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Sample records for hybrid metal-organic interface

  1. Electron-Vibron Coupling at Metal-Organic Interfaces

    CERN Document Server

    Rosenow, Phil; Tonner, Ralf

    2015-01-01

    We study the significance and characteristics of interfacial dynamical charge transfer at metal-organic interfaces for the model system of organic semiconductor NTCDA on Ag(111). We combine infrared absorption spectroscopy and dispersion-corrected density functional theory calculations to analyze dynamic dipole moments and electron-vibron coupling at the interface. We demonstrate that interfacial dynamical charge transfer is the dominant cause of infrared activity in these systems and that it correlates with results from partial charge and density of states analysis. Nuclear motion generates an additional dynamic dipole moment but represents a minor effect except for modes with significant out-of-plane amplitudes.

  2. Melt-Quenched Hybrid Glasses from Metal-Organic Frameworks.

    Science.gov (United States)

    Tao, Haizheng; Bennett, Thomas D; Yue, Yuanzheng

    2017-05-01

    While glasses formed by quenching the molten states of inorganic non-metallic, organic, and metallic species are known, those containing both inorganic and organic moieties are far less prevalent. Network materials consisting of inorganic nodes linked by organic ligands do however exist in the crystalline or amorphous domain. This large family of open framework compounds, called metal-organic frameworks (MOFs) or coordination polymers, has been investigated intensively in the past two decades for a variety of applications, almost all of which stem from their high internal surface areas and chemical versatility. Recently, a selection of MOFs has been demonstrated to undergo melting and vitrification upon cooling. Here, these recent discoveries and the connections between the fields of MOF chemistry and glass science are summarized. Possible advantages and applications for MOF glasses produced by utilizing the tunable chemistry of the crystalline state are also highlighted. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. First-principles study of the dipole layer formation at metal-organic interfaces

    OpenAIRE

    2009-01-01

    We study the dipole layer formed at metal-organic interfaces by means of first-principles calculations. Interface dipoles are monitored by calculating the work function change of Au, Ag, Al, Mg and Ca surfaces upon adsorption of a monolayer of PTCDA (3,4,9,10-perylene-tetra-carboxylic-di-anhydride), perylene or benzene molecules. Adsorption of PTCDA leads to pinning of the work function for a range of metal substrates. It gives interface dipoles that compensate for the difference in the clean...

  4. Second sphere coordination of hybrid metal-organic materials: solid state reactivity.

    Science.gov (United States)

    Guo, Fang; Martí-Rujas, Javier

    2016-09-21

    When compared to other hybrid metal organic materials such as metal-organic frameworks, hydrogen bonded materials self-assembled by metals and organic molecules using second sphere interactions have been poorly investigated. Consequently, their solid-sate properties are also scarce. In this perspective, earlier research mainly on host-guest chemistry and its evolution towards more extended structures by applying crystal engineering principles using second sphere coordination is described. Crystal-to-crystal guest exchange reactions, permanently porous hybrid metal organic materials, mechanochemical reactivity, thermally induced phase transformations as well as some examples of functional technological applications using second sphere adducts such as gas adsorption, separation and non-linear optical phenomena are also reported. Although some tutorial reviews on second sphere adducts have been conducted mainly in the solution state focusing on metal based anion receptors, to the best of our knowledge, an overview on relevant works that focus on the solid-state properties has not been carried out. The aim of this article is to highlight from some of the early fundamental work to the latest reports on hybrid metal-organic materials self-assembled via second sphere interactions with a focus on solid-state chemistry.

  5. Hybrid metal organic scintillator materials system and particle detector

    Science.gov (United States)

    Bauer, Christina A.; Allendorf, Mark D.; Doty, F. Patrick; Simmons, Blake A.

    2011-07-26

    We describe the preparation and characterization of two zinc hybrid luminescent structures based on the flexible and emissive linker molecule, trans-(4-R,4'-R') stilbene, where R and R' are mono- or poly-coordinating groups, which retain their luminescence within these solid materials. For example, reaction of trans-4,4'-stilbenedicarboxylic acid and zinc nitrate in the solvent dimethylformamide (DMF) yielded a dense 2-D network featuring zinc in both octahedral and tetrahedral coordination environments connected by trans-stilbene links. Similar reaction in diethylformamide (DEF) at higher temperatures resulted in a porous, 3-D framework structure consisting of two interpenetrating cubic lattices, each featuring basic to zinc carboxylate vertices joined by trans-stilbene, analogous to the isoreticular MOF (IRMOF) series. We demonstrate that the optical properties of both embodiments correlate directly with the local ligand environments observed in the crystal structures. We further demonstrate that these materials produce high luminescent response to proton radiation and high radiation tolerance relative to prior scintillators. These features can be used to create sophisticated scintillating detection sensors.

  6. Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

    Science.gov (United States)

    Yan, Hao; Hohman, J. Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P.; Shen, Zhi-Xun; Melosh, Nicholas A.

    2016-12-01

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of `solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

  7. Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly

    Science.gov (United States)

    Yan, Hao; Hohman, J. Nathan; Li, Fei Hua; Jia, Chunjing; Solis-Ibarra, Diego; Wu, Bin; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Vailionis, Arturas; Kim, Taeho Roy; Devereaux, Thomas P.; Shen, Zhi-Xun; Melosh, Nicholas A.

    2017-03-01

    Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of `solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

  8. Nano Metal-Organic Framework-Derived Inorganic Hybrid Nanomaterials: Synthetic Strategies and Applications.

    Science.gov (United States)

    Mai, Hien Duy; Rafiq, Khezina; Yoo, Hyojong

    2016-11-11

    Nano- (or micro-scale) metal-organic frameworks (NMOFs), also known as coordination polymer particles (CPPs), have received much attention because of their structural diversities and tunable properties. Besides the direct use, NMOFs can be alternatively used as sacrificial templates/precursors for the preparation of a wide range of hybrid inorganic nanomaterials in straightforward and controllable manners. Distinct advantages of using NMOF templates are correlated to their structural and functional tailorability at molecular levels that is rarely acquired in any other conventional template/precursor. In addition, NMOF-derived inorganic nanomaterials with distinct chemical and physical properties are inferred to dramatically expand the scope of their utilization in many fields. In this review, we aim to provide readers with a comprehensive summary of recent progress in terms of synthetic approaches for the production of diverse inorganic hybrid nanostructures from as-synthesized NMOFs and their promising applications.

  9. A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

    Science.gov (United States)

    Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

    2014-03-17

    This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min.

  10. Hybrid Glasses from Strong and Fragile Metal-Organic Framework Liquids

    DEFF Research Database (Denmark)

    Bennett, T.D.; Tan, J.C.; Yue, Yuanzheng

    2015-01-01

    Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship between...... amorphization and melting has so far not been investigated. Here we show how heating MOFs of zeolitic topology first results in a low density ‘perfect’ glass, similar to those formed in ice, silicon and disaccharides. This order–order transition leads to a super-strong liquid of low fragility that dynamically......-ranging melting temperatures of zeolitic MOFs are related to their network topologies and opens up the possibility of ‘melt-casting’ MOF glasses....

  11. Nanoporous metal organic frameworks as hybrid polymer-metal composites for drug delivery and biomedical applications.

    Science.gov (United States)

    Beg, Sarwar; Rahman, Mahfoozur; Jain, Atul; Saini, Sumant; Midoux, Patrick; Pichon, Chantal; Ahmad, Farhan Jalees; Akhter, Sohail

    2017-04-01

    Metal organic frameworks (MOFs), porous hybrid polymer-metal composites at the nanoscale, are recent innovations in the field of chemistry; they are novel polymeric materials with diverse biomedical applications. MOFs are nanoporous materials, consisting of metal ions linked together by organic bridging ligands. The unique physical and chemical characteristics of MOFs have attracted wider attention from the scientific community, exploring their utility in the field of material science, biology, nanotechnology and drug delivery. The practical feasibility of MOFs is possible owing to their abilities for biodegradability, excellent porosity, high loading capacity, ease of surface modification, among others. In this regard, this review provides an account of various types of MOFs, their physiochemical characteristics and use in diverse disciplines of biomedical sciences - with special emphasis on drug delivery and theranostics. Moreover, this review also highlights the stability and toxicity issues of MOFs, along with their market potential for biomedical applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Hybridization of Metal Nanoparticles with Metal-Organic Frameworks Using Protein as Amphiphilic Stabilizer.

    Science.gov (United States)

    Mao, Hui; Zhang, Weina; Zhou, Weiqiang; Zou, Binghua; Zheng, Bing; Zhao, Shilin; Huo, Fengwei

    2017-07-26

    Here, a facile strategy is reported to efficiently hybridize metal nanoparticles (MNPs) with typical metal-organic frameworks (MOFs) of ZIF-8 (zeolitic imidazolate framework-8), which employs bovine serum albumin (BSA, a serum albumin protein derived from cows) as the amphiphilic stabilizer to increase the affinity of MNP toward MOFs. For instance, the as-synthesized PdNPs/ZIF-8 composites with diameter from 100 to 200 nm always maintain well-defined crystalline structure, and the PdNPs with small size of ∼2 nm are well-dispersed in the crystal of MOFs without serious aggregations due to the BSA stabilizer. In Suzuki cross-coupling reactions of aryl halide, the PdNPs/ZIF-8 as catalysts have exhibited high activity and satisfied reusability owing to the use of BSA stabilizer as well as the fixing of MOFs matrixes. In addition, the strategy also can be extended to synthesize other kinds of MNPs/MOFs hybrid composites with tunable particle size, which brings more opportunity for functional MOFs hybrid materials.

  13. Multifunctional Supramolecular Hybrid Materials Constructed from Hierarchical Self-Ordering of In Situ Generated Metal-Organic Framework (MOF) Nanoparticles.

    Science.gov (United States)

    Chaudhari, Abhijeet K; Han, Intaek; Tan, Jin-Chong

    2015-06-25

    A synergistic approach is described to engineer supramolecular hybrid materials based on metal-organic frameworks, encompassing HKUST-1 nanoparticles formed in situ, coexisting with an electrically conducting gel fiber network. Following findings were made: (a) multistimuli-responsive structural transformation via reversible sol-gel switching, and (b) radical conversion of a soft hybrid gel into a mechanically malleable, viscoelastic matter. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. 3D hybrid-porous carbon derived from carbonization of metal organic frameworks for high performance supercapacitors

    Science.gov (United States)

    Bao, Weizhai; Mondal, Anjon Kumar; Xu, Jing; Wang, Chengyin; Su, Dawei; Wang, Guoxiu

    2016-09-01

    We report a rational design and synthesis of 3D hybrid-porous carbon with a hierarchical pore architecture for high performance supercapacitors. It contains micropores (<2 nm diameter) and mesopores (2-4 nm), derived from carbonization of unique porous metal organic frameworks (MOFs). Owning to the synergistic effect of micropores and mesopores, the hybrid-porous carbon has exceptionally high ion-accessible surface area and low ion diffusion resistance, which is desired for supercapacitor applications. When applied as electrode materials in supercapacitors, 3D hybrid-porous carbon demonstrates a specific capacitance of 332 F g-1 at a constant charge/discharge current of 500 mA g-1. The supercapacitors can endure more than 10,000 cycles without degradation of capacitance.

  15. polyMOFs: A Class of Interconvertible Polymer-Metal-Organic-Framework Hybrid Materials.

    Science.gov (United States)

    Zhang, Zhenjie; Nguyen, Ha Thi Hoang; Miller, Stephen A; Cohen, Seth M

    2015-05-18

    Preparation of porous materials from one-dimensional polymers is challenging because the packing of polymer chains results in a dense, non-porous arrangement. Herein, we demonstrate the remarkable adaptation of an amorphous, linear, non-porous, flexible organic polymer into a three-dimensional, highly porous, crystalline solid, as the organic component of a metal-organic framework (MOF). A polymer with aromatic dicarboxylic acids in the backbone functioned as a polymer ligand upon annealing with Zn(II), generating a polymer-metal-organic framework (polyMOF). These materials break the dogma that MOFs must be prepared from small, rigid ligands. Similarly, polyMOFs contradict conventional polymer chemistry by demonstrating that linear and amorphous polymers can be readily coaxed into a highly crystalline, porous, three-dimensional structure by coordination chemistry.

  16. Fabrication of metal-organic frameworks and graphite oxide hybrid composites for solid-phase extraction and preconcentration of luteolin.

    Science.gov (United States)

    Wang, Yang; Wu, Yichun; Ge, Huali; Chen, Huanhuan; Ye, Guiqin; Hu, Xiaoya

    2014-05-01

    A novel solid-phase extraction sorbent, metal-organic frameworks and graphite oxide hybrid composite, was prepared by a solvothermal technique. The morphology and properties of the resultant material were examined by Fourier transform infrared spectroscopy, X-ray diffraction and field emission scanning electron microscopy. To evaluate the extraction performance of the resultant sorbent, luteolin was chosen as a model analyte. The extraction conditions were optimized. Based on these, a convenient and efficient solid-phase extraction procedure for the determination of luteolin was established and the subsequent quantification step was performed by square wave anodic stripping voltammetry. Under the optimal conditions, the oxidation current increased linearly with increasing the concentration of luteolin in the range of 5.0 × 10(-9)-5.0 × 10(-7)molL(-1) with a correlation coefficient of 0.9983 and a detection limit of 7.9 × 10(-10)molL(-1). The relative standard deviation of seven successive scans was 4.20% for 5.0 × 10(-8)molL(-1) luteolin. This work not only proposes a useful method for sample pretreatment, but also reveals the great potential of metal-organic frameworks based hybrid materials as an excellent sorbent in solid-phase extraction.

  17. Coordination-driven in situ self-assembly strategy for the preparation of metal-organic framework hybrid membranes.

    Science.gov (United States)

    Zhang, Rong; Ji, Shulan; Wang, Naixin; Wang, Lin; Zhang, Guojun; Li, Jian-Rong

    2014-09-08

    Metal-organic frameworks (MOFs) have emerged as porous solids of a superior type for the fabrication of membranes. However, it is still challenging to prepare a uniformly dispersed robust MOF hybrid membrane. Herein, we propose a simple and powerful strategy, namely, coordination-driven in situ self-assembly, for the fabrication of MOF hybrid membranes. On the basis of the coordination interactions between metal ions and ligands and/or the functional groups of the organic polymer, this method was confirmed to be feasible for the production of a stable membrane with greatly improved MOF-particle dispersion in and compatibility with the polymer, thus providing outstanding separation ability. As an experimental proof of concept, a high-quality ZIF-8/PSS membrane was fabricated that showed excellent performance in the nanofiltration and separation of dyes from water.

  18. General Deposition of Metal-Organic Frameworks on Highly Adaptive Organic-Inorganic Hybrid Electrospun Fibrous Substrates.

    Science.gov (United States)

    Liu, Chang; Wu, Yi-Nan; Morlay, Catherine; Gu, Yifan; Gebremariam, Binyam; Yuan, Xiao; Li, Fengting

    2016-02-01

    Electrospun nanofibrous mats are ideal substrates for metal-organic frameworks (MOFs) crystal deposition because of their specific structural parameters and chemical tenability. In this work, we utilized organic-inorganic hybrid electrospun fibrous mats as support material to study the deposition of various MOF particles. HKUST-1 and MIL-53(Al) were produced through solvothermal method, while ZIF-8 and MIL-88B(Fe) were prepared using microwave-induced heating method. The synthesis procedure for both methods were simple and effective because the hybrid nanofibrous mats showed considerable affinity to MOF particles and could be used without additional modifications. The obtained MOF composites exhibited effective incorporation between MOF particles and the porous substrates. MIL-53(Al) composite was applied as fibrous sorbent and showed enhanced adsorption capacity and removal rate, as well as easier operation, compared with thepowdered sample. Moreover, MIL-53(Al) composite was easier to be regenerated compared with powder form.

