. Interfacial behaviour of biopolymer multilayers

    NARCIS (Netherlands)

    Corstens, Meinou N.; Osorio Caltenco, Lilia A.; Vries, de Renko; Schroën, Karin; Berton-Carabin, Claire C.

    2017-01-01

    Although multilayered emulsions have been related to reduced lipolysis, the involved interfacial phenomena have never been studied directly. In this work, we systematically built multilayers of whey protein and pectin, which we further subjected to digestive conditions, using two different

  19. Interfacial passivation of CdS layer to CdSe quantum dots-sensitized electrodeposited ZnO nanowire thin films

    International Nuclear Information System (INIS)

    Zhang, Jingbo; Sun, Chuanzhen; Bai, Shouli; Luo, Ruixian; Chen, Aifan; Sun, Lina; Lin, Yuan

    2013-01-01

    ZnO porous thin films with nanowire structure were deposited by the one-step electrochemical deposition method. And a CdS layer was coated on the as-deposited ZnO nanowire thin films by successive ionic layer adsorption and reaction (SILAR) method to passivate surface states. Then the films were further sensitized by CdSe quantum dots (QDs) to serve as a photoanode for fabricating quantum dots-sensitized solar cells (QDSSCs). The effect of the CdS interfacial passivation layer on the performance of the QDSSCs was systematically investigated by varying the SILAR cycle number and heating the passivation layer. The amorphous CdS layer with an optimized thickness can effectively suppress the recombination of the injected electrons with holes on QDs and the redox electrolyte. The newly formed CdS layer on the surface of the ZnO nanowire thin film obviously prolongs the electron lifetime in the passivated ZnO nanoporous thin film because of the lower surface trap density in the ZnO nanowires after CdS deposition, which is favorable to the higher short-circuit photocurrent density (J sc ). For the CdSe QDs-sensitized ZnO nanoporous thin film with the interfacial passivation layer, the J sc and conversion efficiency can reach a maximum of 8.36 mA cm −2 and 2.36%, respectively. The conversion efficiency was improved by 83.47% compared with that of the cell based on the CdSe QDs-sensitized ZnO nanoporous thin film without CdS interfacial passivation (0.39%)

  20. Li-Doped Ionic Liquid Electrolytes: From Bulk Phase to Interfacial Behavior

    Science.gov (United States)

    Haskins, Justin B.; Lawson, John W.

    2016-01-01

    Ionic liquids have been proposed as candidate electrolytes for high-energy density, rechargeable batteries. We present an extensive computational analysis supported by experimental comparisons of the bulk and interfacial properties of a representative set of these electrolytes as a function of Li-salt doping. We begin by investigating the bulk electrolyte using quantum chemistry and ab initio molecular dynamics to elucidate the solvation structure of Li(+). MD simulations using the polarizable force field of Borodin and coworkers were then performed, from which we obtain an array of thermodynamic and transport properties. Excellent agreement is found with experiments for diffusion, ionic conductivity, and viscosity. Combining MD simulations with electronic structure computations, we computed the electrochemical window of the electrolytes across a range of Li(+)-doping levels and comment on the role of the liquid environment. Finally, we performed a suite of simulations of these Li-doped electrolytes at ideal electrified interfaces to evaluate the differential capacitance and the equilibrium Li(+) distribution in the double layer. The magnitude of differential capacitance is in good agreement with our experiments and exhibits the characteristic camel-shaped profile. In addition, the simulations reveal Li(+) to be highly localized to the second molecular layer of the double layer, which is supported by additional computations that find this layer to be a free energy minimum with respect to Li(+) translation.

  1. The study of optimal conditions of electrochemical etching of tunnel electron microscopy tungsten tips; Estudio de las condiciones optimas para la preparacion electroquimica de puntas de tungsteno para el Microscopio de Efecto Tunel

    Energy Technology Data Exchange (ETDEWEB)

    Anguiano, E; Aguilar, M [Instituto de Ciencia de Materiales del SCIC, Madrid (Spain); Olivar, A I [Centro de Investigacion y de Estudios Avanzados del IPN Unidad Merida. Departamento de fisica Aplicada, Yucatan, Mexico (Mexico)

    1997-12-31

    We present the experimental results obtained during the study made in the electrochemical etching of tunneling electron microscopy tungsten tips. The experiments was made using DC and two usual electrolytes: KOH and NaOH. For the tip preparation we used a electrochemical cell with stainless steel cathode and the tungsten wire as anode. the electrodes was introduced in a glass recipient containing the electrolytic solution. We study the effects of applied voltage, polish time, tip length and electrolyte concentration as process relevant parameters. The best condition for tip preparation was obtained with a metallurgical microscope and with a SEM.EDX and Auger analysis was made. The results shown the better tips was made with KOH as electrolyte with a limited concentration range (2-4 normal) and applied voltage (2-6 volts) (Author) 20 refs.

  2. Effect of surface modifications and environment on the interfacial adhesion of polymer/aluminum alloy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, X.F. [Xi' an High-technology Institute, Xi' an 710025 (China)], E-mail: xiaofang_liu@263.net; Wu, Q.Y.; Wang, H.G. [Xi' an High-technology Institute, Xi' an 710025 (China)

    2008-06-15

    This work investigates the influence of surface modifications and environmental conditions on the interfacial adhesion of epoxy resin films on a 6016 aluminum alloy, as measured by peeling experiments. The alloy surfaces were pretreated with an etching solution, and then modified, respectively, with aminopropyl silane solution, aminopropyl phosphonate solution, and hexamethyldisiloxane plasma. The modified surfaces were examined by scanning electron microscopy and their roughness was quantified by a fractal index. The peeling experiments show that the interfacial adhesion of epoxy on the aluminum alloy mainly results from the chemical and mechanical characteristics of the material surface. Environmental factors such as humidity can also weaken interfacial adhesion.

  3. Effect of surface modifications and environment on the interfacial adhesion of polymer/aluminum alloy

    International Nuclear Information System (INIS)

    Liu, X.F.; Wu, Q.Y.; Wang, H.G.

    2008-01-01

    This work investigates the influence of surface modifications and environmental conditions on the interfacial adhesion of epoxy resin films on a 6016 aluminum alloy, as measured by peeling experiments. The alloy surfaces were pretreated with an etching solution, and then modified, respectively, with aminopropyl silane solution, aminopropyl phosphonate solution, and hexamethyldisiloxane plasma. The modified surfaces were examined by scanning electron microscopy and their roughness was quantified by a fractal index. The peeling experiments show that the interfacial adhesion of epoxy on the aluminum alloy mainly results from the chemical and mechanical characteristics of the material surface. Environmental factors such as humidity can also weaken interfacial adhesion

  4. Interfacial structure of V2AlC thin films deposited on (112-bar 0)-sapphire

    International Nuclear Information System (INIS)

    Sigumonrong, Darwin P.; Zhang, Jie; Zhou, Yanchun; Music, Denis; Emmerlich, Jens; Mayer, Joachim; Schneider, Jochen M.

    2011-01-01

    Local epitaxy between V 2 AlC and sapphire without intentionally or spontaneously formed seed layers was observed by transmission electron microscopy. Our ab initio calculations suggest that the most stable interfacial structure is characterized by the stacking sequence ...C-V-Al-V//O-Al..., exhibiting the largest work of separation for the configurations studied and hence strong interfacial bonding. It is proposed that a small misfit accompanied by strong interfacial bonding enable the local epitaxial growth of V 2 AlC on (112-bar 0)-sapphire.

  5. Interfacial transport processes and rheology

    CERN Document Server

    Brenner, Howard

    1991-01-01

    This textbook is designed to provide the theory, methods of measurement, and principal applications of the expanding field of interfacial hydrodynamics. It is intended to serve the research needs of both academic and industrial scientists, including chemical or mechanical engineers, material and surface scientists, physical chemists, chemical and biophysicists, rheologists, physiochemical hydrodynamicists, and applied mathematicians (especially those with interests in viscous fluid mechanics and continuum mechanics).As a textbook it provides materials for a one- or two-semester graduate-level

  6. In-situ SEM microchip setup for electrochemical experiments with water based solutions

    DEFF Research Database (Denmark)

    Jensen, Eric; Købler, C.; Jensen, Palle Skovhus

    2013-01-01

    Studying electrochemical (EC) processes with electron microscopes offers the possibility of achieving much higher resolution imaging of nanoscale processes in real time than with optical microscopes. We have developed a vacuum sealed liquid sample electrochemical cell with electron transparent wi...

  7. The analysis of interfacial waves

    International Nuclear Information System (INIS)

    Galimov, Azat Yu.; Drew, Donald A.; Lahey, Richard T.; Moraga, Francisco J.

    2005-01-01

    We present analytical results for stable stratified wavy two-phase flow and functional forms for the various interfacial force densities in a two-fluid model. In particular, we have derived analytically the components of the non-drag interfacial force density [Drew, D.A., Passman, S.L., 1998. Theory of Multicomponent Fluids. Springer-Verlag, New York; Nigmatulin, T.R., Drew, D.A., Lahey, R.T., Jr., 2000. An analysis of wavy annular flow. In: International Conference on Multiphase Systems, ICMS'2000, Ufa, Russia, June 15-17], Reynolds stress tensor, and the term, (p-bar cl i -p-bar cl )-bar α cl , where p-bar cl i is interfacial average pressure, p-bar cl the average pressure, and α cl is the volume fraction of the continuous liquid phase. These functional forms should be useful for assessing two-fluid closure relations and Computational Multiphase Fluid Dynamics (CMFD) numerical models for stratified wavy flows. Moreover, it appears that this approach can be generalized to other flow regimes (e.g., annular flows)

  8. Liquid metal actuation by electrical control of interfacial tension

    Energy Technology Data Exchange (ETDEWEB)

    Eaker, Collin B.; Dickey, Michael D., E-mail: michael-dickey@ncsu.edu [Department of Chemical and Biomolecular Engineering, North Carolina State University, 911 Partners Way, Raleigh, North Carolina 27695 (United States)

    2016-09-15

    By combining metallic electrical conductivity with low viscosity, liquid metals and liquid metal alloys offer new and exciting opportunities to serve as reconfigurable components of electronic, microfluidic, and electromagnetic devices. Here, we review the physics and applications of techniques that utilize voltage to manipulate the interfacial tension of liquid metals; such techniques include electrocapillarity, continuous electrowetting, electrowetting-on-dielectric, and electrochemistry. These techniques lower the interfacial tension between liquid metals and a surrounding electrolyte by driving charged species (or in the case of electrochemistry, chemical species) to the interface. The techniques are useful for manipulating and actuating liquid metals at sub-mm length scales where interfacial forces dominate. We focus on metals and alloys that are liquid near or below room temperature (mercury, gallium, and gallium-based alloys). The review includes discussion of mercury—despite its toxicity—because it has been utilized in numerous applications and it offers a way of introducing several phenomena without the complications associated with the oxide layer that forms on gallium and its alloys. The review focuses on the advantages, applications, opportunities, challenges, and limitations of utilizing voltage to control interfacial tension as a method to manipulate liquid metals.

  9. Impact of Interfacial Layers in Perovskite Solar Cells.

    Science.gov (United States)

    Cho, An-Na; Park, Nam-Gyu

    2017-10-09

    Perovskite solar cells (PCSs) are composed of organic-inorganic lead halide perovskite as the light harvester. Since the first report on a long-term-durable, 9.7 % efficient, solid-state perovskite solar cell, organic-inorganic halide perovskites have received considerable attention because of their excellent optoelectronic properties. As a result, a power conversion efficiency (PCE) exceeding 22 % was certified. Controlling the grain size, grain boundary, morphology, and defects of the perovskite layer is important for achieving high efficiency. In addition, interfacial engineering is equally or more important to further improve the PCE through better charge collection and a reduction in charge recombination. In this Review, the type of interfacial layers and their impact on photovoltaic performance are investigated for both the normal and the inverted cell architectures. Four different interfaces of fluorine-doped tin oxide (FTO)/electron-transport layer (ETL), ETL/perovskite, perovskite/hole-transport layer (HTL), and HTL/metal are classified, and their roles are investigated. The effects of interfacial engineering with organic or inorganic materials on photovoltaic performance are described in detail. Grain-boundary engineering is also included because it is related to interfacial engineering and the grain boundary in the perovskite layer plays an important role in charge conduction, recombination, and chargecarrier life time. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Kinetic mechanism for modeling of electrochemical reactions.

    Science.gov (United States)

    Cervenka, Petr; Hrdlička, Jiří; Přibyl, Michal; Snita, Dalimil

    2012-04-01

    We propose a kinetic mechanism of electrochemical interactions. We assume fast formation and recombination of electron donors D- and acceptors A+ on electrode surfaces. These mediators are continuously formed in the electrode matter by thermal fluctuations. The mediators D- and A+, chemically equivalent to the electrode metal, enter electrochemical interactions on the electrode surfaces. Electrochemical dynamics and current-voltage characteristics of a selected electrochemical system are studied. Our results are in good qualitative agreement with those given by the classical Butler-Volmer kinetics. The proposed model can be used to study fast electrochemical processes in microsystems and nanosystems that are often out of the thermal equilibrium. Moreover, the kinetic mechanism operates only with the surface concentrations of chemical reactants and local electric potentials, which facilitates the study of electrochemical systems with indefinable bulk.

  11. Electrochemical cell

    Science.gov (United States)

    Kaun, T.D.

    An improved secondary electrochemical cell is disclosed having a negative electrode of lithium aluminum, a positive electrode of iron sulfide, a molten electrolyte of lithium chloride and potassium chloride, and the combination that the fully charged theoretical capacity of the negative electrode is in the range of 0.5 to 1.0 that of the positive electrode. The cell thus is negative electrode limiting during discharge cycling. Preferably, the negative electrode contains therein, in the approximate range of 1 to 10 volume % of the electrode, an additive from the materials of graphitized carbon, aluminum-iron alloy, and/or magnesium oxide.

  12. Electrochemical Impedance Studies of SOFC Cathodes

    DEFF Research Database (Denmark)

    Hjelm, Johan; Søgaard, Martin; Wandel, Marie

    2007-01-01

    Mixed ion- and electron-conducting composite electrodes consisting of doped ceria and perovskite have been studied by electrochemical impedance spectroscopy (EIS) at different temperatures and oxygen partial pressures. This paper aims to describe the different contributions to the polarisation...

  13. Electrochemical attosyringe.

    Science.gov (United States)

    Laforge, François O; Carpino, James; Rotenberg, Susan A; Mirkin, Michael V

    2007-07-17

    The ability to manipulate ultrasmall volumes of liquids is essential in such diverse fields as cell biology, microfluidics, capillary chromatography, and nanolithography. In cell biology, it is often necessary to inject material of high molecular weight (e.g., DNA, proteins) into living cells because their membranes are impermeable to such molecules. All techniques currently used for microinjection are plagued by two common problems: the relatively large injector size and volume of injected fluid, and poor control of the amount of injected material. Here we demonstrate the possibility of electrochemical control of the fluid motion that allows one to sample and dispense attoliter-to-picoliter (10(-18) to 10(-12) liter) volumes of either aqueous or nonaqueous solutions. By changing the voltage applied across the liquid/liquid interface, one can produce a sufficient force to draw solution inside a nanopipette and then inject it into an immobilized biological cell. A high success rate was achieved in injections of fluorescent dyes into cultured human breast cells. The injection of femtoliter-range volumes can be monitored by video microscopy, and current/resistance-based approaches can be used to control injections from very small pipettes. Other potential applications of the electrochemical syringe include fluid dispensing in nanolithography and pumping in microfluidic systems.

  14. Electrochemical cell structure including an ionomeric barrier

    Science.gov (United States)

    Lambert, Timothy N.; Hibbs, Michael

    2017-06-20

    An apparatus includes an electrochemical half-cell comprising: an electrolyte, an anode; and an ionomeric barrier positioned between the electrolyte and the anode. The anode may comprise a multi-electron vanadium phosphorous alloy, such as VP.sub.x, wherein x is 1-5. The electrochemical half-cell is configured to oxidize the vanadium and phosphorous alloy to release electrons. A method of mitigating corrosion in an electrochemical cell includes disposing an ionomeric barrier in a path of electrolyte or ion flow to an anode and mitigating anion accumulation on the surface of the anode.

  15. Effect of surface treatment on the interfacial contact resistance and corrosion resistance of Fe–Ni–Cr alloy as a bipolar plate for polymer electrolyte membrane fuel cells

    International Nuclear Information System (INIS)

    Yang, Meijun; Zhang, Dongming

    2014-01-01

    The bipolar plate is an important component of the PEMFC (polymer electrolyte membrane fuel cell) because it supplies the pathway of electron flow between each unit cell. Fe–Ni–Cr alloy is considered as a good candidate material for bipolar plate, but it is limited to use as a bipolar plate due to its high ICR (interfacial contact resistance) and corrosion problem. In order to explore a cost-effective method on surface modification, various chemical and electrochemical treatments are performed on Fe–Ni–Cr alloy to acquire the effect of the surface modification on the ICR and corrosion behavior. The ICR and corrosion resistance of Fe–Ni–Cr alloy can be effectively controlled by the chemical treatment of immersion in the mixed acid solution with 10 vol% HNO 3 , 2 vol% HCl and 1 vol% HF for 10 min at 65 °C and then was placed in 30 vol% HNO 3 solution for 5 min. The chemical treatment is more effective on reducing ICR and improving corrosion resistance than that of electrochemical methods (be carried out in the 2 mol/L H 2 SO 4 solution with the electrical potential from −0.4 V to 0.6 V) for Fe–Ni–Cr alloy as a bipolar plate for polymer electrolyte membrane fuel cells. - Highlights: • The procedure of the surface treatments on Fe–Ni–Cr alloy as bipolar plate was described in detail. • Effects of various surface treatments on the interfacial contact resistivity and corrosion behavior were discussed. • The mechanism of the surface modification was particularly analyzed

  16. Polyindole/ carboxylated-multiwall carbon nanotube composites produced by in-situ and interfacial polymerization

    International Nuclear Information System (INIS)

    Joshi, Leela; Singh, Arun Kumar; Prakash, Rajiv

    2012-01-01

    Composites of polyindole (PIn), a conducting polymer, with carboxylated-multiwalled carbon nanotubes (c-MWCNT/PIn) were synthesized; the synthesis was done using (i) two miscible solvents (in-situ method) and (ii) two immiscible solvents (interfacial method). A tubular composite, with a uniform coating of the polymer over c-MWCNTs, was observed in the case of interfacial synthesis. However, the in-situ synthesis of c-MWCNT/PIn composites exhibited a densely packed spherical morphology, with c-MWCNT incorporated within the polymer spheres. The spherical morphology was probably obtained due to fast polymerization kinetics and the formation of micelles in case of in-situ polymerization, whereas tubular morphology was obtained in case of interfacial polymerization due to the sufficient time provided for the growth of polymer chains over the c-MWCNT surfaces. Nanoscale electrical properties of composites, in a metal/(c-MWCNT/PIn) configuration, were studied using current sensing atomic force microscopy. Interfacial c-MWCNT/PIn composite, on Al metal substrate, exhibited a typical rectifying diode behavior. This composite had manifested enormous potential for electronic applications and fabrication of nanoscale organic devices. Highlights: ► Polyindole/c-MWNT nanocomposites produced by in-situ and interfacial polymerization. ► Densely packed spherical morphology was observed in in-situ polymerization route. ► Tubular core-shell morphology was observed in interfacial polymerization route. ► Interfacial nanocomposite manifested a nano-schottky junction with Al metal.

  17. TFB:TPDSi2 interfacial layer usable in organic photovoltaic cells

    Science.gov (United States)

    Marks, Iobin J [Evanston, IL; Hains, Alexander W [Evanston, IL

    2011-02-15

    The present invention, in one aspect, relates to a solar cell. In one embodiment, the solar cell includes an anode; an active organic layer comprising an electron-donating organic material and an electron-accepting organic material; and an interfacial layer formed between the anode and active organic layer, where the interfacial layer comprises a hole-transporting polymer characterized with a hole-mobility higher than that of the electron-donating organic material in the active organic layer, and a small molecule that has a high hole-mobility and is capable of crosslinking on contact with air.

  18. Protein interfacial structure and nanotoxicology

    International Nuclear Information System (INIS)

    White, John W.; Perriman, Adam W.; McGillivray, Duncan J.; Lin, J.-M.

    2009-01-01

    Here we briefly recapitulate the use of X-ray and neutron reflectometry at the air-water interface to find protein structures and thermodynamics at interfaces and test a possibility for understanding those interactions between nanoparticles and proteins which lead to nanoparticle toxicology through entry into living cells. Stable monomolecular protein films have been made at the air-water interface and, with a specially designed vessel, the substrate changed from that which the air-water interfacial film was deposited. This procedure allows interactions, both chemical and physical, between introduced species and the monomolecular film to be studied by reflectometry. The method is briefly illustrated here with some new results on protein-protein interaction between β-casein and κ-casein at the air-water interface using X-rays. These two proteins are an essential component of the structure of milk. In the experiments reported, specific and directional interactions appear to cause different interfacial structures if first, a β-casein monolayer is attacked by a κ-casein solution compared to the reverse. The additional contrast associated with neutrons will be an advantage here. We then show the first results of experiments on the interaction of a β-casein monolayer with a nanoparticle titanium oxide sol, foreshadowing the study of the nanoparticle 'corona' thought to be important for nanoparticle-cell wall penetration.

  19. Protein interfacial structure and nanotoxicology

    Energy Technology Data Exchange (ETDEWEB)

    White, John W. [Research School of Chemistry, Australian National University, Canberra (Australia)], E-mail: jww@rsc.anu.edu.au; Perriman, Adam W.; McGillivray, Duncan J.; Lin, J.-M. [Research School of Chemistry, Australian National University, Canberra (Australia)

    2009-02-21

    Here we briefly recapitulate the use of X-ray and neutron reflectometry at the air-water interface to find protein structures and thermodynamics at interfaces and test a possibility for understanding those interactions between nanoparticles and proteins which lead to nanoparticle toxicology through entry into living cells. Stable monomolecular protein films have been made at the air-water interface and, with a specially designed vessel, the substrate changed from that which the air-water interfacial film was deposited. This procedure allows interactions, both chemical and physical, between introduced species and the monomolecular film to be studied by reflectometry. The method is briefly illustrated here with some new results on protein-protein interaction between {beta}-casein and {kappa}-casein at the air-water interface using X-rays. These two proteins are an essential component of the structure of milk. In the experiments reported, specific and directional interactions appear to cause different interfacial structures if first, a {beta}-casein monolayer is attacked by a {kappa}-casein solution compared to the reverse. The additional contrast associated with neutrons will be an advantage here. We then show the first results of experiments on the interaction of a {beta}-casein monolayer with a nanoparticle titanium oxide sol, foreshadowing the study of the nanoparticle 'corona' thought to be important for nanoparticle-cell wall penetration.

  20. Electrochemical Impedance Spectroscopic Sensing of Methamphetamine by a Specific Aptamer

    Directory of Open Access Journals (Sweden)

    Omid Mashinchian

    2012-05-01

    Full Text Available Introduction: Electrochemical impedance spectroscopy (EIS is a simple and highly sensitive technique that can be used for evaluation of the aptamer-target interaction even in a label-free approach. Methods: To pursue the effectiveness of EIS, in the current study, the folding properties of specific aptamer for methamphetamine (METH (i.e., aptaMETH were evaluated in the presence of METH and amphetamine (Amph. Folded and unfolded aptaMETH was mounted on the gold electrode surface and the electron charge transfer was measured by EIS. Results: The Ret of methamphetamine-aptaMETH was significantly increased in comparison with other folding conditions, indicating specific detection of METH by aptaMETH. Conclusion: Based on these findings, methamphetamine-aptaMETH on the gold electrode surface displayed the most interfacial electrode resistance and thus the most folding situation. This clearly indicates that the aptaMETH can profoundly and specifically pinpoint METH; as a result we suggest utilization of this methodology for fast and cost-effective identification of METH.

  1. Electrochemical oxidation of organic waste

    International Nuclear Information System (INIS)

    Almon, A.C.; Buchanan, B.R.

    1990-01-01

    Both silver catalyzed and direct electrochemical oxidation of organic species are examined in analytical detail. This paper describes the mechanisms, reaction rates, products, intermediates, capabilities, limitations, and optimal reaction conditions of the electrochemical destruction of organic waste. A small bench-top electrocell being tested for the treatment of small quantities of laboratory waste is described. The 200-mL electrochemical cell used has a processing capacity of 50 mL per day, and can treat both radioactive and nonradioactive waste. In the silver catalyzed process, Ag(I) is electrochemically oxidized to Ag(II), which attacks organic species such as tributylphosphate (TBP), tetraphenylborate (TPB), and benzene. In direct electrochemical oxidation, the organic species are destroyed at the surface of the working electrode without the use of silver as an electron transfer agent. This paper focuses on the destruction of tributylphosphate (TBP), although several organic species have been destroyed using this process. The organic species are converted to carbon dioxide, water, and inorganic acids

  2. Spectro-electrochemical and DFT study of tenoxicam metabolites formed by electrochemical oxidation

    International Nuclear Information System (INIS)

    Ramírez-Silva, M.T.; Guzmán-Hernández, D.S.; Galano, A.; Rojas-Hernández, A.; Corona-Avendaño, S.; Romero-Romo, M.; Palomar-Pardavé, M.

    2013-01-01

    Highlights: • Tenoxicam deprotonation and electrochemical oxidation were studied. • Both spectro-electrochemical and theoretical DFT studies were considered. • It was found that the ampholitic species of tenoxicam is a zwitterion. • Electrochemical oxidation of tenoxicam yields two non-electroactive products. • The nature of these fragments was further confirmed by a chromatography study. -- Abstract: From experimental (spectro-electrochemical) and theoretical (DFT) studies, the mechanisms of tenoxicam deprotonation and electrochemical oxidation were assessed. From these studies, new insights on the nature of the ampholitic species involved during tenoxicam's deprotonation in aqueous solution are presented; see scheme A. Moreover, it is shown that, after the analysis of two different reaction schemes that involve up to 10 different molecules and 12 reaction paths, the electrochemical oxidation of tenoxicam, yields two non-electroactive products that are predominately formed by its fragmentation, after the loss of two electrons. The nature of these fragments was further confirmed by a chromatography study

  3. Interfacial heat transfer - State of the art

    International Nuclear Information System (INIS)

    Yadigaroglu, G.

    1987-01-01

    Interfacial heat exchanges control the interfacial mass exchange rate, depend on the interfacial area, and are tied to the prediction of thermal nonequilibrium. The nature of the problem usually requires the formulation of mechanistic laws and precludes the general use of universal correlations. This is partly due to the fact that the length scale controlling the interfacial exchanges varies widely from one situation to another and has a strong influence on the exchange coefficients. Within the framework of the ''two-fluid models'', the exchanges occurring at the interfaces are explicitly taken into consideration by the jump condition linking the volumetric mass exchange (evaporation) rate between the phases, to the interfacial energy transfer rates

  4. Improved electrochemical properties of morphology-controlled titania/titanate nanostructures prepared by in-situ hydrothermal surface modification of self-source Ti substrate for high-performance supercapacitors.

    Science.gov (United States)

    Banerjee, Arghya Narayan; Anitha, V C; Joo, Sang W

    2017-10-16

    Ti substrate surface is modified into two-dimensional (2D) TiO 2 nanoplatelet or one-dimensional (1D) nanorod/nanofiber (or a mixture of both) structure in a controlled manner via a simple KOH-based hydrothermal technique. Depending on the KOH concentration, different types of TiO 2 nanostructures (2D platelets, 1D nanorods/nanofibers and a 2D+1D mixed sample) are fabricated directly onto the Ti substrate surface. The novelty of this technique is the in-situ modification of the self-source Ti surface into titania nanostructures, and its direct use as the electrochemical microelectrode without any modifications. This leads to considerable improvement in the interfacial properties between metallic Ti and semiconducting TiO 2 . Since interfacial states/defects have profound effect on charge transport properties of electronic/electrochemical devices, therefore this near-defect-free interfacial property of Ti-TiO 2 microelectrode has shown high supercapacitive performances for superior charge-storage devices. Additionally, by hydrothermally tuning the morphology of titania nanostructures, the electrochemical properties of the electrodes are also tuned. A Ti-TiO 2 electrode comprising of a mixture of 2D-platelet+1D-nanorod structure reveals very high specific capacitance values (~7.4 mF.cm -2 ) due to the unique mixed morphology which manifests higher active sites (hence, higher utilization of the active materials) in terms of greater roughness at the 2D-platelet structures and higher surface-to-volume-ratio in the 1D-nanorod structures.

  5. Interfacial functionalization and engineering of nanoparticles

    Science.gov (United States)

    Song, Yang

    The intense research interest in nanoscience and nanotechnology is largely fueled by the unique properties of nanoscale materials. In this dissertation, the research efforts are focused on surface functionalization and interfacial engineering of functional nanoparticles in the preparation of patchy nanoparticles (e.g., Janus nanoparticles and Neapolitan nanoparticles) such that the nanoparticle structures and properties may be manipulated to an unprecedented level of sophistication. Experimentally, Janus nanoparticles were prepared by an interfacial engineering method where one hemisphere of the originally hydrophobic nanoparticles was replaced with hydrophilic ligands at the air|liquid or solid|liquid interface. The amphiphilic surface characters of the Janus nanoparticles were verified by contact angle measurements, as compared to those of the bulk-exchange counterparts where the two types of ligands were distributed rather homogeneously on the nanoparticle surface. In a further study, a mercapto derivative of diacetylene was used as the hydrophilic ligands to prepare Janus nanoparticles by using hydrophobic hexanethiolate-protected gold nanoparticles as the starting materials. Exposure to UV irradiation led to effective covalent cross-linking between the diacetylene moieties of neighboring ligands and hence marked enhancement of the structural integrity of the Janus nanoparticles, which was attributable to the impeded surface diffusion of the thiol ligands on the nanoparticle surface, as manifested in fluorescence measurements of aged nanoparticles. More complicated bimetallic AgAu Janus nanoparticles were prepared by interfacial galvanic exchange reactions of a Langmuir-Blodgett monolayer of 1-hexanethiolate-passivated silver nanoparticles on a glass slide with gold(I)-mercaptopropanediol complex in a water/ethanol solution. The resulting nanoparticles exhibited an asymmetrical distribution not only of the organic capping ligands on the nanoparticle surface but

  6. Interfacial charge separation and photovoltaic efficiency in Fe(ii)-carbene sensitized solar cells.

    Science.gov (United States)

    Pastore, Mariachiara; Duchanois, Thibaut; Liu, Li; Monari, Antonio; Assfeld, Xavier; Haacke, Stefan; Gros, Philippe C

    2016-10-12

    The first combined theoretical and photovoltaic characterization of both homoleptic and heteroleptic Fe(ii)-carbene sensitized photoanodes in working dye sensitized solar cells (DSSCs) has been performed. Three new heteroleptic Fe(ii)-NHC dye sensitizers have been synthesized, characterized and tested. Despite an improved interfacial charge separation in comparison to the homoleptic compounds, the heteroleptic complexes did not show boosted photovoltaic performances. The ab initio quantitative analysis of the interfacial electron and hole transfers and the measured photovoltaic data clearly evidenced fast recombination reactions for heteroleptics, even associated with un unfavorable directional electron flow, and hence slower injection rates, in the case of homoleptics. Notably, quantum mechanics calculations revealed that deprotonation of the not anchored carboxylic function in the homoleptic complex can effectively accelerate the electron injection rate and completely suppress the electron recombination to the oxidized dye. This result suggests that introduction of strong electron-donating substituents on the not-anchored carbene ligand in heteroleptic complexes, in such a way of mimicking the electronic effects of the carboxylate functionality, should yield markedly improved interfacial charge generation properties. The present results, providing for the first time a detailed understanding of the interfacial electron transfers and photovoltaic characterization in Fe(ii)-carbene sensitized solar cells, open the way to a rational molecular engineering of efficient iron-based dyes for photoelectrochemical applications.