  19. Hybrid micro-/nano-structures derived from metal-organic frameworks: preparation and applications in energy storage and conversion.

    Science.gov (United States)

    Cao, Xiehong; Tan, Chaoliang; Sindoro, Melinda; Zhang, Hua

    2017-05-22

    Metal-organic frameworks (MOFs), an important class of inorganic-organic hybrid crystals with intrinsic porous structures, can be used as versatile precursors or sacrificial templates for preparation of numerous functional nanomaterials for various applications. Recent developments of MOF-derived hybrid micro-/nano-structures, constructed by more than two components with varied functionalities, have revealed their extensive capabilities to overcome the weaknesses of the individual counterparts and thus give enhanced performance for energy storage and conversion. In this tutorial review, we summarize the recent advances in MOF-derived hybrid micro-/nano-structures. The synthetic strategies for preparing MOF-derived hybrid micro-/nano-structures are first introduced. Focusing on energy storage and conversion, we then discuss their potential applications in lithium-ion batteries, lithium-sulfur batteries, supercapacitors, lithium-oxygen batteries and fuel cells. Finally, we give our personal insights into the challenges and opportunities for the future research of MOF-derived hybrid micro-/nano-structures.

  20. Chemistry and electronic properties of ferromagnetic metal-organic semiconductor interfaces: Fe on CuPc

    Energy Technology Data Exchange (ETDEWEB)

    Aristov, V.Yu. [IFW Dresden, 01069 Dresden (Germany); Institute of Solid State Physics, Russian Academy of Sciences, Chernogolovka, Moscow distr., 142432 (Russian Federation); Molodtsova, O.V.; Knupfer, M. [IFW Dresden, 01069 Dresden (Germany); Ossipyan, Yu.A. [Institute of Solid State Physics, Russian Academy of Sciences, Chernogolovka, Moscow distr., 142432 (Russian Federation); Doyle, B.P. [TASC-INFM Laboratory, Area Science Park - Basovizza, 34012 Trieste (Italy); Department of Physics, University of Johannesburg, PO Box 524, Auckland Park, 2006 (South Africa); Nannarone, S. [TASC-INFM Laboratory, Area Science Park - Basovizza, 34012 Trieste (Italy); Dipartimento di Ingegneria dei Materiali ed Amb., Universita di Modena e Reggio Emilia (Italy)

    2009-12-15

    The chemistry and electronic properties of the interfaces formed between the ferromagnetic metal (Fe) and the model organic semiconductor copper phthalocyanine are investigated in ultra-high vacuum conditions for the case of metal deposition onto the organic molecular thin film. The studies were performed by means of core-level and valence-band high-resolution photoemission electron spectroscopy (PES) as well as near-edge X-ray absorption fine structure using synchrotron radiation. Metal overlayer formation on the top of the organic semiconductor was observed without substantial penetration of deposited metal species into the organic film. At the thin interface layer the ferromagnetic metal shows strong chemical interaction with the nitrogen and carbon of the organic films. Moreover, our results infer that, as a consequence of Fe deposition onto CuPc, central copper atoms of the organic molecules at the interface are reduced from Cu(II) to Cu(I), while Fe atoms are oxidized and/or the ferromagnetic metal replaces this central Cu atom. Further optimization of such an interface is thus required to allow and/or facilitate the injection of spin-polarized carriers into organic semiconductors. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  1. Interdiffusion Reaction-Assisted Hybridization of Two-Dimensional Metal-Organic Frameworks and Ti3C2Tx Nanosheets for Electrocatalytic Oxygen Evolution.

    Science.gov (United States)

    Zhao, Li; Dong, Biliang; Li, Shaozhou; Zhou, Lijun; Lai, Linfei; Wang, Zhiwei; Zhao, Shulin; Han, Min; Gao, Kai; Lu, Min; Xie, Xiaoji; Chen, Bo; Liu, Zhengdong; Wang, Xiangjing; Zhang, Hao; Li, Hai; Liu, Juqing; Zhang, Hua; Huang, Xiao; Huang, Wei

    2017-06-27

    Two-dimensional (2D) metal-organic framework (MOF) nanosheets have been recently regarded as the model electrocatalysts due to their porous structure, fast mass and ion transfer through the thickness, and large portion of exposed active metal centers. Combining them with electrically conductive 2D nanosheets is anticipated to achieve further improved performance in electrocatalysis. In this work, we in situ hybridized 2D cobalt 1,4-benzenedicarboxylate (CoBDC) with Ti3C2Tx (the MXene phase) nanosheets via an interdiffusion reaction-assisted process. The resulting hybrid material was applied in the oxygen evolution reaction and achieved a current density of 10 mA cm(-2) at a potential of 1.64 V vs reversible hydrogen electrode and a Tafel slope of 48.2 mV dec(-1) in 0.1 M KOH. These results outperform those obtained by the standard IrO2-based catalyst and are comparable with or even better than those achieved by the previously reported state-of-the-art transition-metal-based catalysts. While the CoBDC layer provided the highly porous structure and large active surface area, the electrically conductive and hydrophilic Ti3C2Tx nanosheets enabled the rapid charge and ion transfer across the well-defined Ti3C2Tx-CoBDC interface and facilitated the access of aqueous electrolyte to the catalytically active CoBDC surfaces. The hybrid nanosheets were further fabricated into an air cathode for a rechargeable zinc-air battery, which was successfully used to power a light-emitting diode. We believe that the in situ hybridization of MXenes and 2D MOFs with interface control will provide more opportunities for their use in energy-based applications.

  2. Investigation of a metal-organic interface. Realization and understanding of a molecular switch

    Energy Technology Data Exchange (ETDEWEB)

    Neucheva, Olga [Forschungszentrum Juelich (DE). Institute of Bio- and Nanosystems (IBN), Functional Nanostructures at Surfaces (IBN-3)

    2010-07-01

    The field of molecular organic electronics is an emerging and very dynamic area. The continued trend to miniaturisation, combined with increasing complexity and cost of production in conventional semiconductor electronics, forces companies to turn their attention to alternatives that promise the next levels of scale at significantly lower cost. After consumer electronic devices based on organic transistors, such as TVs and book readers, have already been presented, molecular electronics is expected to offer the next breakthrough in feature size. Unfortunately, most of the organic/metal interfaces contain intrinsic defects that break the homogeneity of the interface properties. In this thesis, the electronic and structural properties of such defects were examined in order to understand the influence of the inhomogeneities on the quality of the interface layer. However, the main focus of this work was the investigation of the local properties of a single molecule. Taking advantage of the Scanning Tunnelling Microscope's (STM's) ability to act as a local probe, a single molecular switch was realized and studied. Moreover, in close collaboration with theory groups, the underlying mechanism driving the switching process was identified and described. Besides the investigation of the switching process, the ability of the STM to build nanostructures of different shapes from large organic molecules was shown. Knowing the parameters for realization and control of the switching process and for building the molecular corrals, the results of this investigation enable the reconstruction of the studied molecular ensemble and its deployment in electric molecular circuits, constituting a next step towards further miniaturization of electronic devices. (orig.)

  3. Electronic properties of metal-organic and organic-organic interfaces studied by photoemission and photoabsorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Molodtsova, Olga

    2006-07-01

    In this work systematic studies of the organic semiconductor CuPc have been presented. In general the investigation can be devided in three parts. In the first one we have studied the electronic structure of clean CuPc thin film. The next two parts are devoted to organic-organic and metal-organic interface formation, where one of the interface components is CuPc thin film. The main results of this thesis are: - The electronic structure of the pristine organic semiconductor CuPc has been obtained by a combination of conventional and resonant photoemission, near-edge X-ray absorption, as well as by theoretical ab initio quantum-chemical calculations. The contributions of different atomic species as well as sites of the CuPc molecule to the electronic DOS has been established. A combined experimental and theoretical study of the unoccupied electronic density of states of CuPc was presented. - The electronic properties of the organic heterointerfaces between fullerite and pristine copper phthalocyanine were studied. Both interfaces, CuPc/C{sub 60} and C{sub 60}/CuPc, were found to be non-reactive with pronounced shifts of the vacuum level pointing to the formation of an interfacial dipole mainly at the CuPc side of the heterojunctions. The dipole values are close to the difference of the work functions of the two materials. Important interface parameters and hole-injection barriers were obtained. The sequence of deposition does not influence the electronic properties of the interfaces. - CuPc doped with potassium was studied by means of photoemission and photoabsorption spectroscopy. A detailed analysis of the core-level PE spectra allows one to propose possible lattice sites, which harbor the potassium ions. The films prepared in this thesis showed no finite electronic density of states at the Fermi level. - Two stages of the In/CuPc interface formation have been distinguished. The low-coverage stage is characterized by a strong diffusion of the In atoms into the

  4. New Autonomous Motors of Metal-Organic Framework (MOF) Powered by Reorganization of Self-Assembled Peptides at interfaces

    Science.gov (United States)

    Ikezoe, Yasuhiro; Washino, Gosuke; Uemura, Takashi; Kitagawa, Susumu; Matsui, Hiroshi

    2012-01-01

    There have developed a variety of microsystems that harness energy and convert it to mechanical motion. Here we developed new autonomous biochemical motors by integrating metal-organic framework (MOF) and self-assembling peptides. MOF is applied as an energy-storing cell that assembles peptides inside nanoscale pores of the coordination framework. The robust assembling nature of peptides enables reconfiguring their assemblies at the water-MOF interface, which is converted to fuel energy. Re-organization of hydrophobic peptides could create the large surface tension gradient around the MOF and it efficiently powers the translation motion of MOF. As a comparison, the velocity of normalized by volume for the DPA-MOF particle is faster and the kinetic energy per the unit mass of fuel is more than twice as large as the one for previous gel motor systems. This demonstration opens the new application of MOF and reconfigurable molecular self-assembly and it may evolve into the smart autonomous motor that mimic bacteria to swim and harvest target chemicals by integrating recognition units. PMID:23104155

  5. Hybrid metal-organic conductive network with plasmonic nanoparticles and fluorene (Conference Presentation)

    Science.gov (United States)

    Fontana, Laura; Fratoddi, Ilaria; Matassa, Roberto; Familiari, Giuseppe; Venditti, Iole; Batocchio, Chiara; Magnano, Elena; Nappini, Silvia; Leahu, Grigore; Belardini, Alessandro; Li Voti, Roberto; Sibilia, Concita

    2017-05-01

    For the development of new generation portable electronic devices, the realization of thin and flexible electrodes have a crucial role. Conductive organic systems can address this issue in different ways. Indeed, conductance in organic molecules were studied in different papers starting from seminal papers in last 70's [1] up to recent ones [2]. Among organic species, conduction and electronic characteristics of Fluorene derivatives were studied in different configurations [3,4]. Unfortunately, the conductance of organic materials is limited by charge transport mechanism [5]. Hybrid system with organic conductive compounds covalently linked with metal centres can lead to enhanced conductivity [6]. Here we synthesized gold and silver nanoparticles (AuNPs and AgNPs) stabilized with a fluorene thiolate derivative, namely 9,9-Didodecyl-2,7-bis(acetylthio)fluorene (FL). In the synthesis process the metal nanoparticles (MNPs) size results to be around 5 nm in diameter [7]. When deposited on a planar substrate, the hybrid compound form a regular network of MNPs separated each other by fluorene spacers covalently linked by thiol groups [8]. We deposited the network on substrate with two interdigitated electrodes in order to measure conductive properties (I-V characteristics). In I-V measurements it results to be that AgNPs based network is 200 times more conductive than AuNPs one. Selective oxidation of AgNPs network close to positive electrodes gives rise to a Schottky diode behavior in the I-V characteristic that could find potential applications in nano-electronics devices. The fluorescence and extinction spectra of FL-AgNPs and FL-AuNPs where characterised. References [1] C. K. Chiang, C. R. Fincher, Jr., Y. W. Park, A. J. Heeger, H. Shirakawa, E. J. Louis, S. C. Gau, and Alan G. MacDiarmid, Phys. Rev. Lett. 39, 1098 (1977). [2] Hylke B. Akkerman, Paul W. M. Blom, Dago M. de Leeuw and Bert de Boer, Nature 441, 69 (2006). [3] Rajendra Prasad Kalakodimi, Aletha M. Nowak

  6. Protein-Metal Organic Framework Hybrid Composites with Intrinsic Peroxidase-like Activity as a Colorimetric Biosensing Platform.

    Science.gov (United States)

    Yin, Yuqing; Gao, Chen Ling; Xiao, Qi; Lin, Guo; Lin, Zian; Cai, Zongwei; Yang, Huang-Hao

    2016-10-04

    Artificial enzyme mimetics have received considerable attention because natural enzymes have some significant drawbacks, including enzyme autolysis, low catalytic activity, poor recovery and low stability to environmental changes. Herein, we demonstrated a facile approach for one-pot synthesis of hemeprotein-metal organic framework hybrid composites (H-MOFs) by using bovine hemoglobin (BHb) and zeolitic imidazolate framework-8 (ZIF-8) as a model reaction system. Surprisingly, the new hybrid composites exhibits 423% increase in peroxidase-like catalytic activity compared to free BHb. Taking advantages of the unique pore structure of H-MOFs with high catalytic property, a H-MOFs-based colorimetric biosensing platform was newly constructed and applied for the fast and sensitive detection of hydrogen peroxide (H2O2) and phenol. The corresponding detection limits as low as 1.0 μM for each analyte with wide linear ranges (0-800 μM for H2O2 and 0-200 μM for phenol) were obtained by naked-eye visualization. Significantly, sensitive and selective method for visual assay of trace H2O2 in cell and phenol in sewage was achieved with this platform. The stability of H-MOFs was also examined and excellent reproducibility and recyclability without losing in its activity were observed. In addition, the general applicability of H-MOFs was also investigated by using other hemeproteins (horseradish peroxidase, and myoglobin) and the corresponding catalytic activities were 291% and 273% enhancement, respectively. This present work not only expands the application of MOFs, but also provides an alternative technique for biological and environmental sample assay.

  7. Conversion of cellulose and cellobiose into sorbitol catalyzed by ruthenium supported on a polyoxometalate/metal-organic framework hybrid.

    Science.gov (United States)

    Chen, Jinzhu; Wang, Shengpei; Huang, Jing; Chen, Limin; Ma, Longlong; Huang, Xing

    2013-08-01

    Cellulose and cellobiose were selectively converted into sorbitol over water-tolerant phosphotungstic acid (PTA)/metal- organic-framework-hybrid-supported ruthenium catalysts, Ru-PTA/MIL-100(Cr), under aqueous hydrogenation conditions. The goal was to investigate the relationship between the acid/metal balance of bifunctional catalysts Ru-PTA/MIL-100(Cr) and their performance in the catalytic conversion of cellulose and cellobiose into sugar alcohols. The control of the amount and strength of acid sites in the supported PTA/MIL-100(Cr) was achieved through the effective control of encapsulated-PTA loading in MIL-100(Cr). This design and preparation method led to an appropriately balanced Ru-PTA/MIL-100(Cr) in terms of Ru dispersion and hydrogenation capacity on the one hand, and acid site density of PTA/MIL-100(Cr) (responsible for acid-catalyzed hydrolysis) on the other hand. The ratio of acid site density to the number of Ru surface atoms (nA /nRu ) of Ru-PTA/MIL-100(Cr) was used to monitor the balance between hydrogenation and hydrolysis functions; the optimum balance between the two catalytic functions, that is, 8.84sorbitol of 57.9% at complete conversion of cellulose, and 97.1% yield in hexitols with a selectivity for sorbitol of 95.1% at complete conversion of cellobiose) were obtained using a Ru-PTA/MIL-100(Cr) catalyst with loadings of 3.2 wt % for Ru and 16.7 wt % for PTA. This research thus opens new perspectives for the rational design of acid/metal bifunctional catalysts for biomass conversion.

  8. Interface Characteristics of Wood-hybrid Composites

    Institute of Scientific and Technical Information of China (English)

    XUEFenglian; ZHAOGuangjie

    2005-01-01

    In order to understand the current interface characteristics of wood-hybrid composites, this paper starts off from the concept of composite interface and general theory of interface form, then the inner-surface and microstructure of wood and the interface characteristics of composites, such as wood- inorganic, wood-plastic and wood- metal made by electroless plating technique, are concluded and discussed in detail. Meanwhile,on the basis of that, some points of view about how to develop the wood-hybrid composites interface research in the future are also proposed.

  9. Magnesium nanocrystals embedded in a metal-organic framework: hybrid hydrogen storage with synergistic effect on physi- and chemisorption.

    Science.gov (United States)

    Lim, Dae-Woon; Yoon, Ji Woong; Ryu, Keun Yong; Suh, Myunghyun Paik

    2012-09-24

    Hexagonal-disk-shaped magnesium nanocrystals (MgNCs) are fabricated within a porous metal-organic framework (MOF, see picture). The MgNCs@MOF stores hydrogen by both physi- and chemisorptions, exhibiting synergistic effects to decrease the isosteric heat of H(2) physisorption compared with that of pristine MOF, and decrease the H(2) chemisorption/desorption temperatures by 200 K compared with those of bare Mg powder. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. (Metal-Organic Framework)-Polyaniline sandwich structure composites as novel hybrid electrode materials for high-performance supercapacitor

    Science.gov (United States)

    Guo, ShuaiNan; Zhu, Yong; Yan, YunYun; Min, YuLin; Fan, JinChen; Xu, QunJie; Yun, Hong

    2016-06-01

    Carbonized Zn-(Metal-Organic Framework)MOF- polyaniline composites for high performance of supercapacitor have been developed from zinc acetate, 8-Hydroxyquinoline, and aniline via a simple process. The as-synthesized product has been characterized by X-ray powder diffraction (XRD), Scanning electron microscopy(SEM), Fourier transform infrared spectra (FT-IR), Transmission electron microscope (TEM). The electrochemical properties of carbonized Zn-MOF/polyaniline electrode were investigated by current charge-discharge and cyclic voltammetry. The specific capacitance of MOF/PANI has been approach to be as high as 477 F g-1 at a current density of 1 A g-1.

  11. Comparison of the periodic slab approach with the finite cluster ansatz for metal-organic interfaces at the example of PTCDA on Ag(110)

    CERN Document Server

    Banerjee, Jaita; Galbraith, Martin C E; Mack, Hans-Georg; Settels, Volker; Engels, Bernd; Tonner, Ralf; Fink, Reinhold F

    2016-01-01

    We present a comparative study of metal-organic interface properties obtained from dispersion corrected density functional theory calculations based on two different approaches: the periodic slab supercell technique and cluster models with 18 to 290 Ag atoms. Fermi smearing and fixing of cluster borders are required to make the cluster calculation feasible and realistic. The considered adsorption structure and energy of a PTCDA molecule on the Ag(110) surface is not well reproduced with clusters containing only two metallic layers. However, clusters with four layers of silver atoms and sufficient lateral extension reproduce the adsorbate structure within 0.02 \\AA\\ and adsorption energies within 10\\% of the slab result. A consideration of the computational effort shows that the cluster approach is a competitive alternative to methods using periodic boundary conditions and of particular interest for research at surface defects and other systems that do not show periodic symmetry.

  12. Metal-organic frameworks@graphene hybrid aerogels for solid-phase extraction of non-steroidal anti-inflammatory drugs and selective enrichment of proteins.

    Science.gov (United States)

    Zhang, Xiaoqiong; Liang, Qionglin; Han, Qiang; Wan, Wei; Ding, Mingyu

    2016-06-20

    Graphene aerogel (GA)-supported metal-organic framework (MOF) particles with a three-dimensional (3D) architecture were fabricated for the first time via a facile template-free "sol-cryo" method. The prepared MOFs@graphene hybrid aerogels exhibit a 3D interconnected macroporous framework of graphene sheets with uniform dispersion of MOF particles. We also report the first attempt at using the hybrid aerogels as adsorbents for the solid-phase extraction (SPE) of non-steroidal anti-inflammatory drugs (NSAIDs) and the selective enrichment of proteins. The macroporous skeletons of GA provide both low backpressure and rapid mass transfer in SPE application, thus overcoming the obstacle of high backpressure caused by directly packing submicron or micron sized MOF particles into SPE cartridges. Excellent performances including satisfactory recoveries, high sensitivity and good reproducibility were achieved in the extraction of five NSAIDs. The hybrid aerogels also showed an interesting ability for selective enrichment of ribonuclease A (RNase A) and simultaneous exclusion of cytochrome C (Cyt C) and lysozyme (Lyz), which could be attributed to the electrostatic interactions between proteins and the positively charged coordinatively unsaturated metal sites (CUS) in MIL-101. We believe that this work will promote the application of MOFs in adsorption and separation, and our synthetic strategy could be further extended to develop other graphene-based hybrid aerogels.

  13. Self-assembly of cobalt-centered metal organic framework and multiwalled carbon nanotubes hybrids as a highly active and corrosion-resistant bifunctional oxygen catalyst

    Science.gov (United States)

    Fang, Yiyun; Li, Xinzhe; Li, Feng; Lin, Xiaoqing; Tian, Min; Long, Xuefeng; An, Xingcai; Fu, Yan; Jin, Jun; Ma, Jiantai

    2016-09-01

    Metal organic frameworks (MOF) derived carbonaceous materials have emerged as promising bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts for electrochemical energy conversion and storage. But previous attempts to overcome the poor electrical conductivity of MOFs hybrids involve a harsh high-template pyrolytic process to in situ form carbon, which suffer from extremely complex operation and inevitable carbon corrosion at high positive potentials when OER is operated. Herein, a self-assembly approach is presented to synthesize a non-precious metal-based, high active and strong durable Co-MOF@CNTs bifunctional catalyst for OER and ORR. CNTs not only improve the transportation of the electrons but also can sustain the harsh oxidative environment of OER without carbon corrosion. Meanwhile, the unique 3D hierarchical structure offers a large surface area and stable anchoring sites for active centers and CNTs, which enables the superior durability of hybrid. Moreover, a synergistic catalysis of Co(II), organic ligands and CNTs will enhance the bifunctional electrocatalytic performance. Impressively, the hybrid exhibits comparable OER and ORR catalytic activity to RuO2 and 20 wt% Pt/C catalysts and superior stability. This facile and versatile strategy to fabricating MOF-based hybrids may be extended to other electrode materials for fuel cell and water splitting applications.

  14. Hybrid Photonic Cavity with Metal-Organic Framework Coatings for the Ultra-Sensitive Detection of Volatile Organic Compounds with High Immunity to Humidity

    Science.gov (United States)

    Tao, Jifang; Wang, Xuerui; Sun, Tao; Cai, Hong; Wang, Yuxiang; Lin, Tong; Fu, Dongliang; Ting, Lennon Lee Yao; Gu, Yuandong; Zhao, Dan

    2017-01-01

    Detection of volatile organic compounds (VOCs) at parts-per-billion (ppb) level is one of the most challenging tasks for miniature gas sensors because of the high requirement on sensitivity and the possible interference from moisture. Herein, for the first time, we present a novel platform based on a hybrid photonic cavity with metal-organic framework (MOF) coatings for VOCs detection. We have fabricated a compact gas sensor with detection limitation ranging from 29 to 99 ppb for various VOCs including styrene, toluene, benzene, propylene and methanol. Compared to the photonic cavity without coating, the MOF-coated solution exhibits a sensitivity enhancement factor up to 1000. The present results have demonstrated great potential of MOF-coated photonic resonators in miniaturized gas sensing applications.

  15. Luminescent hybrid materials based on (8-hydroxyquinoline)-substituted metal-organic complexes and lead-borate glasses

    Science.gov (United States)

    Petrova, Olga B.; Anurova, Maria O.; Akkuzina, Alina A.; Saifutyarov, Rasim R.; Ermolaeva, Ekaterina V.; Avetisov, Roman I.; Khomyakov, Andrew V.; Taydakov, Ilya V.; Avetissov, Igor Ch.

    2017-07-01

    Novel luminescent organic-inorganic hybrid materials based on 8-hydroxyquinoline metal complexes (Liq, Kq, Naq, Rbq, Mgq2, Srq2, Znq2, Scq3, Alq3, Gaq3, and Inq3) have been synthesized by a high temperature exchange reaction with 80PbF2-20B2O3 inorganic low-melting glass. The mechanical and optical properties, transmission spectra, emission an excitation photoluminescence, and luminescence kinetic of hybrid materials were studied. All hybrid materials showed a wide luminescence band in the range 400-700 nm.

  16. Single Component Lanthanide Hybrids Based on Metal-Organic Framework for Near-Ultraviolet White Light LED.

    Science.gov (United States)

    Zhao, Yan-Wu; Zhang, Fu-Qiang; Zhang, Xian-Ming

    2016-09-14

    Near-UV single-phase white-light phosphor (Eu0.045Tb0.955CPOMBA/La0.6Eu0.1Tb0.3CPOMBA) based on metal-organic framework was prepared by in situ doping isostructural lanthanide MOF with Eu(3+) and Tb(3+), and it is found that the energy can effectively transfer from organic ligand to lanthanides, which can overcome weak absorption under direct excitation of lanthanide ions due to the forbidden f-f transitions. The photoluminescence and thermostability of the new MOF phosphor are investigated, and effective white-light emission is achieved under 365 and 380 nm excitations. By employing Eu0.045Tb0.955CPOMBA as phosphor, we fabricated a near-ultraviolet white-light-emitting diode (n-UV WLED) (365 nm) with low CCT (5733 K), high CRI (Ra = 73.4), and CIE chromaticity coordinate (0.3264, 0.3427). This approach may open new perspectives for developing single-phase UV phosphors.

  17. Ultraviolet photoconductive devices with an n-GaN nanorod-graphene hybrid structure synthesized by metal-organic chemical vapor deposition.

    Science.gov (United States)

    Kang, San; Mandal, Arjun; Chu, Jae Hwan; Park, Ji-Hyeon; Kwon, Soon-Yong; Lee, Cheul-Ro

    2015-06-01

    The superior photoconductive behavior of a simple, cost-effective n-GaN nanorod (NR)-graphene hybrid device structure is demonstrated for the first time. The proposed hybrid structure was synthesized on a Si (111) substrate using the high-quality graphene transfer method and the relatively low-temperature metal-organic chemical vapor deposition (MOCVD) process with a high V/III ratio to protect the graphene layer from thermal damage during the growth of n-GaN nanorods. Defect-free n-GaN NRs were grown on a highly ordered graphene monolayer on Si without forming any metal-catalyst or droplet seeds. The prominent existence of the undamaged monolayer graphene even after the growth of highly dense n-GaN NRs, as determined using Raman spectroscopy and high-resolution transmission electron microscopy (HR-TEM), facilitated the excellent transport of the generated charge carriers through the photoconductive channel. The highly matched n-GaN NR-graphene hybrid structure exhibited enhancement in the photocurrent along with increased sensitivity and photoresponsivity, which were attributed to the extremely low carrier trap density in the photoconductive channel.

  18. Chemistry and electronic properties of metal-organic semiconductor interfaces: Fe and Co on CuPc

    Energy Technology Data Exchange (ETDEWEB)

    Aristov, Victor; Molodtsova, Olga; Knupfer, Martin [IFW Dresden, D-01069 Dresden (Germany); Ossipyan, Yurii [Institute of Solid State Physics,sian Academy of Sciences, Chernogolovka, Moscow (Russian Federation); Doyle, Bryan [TASC-INFM Laboratory, Trieste (Italy); Nannarone, Stefano [TASC-INFM Laboratory, Trieste (Italy); Dipartimento di Ingegneria dei Materiali ed Amb., Universita di Modena (Italy)

    2007-07-01

    The creation of a spin transistor based on a semiconductor was proposed in 1990 by Datta and Das. Nowadays the attractive idea to create a spin-transistor based on an organic semiconductor thin film (OMTF) has been proposed. The main problem in the development of such a device is to produce ferromagnetic metallic contacts as an injector of spin-polarized electrons into OMTF and as a drain of these spinpolarized electrons from the channel. This problem could be solved by fabrication and investigation of contacts such as Fe(Co,Ni) thin films to an OMTF. In this contribution we present the results of extensive investigations of chemistry and electronic properties of the interface formation between Fe(Co) and the archetypical organic semiconductor copper phthalocyanine (CuPc). The studies were performed by means of core-level and valence-band high-resolution photoemission electron spectroscopy as well as by near-edge X-ray absorption fine structure and using the synchrotron radiation facility ELETTRA (Italy).

  19. Metal-Organic Framework/Chitosan Hybrid Materials Promote Nitric Oxide Release from S-Nitrosoglutathione in Aqueous Solution.

    Science.gov (United States)

    Neufeld, Megan J; Lutzke, Alec; Tapia, Jesus B; Reynolds, Melissa M

    2017-02-15

    It has been previously demonstrated that copper-based metal-organic frameworks (MOFs) accelerate formation of the therapeutically active molecule nitric oxide (NO) from S-nitrosothiols (RSNOs). Because RSNOs are naturally present in blood, this function is hypothesized to permit the controlled production of NO through use of MOF-based blood-contacting materials. The practical implementation of MOFs in this application typically requires incorporation within a polymer support, yet this immobilization has been shown to impair the ability of the MOF to interact with the NO-forming RSNO substrate. Here, the water-stable, copper-based MOF H3[(Cu4Cl)3-(BTTri)8] (H3BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), or Cu-BTTri, was incorporated within the naturally derived polysaccharide chitosan to form membranes that were evaluated for their ability to enhance NO generation from the RSNO S-nitrosoglutathione (GSNO). This is the first report to evaluate MOF-induced NO release from GSNO, the most abundant small-molecule RSNO. At a 20 μM initial GSNO concentration (pH 7.4 phosphate buffered saline, 37 °C), chitosan/Cu-BTTri membranes induced the release of 97 ± 3% of theoretical NO within approximately 4 h, corresponding to a 65-fold increase over the baseline thermal decomposition of GSNO. Furthermore, incorporation of Cu-BTTri within hydrophilic chitosan did not impair the activity of the MOF, unlike earlier efforts using hydrophobic polyurethane or poly(vinyl chloride). The reuse of the membranes continued to enhance NO production from GSNO in subsequent experiments, suggesting the potential for continued use. Additionally, the major organic product of Cu-BTTri-promoted GSNO decomposition was identified as oxidized glutathione via mass spectrometry, confirming prior hypotheses. Structural analysis by pXRD and assessment of copper leaching by ICP-AES indicated that Cu-BTTri retains crystallinity and exhibits no significant degradation following exposure to GSNO. Taken

  20. Synthesis and characterization of bis (acetylacetonato κ-O, O') [zinc(ii)/copper(ii)] hybrid organic-inorganic complexes as solid metal organic precursors.