  7. Interfacial instabilities in vibrated fluids

    Science.gov (United States)

    Porter, Jeff; Laverón-Simavilla, Ana; Tinao Perez-Miravete, Ignacio; Fernandez Fraile, Jose Javier

    2016-07-01

    Vibrations induce a range of different interfacial phenomena in fluid systems depending on the frequency and orientation of the forcing. With gravity, (large) interfaces are approximately flat and there is a qualitative difference between vertical and horizontal forcing. Sufficient vertical forcing produces subharmonic standing waves (Faraday waves) that extend over the whole interface. Horizontal forcing can excite both localized and extended interfacial phenomena. The vibrating solid boundaries act as wavemakers to excite traveling waves (or sloshing modes at low frequencies) but they also drive evanescent bulk modes whose oscillatory pressure gradient can parametrically excite subharmonic surface waves like cross-waves. Depending on the magnitude of the damping and the aspect ratio of the container, these locally generated surfaces waves may interact in the interior resulting in temporal modulation and other complex dynamics. In the case where the interface separates two fluids of different density in, for example, a rectangular container, the mass transfer due to vertical motion near the endwalls requires a counterflow in the interior region that can lead to a Kelvin-Helmholtz type instability and a ``frozen wave" pattern. In microgravity, the dominance of surface forces favors non-flat equilibrium configurations and the distinction between vertical and horizontal applied forcing can be lost. Hysteresis and multiplicity of solutions are more common, especially in non-wetting systems where disconnected (partial) volumes of fluid can be established. Furthermore, the vibrational field contributes a dynamic pressure term that competes with surface tension to select the (time averaged) shape of the surface. These new (quasi-static) surface configurations, known as vibroequilibria, can differ substantially from the hydrostatic state. There is a tendency for the interface to orient perpendicular to the vibrational axis and, in some cases, a bulge or cavity is induced

  8. Indium tin oxide with zwitterionic interfacial design for biosensing applications in complex matrices

    Energy Technology Data Exchange (ETDEWEB)

    Darwish, Nadia T.; Alias, Yatimah; Khor, Sook Mei, E-mail: naomikhor@um.edu.my

    2015-01-15

    Graphical abstract: - Highlights: • The incorporation of a linker and antifouling molecules is an important interfacial design for both affinity and enzymatic biosensors. • The resistance to non-specific protein adsorptions of BSA–FITC and RBITC–Cyt c were determined by confocal laser scanning microscopy. • The antifouling interface allows detection of target analytes in highly complicated biological matrices. - Abstract: Biosensing interfaces consisting of linker molecules (COOH or NH{sub 2}) and charged, antifouling moieties ((-SO{sup 3−} and N{sup +}(Me){sub 3}) for biosensing applications were prepared for the first time by the in situ deposition of mixtures of aryl diazonium cations on indium tin oxide (ITO) electrodes. A linker molecule is required for the attachment of biorecognition molecules (e.g., antibodies, enzymes, DNA chains, and aptamers) close to the transducer surface. The attached molecules improve the biosensing sensitivity and also provide a short response time for analyte detection. Thus, the incorporation of a linker and antifouling molecules is an important interfacial design for both affinity and enzymatic biosensors. The reductive adsorption behavior and electrochemical measurement were studied for (1) an individual compound and (2) a mixture of antifouling zwitterionic molecules together with linker molecules [combination 1: 4-sulfophenyl (SP), 4-trimethylammoniophenyl (TMAP), and 1,4-phenylenediamine (PPD); combination 2: 4-sulfophenyl (SP), 4-trimethylammoniophenyl (TMAP), and 4-aminobenzoic acid (PABA)] of aryl diazonium cations grafted onto an ITO electrode. The mixture ratios of SP:TMAP:PPD and SP:TMAP:PABA that provided the greatest resistance to non-specific protein adsorptions of bovine serum albumin labeled with fluorescein isothiocyanate (BSA–FITC) and cytochrome c labeled with rhodamine B isothiocyanate (RBITC–Cyt c) were determined by confocal laser scanning microscopy (CLSM). For the surface antifouling study

  9. Indium tin oxide with zwitterionic interfacial design for biosensing applications in complex matrices

    International Nuclear Information System (INIS)

    Darwish, Nadia T.; Alias, Yatimah; Khor, Sook Mei

    2015-01-01

    Graphical abstract: - Highlights: • The incorporation of a linker and antifouling molecules is an important interfacial design for both affinity and enzymatic biosensors. • The resistance to non-specific protein adsorptions of BSA–FITC and RBITC–Cyt c were determined by confocal laser scanning microscopy. • The antifouling interface allows detection of target analytes in highly complicated biological matrices. - Abstract: Biosensing interfaces consisting of linker molecules (COOH or NH 2 ) and charged, antifouling moieties ((-SO 3− and N + (Me) 3 ) for biosensing applications were prepared for the first time by the in situ deposition of mixtures of aryl diazonium cations on indium tin oxide (ITO) electrodes. A linker molecule is required for the attachment of biorecognition molecules (e.g., antibodies, enzymes, DNA chains, and aptamers) close to the transducer surface. The attached molecules improve the biosensing sensitivity and also provide a short response time for analyte detection. Thus, the incorporation of a linker and antifouling molecules is an important interfacial design for both affinity and enzymatic biosensors. The reductive adsorption behavior and electrochemical measurement were studied for (1) an individual compound and (2) a mixture of antifouling zwitterionic molecules together with linker molecules [combination 1: 4-sulfophenyl (SP), 4-trimethylammoniophenyl (TMAP), and 1,4-phenylenediamine (PPD); combination 2: 4-sulfophenyl (SP), 4-trimethylammoniophenyl (TMAP), and 4-aminobenzoic acid (PABA)] of aryl diazonium cations grafted onto an ITO electrode. The mixture ratios of SP:TMAP:PPD and SP:TMAP:PABA that provided the greatest resistance to non-specific protein adsorptions of bovine serum albumin labeled with fluorescein isothiocyanate (BSA–FITC) and cytochrome c labeled with rhodamine B isothiocyanate (RBITC–Cyt c) were determined by confocal laser scanning microscopy (CLSM). For the surface antifouling study, we used 2

  10. Interfacial Engineering and Charge Carrier Dynamics in Extremely Thin Absorber Solar Cells

    Science.gov (United States)

    Edley, Michael

    Photovoltaic energy is a clean and renewable source of electricity; however, it faces resistance to widespread use due to cost. Nanostructuring decouples constraints related to light absorption and charge separation, potentially reducing cost by allowing a wider variety of processing techniques and materials to be used. However, the large interfacial areas also cause an increased dark current which negatively affects cell efficiency. This work focuses on extremely thin absorber (ETA) solar cells that used a ZnO nanowire array as a scaffold for an extremely thin CdSe absorber layer. Photoexcited electrons generated in the CdSe absorber are transferred to the ZnO layer, while photogenerated holes are transferred to the liquid electrolyte. The transfer of photoexcited carriers to their transport layer competes with bulk recombination in the absorber layer. After charge separation, transport of charge carriers to their respective contacts must occur faster than interfacial recombination for efficient collection. Charge separation and collection depend sensitively on the dimensions of the materials as well as their interfaces. We demonstrated that an optimal absorber thickness can balance light absorption and charge separation. By treating the ZnO/CdSe interface with a CdS buffer layer, we were able to improve the Voc and fill factor, increasing the ETA cell's efficiency from 0.53% to 1.34%, which is higher than that achievable using planar films of the same material. We have gained additional insight into designing ETA cells through the use of dynamic measurements. Ultrafast transient absorption spectroscopy revealed that characteristic times for electron injection from CdSe to ZnO are less than 1 ps. Electron injection is rapid compared to the 2 ns bulk lifetime in CdSe. Optoelectronic measurements such as transient photocurrent/photovoltage and electrochemical impedance spectroscopy were applied to study the processes of charge transport and interfacial recombination

  11. Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals

    Science.gov (United States)

    Weitzner, Stephen E.; Dabo, Ismaila

    2017-11-01

    The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.

  12. Recent advances in interfacial engineering of perovskite solar cells

    Science.gov (United States)

    Ye, Meidan; He, Chunfeng; Iocozzia, James; Liu, Xueqin; Cui, Xun; Meng, Xiangtong; Rager, Matthew; Hong, Xiaodan; Liu, Xiangyang; Lin, Zhiqun

    2017-09-01

    Due to recent developments, organometallic halide perovskite solar cells (PSCs) have attracted even greater interest owing to their impressive photovoltaic properties and simple device manufacturing processes with the potential for commercial applications. The power conversion efficiencies (PCEs) of PSCs have surged from 3.8% for methyl ammonium lead halide-sensitized liquid solar cells, CH3NH3PbX3 (X  =  Cl, Br, I), in 2009, to more than 22% for all-solid-state solar cells in 2016. Over the past few years, significant effort has been dedicated to realizing PSCs with even higher performance. In this review, recent advances in the interfacial engineering of PSCs are addressed. The specific strategies for the interfacial engineering of PSCs fall into two categories: (1) solvent treatment and additives to improve the light-harvesting capabilities of perovskite films, and (2) the incorporation of various functional materials at the interfaces between the active layers (e.g. electron transporting layer, perovskite layer, and hole transporting layer). This review aims to provide a comprehensive overview of strategies for the interfacial engineering of PSCs with potential benefits including enhanced light harvesting, improved charge separation and transport, improved device stability, and elimination of photocurrent hysteresis.

  13. Electrochemical Sensors Based on Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Md. Aminur Rahman

    2009-03-01

    Full Text Available This review focuses on recent contributions in the development of the electrochemical sensors based on carbon nanotubes (CNTs. CNTs have unique mechanical and electronic properties, combined with chemical stability, and behave electrically as a metal or semiconductor, depending on their structure. For sensing applications, CNTs have many advantages such as small size with larger surface area, excellent electron transfer promoting ability when used as electrodes modifier in electrochemical reactions, and easy protein immobilization with retention of its activity for potential biosensors. CNTs play an important role in the performance of electrochemical biosensors, immunosensors, and DNA biosensors. Various methods have been developed for the design of sensors using CNTs in recent years. Herein we summarize the applications of CNTs in the construction of electrochemical sensors and biosensors along with other nanomaterials and conducting polymers.

  14. Interfacial properties of stanene-metal contacts

    Science.gov (United States)

    Guo, Ying; Pan, Feng; Ye, Meng; Wang, Yangyang; Pan, Yuanyuan; Zhang, Xiuying; Li, Jingzhen; Zhang, Han; Lu, Jing

    2016-09-01

    Recently, two-dimensional buckled honeycomb stanene has been manufactured by molecular beam epitaxy growth. Free-standing stanene is predicted to have a sizable opened band gap of 100 meV at the Dirac point due to spin-orbit coupling (SOC), resulting in many fascinating properties such as quantum spin Hall effect, quantum anomalous Hall effect, and quantum valley Hall effect. In the first time, we systematically study the interfacial properties of stanene-metal interfaces (metals = Ag, Au, Cu, Al, Pd, Pt, Ir, and Ni) by using ab initio electronic structure calculations considering the SOC effects. The honeycomb structure of stanene is preserved on the metal supports, but the buckling height is changed. The buckling of stanene on the Au, Al, Ag, and Cu metal supports is higher than that of free-standing stanene. By contrast, a planar graphene-like structure is stabilized for stanene on the Ir, Pd, Pt, and Ni metal supports. The band structure of stanene is destroyed on all the metal supports, accompanied by a metallization of stanene because the covalent bonds between stanene and the metal supports are formed and the structure of stanene is distorted. Besides, no tunneling barrier exists between stanene and the metal supports. Therefore, stanene and the eight metals form a good vertical Ohmic contact.

  15. The molecular understanding of interfacial interactions of functionalized graphene and chitosan

    International Nuclear Information System (INIS)

    Zhang, Hong-ping; Luo, Xue-gang; Lin, Xiao-yan; Lu, Xiong; Tang, Youhong

    2016-01-01

    Graphical abstract: The type of the functional groups can be used to modulating interactions between graphene sheet and chitosan. - Highlights: • Investigate interfacial interactions between chitosan and functionalized graphene by DFT. • Observe covalent linkages between COOH-modified graphene and chitosan units. • Multi-functionalized graphene regulates the interfacial interactions with chitosan. • It is useful for guiding the preparation of graphene/chitosan composites. - Abstract: Graphene-reinforced chitosan scaffolds have been extensively studied for several years as promising hard tissue replacements. However, the interfacial interactions between graphene and chitosan are strongly related to the solubility, processability, and mechanical properties of graphene-reinforced chitosan (G–C) composites. The functionalization of graphene is regarded as the most effective way to improve the abovementioned properties of the G–C composite. In this study, the interfacial interactions between chitosan and functionalized graphene sheets with carboxylization (COOH-), amination (NH 2 -), and hydroxylation (OH-) groups were systematically studied at the electronic level using the method of ab initio simulations based on quantum mechanics theory and the observations were compared with reported experimental results. The covalent linkages between COOH-modified graphene and the chitosan units were demonstrated and the combination of multi-functionalization on graphene could regulate the interfacial interactions between graphene and the chitosan. The interfacial interactions between chitosan and properly functionalized graphene are critical for the preparation of G–C-based composites for tissue engineering scaffolds and other applications.

  16. The Role of Water in Mediating Interfacial Adhesion and Shear Strength in Graphene Oxide.

    Science.gov (United States)

    Soler-Crespo, Rafael A; Gao, Wei; Mao, Lily; Nguyen, Hoang T; Roenbeck, Michael R; Paci, Jeffrey T; Huang, Jiaxing; Nguyen, SonBinh T; Espinosa, Horacio D

    2018-06-05

    Graphene oxide (GO), whose highly tunable surface chemistry enables the formation of strong interfacial hydrogen bond networks, has garnered increasing interest in the design of devices that operate in the presence of water. For instance, previous studies have suggested that controlling GO's surface chemistry leads to enhancements in interfacial shear strength, allowing engineers to manage deformation pathways and control failure mechanisms. However, these previous reports have not explored the role of ambient humidity, and only offer extensive chemical modifications to GO's surface as the main pathway to control GO's interfacial properties. Herein, through atomic force microscopy experiments on GO-GO interfaces, the adhesion energy and interfacial shear strength of GO were measured as a function of ambient humidity. Experimental evidence shows that adhesion energy and interfacial shear strength can be improved by a factor of two to three when GO is exposed to moderate (~30% water wt.) water content. Furthermore, complementary molecular dynamics simulations uncovered the mechanisms by which these nanomaterial interfaces achieve their properties. They reveal that the strengthening mechanism arises from the formation of strongly interacting hydrogen bond networks, driven by the chemistry of the GO basal plane and intercalated water molecules between two GO surfaces. In summary, the methodology and findings here reported provide pathways to simultaneously optimize GO's interfacial and in-plane mechanical properties, by tailoring the chemistry of GO and accounting for water content, in engineering applications such as sensors, filtration membranes, wearable electronics, and structural materials.

  17. Electrochemical, morphological and microstructural characterization of carbon film resistor electrodes for application in electrochemical sensors

    International Nuclear Information System (INIS)

    Gouveia-Caridade, Carla; Soares, David M.; Liess, Hans-Dieter; Brett, Christopher M.A.

    2008-01-01

    The electrochemical and microstructural properties of carbon film electrodes made from carbon film electrical resistors of 1.5, 15, 140 Ω and 2.0 kΩ nominal resistance have been investigated before and after electrochemical pre-treatment at +0.9 V vs SCE, in order to assess the potential use of these carbon film electrodes as electrochemical sensors and as substrates for sensors and biosensors. The results obtained are compared with those at electrodes made from previously investigated 2 Ω carbon film resistors. Cyclic voltammetry was performed in acetate buffer and phosphate buffer saline electrolytes and the kinetic parameters of the model redox system Fe(CN) 6 3-/4- obtained. The 1.5 Ω resistor electrodes show the best properties for sensor development with wide potential windows, similar electrochemical behaviour to those of 2 Ω and close-to-reversible kinetic parameters after electrochemical pre-treatment. The 15 and 140 Ω resistor electrodes show wide potential windows although with slower kinetics, whereas the 2.0 kΩ resistor electrodes show poor cyclic voltammetric profiles even after pre-treatment. Electrochemical impedance spectroscopy related these findings to the interfacial properties of the electrodes. Microstructural and morphological studies were carried out using contact mode Atomic Force Microscopy (AFM), Confocal Raman spectroscopy and X-ray diffraction. AFM showed more homogeneity of the films with lower nominal resistances, related to better electrochemical characteristics. X-ray diffraction and Confocal Raman spectroscopy indicate the existence of a graphitic structure in the carbon films

  18. Incorporating interfacial phenomena in solidification models

    Science.gov (United States)

    Beckermann, Christoph; Wang, Chao Yang

    1994-01-01

    A general methodology is available for the incorporation of microscopic interfacial phenomena in macroscopic solidification models that include diffusion and convection. The method is derived from a formal averaging procedure and a multiphase approach, and relies on the presence of interfacial integrals in the macroscopic transport equations. In a wider engineering context, these techniques are not new, but their application in the analysis and modeling of solidification processes has largely been overlooked. This article describes the techniques and demonstrates their utility in two examples in which microscopic interfacial phenomena are of great importance.

  19. An ultrasensitive electrochemical biosensor for glucose using CdTe-CdS core-shell quantum dot as ultrafast electron transfer relay between graphene-gold nanocomposite and gold nanoparticle

    International Nuclear Information System (INIS)

    Gu Zhiguo; Yang Shuping; Li Zaijun; Sun Xiulan; Wang Guangli; Fang Yinjun; Liu Junkang

    2011-01-01

    Graphical abstract: We first reported an ultrasensitive electrochemical biosensor for glucose using CdTe-CdS core-shell quantum dot as ultrafast electron transfer relay between graphene-gold nanocomposite and gold nanoparticle. Since promising their electrocatalytic synergy towards glucose was achieved, the biosensor showed high sensitivity (5762.8 nA nM -1 cm -2 ), low detection limit (S/N = 3) (3 x 10 -12 M) and fast response time (0.045 s). - Abstract: The paper reported an ultrasensitive electrochemical biosensor for glucose which was based on CdTe-CdS core-shell quantum dot as ultrafast electron transfer relay between graphene-gold nanocomposite and gold nanoparticle. Since efficient electron transfer between glucose oxidase and the electrode was achieved, the biosensor showed high sensitivity (5762.8 nA nM -1 cm -2 ), low detection limit (S/N = 3) (3 x 10 -12 M), fast response time (0.045 s), wide calibration range (from 1 x 10 -11 M to 1 x 10 -8 M) and good long-term stability (26 weeks). The apparent Michaelis-Menten constant of the glucose oxidase on the medium, 5.24 x 10 -6 mM, indicates excellent bioelectrocatalytic activity of the immobilized enzyme towards glucose oxidation. Moreover, the effects of omitting graphene-gold nanocomposite, CdTe-CdS core-shell quantum dot and gold nanoparticle were also investigated. The result showed sensitivity of the biosensor is 7.67-fold better if graphene-gold nanocomposite, CdTe-CdS core-shell quantum dot and gold nanoparticle are used. This could be ascribed to improvement of the conductivity between graphene nanosheets due to introduction of gold nanoparticles, ultrafast charge transfer from CdTe-CdS core-shell quantum dot to graphene nanosheets and gold nanoparticle due to unique electrochemical properties of the CdTe-CdS core-shell quantum dot and good biocompatibility of gold nanoparticle for glucose oxidase. The biosensor is of best sensitivity in all glucose biosensors based on graphene nanomaterials up to

  20. An ultrasensitive electrochemical biosensor for glucose using CdTe-CdS core-shell quantum dot as ultrafast electron transfer relay between graphene-gold nanocomposite and gold nanoparticle

    Energy Technology Data Exchange (ETDEWEB)

    Gu Zhiguo; Yang Shuping [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Li Zaijun, E-mail: zaijunli@263.net [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Sun Xiulan [School of Food Science and Technology, Jiangnan University, Wuxi 214122 (China); Wang Guangli [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Fang Yinjun [Zhejiang Zanyu Technology Co., Ltd., Hangzhou 310009 (China); Liu Junkang [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China)

    2011-10-30

    Graphical abstract: We first reported an ultrasensitive electrochemical biosensor for glucose using CdTe-CdS core-shell quantum dot as ultrafast electron transfer relay between graphene-gold nanocomposite and gold nanoparticle. Since promising their electrocatalytic synergy towards glucose was achieved, the biosensor showed high sensitivity (5762.8 nA nM{sup -1} cm{sup -2}), low detection limit (S/N = 3) (3 x 10{sup -12} M) and fast response time (0.045 s). - Abstract: The paper reported an ultrasensitive electrochemical biosensor for glucose which was based on CdTe-CdS core-shell quantum dot as ultrafast electron transfer relay between graphene-gold nanocomposite and gold nanoparticle. Since efficient electron transfer between glucose oxidase and the electrode was achieved, the biosensor showed high sensitivity (5762.8 nA nM{sup -1} cm{sup -2}), low detection limit (S/N = 3) (3 x 10{sup -12} M), fast response time (0.045 s), wide calibration range (from 1 x 10{sup -11} M to 1 x 10{sup -8} M) and good long-term stability (26 weeks). The apparent Michaelis-Menten constant of the glucose oxidase on the medium, 5.24 x 10{sup -6} mM, indicates excellent bioelectrocatalytic activity of the immobilized enzyme towards glucose oxidation. Moreover, the effects of omitting graphene-gold nanocomposite, CdTe-CdS core-shell quantum dot and gold nanoparticle were also investigated. The result showed sensitivity of the biosensor is 7.67-fold better if graphene-gold nanocomposite, CdTe-CdS core-shell quantum dot and gold nanoparticle are used. This could be ascribed to improvement of the conductivity between graphene nanosheets due to introduction of gold nanoparticles, ultrafast charge transfer from CdTe-CdS core-shell quantum dot to graphene nanosheets and gold nanoparticle due to unique electrochemical properties of the CdTe-CdS core-shell quantum dot and good biocompatibility of gold nanoparticle for glucose oxidase. The biosensor is of best sensitivity in all glucose

  1. International Symposium on Interfacial Joining and Surface Technology (IJST2013)

    Science.gov (United States)

    Takahashi, Yasuo

    2014-08-01

    Interfacial joining (bonding) is a widely accepted welding process and one of the environmentally benign technologies used in industrial production. As the bonding temperature is lower than the melting point of the parent materials, melting of the latter is kept to a minimum. The process can be based on diffusion bonding, pressure welding, friction welding, ultrasonic bonding, or brazing-soldering, all of which offer many advantages over fusion welding. In addition, surface technologies such as surface modification, spraying, coating, plating, and thin-film formation are necessary for advanced manufacturing, fabrication, and electronics packaging. Together, interfacial joining and surface technology (IJST) will continue to be used in various industrial fields because IJST is a very significant form of environmentally conscious materials processing. The international symposium of IJST 2013 was held at Icho Kaikan, Osaka University, Japan from 27-29 November, 2013. A total of 138 participants came from around the world to attend 56 oral presentations and 36 posters presented at the symposium, and to discuss the latest research and developments on interfacial joining and surface technologies. This symposium was also held to commemorate the 30th anniversary of the Technical Commission on Interfacial Joining of the Japan Welding Society. On behalf of the chair of the symposium, it is my great pleasure to present this volume of IOP Conference Series: Materials Science and Engineering (MSE). Among the presentations, 43 papers are published here, and I believe all of the papers have provided the welding community with much useful information. I would like to thank the authors for their enthusiastic and excellent contributions. Finally, I would like to thank all members of the committees, secretariats, participants, and everyone who contributed to this symposium through their support and invaluable effort for the success of IJST 2013. Yasuo Takahashi Chair of IJST 2013

  2. International Symposium on Interfacial Joining and Surface Technology (IJST2013)

    International Nuclear Information System (INIS)

    Takahashi, Yasuo

    2014-01-01

    Interfacial joining (bonding) is a widely accepted welding process and one of the environmentally benign technologies used in industrial production. As the bonding temperature is lower than the melting point of the parent materials, melting of the latter is kept to a minimum. The process can be based on diffusion bonding, pressure welding, friction welding, ultrasonic bonding, or brazing-soldering, all of which offer many advantages over fusion welding. In addition, surface technologies such as surface modification, spraying, coating, plating, and thin-film formation are necessary for advanced manufacturing, fabrication, and electronics packaging. Together, interfacial joining and surface technology (IJST) will continue to be used in various industrial fields because IJST is a very significant form of environmentally conscious materials processing. The international symposium of IJST 2013 was held at Icho Kaikan, Osaka University, Japan from 27–29 November, 2013. A total of 138 participants came from around the world to attend 56 oral presentations and 36 posters presented at the symposium, and to discuss the latest research and developments on interfacial joining and surface technologies. This symposium was also held to commemorate the 30th anniversary of the Technical Commission on Interfacial Joining of the Japan Welding Society. On behalf of the chair of the symposium, it is my great pleasure to present this volume of IOP Conference Series: Materials Science and Engineering (MSE). Among the presentations, 43 papers are published here, and I believe all of the papers have provided the welding community with much useful information. I would like to thank the authors for their enthusiastic and excellent contributions. Finally, I would like to thank all members of the committees, secretariats, participants, and everyone who contributed to this symposium through their support and invaluable effort for the success of IJST 2013. Yasuo Takahashi Chair of IJST 2013

  3. Electrochemical behavior of two and one electron redox systems adsorbed on to micro- and mesoporous silicate materials: Influence of the channels and the cationic environment of the host materials

    International Nuclear Information System (INIS)

    Senthil Kumar, K.; Natarajan, P.

    2009-01-01

    Electrochemical behavior of two electron redox system, phenosafranine (PS + ) adsorbed on to micro- and mesoporous materials is investigated by cyclic voltammetry and differential pulse voltammetry using modified micro- and mesoporous host electrodes. Two redox peaks were observed when phenosafranine is adsorbed on the surface of microporous materials zeolite-Y and ZSM-5. However, only a single redox peak was observed in the modified electrode with phenosafranine encapsulated into the mesoporous material MCM-41 and when adsorbed on the external surface of silica. The observed redox peaks for the modified electrodes with zeolite-Y and ZSM-5 host are suggested to be primarily due to consecutive two electron processes. The peak separation ΔE and peak potential of phenosafranine adsorbed on zeolite-Y and ZSM-5 were found to be influenced by the pH of the electrolyte solution. The variation of the peak current in the cyclic voltammogram and differential pulse voltammetry with scan rate shows that electrodic processes are controlled by the nature of the surface of the host material. The heterogeneous electron transfer rate constants for phenosafranine adsorbed on to micro- and mesoporous materials were calculated using the Laviron model. Higher rate constant observed for the dye encapsulated into the MCM-41 indicates that the one-dimensional channel of the mesoporous material provides a more facile micro-environment for phenosafranine for the electron transfer reaction as compared to the microporous silicate materials. The stability of the modified electrode surface was investigated by multisweep cyclic voltammetry.

  4. Sensing Properties of Multiwalled Carbon Nanotubes Grown in MW Plasma Torch: Electronic and Electrochemical Behavior, Gas Sensing, Field Emission, IR Absorption

    Directory of Open Access Journals (Sweden)

    Petra Majzlíková

    2015-01-01

    Full Text Available Vertically aligned multi-walled carbon nanotubes (VA-MWCNTs with an average diameter below 80 nm and a thickness of the uniform VA-MWCNT layer of about 16 µm were grown in microwave plasma torch and tested for selected functional properties. IR absorption important for a construction of bolometers was studied by Fourier transform infrared spectroscopy. Basic electrochemical characterization was performed by cyclic voltammetry. Comparing the obtained results with the standard or MWCNT‑modified screen-printed electrodes, the prepared VA-MWCNT electrodes indicated their high potential for the construction of electrochemical sensors. Resistive CNT gas sensor revealed a good sensitivity to ammonia taking into account room temperature operation. Field emission detected from CNTs was suitable for the pressure sensing application based on the measurement of emission current in the diode structure with bending diaphragm. The advantages of microwave plasma torch growth of CNTs, i.e., fast processing and versatility of the process, can be therefore fully exploited for the integration of surface-bound grown CNTs into various sensing structures.

  5. Organic electrochemical transistors

    Science.gov (United States)

    Rivnay, Jonathan; Inal, Sahika; Salleo, Alberto; Owens, Róisín M.; Berggren, Magnus; Malliaras, George G.

    2018-02-01

    Organic electrochemical transistors (OECTs) make effective use of ion injection from an electrolyte to modulate the bulk conductivity of an organic semiconductor channel. The coupling between ionic and electronic charges within the entire volume of the channel endows OECTs with high transconductance compared with that of field-effect transistors, but also limits their response time. The synthetic tunability, facile deposition and biocompatibility of organic materials make OECTs particularly suitable for applications in biological interfacing, printed logic circuitry and neuromorphic devices. In this Review, we discuss the physics and the mechanism of operation of OECTs, focusing on their identifying characteristics. We highlight organic materials that are currently being used in OECTs and survey the history of OECT technology. In addition, form factors, fabrication technologies and applications such as bioelectronics, circuits and memory devices are examined. Finally, we take a critical look at the future of OECT research and development.

  6. Organic electrochemical transistors

    KAUST Repository

    Rivnay, Jonathan

    2018-01-16

    Organic electrochemical transistors (OECTs) make effective use of ion injection from an electrolyte to modulate the bulk conductivity of an organic semiconductor channel. The coupling between ionic and electronic charges within the entire volume of the channel endows OECTs with high transconductance compared with that of field-effect transistors, but also limits their response time. The synthetic tunability, facile deposition and biocompatibility of organic materials make OECTs particularly suitable for applications in biological interfacing, printed logic circuitry and neuromorphic devices. In this Review, we discuss the physics and the mechanism of operation of OECTs, focusing on their identifying characteristics. We highlight organic materials that are currently being used in OECTs and survey the history of OECT technology. In addition, form factors, fabrication technologies and applications such as bioelectronics, circuits and memory devices are examined. Finally, we take a critical look at the future of OECT research and development.

  7. Electrochemical energy generation

    International Nuclear Information System (INIS)

    Kreysa, G.; Juettner, K.

    1993-01-01

    The proceedings encompass 40 conference papers belonging to the following subject areas: Baseline and review papers; electrochemical fuel cells; batteries: Primary and secondary cells; electrochemical, regenerative systems for energy conversion; electrochemical hydrogen generation; electrochemistry for nuclear power plant; electrochemistry for spent nuclear fuel reprocessing; energy efficiency in electrochemical processes. There is an annex listing the authors and titles of the poster session, and compacts of the posters can be obtained from the office of the Gesellschaft Deutscher Chemiker, Abteilung Tagungen. (MM) [de

  8. Interfacial structures - Thermodynamical and experimental studies of the interfacial mass transfer

    International Nuclear Information System (INIS)

    Morel, Jean-Emile

    1972-01-01

    In the first section, we put forward hypotheses concerning the structure of the interfacial regions between two immiscible liquid phases. It appears that the longitudinal structure is comparable with that of a crystallized solid and that the transversal structure is nearest of that of a liquid. In the second section, we present a thermodynamical treatment of the irreversible phenomena in the interfacial region. The equation of evolution of a system consisting of two immiscible liquid phases are deduced. The third part allows an experimental verification of the theoretical relations. We also make clear, in certain cases, the appearance of a great 'interfacial resistance' which slows down the interfacial mass transfer. (author) [fr

  9. Multifunctional Graphene-based Hybrid Nanomaterials for Electrochemical Energy Storage.

    Science.gov (United States)

    Gupta, Sanju

    Intense research in renewable energy is stimulated by global demand of electric energy. Electrochemical energy storage and conversion systems namely, supercapacitors and batteries, represent the most efficient and environmentally benign technologies. Moreover, controlled nanoscaled architectures and surface chemistry of electrochemical electrodes is enabling emergent next-generation efficient devices approaching theoretical limit of energy and power densities. This talk will present our recent activities to advance design, development and deployment of composition, morphology and microstructure controlled two- and three-dimensional graphene-based hybrids architectures. They are chemically and molecularly bridged with carbon nanotubes, conducting polymers, transition metal oxides and mesoproprous silicon wrapped with graphene nanosheets as engineered electrodes for supercapacitor cathodes and battery anodes. They showed significant enhancement in terms of gravimetric specific capacitance, interfacial capacitance, charging-discharging rate and cyclability. We will also present fundamental physical-chemical interfacial processes (ion transfer kinetics and diffusion), imaging electroactive sites, and topography at electrode/electrolyte interface governing underlying electrochemical mechanisms via scanning electrochemical microscopy. KY NSF EPSCoR.

  10. Electrochemical evaluation of avidin-biotin interaction on self-assembled gold electrodes

    International Nuclear Information System (INIS)

    Ding, S.-J.; Chang, B.-W.; Wu, C.-C.; Lai, M.-F.; Chang, H.-C.

    2005-01-01

    The avidin-biotin interaction on 11-mercaptoundecanoic acid self-assembled gold electrodes was investigated by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The interfacial properties of the modified electrodes were evaluated in the presence of the Fe(China) 6 3-/4- couple redox as a probe. A simple equivalent circuit model with a constant phase element was used to interpret the obtained impedance spectra. The results of cyclic voltammetry showed that the voltammetric behavior of the redox probe was influenced by the electrode surface modification. It is evident that the accumulation of treated substances and the binding of biotin to avidin on the electrode surface resulted in the increasing electron-transfer resistance and the decreasing capacitance. The changes in the electron-transfer resistance on the avidin-modified electrodes were more sensitive than that in the capacitance while detecting biotin over the 2-10 μg/mL concentration. The detection amount can be as low as 20 ng/mL based on the electron-transfer resistance that presented the change of 4.3 kΩ without the use of labels. The development of a rapid, facile, and sensitive method for the quantitation of nanogram quantities of biomolecules utilizing EIS may be achieved

  11. Computing optimal interfacial structure of modulated phases

    OpenAIRE

    Xu, Jie; Wang, Chu; Shi, An-Chang; Zhang, Pingwen

    2016-01-01

    We propose a general framework of computing interfacial structures between two modulated phases. Specifically we propose to use a computational box consisting of two half spaces, each occupied by a modulated phase with given position and orientation. The boundary conditions and basis functions are chosen to be commensurate with the bulk structures. It is observed that the ordered nature of modulated structures stabilizes the interface, which enables us to obtain optimal interfacial structures...

  12. Electronic, Spectral, and Electrochemical Properties of (TPPBr(x)())Zn Where TPPBr(x)() Is the Dianion of beta-Brominated-Pyrrole Tetraphenylporphyrin and x Varies from 0 to 8.

    Science.gov (United States)

    D'Souza, Francis; Zandler, Melvin E.; Tagliatesta, Pietro; Ou, Zhongping; Shao, Jianguo; Van Caemelbecke, Eric; Kadish, Karl M.

    1998-09-07

    The electronic, spectral, and electrochemical characterization of (meso-tetraphenylporphyrinato)zinc(II) complexes bearing between 0 and 8 bromo substituents at the beta-pyrrole positions is reported. The investigated compounds are represented as (TPPBr(x)())Zn where TPPBr(x)() is the dianion of brominated 5,10,15,20-tetraphenylporphyrin and x varies between 0 and 8. Each porphyrin undergoes four well-defined one-electron transfer reactions to yield porphyrin pi-cation radicals and dications upon oxidation and porphyrin pi-anion radicals and dianions upon reduction. Half-wave potentials for the first reduction of (TPPBr(x)())Zn can be described by a single linear free energy relationship, and plots of E(1/2) versus the number of Br groups on the complex show a linear correlation with a positive slope of 63 mV per Br group. This is not the case for the other three electron transfer processes of the compounds where plots of E(1/2) versus the number of Br groups show distinctly different linear correlations for derivatives with 0-4 Br groups and those with 4-8 Br groups. The effect of increasing number of Br groups on the spectral and electrochemical properties of the neutral complexes was examined over the whole series of compounds, and these experimental results are compared to results of theoretical calculations by semiempirical molecular orbital AM1 methods using configurational interactions (CI) over the four Gouterman frontier pi-orbitals. The dihedral angle containing the four porphyrin macrocycle ring nitrogens is proposed as a measure of porphyrin ring nonplanarity, and this value increases with increasing number of Br substituents on (TPPBr(x)())Zn. Results of the AM1-CI = 4 calculations indicate that the spectrally determined HOMO-LUMO gap, i.e., the energy corresponding to the low-energy absorption band, varies in a nonlinear fashion with increasing number of Br substituents on the macrocycle and this is due to both the electronic effect of the

  13. Modeling interfacial fracture in Sierra.

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Arthur A.; Ohashi, Yuki; Lu, Wei-Yang; Nelson, Stacy A. C.; Foulk, James W.,; Reedy, Earl David,; Austin, Kevin N.; Margolis, Stephen B.

    2013-09-01

    This report summarizes computational efforts to model interfacial fracture using cohesive zone models in the SIERRA/SolidMechanics (SIERRA/SM) finite element code. Cohesive surface elements were used to model crack initiation and propagation along predefined paths. Mesh convergence was observed with SIERRA/SM for numerous geometries. As the funding for this project came from the Advanced Simulation and Computing Verification and Validation (ASC V&V) focus area, considerable effort was spent performing verification and validation. Code verification was performed to compare code predictions to analytical solutions for simple three-element simulations as well as a higher-fidelity simulation of a double-cantilever beam. Parameter identification was conducted with Dakota using experimental results on asymmetric double-cantilever beam (ADCB) and end-notched-flexure (ENF) experiments conducted under Campaign-6 funding. Discretization convergence studies were also performed with respect to mesh size and time step and an optimization study was completed for mode II delamination using the ENF geometry. Throughout this verification process, numerous SIERRA/SM bugs were found and reported, all of which have been fixed, leading to over a 10-fold increase in convergence rates. Finally, mixed-mode flexure experiments were performed for validation. One of the unexplained issues encountered was material property variability for ostensibly the same composite material. Since the variability is not fully understood, it is difficult to accurately assess uncertainty when performing predictions.

  14. Effect of Atmospheric Ions on Interfacial Water

    Directory of Open Access Journals (Sweden)

    Chien-Chang Kurt Kung

    2014-11-01

    Full Text Available The effect of atmospheric positivity on the electrical properties of interfacial water was explored. Interfacial, or exclusion zone (EZ water was created in the standard way, next to a sheet of Nafion placed horizontally at the bottom of a water-filled chamber. Positive atmospheric ions were created from a high voltage source placed above the chamber. Electrical potential distribution in the interfacial water was measured using microelectrodes. We found that beyond a threshold, the positive ions diminished the magnitude of the negative electrical potential in the interfacial water, sometimes even turning it to positive. Additionally, positive ions produced by an air conditioner were observed to generate similar effects; i.e., the electrical potential shifted in the positive direction but returned to negative when the air conditioner stopped blowing. Sometimes, the effect of the positive ions from the air conditioner was strong enough to destroy the structure of interfacial water by turning the potential decidedly positive. Thus, positive air ions can compromise interfacial water negativity and may explain the known negative impact of positive ions on health.

  15. Monolithic All-Phosphate Solid-State Lithium-Ion Battery with Improved Interfacial Compatibility.

    Science.gov (United States)

    Yu, Shicheng; Mertens, Andreas; Tempel, Hermann; Schierholz, Roland; Kungl, Hans; Eichel, Rüdiger-A

    2018-06-22

    High interfacial resistance between solid electrolyte and electrode of ceramic all-solid-state batteries is a major reason for the reduced performance of these batteries. A solid-state battery using a monolithic all-phosphate concept based on screen printed thick LiTi 2 (PO 4 ) 3 anode and Li 3 V 2 (PO 4 ) 3 cathode composite layers on a densely sintered Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 solid electrolyte has been realized with competitive cycling performance. The choice of materials was primarily based on the (electro-)chemical and mechanical matching of the components instead of solely focusing on high-performance of individual components. Thus, the battery utilized a phosphate backbone in combination with tailored morphology of the electrode materials to ensure good interfacial matching for a durable mechanical stability. Moreover, the operating voltage range of the active materials matches with the intrinsic electrochemical window of the electrolyte which resulted in high electrochemical stability. A highly competitive discharge capacity of 63.5 mAh g -1 at 0.39 C after 500 cycles, corresponding to 84% of the initial discharge capacity, was achieved. The analysis of interfacial charge transfer kinetics confirmed the structural and electrical properties of the electrodes and their interfaces with the electrolyte, as evidenced by the excellent cycling performance of the all-phosphate solid-state battery. These interfaces have been studied via impedance analysis with subsequent distribution of relaxation times analysis. Moreover, the prepared solid-state battery could be processed and operated in air atmosphere owing to the low oxygen sensitivity of the phosphate materials. The analysis of electrolyte/electrode interfaces after cycling demonstrates that the interfaces remained stable during cycling.

  16. Interfacial Charge Transfer States in Condensed Phase Systems

    Science.gov (United States)

    Vandewal, Koen

    2016-05-01

    Intermolecular charge transfer (CT) states at the interface between electron-donating (D) and electron-accepting (A) materials in organic thin films are characterized by absorption and emission bands within the optical gap of the interfacing materials. CT states efficiently generate charge carriers for some D-A combinations, and others show high fluorescence quantum efficiencies. These properties are exploited in organic solar cells, photodetectors, and light-emitting diodes. This review summarizes experimental and theoretical work on the electronic structure and interfacial energy landscape at condensed matter D-A interfaces. Recent findings on photogeneration and recombination of free charge carriers via CT states are discussed, and relations between CT state properties and optoelectronic device parameters are clarified.

  17. Electrochemical impedance spectroscopy of oxidized porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Mula, Guido, E-mail: guido.mula@unica.it [Dipartimento di Fisica, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, S.P. 8 km 0.700, 09042 Cagliari (Italy); Tiddia, Maria V. [Dipartimento di Fisica, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, S.P. 8 km 0.700, 09042 Cagliari (Italy); Ruffilli, Roberta [Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova (Italy); Falqui, Andrea [Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova (Italy); Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, S.P. 8 km 0.700, 09042 Cagliari (Italy); Palmas, Simonetta; Mascia, Michele [Dipartimento di Ingegneria Meccanica Chimica e dei Materiali, Università degli Studi di Cagliari, Piazza d' Armi, 09126 Cagliari (Italy)

    2014-04-01

    We present a study of the electrochemical oxidation process of porous silicon. We analyze the effect of the layer thickness (1.25–22 μm) and of the applied current density (1.1–11.1 mA/cm{sup 2}, values calculated with reference to the external samples surface) on the oxidation process by comparing the galvanostatic electrochemical impedance spectroscopy (EIS) measurements and the optical specular reflectivity of the samples. The results of EIS were interpreted using an equivalent circuit to separate the contribution of different sample parts. A different behavior of the electrochemical oxidation process has been found for thin and thick samples: whereas for thin samples the oxidation process is univocally related to current density and thickness, for thicker samples this is no more true. Measurements by Energy Dispersive Spectroscopy using a Scanning Electron Microscopy confirmed that the inhomogeneity of the electrochemical oxidation process is increased by higher thicknesses and higher currents. A possible explanation is proposed to justify the different behavior of thin and thick samples during the electrochemical process. - Highlights: • A multidisciplinary approach on porous Si electrochemical oxidation is proposed. • Electrochemical, optical, and structural characterizations are used. • Layer thickness and oxidation current effects are shown. • An explanation of the observed behavior is proposed.

  18. Interfacial area and interfacial transfer in two-phase systems. DOE final report

    Energy Technology Data Exchange (ETDEWEB)

    Ishii, Mamoru; Hibiki, T.; Revankar, S.T.; Kim, S.; Le Corre, J.M.

    2002-07-01

    In the two-fluid model, the field equations are expressed by the six conservation equations consisting of mass, momentum and energy equations for each phase. The existence of the interfacial transfer terms is one of the most important characteristics of the two-fluid model formulation. The interfacial transfer terms are strongly related to the interfacial area concentration and to the local transfer mechanisms such as the degree of turbulence near interfaces. This study focuses on the development of a closure relation for the interfacial area concentration. A brief summary of several problems of the current closure relation for the interfacial area concentration and a new concept to overcome the problem are given.

  19. Synthesis and characterization of Nitrogen-doped &CaCO3-decorated reduced graphene oxide nanocomposite for electrochemical supercapacitors

    International Nuclear Information System (INIS)

    Ghouri, Zafar Khan; Barakat, Nasser A.M.; Alam, Al-Mahmnur; Alsoufi, Mohammad S.; Bawazeer, Tahani M.; Mohamed, Ahmed F.; Kim, Hak Yong

    2015-01-01

    Alone, it is expected, and also was experimentally proved, that calcium carbonate and reduced graphene oxide do have negligible specific capacitance due to the chemical composition of both materials. However, synthesis of CaCO 3 on the form of very thin sporadic layer attaching rGO results in dramatic increase in the specific capacitance of the obtained composite due to formation of the electrochemical double layer at the interfacial area. Moreover, the specific capacitance could be further enhanced by nitrogen-doping of the rGO sheets. Typically, a novel N-rGO/CaCO 3 composite has been successfully synthesized by heat reflux strategy with graphite powder, calcium acetate and urea as raw materials.The composite was characterized by X-Ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), field-emission scanning electron microscopy (FESEM), coupled with rapid EDAX (energy dispersive analysis of X-Ray) and X-ray photoelectron spectroscopy. The utilized physiochemical characterizations indicated that the final prepared composite can be demonstrated as N-doped rGO decorated by very thin discrete layer from calcium carbonate. Supercapacitive performance of N-rGO/CaCO 3 composite has been investigated by cyclic voltammetry (CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy in 1 M KOH solution. The results reveal that the N-rGO/CaCO 3 composite delivers a large specific capacitance of as high as 214 Fg −1 and 188 Fg −1 at 5 mV s −1 and 1.0 Ag −1 , according to CV and galvanostatic charge-discharge tests, respectively; while the CaCO 3 , rGO, rGO/CaCO 3 , N-rGO based electrodes has a poor electrochemical performance at the same conditions. Moreover, the as-prepared composite exhibited excellent long cycle stability with about 88.7% specific capacitance retained after 10,000 cycles.

  20. Effects of oxygen plasma treatment on domestic aramid fiber III reinforced bismaleimide composite interfacial properties

    Science.gov (United States)

    Shi, Chen; Wang, Jing; Chen, Ping; Feng, Jiayue; Cui, Jinyuan; Yang, Faze

    2017-12-01

    Domestic Aramid Fiber III (DAF III) was modified by oxygen plasma treatment. The fiber surface characteristics was observed by Scanning Electron Microscopy. The results showed that oxygen plasma treatment changed surface morphologies. The effects of oxygen plasma treatment on DAF III reinforced bismaleimides (BMI) composite bending and interfacial properties were investigated, respectively. The ILSS value increased from 49.3 MPa to 56.0 MPa (by 13.5%) after oxygen plasma treatment. The bending strength changed a little. Furthermore, the composite rupture mode changed from interfacial rupture to fiber or resin bulk rupture.

  1. The Interfacial Transition Zone in Alkali-Activated Slag Mortars

    Directory of Open Access Journals (Sweden)

    Rackel eSan Nicolas

    2015-12-01

    Full Text Available The interfacial transition zone (ITZ is known to strongly influence the mechanical and transport properties of mortars and concretes. This paper studies the ITZ between siliceous (quartz aggregates and alkali activated slag binders in the context of mortar specimens. Backscattered electron images (BSE generated in an environmental scanning electron microscope (ESEM are used to identify unreacted binder components, reaction products and porosity in the zone surrounding aggregate particles, by composition and density contrast. X-ray mapping is used to exclude the regions corresponding to the aggregates from the BSE image of the ITZ, thus enabling analysis of only the binder phases, which are segmented into binary images by grey level discrimination. A distinct yet dense ITZ region is present in the alkali-activated slag mortars, containing a reduced content of unreacted slag particles compared to the bulk binder. The elemental analysis of this region shows that it contains a (C,N-A-S-H gel which seems to have a higher content of Na (potentially deposited through desiccation of the pore solution and a lower content of Ca than the bulk inner and outer products forming in the main binding region. These differences are potentially important in terms of long-term concrete performance, as the absence of a highly porous interfacial transition zone region is expected to provide a positive influence on the mechanical and transport properties of alkali-activated slag concretes.

  2. Bio-electrochemical remediation of real field petroleum sludge as an electron donor with simultaneous power generation facilitates biotransformation of PAH: effect of substrate concentration.

    Science.gov (United States)

    Chandrasekhar, K; Venkata Mohan, S

    2012-04-01

    Remediation of real-field petroleum sludge was studied under self-induced electrogenic microenvironment with the function of variable organic loads (OLs) in bio-electrochemical treatment (BET) systems. Operation under various OLs documented marked influence on both electrogenic activity and remediation efficiency. Both total petroleum hydrocarbons (TPH) and its aromatic fraction documented higher removal with OL4 operation followed by OL3, OL2, OL1 and control. Self-induced biopotential and associated multiple bio-electrocatalytic reactions during BET operation facilitated biotransformation of higher ring aromatics (5-6) to lower ring aromatic (2-3) compounds. Asphaltenes and NSO fractions showed negligible removal during BET operation. Higher electrogenic activity was recorded at OL1 (343mV; 53.11mW/m(2), 100Ω) compared to other three OLs operation. Bioaugmentation to anodic microflora with anaerobic culture documented enhanced electrogenic activity at OL4 operation. Voltammetric profiles, Tafel analysis and VFA generation were in agreement with the observed power generation and degradation efficiency. Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. Comparison of crude oil interfacial behavior

    Energy Technology Data Exchange (ETDEWEB)

    Beetge, J.H.; Panchev, N. [Champion Technologies Inc., Fresno, TX (United States)

    2008-07-01

    The bulk properties of crude oil are used to predict its behaviour with regards to treatment, transport and processing. Surface active components, such as asphaltenes, are often used to study or explain critical interfacial behaviour of crude oil. This study investigated the differences and similarities in the interfacial behaviour of the collective surface active component in various crude oils from different sources. The properties of interfaces between crude oil and water were compared using a Teclis drop shape tensiometer. A portion of a crude oil sample was diluted in toluene and contacted with water in a rising drop configuration. Dynamic surface tension and interfacial rheology was examined as a function of time from the early stages of interface formation. Sinusoidal oscillation of the drop volume allowed for the evaluation of visco-elastic behaviour of the crude oil/water interface as it developed with time. The Gibbs elastic modulus, as well as its elastic and viscose components were calculated from the drop shape. The interfacial behaviour was expressed in terms of concentration, oscillation frequency and interface age. It was concluded that knowledge of crude oil interfacial character could be of value in the treatment, transport and processing of crude oils because the its behaviour may play a significant role in crude oil production and processing.

  4. Electrochemical Grafting of Graphene Nano Platelets with Aryl Diazonium Salts.

    Science.gov (United States)

    Qiu, Zhipeng; Yu, Jun; Yan, Peng; Wang, Zhijie; Wan, Qijin; Yang, Nianjun

    2016-10-26

    To vary interfacial properties, electrochemical grafting of graphene nano platelets (GNP) with 3,5-dichlorophenyl diazonium tetrafluoroborate (aryl-Cl) and 4-nitrobenzene diazonium tetrafluoroborate (aryl-NO 2 ) was realized in a potentiodynamic mode. The covalently bonded aryl layers on GNP were characterized using atomic force microscopy and X-ray photoelectron spectroscopy. Electrochemical conversion of aryl-NO 2 into aryl-NH 2 was conducted. The voltammetric and impedance behavior of negatively and positively charged redox probes (Fe(CN) 6 3-/4- and Ru(NH 3 ) 6 2+/3+ ) on three kinds of aryl layers grafted on GNP reveal that their interfacial properties are determined by the charge states of redox probes and reactive terminal groups (-Cl, -NO 2 , -NH 2 ) in aryl layers. On aryl-Cl and aryl-NH 2 garted GNP, selective and sensitive monitoring of positively charged lead ions as well as negatively charged nitrite and sulfite ions was achieved, respectively. Such a grafting procedure is thus a perfect way to design and control interfacial properties of graphene.

  5. Electrochemical Applications in Metal Bioleaching.

    Science.gov (United States)

    Tanne, Christoph Kurt; Schippers, Axel

    2017-12-10

    Biohydrometallurgy comprises the recovery of metals by biologically catalyzed metal dissolution from solids in an aqueous solution. The application of this kind of bioprocessing is described as "biomining," referring to either bioleaching or biooxidation of sulfide metal ores. Acidophilic iron- and sulfur-oxidizing microorganisms are the key to successful biomining. However, minerals such as primary copper sulfides are recalcitrant to dissolution, which is probably due to their semiconductivity or passivation effects, resulting in low reaction rates. Thus, further improvements of the bioleaching process are recommendable. Mineral sulfide dissolution is based on redox reactions and can be accomplished by electrochemical technologies. The impact of electrochemistry on biohydrometallurgy affects processing as well as analytics. Electroanalysis is still the most widely used electrochemical application in mineralogical research. Electrochemical processing can contribute to bioleaching in two ways. The first approach is the coupling of a mineral sulfide to a galvanic partner or electrocatalyst (spontaneous electron transfer). This approach requires only low energy consumption and takes place without technical installations by the addition of higher redox potential minerals (mostly pyrite), carbonic material, or electrocatalytic ions (mostly silver ions). Consequently, the processed mineral (often chalcopyrite) is preferentially dissolved. The second approach is the application of electrolytic bioreactors (controlled electron transfer). The electrochemical regulation of electrolyte properties by such reactors has found most consideration. It implies the regulation of ferrous and ferric ion ratios, which further results in optimized solution redox potential, less passivation effects, and promotion of microbial activity. However, many questions remain open and it is recommended that reactor and electrode designs are improved, with the aim of finding options for simplified

  6. Electronic, Structural, and Electrochemical Properties of LiNixCuyMn2-x-yO4 (0 < x < 0.5, 0 < y < 0.5) High-Voltage Spinel Materials

    International Nuclear Information System (INIS)

    Yang, Ming-Che; Xu, Bo; Cheng, Ju-Hsiang; Pan, Chun-Jern; Hwang, Bing-Joe; Meng, Ying S.

    2011-01-01

    First principles computation is carried out for investigating the electronic, structural, and electrochemical properties of LiM 1/2 Mn 3/2 O 4 (M = Ti, V, Cr, Fe, Co, Ni, and Cu). The computation results suggest that doping with Co or Cu can potentially lower Li diffusion barrier as compared to Ni doping. Our experimental research has focused on LiNi x Cu y Mn 2-x-y O 4 (0 x Cu y Mn 2-x-6 O 4 (0 0.25 Cu 0.25 Mn 1.50 O 4 , the proposed explanation of the voltage profile by the first principles computation was proven, a second plateau at 4.2 V originates from the oxidation of Cu 2+ to Cu 3+ , and the plateau at 4.95 V may originate from extra electrons provided by oxygen ions. Although the reversible discharge capacity decreases with increasing Cu amount, optimized composition such as LiCu 0.25 Ni 0.25 Mn 1.5 O 4 exhibits high capacities at high rates.

  7. Chemical sensitive interfacial free volume studies of nanophase Al-rich alloys

    International Nuclear Information System (INIS)

    Lechner, W.; Puff, W.; Wuerschum, R.; Wilde, G.

    2006-01-01

    Full text: Al-based nanocrystalline alloys have attracted substantial interest due to their outstanding mechanical properties. These alloys can be obtained by crystallization of melt-spun amorphous precursors or by grain refinement upon repeated cold-rolling of elemental layers. For both synthesis routes, the nanocrystallization process is sensitively affected by interfacial chemistry and free volumes. In order to contribute to an atomistic understanding of the interfacial structure and processes during nanocrystallization, the present work deals with studies of interfacial free volumes by means of positron-annihilation-spectroscopy. In addition to positron lifetime spectroscopy which yields information on the size of free volumes, coincident Doppler broadening of the positron-electron annihilation photons is applied as novel technique for studying the chemistry of interfaces in nanophase materials on an atomistic scale. Al-rich alloys of the above mentioned synthesis routes were studied in this work. (author)

  8. Static gas-liquid interfacial direct current discharge plasmas using ionic liquid cathode

    International Nuclear Information System (INIS)

    Kaneko, T.; Baba, K.; Hatakeyama, R.

    2009-01-01

    Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we have succeeded in creating the static and stable gas (plasmas)-liquid (ionic liquids) interfacial field using a direct current discharge under a low gas pressure condition. It is clarified that the ionic liquid works as a nonmetal liquid electrode, and furthermore, a secondary electron emission coefficient of the ionic liquid is larger than that of conventional metal electrodes. The plasma potential structure of the gas-liquid interfacial region, and resultant interactions between the plasma and the ionic liquid are revealed by changing a polarity of the electrode in the ionic liquid. By utilizing the ionic liquid as a cathode electrode, the positive ions in the plasma region are found to be irradiated to the ionic liquid. This ion irradiation causes physical and chemical reactions at the gas-liquid interfacial region without the vaporization of the ionic liquid.

  9. Effects of roughness on interfacial performances of silica glass and non-polar polyarylacetylene resin composites

    International Nuclear Information System (INIS)

    Jiang, Z.X.; Huang, Y.D.; Liu, L.; Long, J.

    2007-01-01

    The influence of roughness on interfacial performances of silica glass/polyarylacetylene resin composites was investigated. In order to obtain different roughness, silica glass surface was abraded by different grits of abrasives and its topography was observed by scanning electron microscopy and atomic force microscopy. At the same time, the failure mechanisms of composites were analyzed by fracture morphologies and the interfacial adhesion was evaluated by shear strength test. The results indicated that shear strength of silica glass/polyarylacetylene resin composites firstly increased and then decreased with the surface roughness of silica glass increased. The best surface roughness range of silica glass was 40-60 nm. The main mechanism for the improvement of the interfacial adhesion was physical interlocking at the interface

  10. Photo-electrochemical properties of graphene wrapped hierarchically branched nanostructures obtained through hydrothermally transformed TiO2 nanotubes

    Science.gov (United States)

    Rambabu, Y.; Jaiswal, Manu; Roy, Somnath C.

    2017-10-01

    Hierarchically structured nanomaterials play an important role in both light absorption and separation of photo-generated charges. In the present study, hierarchically branched TiO2 nanostructures (HB-MLNTs) are obtained through hydrothermal transformation of electrochemically anodized TiO2 multi-leg nanotubes (MLNT) arrays. Photo-anodes based on HB-MLNTs demonstrated 5 fold increase in applied bias to photo-conversion efficiency (%ABPE) over that of TiO2 MLNTs without branches. Further, such nanostructures are wrapped with reduced graphene oxide (rGO) films to enhance the charge separation, which resulted in ∼6.5 times enhancement in %ABPE over that of bare MLNTs. We estimated charge transport (η tr) and charge transfer (η ct) efficiencies by analyzing the photo-current data. The ultra-fine nano branches grown on the MLNTs are effective in increasing light absorption through multiple scattering and improving charge transport/transfer efficiencies by enlarging semiconductor/electrolyte interface area. The charge transfer resistance, interfacial capacitance and electron decay time have been estimated through electrochemical impedance measurements which correlate with the results obtained from photocurrent measurements.

  11. Quasi 2D Mesoporous Carbon Microbelts Derived from Fullerene Crystals as an Electrode Material for Electrochemical Supercapacitors.

    Science.gov (United States)

    Tang, Qin; Bairi, Partha; Shrestha, Rekha Goswami; Hill, Jonathan P; Ariga, Katsuhiko; Zeng, Haibo; Ji, Qingmin; Shrestha, Lok Kumar

    2017-12-27

    Fullerene C 60 microbelts were fabricated using the liquid-liquid interfacial precipitation method and converted into quasi 2D mesoporous carbon microbelts by heat treatment at elevated temperatures of 900 and 2000 °C. The carbon microbelts obtained by heat treatment of fullerene C 60 microbelts at 900 °C showed excellent electrochemical supercapacitive performance, exhibiting high specific capacitances ca. 360 F g -1 (at 5 mV s -1 ) and 290 F g -1 (at 1 A g -1 ) because of the enhanced surface area and the robust mesoporous framework structure. Additionally, the heat-treated carbon microbelt showed good rate performance, retaining 49% of capacitance at a high scan rate of 10 A g -1 . The carbon belts exhibit super cyclic stability. Capacity loss was not observed even after 10 000 charge/discharge cycles. These results demonstrate that the quasi 2D mesoporous carbon microbelts derived from a π-electron-rich carbon source, fullerene C 60 crystals, could be used as a new candidate material for electrochemical supercapacitor applications.

  12. Pursuing Polymer Dielectric Interfacial Effect in Organic Transistors for Photosensing Performance Optimization.

    Science.gov (United States)

    Wu, Xiaohan; Chu, Yingli; Liu, Rui; Katz, Howard E; Huang, Jia

    2017-12-01

    Polymer dielectrics in organic field-effect transistors (OFETs) are essential to provide the devices with overall flexibility, stretchability, and printability and simultaneously introduce charge interaction on the interface with organic semiconductors (OSCs). The interfacial effect between various polymer dielectrics and OSCs significantly and intricately influences device performance. However, understanding of this effect is limited because the interface is buried and the interfacial charge interaction is difficult to stimulate and characterize. Here, this challenge is overcome by utilizing illumination to stimulate the interfacial effect in various OFETs and to characterize the responses of the effect by measuring photoinduced changes of the OFETs performances. This systemic investigation reveals the mechanism of the intricate interfacial effect in detail, and mathematically explains how the photosensitive OFETs characteristics are determined by parameters including polar group of the polymer dielectric and the OSC side chain. By utilizing this mechanism, performance of organic electronics can be precisely controlled and optimized. OFETs with strong interfacial effect can also show a signal additivity caused by repeated light pulses, which is applicable for photostimulated synapse emulator. Therefore, this work enlightens a detailed understanding on the interface effect and provides novel strategies for optimizing OFET photosensory performances.

  13. Release of surfactant cargo from interfacially-active halloysite clay nanotubes for oil spill remediation.

    Science.gov (United States)

    Owoseni, Olasehinde; Nyankson, Emmanuel; Zhang, Yueheng; Adams, Samantha J; He, Jibao; McPherson, Gary L; Bose, Arijit; Gupta, Ram B; John, Vijay T

    2014-11-18

    Naturally occurring halloysite clay nanotubes are effective in stabilizing oil-in-water emulsions and can serve as interfacially-active vehicles for delivering oil spill treating agents. Halloysite nanotubes adsorb at the oil-water interface and stabilize oil-in-water emulsions that are stable for months. Cryo-scanning electron microscopy (Cryo-SEM) imaging of the oil-in-water emulsions shows that these nanotubes assemble in a side-on orientation at the oil-water interface and form networks on the interface through end-to-end linkages. For application in the treatment of marine oil spills, halloysite nanotubes were successfully loaded with surfactants and utilized as an interfacially-active vehicle for the delivery of surfactant cargo. The adsorption of surfactant molecules at the interface serves to lower the interfacial tension while the adsorption of particles provides a steric barrier to drop coalescence. Pendant drop tensiometry was used to characterize the dynamic reduction in interfacial tension resulting from the release of dioctyl sulfosuccinate sodium salt (DOSS) from halloysite nanotubes. At appropriate surfactant compositions and loadings in halloysite nanotubes, the crude oil-saline water interfacial tension is effectively lowered to levels appropriate for the dispersion of oil. This work indicates a novel concept of integrating particle stabilization of emulsions together with the release of chemical surfactants from the particles for the development of an alternative, cheaper, and environmentally-benign technology for oil spill remediation.

  14. Direct observation of interfacial Au atoms on TiO₂ in three dimensions.

    Science.gov (United States)

    Gao, Wenpei; Sivaramakrishnan, Shankar; Wen, Jianguo; Zuo, Jian-Min

    2015-04-08

    Interfacial atoms, which result from interactions between the metal nanoparticles and support, have a large impact on the physical and chemical properties of nanoparticles. However, they are difficult to observe; the lack of knowledge has been a major obstacle toward unraveling their role in chemical transformations. Here we report conclusive evidence of interfacial Au atoms formed on the rutile (TiO2) (110) surfaces by activation using high-temperature (∼500 °C) annealing in air. Three-dimensional imaging was performed using depth-sectioning enabled by aberration-corrected scanning transmission electron microscopy. Results show that the interface between Au nanocrystals and TiO2 (110) surfaces consists of a single atomic layer with Au atoms embedded inside Ti-O. The number of interfacial Au atoms is estimated from ∼1-8 in an interfacial atomic column. Direct impact of interfacial Au atoms is observed on an enhanced Au-TiO2 interaction and the reduction of surface TiO2; both are critical to Au catalysis.

  15. Molecular dynamics simulation of thin film interfacial strength dependency on lattice mismatch

    International Nuclear Information System (INIS)

    Yang, Zhou; Lian, Jie; Wang, Junlan

    2013-01-01

    Laser-induced thin film spallation experiments have been previously developed to characterize the intrinsic interfacial strength of thin films. In order to gain insights of atomic level thin film debonding processes and the interfacial strength dependence on film/substrate lattice structures, in this study, molecular dynamics simulations of thin film interfacial failure under laser-induced stress waves were performed. Various loading amplitudes and pulse durations were employed to identify the optimum simulation condition. Stress propagation as a function of time was revealed in conjunction with the interface structures. Parametric studies confirmed that while the interfacial strength between a thin film and a substrate does not depend on the film thickness and the duration of the laser pulse, a thicker film and a shorter duration do provide advantage to effectively load the interface to failure. With the optimized simulation condition, further studies were focused on bulk Au/Au bi-crystals with mismatched orientations, and Ni/Al, Cu/Al, Cu/Ag and Cu/Au bi-crystals with mismatched lattices. The interfacial strength was found to decrease with increasing orientation mismatch and lattice mismatch but more significantly dominated by the bonding elements' atomic structure and valence electron occupancy. - Highlights: • Molecular dynamics simulation was done on stress wave induced thin film spallation. • Atomic structure was found to be a primary strength determining factor. • Lattice mismatch was found to be a secondary strength determining factor

  16. Interfacial fracture of dentin adhesively bonded to quartz-fiber reinforced composite

    International Nuclear Information System (INIS)

    Melo, Renata M.; Rahbar, Nima; Soboyejo, Wole

    2011-01-01

    The paper presents the results of an experimental study of interfacial failure in a multilayered structure consisting of a dentin/resin cement/quartz-fiber reinforced composite (FRC). Slices of dentin close to the pulp chamber were sandwiched by two half-circle discs made of a quartz-fiber reinforced composite, bonded with bonding agent (All-bond 2, BISCO, Schaumburg) and resin cement (Duo-link, BISCO, Schaumburg) to make Brazil-nut sandwich specimens for interfacial toughness testing. Interfacial fracture toughness (strain energy release rate, G) was measured as a function of mode mixity by changing loading angles from 0 deg. to 15 deg. The interfacial fracture surfaces were then examined using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX) to determine the failure modes when loading angles changed. A computational model was also developed to calculate the driving forces, stress intensity factors and mode mixities. Interfacial toughness increased from ∼ 1.5 to 3.2 J/m 2 when the loading angle increases from ∼ 0 to 15 deg. The hybridized dentin/cement interface appeared to be tougher than the resin cement/quartz-fiber reinforced epoxy. The Brazil-nut sandwich specimen was a suitable method to investigate the mechanical integrity of dentin/cement/FRC interfaces.

  17. Electrochemical Impedance Analysis of a PEDOT:PSS-Based Textile Energy Storage Device

    Directory of Open Access Journals (Sweden)

    Ida Nuramdhani

    2017-12-01

    Full Text Available A textile-based energy storage device with electroactive PEDOT:PSS (poly(3,4-ethylenedioxythiophene/poly(4-styrenesulfonate polymer functioning as a solid-state polyelectrolyte has been developed. The device was fabricated on textile fabric with two plies of stainless-steel electroconductive yarn as the electrodes. In this study, cyclic voltammetry and electrochemical impedance analysis were used to investigate ionic and electronic activities in the bulk of PEDOT:PSS and at its interfaces with stainless steel yarn electrodes. The complex behavior of ionic and electronic origins was observed in the interfacial region between the conductive polymer and the electrodes. The migration and diffusion of the ions involved were confirmed by the presence of the Warburg element with a phase shift of 45° (n = 0.5. Two different equivalent circuit models were found by simulating the model with the experimental results: (QR(QR(QR for uncharged and (QR(QR(Q(RW for charged samples. The analyses also showed that the further the distance between electrodes, the lower the capacitance of the cell. The distribution of polymer on the cell surface also played important role to change the capacitance of the device. The results of this work may lead to a better understanding of the mechanism and how to improve the performance of the device.

  18. Microfluidic ultralow interfacial tensiometry with magnetic particles.

    Science.gov (United States)

    Tsai, Scott S H; Wexler, Jason S; Wan, Jiandi; Stone, Howard A

    2013-01-07

    We describe a technique that measures ultralow interfacial tensions using paramagnetic spheres in a co-flow microfluidic device designed with a magnetic section. Our method involves tuning the distance between the co-flowing interface and the magnet's center, and observing the behavior of the spheres as they approach the liquid-liquid interface-the particles either pass through or are trapped by the interface. Using threshold values of the magnet-to-interface distance, we make estimates of the two-fluid interfacial tension. We demonstrate the effectiveness of this technique for measuring very low interfacial tensions, O(10(-6)-10(-5)) N m(-1), by testing solutions of different surfactant concentrations, and we show that our results are comparable with measurements made using a spinning drop tensiometer.

  19. Interfacial charge distributions in carbon-supported palladium catalysts

    DEFF Research Database (Denmark)

    Rao, Radhika G.; Blume, Raoul; Hansen, Thomas Willum

    2017-01-01

    Controlling the charge transfer between a semiconducting catalyst carrier and the supported transition metal active phase represents an elite strategy for fine turning the electronic structure of the catalytic centers, hence their activity and selectivity. These phenomena have been theoretically...... and experimentally elucidated for oxide supports but remain poorly understood for carbons due to their complex nanoscale structure. Here, we combine advanced spectroscopy and microscopy on model Pd/C samples to decouple the electronic and surface chemistry effects on catalytic performance. Our investigations reveal...... treatments can be used to tune the interfacial charge distribution, hereby providing a strategy to rationally design carbon-supported catalysts.Control over charge transfer in carbon-supported metal nanoparticles is essential for designing new catalysts. Here, the authors show that thermal treatments...