    Science.gov (United States)

    Rooydell, Reza; Wang, Ruey-Chi; Brahma, Sanjaya; Ebrahimzadeh, Farzaneh; Liu, Chuan-Pu

    2015-05-07

    We have synthesized novel metal organic hybrid mixed compounds of bis (acetylacetonato κ-O, O') [zinc(ii)/copper(ii)]. Taking C10H14O4Zn0.7Cu0.3 (Z0.7C0.3AA) as an example, the crystals are composed of Z0.7C0.3AA units and uncoordinated water molecules. Single-crystal X-ray diffraction results show that the complex Z0.7C0.3AA crystallizes in the monoclinic system, space group P21/n. The unit cell dimensions are a = 10.329(4) Å, b = 4.6947(18) Å, and c = 11.369(4) Å; the angles are α = 90°, β = 91.881(6)°, and γ = 90°, the volume is 551.0(4) Å(3), and Z = 2. In this process, the M(ii) ions of Zn and Cu mix and occupy the centers of symmetrical structural units, which are coordinated to two ligands. The measured bond lengths and angles of O-M-O vary with the ratio of metal species over the entire series of the complexes synthesized. The chemistry of the as-synthesized compounds has been characterized using infrared spectroscopy, mass spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis, and the morphology of the products has been characterized using scanning electron microscopy. The thermal decomposition of the Z0.7C0.3AA composites measured by thermogravimetric analysis suggests that these complexes are volatile. The thermal characteristics of these complexes make them attractive precursors for metal organic chemical vapor deposition.

  1. Photonic hybrid crystals constructed from in situ host-guest nanoconfinement of a light-emitting complex in metal-organic framework pores

    Science.gov (United States)

    Chaudhari, Abhijeet K.; Ryder, Matthew R.; Tan, Jin-Chong

    2016-03-01

    We report the concept underpinning the facile nanoconfinement of a bulky luminous guest molecule in the pores of a metal-organic framework (MOF) host, which yields a hybrid host ⊃ guest nanomaterial with tunable opto-electronic characteristics and enhanced photostability. Utilizing an in situ host-guest confinement strategy enabled by molecular self-assembly, we show that the highly emitting ZnQ [Zn-(bis-8-hydroxyquinoline)] guest complexes could be rapidly encapsulated within the sodalite nanocages of zeolitic imidazolate framework (ZIF-8) host crystals. The nature of optical and electronic transitions phenomena of the guest-encapsulated ZIF-8 ⊃ ZnQ has been elucidated by means of fluorescence and absorption spectroscopy measurements, and substantiated further via theoretical molecular orbital calculations revealing the plausible host-guest charge transfer mechanism involved. Evidence suggests that its photophysical properties are not only strongly determined by the host-guest co-operative bonding interactions within the environment of the confined MOF nanocage, but also can be engineered to manipulate its emission color chromaticity or to shield light-sensitive emitting guests against rapid photochemical degradation.We report the concept underpinning the facile nanoconfinement of a bulky luminous guest molecule in the pores of a metal-organic framework (MOF) host, which yields a hybrid host ⊃ guest nanomaterial with tunable opto-electronic characteristics and enhanced photostability. Utilizing an in situ host-guest confinement strategy enabled by molecular self-assembly, we show that the highly emitting ZnQ [Zn-(bis-8-hydroxyquinoline)] guest complexes could be rapidly encapsulated within the sodalite nanocages of zeolitic imidazolate framework (ZIF-8) host crystals. The nature of optical and electronic transitions phenomena of the guest-encapsulated ZIF-8 ⊃ ZnQ has been elucidated by means of fluorescence and absorption spectroscopy measurements, and

  2. In-situ Fabrication of Graphene Oxide Hybrid Ni-based Metal-Organic Framework (Ni-MOFs@GO) with Ultrahigh Capacitance as Electrochemical Pseudocapacitor Materials.

    Science.gov (United States)

    Zhou, Yingjie; Mao, Zemin; Wang, Wei; Yang, Zhengkai; Liu, Xiang

    2016-10-03

    This paper reports a series of novel Ni-based metal-organic framework (Ni-MOFs) prepared by a facile solvothermal process. The synthetic conditions have great effects on the Ni-MOFs morphologies, porous textures and their electrochemical performances. Improved capacitance performance was successfully realized by the in-situ hybrid of Ni-MOFs with graphene oxide (GO) nanosheets (Ni-MOFs@GO). The pseudocapacitance ca. 1457.7 F/g for Ni-MOFs obtained at 180 ºC with HCl as the modulator was elevated to ca. 2192.4 F/g at the current density of 1 A/g for the Ni-MOFs@GO with the GO contents of 3 wt%. Additionally, the capacitance retention was also promoted from ca. 83.5% to 85.1% of its original capacitance at 10 A/g even after 3000 cycles accordingly. These outstanding electrochemical properties of Ni-based MOF materials may be related to their inherent characteristics, such as the unique flower-like architecture, fascinating synergetic effect between the Ni-MOFs and the GO nanosheets.

  3. Triple Hybrid Energy Harvesting Interface Electronics

    Science.gov (United States)

    Uluşan, H.; Chamanian, S.; Pathirana, W. M. P. R.; Zorlu, Ö.; Muhtaroğlu, A.; Külah, H.

    2016-11-01

    This study presents a novel triple hybrid system that combines simultaneously generated power from thermoelectric (TE), vibration-based electromagnetic (EM) and piezoelectric (PZT) harvesters for a relatively high power supply capability. In the proposed solution each harvesting source utilizes a distinct power management circuit that generates a DC voltage suitable for combining the three parallel supplies. The circuits are designed and implemented in 180 nm standard CMOS technology, and are terminated with a schottky diode to avoid reverse current flow. The harvested AC signal from the EM harvester is rectified with a self-powered AC-DC doubler, which utilizes active diode structures to minimize the forward- bias voltage drop. The PZT interface electronics utilizes a negative voltage converter as the first stage, followed by synchronous power extraction and DC-to-DC conversion through internal switches, and an external inductor. The ultra-low voltage DC power harvested by the TE generator is stepped up through a charge-pump driven by an LC oscillator with fully- integrated center-tapped differential inductors. Test results indicate that hybrid energy harvesting circuit provides more than 1 V output for load resistances higher than 100 kΩ (10 μW) where the stand-alone harvesting circuits are not able to reach 1 V output. This is the first hybrid harvester circuit that simultaneously extracts energy from three independent sources, and delivers a single DC output.

  4. Metal-organic framework-199/graphite oxide hybrid composites coated solid-phase microextraction fibers coupled with gas chromatography for determination of organochlorine pesticides from complicated samples.

    Science.gov (United States)

    Zhang, Suling; Du, Zhuo; Li, Gongke

    2013-10-15

    The hybrid material of a copper-based metal-organic framework (MOF-199) and graphite oxide (GO) was explored as the solid-phase microextraction (SPME) coating for the first time. This fiber was fabricated by using 3-amino-propyltriethoxysilane (APTES) as the cross-linking agent, which enhanced its durability and allowed more than 140 replicate extractions. With the incorporation of GO, the MOF-199/GO fibers with GO contents ranging from 5 to 15 wt% exhibited enhanced adsorption affinity to organochlorine pesticides (OCPs) compared to MOF or GO individually. This improvement was linked to the enhanced dispersive forces (increased volume of small pores) that provided by the dense carbon layers of GO. Combining the superior properties of high porosity of MOFs and the unique layered character of GO, the MOF-199/GO (10 wt%) fiber exhibited higher adsorption affinity to some OCPs than commercial polydimethylsiloxane (PDMS) and polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibers. This new fiber was developed for headspace (HS) SPME of eight OCPs followed by GC/ECD analysis. The limits of detection were 2.3-6.9 ng/L. The relative standard deviation (RSD) for five replicate extractions using one fiber ranged from 5.3% to 8.8%. The fiber-to-fiber reproducibility was 5.2-12.8%. This method was successfully used for simultaneous determination of eight OCPs from river water, soil, water convolvulus and longan with satisfactory recoveries of 90.6-104.4%, 82.7-96.8%, 72.2-107.7% and 82.8-94.3%, respectively. These results indicated the MOF-199/GO composite provided a promising alternative in sample pretreatment.

  5. Synthesis of Hierarchically Structured Hybrid Materials by Controlled Self-Assembly of Metal-Organic Framework with Mesoporous Silica for CO2 Adsorption.

    Science.gov (United States)

    Chen, Chong; Li, Bingxue; Zhou, Lijin; Xia, Zefeng; Feng, Nengjie; Ding, Jing; Wang, Lei; Wan, Hui; Guan, Guofeng

    2017-07-12

    The HKUST-1@SBA-15 composites with hierarchical pore structure were constructed by in situ self-assembly of metal-organic framework (MOF) with mesoporous silica. The structure directing role of SBA-15 had an obvious impact on the growth of MOF crystals, which in turn affected the morphologies and structural properties of the composites. The pristine HKUST-1 and the composites with different content of SBA-15 were characterized by XRD, N2 adsorption-desorption, SEM, TEM, FT-IR, TG, XPS, and CO2-TPD techniques. It was found that the composites were assembled by oriented growth of MOF nanocrystals on the surfaces of SBA-15 matrix. The interactions between surface silanol groups and metal centers induced structural changes and resulted in the increases in surface areas as well as micropore volumes of hybrid materials. Besides, the additional constraints from SBA-15 also restrained the expansion of HKUST-1, contributing to their smaller crystal sizes in the composites. The adsorption isotherms of CO2 on the materials were measured and applied to calculate the isosteric heats of adsorption. The HS-1 composite exhibited an increase of 15.9% in CO2 uptake capacity compared with that of HKUST-1. Moreover, its higher isosteric heats of CO2 adsorption indicated the stronger interactions between the surfaces and CO2 molecules. The adsorption rate of the composite was also improved due to the introduction of mesopores. Ten cycles of CO2 adsorption-desorption experiments implied that the HS-1 had excellent reversibility of CO2 adsorption. This study was intended to provide the possibility of assembling new composites with tailored properties based on MOF and mesoporous silica to satisfy the requirements of various applications.

  6. Covalent Bonding of Metal-Organic Framework-5/Graphene Oxide Hybrid Composite to Stainless Steel Fiber for Solid-Phase Microextraction of Triazole Fungicides from Fruit and Vegetable Samples.

    Science.gov (United States)

    Zhang, Shuaihua; Yang, Qian; Wang, Wenchang; Wang, Chun; Wang, Zhi

    2016-04-06

    A hybrid material of the zinc-based metal-organic framework-5 and graphene oxide (metal-organic framework-5/graphene oxide) was prepared as a novel fiber coating material for solid-phase microextraction (SPME). The SPME fibers were fabricated by covalent bonding via chemical cross-linking between the coating material metal-organic framework-5/graphene oxide and stainless steel wire. The prepared fiber was used for the extraction of five triazole fungicides from fruit and vegetable samples. Gas chromatography coupled with microelectron capture detector (GC-μECD) was used for quantification. The developed method gave a low limit of detection (0.05-1.58 ng g(-1)) and good linearity (0.17-100 ng g(-1)) for the determination of the triazole fungicides in fruit and vegetable samples. The relative standard deviations (RSDs) for five replicate extractions of the triazole fungicides ranged from 3.7 to 8.9%. The method recoveries for spiked fungicides (5, 20, and 50 ng g(-1)) in grape, apple, cucumber, celery cabbage, pear, cabbage, and tomato samples were in the range of 85.6-105.8% with the RSDs ranging from 3.6 to 11.4%, respectively, depending on both the analytes and samples. The metal-organic framework-5/graphene oxide coated fiber was stable enough for 120 extraction cycles without a significant loss of extraction efficiency. The method was suitable for the determination of triazole fungicides in fruit and vegetable samples.

  7. Interface engineering in inorganic hybrid structures towards improved photocatalysis (Conference Presentation)

    Science.gov (United States)

    Xiong, Yujie

    2016-10-01

    Designing new photocatalytic materials for improving photoconversion efficiency is a promising route to alleviate the steadily worsening environmental issues and energy crisis. Despite the invention of a large number of catalytic materials with well-defined structures, their overall efficiency in photocatalysis is still quite limited as the three key steps - light harvesting, charge generation and separation, and charge transfer to surface for redox reactions - have not been substantially improved. To improve each step in the complex process, there is a major trend to develop materials based on inorganic hybrid structures. In this case, interface engineering holds the promise for boosting the overall efficiency, given the key roles of interface structures in charge and energy transfer. In this talk, I will demonstrate several different approaches to designing inorganic hybrid structures with improved photocatalytic performance via interface engineering. The typical demonstrations include semiconductor-plasmonics systems for broad-spectrum light harvesting, metal-semiconductor interfaces for improved charge separation, semiconductor-MOF (metal-organic framework) configurations for activated surface reactions. It is anticipated that this series of works open a new window to rationally designing inorganic hybrid materials for photo-induced applications. References: (1) Bai, S.; Yang, L.; Wang, C.; Lin, Y.; Lu, J.; Jiang, J. and Xiong, Y.*, Angew. Chem. Int. Ed. 54, 14810-14814 (2015). (2) Bai, S.; Jiang, J.; Zhang, Q. and Xiong, Y.*, Chem. Soc. Rev. 44, 2893-2939 (2015). (3) Bai, S.; Li, X.; Kong, Q.; Long, R.; Wang, C.; Jiang, J. and Xiong, Y.*, Adv. Mater. 27, 3444-3452 (2015). (4) Bai, S.; Ge, J.; Wang, L.; Gong, M.; Deng, M.; Kong, Q.; Song, L.; Jiang, J.;* Zhang, Q.;* Luo, Y.; Xie, Y. and Xiong, Y.*, Adv. Mater. 26, 5689-5695 (2014). (5) Li, R.; Hu, J.; Deng, M.; Wang, H.; Wang, X.; Hu, Y.; Jiang, H. L.; Jiang, J.;* Zhang, Q.;* Xie, Y. and Xiong, Y.*, Adv. Mater

  8. The role of synchrotron radiation in examining the self-assembly of crystalline nanoporous framework materials: from zeolites and aluminophosphates to metal organic hybrids

    NARCIS (Netherlands)

    O'Brien, M.G.; Beale, A.M.; Weckhuysen, B.M.