  20. Interfacial spectroscopic characterization of organic/ferromagnet hetero-junction of 3,4,9,10-perylene-teracarboxylic dianhydride-based organic spin valves

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Jhen-Yong; Ou Yang, Kui-Hon; Li, Kai-Shin [Department of Physics, National Taiwan University, 10617 Taipei, Taiwan (China); Wang, Bo-Yao [Department of Physics, National Taiwan University, 10617 Taipei, Taiwan (China); Department of Physics, National Changhua University of Education, Changhua 500, Taiwan (China); Shiu, Hung-Wei; Chen, Chia-Hao; Chan, Yuet-Loy; Wei, Der-Hsin; Chang, Fan-Hsiu; Lin, Hong-Ji [National Synchrotron Radiation Research Center, 30076 Hsinchu, Taiwan (China); Chiang, Wen-Chung, E-mail: wchiang@faculty.pccu.edu.tw [Department of Physics, Chinese Culture University, 11114 Taipei, Taiwan (China); Lin, Minn-Tsong, E-mail: mtlin@phys.ntu.edu.tw [Department of Physics, National Taiwan University, 10617 Taipei, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, 10617 Taipei, Taiwan (China)

    2014-02-24

    We report interfacial characterization of 3,4,9,10-perylene-teracarboxylic dianhydride (PTCDA)-based organic spin valves (OSV) dusted with a thin layer of partially oxidized alumina at the organic semiconductor (OSC)/ferromagnet (FM) interfaces. Up to 13.5% magnetoresistance is achieved at room temperature. X-ray photoelectron spectroscopy measurements reveal interfacial electronic interaction between PTCDA and FM while the application of a thin alumina layer at the PTCDA/FM interfaces prevents the electronic hybridization and effectively preserves the spin injection into the OSC spacer. This finding demonstrates the critical effect of interfacial structure on magnetotransport behavior in OSV.

  1. Evolution of interfacial toughness of a thermal barrier system with a Pt-diffused {gamma}/{gamma}' bond coat

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, X.; Liu, J. [School of Materials, University of Manchester, Manchester M1 7HS (United Kingdom); Rickerby, D.S.; Jones, R.J. [Rolls-Royce Plc., PO Box 31, Derby DE24 8BJ (United Kingdom); Xiao, P., E-mail: ping.xiao@manchester.ac.uk [School of Materials, University of Manchester, Manchester M1 7HS (United Kingdom)

    2011-09-15

    A strain-to-fail method has been employed to examine the interfacial adhesion of electron beam-physical vapor deposited thermal barrier coatings (TBCs) with a Pt-diffused {gamma}/{gamma}' bond coat. Based on a previously established model, the estimated interfacial toughness decreases with oxidation time of TBCs. Furthermore, the interfacial toughness value varies considerably with the use of different Young's moduli in the model. It is believed that the modulus obtained from beam bending represents the columnar structure of the TBC. In this case, the mode I interfacial toughness was found to vary from 10 J m{sup -2} for as-deposited TBCs to 0.79 J m{sup -2} for the 60 h oxidized TBCs. The degradation of adhesion could be attributed to the defect formation and impurity segregation at the TGO/bond coat interface, which is associated with the diffusion of Pt.

  2. EFFECT OF INTERFACIAL ADHESION ON CRYSTALLIZATION AND MECHANICAL PROPERTIES OF POLY (ETHYLENE TEREPHTHALATE)/GLASS BEAD COMPOSITES

    Institute of Scientific and Technical Information of China (English)

    OU Yuchun; YU Zhongzhen; ZHU Jin; LI Ge; ZHU Shanguang

    1996-01-01

    The interfacial adhesion between poly (ethylene terephthalate) (PET) and glass bead was investigated by scanning electron microscope and parallel-plate rheometer. Effect of interfacial adhesion on the crystallization and mechanical properties of PET/glass bead composites was also studied by differential scanning calorimeter and mechanical testers.The results obtained indicate that the glass bead has a heterogeneous nucleation effect on the PET crystallization. Although better interfacial adhesion is advantageous to the increase of the tensile strength of the composite, yet it is unfavorable to the crystallization of PET. It should be pointed out that the crystallization rate of filled PET is always higher than that of pure PET, regardless of the state of interfacial adhesion.

  3. Electrochemical stability of subnanometer Pt clusters

    DEFF Research Database (Denmark)

    Quinson, Jonathan; Röefzaad, Melanie; Deiana, Davide

    2018-01-01

    In the present work, the degradation of size-selected Pt nanoclusters is studied under electrochemical conditions. This model catalyst mimics carbon supported Pt nanoclusters and nanoparticles typically employed in proton exchange membrane fuel cells (PEMFCs). Insight into the early stage...... of degradation is given by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and confirmed by transmission electron microscopy (TEM). In contrast to common assumptions, it is demonstrated that even extremely small Pt clusters exhibit a remarkable stability under electrochemical...... - is observed. In light of the findings reported, developing highly-dispersed subnanometer Pt clusters as catalyst for PEMFCs is a realistic approach provided the operation conditions are suitably adjusted. Furthermore, mitigation strategies to improve the stability of few-atoms catalyst under electrochemical...

  4. Influence of the substituents on the electronic and electrochemical properties of a new square-planar nickel-bis(quinoxaline-6,7-dithiolate) system: synthesis, spectroscopy, electrochemistry, crystallography, and theoretical investigation.

    Science.gov (United States)

    Bolligarla, Ramababu; Reddy, Samala Nagaprasad; Durgaprasad, Gummadi; Sreenivasulu, Vudagandla; Das, Samar K

    2013-01-07

    We describe the synthesis, crystal structures, electronic absorption spectra, and electrochemistry of a series of square-planar nickel-bis(quinoxaline-6,7-dithiolate) complexes with the general formula [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)], where X = H (1a), Ph (2a), Cl (3), and Me (4). The solution and solid-state electronic absorption spectral behavior and electrochemical properties of these compounds are strongly dependent on the electron donating/accepting nature of the substituent X, attached to the quinoxaline-6,7-dithiolate ring in the system [Bu(4)N](2)[Ni(X(2)6,7-qdt)(2)]. Particularly, the charge transfer (CT) transition bands observed in the visible region are greatly affected by the electronic nature of the substituent. A possible explanation for this influence of the substituents on electronic absorption and electrochemistry is described based on highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) gaps, which is further supported by ground-state electronic structure calculations. In addition to this, the observed CT bands in all the complexes are sensitive to the solvent polarity. Interestingly, compounds 1a, 2a, 3, and 4 undergo reversible oxidation at very low oxidation potentials appearing at E(1/2) = +0.12 V, 0.033 V, 0.18 V, and 0.044 V vs Ag/AgCl, respectively, in MeOH solutions, corresponding to the respective couples [Ni(X(2)6,7-qdt)(2)](-)/[Ni(X(2)6,7-qdt)(2)](2-). Compounds 1a, 3, and 4 have been characterized unambiguously by single crystal X-ray structural analysis; compound 2a could not be characterized by single crystal X-ray structure determination because of the poor quality of the concerned crystals. Thus, we have synthesized the tetraphenyl phosphonium salt of the complex anion of 2a, [PPh(4)](2)[Ni(Ph(2)6,7-qdt)(2)]·3DMF (2b) for its structural characterization.

  5. Electrochemical and Electron Paramagnetic Resonance Study of the Mechanism of Oxidation of Phenazine-di-N-oxide in the Presence of Isopropyl alcohol at Glassy Carbon and Single-Walled Carbon Nanotube Electrodes

    International Nuclear Information System (INIS)

    Kulakovskaya, S.I.; Kulikov, A.V.; Sviridova, L.N.; Stenina, E.V.

    2014-01-01

    Graphical abstract: - Highlights: • The mechanism of oxidation of phenazine-di-N-oxide in the presence of isopropyl alcohol was studied. • The results are explained in terms of the E 1 C 1 E 2 C 2 mechanism of the two-stage electrode process. • The total two-electron catalytic oxidation of i-PrOH in the complex with the phenazine-di-N-oxide radical cation was assumed to occur. - Abstract: The mechanism of oxidation of phenazine-di-N-oxide in the presence of isopropyl alcohol was studied by cyclic voltammetry at glassy carbon (GC) and single-walled carbon nanotubes (SWCNT) electrodes in 0.1 M LiClO 4 solutions in acetonitrile. The adsorption of phenazine-di-N-oxide at SWCNT electrode in 0.1 M LiClO 4 solution in acetonitrile was investigated by measurement of the dependence of the differential double layer capacitance of the electrode C on potential E. The effect of isopropyl alcohol on the shape of cyclic voltammograms (CVs) of phenazine-di-N-oxide and the intensity of Electron Paramagnetic Resonance (EPR) signal of its radical cation was investigated. The catalytic currents were recorded at the oxidation of phenazine-di-N-oxide at SWCNT and GC electrodes in the presence of isopropyl alcohol. The results were explained in terms of the E 1 C 1 E 2 C 2 mechanism of two-stage electrode process characterized by catalytic current recorded at the second electrode stage. The overall two-electron catalytic oxidation of isopropyl alcohol in complex with the phenazine-di-N-oxide radical cation was assumed to occur. It was shown that SWCNT electrodes can be used in the electrocatalytic oxidation of organic compounds in the presence of electrochemically generated phenazine-di-N-oxide radical cation

  6. Electrochemical study on PVDF-HFP/silylated AI2O3-coated PE separators using the electron beam irradiation for lithium secondary battery

    International Nuclear Information System (INIS)

    Sohn, Joon Yong; Shin, Jun Hwa; Nho, Young Chang

    2010-01-01

    PVDF-HFP (binder)/silylated alumina (inorganic particle)-coated PE (polyethylene)separators were with various compositions of binder and inorganic particle were prepared by a dip-coating process with humidity control (R.H. 25% and 50%) using electron beam irradiation. The morphology of the coated PVDF-HFP/AI 2 O 3 layer with various compositions of PVDF-HFP and AI 2 O 3 , and humidity condition was found to be an important factor in determining ionic conductivity of the prepared separators. The PVDF-HFP/AI 2 O 3 (5/5)-coated PE separator prepared at R.H. 50% followed by electron beam irradiation at 200 kGy was applied for lithium-ion polymer battery and cell test results showed improved high-rate discharge performance and better cyclic stability compared to the cells with the bare PE and the PVDF-HFP-coated PE separators

  7. Probing electronic and vibrational properties at the electrochemical interface using SFG spectroscopy: Methanol electro-oxidation on Pt(1 1 0)

    Science.gov (United States)

    Vidal, F.; Busson, B.; Tadjeddine, A.

    2005-02-01

    We report the study of methanol electro-oxidation on Pt(1 1 0) using infrared-visible sum-frequency generation (SFG) vibrational spectroscopy. The use of this technique enables to probe the vibrational and electronic properties of the interface simultaneously in situ. We have investigated the vibrational properties of the interface in the CO ads internal stretch spectral region (1700-2150 cm -1) over a wide range of potentials. The analysis of the evolution of the C-O stretch line shape, which is related to the interference between the vibrational and electronic parts of the non-linear response, with the potential allows us to show that the onset of bulk methanol oxidation corresponds to the transition from a negatively to a positively charged surface.

  8. Electronics

    Science.gov (United States)

    2001-01-01

    International Acer Incorporated, Hsin Chu, Taiwan Aerospace Industrial Development Corporation, Taichung, Taiwan American Institute of Taiwan, Taipei, Taiwan...Singapore and Malaysia .5 - 4 - The largest market for semiconductor products is the high technology consumer electronics industry that consumes up...Singapore, and Malaysia . A new semiconductor facility costs around $3 billion to build and takes about two years to become operational

  9. Interfacial Energy and Fine Defect Structures for Incoherent Films

    OpenAIRE

    Cermelli, Paolo; Gurtin, Morton E.; Leoni, Giovanni

    1999-01-01

    This note summarizes recent results in which modern techniques of the calculus of variations are used to obtain qualitative features of film-substrate interfaces for a broad class of interfacial energies. In particular, we show that the existence of a critical thickness for incoherency and the formation of interfacial dislocations depend strongly on the convexity and smoothness of the interfacial energy function.

  10. Development of interfacial area transport equation

    International Nuclear Information System (INIS)

    Kim, Seung Jin; Ishii, Mamoru; Kelly, Joseph

    2005-01-01

    The interfacial area transport equation dynamically models the changes in interfacial structures along the flow field by mechanistically modeling the creation and destruction of dispersed phase. Hence, when employed in the numerical thermal-hydraulic system analysis codes, it eliminates artificial bifurcations stemming from the use of the static flow regime transition criteria. Accounting for the substantial differences in the transport mechanism for various sizes of bubbles, the transport equation is formulated for two characteristic groups of bubbles. The group 1 equation describes the transport of small-dispersed bubbles, whereas the group 2 equation describes the transport of large cap, slug or churn-turbulent bubbles. To evaluate the feasibility and reliability of interfacial area transport equation available at present, it is benchmarked by an extensive database established in various two-phase flow configurations spanning from bubbly to churn-turbulent flow regimes. The geometrical effect in interfacial area transport is examined by the data acquired in vertical air-water two-phase flow through round pipes of various sizes and a confined flow duct, and by those acquired in vertical co-current downward air-water two-phase flow through round pipes of two different sizes

  11. Gelation and interfacial behaviour of vegetable proteins

    NARCIS (Netherlands)

    Vliet, T. van; Martin, A.H.; Bos, M.A.

    2002-01-01

    Recent studies on gelation and interfacial properties of vegetable protiens are reviewed. Attention is focused on legume proteins, mainly soy proteins, and on wheat proteins. The rheological properteis of vegetable protein gels as a function of heating time or temperature is discussed as well as the

  12. Gelation and interfacial behaviour of vegetable proteins

    NARCIS (Netherlands)

    Vliet, van T.; Martin, A.H.; Bos, M.A.

    2002-01-01

    Recent studies on gelation and interfacial properties of vegetable proteins are reviewed. Attention is focused on legume proteins, mainly soy proteins, and on wheat proteins. The rheological properties of vegetable protein gels as a function of heating time or temperature is discussed as well as the

  13. Exchange bias mediated by interfacial nanoparticles (invited)

    Energy Technology Data Exchange (ETDEWEB)

    Berkowitz, A. E., E-mail: aberk@ucsd.edu [Department of Physics, University of California, San Diego, La Jolla, California 92093 (United States); Center for Magnetic Recording Research, University of California, California 92093 (United States); Sinha, S. K. [Department of Physics, University of California, San Diego, La Jolla, California 92093 (United States); Fullerton, E. E. [Center for Magnetic Recording Research, University of California, California 92093 (United States); Smith, D. J. [Department of Physics, Arizona State University, Tempe, Arizona 85287 (United States)

    2015-05-07

    The objective of this study on the iconic exchange-bias bilayer Permalloy/CoO has been to identify those elements of the interfacial microstructure and accompanying magnetic properties that are responsible for the exchange-bias and hysteretic properties of this bilayer. Both epitaxial and polycrystalline samples were examined. X-ray and neutron reflectometry established that there existed an interfacial region, of width ∼1 nm, whose magnetic properties differed from those of Py or CoO. A model was developed for the interfacial microstructure that predicts all the relevant properties of this system; namely; the temperature and Permalloy thickness dependence of the exchange-bias, H{sub EX}, and coercivity, H{sub C}; the much smaller measured values of H{sub EX} from what was nominally expected; the different behavior of H{sub EX} and H{sub C} in epitaxial and polycrystalline bilayers. A surprising result is that the exchange-bias does not involve direct exchange-coupling between Permalloy and CoO, but rather is mediated by CoFe{sub 2}O{sub 4} nanoparticles in the interfacial region.

  14. The electrostatic interaction between interfacial colloidal particles

    Science.gov (United States)

    Hurd, A. J.

    1985-11-01

    The electrostatic interaction between charged, colloidal particles trapped at an air-water interface is considered using linearised Poisson-Boltzmann results for point particles. In addition to the expected screened-Coulomb contribution, which decays exponentially, an algebraic dipole-dipole interaction occurs that may account for long-range interactions in interfacial colloidal systems.

  15. Influence of interfacial layer on contact resistance

    NARCIS (Netherlands)

    Roy, D.; In 't Zand, M.A.A.; Delhounge, R.; Klootwijk, J.H.; Wolters, Robertus A.M.

    2008-01-01

    The contact resistance between two materials is dependent on the intrinsic properties of the materials in contact and the presence and properties of an interfacial layer at the contact. This article presents the difference in contact resistance measurements with and without the presence of a process

  16. Electrochemical solar energy conversion

    International Nuclear Information System (INIS)

    Gerischer, H.

    1991-01-01

    The principles of solar energy conversion in photoelectrochemical cells are briefly reviewed. Cells for the generation of electric power and for energy storage in form of electrochemical energy are described. These systems are compared with solid state photovoltaic devices, and the inherent difficulties for the operation of the electrochemical systems are analyzed. (author). 28 refs, 10 figs

  17. The interfacial capacitance of an oxidised polycrystalline gold electrode in an aqueous HClO4 electrolyte

    International Nuclear Information System (INIS)

    Grdeń, M.

    2013-01-01

    The interfacial capacitance of a polycrystalline gold electrode electrochemically oxidised in an aqueous 0.1 M HClO 4 electrolyte has been investigated by means of the electrochemical impedance spectroscopy. From 1.3 to 3 monolayers of Au atoms were oxidised under constant potential conditions and for various oxidation times. The capacitance of the oxidised layers was analysed as a function of the electrode potential and the extent of the surface oxidation. It was found that the interfacial capacitance decreases upon surface oxidation. The components of the interfacial capacitance of the oxidised layer: the double layer capacitance and the capacitance of the oxidised layer; have been separated. The capacitance of the double layer of the oxidised surface was found to be comparable to the capacitance measured for the metallic surface. - Highlights: • The impedance spectra for thin layers of Au oxides/hydroxides were acquired. • Separate determination of the double layer and the oxide capacitances of oxidised Au • The double layer capacitances of oxidised and non-oxidised Au surfaces are comparable

  18. Electrochemical thermodynamic measurement system

    Science.gov (United States)

    Reynier, Yvan [Meylan, FR; Yazami, Rachid [Los Angeles, CA; Fultz, Brent T [Pasadena, CA

    2009-09-29

    The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.

  19. Modulating the electronic properties of asymmetric push–pull and symmetric Zn(II)-diarylporphyrinates with para substituted phenylethynyl moieties in 5,15 meso positions: A combined electrochemical and spectroscopic investigation

    International Nuclear Information System (INIS)

    Mussini, Patrizia Romana; Orbelli Biroli, Alessio; Tessore, Francesca; Pizzotti, Maddalena; Biaggi, Cinzia; Di Carlo, Gabriele; Lobello, Maria Grazia; De Angelis, Filippo

    2012-01-01

    Graphical abstract: - Abstract: Push–pull Zn(II)-porphyrinates have recently shown attracting performances as light harvesting systems in dye-sensitized solar cells (DSSCs). To fully exploit their intrinsically high efficiency it is important to finely tune their HOMO and LUMO levels, which can be achieved by proper choice of the push and pull substituents. Of course such target-oriented molecular design requires the availability of reliable relationships between molecular structure and electronic properties; therefore we have carried out a combined electrochemical, spectroscopic and computational investigation on a wide, systematic range of Zn(II)-porphyrinates 5,15 meso substituted with phenylethynyl linkers, including a first symmetric series carrying on the opposite terminals the same substituent (-N(CH 3 ) 2 , -OCH 3 , -COOCH 3 , -COOH, -NO 2 ); and a second push–pull one, with the terminal positions carrying one donor and one acceptor group belonging to the series above. Moreover, two suitably modified porphyrins allowed evaluation of the effects of (i) the presence or absence of the phenyl group in the linker between the porphyrin core and the acceptor group, and (ii) the effect of perfluorination on the same phenyl group. A rationalization scheme is proposed encompassing the whole porphyrin set, affording inter alia interesting clues on the different localization of the redox centres and effective conjugation between the porphyrin core and the side chains as a function of the molecular design.

  20. Electrochemical reduction of trinitrotoluene on core-shell tin-carbon electrodes

    International Nuclear Information System (INIS)

    Grigoriants, Irena; Markovsky, Boris; Persky, Rachel; Perelshtein, Ilana; Gedanken, Aharon; Aurbach, Doron; Filanovsky, Boris; Bourenko, Tatiana; Felner, Israel

    2008-01-01

    In this work, we studied the electrochemical process of 2,4,6-trinitrotoluene (TNT) reduction on a new type of electrodes based on a core-shell tin-carbon Sn(C) structure. The Sn(C) composite was prepared from the precursor tetramethyl-tin Sn(CH 3 ) 4 , and the product contained a core of submicron-sized tin particles uniformly enveloped with carbon shells. Cyclic voltammograms of Sn(C) electrodes in aqueous sodium chloride solutions containing TNT show three well-pronounced reduction waves in the potential range of -0.50 to -0.80 V (vs. an Ag/AgCl/Cl - reference electrode) that correspond to the multistep process of TNT reduction. Electrodes containing Sn(C) particles annealed at 800 deg. C under argon develop higher voltammetric currents of TNT reduction (comparing to the as-prepared tin-carbon material) due to stabilization of the carbon shell. It is suggested that the reduction of TNT on core-shell tin-carbon electrodes is an electrochemically irreversible process. A partial oxidation of the TNT reduction products occurred at around -0.20 V. The electrochemical response of TNT reduction shows that it is not controlled by the diffusion of the active species to/from the electrodes but rather by interfacial charge transfer and possible adsorption phenomena. The tin-carbon electrodes demonstrate significantly stable behavior for TNT reduction in NaCl solutions and provide sufficient reproducibility with no surface fouling through prolonged voltammetric cycling. It is presumed that tin nanoparticles, which constitute the core, are electrochemically inactive towards TNT reduction, but Sn or SnO 2 formed on the electrodes during TNT reduction may participate in this reaction as catalysts or carbon-modifying agents. The nitro-groups of TNT can be reduced irreversibly (via two possible paths) by three six-electron transfers, to 2,4,6-triaminotoluene, as follows from mass-spectrometric studies. The tin-carbon electrodes described herein may serve as amperometric sensors

  1. Monte Carlo studies on the interfacial properties and interfacial structures of ternary symmetric blends with gradient copolymers.

    Science.gov (United States)

    Sun, Dachuan; Guo, Hongxia

    2012-08-09

    Using Monte Carlo simulation methods, the effects of the comonomer sequence distribution on the interfacial properties (including interfacial tension, interfacial thickness, saturated interfacial area per copolymer, and bending modulus) and interfacial structures (including chain conformations and comonomer distributions of the simulated copolymers at the interfaces) of a ternary symmetric blend containing two immiscible homopolymers and one gradient copolymer are investigated. We find that copolymers with a larger composition gradient width have a broader comonomer distribution along the interface normal, and hence more pronouncedly enlarge the interfacial thickness and reduce the interfacial tension. Furthermore, the counteraction effect, which arises from the tendency of heterogeneous segments in gradient copolymers to phase separate and enter their miscible phases to reduce the local enthalpy, decreases the stretching of copolymers along the interface normal direction. As a result, copolymers with a larger width of gradient composition can occupy a larger interfacial area and form softer monolayers at saturation and are more efficient in facilitating the formation of bicontinuous microemulsions. Additionally, chain length ratio, segregation strength, and interactions between homopolymers and copolymers can alter the interfacial character of gradient copolymers. There exists a strong coupling between the comonomer sequence distribution, chain conformation, and interfacial properties. Especially, bending modulus is mainly determined by the complicated interplay of interfacial copolymer density and interfacial chain conformation.

  2. pH in atomic scale simulations of electrochemical interfaces

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Chan, Karen; Ahmed, Rizwan

    2013-01-01

    Electrochemical reaction rates can strongly depend on pH, and there is increasing interest in electrocatalysis in alkaline solution. To date, no method has been devised to address pH in atomic scale simulations. We present a simple method to determine the atomic structure of the metal......|solution interface at a given pH and electrode potential. Using Pt(111)|water as an example, we show the effect of pH on the interfacial structure, and discuss its impact on reaction energies and barriers. This method paves the way for ab initio studies of pH effects on the structure and electrocatalytic activity...

  3. Quantifying Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction.

    Science.gov (United States)

    Ryu, Jaeyune; Wuttig, Anna; Surendranath, Yogesh

    2018-05-15

    We quantify changes in the interfacial pH local to the electrochemical double layer during electrocatalysis, using a concurrent non-faradaic probe reaction. In the absence of electrocatalysis, nanostructured Pt/C surfaces mediate the reaction of H2 with cis-2-butene-1,4-diol to form a mixture of 1,4-butanediol and n-butanol with a selectivity that is linearly dependent on the bulk solution pH. We show that kinetic branching occurs from a common surface-bound intermediate, ensuring that this probe reaction is uniquely sensitive to the interfacial pH within molecular length scales of the surface. We use the pH-dependent selectivity of this reaction to track changes in interfacial pH during concurrent hydrogen oxidation electrocatalysis and find that the local pH can vary dramatically, > 3 units, relative to the bulk value even at modest current densities in well-buffered electrolytes. This work highlights the key role that interfacial pH variation plays in modulating inner-sphere electrocatalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Infrared spectroscopy of model electrochemical interfaces in ultrahigh vacuum: some implications for ionic and chemisorbate solvation at electrode surfaces

    Science.gov (United States)

    Villegas, Ignacio; Kizhakevariam, Naushad; Weaver, Michael J.

    1995-07-01

    The utility of infrared reflection-absorption spectroscopy (IRAS) for examining structure and bonding for model electrochemical interfaces in ultrahigh vacuum (UHV) is illustrated, focusing specifically on the solvation of cations and chemisorbed carbon monoxide on Pt(111). These systems were chosen partly in view of the availability of IRAS data (albeit limited to chemisorbate vibrations) for the corresponding in-situ metal-solution interfaces, enabling direct spectral comparisons to be made with the "UHV electrochemical model" systems. Kelvin probe measurements of the metal-UHV surface potential changes (ΔΦ) attending alterations in the interfacial composition are also described: these provide the required link to the in-situ electrode potentials as well as yielding additional insight into surface solvation. Variations in the negative electronic charge density and, correspondingly, in the cation surface concentration (thereby mimicking charge-induced alterations in the electrode potential below the potential of zero charge) are achieved by potassium atom dosage onto Pt(111). Of the solvents selected for discussion here — deuterated water, methanol, and acetonitrile — the first two exhibit readily detectable vibrational bands which provide information on the ionic solvation structure. Progressively dosing these solvents onto Pt(111) in the presence of low potassium coverages yields marked alterations in the solvent vibrational bands which can be understood in terms of sequential cation solvation. Comparison between these spectra for methanol with analogous data for sequential methanol solvation of gas-phase alkali cations enables the influence of the interfacial environment to be assessed. The effects of solvating chemisorbed CO are illustrated for acetonitrile; the markedly larger shifts in CO frequencies and binding sites for dilute CO adlayers can be accounted for in terms of short-range coadsorbate interactions in addition to longer-range Stark effects

  5. Electrochemically deposited conducting polymers for reliable biomedical interfacing materials: Formulation, mechanical characterization, and failure analysis

    Science.gov (United States)

    Qu, Jing

    Conjugated polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT) are of interest for a variety of applications including interfaces between electronic biomedical devices and living tissue. These polymers provide an improved interface compared to metal and semiconducting electrodes because of their ionic conductivity, relatively lower stiffness, and ability to incorporate biological molecules. Even though the signal transfer and biocompatibility of conjugated polymers are superior compared as the biointerfacing materials, the durability has been the weakest part for the long-term applications. Even though some efforts have been made to improve the durability of conjugated polymers, little quantitative information of the improved cohesion, adhesion and durability has been reported. In this thesis, the methods of improving the durability of conjugated polymer films, especially PEDOT, were investigated, including alternating the processing methods and components in synthesis. The 7-month in vivo testing showed that the durability of PEDOT films still needed to be improved. As a coating for biosignal transfer, the cohesion, adhesion and electrochemical stability of PEDOT are vital to determine the long-term performance. Not much information hd been developed around the cohesion and adhesion. A thin film cracking method was developed to measure the stiffness, strength and the interfacial shear strength (adhesion) of electrochemically deposited PEDOT. The estimated Young’s modulus of the PEDOT films was 2.6 ± 1.4 GPa, and the strain to failure was around 2%. The tensile strength was measured to be 56 ± 27 MPa. The effectiveness of crosslinker and adhesion promoter was demonstrated by this method. It was shown that 5 mole% addition of a tri-functional EDOT crosslinker (EPh) increased the tensile strength of the films to 283 ± 67 MPa, while the strain to failure remained about the same (2%). With the modification of EDOT-acid to the surface of stainless steel

  6. Electrochemical Behavior and Hydrophobic Properties of CrN and CrNiN Coatings in Simulated Proton Exchange Membrane Fuel Cell Environment

    Directory of Open Access Journals (Sweden)

    JIN Jie

    2016-10-01

    Full Text Available The CrN and CrNiN coatings were prepared on the surface of 304 stainless steel by closed field unbalanced magnetron sputtering.X ray diffraction and field emission scanning electron microscopy were used to characterize the structure and morphology of the coatings.The electrochemical corrosion properties under the simulated proton exchange membrane fuel cell(PEMFC environment, interfacial contact resistance and hydrophobic properties of the two kinds of different coatings were investigated by electrochemical methods,contact resistance test and hydrophobic test,respectively.The results indicate that CrN coating mainly consists of CrN and Cr2N phase,CrN and Cr2N phases in the CrNiN coating are less compared to CrN film, and Ni exist as element in CrNiN coating; dynamic polarization tests show the coating is of better corrosion resistance,whereas the corrosion resistance of CrNiN coating is worse than that of CrN coating,constant potential polarization test shows the corrosion current density of CrN and CrNiN coatings are equivalent; CrN and CrNiN coatings significantly reduce the interfacial contact resistance of the 304 stainless steel,among which CrN coating has the smallest contact resistance; and CrNiN coating which has better hydrophobicity than that of CrN coating is more beneficial for the water management in proton exchange membrane fuel cell.

  7. Synthesis of core/shell ZnO/ZnSe nanowires using novel low cost two-steps electrochemical deposition technique

    Energy Technology Data Exchange (ETDEWEB)

    Ghoul, M., E-mail: ghoulmed2009@yahoo.fr [Laboratoire Photovoltaïque, Centre de Recherches et des Technologies de l' Energie Technopole BorjCedria, Bp 95, Hammammlif 2050 (Tunisia); Braiek, Z. [Laboratoire Photovoltaïque, Centre de Recherches et des Technologies de l' Energie Technopole BorjCedria, Bp 95, Hammammlif 2050 (Tunisia); Brayek, A. [Laboratoire Photovoltaïque, Centre de Recherches et des Technologies de l' Energie Technopole BorjCedria, Bp 95, Hammammlif 2050 (Tunisia); ITODYS, Université Paris Diderot, Sorbonne Paris Cité, CNRS UMR – 7086, 75205 Paris (France); Ben Assaker, I.; Khalifa, N.; Ben Naceur, J.; Souissi, A.; Lamouchi, A. [Laboratoire Photovoltaïque, Centre de Recherches et des Technologies de l' Energie Technopole BorjCedria, Bp 95, Hammammlif 2050 (Tunisia); Ammar, S. [ITODYS, Université Paris Diderot, Sorbonne Paris Cité, CNRS UMR – 7086, 75205 Paris (France); Chtourou, R. [Laboratoire Photovoltaïque, Centre de Recherches et des Technologies de l' Energie Technopole BorjCedria, Bp 95, Hammammlif 2050 (Tunisia)

    2015-10-25

    This work highlights the original use of a two-step electrochemical deposition protocol to grow ZnO/ZnSe core/shell nanowires on a Sn-doped In{sub 2}O{sub 3} (ITO)/glass substrate. The good alignment of the nanowires is verified by the scanning electron microscopy characterization technique in addition to the surface roughness after the ZnSe electrodeposition on the ZnO nanowires lateral facets. The X-ray diffraction patterns and Raman spectra allow estimating that ZnO has grown along the wurtzite (W) structure c-axis. The presence of the type-II interfacial transition between the valence band of ZnSe and the conduction band of ZnO was confirmed by UV–visible spectroscopy. It was proved that the absorbed energy of the developed nanostructures is extended to the near infrared which is well recommended for the photovoltaic applications. - Graphical abstract: Fabrication of the ZnO–ZnSe core–shell nanowires through a solution based all-electrochemical approach, and their application as photoanodes in photoelectrochemical water splitting cells. - Highlights: • Deposition of ZnO/ZnSe nanowires by two steps electrodeposition method. • The morphology studies show the formation of ZnO/ZnSe core/Shell nanowires. • XRD and Raman spectroscopy confirm the presence of the wurtzite ZnO and blende ZnSe junction. • Optical properties demonstrate the evidence type-II interfacial transition between the two semiconductors.

  8. Interfacial Properties of CZTS Thin Film Solar Cell

    Directory of Open Access Journals (Sweden)

    N. Muhunthan

    2014-01-01

    Full Text Available Cu-deficient CZTS (copper zinc tin sulfide thin films were grown on soda lime as well as molybdenum coated soda lime glass by reactive cosputtering. Polycrystalline CZTS film with kesterite structure was produced by annealing it at 500°C in Ar atmosphere. These films were characterized for compositional, structural, surface morphological, optical, and transport properties using energy dispersive X-ray analysis, glancing incidence X-ray diffraction, Raman spectroscopy, scanning electron microscopy, atomic force microscopy, UV-Vis spectroscopy, and Hall effect measurement. A CZTS solar cell device having conversion efficiency of ~0.11% has been made by depositing CdS, ZnO, ITO, and Al layers over the CZTS thin film deposited on Mo coated soda lime glass. The series resistance of the device was very high. The interfacial properties of device were characterized by cross-sectional SEM and cross-sectional HRTEM.

  9. Amino-Acid-Induced Preferential Orientation of Perovskite Crystals for Enhancing Interfacial Charge Transfer and Photovoltaic Performance.

    Science.gov (United States)

    Shih, Yen-Chen; Lan, Yu-Bing; Li, Chia-Shuo; Hsieh, Hsiao-Chi; Wang, Leeyih; Wu, Chih-I; Lin, King-Fu

    2017-06-01

    Interfacial engineering of perovskite solar cells (PSCs) is attracting intensive attention owing to the charge transfer efficiency at an interface, which greatly influences the photovoltaic performance. This study demonstrates the modification of a TiO 2 electron-transporting layer with various amino acids, which affects charge transfer efficiency at the TiO 2 /CH 3 NH 3 PbI 3 interface in PSC, among which the l-alanine-modified cell exhibits the best power conversion efficiency with 30% enhancement. This study also shows that the (110) plane of perovskite crystallites tends to align in the direction perpendicular to the amino-acid-modified TiO 2 as observed in grazing-incidence wide-angle X-ray scattering of thin CH 3 NH 3 PbI 3 perovskite film. Electrochemical impedance spectroscopy reveals less charge transfer resistance at the TiO 2 /CH 3 NH 3 PbI 3 interface after being modified with amino acids, which is also supported by the lower intensity of steady-state photoluminescence (PL) and the reduced PL lifetime of perovskite. In addition, based on the PL measurement with excitation from different side of the sample, amino-acid-modified samples show less surface trapping effect compared to the sample without modification, which may also facilitate charge transfer efficiency at the interface. The results suggest that appropriate orientation of perovskite crystallites at the interface and trap-passivation are the niche for better photovoltaic performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Nanodevices in nature: Electrochemical aspects

    International Nuclear Information System (INIS)

    Volkov, Alexander G.; Volkova-Gugeshashvili, Maya I.; Brown-McGauley, Courtney L.; Osei, Albert J.