    2013-01-01

    This tutorial review describes the role of synchrotron-based techniques in the study of the formation of Crystalline Nanoporous Framework Materials (CNFMs), such as zeolites, aluminophosphates (AlPOs) and metal organic frameworks (MOFs). Initially, a general formation process for CNFMs is described

  9. Mixed-Matric Membranes for CO2 and H2 Gas Separations Using Metal-Organic Framework and Mesoporus Hybrid Silicas

    Energy Technology Data Exchange (ETDEWEB)

    Inga Musselman; Kenneth Balkus, Jr.; John Ferraris

    2009-01-07

    In this work, we have investigated the separation performance of polymer-based mixed-matrix membranes containing metal-organic frameworks and mesoporous hybrid silicas. The MOF/Matrimid{reg_sign} and MOP-18/Matrimid{reg_sign} membranes exhibited improved dispersion and mechanical strength that allowed high additive loadings with reduced aggregation, as is the case of the 80 wt% MOP-18/Matrimid{reg_sign} and the 80% (w/w) Cu-MOF/Matrimid{reg_sign} membranes. Membranes with up to 60% (w/w) ZIF-8 content exhibited similar mechanical strength and improved dispersion. The H{sub 2}/CO{sub 2} separation properties of MOF/Matrimid{reg_sign} mixed-matrix membranes was improved by either keeping the selectivity constant and increasing the permeability (MOF-5, Cu-MOF) or by improving both selectivity and permeability (ZIF-8). In the case of MOF-5/Matrimid{reg_sign} mixed-matrix membranes, the H{sub 2}/CO{sub 2} selectivity was kept at 2.6 and the H{sub 2} permeability increased from 24.4 to 53.8 Barrers. For the Cu-MOF/Matrimid{reg_sign} mixed-matrix membranes, the H{sub 2}/CO{sub 2} selectivity was kept at 2.05 and the H{sub 2} permeability increased from 17.1 to 158 Barrers. These two materials introduced porosity and uniform paths that enhanced the gas transport in the membranes. When ZIF-8/Matrimid{reg_sign} mixed-matrix membranes were studied, the H{sub 2}/CO{sub 2} selectivity increased from 2.9 to 4.4 and the permeability of H{sub 2} increased from 26.5 to 35.8 Barrers. The increased H{sub 2}/CO{sub 2} selectivity in ZIF-8/Matrimid{reg_sign} membranes was explained by the sieving effect introduced by the ZIF-8 crystals (pore window 0.34 nm) that restricted the transport of molecules larger than H{sub 2}. Materials with microporous and/or mesoporous cavities like carbon aerogel composites with zeolite A and zeolite Y, and membranes containing mesoporous ZSM-5 showed sieving effects for small molecules (e.g. H{sub 2} and CO{sub 2}), however, the membranes were most

  10. Recent applications of metal-organic frameworks in sample pretreatment.

    Science.gov (United States)

    Wang, Yonghua; Rui, Min; Lu, Guanghua

    2017-06-19

    Metal-organic frameworks are promising materials in diverse analytical applications especially in sample pretreatment by virtue of their diverse structure topology, tunable pore size, permanent nanoscale porosity, high surface area, and good thermostability. According to hydrostability, metal-organic frameworks are divided into moisture-sensitive and water-stable types. In the actual applications, both kinds of metal-organic frameworks are usually engineered into hybrid composites containing magnetite, silicon dioxide, graphene, or directly carbonized to metal-organic frameworks derived carbon. These metal-organic frameworks based materials show good extraction performance to environmental pollutants. This review provides a critical overview of the applications of metal-organic frameworks and their composites in sample pretreatment modes, that is, solid-phase extraction, magnetic solid-phase extraction, micro-solid-phase extraction, solid-phase microextraction, and stir bar solid extraction. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Understanding Interfaces in Metal-Graphitic Hybrid Nanostructures”

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Mengning; Tang, Yifan; Star, Alexander

    2013-01-03

    Metal–graphitic interfaces formed between metal nanoparticles (MNPs) and carbon nanotubes (CNTs) or graphene play an important role in the properties of such hybrid nanostructures. This Perspective summarizes different types of interfaces that exist within the metal–carbon nanoassemblies and discusses current efforts on understanding and modeling the interfacial conditions and interactions. Characterization of the metal–graphitic interfaces is described here, including microscopy, spectroscopy, electrochemical techniques, and electrical measurements. Recent studies on these nanohybrids have shown that the metal–graphitic interfaces play critical roles in both controlled assembly of nanoparticles and practical applications of nanohybrids in chemical sensors and fuel cells. Better understanding, design, and manipulation of metal–graphitic interfaces could therefore become the new frontier in the research of MNP/CNT or MNP/graphene hybrid systems.

  12. A hybrid bioorganic interface for neuronal photoactivation.

    Science.gov (United States)

    Ghezzi, Diego; Antognazza, Maria Rosa; Dal Maschio, Marco; Lanzarini, Erica; Benfenati, Fabio; Lanzani, Guglielmo

    2011-01-25

    A key issue in the realization of retinal prosthetic devices is reliable transduction of information carried by light into specific patterns of electrical activity in visual information processing networks. Soft organic materials can be used to couple artificial sensors with neuronal tissues. Here, we interface a network of primary neurons with an organic blend. We show that primary neurons can be successfully grown onto the polymer layer without affecting the optoelectronic properties of the active material or the biological functionality of neuronal network. Moreover, action potentials can be triggered in a temporally reliable and spatially selective manner with short pulses of visible light. Our results may lead to new neuronal communication and photo manipulation techniques, thus paving way to the development of artificial retinas and other neuroprosthetic interfaces based on organic photodetectors.

  13. Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

    Science.gov (United States)

    Liu, Zhen-Fei; Egger, David A.; Refaely-Abramson, Sivan; Kronik, Leeor; Neaton, Jeffrey B.

    2017-03-01

    The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density functional theory calculations, especially those using local and semi-local functionals, often underestimate level alignment leading to inaccurate electronic structure and charge transport properties. In this work, we develop a new fully self-consistent predictive scheme to accurately compute level alignment at certain classes of complex heterogeneous molecule-metal interfaces based on optimally tuned range-separated hybrid functionals. Starting from a highly accurate description of the gas-phase electronic structure, our method by construction captures important nonlocal surface polarization effects via tuning of the long-range screened exchange in a range-separated hybrid in a non-empirical and system-specific manner. We implement this functional in a plane-wave code and apply it to several physisorbed and chemisorbed molecule-metal interface systems. Our results are in quantitative agreement with experiments, the both the level alignment and work function changes. Our approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.

  14. Synthesis, crystal structure and photo luminescent property of a 3D metal-organic hybrid of Cd(II) constructed by two different bridging carboxylate

    Indian Academy of Sciences (India)

    Biswajit Bhattacharya; Rajdip Dey; Debajyoti Ghoshal

    2013-05-01

    A solvothermal reaction of cadmium (II) nitrate with succinic acid and isonicotinic acid creates a novel 3D metal-organic framework, [Cd3(isonicotinate)2(suc)2] (1). Single crystal X-ray structure determination reveals that complex 1 posses two crystallographically independent Cd(II) centres. The succinate anion acts here as a heptadented ligand and binds five Cd(II) centre simultaneously. The heptacoordinated Cd(II) centres are oxo-bridged by succinate moiety and the hexacoordinated metal centres are terminally connected through four different succinate moiety to make the overall 2D sheet arrangement. In unit cell, the ratio of hexadented Cd(II) and heptadented Cd(II) is 1:2. The new compound was also characterized by luminescence spectra and compared with the luminescence spectra of the pure isonicotinic acid.

  15. HYBRID SHEARWALL SYSTEM — SHEAR STRENGTH AT THE INTERFACE CONNECTION

    Directory of Open Access Journals (Sweden)

    Ulrich Wirth

    2013-12-01

    Full Text Available Based on a series of alternating, displacement-controlled load tests on ten one-third scale models, to study the behaviour of the interface of a hybrid shear wall system, it was proved that the concept of hybrid construction in earthquake prone regions is feasible. The hybrid shear-wall system consists of typical reinforced concrete shear walls with composite edge members or flanges. Ten different anchorage bar arrangements were developed and tested to evaluate the column-shearwall interface behaviour under cyclic shear forces acting along the interface between column and wall panel. Finite element models of the test specimens were developed that were capable of capturing the integrated concrete and reinforcing steel behaviour in the wall panels. Special models were  developed to capture the interface behaviour between the edge columns and the shear wall. A comparison between the experimental results and the numerical results shows excellent agreement, and clearly supports the validity of the model developed for predicting the non-linear response of the hybrid wall system under various load conditions.

  16. An Improved Implementation and Abstract Interface for Hybrid

    CERN Document Server

    Martin, Alan J; 10.4204/EPTCS.71.6

    2011-01-01

    Hybrid is a formal theory implemented in Isabelle/HOL that provides an interface for representing and reasoning about object languages using higher-order abstract syntax (HOAS). This interface is built around an HOAS variable-binding operator that is constructed definitionally from a de Bruijn index representation. In this paper we make a variety of improvements to Hybrid, culminating in an abstract interface that on one hand makes Hybrid a more mathematically satisfactory theory, and on the other hand has important practical benefits. We start with a modification of Hybrid's type of terms that better hides its implementation in terms of de Bruijn indices, by excluding at the type level terms with dangling indices. We present an improved set of definitions, and a series of new lemmas that provide a complete characterization of Hybrid's primitives in terms of properties stated at the HOAS level. Benefits of this new package include a new proof of adequacy and improvements to reasoning about object logics. Such...

  17. A Hybrid Brain-Computer Interface-Based Mail Client

    Directory of Open Access Journals (Sweden)

    Tianyou Yu

    2013-01-01

    Full Text Available Brain-computer interface-based communication plays an important role in brain-computer interface (BCI applications; electronic mail is one of the most common communication tools. In this study, we propose a hybrid BCI-based mail client that implements electronic mail communication by means of real-time classification of multimodal features extracted from scalp electroencephalography (EEG. With this BCI mail client, users can receive, read, write, and attach files to their mail. Using a BCI mouse that utilizes hybrid brain signals, that is, motor imagery and P300 potential, the user can select and activate the function keys and links on the mail client graphical user interface (GUI. An adaptive P300 speller is employed for text input. The system has been tested with 6 subjects, and the experimental results validate the efficacy of the proposed method.

  18. Metal-dielectric hybrid surfaces as integrated optoelectronic interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Narasimhan, Vijay K.; Hymel, Thomas M.; Lai, Ruby A.; Cui, Yi

    2017-01-03

    An optoelectronic device has a hybrid metal-dielectric optoelectronic interface including an array of nanoscale dielectric resonant elements (e.g., nanopillars), and a metal film disposed between the dielectric resonant elements and below a top surface of the resonant elements such that the dielectric resonant elements protrude through the metal film. The device may also include an anti-reflection coating. The device may further include a metal film layer on each of the dielectric resonant elements.

  19. Enhanced proton conductivity of Nafion hybrid membrane under different humidities by incorporating metal-organic frameworks with high phytic acid loading.

    Science.gov (United States)

    Li, Zhen; He, Guangwei; Zhang, Bei; Cao, Ying; Wu, Hong; Jiang, Zhongyi; Tiantian, Zhou

    2014-06-25

    In this study, phytic acid (myo-inositol hexaphosphonic acid) was first immobilized by MIL101 via vacuum-assisted impregnation method. The obtained phytic@MIL101 was then utilized as a novel filler to incorporate into Nafion to fabricate hybrid proton exchange membrane for application in PEMFC under different relative humidities (RHs), especially under low RHs. High loading and uniform dispersion of phytic acid in MIL 101(Cr) were achieved as demonstrated by ICP, FT-IR, XPS, and EDS-mapping. The phytic@MIL101 was dispersed homogeneously in the Nafion matrix when the filler content was less than 12%. Hybrid membranes were evaluated by proton conductivity, mechanical property, thermal stability, and so forth. Remarkably, the Nafion/phytic@MIL hybrid membranes showed high proton conductivity at different RHs, especially under low RHs, which was up to 0.0608 S cm(-1) and 7.63 × 10(-4) S cm(-1) at 57.4% RH and 10.5% RH (2.8 and 11.0 times higher than that of pristine membrane), respectively. Moreover, the mechanical property of Nafion/phtic@MIL hybrid membranes was substantially enhanced and the thermal stability of membranes was well preserved.

  20. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-08-22

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  1. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-02-07

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  2. Metal-Organic Frameworks Derived Porous Core/Shell Structured ZnO/ZnCo2O4/C Hybrids as Anodes for High-Performance Lithium-Ion Battery.

    Science.gov (United States)

    Ge, Xiaoli; Li, Zhaoqiang; Wang, Chengxiang; Yin, Longwei

    2015-12-01

    Metal-organic frameworks (MOFs) derived porous core/shell ZnO/ZnCo2O4/C hybrids with ZnO as a core and ZnCo2O4 as a shell are for the first time fabricated by using core/shell ZnCo-MOF precursors as reactant templates. The unique MOFs-derived core/shell structured ZnO/ZnCo2O4/C hybrids are assembled from nanoparticles of ZnO and ZnCo2O4, with homogeneous carbon layers coated on the surface of the ZnCo2O4 shell. When acting as anode materials for lithium-ion batteries (LIBs), the MOFs-derived porous ZnO/ZnCo2O4/C anodes exhibit outstanding cycling stability, high Coulombic efficiency, and remarkable rate capability. The excellent electrochemical performance of the ZnO/ZnCo2O4/C LIB anodes can be attributed to the synergistic effect of the porous structure of the MOFs-derived core/shell ZnO/ZnCo2O4/C and homogeneous carbon layer coating on the surface of the ZnCo2O4 shells. The hierarchically porous core/shell structure offers abundant active sites, enhances the electrode/electrolyte contact area, provides abundant channels for electrolyte penetration, and also alleviates the structure decomposition induced by Li(+) insertion/extraction. The carbon layers effectively improve the conductivity of the hybrids and thus enhance the electron transfer rate, efficiently prevent ZnCo2O4 from aggregation and disintegration, and partially buffer the stress induced by the volume change during cycles. This strategy may shed light on designing new MOF-based hybrid electrodes for energy storage and conversion devices.

  3. A hybrid brain interface for a humanoid robot assistant.

    Science.gov (United States)

    Finke, Andrea; Knoblauch, Andreas; Koesling, Hendrik; Ritter, Helge

    2011-01-01

    We present an advanced approach towards a semi-autonomous, robotic personal assistant for handicapped people. We developed a multi-functional hybrid brain-robot interface that provides a communication channel between humans and a state-of-the-art humanoid robot, Honda's Humanoid Research Robot. Using cortical signals, recorded, processed and translated by an EEG-based brain-machine interface (BMI), human-robot interaction functions independently of users' motor control deficits. By exploiting two distinct cortical activity patterns, P300 and event-related desynchronization (ERD), the interface provides different dimensions for robot control. An empirical study demonstrated the functionality of the BMI guided humanoid robot. All participants could successfully control the robot that accomplished a shopping task.

  4. Bio-inspired strategy for on-surface synthesis of silver nanoparticles for metal/organic hybrid nanomaterials and LDI-MS substrates.

    Science.gov (United States)

    Hong, Seonki; Lee, Joon Seok; Ryu, Jungki; Lee, Sahng Ha; Lee, Dong Yun; Kim, Dong-Pyo; Park, Chan Beum; Lee, Haeshin

    2011-12-09

    A strategy for the on-surface synthesis of silver nanoparticles (AgNPs) on a variety of two- to three-dimensional material surfaces, utilizing polydopamine, an emerging surface modifying agent, is reported in this paper. This material-independent platform for AgNP synthesis is useful for fabricating organic/inorganic hybrid nanomaterials and for preparing substrates for laser desorption-ionization time-of-flight mass spectrometry (LDI-ToF MS).

  5. Electrical properties of GaAs metal-oxide-semiconductor structure comprising Al2O3 gate oxide and AlN passivation layer fabricated in situ using a metal-organic vapor deposition/atomic layer deposition hybrid system

    Science.gov (United States)

    Aoki, Takeshi; Fukuhara, Noboru; Osada, Takenori; Sazawa, Hiroyuki; Hata, Masahiko; Inoue, Takayuki

    2015-08-01

    This paper presents a compressive study on the fabrication and optimization of GaAs metal-oxide-semiconductor (MOS) structures comprising a Al2O3 gate oxide, deposited via atomic layer deposition (ALD), with an AlN interfacial passivation layer prepared in situ via metal-organic chemical vapor deposition (MOCVD). The established protocol afforded self-limiting growth of Al2O3 in the atmospheric MOCVD reactor. Consequently, this enabled successive growth of MOCVD-formed AlN and ALD-formed Al2O3 layers on the GaAs substrate. The effects of AlN thickness, post-deposition anneal (PDA) conditions, and crystal orientation of the GaAs substrate on the electrical properties of the resulting MOS capacitors were investigated. Thin AlN passivation layers afforded incorporation of optimum amounts of nitrogen, leading to good capacitance-voltage (C-V) characteristics with reduced frequency dispersion. In contrast, excessively thick AlN passivation layers degraded the interface, thereby increasing the interfacial density of states (Dit) near the midgap and reducing the conduction band offset. To further improve the interface with the thin AlN passivation layers, the PDA conditions were optimized. Using wet nitrogen at 600 °C was effective to reduce Dit to below 2 × 1012 cm-2 eV-1. Using a (111)A substrate was also effective in reducing the frequency dispersion of accumulation capacitance, thus suggesting the suppression of traps in GaAs located near the dielectric/GaAs interface. The current findings suggest that using an atmosphere ALD process with in situ AlN passivation using the current MOCVD system could be an efficient solution to improving GaAs MOS interfaces.

  6. User-interfaces for hybrid systems: Analysis and design through hybrid reachability

    Science.gov (United States)

    Oishi, Meeko Mitsuko Karen

    Hybrid systems combine discrete state dynamics, which model mode switching, with continuous state dynamics, which model the physical processes themselves. Applications of hybrid system theory to automated systems have traditionally assumed that the controller itself is an automaton which runs in parallel with the system under control. We model human interaction with hybrid systems, which involves the user; the automation's discrete mode-logic, and the underlying continuous dynamics of the physical system. Often in safety-critical systems, user-interfaces display a reduced set of information about the entire system, however must still provide adequate information and must not confuse the user. We present (1) a method of designing a discrete event system abstraction of the hybrid system, in order to verify or design user-interfaces for hybrid human-automation systems, and (2) the relationship between user-interfaces and discrete observability properties. Using a hybrid computational tool for reachability, we find the largest region in which the system can always remain---this is the safe region of operation. By implementing a controller which arises from this computation, we mathematically guarantee that this safe region is invariant. Assigning discrete states to the computed invariant regions, we create a discrete event system from this hybrid system with safety restrictions. This abstraction can then be used in existing interface verification and design methods. A user-interface, modeled as a discrete system, must, not only be reduced (extraneous information has been eliminated), but also "immediately observable". We derive conditions for immediate observability, in which the current state can be constructed from the current output and last occurring event. Based on finite state machine state-reduction techniques, we synthesize an output for remote user-interfaces which fulfills this property. Aircraft are prime examples of complex, safety-critical systems. In

  7. Evaluation of a Compact Hybrid Brain-Computer Interface System

    Directory of Open Access Journals (Sweden)

    Jaeyoung Shin

    2017-01-01

    Full Text Available We realized a compact hybrid brain-computer interface (BCI system by integrating a portable near-infrared spectroscopy (NIRS device with an economical electroencephalography (EEG system. The NIRS array was located on the subjects’ forehead, covering the prefrontal area. The EEG electrodes were distributed over the frontal, motor/temporal, and parietal areas. The experimental paradigm involved a Stroop word-picture matching test in combination with mental arithmetic (MA and baseline (BL tasks, in which the subjects were asked to perform either MA or BL in response to congruent or incongruent conditions, respectively. We compared the classification accuracies of each of the modalities (NIRS or EEG with that of the hybrid system. We showed that the hybrid system outperforms the unimodal EEG and NIRS systems by 6.2% and 2.5%, respectively. Since the proposed hybrid system is based on portable platforms, it is not confined to a laboratory environment and has the potential to be used in real-life situations, such as in neurorehabilitation.

  8. A Hybrid Tool for User Interface Modeling and Prototyping

    Science.gov (United States)

    Trætteberg, Hallvard

    Although many methods have been proposed, model-based development methods have only to some extent been adopted for UI design. In particular, they are not easy to combine with user-centered design methods. In this paper, we present a hybrid UI modeling and GUI prototyping tool, which is designed to fit better with IS development and UI design traditions. The tool includes a diagram editor for domain and UI models and an execution engine that integrates UI behavior, live UI components and sample data. Thus, both model-based user interface design and prototyping-based iterative design are supported

  9. Nanoscale metal-organic materials.

    Science.gov (United States)

    Carné, Arnau; Carbonell, Carlos; Imaz, Inhar; Maspoch, Daniel

    2011-01-01

    Metal-organic materials are found to be a fascinating novel class of functional nanomaterials. The limitless combinations between inorganic and organic building blocks enable researchers to synthesize 0- and 1-D metal-organic discrete nanostructures with varied compositions, morphologies and sizes, fabricate 2-D metal-organic thin films and membranes, and even structure them on surfaces at the nanometre length scale. In this tutorial review, the synthetic methodologies for preparing these miniaturized materials as well as their potential properties and future applications are discussed. This review wants to offer a panoramic view of this embryonic class of nanoscale materials that will be of interest to a cross-section of researchers working in chemistry, physics, medicine, nanotechnology, materials chemistry, etc., in the next years.

  10. Synthesis of hybrid metal-organic frameworks of {FexMyM'1-x-y}-MIL-88B and the use of anions to control their structural features.

    Science.gov (United States)

    Choi, Sora; Cha, Wonhee; Ji, Hoyeon; Kim, Dooyoung; Lee, Hee Jung; Oh, Moonhyun

    2016-09-22

    The controlled formation of metal-organic frameworks (MOFs) or coordination polymers (CPs) with suitable components and structural features is one of the most important themes in MOF research. In particular, the reliable preparation of hybrid MOFs containing more than two different kinds of metal ions or organic linkers and a comprehensive understanding of the structural flexibility of MOFs are the central issues for the production of MOFs with the desired properties. We report the synthesis of micro-sized hybrid MOF particles [also known as coordination polymer particles (CPPs)] containing two or three kinds of metal ions in each particle: {FexMyM'1-x-y}-MIL-88B (MIL stands for Materials of Institut Lavoisier, M and M' = Ga, Co, or Mn). Scanning electron microscopy images revealed the formation of well-defined uniform micro-sized hexagonal rods, and energy-dispersive X-ray spectroscopy and elemental mapping images verified the simultaneous incorporation of two or three kinds of metal ions within the CPPs. Interestingly, the structural features of CPPs made from MIL-88B were controlled by altering the anions involved in the structure. Incorporating large acetylacetonate anions within the structure resulted in the closed MIL-88B structure with a small cell volume. However, the open MIL-88B structure with a large cell volume was obtained when small chloride anions were incorporated. The intermediate semi-open MIL-88B structure was also prepared using nitrate anions. Three different structural forms of MIL-88B were verified by powder X-ray diffraction, whole pattern fitting, and thermogravimetric analysis.

  11. First Principles Study on the Electronic Structure and Interface Stability of Hybrid Silicene/Fluorosilicene Nanoribbons

    National Research Council Canada - National Science Library

    Jiang, Q G; Zhang, J F; Ao, Z M; Wu, Y P

    2015-01-01

    The interface stability of hybrid silicene/fluorosilicene nanoribbons (SFNRs) has been investigated by using density functional theory calculations, where fluorosilicene is the fully fluorinated silicene...

  12. A Review of Hybrid Brain-Computer Interface Systems

    Directory of Open Access Journals (Sweden)

    Setare Amiri

    2013-01-01

    Full Text Available Increasing number of research activities and different types of studies in brain-computer interface (BCI systems show potential in this young research area. Research teams have studied features of different data acquisition techniques, brain activity patterns, feature extraction techniques, methods of classifications, and many other aspects of a BCI system. However, conventional BCIs have not become totally applicable, due to the lack of high accuracy, reliability, low information transfer rate, and user acceptability. A new approach to create a more reliable BCI that takes advantage of each system is to combine two or more BCI systems with different brain activity patterns or different input signal sources. This type of BCI, called hybrid BCI, may reduce disadvantages of each conventional BCI system. In addition, hybrid BCIs may create more applications and possibly increase the accuracy and the information transfer rate. However, the type of BCIs and their combinations should be considered carefully. In this paper, after introducing several types of BCIs and their combinations, we review and discuss hybrid BCIs, different possibilities to combine them, and their advantages and disadvantages.

  13. Hydrogen storage in metal-organic frameworks: A review

    CSIR Research Space (South Africa)

    Langmi, Henrietta W

    2014-05-01

    Full Text Available Metal-organic frameworks (MOFs) for hydrogen storage have continued to receive intense interest over the past decade. MOFs are a class of organic-inorganic hybrid crystalline materials consisting of metallic moieties that are linked by strong...

  14. Overestimating hybrid layer quality in polished adhesive/dentin interfaces.

    Science.gov (United States)

    Wang, Yong; Spencer, Paulette

    2004-03-15

    The most popular techniques for determining the quality of the hybrid layer (HL) have relied on morphologic characterization of the polished adhesive/dentin (a/d) interfaces before and after acid-bleach chemical treatment. Using these techniques, the existence of smooth, acid-resistant layers has been consistently reported for most adhesive systems. The purpose of this study was to determine whether popular specimen preparation techniques that include polishing and acid-bleach treatment modify the a/d interface, mask the complexity of the HL, and lead to inaccurate assessment of the quality of the HL. To understand the impact of specimen preparation techniques on the morphology of the resin-dentin interface, polished and unpolished specimens from the same tooth were closely compared after different acid-bleach chemical treatment procedures. Two one-bottle adhesives, that is, 3M Single Bond and Pulpdent UNO, exhibiting distinct differences in hydrophilic/hydrophobic composition, were used in this investigation. Using specimens from the same tooth, the effect of chemical treatments on the morphology of the resin-dentin interdiffusion zone and the differences in the morphology of polished and unpolished specimens after these same treatments were studied with scanning electron microscopy. It was shown that conventional specimen preparation techniques that include polishing and acid-bleach treatment can adversely affect and even obscure the structural detail of the a/d interface in specimens that possess a porous HL. The results indicated that the Pulpdent UNO/dentin interface had better quality than the 3M Single Bond/dentin interface. The difference in the quality of HL can be attributed to factors such as compositional differences that impact the adhesive interaction with water, that is present within the substrate during wet bonding. The inability of the conventional acid-bleach procedure to reveal the differences in the scanning electron microscopy interfacial

  15. Substitution reactions in metal-organic frameworks and metal-organic polyhedra.

    Science.gov (United States)

    Han, Yi; Li, Jian-Rong; Xie, Yabo; Guo, Guangsheng

    2014-08-21

    Substitution reaction, as one of the most powerful and efficient chemical reactions, has been widely used in various syntheses, including those for the design and preparation of functional molecules or materials. In the past decade, a class of newly developed inorganic-organic hybrid materials, namely metal-organic materials (MOMs), has experienced a rapid development. MOMs are composed of metal-containing nodes connected by organic linkers through strong chemical bonds, and can be divided into metal-organic frameworks (MOFs) and metal-organic polygons/polyhedra (MOPs) with infinite and discrete structural features, respectively. Recent research has shown that the substitution reaction can be used as a new strategy in the synthesis and modification of MOFs and MOPs, particularly for pre-designed ones with desired structures and functions, which are usually difficult to access by a direct one-pot self-assembly synthetic approach. This review highlights the implementation of the substitution reaction in MOFs and MOPs. Examples of substitution reactions at metal ions, organic ligands, and free guest molecules of MOFs and MOPs are listed and analyzed. The changes or modifications in the structures and/or properties of these materials induced by the substitutions, as well as the nature of the associated reaction, are discussed, with the conclusion that the substitution reaction is really feasible and powerful in synthesizing and tailoring MOMs.

  16. Recent Advances as Materials of Functional Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Xiao-Lan Tong

    2013-01-01

    Full Text Available Metal-organic frameworks (MOFs, also known as hybrid inorganic-organic materials, represent an emerging class of materials that have attracted the imagination of solid-state chemists because MOFs combine unprecedented levels of porosity with a range of other functional properties that occur through the metal moiety and/or the organic ligand. The purpose of this critical review is to give a representative and comprehensive overview of the arising developments in the field of functional metal-organic frameworks, including luminescence, magnetism, and porosity through presenting examples. This review will be of interest to researchers and synthetic chemists attempting to design multifunctional MOFs.

  17. Interfaces in superconducting hybrid heterostructures with an antiferromagnetic interlayer

    Science.gov (United States)

    Constantinian, K. Y.; Kislinskii, Yu. V.; Ovsyannikov, G. A.; Shadrin, A. V.; Sheyerman, A. E.; Vasil'ev, A. L.; Presnyakov, M. Yu.; Komissinskiy, P. V.

    2013-03-01

    The structural, X-ray diffraction, and electrophysical studies of hybrid superconducting hetero-structures with an interlayer of cuprate antiferromagnetic Ca1 - x Sr x CuO2 (CSCO) with the upper electrode Nb/Au and the lower electrode YBa2Cu3O7 - δ (YBCO) have been carried out. It has been experimentally shown that the epitaxial growth of two cuprates, YBCO and CSCO, results in the formation of an interface on which the enrichment of the CSCO interlayer with charge carriers proceeds to a depth of about 20 nm. In this case, the conduction of the enriched CSCO region proves to be closer to metallic, whereas the CSCO film deposited onto the NdGaO3 substrate is a Mott insulator with hopping conduction.

  18. Hybrid of g-C3N4 Assisted Metal-Organic Frameworks and Their Derived High-Efficiency Oxygen Reduction Electrocatalyst in the Whole pH Range.

    Science.gov (United States)

    Gu, Wenling; Hu, Liuyong; Li, Jing; Wang, Erkang

    2016-12-28

    A highly active electrocatalyst in the whole pH range for oxygen reduction reaction (ORR) is produced by employing the g-C3N4 assisted metal-organic frameworks (MOF) of C3N4@NH2-MIL-101 as the precursor. By pyrolyzing the hybrid at 700 °C, the C3N4@NH2-MIL-101 could be easily transformed into an abundant iron and nitrogen codoped porous carbon skeleton. The selective use of g-C3N4 as a support template plays a critical role in facilitating the formation of the architecture with high surface area and rich N content. The obtained catalyst of C3N4@NH2-MIL-101-700 manifested remarkable oxygen reduction activity over the pH 0-14. Noteworthy, the catalyst displayed outstanding ORR activity with more positive half-wave potential than that of the commercial Pt/C catalyst in both alkaline and neutral conditions. Additionally, the optimal C3N4@NH2-MIL-101-700 also exhibited prominent ORR activity which is almost equal to that of commercial Pt/C in acidic electrolyte with high selectivity and very low H2O2 yield. Most importantly, the better methanol tolerance and much higher stability than the commercial Pt/C of C3N4@NH2-MIL-101-700 no matter under alkaline, neutral, or acid conditions further demonstrate the catalyst to be a promising candidate for practical electrocatalytic applications.