    2007-01-01

    Electrochemical multielectron reactions in photosynthesis and respiration are evaluated by thermodynamic and kinetic analysis. Kharkats and Volkov [Yu.I. Kharkats, A.G. Volkov, Biochim. Biophys. Acta 891 (1987) 56] were the first to present proof that cytochrome c oxidase reduces molecular oxygen by synchronous multielectron mechanism without O 2 - intermediate formation. After this pioneering observation, it became clear that the first step of oxygen reduction is two-electron concerted process. The energy for the H + -pump of cytochrome oxidase is liberated when the third and fourth electrons are added in the last two steps of water formation independent of the reaction pathway. Electrochemical principles govern many biological properties of organisms, such as the generation of electric fields, and the conduction of fast excitation waves. These properties are supported by the function of a variety of natural nanodevices. Ionic channels, as natural nanodevices, control the plasma membrane potential, and the movement of ions across membranes; thereby, regulating various biological functions. Some voltage-gated ion channels work as plasma membrane nanopotentiostats. In plants, excitation waves are possible mechanisms for intercellular and intracellular communication in response to environmental changes. The role of electrified nanointerface of the plasma membrane in signal transduction is discussed as well

  11. Electrochemical force microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kalinin, Sergei V.; Jesse, Stephen; Collins, Liam F.; Rodriguez, Brian J.

    2017-01-10

    A system and method for electrochemical force microscopy are provided. The system and method are based on a multidimensional detection scheme that is sensitive to forces experienced by a biased electrode in a solution. The multidimensional approach allows separation of fast processes, such as double layer charging, and charge relaxation, and slow processes, such as diffusion and faradaic reactions, as well as capturing the bias dependence of the response. The time-resolved and bias measurements can also allow probing both linear (small bias range) and non-linear (large bias range) electrochemical regimes and potentially the de-convolution of charge dynamics and diffusion processes from steric effects and electrochemical reactivity.

  12. Electrochemical impedance spectroscopy characterization of LiFePO4 cathode material with carboxymethylcellulose and poly-3,4-ethylendioxythiophene/polystyrene sulfonate

    International Nuclear Information System (INIS)

    Eliseeva, S.N.; Apraksin, R.V.; Tolstopjatova, E.G.; Kondratiev, V.V.

    2017-01-01

    Highlights: • New composition of perspective LiFePO 4 /PEDOT:PSS/CMC cathode material are explored. • Conducting polymer binder markedly reduce an interfacial resistance. • High rate performance due to enhanced ionic and electronic conductivity. • Comparison of kinetic parameters obtained from fitting of EIS data was performed. - Abstract: Novel cathode material compositions based on lithium iron phosphate (LFP) were prepared using conducting polymer dispersion poly-3,4-ethylenedioxythiopene/polystyrene sulfonate (PEDOT:PSS) and water-based carboxymethylcellulose (РЎРњРЎ) as a binder solely and in mixture PEDOT:PSS/РЎРњРЎ. The electrochemical properties of materials in lithium-ion batteries were investigated by galvanostatic charge-discharge curves and by electrochemical impedance spectroscopy and the results were compared with conventional PVDF-bound material. Our best materials consisting of 92 wt% of C-LiFePO 4 , 4 wt% of carbon black and 4 wt% of conducting polymer binder exhibited excellent rate capability with discharge capacity 148 mAh g −1 (at 0.2C, normalized by the electrode mass), 143 mAh g −1 at 1C and 128 mAh g −1 at 5C as well as good cycling stability at 1C (less than 1% decay after 100 cycles). Impedance spectra of batteries with different compositions were measured and analyzed. Comparison of kinetic parameters obtained for different electrodes revealed main factors responsible for significant improvement of electrochemical performance of LFP-based cathode materials modified with conducting polymer in comparison with conventional electrode. The transition from conventional PVDF-bound LFP-based cathode composition to modified by conducting polymer PEDOT:PSS/CMC was found very effective. The electrode with optimal composition showed substantial decrease of interfacial charge transfer resistance for 30 times, and decrease of Warburg diffusion resistance. The mechanism of positive influence of

  13. Electrical and Electrochemical Properties of Conducting Polymers

    Directory of Open Access Journals (Sweden)

    Thanh-Hai Le

    2017-04-01

    Full Text Available Conducting polymers (CPs have received much attention in both fundamental and practical studies because they have electrical and electrochemical properties similar to those of both traditional semiconductors and metals. CPs possess excellent characteristics such as mild synthesis and processing conditions, chemical and structural diversity, tunable conductivity, and structural flexibility. Advances in nanotechnology have allowed the fabrication of versatile CP nanomaterials with improved performance for various applications including electronics, optoelectronics, sensors, and energy devices. The aim of this review is to explore the conductivity mechanisms and electrical and electrochemical properties of CPs and to discuss the factors that significantly affect these properties. The size and morphology of the materials are also discussed as key parameters that affect their major properties. Finally, the latest trends in research on electrochemical capacitors and sensors are introduced through an in-depth discussion of the most remarkable studies reported since 2003.

  14. Interfacial reactions in lithium batteries

    International Nuclear Information System (INIS)

    Chen, Zonghai; Amine, Khalil; Amine, Rachid; Ma, Zi-Feng

    2017-01-01

    The lithium-ion battery was first commercially introduced by Sony Corporation in 1991 using LiCoO 2 as the cathode material and mesocarbon microbeads (MCMBs) as the anode material. After continuous research and development for 25 years, lithium-ion batteries have been the dominant energy storage device for modern portable electronics, as well as for emerging applications for electric vehicles and smart grids. It is clear that the success of lithium-ion technologies is rooted to the existence of a solid electrolyte interphase (SEI) that kinetically suppresses parasitic reactions between the lithiated graphitic anodes and the carbonate-based non-aqueous electrolytes. Recently, major attention has been paid to the importance of a similar passivation/protection layer on the surface of cathode materials, aiming for a rational design of high-energy-density lithium-ion batteries with extended cycle/calendar life. In this article, the physical model of the SEI, as well as recent research efforts to understand the nature and role of the SEI are summarized, and future perspectives on this important research field will also be presented. (topical review)

  15. Interfacial reactions in lithium batteries

    Science.gov (United States)

    Chen, Zonghai; Amine, Rachid; Ma, Zi-Feng; Amine, Khalil

    2017-08-01

    The lithium-ion battery was first commercially introduced by Sony Corporation in 1991 using LiCoO2 as the cathode material and mesocarbon microbeads (MCMBs) as the anode material. After continuous research and development for 25 years, lithium-ion batteries have been the dominant energy storage device for modern portable electronics, as well as for emerging applications for electric vehicles and smart grids. It is clear that the success of lithium-ion technologies is rooted to the existence of a solid electrolyte interphase (SEI) that kinetically suppresses parasitic reactions between the lithiated graphitic anodes and the carbonate-based non-aqueous electrolytes. Recently, major attention has been paid to the importance of a similar passivation/protection layer on the surface of cathode materials, aiming for a rational design of high-energy-density lithium-ion batteries with extended cycle/calendar life. In this article, the physical model of the SEI, as well as recent research efforts to understand the nature and role of the SEI are summarized, and future perspectives on this important research field will also be presented.

  16. Evidence for Interfacial Halogen Bonding.

    Science.gov (United States)

    Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

    2016-05-10

    A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Indium tin oxide with zwitterionic interfacial design for biosensing applications in complex matrices

    Science.gov (United States)

    Darwish, Nadia T.; Alias, Yatimah; Khor, Sook Mei

    2015-01-01

    Biosensing interfaces consisting of linker molecules (COOH or NH2) and charged, antifouling moieties ((sbnd SO3- and N+(Me)3) for biosensing applications were prepared for the first time by the in situ deposition of mixtures of aryl diazonium cations on indium tin oxide (ITO) electrodes. A linker molecule is required for the attachment of biorecognition molecules (e.g., antibodies, enzymes, DNA chains, and aptamers) close to the transducer surface. The attached molecules improve the biosensing sensitivity and also provide a short response time for analyte detection. Thus, the incorporation of a linker and antifouling molecules is an important interfacial design for both affinity and enzymatic biosensors. The reductive adsorption behavior and electrochemical measurement were studied for (1) an individual compound and (2) a mixture of antifouling zwitterionic molecules together with linker molecules [combination 1: 4-sulfophenyl (SP), 4-trimethylammoniophenyl (TMAP), and 1,4-phenylenediamine (PPD); combination 2: 4-sulfophenyl (SP), 4-trimethylammoniophenyl (TMAP), and 4-aminobenzoic acid (PABA)] of aryl diazonium cations grafted onto an ITO electrode. The mixture ratios of SP:TMAP:PPD and SP:TMAP:PABA that provided the greatest resistance to non-specific protein adsorptions of bovine serum albumin labeled with fluorescein isothiocyanate (BSA-FITC) and cytochrome c labeled with rhodamine B isothiocyanate (RBITC-Cyt c) were determined by confocal laser scanning microscopy (CLSM). For the surface antifouling study, we used 2-[2-(2-methoxyethoxy) ethoxy]acetic acid (OEG) as a standard control because of its prominent antifouling properties. Surface compositions of combinations 1 and 2 were characterized using X-ray photoelectron spectroscopy (XPS). Field-emission scanning electron microscopy (FE-SEM) was used to characterize the morphology of the grafted films to confirm the even distribution between linker and antifouling molecules grafted onto the ITO surfaces

  18. Frontiers of interfacial water research :workshop report.

    Energy Technology Data Exchange (ETDEWEB)

    Cygan, Randall Timothy; Greathouse, Jeffery A.

    2005-10-01

    Water is the critical natural resource of the new century. Significant improvements in traditional water treatment processes require novel approaches based on a fundamental understanding of nanoscale and atomic interactions at interfaces between aqueous solution and materials. To better understand these critical issues and to promote an open dialog among leading international experts in water-related specialties, Sandia National Laboratories sponsored a workshop on April 24-26, 2005 in Santa Fe, New Mexico. The ''Frontiers of Interfacial Water Research Workshop'' provided attendees with a critical review of water technologies and emphasized the new advances in surface and interfacial microscopy, spectroscopy, diffraction, and computer simulation needed for the development of new materials for water treatment.

  19. Mesoscale Interfacial Dynamics in Magnetoelectric Nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Shashank, Priya [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

    2009-12-14

    Biphasic composites are the key towards achieving enhanced magnetoelectric response. In order understand the control behavior of the composites and resultant symmetry of the multifunctional product tensors, we need to synthesized model material systems with the following features (i) interface formation through either deposition control or natural decomposition; (ii) a very high interphase-interfacial area, to maximize the ME coupling; and (iii) an equilibrium phase distribution and morphology, resulting in preferred crystallographic orientation relations between phases across the interphase-interfacial boundaries. This thought process guided the experimental evolution in this program. We initiated the research with the co-fired composites approach and then moved on to the thin film laminates deposited through the rf-magnetron sputtering and pulsed laser deposition process

  20. Interfacial Fluid Mechanics A Mathematical Modeling Approach

    CERN Document Server

    Ajaev, Vladimir S

    2012-01-01

    Interfacial Fluid Mechanics: A Mathematical Modeling Approach provides an introduction to mathematical models of viscous flow used in rapidly developing fields of microfluidics and microscale heat transfer. The basic physical effects are first introduced in the context of simple configurations and their relative importance in typical microscale applications is discussed. Then,several configurations of importance to microfluidics, most notably thin films/droplets on substrates and confined bubbles, are discussed in detail.  Topics from current research on electrokinetic phenomena, liquid flow near structured solid surfaces, evaporation/condensation, and surfactant phenomena are discussed in the later chapters. This book also:  Discusses mathematical models in the context of actual applications such as electrowetting Includes unique material on fluid flow near structured surfaces and phase change phenomena Shows readers how to solve modeling problems related to microscale multiphase flows Interfacial Fluid Me...

  1. Evaluating interfacial shear stresses in composite hollo

    Directory of Open Access Journals (Sweden)

    Aiham Adawi

    2016-09-01

    Full Text Available Analytical evaluation of the interfacial shear stresses for composite hollowcore slabs with concrete topping is rare in the literature. Adawi et al. (2014 estimated the interfacial shear stiffness coefficient (ks that governs the behavior of the interface between hollowcore slabs and the concrete topping using push-off tests. This parameter is utilized in this paper to provide closed form solutions for the differential equations governing the behavior of simply supported composite hollowcore slabs. An analytical solution based on the deformation compatibility of the composite section and elastic beam theory, is developed to evaluate the shear stresses along the interface. Linear finite element modeling of the full-scale tests presented in Adawi et al. (2015 is also conducted to validate the developed analytical solution. The proposed analytical solution was found to be adequate in estimating the magnitude of horizontal shear stress in the studied composite hollowcore slabs.

  2. New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics.

    Science.gov (United States)

    Drüschler, Marcel; Borisenko, Natalia; Wallauer, Jens; Winter, Christian; Huber, Benedikt; Endres, Frank; Roling, Bernhard

    2012-04-21

    Ionic liquids are of high interest for the development of safe electrolytes in modern electrochemical cells, such as batteries, supercapacitors and dye-sensitised solar cells. However, electrochemical applications of ionic liquids are still hindered by the limited understanding of the interface between electrode materials and ionic liquids. In this article, we first review the state of the art in both experiment and theory. Then we illustrate some general trends by taking the interface between the extremely pure ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and an Au(111) electrode as an example. For the study of this interface, electrochemical impedance spectroscopy was combined with in situ STM and in situ AFM techniques. In addition, we present new results for the temperature dependence of the interfacial capacitance and dynamics. Since the interfacial dynamics are characterised by different processes taking place on different time scales, the temperature dependence of the dynamics can only be reliably studied by recording and carefully analysing broadband capacitance spectra. Single-frequency experiments may lead to artefacts in the temperature dependence of the interfacial capacitance. We demonstrate that the fast capacitive process exhibits a Vogel-Fulcher-Tamman temperature dependence, since its time scale is governed by the ionic conductivity of the ionic liquid. In contrast, the slower capacitive process appears to be Arrhenius activated. This suggests that the time scale of this process is determined by a temperature-independent barrier, which may be related to structural reorganisations of the Au surface and/or to charge redistributions in the strongly bound innermost ion layer. This journal is © the Owner Societies 2012

  3. Electrochemical non-enzymatic glucose sensors

    International Nuclear Information System (INIS)

    Park, Sejin; Boo, Hankil; Chung, Taek Dong

    2006-01-01

    The electrochemical determination of glucose concentration without using enzyme is one of the dreams that many researchers have been trying to make come true. As new materials have been reported and more knowledge on detailed mechanism of glucose oxidation has been unveiled, the non-enzymatic glucose sensor keeps coming closer to practical applications. Recent reports strongly imply that this progress will be accelerated in 'nanoera'. This article reviews the history of unraveling the mechanism of direct electrochemical oxidation of glucose and making attempts to develop successful electrochemical glucose sensors. The electrochemical oxidation of glucose molecules involves complex processes of adsorption, electron transfer, and subsequent chemical rearrangement, which are combined with the surface reactions on the metal surfaces. The information about the direct oxidation of glucose on solid-state surfaces as well as new electrode materials will lead us to possible breakthroughs in designing the enzymeless glucose sensing devices that realize innovative and powerful detection. An example of those is to introduce nanoporous platinum as an electrode, on which glucose is oxidized electrochemically with remarkable sensitivity and selectivity. Better model of such glucose sensors is sought by summarizing and revisiting the previous reports on the electrochemistry of glucose itself and new electrode materials

  4. Fundamentals of electrochemical science

    CERN Document Server

    Oldham, Keith

    1993-01-01

    Key Features* Deals comprehensively with the basic science of electrochemistry* Treats electrochemistry as a discipline in its own right and not as a branch of physical or analytical chemistry* Provides a thorough and quantitative description of electrochemical fundamentals

  5. Electrochemical Analysis of Neurotransmitters

    Science.gov (United States)

    Bucher, Elizabeth S.; Wightman, R. Mark

    2015-07-01

    Chemical signaling through the release of neurotransmitters into the extracellular space is the primary means of communication between neurons. More than four decades ago, Ralph Adams and his colleagues realized the utility of electrochemical methods for the study of easily oxidizable neurotransmitters, such as dopamine, norepinephrine, and serotonin and their metabolites. Today, electrochemical techniques are frequently coupled to microelectrodes to enable spatially resolved recordings of rapid neurotransmitter dynamics in a variety of biological preparations spanning from single cells to the intact brain of behaving animals. In this review, we provide a basic overview of the principles underlying constant-potential amperometry and fast-scan cyclic voltammetry, the most commonly employed electrochemical techniques, and the general application of these methods to the study of neurotransmission. We thereafter discuss several recent developments in sensor design and experimental methodology that are challenging the current limitations defining the application of electrochemical methods to neurotransmitter measurements.

  6. Electrochemical polymer electrolyte membranes

    CERN Document Server

    Fang, Jianhua; Wilkinson, David P

    2015-01-01

    Electrochemical Polymer Electrolyte Membranes covers PEMs from fundamentals to applications, describing their structure, properties, characterization, synthesis, and use in electrochemical energy storage and solar energy conversion technologies. Featuring chapters authored by leading experts from academia and industry, this authoritative text: Discusses cutting-edge methodologies in PEM material selection and fabricationPoints out important challenges in developing PEMs and recommends mitigation strategies to improve PEM performanceAnalyzes the cur

  7. Improving interfacial, mechanical and tribological properties of alumina coatings on Al alloy by plasma arc heat-treatment of substrate

    Science.gov (United States)

    Hou, Guoliang; An, Yulong; Zhao, Xiaoqin; Zhou, Huidi; Chen, Jianmin; Li, Shuangjian; Liu, Xia; Deng, Wen

    2017-07-01

    Plasma sprayed ceramic coatings can be used to improve the mechanical properties and wear resistance of aluminum alloys, but there are still some challenges to effectively increase their interfacial adhesion. Thus we conducted plasma arc-heat treatment (PA-HT) of Al alloy substrate before plasma spraying, hoping to tune the microstructure of Al2O3 coatings and improve their interfacial strength as well as mechanical and tribological properties. The influences of PA-HT on the microstructure of alumina coatings were analyzed by X-ray diffraction, transmission electron microscopy and scanning electron microscopy, while its effect on mechanical and tribological properties were evaluated by a nano-indentation tester and a friction and wear tester. Results demonstrate that a few columnar δ-Al2O3 generated on substrate surface after PA-HT at 200-250 °C can induce the epitaxial growth of γ-Al2O3 grains in Al2O3 coatings, thereby enhancing their interfacial bonding. Besides, elevating substrate temperature can help alumina droplets to melt into the interior of substrate and eliminate holes at the interface, finally increasing the interfacial anchorage force. More importantly, no interfacial holes can allow the heat of droplets to be rapidly transmitted to substrate, which is beneficial to yield smaller crystals in coatings and greatly enhance their strength, hardness and wear resistance.

  8. Interfacial electron transfer dynamics of photosensitized zinc oxide nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Murakoshi, Kei; Yanagida, Shozo [Osaka Univ. (Japan). Graduate School of Engineering; Capel, M. [Brookhaven National Lab., Upton, NY (United States)] [and others

    1997-06-01

    The authors have prepared and characterized photosensitized zinc oxide (ZnO) nanoclusters, dispersed in methanol, using carboxylated coumarin dyes for surface adsorption. Femtosecond time-resolved emission spectroscopy allows the authors to measure the photo-induced charge carrier injection rate constant from the adsorbed photosensitizer to the n-type semiconductor nanocluster. These results are compared with other photosensitized semiconductors.

  9. Effect of strong coupling on interfacial electron transfer dynamics in ...

    Indian Academy of Sciences (India)

    Unknown

    regarded as the best sensitizing dyes for solar energy conversion for their strong visible absorption bands, long-lived ... solar cells based on dye-sensitized nanocrystalline. TiO2. High affinity for the TiO2 surface, which is ... pump pulses at 400 nm, one part of 800 nm with. 200 µJ/pulse, is frequency doubled in BBO crystals.

  10. Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tiwen [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Jia, Zhixin, E-mail: zxjia@scut.edu.cn [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Luo, Yuanfang; Jia, Demin [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Peng, Zheng [Agricultural Product Processing Research Institute, Chinese Academy of Tropical Agriculture Sciences, Zhanjiang 524001 (China)

    2015-02-15

    Highlights: • Substantiate the ring open reaction between Si-OH of silica and epoxy groups of ENR. • ENR can act as a bridge between NR and silica to enhance the interfacial interaction. • As a modifier, ENR gets the potential to be used in the tread of green tire for improving the wet skid resistance apparently. - Abstract: The epoxidized natural rubber (ENR) as an interfacial modifier was used to improve the mechanical and dynamical mechanical properties of NR/silica composites. In order to reveal the interaction mechanism between ENR and silica, the ENR/Silica model compound was prepared by using an open mill and the interfacial interaction of ENR with silica was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and stress–strain testing. The results indicated that the ring-opening reaction occurs between the epoxy groups of ENR chains and Si-OH groups on the silica surfaces and the covalent bonds are formed between two phases, which can improve the dispersion of silica in the rubber matrix and enhance the interfacial combination between rubber and silica. The ring-opening reaction occurs not only in vulcanization process but also in mixing process, meanwhile, the latter seems to be more important due to the simultaneous effects of mechanical force and temperature.

  11. Modification of the Interfacial Interaction between Carbon Fiber and Epoxy with Carbon Hybrid Materials

    Directory of Open Access Journals (Sweden)

    Kejing Yu

    2016-05-01

    Full Text Available The mechanical properties of the hybrid materials and epoxy and carbon fiber (CF composites were improved significantly as compared to the CF composites made from unmodified epoxy. The reasons could be attributed to the strong interfacial interaction between the CF and the epoxy composites for the existence of carbon nanomaterials. The microstructure and dispersion of carbon nanomaterials were characterized by transmission electron microscopy (TEM and optical microscopy (OM. The results showed that the dispersion of the hybrid materials in the polymer was superior to other carbon nanomaterials. The high viscosity and shear stress characterized by a rheometer and the high interfacial friction and damping behavior characterized by dynamic mechanical analysis (DMA indicated that the strong interfacial interaction was greatly improved between fibers and epoxy composites. Remarkably, the tensile tests presented that the CF composites with hybrid materials and epoxy composites have a better reinforcing and toughening effect on CF, which further verified the strong interfacial interaction between epoxy and CF for special structural hybrid materials.

  12. Interfacial layers in tape cast anode-supported doped lanthanum gallate SOFC elements

    Energy Technology Data Exchange (ETDEWEB)

    Maffei, N.; De Silveira, G. [Materials Technology Laboratory, Natural Resources Canada, CANMET, 405 Rochester Street, Ottawa, Ontario (Canada) K1A OG3

    2003-04-01

    Lanthanum gallate doped with strontium and magnesium (LSGM) is a promising electrolyte system for intermediate temperature solid oxide fuel cells (SOFCs). The reported formation of interfacial layers in monolithic type SOFCs based on lanthanum gallate is of concern because of its impact on the performance of the fuel cell. Planar anode-supported SOFC elements (without the cathode) were prepared by the tape casting technique in order to determine the nature of the anode/electrolyte interface after sintering. Two anode systems were studied, one a NiO-CeO{sub 2} cermet, and the other, a modified lanthanum gallate anode containing manganese. Sintering studies were conducted at 1250, 1300, 1350, 1400 and 1450 C to determine the effect of temperature on the interfacial characteristics. Scanning electron microscopy (SEM) revealed a significant diffusion of Ni from the NiO-CeO{sub 2} anode resulting in the formation of an interfacial layer regardless of sintering temperature. Significant La diffusion from the electrolyte into the anode was also observed. In the case of the modified lanthanum gallate anode containing manganese, there was no interfacial layer formation, but a significant diffusion of Mn into the electrolyte was observed.

  13. The interfacial strength of carbon nanofiber epoxy composite using single fiber pullout experiments.

    Science.gov (United States)

    Manoharan, M P; Sharma, A; Desai, A V; Haque, M A; Bakis, C E; Wang, K W

    2009-07-22

    Carbon nanotubes and nanofibers are extensively researched as reinforcing agents in nanocomposites for their multifunctionality, light weight and high strength. However, it is the interface between the nanofiber and the matrix that dictates the overall properties of the nanocomposite. The current trend is to measure elastic properties of the bulk nanocomposite and then compare them with theoretical models to extract the information on the interfacial strength. The ideal experiment is single fiber pullout from the matrix because it directly measures the interfacial strength. However, the technique is difficult to apply to nanocomposites because of the small size of the fibers and the requirement for high resolution force and displacement sensing. We present an experimental technique for measuring the interfacial strength of nanofiber-reinforced composites using the single fiber pullout technique and demonstrate the technique for a carbon nanofiber-reinforced epoxy composite. The experiment is performed in situ in a scanning electron microscope and the interfacial strength for the epoxy composite was measured to be 170 MPa.

  14. Morphological reason for enhancement of electrochemical double layer capacitances of various acetylene blacks by electrochemical polarization

    International Nuclear Information System (INIS)

    Kim, Taegon; Ham, Chulho; Rhee, Choong Kyun; Yoon, Seong-Ho; Tsuji, Masaharu; Mochida, Isao

    2008-01-01

    Enhancement of electrochemical capacitance and morphological variations of various acetylene blacks caused by electrochemical polarization are presented. Acetylene blacks of different mean particle diameters were modified by air-oxidation and heat treatment to diversify the morphologies of the acetylene blacks before electrochemical polarization. The various acetylene blacks were electrochemically oxidized at 1.6 V (vs. Ag/AgCl) for 10 s and the polarization step was repeated until the capacitance values did not change any longer. These polarization steps enhanced the capacitances of the acetylene blacks and the specific enhancement factors range from 2 to 5.5. Such an enhancement is strongly related to morphological modification as revealed by transmission electron microscopic observations. The electrochemical polarization resulted in formation of tiny graphene sheets on the wide graphitic carbon surfaces, which were most responsible for the observed capacitive enhancement. Although the pseudo-capacitance increased after polarization by forming oxygenated species on the surfaces, its contribution to the total capacitance was less than 10%. The mechanism of the formation of the tiny graphene sheets during the electrochemical oxidation is described schematically

  15. Stress evolution in elastic-plastic electrodes during electrochemical processes: A numerical method and its applications

    Science.gov (United States)

    Wen, Jici; Wei, Yujie; Cheng, Yang-Tse

    2018-07-01

    Monitoring in real time the stress state in high capacity electrodes during charge-discharge processes is pivotal to the performance assessment and structural optimization of advanced batteries. The wafer curvature measurement technique broadly employed in thin-film industry, together with stress analysis using the Stoney equation, has been successfully adopted to measure in situ the stress in thin film electrodes. How large plastic deformation or interfacial delamination during electrochemical cycles in such electrodes affects the applicability of Stoney equation remains unclear. Here we develop a robust electrochemical-mechanical coupled numerical procedure to investigate the influence of large plastic deformation and interfacial failure on the measured stress in thin film electrodes. We identify how the constitutive behavior of electrode materials and film-substrate interfacial properties affect the measured stress-capacity curves of electrodes, and hence establish the relationship of electrode material parameters with the characteristics of stress-capacity curves. Using Li-ions batteries as examples, we show that plastic deformation and interfacial delamination account for the asymmetric stress-capacity loops seen in in situ stress measurements. The methods used here, along with the finite-element code in the supplementary material, may be used to model the electrode behavior as a function of the state of charge.

  16. Chemical Production of Graphene Catalysts for Electrochemical Energy Conversion

    DEFF Research Database (Denmark)

    Seselj, Nedjeljko

    by scanning tunneling microscopy (STM), to investigate the nature of L-cysteine bonds on Au. Synthesized electrocatalysts were characterized by spectroscopic, microscopic and electrochemical techniques. Electrocatalysis was examined by electrochemical oxidation of formic acid, methanol and ethanol, and oxygen......Recently developed FC technology is among many approaches aiming at solving the global energy challenges. FCs are electrochemical devices that convert chemical energy from fuel molecules into electrical energy via electrochemical reactions. FCs are, however, limited by the scarce and expensive...... was achieved via L-cysteine linker molecules that provided pathways for fast electron transfers during the electrocatalytic reactions. Electrochemical properties of selfassembled L-cysteine monolayers immobilized on single-crystal Au(111) surfaces were studied in ionic liquids and their structures imaged...

  17. Decreased Charge Transport Barrier and Recombination of Organic Solar Cells by Constructing Interfacial Nanojunction with Annealing-Free ZnO and Al Layers.

    Science.gov (United States)

    Liu, Chunyu; Zhang, Dezhong; Li, Zhiqi; Zhang, Xinyuan; Guo, Wenbin; Zhang, Liu; Ruan, Shengping; Long, Yongbing

    2017-07-05

    To overcome drawbacks of the electron transport layer, such as complex surface defects and unmatched energy levels, we successfully employed a smart semiconductor-metal interfacial nanojunciton in organic solar cells by evaporating an ultrathin Al interlayer onto annealing-free ZnO electron transport layer, resulting in a high fill factor of 73.68% and power conversion efficiency of 9.81%. The construction of ZnO-Al nanojunction could effectively fill the surface defects of ZnO and reduce its work function because of the electron transfer from Al to ZnO by Fermi level equilibrium. The filling of surface defects decreased the interfacial carrier recombination in midgap trap states. The reduced surface work function of ZnO-Al remodulated the interfacial characteristics between ZnO and [6,6]-phenyl C71-butyric acid methyl ester (PC 71 BM), decreasing or even eliminating the interfacial barrier against the electron transport, which is beneficial to improve the electron extraction capacity. The filled surface defects and reduced interfacial barrier were realistically observed by photoluminescence measurements of ZnO film and the performance of electron injection devices, respectively. This work provides a simple and effective method to simultaneously solve the problems of surface defects and unmatched energy level for the annealing-free ZnO or other metal oxide semiconductors, paving a way for the future popularization in photovoltaic devices.

  18. Electrochemical Biosensors - Sensor Principles and Architectures

    Science.gov (United States)

    Grieshaber, Dorothee; MacKenzie, Robert; Vörös, Janos; Reimhult, Erik

    2008-01-01

    Quantification of biological or biochemical processes are of utmost importance for medical, biological and biotechnological applications. However, converting the biological information to an easily processed electronic signal is challenging due to the complexity of connecting an electronic device directly to a biological environment. Electrochemical biosensors provide an attractive means to analyze the content of a biological sample due to the direct conversion of a biological event to an electronic signal. Over the past decades several sensing concepts and related devices have been developed. In this review, the most common traditional techniques, such as cyclic voltammetry, chronoamperometry, chronopotentiometry, impedance spectroscopy, and various field-effect transistor based methods are presented along with selected promising novel approaches, such as nanowire or magnetic nanoparticle-based biosensing. Additional measurement techniques, which have been shown useful in combination with electrochemical detection, are also summarized, such as the electrochemical versions of surface plasmon resonance, optical waveguide lightmode spectroscopy, ellipsometry, quartz crystal microbalance, and scanning probe microscopy. The signal transduction and the general performance of electrochemical sensors are often determined by the surface architectures that connect the sensing element to the biological sample at the nanometer scale. The most common surface modification techniques, the various electrochemical transduction mechanisms, and the choice of the recognition receptor molecules all influence the ultimate sensitivity of the sensor. New nanotechnology-based approaches, such as the use of engineered ion-channels in lipid bilayers, the encapsulation of enzymes into vesicles, polymersomes, or polyelectrolyte capsules provide additional possibilities for signal amplification. In particular, this review highlights the importance of the precise control over the delicate

  19. Enhanced Corrosion Resistance and Interfacial Conductivity of TiC x/a-C Nanolayered Coatings via Synergy of Substrate Bias Voltage for Bipolar Plates Applications in PEMFCs.

    Science.gov (United States)

    Yi, Peiyun; Zhang, Weixin; Bi, Feifei; Peng, Linfa; Lai, Xinmin

    2018-06-06

    Proton-exchange membrane fuel cells are one kind of renewable and clean energy conversion device, whose metallic bipolar plates are one of the key components. However, high interfacial contact resistance and poor corrosion resistance are still great challenges for the commercialization of metallic bipolar plates. In this study, we demonstrated a novel strategy for depositing TiC x /amorphous carbon (a-C) nanolayered coatings by synergy of 60 and 300 V bias voltage to enhance corrosion resistance and interfacial conductivity. The synergistic effects of bias voltage on the composition, microstructure, surface roughness, electrochemical corrosion behaviors, and interfacial conductivity of TiC x /a-C coatings were explored. The results revealed that the columnar structures in the inner layer were suppressed and the surface became rougher with the 300 V a-C layer outside. The composition analysis indicated that the sp 2 content increased with an increase of 300 V sputtering time. Due to the synergy strategy of bias voltage, lower corrosion current densities were achieved both in potentiostatic polarization (1.6 V vs standard hydrogen electrode) and potentiodynamic polarization. With the increase of 300 V sputtering time, the interfacial conductivity was improved. The enhanced corrosion resistance and interfacial conductivity of the TiC x /a-C coatings would provide new opportunities for commercial bipolar plates.