  19. Automated growth of metal-organic framework coatings on flow-through functional supports.

    Science.gov (United States)

    Maya, F; Palomino Cabello, C; Clavijo, S; Estela, J M; Cerdà, V; Turnes Palomino, G

    2015-05-11

    A fully automated method for the controlled growth of metal-organic framework coatings on flow-through functional supports is reported. The obtained hybrid flow-through supports show high performance for the automated extraction of water pollutants.

  20. Thermodynamics of metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Di; Navrotsky, Alexandra, E-mail: anavrotsky@ucdavis.edu

    2015-03-15

    Although there have been extensive studies over the past decade in the synthesis and application of metal-organic frameworks (MOFs), investigation of their thermodynamic stability and of the energetics of guest–host interactions has been much more limited. This review summarizes recent progress in experimental (calorimetric) determination of the thermodynamics of MOF materials. The enthalpies of MOFs relative to dense phase assemblages suggest only modest metastability, with a general increase of enthalpy with increasing molar volume, which becomes less pronounced at higher porosity. The energy landscape of nanoporous materials (inorganic and hybrid) consists of a pair of parallel patterns within a fairly narrow range of metastability of 5–30 kJ per mole of tetrahedra in zeolites and mesoporous silicas or per mole of metal in MOFs. Thus strong thermodynamic instability does not seem to limit framework formation. There are strong interactions within the chemisorption range for small molecule–MOF interactions with defined chemical binding at the metal centers or other specific locations. Coexistence of surface binding and confinement can lead to much stronger guest–host interactions. - Graphical abstract: Energy landscape of inorganic and hybrid porous materials. - Highlights: • Thermochemical data on various MOF structures were experimentally determined. • MOFs are moderately unstable relative to their dense phase assemblage. • Overall energetic landscape of porous materials was revealed. • Guest–host interactions in MOFs were evaluated directly using calorimetry. • Confinement effect and defined chemical binding lead to strong interactions.

  1. A Formal Approach to User Interface Design using Hybrid System Theory Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Optimal Synthesis Inc.(OSI) proposes to develop an aiding tool for user interface design that is based on mathematical formalism of hybrid system theory. The...

  2. Interface Modifications for Applications in Organic and Hybrid Photovoltaics

    Science.gov (United States)

    Mazzio, Katherine A.

    -type pendant chains. Chapter 4 examines the synthesis of poly(3-methylthiophene) via surface initiated Kumada catalyst transfer polymerization from indium tin oxide where it was found that the thickness of the polymer layers could be controlled by controlling the monomer concentration in solution. These films proved to be robust interface layers that exhibit work functions that are tunable by electrochemical doping; when in the doped state, they show fast electron dynamics, while in the neutral state, they may be applicable as electron blocking layers for organic photovoltaics. In chapter 5, a new method for the in-situ functionalization of CdSe quantum dots with pi-conjugated ligands during synthesis is presented. This technique is useful for controlling the composition of the surface of colloidal CdSe quantum dots when traditional ligand exchange processes prove difficult. This synthetic technique is then used in chapter 6 to functionalize CdSe nanocrystals with poly(3-hexylthiophene) in an attempt to promote good interfacial charge transport properties for use in hybrid photovoltaics. The photophysics of a series of these hybrid CdSe/polymer materials were investigated by steady state and time-resolved spectroscopies, and ultimately it was found that there is a strong propensity for fluorescence resonance energy transfer between the two materials owing to their intimate contact, good resonance, and large spectral overlap. Finally, a brief future work section is presented that is required to wrap up the study of the photophysical processes for these hybrid materials.

  3. An investigation on hybrid interface using on-line monitoring experiment and finite element analyses

    NARCIS (Netherlands)

    Truong, H.T.X.; Martinez, M.J.; Ochoa, O.O.; Lagoudas, D.C.

    2015-01-01

    In this work, the hybrid interface between metal and thermosetting polymer matrix composite was studied via experimental and numerical investigations. Hybrid laminates, whose constituents are aluminum foil, carbon fabric and epoxy matrix, were manufactured using the vacuum assisted resin transfer mo

  4. Multiaxis sensing using metal organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Talin, Albert Alec; Allendorf, Mark D.; Leonard, Francois; Stavila, Vitalie

    2017-01-17

    A sensor device including a sensor substrate; and a thin film comprising a porous metal organic framework (MOF) on the substrate that presents more than one transduction mechanism when exposed to an analyte. A method including exposing a porous metal organic framework (MOF) on a substrate to an analyte; and identifying more than one transduction mechanism in response to the exposure to the analyte.

  5. The importance of gap states for energy level alignment at hybrid interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Racke, D.A.; Kelly, L.L.; Monti, O.L.A., E-mail: monti@u.arizona.edu

    2015-10-01

    Highlights: • The electronic structure of CuPc on related layered van der Waals materials is compared. • Gap states need to be considered to understand energy level alignment. • Hybrid interfaces require new models of the interfacial electronic structure. - Abstract: Energy level alignment and electronic structure at organic semiconductor interfaces must be controlled to ensure efficient carrier harvesting or injection in next-generation organic optoelectronic technologies. In this context, hybrid organic/inorganic semiconductor interfaces exhibit particularly rich physics. Here, we show that states in the band gap of the inorganic layered van der Waals dichalcogenide SnS{sub 2} play an important role in determining energy level alignment at the hybrid interface with copper phthalocyanine (CuPc). By taking advantage of the closely related CuPc film growth on SnS{sub 2} and the well-studied interface of CuPc/HOPG, we are able to trace spectroscopic differences to the fundamentally different electronic interactions across the two interfaces. We provide a detailed picture of the role of gap states at the hybrid interface and shed light on the electronic properties of inorganic semiconductors in general and metal dichalcogenides in particular.

  6. Multi-walled carbon nanotubes and metal-organic framework nanocomposites as novel hybrid electrode materials for the determination of nano-molar levels of lead in a lab-on-valve format.

    Science.gov (United States)

    Wang, Yang; Wu, Yichun; Xie, Jing; Ge, Huali; Hu, Xiaoya

    2013-09-07

    Metal-organic frameworks have been the subject of intense research because of their unique physicochemical properties. The presented study investigates the application of multi-wall carbon nanotubes and metal-organic frameworks (MWCNTs@Cu3(BTC)2) nanoparticles-modified electrode for the determination of trace levels of lead. The nanocomposites were prepared by solvothermal synthesis and characterized in detail. The experimental procedure was carried out by accumulating lead on the electrode surface and subsequently measuring with differential pulse anodic stripping voltammetry in a lab-on-valve format. The main parameters affecting the analytical performance, including the amount of MWCNTs@Cu3(BTC)2 suspension, supporting electrolyte and its pH, stripping mode, and flow rate, have been investigated in detail. Under the optimum conditions, the oxidation peak current displayed a calibration response for lead over a concentration range from 1.0 × 10(-9) to 5.0 × 10(-8) mol L(-1) with a excellent detection limit of 7.9 × 10(-10) mol L(-1). The relative standard deviation of 7 successive scans was 3.10% for 1.0 × 10(-8) mol L(-1) lead. The established method showed a great improvement in sensitivity and sample throughput for lead analysis.

  7. High-internal-phase emulsions stabilized by metal-organic frameworks and derivation of ultralight metal-organic aerogels

    Science.gov (United States)

    Zhang, Bingxing; Zhang, Jianling; Liu, Chengcheng; Peng, Li; Sang, Xinxin; Han, Buxing; Ma, Xue; Luo, Tian; Tan, Xiuniang; Yang, Guanying

    2016-01-01

    To design high-internal-phase emulsion (HIPE) systems is of great interest from the viewpoints of both fundamental researches and practical applications. Here we demonstrate for the first time the utilization of metal-organic framework (MOF) for HIPE formation. By stirring the mixture of water, oil and MOF at room temperature, the HIPE stabilized by the assembly of MOF nanocrystals at oil-water interface could be formed. The MOF-stabilized HIPE provides a novel route to produce highly porous metal-organic aerogel (MOA) monolith. After removing the liquids from the MOF-stabilized HIPE, the ultralight MOA with density as low as 0.01 g·cm−3 was obtained. The HIPE approach for MOA formation has unique advantages and is versatile in producing different kinds of ultralight MOAs with tunable porosities and structures. PMID:26892258

  8. Magnetism in metal-organic capsules

    Energy Technology Data Exchange (ETDEWEB)

    Atwood, Jerry L.; Brechin, Euan K; Dalgarno, Scott J.; Inglis, Ross; Jones, Leigh F.; Mossine, Andrew; Paterson, Martin J.; Power, Nicholas P.; Teat, Simon J.

    2010-01-07

    Nickel and cobalt seamed metal-organic capsules have been isolated and studied using structural, magnetic and computational approaches. Antiferromagnetic exchange in the Ni capsule results from coordination environments enforced by the capsule framework.

  9. Magnetism in metal-organic capsules

    Energy Technology Data Exchange (ETDEWEB)

    Atwood, Jerry L.; Brechin, Euan K; Dalgarno, Scott J.; Inglis, Ross; Jones, Leigh F.; Mossine, Andrew; Paterson, Martin J.; Power, Nicholas P.; Teat, Simon J.

    2010-01-07

    Nickel and cobalt seamed metal-organic capsules have been isolated and studied using structural, magnetic and computational approaches. Antiferromagnetic exchange in the Ni capsule results from coordination environments enforced by the capsule framework.

  10. Gas adsorption on metal-organic frameworks

    Science.gov (United States)

    Willis, Richard R [Cary, IL; Low, John J. , Faheem, Syed A.; Benin, Annabelle I [Oak Forest, IL; Snurr, Randall Q [Evanston, IL; Yazaydin, Ahmet Ozgur [Evanston, IL

    2012-07-24

    The present invention involves the use of certain metal organic frameworks that have been treated with water or another metal titrant in the storage of carbon dioxide. The capacity of these frameworks is significantly increased through this treatment.

  11. Metal organic frameworks for gas storage

    KAUST Repository

    Alezi, Dalal

    2016-06-09

    Embodiments provide a method of storing a compound using a metal organic framework (MOF). The method includes contacting one or more MOFs with a fluid and sorbing one or more compounds, such as O2 and CH4. O2 and CH4 can be sorbed simultaneously or in series. The metal organic framework can be an M-soc-MOF, wherein M can include aluminum, iron, gallium, indium, vanadium, chromium, titanium, or scandium.

  12. Hybrid systems: a real-time interface to control engineering

    DEFF Research Database (Denmark)

    Eriksen, Thomas Juul; Heilmann, Søren; Holdgaard, Michael

    1996-01-01

    are usually investigated by control engineers that base their work on the theory of dynamic systems. The mathematical tool for this work is thus mathematical analysis, in particular the theory of differential equations. The paper gives an introduction to a general hybrid systems model for definition of system...

  13. Hybridization-Induced Carrier Localization at the C60/ZnO Interface

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, Leah L.; Racke, David A.; Kim, Hyungchul; Ndione, Paul; Sigdel, Ajaya K.; Berry, Joseph J.; Graham, Samuel; Nordlund, Dennis; Monti, Oliver L. A.

    2016-05-25

    Electronic coupling and ground-state charge transfer at the C60/ZnO hybrid interface is shown to localize carriers in the C60 phase. This effect, revealed by resonant X-ray photoemission, arises from interfacial hybridization between C60 and ZnO. Such localization at carrier-selective electrodes and interlayers may lead to severely reduced carrier harvesting efficiencies and increased recombination rates in organic electronic devices.

  14. First Principles Study on the Electronic Structure and Interface Stability of Hybrid Silicene/Fluorosilicene Nanoribbons

    OpenAIRE

    Jiang, Q G; Zhang, J. F.; Ao, Z. M.; Y. P. Wu

    2015-01-01

    The interface stability of hybrid silicene/fluorosilicene nanoribbons (SFNRs) has been investigated by using density functional theory calculations, where fluorosilicene is the fully fluorinated silicene. It is found that the diffusion of F atoms at the zigzag and armchair interfaces of SFNRs is endothermic, and the corresponding minimum energy barriers are respectively 1.66 and 1.56?eV, which are remarkably higher than the minimum diffusion energy barrier of one F atom and two F atoms on pri...

  15. Electronic structure of hybrid interfaces for polymer-based electronics.

    Science.gov (United States)

    Fahlman, M; Crispin, A; Crispin, X; Henze, S K M; de Jong, M P; Osikowicz, W; Tengstedt, C; Salaneck, W R

    2007-05-08

    The fundamentals of the energy level alignment at anode and cathode electrodes in organic electronics are described. We focus on two different models that treat weakly interacting organic/metal (and organic/organic) interfaces: the induced density of interfacial states model and the so-called integer charge transfer model. The two models are compared and evaluated, mainly using photoelectron spectroscopy data of the energy level alignment of conjugated polymers and molecules at various organic/metal and organic/organic interfaces. We show that two different alignment regimes are generally observed: (i) vacuum level alignment, which corresponds to the lack of vacuum level offsets (Schottky-Mott limit) and hence the lack of charge transfer across the interface, and (ii) Fermi level pinning where the resulting work function of an organic/metal and organic/organic bilayer is independent of the substrate work function and an interface dipole is formed due to charge transfer across the interface. We argue that the experimental results are best described by the integer charge transfer model which predicts the vacuum level alignment when the substrate work function is above the positive charge transfer level and below the negative charge transfer level of the conjugated material. The model further predicts Fermi level pinning to the positive (negative) charge transfer level when the substrate work function is below (above) the positive (negative) charge transfer level. The nature of the integer charge transfer levels depend on the materials system: for conjugated large molecules and polymers, the integer charge transfer states are polarons or bipolarons; for small molecules' highest occupied and lowest unoccupied molecular orbitals and for crystalline systems, the relevant levels are the valence and conduction band edges. Finally, limits and further improvements to the integer charge transfer model are discussed as well as the impact on device design.

  16. Integration of Biomolecules with Metal-Organic Frameworks.

    Science.gov (United States)

    Zhuang, Jia; Young, Allison P; Tsung, Chia-Kuang

    2017-08-01

    Owing to the progressive development of metal-organic-frameworks (MOFs) synthetic processes and considerable potential applications in last decade, integrating biomolecules into MOFs has recently gain considerable attention. Biomolecules, including lipids, oligopeptides, nucleic acids, and proteins have been readily incorporated into MOF systems via versatile formulation methods. The formed biomolecule-MOF hybrid structures have shown promising prospects in various fields, such as antitumor treatment, gene delivery, biomolecular sensing, and nanomotor device. By optimizing biomolecule integration methods while overcoming existing challenges, biomolecule-integrated MOF platforms are very promising to generate more practical applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Skin-inspired hydrogel-elastomer hybrids with robust interfaces and functional microstructures

    Science.gov (United States)

    Yuk, Hyunwoo; Zhang, Teng; Parada, German Alberto; Liu, Xinyue; Zhao, Xuanhe

    2016-06-01

    Inspired by mammalian skins, soft hybrids integrating the merits of elastomers and hydrogels have potential applications in diverse areas including stretchable and bio-integrated electronics, microfluidics, tissue engineering, soft robotics and biomedical devices. However, existing hydrogel-elastomer hybrids have limitations such as weak interfacial bonding, low robustness and difficulties in patterning microstructures. Here, we report a simple yet versatile method to assemble hydrogels and elastomers into hybrids with extremely robust interfaces (interfacial toughness over 1,000 Jm-2) and functional microstructures such as microfluidic channels and electrical circuits. The proposed method is generally applicable to various types of tough hydrogels and diverse commonly used elastomers including polydimethylsiloxane Sylgard 184, polyurethane, latex, VHB and Ecoflex. We further demonstrate applications enabled by the robust and microstructured hydrogel-elastomer hybrids including anti-dehydration hydrogel-elastomer hybrids, stretchable and reactive hydrogel-elastomer microfluidics, and stretchable hydrogel circuit boards patterned on elastomer.