  20. Scaling of interfacial jump conditions; Escalamiento de condiciones de salto interfacial

    Energy Technology Data Exchange (ETDEWEB)

    Quezada G, S.; Vazquez R, A.; Espinosa P, G., E-mail: sequga@gmail.com [Universidad Autonoma Metropolitana, Unidad Iztapalapa, Area de Ingenieria en Recursos Energeticos, Apdo. Postal 55-535, 09340 Ciudad de Mexico (Mexico)

    2015-09-15

    To model the behavior of a nuclear reactor accurately is needed to have balance models that take into account the different phenomena occurring in the reactor. These balances have to be coupled together through boundary conditions. The boundary conditions have been studied and different treatments have been given to the interface. In this paper is a brief description of some of the interfacial jump conditions that have been proposed in recent years. Also, the scaling of an interfacial jump condition is proposed, for coupling the different materials that are in contact within a nuclear reactor. (Author)

  1. Bioinspired design and interfacial failure of biomedical systems

    Science.gov (United States)

    Rahbar, Nima

    is investigated using Brazil-nut specimens. The kinking in-and-out of the interface that occurs between glass/cement and zirconia/cement interfaces, is also shown to be consistent with predictions from a microstructure-based finite element model. The predictions are later verified using focused ion beam and scanning electron microscopy images. Finally, the adhesion between layers that are relevant to drug-eluting stents is explored. Brazil disk specimens were used to measure the interfacial fracture energies between the layers of a model drug eluting stent over a wide range of mode mixities. The trends in the overall fracture energies are predicted using a combination of adhesion theories and fracture mechanics concepts. The measured interfacial fracture energies are shown to be in good agreement with the predictions.

  2. Stability of interfacial waves in two-phase flows

    Energy Technology Data Exchange (ETDEWEB)

    Liu, W S [Ontario Hydro, Toronto, ON (Canada)

    1996-12-31

    The influence of the interfacial pressure and the flow distribution in the one-dimensional two-fluid model on the stability problems of interfacial waves is discussed. With a proper formulation of the interfacial pressure, the following two-phase phenomena can be predicted from the stability and stationary criteria of the interfacial waves: onset of slug flow, stationary hydraulic jump in a stratified flow, flooding in a vertical pipe, and the critical void fraction of a bubbly flow. It can be concluded that the interfacial pressure plays an important role in the interfacial wave propagation of the two-fluid model. The flow distribution parameter may enhance the flow stability range, but only plays a minor role in the two-phase characteristics. (author). 20 refs., 3 tabs., 4 figs.

  3. Electrochemical impedance characterization of FeSn2 electrodes for Li-ion batteries

    International Nuclear Information System (INIS)

    Chamas, M.; Lippens, P-E.; Jumas, J-C.; Hassoun, J.; Panero, S.; Scrosati, B.

    2011-01-01

    Highlights: → In this paper we study a tin based, FeSn 2 , high capacity lithium-alloying electrode. → The electrochemical performance of this electrode in lithium batteries is remarkably influenced by the current rate. → This aspect is investigated by electrochemical techniques such as galvanostatic cycling and impedance spectroscopy. → The results demonstrated that the good electrochemical behavior of the electrode at the higher currents is due to the formation of a stable solid electrolyte interphase (SEI) film. - Abstract: This work reports the electrochemical characterization of a micro-scale FeSn 2 electrode in a lithium battery. The electrode is proposed as anode material for advanced lithium ion batteries due to its characteristics of high capacity (500 mAh g -1 ) and low working voltage (0.6 V vs. Li). The electrochemical alloying process is studied by cyclic voltammetry and galvanostatic cycling while the interfacial properties are investigated by electrochemical impedance spectroscopy. The impedance measurements in combination with the galvanostatic cycling tests reveal relatively low overall impedance values and good electrochemical performance for the electrode, both in terms of delivered capacity and cycling stability, even at the higher C-rate regimes.

  4. Electrochemical studies of a reconstituted photosynthetic electron-transfer chain or towards a biomimetic photoproduction of hydrogen; Etudes electrochimiques de chaines de transfert d'electrons photosynthetiques ou vers une photoproduction biomimetique d'hydrogene

    Energy Technology Data Exchange (ETDEWEB)

    Fourmond, V

    2007-04-15

    The aim of this work is to find an efficient process to convert solar energy into hydrogen. The electrons transfers in reconstituted photosynthetic chains have been particularly studied with the aims 1)in one hand, to better understand the interactions of the different molecules of the photosynthetic chain in order to optimize the changes of the entire organisms for hydrogen production 2)in another hand, to insert the hydrogenases in a photosynthetic chain and then to photo reduce them in order to obtain kinetic data to better understand how it works. (O.M.)

  5. A nanoscale study of charge extraction in organic solar cells: the impact of interfacial molecular configurations.

    Science.gov (United States)

    Tang, Fu-Ching; Wu, Fu-Chiao; Yen, Chia-Te; Chang, Jay; Chou, Wei-Yang; Gilbert Chang, Shih-Hui; Cheng, Horng-Long

    2015-01-07

    In the optimization of organic solar cells (OSCs), a key problem lies in the maximization of charge carriers from the active layer to the electrodes. Hence, this study focused on the interfacial molecular configurations in efficient OSC charge extraction by theoretical investigations and experiments, including small molecule-based bilayer-heterojunction (sm-BLHJ) and polymer-based bulk-heterojunction (p-BHJ) OSCs. We first examined a well-defined sm-BLHJ model system of OSC composed of p-type pentacene, an n-type perylene derivative, and a nanogroove-structured poly(3,4-ethylenedioxythiophene) (NS-PEDOT) hole extraction layer. The OSC with NS-PEDOT shows a 230% increment in the short circuit current density compared with that of the conventional planar PEDOT layer. Our theoretical calculations indicated that small variations in the microscopic intermolecular interaction among these interfacial configurations could induce significant differences in charge extraction efficiency. Experimentally, different interfacial configurations were generated between the photo-active layer and the nanostructured charge extraction layer with periodic nanogroove structures. In addition to pentacene, poly(3-hexylthiophene), the most commonly used electron-donor material system in p-BHJ OSCs was also explored in terms of its possible use as a photo-active layer. Local conductive atomic force microscopy was used to measure the nanoscale charge extraction efficiency at different locations within the nanogroove, thus highlighting the importance of interfacial molecular configurations in efficient charge extraction. This study enriches understanding regarding the optimization of the photovoltaic properties of several types of OSCs by conducting appropriate interfacial engineering based on organic/polymer molecular orientations. The ultimate power conversion efficiency beyond at least 15% is highly expected when the best state-of-the-art p-BHJ OSCs are combined with present arguments.

  6. Electrochemical synthesis of polydiphenylamine nanofibrils through AAO template

    International Nuclear Information System (INIS)

    Zhao Yanchun; Chen Miao; Liu Xiang; Xu Tao; Liu Weimin

    2005-01-01

    Highly ordered polydiphenylamine (PDPA) nanofibrils arrays have been fabricated within the pores of porous anodic aluminum oxide (AAO) template membrane by electrochemical polymerization. The morphology of PDPA nanofibrils array was observed using transmission electron microscopy (TEM) and its electrochemical behavior and structure were examined by cyclic voltammetry, UV-vis spectroscopy and Fourier transmission infrared spectrum. The result of TEM revealed that the obtained PDPA nanofibrils had uniform and well-aligned array. The UV-vis spectroscopy and electrochemical experimental result indicated that the spatial restraint in the pores of AAO membrane is sufficient to induce the formation of more ordered PDPA chains in the AAO membrane

  7. Electrochemical synthesis of polydiphenylamine nanofibrils through AAO template

    Energy Technology Data Exchange (ETDEWEB)

    Yanchun, Zhao [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Miao, Chen [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Xiang, Liu [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Tao, Xu [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); Weimin, Liu [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China)

    2005-06-15

    Highly ordered polydiphenylamine (PDPA) nanofibrils arrays have been fabricated within the pores of porous anodic aluminum oxide (AAO) template membrane by electrochemical polymerization. The morphology of PDPA nanofibrils array was observed using transmission electron microscopy (TEM) and its electrochemical behavior and structure were examined by cyclic voltammetry, UV-vis spectroscopy and Fourier transmission infrared spectrum. The result of TEM revealed that the obtained PDPA nanofibrils had uniform and well-aligned array. The UV-vis spectroscopy and electrochemical experimental result indicated that the spatial restraint in the pores of AAO membrane is sufficient to induce the formation of more ordered PDPA chains in the AAO membrane.

  8. Materials for electrochemical capacitors

    Science.gov (United States)

    Simon, Patrice; Gogotsi, Yury

    2008-11-01

    Electrochemical capacitors, also called supercapacitors, store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). They can complement or replace batteries in electrical energy storage and harvesting applications, when high power delivery or uptake is needed. A notable improvement in performance has been achieved through recent advances in understanding charge storage mechanisms and the development of advanced nanostructured materials. The discovery that ion desolvation occurs in pores smaller than the solvated ions has led to higher capacitance for electrochemical double layer capacitors using carbon electrodes with subnanometre pores, and opened the door to designing high-energy density devices using a variety of electrolytes. Combination of pseudo-capacitive nanomaterials, including oxides, nitrides and polymers, with the latest generation of nanostructured lithium electrodes has brought the energy density of electrochemical capacitors closer to that of batteries. The use of carbon nanotubes has further advanced micro-electrochemical capacitors, enabling flexible and adaptable devices to be made. Mathematical modelling and simulation will be the key to success in designing tomorrow's high-energy and high-power devices.

  9. Electrochemical reduction of NOx

    DEFF Research Database (Denmark)

    Traulsen, Marie Lund

    NO and NO2 (collectively referred to as NOx) are air pollutants, and the largest single contributor to NOx pollution is automotive exhaust. This study investigates electrochemical deNOx, a technology which aims to remove NOx from automotive diesel exhaust by electrochemical reduction of NOx to N2...... and O2. The focus in this study is on improving the activity and selectivity of solid oxide electrodes for electrochemical deNOx by addition of NOx storage compounds to the electrodes. Two different composite electrodes, La0.85Sr0.15MnO3-δ-Ce0.9Gd0.1O1.95 (LSM15-CGO10) and La0.85Sr0.15FeO3-δ-Ce0.9Gd0.1O......1.95 (LSF15-CGO10), have been investigated in combination with three different NOx storage compounds: BaO, K2O and MnOx. The main focus in the investigation has been on conversion measurements and electrochemical characterization, the latter by means of electrochemical impedance spectroscopy...

  10. Measurement of local interfacial area concentration in boiling loop

    International Nuclear Information System (INIS)

    Kyoung, Ho Kang; Byong, Jo Yun; Goon, Cherl Park

    1995-01-01

    An accurate prediction of two-phase flow is essential to many energy systems, including nuclear reactors. To model the two-phase flow, detailed information on the internal flow structure is required. The void fraction and interfacial area concentration are important fundamental parameters characterizing the internal structure of two-phase flow. The interfacial area concentration is defined as the available interfacial area per unit volume of the two-phase mixture in calculations of the interfacial transport of mass, momentum, and energy. Although a number of studies have been made in this area, the interfacial area concentration in two-phase flow has not been sufficiently investigated either experimentally or analytically. Most existing models for interfacial area concentration are limited to area-averaged interfacial area concentration in a flow channel. And the studies on local interfacial area concentration are limited to the case of air-water two-phase flow. However, the internal flow structure of steam-water two-phase flow having various bubble sizes could be quite different from that of air-water two-phase flow, the reliability of which weak in practical applications. In this study, the local interfacial area concentration steam-water two-phase flow has been investigated experimentally in a circular boiling tube having a heating rod in the center, and for the low flow with liquid superficial velocity <1 m/s

  11. Mean free path dependent phonon contributions to interfacial thermal conductance

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Yi; Liu, Chenhan; Chen, Weiyu; Cai, Shuang; Chen, Chen; Wei, Zhiyong; Bi, Kedong; Yang, Juekuan; Chen, Yunfei, E-mail: yunfeichen@seu.edu.cn

    2017-06-15

    Interfacial thermal conductance as an accumulation function of the phonon mean free path is rigorously derived from the thermal conductivity accumulation function. Based on our theoretical model, the interfacial thermal conductance accumulation function between Si/Ge is calculated. The results show that the range of mean free paths (MFPs) for phonons contributing to the interfacial thermal conductance is far narrower than that for phonons contributing to the thermal conductivity. The interfacial thermal conductance is mainly contributed by phonons with shorter MFPs, and the size effects can be observed only for an interface constructed by nanostructures with film thicknesses smaller than the MFPs of those phonons mainly contributing to the interfacial thermal conductance. This is why most experimental measurements cannot detect size effects on interfacial thermal conductance. A molecular dynamics simulation is employed to verify our proposed model. - Highlights: • A model to account for the interfacial thermal conductance as an accumulation function of phonon mean free path is proposed; • The model predicts that the range of mean free paths (MFPs) for phonons contributing to the interfacial thermal conductance is far narrower than that contributing to the thermal conductivity; • This model can be conveniently implemented to estimate the size effects on the interfacial thermal conductance for the interfaces formed by a nanostructure contacting a substrate.

  12. Interfacial binding of cutinase rather than its catalytic activity determines the steady state interfacial tension during oil drop lipid hydrolysis.

    Science.gov (United States)

    Flipsen, J A; van Schaick, M A; Dijkman, R; van der Hijden, H T; Verheij, H M; Egmond, M R

    1999-02-01

    Hydrolysis of triglycerides by cutinase from Fusarium solani pisi causes in oil drop tensiometer experiments a decrease of the interfacial tension. A series of cutinase variants with amino acid substitutions at its molecular surface yielded different values of the steady state interfacial tension. This tension value poorly correlated with the specific activity as such nor with the total activity (defined as the specific activity multiplied by the amount of enzyme bound) of the cutinase variants. Moreover, it appeared that at activity levels above 15% of that of wild type cutinase the contribution of hydrolysis to the decrease of the tension is saturating. A clear positive correlation was found between the interfacial tension plateau value and the interfacial binding of cutinase, as determined with attenuated total reflection Fourier transformed infrared spectroscopy (ATR-FTIR). These results indicate that the interfacial steady state level is not determined by the rate of hydrolysis, but mainly by the interfacial binding of cutinase.

  13. Electrochemical investigation on an acrylated thiophene

    Energy Technology Data Exchange (ETDEWEB)

    Hogervorst, A.C.R. (TNO Plastics and Rubber Research Inst., Delft (Netherlands)); Kock, T.J.J.M. (TNO Plastics and Rubber Research Inst., Delft (Netherlands)); Ruiter, B. de (TNO Plastics and Rubber Research Inst., Delft (Netherlands)); Waal, A. van der (TNO Plastics and Rubber Research Inst., Delft (Netherlands))

    1993-03-22

    The electrochemical behaviour of electropolymerized 2-(3-thienyl)ethyl acrylate (PAcrT) has been investigated, and compared to the behaviour of electropolymerized thiophene and 3-n-decylthiophene (PDT). The effect of electron beam irradiation on the electrochemical properties of these three polymers has been studied. It has been found that for PAcrT the oxidation wave shifts to higher potentials upon electron beam irradiation. For PDT a similar but smaller change occurs. We suggest that the shift of the oxidation wave of PAcrT is caused by cross-links, formed between the acrylate substituents, which fixate the main chain parts in twisted states and reduce the conjugation length. (orig.)

  14. Electrochemical properties of double wall carbon nanotube electrodes

    OpenAIRE

    Pumera, Martin

    2007-01-01

    AbstractElectrochemical properties of double wall carbon nanotubes (DWNT) were assessed and compared to their single wall (SWNT) counterparts. The double and single wall carbon nanotube materials were characterized by Raman spectroscopy, scanning and transmission electron microscopy and electrochemistry. The electrochemical behavior of DWNT film electrodes was characterized by using cyclic voltammetry of ferricyanide and NADH. It is shown that while both DWNT and SWNT were significantly funct...

  15. Adsorption induced losses in interfacial cohesion

    International Nuclear Information System (INIS)

    Asaro, R.J.

    1977-07-01

    A model for interfacial cohesion is developed which describes the loss in the strength of an interface due to the segregation and adsorption of impurities on it. Distinctions are made between interface separations that occur too rapidly for any significant redistribution of adsorbing matter to take place and separations that are slow enough to allow full adsorption equilibrium. Expressions for the total work of complete decohesion are presented for both cases. The results are applied to well-known model adsorption isotherms and some experimental data for grain boundary adsorption of phosphorus in iron is analyzed with respect to the losses in intergranular cohesion

  16. Interfacial fluid dynamics and transport processes

    CERN Document Server

    Schwabe, Dietrich

    2003-01-01

    The present set of lectures and tutorial reviews deals with various topical aspects related to instabilities of interfacial processes and driven flows from both the theoretical and experimental point of views. New research has been spurred by the many demands for applications in material sciences (melting, solidification, electro deposition), biomedical engineering and processing in microgravity environments. This book is intended as both a modern source of reference for researchers in the field as well as an introduction to postgraduate students and non-specialists from related areas.

  17. Viscosity of interfacial water regulates ice nucleation

    International Nuclear Information System (INIS)

    Li, Kaiyong; Chen, Jing; Zhang, Qiaolan; Zhang, Yifan; Xu, Shun; Zhou, Xin; Cui, Dapeng; Wang, Jianjun; Song, Yanlin

    2014-01-01

    Ice formation on solid surfaces is an important phenomenon in many fields, such as cloud formation and atmospheric icing, and a key factor for applications in preventing freezing. Here, we report temperature-dependent nucleation rates of ice for hydrophilic and hydrophobic surfaces. The results show that hydrophilic surface presents a lower ice nucleation rate. We develop a strategy to extract the thermodynamic parameters, J 0 and Γ, in the context of classical nucleation theory. From the extracted J 0 and Γ, we reveal the dominant role played by interfacial water. The results provide an insight into freezing mechanism on solid surfaces

  18. Neutron reflectometry for interfacial materials characterization

    International Nuclear Information System (INIS)

    Lin, Eric K.; Pochan, Darrin J.; Kolb, Rainer; Wu Wenli; Satija, Sushil K.

    1998-01-01

    Neutron reflectometry provides a powerful non-destructive analytic technique to measure physical properties of interfacial materials. The sample reflectivity provides information about composition, thickness, and roughness of films with 0.1 nm resolution. The use of neutrons has the additional advantage of being able to label selected atomic species by using different isotopes. Two examples are presented to demonstrate the use of neutron reflectometry in measuring the thermal expansion of a buried thin polymer film and measuring the change in polymer mobility near a solid substrate

  19. Interfacial stability with mass and heat transfer

    International Nuclear Information System (INIS)

    Hsieh, D.Y.

    1977-07-01

    A simplified formulation is presented to deal with interfacial stability problems with mass and heat transfer. For Rayleigh-Taylor stability problems of a liquid-vapor system, it was found that the effect of mass and heat transfer tends to enhance the stability of the system when the vapor is hotter than the liquid, although the classical stability criterion is still valid. For Kelvin-Holmholtz stability problems, however, the classical stability criterion was found to be modified substantially due to the effect of mass and heat transfer

  20. Local measurement of interfacial area, interfacial velocity and liquid turbulence in two-phase flow

    International Nuclear Information System (INIS)

    Hibiki, T.; Hogsett, S.; Ishii, M.

    1998-01-01

    Double sensor probe and hotfilm anemometry methods were developed for measuring local flow characteristics in bubbly flow. The formulation for the interfacial area concentration measurement was obtained by improving the formulation derived by Kataoka and Ishii. The assumptions used in the derivation of the equation were verified experimentally. The interfacial area concentration measured by the double sensor probe agreed well with one by the photographic method. The filter to validate the hotfilm anemometry for measuring the liquid velocity and turbulent intensity in bubbly flow was developed based on removing the signal due to the passing bubbles. The local void fraction, interfacial area concentration, interfacial velocity, Sauter mean diameter, liquid velocity, and turbulent intensity of vertical upward air-water flow in a round tube with inner diameter of 50.8 mm were measured by using these methods. A total of 54 data sets were acquired consisting of three superficial gas flow rates, 0.039, 0.067, and 0.147 m/s, and three superficial liquid flow rates, 0.60, 1.00, and 1.30 m/s. The measurements were performed at the three locations: L/D=2, 32, and 62. This data is expected to be used for the development of reliable constitutive relations which reflect the true transfer mechanisms in two-phase flow. (author)

  1. Integrating Electrochemical Detection with Centrifugal Microfluidics for Real-Time and Fully Automated Sample Testing

    DEFF Research Database (Denmark)

    Andreasen, Sune Zoëga; Kwasny, Dorota; Amato, Letizia

    2015-01-01

    Here we present a robust, stable and low-noise experimental set-up for performing electrochemical detection on a centrifugal microfluidic platform. By using a low-noise electronic component (electrical slip-ring) it is possible to achieve continuous, on-line monitoring of electrochemical experime......Here we present a robust, stable and low-noise experimental set-up for performing electrochemical detection on a centrifugal microfluidic platform. By using a low-noise electronic component (electrical slip-ring) it is possible to achieve continuous, on-line monitoring of electrochemical...

  2. Characterization of redox proteins using electrochemical methods

    OpenAIRE

    Verhagen, M.

    1995-01-01

    The use of electrochemical techniques in combination with proteins started approximately a decade ago and has since then developed into a powerfull technique for the study of small redox proteins. In addition to the determination of redox potentials, electrochemistry can be used to obtain information about the kinetics of electron transfer between proteins and about the dynamic behaviour of redox cofactors in proteins. This thesis describes the results of a study, initiated to get a ...

  3. Use of interfacial layers to prolong hole lifetimes in hematite probed by ultrafast transient absorption spectroscopy

    Science.gov (United States)

    Paradzah, Alexander T.; Diale, Mmantsae; Maabong, Kelebogile; Krüger, Tjaart P. J.

    2018-04-01

    Hematite is a widely investigated material for applications in solar water oxidation due primarily to its small bandgap. However, full realization of the material continues to be hampered by fast electron-hole recombination rates among other weaknesses such as low hole mobility, short hole diffusion length and low conductivity. To address the problem of fast electron-hole recombination, researchers have resorted to growth of nano-structured hematite, doping and use of under-layers. Under-layer materials enhance the photo-current by minimising electron-hole recombination through suppressing of back electron flow from the substrate, such as fluorine-doped tin oxide (FTO), to hematite. We have carried out ultrafast transient absorption spectroscopy on hematite in which Nb2O5 and SnO2 materials were used as interfacial layers to enhance hole lifetimes. The transient absorption data was fit with four different lifetimes ranging from a few hundred femtoseconds to a few nanoseconds. We show that the electron-hole recombination is slower in samples where interfacial layers are used than in pristine hematite. We also develop a model through target analysis to illustrate the effect of under-layers on electron-hole recombination rates in hematite thin films.

  4. Effects of Ag addition on solid–state interfacial reactions between Sn–Ag–Cu solder and Cu substrate

    International Nuclear Information System (INIS)

    Yang, Ming; Ko, Yong-Ho; Bang, Junghwan; Kim, Taek-Soo; Lee, Chang-Woo; Li, Mingyu

    2017-01-01

    Low–Ag–content Sn–Ag–Cu (SAC) solders have attracted much recent attention in electronic packaging for their low cost. To reasonably reduce the Ag content in Pb–free solders, a deep understanding of the basic influence of Ag on the SAC solder/Cu substrate interfacial reaction is essential. Previous studies have discussed the influence of Ag on the interfacial intermetallic compound (IMC) thickness. However, because IMC growth is the joint result of multiple factors, such characterizations do not reveal the actual role of Ag. In this study, changes in interfacial IMCs after Ag introduction were systemically and quantitatively characterized in terms of coarsening behaviors, orientation evolution, and growth kinetics. The results show that Ag in the solder alloy affects the coarsening behavior, accelerates the orientation concentration, and inhibits the growth of interfacial IMCs during solid–state aging. The inhibition mechanism was quantitatively discussed considering the individual diffusion behaviors of Cu and Sn atoms, revealing that Ag inhibits interfacial IMC growth primarily by slowing the diffusion of Cu atoms through the interface. - Highlights: •Role of Ag in IMC formation during Sn–Ag–Cu soldering was investigated. •Ag affects coarsening, crystallographic orientation, and IMC growth. •Diffusion pathways of Sn and Cu are affected differently by Ag. •Ag slows Cu diffusion to inhibit IMC growth at solder/substrate interface.

  5. Effects of Ag addition on solid–state interfacial reactions between Sn–Ag–Cu solder and Cu substrate

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ming [Micro-Joining Center, Korea Institute of Industrial Technology (KITECH), Incheon 21999 (Korea, Republic of); Ko, Yong-Ho [Micro-Joining Center, Korea Institute of Industrial Technology (KITECH), Incheon 21999 (Korea, Republic of); Department of Mechanical Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291, Daehak-ro, Yuseong-gu, Daejeon 34141 (Korea, Republic of); Bang, Junghwan [Micro-Joining Center, Korea Institute of Industrial Technology (KITECH), Incheon 21999 (Korea, Republic of); Kim, Taek-Soo [Department of Mechanical Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291, Daehak-ro, Yuseong-gu, Daejeon 34141 (Korea, Republic of); Lee, Chang-Woo, E-mail: cwlee@kitech.re.kr [Micro-Joining Center, Korea Institute of Industrial Technology (KITECH), Incheon 21999 (Korea, Republic of); Li, Mingyu, E-mail: myli@hit.edu.cn [Shenzhen Key Laboratory of Advanced Materials, Harbin Institute of Technology Shenzhen Graduate School, Shenzhen 518055 (China)

    2017-02-15

    Low–Ag–content Sn–Ag–Cu (SAC) solders have attracted much recent attention in electronic packaging for their low cost. To reasonably reduce the Ag content in Pb–free solders, a deep understanding of the basic influence of Ag on the SAC solder/Cu substrate interfacial reaction is essential. Previous studies have discussed the influence of Ag on the interfacial intermetallic compound (IMC) thickness. However, because IMC growth is the joint result of multiple factors, such characterizations do not reveal the actual role of Ag. In this study, changes in interfacial IMCs after Ag introduction were systemically and quantitatively characterized in terms of coarsening behaviors, orientation evolution, and growth kinetics. The results show that Ag in the solder alloy affects the coarsening behavior, accelerates the orientation concentration, and inhibits the growth of interfacial IMCs during solid–state aging. The inhibition mechanism was quantitatively discussed considering the individual diffusion behaviors of Cu and Sn atoms, revealing that Ag inhibits interfacial IMC growth primarily by slowing the diffusion of Cu atoms through the interface. - Highlights: •Role of Ag in IMC formation during Sn–Ag–Cu soldering was investigated. •Ag affects coarsening, crystallographic orientation, and IMC growth. •Diffusion pathways of Sn and Cu are affected differently by Ag. •Ag slows Cu diffusion to inhibit IMC growth at solder/substrate interface.

  6. Electrochemical energy storage

    CERN Document Server

    Tarascon, Jean-Marie

    2015-01-01

    The electrochemical storage of energy has become essential in assisting the development of electrical transport and use of renewable energies. French researchers have played a key role in this domain but Asia is currently the market leader. Not wanting to see history repeat itself, France created the research network on electrochemical energy storage (RS2E) in 2011. This book discusses the launch of RS2E, its stakeholders, objectives, and integrated structure that assures a continuum between basic research, technological research and industries. Here, the authors will cover the technological

  7. Electrochemical Hydrogen Evolution

    DEFF Research Database (Denmark)

    Laursen, A.B.; Varela Gasque, Ana Sofia; Dionigi, F.

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experiment...... catalysts based on this. Suited for upper-level high school and first-year university students, this exercise involves using a basic two-cell electrochemical setup to test multiple electrode materials as catalysts at one applied potential, and then constructing a volcano curve with the resulting currents...

  8. Pressure dependence of the interfacial structure of potassium chloride films on iron

    International Nuclear Information System (INIS)

    Olson, Dustin; Gao, Hongyu; Tang, Chun; Tysoe, Wilfred T.; Martini, Ashlie

    2015-01-01

    Potassium chloride films on a clean iron surface are used as a model system to explore the interfacial structure of the films and the dependence of that structure on film thickness and pressure. The interfacial structure of one-, two-, three- and four-layer films is measured experimentally using low-energy electron diffraction. Those findings are then complemented by molecular dynamics simulations in which the atomic interaction between the film and substrate is tuned to match film thickness-dependent sublimation activation energy obtained from temperature-programmed desorption measurements. The resultant simulation reliably predicts the structure of thicker films and is then used to study the effect of pressure on the distribution of the lattice constant within and between each layer of the potassium chloride films. Findings indicate that both film thickness and pressure affect the structure within the films as well as the degree of registry between the film and adjacent substrate. - Highlights: • KCl films on an Fe surface are used as a model system to explore interfacial structure • Thin film structure is measured using low-energy electron diffraction • An empirical potential is tuned to match sublimation activation energy • Simulations reveal the effect of pressure on the lattice constant within the KCl films • Pressure affects the film structure and registry between film and substrate

  9. Thermal and mechanical interfacial properties of epoxy composites based on functionalized carbon nanotubes

    International Nuclear Information System (INIS)

    Jin Fanlong; Ma Changjie; Park, Soo-Jin

    2011-01-01

    Highlights: → CNTs were functionalized by acid and amine treatments. → Epoxy resin/CNT composites were prepared. → T g of the composites increased by about 10 deg. C compared to neat epoxy resins. → Toughness of the composites was significantly improved by the addition of functionalized CNTs. - Abstract: Carbon nanotubes (CNTs) were treated by a mixture of acid and functionalized subsequently by amine treatment to improve interfacial interactions and dispersion of CNTs in epoxy matrix. The thermal stabilities and mechanical interfacial properties of epoxy/CNT composites were investigated using several techniques. The dispersion state of CNTs in the epoxy matrix was observed by scanning electron microscope (SEM) and transmission electron microscopy (TEM). As a result, the glass transition temperature of epoxy/CNT composites increased by about 11 deg. C compared to neat epoxy resins. The mechanical interfacial property of the composites was significantly increased by the addition of amine treated CNTs. The SEM and TEM results showed that the separation and uniform dispersion of CNTs in the epoxy matrix.

  10. Pressure dependence of the interfacial structure of potassium chloride films on iron

    Energy Technology Data Exchange (ETDEWEB)

    Olson, Dustin [Department of Chemistry and Laboratory for Surface Studies, University of Wisconsin—Milwaukee, Milwaukee, WI 53211 (United States); Gao, Hongyu; Tang, Chun [School of Engineering, University of California Merced, Merced CA 95343 (United States); Tysoe, Wilfred T. [Department of Chemistry and Laboratory for Surface Studies, University of Wisconsin—Milwaukee, Milwaukee, WI 53211 (United States); Martini, Ashlie [School of Engineering, University of California Merced, Merced CA 95343 (United States)

    2015-10-30

    Potassium chloride films on a clean iron surface are used as a model system to explore the interfacial structure of the films and the dependence of that structure on film thickness and pressure. The interfacial structure of one-, two-, three- and four-layer films is measured experimentally using low-energy electron diffraction. Those findings are then complemented by molecular dynamics simulations in which the atomic interaction between the film and substrate is tuned to match film thickness-dependent sublimation activation energy obtained from temperature-programmed desorption measurements. The resultant simulation reliably predicts the structure of thicker films and is then used to study the effect of pressure on the distribution of the lattice constant within and between each layer of the potassium chloride films. Findings indicate that both film thickness and pressure affect the structure within the films as well as the degree of registry between the film and adjacent substrate. - Highlights: • KCl films on an Fe surface are used as a model system to explore interfacial structure • Thin film structure is measured using low-energy electron diffraction • An empirical potential is tuned to match sublimation activation energy • Simulations reveal the effect of pressure on the lattice constant within the KCl films • Pressure affects the film structure and registry between film and substrate.

  11. An Implementation of Interfacial Transport Equation into the CUPID code

    Energy Technology Data Exchange (ETDEWEB)

    Park, Ik Kyu; Cho, Heong Kyu; Yoon, Han Young; Jeong, Jae Jun

    2009-11-15

    A component scale thermal hydraulic analysis code, CUPID (Component Unstructured Program for Interfacial Dynamics), is being developed for the analysis of components for a nuclear reactor, such as reactor vessel, steam generator, containment, etc. It adopted a three-dimensional, transient, two phase and three-field model. In order to develop the numerical schemes for the three-field model, various numerical schemes have been examined including the SMAS, semi-implicit ICE, SIMPLE. The governing equations for a 2-phase flow are composed of mass, momentum, and energy conservation equations for each phase. These equation sets are closed by the interfacial transfer rate of mass, momentum, and energy. The interfacial transfer of mass, momentum, and energy occurs through the interfacial area, and this area plays an important role in the transfer rate. The flow regime based correlations are used for calculating the interracial area in the traditional style 2-phase flow model. This is dependent upon the flow regime and is limited to the fully developed 2-phase flow region. Its application to the multi-dimensional 2-phase flow has some limitation because it adopts the measured results of 2-phase flow in the 1-dimensional tube. The interfacial area concentration transport equation had been suggested in order to calculate the interfacial area without the interfacial area correlations. The source terms to close the interfacial area transport equation should be further developed for a wide ranger usage of it. In this study, the one group interfacial area concentration transport equation has been implemented into the CUPID code. This interfacial area concentration transport equation can be used instead of the interfacial area concentration correlations for the bubbly flow region.

  12. An Implementation of Interfacial Transport Equation into the CUPID code

    International Nuclear Information System (INIS)

    Park, Ik Kyu; Cho, Heong Kyu; Yoon, Han Young; Jeong, Jae Jun

    2009-11-01

    A component scale thermal hydraulic analysis code, CUPID (Component Unstructured Program for Interfacial Dynamics), is being developed for the analysis of components for a nuclear reactor, such as reactor vessel, steam generator, containment, etc. It adopted a three-dimensional, transient, two phase and three-field model. In order to develop the numerical schemes for the three-field model, various numerical schemes have been examined including the SMAS, semi-implicit ICE, SIMPLE. The governing equations for a 2-phase flow are composed of mass, momentum, and energy conservation equations for each phase. These equation sets are closed by the interfacial transfer rate of mass, momentum, and energy. The interfacial transfer of mass, momentum, and energy occurs through the interfacial area, and this area plays an important role in the transfer rate. The flow regime based correlations are used for calculating the interracial area in the traditional style 2-phase flow model. This is dependent upon the flow regime and is limited to the fully developed 2-phase flow region. Its application to the multi-dimensional 2-phase flow has some limitation because it adopts the measured results of 2-phase flow in the 1-dimensional tube. The interfacial area concentration transport equation had been suggested in order to calculate the interfacial area without the interfacial area correlations. The source terms to close the interfacial area transport equation should be further developed for a wide ranger usage of it. In this study, the one group interfacial area concentration transport equation has been implemented into the CUPID code. This interfacial area concentration transport equation can be used instead of the interfacial area concentration correlations for the bubbly flow region

  13. Multiscale Interfacial Strategy to Engineer Mixed Metal-Oxide Anodes toward Enhanced Cycling Efficiency.

    Science.gov (United States)

    Ma, Yue; Tai, Cheuk-Wai; Li, Shaowen; Edström, Kristina; Wei, Bingqing

    2018-06-13

    Interconnected macro/mesoporous structures of mixed metal oxide (MMO) are developed on nickel foam as freestanding anodes for Li-ion batteries. The sustainable production is realized via a wet chemical etching process with bio-friendly chemicals. By means of divalent iron doping during an in situ recrystallization process, the as-developed MMO anodes exhibit enhanced levels of cycling efficiency. Furthermore, this atomic-scale modification coherently synergizes with the encapsulation layer across a micrometer scale. During this step, we develop a quasi-gel-state tri-copolymer, i.e., F127-resorcinol-melamine, as the N-doped carbon source to regulate the interfacial chemistry of the MMO electrodes. Electrochemical tests of the modified Fe x Ni 1- x O@NC-NiF anode in both half-cell and full-cell configurations unravel the favorable suppression of the irreversible capacity loss and satisfactory cyclability at the high rates. This study highlights a proof-of-concept modification strategy across multiple scales to govern the interfacial chemical process of the electrodes toward better reversibility.

  14. Heterolytic dissociative adsorption state of dihydrogen favored by interfacial defects

    Science.gov (United States)

    Song, Zhenjun; Hu, Hanshi; Xu, Hu; Li, Yong; Cheng, Peng; Zhao, Bin

    2018-03-01

    The atomic-scale insight into dihydrogen on MgO(001) surface deposited on molybdenum substrate with interfacial defects was investigated in detail by employing density functional methods Here we report novel dissociative adsorption behaviors of single hydrogen molecule on the usually inert oxide surfaces, with consideration of two types of dissociation schemes. The heterolytic dissociation state -Mg(H)-O(H)- of dihydrogen is impossible to obtain on neighboring O-Mg sites of perfect bulk MgO(001) terraces. Unusually, the hydrogen molecule can form heterolytic fragmentation states on metal supported MgO(001) films with very low activation barrier (0.398 eV), and the heterolytic dissociation state is much more favorable than homolytic dissociation state both energetically and kinetically in all cases. Electronic properties and bonding attribution of adsorbates and the oxide-metal hybrid structure are revealed by analyzing density of states, differential charge densities, orbital interaction and electron localization function. The characteristic changes to the property and activity of magnesia (001) can have potential application in catalytic reactions.

  15. Atomic Layer Deposition of Stable LiAlF4 Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling.

    Science.gov (United States)

    Xie, Jin; Sendek, Austin D; Cubuk, Ekin D; Zhang, Xiaokun; Lu, Zhiyi; Gong, Yongji; Wu, Tong; Shi, Feifei; Liu, Wei; Reed, Evan J; Cui, Yi

    2017-07-25

    Modern lithium ion batteries are often desired to operate at a wide electrochemical window to maximize energy densities. While pushing the limit of cutoff potentials allows batteries to provide greater energy densities with enhanced specific capacities and higher voltage outputs, it raises key challenges with thermodynamic and kinetic stability in the battery. This is especially true for layered lithium transition-metal oxides, where capacities can improve but stabilities are compromised as wider electrochemical windows are applied. To overcome the above-mentioned challenges, we used atomic layer deposition to develop a LiAlF 4 solid thin film with robust stability and satisfactory ion conductivity, which is superior to commonly used LiF and AlF 3 . With a predicted stable electrochemical window of approximately 2.0 ± 0.9 to 5.7 ± 0.7 V vs Li + /Li for LiAlF 4 , excellent stability was achieved for high Ni content LiNi 0.8 Mn 0.1 Co 0.1 O 2 electrodes with LiAlF 4 interfacial layer at a wide electrochemical window of 2.75-4.50 V vs Li + /Li.

  16. On the interfacial energy of coherent interfaces

    International Nuclear Information System (INIS)

    Kaptay, G.

    2012-01-01

    A thermodynamic model has been developed for interfacial energies of coherent interfaces using only the molar Gibbs energy and the molar volume of the two phases surrounding the interface as the initial data. The analysis is started from the simplest case of the interface formed by two solutions on the two sides of a miscibility gap, when both phases are described by the same Gibbs energy and molar volume functions. This method is applied to the fcc Au–Ni, liquid Ga–Pb and liquid Al–Bi systems. Reasonable agreement was found with the measured values in liquid Ga–Pb and Al–Bi systems. It was shown that the calculated results are sensitive to the choice of the Calphad-estimated thermodynamic data. The method is extended to the case where the two phases are described by different Gibbs energy and molar volume functions. The extended model is applied to the interface present in an Ni-based superalloy between the AlNi 3 face-centered cubic (fcc) compound and the Ni–Al fcc disordered solid solution. The calculated results are found to be similar to other values recently obtained from the combination of kinetic and thermodynamic data. The method is extended to ternary and higher order systems. It is predicted that the interfacial energy will gradually decrease with the increase in number of components in the system.

  17. Interfacial Friction and Adhesion of Polymer Brushes

    KAUST Repository

    Landherr, Lucas J. T.

    2011-08-02

    A bead-probe lateral force microscopy (LFM) technique is used to characterize the interfacial friction and adhesion properties of polymer brushes. Our measurements attempt to relate the physical structure and chemical characteristics of the brush to their properties as thin-film, tethered lubricants. Brushes are synthesized at several chain lengths and surface coverages from polymer chains of polydimethylsiloxane (PDMS), polystyrene (PS), and a poly(propylene glycol)-poly(ethylene glycol) block copolymer (PPG/PEG). At high surface coverage, PDMS brushes manifest friction coefficients (COFs) that are among the lowest recorded for a dry lubricant film (μ ≈ 0.0024) and close to 1 order of magnitude lower than the COF of a bare silicon surface. Brushes synthesized from higher molar mass chains exhibit higher friction forces than those created using lower molar mass polymers. Increased grafting density of chains in the brush significantly reduces the COF by creating a uniform surface of stretched chains with a decreased surface viscosity. Brushes with lower surface tension and interfacial shear stresses manifest the lowest COF. In particular, PDMS chains exhibit COFs lower than PS by a factor of 3.7 and lower than PPG/PEG by a factor of 4.7. A scaling analysis conducted on the surface coverage (δ) in relation to the fraction (ε) of the friction force developing from adhesion predicts a universal relation ε ∼ δ4/3, which is supported by our experimental data. © 2011 American Chemical Society.

  18. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    Science.gov (United States)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Ma, Lichun; Qi, Meiwei; Yu, Jiali; Huang, Yudong

    2014-10-01

    Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction "on water" to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction "on water" could be a facile green platform to functionalize carbon fibers for many interesting applications.

  19. First-principle study of the AlP/Si interfacial adhesion

    Energy Technology Data Exchange (ETDEWEB)

    Dai Hongshang [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, 73 Jingshi Road, Jinan 250061 (China); Du Jing [School of Science, Shandong Jianzhu University, Jinan 250101 (China); Wang Li; Peng Chuanxiao [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, 73 Jingshi Road, Jinan 250061 (China); Liu Xiangfa, E-mail: xfliu@sdu.edu.c [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, 73 Jingshi Road, Jinan 250061 (China); Shandong Binzhou Bohai Piston Co. Ltd., Binzhou 256602, Shandong (China)

    2010-01-15

    AlP is heterogeneous nucleation substrate of primary Si in hypereutectic Al-Si alloys, while studies on the nucleation mechanism at atomic level are absent. The pseudopotential-based DFT calculations have been carried out to investigate the atomic and electronic structure, bonding and adhesion of the AlP/Si interface. In total, eight geometries have been investigated, in which the interfacial stacking sequence is different. The favorable interfaces can be deduced for the reason that adhesive interface energies (W{sub ad}) are different, which cannot be obtained from the traditional mismatch theory. The interfacial density of states and Mulliken population are also investigated. It is found that the main bond between AlP and Si is covalent Al-Si or P-Si bond, accompanying some ionic characteristic.

  20. The enhancement of photoresponse of an ordered inorganic-organic hybrid architecture by increasing interfacial contacts

    International Nuclear Information System (INIS)

    Zhang Bin; Chen Xudong; Ma Shaohua; Yang Jin; Zhang Mingqiu; Chen Yujie

    2010-01-01

    A modified ZnO quantum dot/polythiophene (ZnO/PTh) inorganic-organic hybrid architecture was fabricated by using ordered mesoporous silica (SBA-15) as the retaining template. First, a two-step strategy was developed to synthesize an ordered organic conducting polymer composite (PTh/SBA-15). Then, ZnO quantum dots were in situ formed on the pore walls of the ordered PTh/SBA-15 composite. Photoresponse of the inorganic-organic hybrid was studied with respect to its incident photon to collected electron conversion efficiency (IPCE) and morphology. The presence of SBA-15 proved to be critical for controlling the interfacial morphology and hence enlarging the interfacial area of the inorganic-organic heterojunction. The proposed approach may act as a key method to open up potential applications in photovoltaic devices.

  1. The enhancement of photoresponse of an ordered inorganic-organic hybrid architecture by increasing interfacial contacts.

    Science.gov (United States)

    Zhang, Bin; Chen, Xudong; Ma, Shaohua; Chen, Yujie; Yang, Jin; Zhang, Mingqiu

    2010-02-10

    A modified ZnO quantum dot/polythiophene (ZnO/PTh) inorganic-organic hybrid architecture was fabricated by using ordered mesoporous silica (SBA-15) as the retaining template. First, a two-step strategy was developed to synthesize an ordered organic conducting polymer composite (PTh/SBA-15). Then, ZnO quantum dots were in situ formed on the pore walls of the ordered PTh/SBA-15 composite. Photoresponse of the inorganic-organic hybrid was studied with respect to its incident photon to collected electron conversion efficiency (IPCE) and morphology. The presence of SBA-15 proved to be critical for controlling the interfacial morphology and hence enlarging the interfacial area of the inorganic-organic heterojunction. The proposed approach may act as a key method to open up potential applications in photovoltaic devices.

  2. Interfacial morphology and domain configurations in 0-3 PZT-Portland cement composites

    International Nuclear Information System (INIS)

    Jaitanong, N.; Zeng, H.R.; Li, G.R.; Yin, Q.R.; Vittayakorn, W.C.; Yimnirun, R.; Chaipanich, A.

    2010-01-01

    Cement-based piezoelectric composites have attracted great attention recently due to their promising applications as sensors in smart structures. Lead zirconate titanate (PZT) and Portland cement (PC) composite were fabricated using 60% of PZT by volume. Scanning Electron Microscope and piezoresponse force microscope were used to investigate the morphology and domain configurations at the interfacial zone of PZT-Portland cement composites. Angular PZT ceramic grains were found to bind well with the cement matrix. The submicro-scale domains were clearly observed by piezoresponse force microscope at the interfacial regions between the piezoelectric PZT phase and Portland cement phase, and are clearer than the images obtained for pure PZT. This is thought to be due to the applied internal stress of cement to the PZT ceramic particle which resulted to clearer images.

  3. Interfacial stresses in a bi-material assembly with a compliant bonding layer

    International Nuclear Information System (INIS)

    Suhir, E; Vujosevic, M

    2008-01-01

    We examine an elongated bi-material adhesively bonded or soldered assembly with a continuous compliant attachment (bonding layer). The assembly is subjected to external tensile forces or to bending moments applied to one of the assembly components. We develop simple predictive analytical ('mathematical') models for the evaluation of interfacial shearing (in the case of external tensile forces) and peeling (in the case of external bending moments) stresses and strains in the bonding material. The developed models can be helpful in stress-strain analyses of assemblies of the type in question and particularly for printed-circuit-board (PCB)/surface-mounted-device (SMD) assemblies employed in electronic packaging. These models enable one to particularly evaluate the maximum interfacial stresses in the bonding material from the predicted or measured strains in the PCB in the vicinity of but still outside the surface-mounted package

  4. Enhancement of interfacial properties of basalt fiber reinforced nylon 6 matrix composites with silane coupling agents

    Directory of Open Access Journals (Sweden)

    2010-10-01

    Full Text Available In this work solution surface treatment was applied for producing basalt fiber reinforced PA6 matrix composites. Beyond scanning electron microscopy, static and dynamic mechanical tests, dynamic mechanical analysis of composites was used for qualifying the interfacial adhesion in a wide temperature range. The loss factor peak height of loss factor is particularly important, because it is in close relationship with the mobility of polymer molecular chain segments and side groups, hence it correlates with the number and strength of primary or secondary bondings established between the matrix and the basalt fibers. It was proven, that the interfacial adhesion between basalt fibers and polyamide can be largely improved by the application of silane coupling agents in the entire usage temperature range of composites. The presence of coupling agents on the surface of basalt fibers was proven by Fourier transform infrared spectroscopy. The best results were obtained by 3-glycidoxypropyltrimethoxysilane coupling agent.

  5. Efficient electrochemical degradation of multiwall carbon nanotubes.

    Science.gov (United States)

    Reipa, Vytas; Hanna, Shannon K; Urbas, Aaron; Sander, Lane; Elliott, John; Conny, Joseph; Petersen, Elijah J

    2018-07-15

    As the production mass of multiwall carbon nanotubes (MWCNT) increases, the potential for human and environmental exposure to MWCNTs may also increase. We have shown that exposing an aqueous suspension of pristine MWCNTs to an intense oxidative treatment in an electrochemical reactor, equipped with an efficient hydroxyl radical generating Boron Doped Diamond (BDD) anode, leads to their almost complete mineralization. Thermal optical transmittance analysis showed a total carbon mass loss of over two orders of magnitude due to the electrochemical treatment, a result consistent with measurements of the degraded MWCNT suspensions using UV-vis absorbance. Liquid chromatography data excludes substantial accumulation of the low molecular weight reaction products. Therefore, up to 99% of the initially suspended MWCNT mass is completely mineralized into gaseous products such as CO 2 and volatile organic carbon. Scanning electron microscopy (SEM) images show sporadic opaque carbon clusters suggesting the remaining nanotubes are transformed into structure-less carbon during their electrochemical mineralization. Environmental toxicity of pristine and degraded MWCNTs was assessed using Caenorhabditis elegans nematodes and revealed a major reduction in the MWCNT toxicity after treatment in the electrochemical flow-by reactor. Published by Elsevier B.V.

  6. Interfacial adhesion of laser clad functionally graded materials

    NARCIS (Netherlands)

    Pei, Y. T.; Ocelik, V.; De Hosson, J. T. M.

    2003-01-01

    Specially designed samples of laser clad AlSi40 functionally graded materials (FGM) are made for evaluating the interfacial adhesion. To obtain the interfacial bond strength notches are made right at the interface of the FGMs. In-situ microstructural observations during straining in a field-emission

  7. Interfacial adhesion of laser clad functionally graded materials

    NARCIS (Netherlands)

    De Hosson, JTM; Pei, YT; Ocelik, [No Value; Sudarshan, TS; Stiglich, JJ; Jeandin, M

    2002-01-01

    Specially designed samples of laser clad AlSi40 functionally graded materials (FGM) are made for evaluating the interfacial adhesion. To obtain the interfacial bond strength notches are made right at the interface of the FGMs. In-sitit microstructural observations during straining in an FEG-ESEM

  8. Curvature dependence of the electrolytic liquid-liquid interfacial tension

    NARCIS (Netherlands)

    Bier, Markus; de Graaf, J.; Zwanikken, J.W.; van Roij, R.H.H.G.

    2009-01-01

    The interfacial tension of a liquid droplet surrounded by another liquid in the presence of microscopic ions is studied as a function of the droplet radius. An analytical expression for the interfacial tension is obtained within a linear Poisson–Boltzmann theory and compared with numerical results

  9. Interfacial stresses in strengthened beam with shear cohesive zone ...

    Indian Academy of Sciences (India)

    The results of parametric study are compared with those of Smith and Teng. They confirm the accuracy of the proposed approach in predicting both interfacial shear and normal stresses. Keywords. Strengthened beam; interfacial stresses; cohesive zone; shear deformation. 1. Introduction. The FRP plates can be either ...

  10. Electrochemical Power Sources

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 6; Issue 7. Electrochemical Power Sources - Rechargeable Batteries. A K Shukla S K Martha. General Article Volume 6 Issue 7 July 2001 pp 52-63. Fulltext. Click here to view fulltext PDF. Permanent link:

  11. Electro-chemical grinding

    Science.gov (United States)

    Feagans, P. L.

    1972-01-01

    Electro-chemical grinding technique has rotation speed control, constant feed rates, and contour control. Hypersonic engine parts of nickel alloys can be almost 100% machined, keeping tool pressure at virtual zero. Technique eliminates galling and permits constant surface finish and burr-free interrupted cutting.

  12. Electrochemical performances of lithium ion battery using alkoxides of group 13 as electrolyte solvent

    International Nuclear Information System (INIS)

    Kaneko, Fuminari; Masuda, Yuki; Nakayama, Masanobu; Wakihara, Masataka

    2007-01-01

    Tris(methoxy polyethylenglycol) borate ester (B-PEG) and aluminum tris(polyethylenglycoxide) (Al-PEG) were used as electrolyte solvent for lithium ion battery, and the electrochemical property of these electrolytes were investigated. These electrolytes, especially B-PEG, showed poor electrochemical stability, leading to insufficient discharge capacity and rapid degradation with cycling. These observations would be ascribed to the decomposition of electrolyte, causing formation of unstable passive layer on the surface of electrode in lithium ion battery at high voltage. However, significant improvement was observed by the addition of aluminum phosphate (AlPO 4 ) powder into electrolyte solvent. AC impedance technique revealed that the increase of interfacial resistance of electrode/electrolyte during cycling was suppressed by adding AlPO 4 , and this suppression could enhance the cell capabilities. We infer that dissolved AlPO 4 components formed electrochemically stable layer on the surface of electrode

  13. Interfacial potential approach for Ag/ZnO (0001) interfaces

    International Nuclear Information System (INIS)

    Song Hong-Quan; Shen Jiang; Qian Ping; Chen Nan-Xian

    2014-01-01

    Systematic approaches are presented to extract the interfacial potentials from the ab initio adhesive energy of the interface system by using the Chen—Möbius inversion method. We focus on the interface structure of the metal (111)/ZnO (0001) in this work. The interfacial potentials of Ag—Zn and Ag—O are obtained. These potentials can be used to solve some problems about Ag/ZnO interfacial structure. Three metastable interfacial structures are investigated in order to check these potentials. Using the interfacial potentials we study the procedure of interface fracture in the Ag/ZnO (0001) interface and discuss the change of the energy, stress, and atomic structures in tensile process. The result indicates that the exact misfit dislocation reduces the total energy and softens the fracture process. Meanwhile, the formation and mobility of the vacancy near the interface are observed. (condensed matter: structural, mechanical, and thermal properties)

  14. Role of interfacial rheological properties in oil field chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Lakatos-Szabo, J.; Lakatos, I.; Kosztin, B.

    1996-12-31

    Interfacial rheological properties of different Hungarian crude oil/water systems were determined in wide temperature and shear rate range and in presence of inorganic electrolytes, tensides, alkaline materials and polymers. The detailed laboratory study definitely proved that the interfacial rheological properties are extremely sensitive parameters towards the chemical composition of inmiscible formation liquids. Comparison and interpretation of the interfacial rheological properties may contribute significantly to extension of the weaponry of the reservoir characterization, better understanding of the displacement mechanism, development of the more profitable EOR/IOR methods, intensification of the surface technologies, optimization of the pipeline transportation and improvement of the refinery operations. It was evidenced that the interfacial rheology is an efficient and powerful detection technique, which may enhance the knowledge on formation, structure, properties and behaviour of interfacial layers. 17 refs., 18 figs., 2 tabs.

  15. Electrochemical Biosensors - Sensor Principles and Architectures

    Directory of Open Access Journals (Sweden)

    Erik Reimhult

    2008-03-01

    Full Text Available Quantification of biological or biochemical processes are of utmost importancefor medical, biological and biotechnological applications. However, converting the biologicalinformation to an easily processed electronic signal is challenging due to the complexity ofconnecting an electronic device directly to a biological environment. Electrochemical biosensorsprovide an attractive means to analyze the content of a biological sample due to thedirect conversion of a biological event to an electronic signal. Over the past decades severalsensing concepts and related devices have been developed. In this review, the most commontraditional techniques, such as cyclic voltammetry, chronoamperometry, chronopotentiometry,impedance spectroscopy, and various field-effect transistor based methods are presented alongwith selected promising novel approaches, such as nanowire or magnetic nanoparticle-basedbiosensing. Additional measurement techniques, which have been shown useful in combinationwith electrochemical detection, are also summarized, such as the electrochemical versionsof surface plasmon resonance, optical waveguide lightmode spectroscopy, ellipsometry,quartz crystal microbalance, and scanning probe microscopy.The signal transduction and the general performance of electrochemical sensors are often determinedby the surface architectures that connect the sensing element to the biological sampleat the nanometer scale. The most common surface modification techniques, the various electrochemicaltransduction mechanisms, and the choice of the recognition receptor moleculesall influence the ultimate sensitivity of the sensor. New nanotechnology-based approaches,such as the use of engineered ion-channels in lipid bilayers, the encapsulation of enzymesinto vesicles, polymersomes, or polyelectrolyte capsules provide additional possibilities forsignal amplification.In particular, this review highlights the importance of the precise control over the

  16. Fabrication and electrochemical performance of graphene—ZnO nanocomposites

    International Nuclear Information System (INIS)

    Li Zhen-Peng; Men Chuan-Ling; Wang Wan; Cao Jun

    2014-01-01

    Graphene—ZnO nanocomposites were synthesized successfully through a one-step solvothermal approach. The morphology, structure, and composition of the prepared nanocomposites were investigated by scanning electron microscopy (SEM), transmission electron microscope (TEM), laser micro Raman spectroscopy, and Fourier transform infra-red spectroscopy (FT-IR). The outcomes confirmed that this approach is comparatively steady, practicable, and operable compared with other reported methods. The electrochemical performance of the graphene-ZnO electrodes was analyzed through cyclic voltammetry, altering-current (AC) impedance, and chronopotentiometry tests. The graphene—ZnO electrodes exhibited an improved electrode performance with higher specific capacitance (115 F·g −1 ), higher electrochemical stability, and higher energy density than the graphene electrodes and most reported graphene—ZnO electrodes. Graphene—ZnO nanocomposites have a steady reversible charge/discharge behavior, which makes them promising candidates for electrochemical capacitors (ECs). (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  17. Graphene Ink Film Based Electrochemical Detector for Paracetamol Analysis

    Directory of Open Access Journals (Sweden)

    Li Fu

    2018-01-01

    Full Text Available Graphene ink is a commercialized product in the graphene industry with promising potential application in electronic device design. However, the limitation of the graphene ink is its low electronic performance due to the ink preparation protocol. In this work, we proposed a simple post-treatment of graphene ink coating via electrochemical oxidation. The electronic conductivity of the graphene ink coating was enhanced as expected after the treatment. The proposed electrochemical oxidation treatment also exposes the defects of graphene and triggered an electrocatalytic reaction during the sensing of paracetamol (PA. The overpotential of redox is much lower than conventional PA redox potential, which is favorable for avoiding the interference species. Under optimum conditions, the graphene ink-based electrochemical sensor could linearly detect PA from 10 to 500 micro molar (μM, with a limit of detection of 2.7 μM.

  18. Surface Redox Chemistry of Immobilized Nanodiamond: Effects of Particle Size and Electrochemical Environment

    Science.gov (United States)

    Gupta, S.; McDonald, B.; Carrizosa, S. B.

    2017-07-01

    The size of the diamond particle is tailored to nanoscale (nanodiamond, ND), and the ND surface is engineered targeting specific (electrochemical and biological) applications. In this work, we investigated the complex surface redox chemistry of immobilized ND layer on conductive boron-doped diamond electrode with a broad experimental parameter space such as particle size (nano versus micron), scan rate, pH (cationic/acidic versus anionic/basic), electrolyte KCl concentration (four orders of magnitude), and redox agents (neutral and ionic). We reported on the significant enhancement of ionic currents while recording reversible oxidation of neutral ferrocene methanol (FcMeOH) by almost one order of magnitude than traditional potassium ferricyanide (K3Fe(CN)6) redox agent. The current enhancement is inversely related to ND particle diameter in the following order: 1 μm << 1000 nm < 100 nm < 10 nm ≤ 5 nm < 2 nm. We attribute the current enhancement to concurrent electrocatalytic processes, i.e. the electron transfer between redox probes and electroactive surface functional (e.g. hydroxyl, carboxyl, epoxy) moieties and the electron transfer mediated by adsorbed FcMeOH+ (or Fe(CN) 6 3+ ) ions onto ND surface. The first process is pH dependent since it depends upon ND surface functionalities for which the electron transfer is coupled to proton transfer. The adsorption mediated process is observed most apparently at slower scan rates owing to self-exchange between adsorbed FcMeOH+ ions and FcMeOH redox agent molecules in diffusion-limited bulk electrolyte solution. Alternatively, it is hypothesized that the surface functionality and defect sites ( sp 2-bonded C shell and unsaturated bonds) give rise to surface electronic states with energies within the band gap (midgap states) in undoped ND. These surface states serve as electron donors (and acceptors) depending upon their bonding (and antibonding) character and, therefore, they can support electrocatalytic redox

  19. Do uniform tangential interfacial stresses enhance adhesion?

    Science.gov (United States)

    Menga, Nicola; Carbone, Giuseppe; Dini, Daniele

    2018-03-01

    We present theoretical arguments, based on linear elasticity and thermodynamics, to show that interfacial tangential stresses in sliding adhesive soft contacts may lead to a significant increase of the effective energy of adhesion. A sizable expansion of the contact area is predicted in conditions corresponding to such scenario. These results are easily explained and are valid under the assumptions that: (i) sliding at the interface does not lead to any loss of adhesive interaction and (ii) spatial fluctuations of frictional stresses can be considered negligible. Our results are seemingly supported by existing experiments, and show that frictional stresses may lead to an increase of the effective energy of adhesion depending on which conditions are established at the interface of contacting bodies in the presence of adhesive forces.

  20. Liquid-liquid interfacial nanoparticle assemblies

    Science.gov (United States)

    Emrick, Todd S [South Deerfield, MA; Russell, Thomas P [Amherst, MA; Dinsmore, Anthony [Amherst, MA; Skaff, Habib [Amherst, MA; Lin, Yao [Amherst, MA

    2008-12-30

    Self-assembly of nanoparticles at the interface between two fluids, and methods to control such self-assembly process, e.g., the surface density of particles assembling at the interface; to utilize the assembled nanoparticles and their ligands in fabrication of capsules, where the elastic properties of the capsules can be varied from soft to tough; to develop capsules with well-defined porosities for ultimate use as delivery systems; and to develop chemistries whereby multiple ligands or ligands with multiple functionalities can be attached to the nanoparticles to promote the interfacial segregation and assembly of the nanoparticles. Certain embodiments use cadmium selenide (CdSe) nanoparticles, since the photoluminescence of the particles provides a convenient means by which the spatial location and organization of the particles can be probed. However, the systems and methodologies presented here are general and can, with suitable modification of the chemistries, be adapted to any type of nanoparticle.

  1. An interfacial stress sensor for biomechanical applications

    International Nuclear Information System (INIS)

    Sundara-Rajan, K; Bestick, A; Rowe, G I; Mamishev, A V; Klute, G K; Ledoux, W R; Wang, H C

    2012-01-01

    This paper presents a capacitive sensor that measures interfacial forces in prostheses and is promising for other biomedical applications. These sensors can be integrated into prosthetic devices to measure both normal and shear stress simultaneously, allowing for the study of prosthetic limb fit, and ultimately for the ability to better adapt prosthetics to individual users. A sensing cell with a 1.0 cm 2 spatial resolution and a measurement range of 0–220 kPa of shear and 0–2 MPa of pressure was constructed. The cell was load tested and found to be capable of isolating the applied shear and pressure forces. This paper discusses the construction of the prototype, the mechanical and electrode design, fabrication and characterization. The work presented is aimed at creating a class of adaptive prosthetic interfaces using a capacitive sensor. (paper)

  2. Solid-liquid interfacial energy of aminomethylpropanediol

    International Nuclear Information System (INIS)

    Ocak, Yavuz; Keslioglu, Kazim; Marasli, Necmettin; Akbulut, Sezen

    2008-01-01

    The grain boundary groove shapes for equilibrated solid aminomethylpropanediol, 2-amino-2 methyl-1.3 propanediol (AMPD) with its melt were directly observed by using a horizontal temperature gradient stage. From the observed grain boundary groove shapes, the Gibbs-Thomson coefficient (Γ), solid-liquid interfacial energy (σ SL ) and grain boundary energy (σ gb ) of AMPD have been determined to be (5.4 ± 0.5) x 10 -8 K m, (8.5 ± 1.3) x 10 -3 J m -2 and (16.5 ± 2.8) x 10 -3 J m -2 , respectively. The ratio of thermal conductivity of equilibrated liquid phase to solid phase for the AMPD has also been measured to be 1.12 at the melting temperature

  3. Solid-liquid interfacial energy of aminomethylpropanediol

    Energy Technology Data Exchange (ETDEWEB)

    Ocak, Yavuz; Keslioglu, Kazim; Marasli, Necmettin [Department of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri (Turkey); Akbulut, Sezen [Department of Physics, Institute of Science and Technology, Erciyes University, 38039 Kayseri (Turkey)], E-mail: marasli@erciyes.edu.tr

    2008-03-21

    The grain boundary groove shapes for equilibrated solid aminomethylpropanediol, 2-amino-2 methyl-1.3 propanediol (AMPD) with its melt were directly observed by using a horizontal temperature gradient stage. From the observed grain boundary groove shapes, the Gibbs-Thomson coefficient ({gamma}), solid-liquid interfacial energy ({sigma}{sub SL}) and grain boundary energy ({sigma}{sub gb}) of AMPD have been determined to be (5.4 {+-} 0.5) x 10{sup -8} K m, (8.5 {+-} 1.3) x 10{sup -3} J m{sup -2} and (16.5 {+-} 2.8) x 10{sup -3} J m{sup -2}, respectively. The ratio of thermal conductivity of equilibrated liquid phase to solid phase for the AMPD has also been measured to be 1.12 at the melting temperature.

  4. Tuning of Ag doped core−shell ZnO NWs/Cu2O grown by electrochemical deposition

    International Nuclear Information System (INIS)

    Makhlouf, Houssin; Messaoudi, Olfa; Souissi, Ahmed; Ben Assaker, Ibtissem; Oueslati, Mihrez; Bechelany, Mikhael; Chtourou, Radhouane

    2015-01-01

    ZnO nanowires (NWs)/Cu 2 O–Ag core–shell nanostructures (NSs) have been synthesized by electrochemical deposition method on ITO-coated glass substrates in order to improve the efficiency of the type-II transition of core–shell ZnO NWs/Cu 2 O–Ag NSs. The morphologies of the obtained NSs were studied by scanning electron microscopy confirming the presence of core–shell NSs. The crystalline proprieties were analyzed by x-ray diffraction and micro-Raman measurement: wurtzite ZnO and cuprit Cu 2 O phase were founded. The presence of Ag content in core–shell NS was detected by EDX. Optical measurement reveals an additional contribution δE at about 1.72 eV attributed to the type-II interfacial transition between the valance band of cuprit−Cu 2 O and the conduction band of W−ZnO. The effect of the Ag doping into the type-II transition was investigated. A red shift of the type-II transition was detected according to the Ag concentration. These materials could have potential applications in photocatalytic and photovoltaic fields. (paper)

  5. Electrochemical capacitance performance of titanium nitride nanoarray

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Yibing, E-mail: ybxie@seu.edu.cn [School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); Suzhou Research Institute of Southeast University, Suzhou 215123 (China); Wang, Yong [School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); Du, Hongxiu [School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); Suzhou Research Institute of Southeast University, Suzhou 215123 (China)

    2013-12-01

    Highlights: • TiN nanoarray is formed by a nitridation process of TiO{sub 2} in ammonia atmosphere. • TiN nanoarray exhibits much higher EDLC capacitance than TiO{sub 2} nanoarray. • The specific capacitance of TiN nanoarray achieves a high level of 99.7 mF cm{sup −2}. • A flexible solid-state supercapacitor is constructed by TiN nanoarray and PVA gel. -- Abstract: In this study, titanium nitride (TiN) nanoarrays with a short nanotube and long nanopore structure have been prepared by an anodization process of ultra thin titanium foil in ethylene glycol (EG) solution containing ammonium fluoride, subsequent calcination process in an air atmosphere, and final nitridation process in an ammonia atmosphere. The morphology and microstructure characterization has been conducted using field emission scanning electron microscope and X-ray diffraction. The electrochemical properties have been investigated through cyclic voltammetry and electrochemical impedance spectrum measurements. The electrochemical capacitance performance has been investigated by galvanostatic charge–discharge measurements in the acidic, neural and alkali electrolyte solution. Well-defined TiN nanoarrays contribute a much higher capacitance performance than titania (TiO{sub 2}) in the supercapacitor application due to the extraordinarily improved electrical conductivity. Such an electrochemical capacitance can be further enhanced by increasing aspect ratio of TiN nanoarray from short nanotubes to long nanopores. A flexible supercapacitor has been constructed using two symmetrical TiN nanoarray electrodes and a polyvinyl alcohol (PVA) gel electrolyte with H{sub 2}SO{sub 4}–KCl–H{sub 2}O–EG. Such a supercapacitor has a highly improved potential window and still keeps good electrochemical energy storage. TiN nanoarray with a high aspect ratio can act well as an ultra thin film electrode material of flexible supercapacitor to contribute a superior capacitance performance.

  6. Gold nanoparticle-based electrochemical biosensors

    Energy Technology Data Exchange (ETDEWEB)

    Pingarron, Jose M.; Yanez-Sedeno, Paloma; Gonzalez-Cortes, Araceli [Department of Analytical Chemistry, Faculty of Chemistry, University Complutense of Madrid, 28040 Madrid (Spain)

    2008-08-01

    The unique properties of gold nanoparticles to provide a suitable microenvironment for biomolecules immobilization retaining their biological activity, and to facilitate electron transfer between the immobilized proteins and electrode surfaces, have led to an intensive use of this nanomaterial for the construction of electrochemical biosensors with enhanced analytical performance with respect to other biosensor designs. Recent advances in this field are reviewed in this article. The advantageous operational characteristics of the biosensing devices designed making use of gold nanoparticles are highlighted with respect to non-nanostructured biosensors and some illustrative examples are commented. Electrochemical enzyme biosensors including those using hybrid materials with carbon nanotubes and polymers, sol-gel matrices, and layer-by-layer architectures are considered. Moreover, electrochemical immunosensors in which gold nanoparticles play a crucial role in the electrode transduction enhancement of the affinity reaction as well as in the efficiency of immunoreagents immobilization in a stable mode are reviewed. Similarly, recent advances in the development of DNA biosensors using gold nanoparticles to improve DNA immobilization on electrode surfaces and as suitable labels to improve detection of hybridization events are considered. Finally, other biosensors designed with gold nanoparticles oriented to electrically contact redox enzymes to electrodes by a reconstitution process and to the study of direct electron transfer between redox proteins and electrode surfaces have also been treated. (author)

  7. Gold nanoparticle-based electrochemical biosensors

    International Nuclear Information System (INIS)

    Pingarron, Jose M.; Yanez-Sedeno, Paloma; Gonzalez-Cortes, Araceli

    2008-01-01

    The unique properties of gold nanoparticles to provide a suitable microenvironment for biomolecules immobilization retaining their biological activity, and to facilitate electron transfer between the immobilized proteins and electrode surfaces, have led to an intensive use of this nanomaterial for the construction of electrochemical biosensors with enhanced analytical performance with respect to other biosensor designs. Recent advances in this field are reviewed in this article. The advantageous operational characteristics of the biosensing devices designed making use of gold nanoparticles are highlighted with respect to non-nanostructured biosensors and some illustrative examples are commented. Electrochemical enzyme biosensors including those using hybrid materials with carbon nanotubes and polymers, sol-gel matrices, and layer-by-layer architectures are considered. Moreover, electrochemical immunosensors in which gold nanoparticles play a crucial role in the electrode transduction enhancement of the affinity reaction as well as in the efficiency of immunoreagents immobilization in a stable mode are reviewed. Similarly, recent advances in the development of DNA biosensors using gold nanoparticles to improve DNA immobilization on electrode surfaces and as suitable labels to improve detection of hybridization events are considered. Finally, other biosensors designed with gold nanoparticles oriented to electrically contact redox enzymes to electrodes by a reconstitution process and to the study of direct electron transfer between redox proteins and electrode surfaces have also been treated

  8. The Interfacial Thermal Conductance of Epitaxial Metal-Semiconductor Interfaces

    Science.gov (United States)

    Ye, Ning

    -silicon), interfaces with varying levels of disorder (epitaxial and non-epitaxial). The ITC values of silicides-silicon interfaces observed in this study are higher than those of other metallic interfaces to Si found in literature. Most surprisingly, it is experimentally found that ITC values are independent of interfacial quality and substrate orientation. Computationally, it is found that the non-equilibrium atomistic Green's Function technique (NEGF), which is specically designed to simulate coherent elastic phonon transport across interfaces, significantly underpredicts ITC values for CoSi2-Si interfaces, suggesting that energy transport does not occur purely by coherent transmission of phonons, even for epitaxial interfaces. In contrast, the Diffuse Mismatch Model closely mimics the experimentally observed ITC values for CoSi 2-Si, NiSi-Si and TiSi2-Si interfaces, and only slightly overestimating the same for PtSi-Si interfaces. Furthermore, the results also show that ITC is independent of degenerate doping up to doping levels of ≈1 x 1019 cm-3, indicating there is no significant direct electronic transport or transport effects which depend on long-range metal-semiconductor band alignment. Then, I study the effect of phonon band structure on ITC through measurements of epitaxial NiAl1-xGax-GaAs interfaces for varying levels of alloy composition, which independently tunes the mass of the metal's heavy atom without much affect on the lattice structure or interatomic force constants. The ITC values are found to linearly increase with increasing Ga content, consistent with the disappearance of a phonon band gap in NiAl 1-xGax films with increasing Ga content, which enhances the phonon transmission coefficients due to a better density of states overlap between the two (NiAl1-xGax, GaAs) materials. Finally, I study a unique subset of epitaxial rocksalt interfaces between the Group IV metal nitrides (TiN, ZrN, and HfN) to MgO substrates as well as ScN layers. Prior to the currrent

  9. Laser Ablation Increases PEM/Catalyst Interfacial Area

    Science.gov (United States)

    Whitacre, Jay; Yalisove, Steve

    2009-01-01

    An investigational method of improving the performance of a fuel cell that contains a polymer-electrolyte membrane (PEM) is based on the concept of roughening the surface of the PEM, prior to deposition of a thin layer of catalyst, in order to increase the PEM/catalyst interfacial area and thereby increase the degree of utilization of the catalyst. The roughening is done by means of laser ablation under carefully controlled conditions. Next, the roughened membrane surface is coated with the thin layer of catalyst (which is typically platinum), then sandwiched between two electrode/catalyst structures to form a membrane/ele c t - rode assembly. The feasibility of the roughening technique was demonstrated in experiments in which proton-conducting membranes made of a perfluorosulfonic acid-based hydrophilic, protonconducting polymer were ablated by use of femtosecond laser pulses. It was found that when proper combinations of the pulse intensity, pulse-repetition rate, and number of repetitions was chosen, the initially flat, smooth membrane surfaces became roughened to such an extent as to be converted to networks of nodules interconnected by filaments (see Figure 1). In further experiments, electrochemical impedance spectroscopy (EIS) was performed on a pristine (smooth) membrane and on two laser-roughened membranes after the membranes were coated with platinum on both sides. Some preliminary EIS data were interpreted as showing that notwithstanding the potential for laser-induced damage, the bulk conductivities of the membranes were not diminished in the roughening process. Other preliminary EIS data (see Figure 2) were interpreted as signifying that the surface areas of the laser-roughened membranes were significantly greater than those of the smooth membrane. Moreover, elemental analyses showed that the sulfur-containing molecular groups necessary for proton conduction remained intact, even near the laser-roughened surfaces. These preliminary results can be taken

  10. Electrochemically controlled iron isotope fractionation

    Science.gov (United States)

    Black, Jay R.; Young, Edward D.; Kavner, Abby

    2010-02-01

    Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

  11. Interfacial effects in a multistage mixer-settler operation

    International Nuclear Information System (INIS)

    Jiinshiung Horng; Daluh Lu; Yingchu Hoh

    1988-01-01

    A pilot-scale mixer-settler with twenty-one stages was used to investigate the interfacial tension change during extraction cycle for the complicated system: NdCl 3 -SmCl 3 -EuCl 3 -GdCl 3 -TbCl 3 -DyCl 3 -HCl- 1 M D2EHPA-kerosene. Interfacial tension, total rare earth (TRE) concentrations in both phases, aqueous acidities, and organic entrainment in the raffinate, etc., were measured for each stage. Murphree stage efficiencies based on organic phase were calculated and related to the interfacial tension profiles. In general, the lower the interfacial tension, the higher the stage efficiency observed. For the extraction section, the stage efficiency ranged from 80% - 100%, but for stripping (including scrubbing) section, it varied from 100% - 15%. For high acidic stripping agent, 5 M HCl, the relatively lower stage efficiency might be due to the protonation of the acidic extractant, therefore the interfacial resistance increased significantly. From the information of stage efficiency, mass transfer direction, and interfacial tension versus solute concentration etc., the Marangoni effect could be used to explain the interfacial phenomena of this complicated extraction system. The results of real stream tests in this investigation will be useful in future plant design. (author)

  12. Electrochemical aptasensor for detecting tetracycline in milk

    International Nuclear Information System (INIS)

    Le, Thi Hanh; Pham, Van Phuc; La, Thi Huyen; Le, Quang Huan; Phan, Thi Binh

    2016-01-01

    A rapid, simple and sensitive biosensor system for tetracycline detection is very important in food safety. In this paper we developed a label-free aptasensor for electrochemical detection of tetracycline. According to the electrochemical impendence spectroscopy (EIS) analysis, there was a linear relationship between the concentration of tetracycline and the electron transfer resistance from 10 to 3000 ng ml −1 of the tetracycline concentration. The detection limit was 10 ng ml −1 in 15 min detection duration. The prepared aptasensor showed a good reproducibility with an acceptable stability in tetracycline detection. The recoveries of tetracycline in spiked milk samples were in the range of 88.1%–94.2%. The aptasensor has sensitivity 98% and specificity of 100%. (paper)

  13. Electrochemical Approaches to Renewable Energy

    Science.gov (United States)

    Lobaccaro, Peter

    Renewable energy is becoming an increasingly important component of the world's energy supply as the threat of global warming continues to rise. There is a need to reduce the cost of this renewable energy and a future challenge to deal with the strain intermittent power sources like renewables place on the power grid. In this dissertation, electrochemistry is harnessed to address possible solutions to both of these issues. First, it is used to develop a low cost alternative photovoltaic material. Then, it is used to investigate the production of chemical fuel stocks which can be used for energy storage. In chapter 2, advances are made in the electrochemical deposition of indium (In) on molybdenum foil which enables the deposition of electronic-grade purity, continuous films with thicknesses in the micron range. As an example application, the electrodeposited In films are phosphorized via the thin-film vapor-liquid-solid growth method. The resulting poly-crystalline InP films display excellent optoelectronic quality, comparable to films grown from more standard vacuum deposition techniques. This demonstrates the versatility of the developed electrochemical deposition procedure. In the remaining chapters, renewable fuel production is investigated. First in chapter 3, molybdenum disulfide (MoS2) is examined as a catalyst for the hydrogen evolution reaction (HER). Typically, high-cost synthesized MoS2 is used as the catalyst because the pristine MoS 2 mineral is known to be a poor catalyst. The fundamental challenge with pristine MoS2 is the inert HER activity of the predominant (0001) basal surface plane. Here, we report a general thermal process in which the basal plane is texturized to increase the density of HER-active edge sites. The process generates high HER catalytic performance in pristine MoS 2 across various morphologies such as the bulk mineral, films composed of micron-scale flakes, and even films of a commercially-available spray of nanoflake MoS2. In

  14. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yuwei [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Meng, Linghui [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Fan, Liquan [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006 (China); Ma, Lichun; Qi, Meiwei; Yu, Jiali [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China); Huang, Yudong, E-mail: ydhuang.hit1@yahoo.com.cn [School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001 (China)

    2014-10-15

    Highlights: • Carbon fibers are grafted with phenyl amine group via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 73%. • Tensile strength of the carbon fibers does not decrease distinctly. • Using water as the reaction medium can avoid pollution from organic solvents. • Grafting via aryl diazonium reaction in one step can improve modification efficiency. - Abstract: Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction “on water” to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction “on water” could be a facile green platform to functionalize carbon fibers for many interesting applications.

  15. Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites

    Science.gov (United States)

    Xu, Tiwen; Jia, Zhixin; Luo, Yuanfang; Jia, Demin; Peng, Zheng

    2015-02-01

    The epoxidized natural rubber (ENR) as an interfacial modifier was used to improve the mechanical and dynamical mechanical properties of NR/silica composites. In order to reveal the interaction mechanism between ENR and silica, the ENR/Silica model compound was prepared by using an open mill and the interfacial interaction of ENR with silica was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and stress-strain testing. The results indicated that the ring-opening reaction occurs between the epoxy groups of ENR chains and Si-OH groups on the silica surfaces and the covalent bonds are formed between two phases, which can improve the dispersion of silica in the rubber matrix and enhance the interfacial combination between rubber and silica. The ring-opening reaction occurs not only in vulcanization process but also in mixing process, meanwhile, the latter seems to be more important due to the simultaneous effects of mechanical force and temperature.

  16. Interfacial adsorption and surfactant release characteristics of magnetically functionalized halloysite nanotubes for responsive emulsions.

    Science.gov (United States)

    Owoseni, Olasehinde; Nyankson, Emmanuel; Zhang, Yueheng; Adams, Daniel J; He, Jibao; Spinu, Leonard; McPherson, Gary L; Bose, Arijit; Gupta, Ram B; John, Vijay T

    2016-02-01

    Magnetically responsive oil-in-water emulsions are effectively stabilized by a halloysite nanotube supported superparamagnetic iron oxide nanoparticle system. The attachment of the magnetically functionalized halloysite nanotubes at the oil-water interface imparts magnetic responsiveness to the emulsion and provides a steric barrier to droplet coalescence leading to emulsions that are stabilized for extended periods. Interfacial structure characterization by cryogenic scanning electron microscopy reveals that the nanotubes attach at the oil-water interface in a side on-orientation. The tubular structure of the nanotubes is exploited for the encapsulation and release of surfactant species that are typical of oil spill dispersants such as dioctyl sulfosuccinate sodium salt and polyoxyethylene (20) sorbitan monooleate. The magnetically responsive halloysite nanotubes anchor to the oil-water interface stabilizing the interface and releasing the surfactants resulting in reduction in the oil-water interfacial tension. The synergistic adsorption of the nanotubes and the released surfactants at the oil-water interface results in oil emulsification into very small droplets (less than 20μm). The synergy of the unique nanotubular morphology and interfacial activity of halloysite with the magnetic properties of iron oxide nanoparticles has potential applications in oil spill dispersion, magnetic mobilization and detection using magnetic fields. Copyright © 2015 Elsevier Inc. All rights reserved.

  17. Effective Interfacially Polymerized Polyester Solvent Resistant Nanofiltration Membrane from Bioderived Materials

    KAUST Repository

    Abdellah, Mohamed H.

    2018-05-18

    Utilization of sustainable and environmentally friendly solvents for the preparation of membranes has attracted growing interest in recent years. In this work, a polyester thin film composite solvent resistant nanofiltration (SRNF) membrane is prepared by interfacial polymerization on a cellulose support. The cellulose support is prepared by nonsolvent‐induced phase separation from a dope solution containing an ionic liquid as an environmentally friendly solvent (negligible vapor pressure). The polyester film is formed via the interfacial reaction between quercetin, a plant‐derived polyphenol, and terephthaloyl chloride. Alpha‐pinene is used as a green alternative solvent to dissolve terephthaloyl chloride (TPC) while quercetin is dissolved in a 0.2 m NaOH solution. The interfacial polymerization reaction is successfully confirmed by Fourier transform infrared and X‐ray photoelectron spectroscopy while scanning electron and atomic force microscopy are used to characterize the membrane structure. The composite membrane shows an outstanding performance with a molecular weight cut‐off around 330 Da combined with a dimethylformamide (DMF) permeance up to 2.8 L m−2 bar−1 h−1. The membrane is stable in strong aprotic solvents such as DMF offering potential application in the pharmaceutical and petrochemical industries.

  18. Effects of atmospheric air plasma treatment on interfacial properties of PBO fiber reinforced composites

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Chengshuang, E-mail: cszhang83@163.com; Li, Cuiyun; Wang, Baiya; Wang, Bin; Cui, Hong

    2013-07-01

    Poly(p-phenylene benzobisoxazole) (PBO) fiber was modified by atmospheric air plasma treatment. The effects of plasma treatment power and speed on both surface properties of PBO fibers and interfacial properties of PBO/epoxy composites were investigated. Surface chemical composition of PBO fibers were analyzed by X-ray photoelectron spectroscopy (XPS). Surface morphologies of the fibers and interface structures of the composites were examined using scanning electron microscopy (SEM). Interfacial adhesion property of the composites was evaluated by interlaminar shear strength (ILSS). Mechanical properties of PBO multifilament were measured by universal testing machine. The results indicate that atmospheric air plasma treatment introduced some polar or oxygen-containing groups to PBO fiber surfaces, enhanced surface roughness and changed surface morphologies of PBO fibers by plasma etching and oxidative reactions. The plasma treatment also improved interfacial adhesion of PBO/epoxy composites but has little effect on tensile properties of PBO multifilament. The ILSS of PBO/epoxy composites increased to 40.0 MPa after atmospheric air plasma treatment with plasma treatment power of 300 W and treatment speed of 6 m/min.

  19. Interfacial behaviour of sodium stearoyllactylate (SSL) as an oil-in-water pickering emulsion stabiliser.

    Science.gov (United States)

    Kurukji, D; Pichot, R; Spyropoulos, F; Norton, I T

    2013-11-01

    The ability of a food ingredient, sodium stearoyllactylate (SSL), to stabilise oil-in-water (O/W) emulsions against coalescence was investigated, and closely linked to its capacity to act as a Pickering stabiliser. Results showed that emulsion stability could be achieved with a relatively low SSL concentration (≥0.1 wt%), and cryogenic-scanning electron microscopy (cryo-SEM) visualisation of emulsion structure revealed the presence of colloidal SSL aggregates adsorbed at the oil-water interface. Surface properties of SSL could be modified by altering the size of these aggregates in water; a faster decrease in surface tension was observed when SSL dispersions were subjected to high pressure homogenisation (HPH). The rate of SSL adsorption at the sunflower oil-water interface also increased after HPH, and a higher interfacial tension (IFT) was observed with increasing SSL concentration. Differential scanning calorimetry (DSC) enabled a comparison of the thermal behaviour of SSL in aqueous dispersions with SSL-stabilised O/W emulsions. SSL melting enthalpy depended on emulsion interfacial area and the corresponding DSC data was used to determine the amount of SSL adsorbed at the oil-water interface. An idealised theoretical interfacial coverage calculation based on Pickering emulsion theory was in general agreement with the mass of SSL adsorbed as predicted by DSC. Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.

  20. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    International Nuclear Information System (INIS)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Ma, Lichun; Qi, Meiwei; Yu, Jiali; Huang, Yudong

    2014-01-01

    Highlights: • Carbon fibers are grafted with phenyl amine group via aryl diazonium reaction. • Interfacial shear strength of the carbon fibers increases by 73%. • Tensile strength of the carbon fibers does not decrease distinctly. • Using water as the reaction medium can avoid pollution from organic solvents. • Grafting via aryl diazonium reaction in one step can improve modification efficiency. - Abstract: Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction “on water” to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction “on water” could be a facile green platform to functionalize carbon fibers for many interesting applications

  1. Interfacial reactions in the Sb–Sn/(Cu, Ni) systems: Wetting experiments

    International Nuclear Information System (INIS)

    Novakovic, R.; Lanata, T.; Delsante, S.; Borzone, G.

    2012-01-01

    Interfacial reactions in the Sb–Sn/Cu and Sb–Sn/Ni systems have been investigated by means of wetting experiments. The wetting behaviour of two lead-free alloys, namely, Sb 2.5 Sn 97.5 and Sb 14.5 Sn 85.5 (at.%), in contact with Cu and Ni-substrates has been studied in view of possible applications as high-temperature solders in the electronics industry. The contact angle measurements on Cu and Ni plates were performed by using a sessile drop apparatus. The solder/substrate interface was characterised by the SEM-EDS analyses. -- Highlights: ► Sb–Sn alloys are used as high temperature lead-free solders. ► Sb–Sn alloys have good wetting properties on Cu and Ni substrates. ► Interfacial reactions and products are important for joint properties. ► Interfacial reactions/products data can be used to study the phase diagrams.

  2. Loading nature of the interfacial cracks in a joint component under fusion-relevant thermal loads

    International Nuclear Information System (INIS)

    You, J.H.

    1998-01-01

    One of the standard design concepts for divertor components in a fusion reactor is the bonded joint structure. Understanding the loading nature of interfacial cracks are significant for the assessment of structural integrity of divertor joint components. In this paper, the thermomechanical loading nature of interfacial cracks is discussed. A bi-material joint element consisting of the CFC/TZM system is considered. A typical fusion operation condition is simulated assuming a pulsed high heat flux loading. Stress singularities near the interfacial crack tips are characterized quantitatively in terms of the fracture mechanical parameters. The evolution of the stress intensity factors and the energy release rate during the given transient thermal load are determined. The difference in loading characteristics between the edge crack and the center crack is discussed. High heat flux cycling tests are performed on brazed CFC/TZM divertor elements in an electron beam test facility. The microstructures of the damaged interface agree with the predicted fracture modes. The loading nature and possible failure mechanisms are discussed for a fusion-relevant thermal loading. (orig.)

  3. Effect of modified polypropylene on the interfacial bonding of polymer–aluminum laminated films

    International Nuclear Information System (INIS)

    Liang, Chang-Sheng; Lv, Zhong-Fei; Bo, Yang; Cui, Jia-Yang; Xu, Shi-Ai

    2015-01-01

    Highlights: • Aluminium-polymer composite packing material with high T-peel strength was prepared. • Polypropylene was grafted by acrylic acid, glycidyl methacrylate, maleic anhydride. • Grafted polypropylene greatly improved the T-peel strength. • Chemical bonding plays an important role in improving the adhesion strength. - Abstract: The interfacial bonding between functionalized polymers and chromate–phosphate treated aluminum (Al) foil were investigated in this study. Glycidyl methacrylate (GMA), acrylic acid (AA) and maleic anhydride (MAH) were grafted onto polypropylene (PP) to improve its adhesion strength with the treated Al foil. The interfacial peel strength was evaluated by the T-peel test, and the results showed that modification of PP resulted in a significant improvement in the interfacial peel strength from 1 N/15 mm for pure PP to 10–14 N/15 mm for the modified PP. The surface chemistry, topography and surface energy of the modified PP and Al foil after peeling were characterized by time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM) and contact angle measurement. The treated Al foil could react with the functional groups of PP, resulting in the formation of new carboxylates. The new chemical bonding rather than the mechanical interlocking contributed to the improvement of adhesion strength

  4. Focused-ion-beam induced interfacial intermixing of magnetic bilayers for nanoscale control of magnetic properties

    International Nuclear Information System (INIS)

    Burn, D M; Atkinson, D; Hase, T P A

    2014-01-01

    Modification of the magnetic properties in a thin-film ferromagnetic/non-magnetic bilayer system by low-dose focused ion-beam (FIB) induced intermixing is demonstrated. The highly localized capability of FIB may be used to locally control magnetic behaviour at the nanoscale. The magnetic, electronic and structural properties of NiFe/Au bilayers were investigated as a function of the interfacial structure that was actively modified using focused Ga + ion irradiation. Experimental work used MOKE, SQUID, XMCD as well as magnetoresistance measurements to determine the magnetic behavior and grazing incidence x-ray reflectivity to elucidate the interfacial structure. Interfacial intermixing, induced by low-dose irradiation, is shown to lead to complex changes in the magnetic behavior that are associated with monotonic structural evolution of the interface. This behavior may be explained by changes in the local atomic environment within the interface region resulting in a combination of processes including the loss of moment on Ni and Fe, an induced moment on Au and modifications to the spin-orbit coupling between Au and NiFe. (paper)

  5. Interfacial Microstructure and Properties of Steel/Aluminum Powder Additive

    Directory of Open Access Journals (Sweden)

    YUAN Jiang

    2017-09-01

    Full Text Available Based on first-principles density functional theory, the Fe/Al interface model of steel/aluminum laser welding was constructed by layer technique. The Fe/Al interface was studied by metal atom X (X=Sn, Sr, Zr, Ce, La.The results show that Sn, Sr and Ce preferentially displace the Al atoms at the Fe/Al interface, while La and Zr preferentially displace the Fe atoms at the Fe/Al interface. Alloying promotes the transfer of Fe/Al interfacial electrons between different orbits, enhances the ionic bond properties of Fe-Al, improves the Fe/Al interface binding capacity, improves the brittle fracture of Fe/Al interface, and the alloying effect of Sn most notable. On the basis of this, the laser lap welding test of Sn and Zr powder was carried out on 1.4mm thick DC51D+ZF galvanized steel and 1.2mm thick 6016 aluminum alloy specimen. The results show that the addition of powder can promote the flowability of the molten bath and change the composition and microstructure of the joint interface. The tensile strength of the steel/aluminum joint is 327.41MPa and the elongation is 22.93% with the addition of Sn powder, which is obviously improved compared with the addition of Zr powder and without the addition of powder.

  6. Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides

    KAUST Repository

    Paniagua, Sergio A.

    2016-05-26

    Transparent conducting oxides (TCOs), such as indium tin oxide and zinc oxide, play an important role as electrode materials in organic-semiconductor devices. The properties of the inorganic-organic interface - the offset between the TCO Fermi level and the relevant transport level, the extent to which the organic semiconductor can wet the oxide surface, and the influence of the surface on semiconductor morphology - significantly affect device performance. This review surveys the literature on TCO modification with phosphonic acids (PAs), which has increasingly been used to engineer these interfacial properties. The first part outlines the relevance of TCO surface modification to organic electronics, surveys methods for the synthesis of PAs, discusses the modes by which they can bind to TCO surfaces, and compares PAs to alternative organic surface modifiers. The next section discusses methods of PA monolayer deposition, the kinetics of monolayer formation, and structural evidence regarding molecular orientation on TCOs. The next sections discuss TCO work-function modification using PAs, tuning of TCO surface energy using PAs, and initiation of polymerizations from TCO-tethered PAs. Finally, studies that examine the use of PA-modified TCOs in organic light-emitting diodes and organic photovoltaics are compared. © 2016 American Chemical Society.

  7. Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides

    KAUST Repository

    Paniagua, Sergio A.; Giordano, Anthony J.; Smith, O’ Neil L.; Barlow, Stephen; Li, Hong; Armstrong, Neal R.; Pemberton, Jeanne E.; Bredas, Jean-Luc; Ginger, David; Marder, Seth R.

    2016-01-01

    Transparent conducting oxides (TCOs), such as indium tin oxide and zinc oxide, play an important role as electrode materials in organic-semiconductor devices. The properties of the inorganic-organic interface - the offset between the TCO Fermi level and the relevant transport level, the extent to which the organic semiconductor can wet the oxide surface, and the influence of the surface on semiconductor morphology - significantly affect device performance. This review surveys the literature on TCO modification with phosphonic acids (PAs), which has increasingly been used to engineer these interfacial properties. The first part outlines the relevance of TCO surface modification to organic electronics, surveys methods for the synthesis of PAs, discusses the modes by which they can bind to TCO surfaces, and compares PAs to alternative organic surface modifiers. The next section discusses methods of PA monolayer deposition, the kinetics of monolayer formation, and structural evidence regarding molecular orientation on TCOs. The next sections discuss TCO work-function modification using PAs, tuning of TCO surface energy using PAs, and initiation of polymerizations from TCO-tethered PAs. Finally, studies that examine the use of PA-modified TCOs in organic light-emitting diodes and organic photovoltaics are compared. © 2016 American Chemical Society.

  8. A new approach for enhancement of the corrosion protection properties and interfacial adhesion bonds between the epoxy coating and steel substrate through surface treatment by covalently modified amino functionalized graphene oxide film

    International Nuclear Information System (INIS)

    Parhizkar, N.; Shahrabi, T.; Ramezanzadeh, B.

    2017-01-01

    Highlights: •The steel substrate was treated by a covalently modified amino functionalized graphene oxide (fGO) film. •Deposition of fGO film at the interface of steel and epoxy could effectively improve the adhesion strength and corrosion protection properties. •More stable and stronger interfacial bonds was obtained when treating the interface by fGO film. -- Abstract: This study introduces a novel surface treatment approach of steel substrate by covalent modification of graphene oxide (fGO) nanosheets with 3-aminopropyltriethoxysilane to improve the adhesion and corrosion protection properties of an epoxy coating. The effect of fGO film on the epoxy coating performance was studied by field-emission scanning electron microscopy (FE-SEM), X-Ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), Pull-off adhesion, salt spray and cathodic delamination tests. Results revealed that deposition of fGO film on steel surface can effectively improve the adhesion strength and corrosion protection properties and reduce the cathodic delamination rate of the epoxy coating.

  9. Interfacial and transport properties of nanoconstrained inorganic and organic materials

    Science.gov (United States)

    Kocherlakota, Lakshmi Suhasini

    Nanoscale constraints impact the material properties of both organic and inorganic systems. The systems specifically studied here are (i) nanoconstrained polymeric systems, poly(l-trimethylsilyl-1-propyne) (PTMSP) and poly(ethylene oxide) (PEO) relevant to gas separation membranes (ii) Zwitterionic polymers poly(sulfobetaine methacrylate)(pSBMA), poly(carboxybetaine acrylamide) (pCBAA), and poly(oligo(ethylene glycol) methyl methacrylate) (PEGMA) brushes critical for reducing bio-fouling (iii) Surface properties of N-layer graphene sheets. Interfacial constraints in ultrathin poly(l-trimethylsilyl-1-propyne) (PTMSP) membranes yielded gas permeabilities and CO2/helium selectivities that exceed bulk PTMSP membrane transport properties by up to three-fold for membranes of submicrometer thickness. Indicative of a free volume increase, a molecular energetic mobility analysis (involving intrinsic friction analysis) revealed enhanced methyl side group mobilities in thin PTMSP membranes with maximum permeation, compared to bulk films. Aging studies conducted over the timescales relevant to the conducted experiments signify that the free volume states in the thin film membranes are highly unstable in the presence of sorbing gases such as CO2. To maintain this high free volume configuration of polymer while improving the temporal stability an "inverse" architecture to conventional polymer nanocomposites was investigated, in which the polymer phase of PTMSP and PEO were interfacially and dimensionally constrained in nanoporous anodic aluminum oxide (AAO) membranes. While with this architecture the benefits of nanocomposite and ultrathin film membranes of PTMSP could be reproduced and improved upon, also the temporal stability could be enhanced substantially. The PEO-AAO nanocomposite membranes also revealed improved gas selectivity properties of CO2 over helium. In the thermal transition studies of zwitterionic pSBMA brushes a reversible critical transition temperature of 60

  10. Interfacial Micromechanics in Fibrous Composites: Design, Evaluation, and Models

    Science.gov (United States)

    Lei, Zhenkun; Li, Xuan; Qin, Fuyong; Qiu, Wei

    2014-01-01

    Recent advances of interfacial micromechanics in fiber reinforced composites using micro-Raman spectroscopy are given. The faced mechanical problems for interface design in fibrous composites are elaborated from three optimization ways: material, interface, and computation. Some reasons are depicted that the interfacial evaluation methods are difficult to guarantee the integrity, repeatability, and consistency. Micro-Raman study on the fiber interface failure behavior and the main interface mechanical problems in fibrous composites are summarized, including interfacial stress transfer, strength criterion of interface debonding and failure, fiber bridging, frictional slip, slip transition, and friction reloading. The theoretical models of above interface mechanical problems are given. PMID:24977189

  11. Nanoparticle packing within block copolymer micelles prepared by the interfacial instability method.

    Science.gov (United States)

    Nabar, Gauri M; Winter, Jessica O; Wyslouzil, Barbara E

    2018-05-02

    The interfacial instability method has emerged as a viable approach for encapsulating high concentrations of nanoparticles (NPs) within morphologically diverse micelles. In this method, transient interfacial instabilities at the surface of an emulsion droplet guide self-assembly of block co-polymers and NP encapsulants. Although used by many groups, there are no systematic investigations exploring the relationship between NP properties and micelle morphology. Here, the effect of quantum dot (QD) and superparamagnetic iron oxide NP (SPION) concentration on the shape, size, and surface deformation of initially spherical poly(styrene-b-ethylene oxide) (PS-b-PEO) micelles was examined. Multi-NP encapsulation and uniform dispersion within micelles was obtained even at low NP concentrations. Increasing NP concentration initially resulted in larger numbers of elongated micelles and cylinders with tightly-controlled diameters smaller than those of spherical micelles. Beyond a critical NP concentration, micelle formation was suppressed; the dominant morphology became densely-loaded NP structures that were coated with polymer and exhibited increased polydispersity. Transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) revealed that NPs in densely-loaded structures can be well-ordered, with packing volume fractions of up to 24%. These effects were enhanced in magnetic composites, possibly by dipole interactions. Mechanisms governing phase transitions triggered by NP loading in the interfacial instability process were proposed. The current study helps establish and elucidate the active role played by NPs in directing block copolymer assembly in the interfacial instability process, and provides important guiding principles for the use of this approach in generating NP-loaded block copolymer composites.

  12. Interfacial Behavior of Polymers: Using Interfaces to Manipulate Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Russell, Thomas P. [Univ. of Massachusetts, Amherst, MA (United States). Dept. of Polymer Science and Engineering

    2015-02-26

    most rapid solvent removal process drives the copolymer film to below its glass transition temperature, freezing in the lateral order. We have quantitatively described the ordering and the parameters influencing the disruption of the ordering in these studies. We have also used e-beam lithography to generate shallow trench patterns on planar surface where the topographic patterning provides an additional constraint on the self-assembly of the block copolymer. The pitches of the trenches were varied while the depth and the trench width of patterns were maintained by constant at 89 and 30nm, respectively. Unidirectional PS-b-PEO line patterns over large area on the shallow trench patterns were obtained by solvent vapor annealing. We extended the solvent annealing process to an in-line coating process using a mini-slot die coater developed in our laboratories. This coater uses minimal materials with operating parameters that can mimic actual industrial processing on a roll-to-roll line. Most important, with this mini-slot die coater, it could also characterize the structure of the film using grazing incidence x-ray scattering. Using the fundamental characterization of the ordering of the block copolymers, we could optimize the coating conditions to enhance lateral ordering of block copolymer in a well-defined manner. The structures produced in this process are directly transferable to flexible electronics where the arrays of block copolymer microdomains can be used for the fabrication of nanostructured components. We have also controlled the orientation of BCP microdomains at the air and substrate interfaces by manipulating the interfacial interactions with selective solvents. This has enabled us to generate nanoporous membranes where the size of the pores is dictated by the size of the bloc copolymer microdomains. We have produced robust nanoporous membranes that can tolerate high pressures and have high throughput using thick films of block copolymers. Exceptional size

  13. Suitability of olive oil washing water as an electron donor in a feed batch operating bio-electrochemical system; Idoneidad del agua de lavado de aceites de oliva como donador de electrones en un sistema alimentado por lotes bioelectroquímico

    Energy Technology Data Exchange (ETDEWEB)

    Fermoso, F.G.; Fernández-Rodríguez, M.J.; Jiménez-Rodríguez, A.; Serrano, A.; Borja, R.

    2017-07-01

    Olive oil washing water derived from the two-phase manufacturing process was assessed as an electron donor in a bio-electrochemical system (BES) operating at 35 ºC. Start-up was carried out by using acetate as a substrate for the BES, reaching a potential of around +680 mV. After day 54, BES was fed with olive oil