  18. Skin-inspired hydrogel–elastomer hybrids with robust interfaces and functional microstructures

    Science.gov (United States)

    Yuk, Hyunwoo; Zhang, Teng; Parada, German Alberto; Liu, Xinyue; Zhao, Xuanhe

    2016-01-01

    Inspired by mammalian skins, soft hybrids integrating the merits of elastomers and hydrogels have potential applications in diverse areas including stretchable and bio-integrated electronics, microfluidics, tissue engineering, soft robotics and biomedical devices. However, existing hydrogel–elastomer hybrids have limitations such as weak interfacial bonding, low robustness and difficulties in patterning microstructures. Here, we report a simple yet versatile method to assemble hydrogels and elastomers into hybrids with extremely robust interfaces (interfacial toughness over 1,000 Jm−2) and functional microstructures such as microfluidic channels and electrical circuits. The proposed method is generally applicable to various types of tough hydrogels and diverse commonly used elastomers including polydimethylsiloxane Sylgard 184, polyurethane, latex, VHB and Ecoflex. We further demonstrate applications enabled by the robust and microstructured hydrogel–elastomer hybrids including anti-dehydration hydrogel–elastomer hybrids, stretchable and reactive hydrogel–elastomer microfluidics, and stretchable hydrogel circuit boards patterned on elastomer. PMID:27345380

  19. Surface functionalization of metal organic frameworks for mixed matrix membranes

    Energy Technology Data Exchange (ETDEWEB)

    Albenze, Erik; Lartey, Michael; Li, Tao; Luebke, David R.; Nulwala, Hunaid B.; Rosi, Nathaniel L.; Venna, Surendar R.

    2017-03-21

    Mixed Matrix Membrane (MMM) are composite membranes for gas separation and comprising a quantity of inorganic filler particles, in particular metal organic framework (MOF), dispersed throughout a polymer matrix comprising one or more polymers. This disclosure is directed to MOF functionalized through addition of a pendant functional group to the MOF, in order to improve interaction with a surrounding polymer matrix in a MMM. The improved interaction aids in avoiding defects in the MMM due to incompatible interfaces between the polymer matrix and the MOF particle, in turn increasing the mechanical and gas separation properties of the MMM. The disclosure is also directed to a MMM incorporating the surface functionalized MOF.

  20. Probing Structure and Composition of Nickel/Titanium Carbide Hybrid Interfaces at the Atomic Scale (Preprint)

    Science.gov (United States)

    2010-01-01

    The transition in structure and composition across the titanium carbide /nickel hybrid interface has been determined at near atomic resolution by...coupling high-resolution transmission electron microscopy with three-dimensional atom probe tomography. The titanium carbide phase adopts a rocksalt-type

  1. On the Design, Characterization and Simulation of Hybrid Metal-Composite Interfaces

    Science.gov (United States)

    Kießling, R.; Ihlemann, J.; Pohl, M.; Stommel, M.; Dammann, C.; Mahnken, R.; Bobbert, M.; Meschut, G.; Hirsch, F.; Kästner, M.

    2017-02-01

    Multi-material lightweight designs are a key feature for the development of innovative and resource-efficient products. In the development of a hybrid composite, the interface between the joined components has to be considered in detail as it represents a typical location of the initialization of failure. This contribution gives an overview of the simulative engineering of metal-composite interfaces. To this end, several design aspects on the microscale and macroscale are explained and methods to model the mechanical behavior of the interface within finite element simulations. This comprises the utilization of cohesive elements with a continuum description of the interface. Likewise, traction-separation based cohesive elements, i.e. a zero-thickness idealization of the interface, are outlined and applied to a demonstration example. Within these finite element simulations, the constitutive behavior of the connected components has to be described by suitable material models. Therefore, inelastic material models at large strains are formulated based on rheological models.

  2. On the Design, Characterization and Simulation of Hybrid Metal-Composite Interfaces

    Science.gov (United States)

    Kießling, R.; Ihlemann, J.; Pohl, M.; Stommel, M.; Dammann, C.; Mahnken, R.; Bobbert, M.; Meschut, G.; Hirsch, F.; Kästner, M.

    2016-09-01

    Multi-material lightweight designs are a key feature for the development of innovative and resource-efficient products. In the development of a hybrid composite, the interface between the joined components has to be considered in detail as it represents a typical location of the initialization of failure. This contribution gives an overview of the simulative engineering of metal-composite interfaces. To this end, several design aspects on the microscale and macroscale are explained and methods to model the mechanical behavior of the interface within finite element simulations. This comprises the utilization of cohesive elements with a continuum description of the interface. Likewise, traction-separation based cohesive elements, i.e. a zero-thickness idealization of the interface, are outlined and applied to a demonstration example. Within these finite element simulations, the constitutive behavior of the connected components has to be described by suitable material models. Therefore, inelastic material models at large strains are formulated based on rheological models.

  3. Discrete Abstractions of Hybrid Systems: Verification of Safety and Application to User-Interface Design

    Science.gov (United States)

    Oishi, Meeko; Tomlin, Claire; Degani, Asaf

    2003-01-01

    Human interaction with complex hybrid systems involves the user, the automation's discrete mode logic, and the underlying continuous dynamics of the physical system. Often the user-interface of such systems displays a reduced set of information about the entire system. In safety-critical systems, how can we identify user-interface designs which do not have adequate information, or which may confuse the user? Here we describe a methodology, based on hybrid system analysis, to verify that a user-interface contains information necessary to safely complete a desired procedure or task. Verification within a hybrid framework allows us to account for the continuous dynamics underlying the simple, discrete representations displayed to the user. We provide two examples: a car traveling through a yellow light at an intersection and an aircraft autopilot in a landing/go-around maneuver. The examples demonstrate the general nature of this methodology, which is applicable to hybrid systems (not fully automated) which have operational constraints we can pose in terms of safety. This methodology differs from existing work in hybrid system verification in that we directly account for the user's interactions with the system.

  4. Deciphering Molecular Mechanisms of Interface Buildup and Stability in Porous Si/Eumelanin Hybrids

    Directory of Open Access Journals (Sweden)

    Elisa Pinna

    2017-07-01

    Full Text Available Porous Si/eumelanin hybrids are a novel class of organic–inorganic hybrid materials that hold considerable promise for photovoltaic applications. Current progress toward device setup is, however, hindered by photocurrent stability issues, which require a detailed understanding of the mechanisms underlying the buildup and consolidation of the eumelanin–silicon interface. Herein we report an integrated experimental and computational study aimed at probing interface stability via surface modification and eumelanin manipulation, and at modeling the organic–inorganic interface via formation of a 5,6-dihydroxyindole (DHI tetramer and its adhesion to silicon. The results indicated that mild silicon oxidation increases photocurrent stability via enhancement of the DHI–surface interaction, and that higher oxidation states in DHI oligomers create more favorable conditions for the efficient adhesion of growing eumelanin.

  5. Symmetry-selected spin-split hybrid states in C-60/ferromagnetic interfaces

    DEFF Research Database (Denmark)

    Li, Dongzhe; Barreteau, Cyrille; Kawahara, Seiji Leo

    2016-01-01

    The understanding of orbital hybridization and spin polarization at the organic-ferromagnetic interface is essential in the search for efficient hybrid spintronic devices. Here, using first-principles calculations, we report a systematic study of spin-split hybrid states of C60 deposited on various...

  6. Electroactive SWNT/PEGDA hybrid hydrogel coating for bio-electrode interface.

    Science.gov (United States)

    He, Lei; Lin, Demeng; Wang, Yanping; Xiao, Yinghong; Che, Jianfei

    2011-10-15

    Electric interface between neural tissue and electrode plays a significant role in the development of implanted devices for continuous monitoring and functional stimulation of central nervous system in terms of electroactivity, biocompatibility and long-term stability. To engineer an interface that possesses these merits, a polymeric hydrogel based on poly(ethylene glycol) diacrylate (PEGDA) and single-walled carbon nanotubes (SWNTs) were employed to fabricate a hybrid hydrogel via covalent anchoring strategy, i.e., self-assembly of cysteamine (Cys) followed by Michael addition between Cys and PEGDA. XPS characterization proves that the Cys molecules are linked to gold surface via the strong S-Au bond and that the PEGDA macromers are covalently bonded to Cys. FTIR spectra indicate the formation of hybrid hydrogel coating during photopolymerization. Electrochemical measurements using cyclic voltammetry (CV) and impedance spectrum clearly show the enhancement of electric properties to the hydrogel by the SWNTs. The charge transfer of the hybrid hydrogel-based electrode is quasi-reversible and charge transfer resistance decreases to the tenth of that of the pure hydrogel due to electron hopping along the SWNTs. Additionally, this hybrid hydrogel provides a favorable biomimetic microenvironment for cell attachment and growth due to its inherent biocompatibility. Combination of these merits yields hybrid hydrogels that can be good candidates for application to biosensors and biomedical devices. More importantly, the hybrid hydrogel coatings fabricated via the current strategy have good adhesion to the electrode substrate which is highly desired for chronically implantable devices.

  7. Self-Exfoliated Metal-Organic Nanosheets through Hydrolytic Unfolding of Metal-Organic Polyhedra.

    Science.gov (United States)

    Garai, Bikash; Mallick, Arijit; Das, Anuja; Mukherjee, Rabibrata; Banerjee, Rahul

    2017-05-29

    Few-layers thick metal-organic nanosheets have been synthesized using water-assisted solid-state transformation through a combined top-down and bottom-up approach. The metal-organic polyhedra (MOPs) convert into metal-organic frameworks (MOFs) which subsequently self-exfoliate into few-layered metal-organic nanosheets. These MOP crystals experience a hydrophobicity gradient with the inner surface during contact with water because of the existence of hydrophobic spikes on their outer surface. When the amount of water available for interaction is higher, the resultant layers are not stacked to form bulk materials; instead few-layered nanosheets with high uniformity were obtained in high yield. The phenomenon has resulted high yield production of uniformly distributed layered metal-organic nanosheets from three different MOPs, showing its general adaptability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. An investigation into photofunctional interfaces of 8-hydroxyquinoline/hydroxyapatite hybrids

    Science.gov (United States)

    Tagaya, Motohiro; Motozuka, Satoshi

    2017-04-01

    Organic/inorganic hybrids of 8-hydroxyquinoline (8Hq) molecule and hydroxyapatite nanocrystal (HAp) were mechanochemically prepared. In the hybrids, a green photoluminescence peak at 500 nm newly appeared, suggesting the chemical bonding of the 8Hq molecule with the Ca2+ ions of HAp. Then, the organic/inorganic interfacial photofunction was clarified by a molecular orbital calculation. The interfacial chemical bonding between the O and N atoms of 8Hq and the Ca2+ ions of HAp was attributed to both covalent Osbnd Ca and ionic Nsbnd Ca. The resultant wave functions revealed that the green luminescence was attributed to metal-to-ligand charge transfer (MLCT) from the O atoms of phosphate group (HAp) to the π-cloud (8Hq) in the HOMO of the hybrids. Therefore, the photofunctional interfaces of the hybrids were successfully demonstrated.

  9. Barium Titanate Film Interfaces for Hybrid Composite Energy Harvesters.

    Science.gov (United States)

    Bowland, Christopher C; Malakooti, Mohammad H; Sodano, Henry A

    2017-02-01

    Energy harvesting utilizing piezoelectric materials has become an attractive approach for converting mechanical energy into electrical power for low-power electronics. Structural composites are ideally suited for energy scavenging due to the large amount of mechanical energy they are subjected to. Here, a multifunctional composite with embedded sensing and energy harvesting is developed by integrating an active interface into carbon fiber reinforced polymer composites. By modifying the composite matrix, both rigid and flexible multifunctional composites are fabricated. Through electromechanical testing of a cantilever beam of the rigid composite, it reveals a power density of 217 pW/cc from only 1 g root-mean-square acceleration when excited at its resonant frequency of 47 Hz. Electromechanical sensor testing of the flexible multifunctional composite reveals an average voltage generation of 23.5 mV/g at its resonant frequency of 96 Hz. This research introduces a route for integrating nonstructural functionality into structural fiber composites by utilizing BaTiO3 coated woven carbon fiber fabrics with power scavenging and passive sensing capabilities.

  10. Metal-Organic Frameworks as Platforms for Functional Materials.

    Science.gov (United States)

    Cui, Yuanjing; Li, Bin; He, Huajun; Zhou, Wei; Chen, Banglin; Qian, Guodong

    2016-03-15

    Discoveries of novel functional materials have played very important roles to the development of science and technologies and thus to benefit our daily life. Among the diverse materials, metal-organic framework (MOF) materials are rapidly emerging as a unique type of porous and organic/inorganic hybrid materials which can be simply self-assembled from their corresponding inorganic metal ions/clusters with organic linkers, and can be straightforwardly characterized by various analytical methods. In terms of porosity, they are superior to other well-known porous materials such as zeolites and carbon materials; exhibiting extremely high porosity with surface area up to 7000 m(2)/g, tunable pore sizes, and metrics through the interplay of both organic and inorganic components with the pore sizes ranging from 3 to 100 Å, and lowest framework density down to 0.13 g/cm(3). Such unique features have enabled metal-organic frameworks to exhibit great potentials for a broad range of applications in gas storage, gas separations, enantioselective separations, heterogeneous catalysis, chemical sensing and drug delivery. On the other hand, metal-organic frameworks can be also considered as organic/inorganic self-assembled hybrid materials, we can take advantages of the physical and chemical properties of both organic and inorganic components to develop their functional optical, photonic, and magnetic materials. Furthermore, the pores within MOFs can also be utilized to encapsulate a large number of different species of diverse functions, so a variety of functional MOF/composite materials can be readily synthesized. In this Account, we describe our recent research progress on pore and function engineering to develop functional MOF materials. We have been able to tune and optimize pore spaces, immobilize specific functional groups, and introduce chiral pore environments to target MOF materials for methane storage, light hydrocarbon separations, enantioselective recognitions

  11. Transverse fracture and fiber/matrix interface characteristics of hybrid ceramic matrix composites

    Science.gov (United States)

    Haug, Stephen Berry

    Ceramic Matrix Composites (CMCs) represent an attractive class of engineering materials for use in high temperature, high wear and corrosive environments. Much effort has been made to ascertain and improve the strength and fracture characteristics of these materials. Approaches that have received a significant amount of attention include enhancing a ceramic material's mechanical properties through the use of continuous fiber reinforcement; fine, randomly dispersed discontinuous fiber (or whisker) reinforcement; and a hybrid combination of both continuous and discontinuous fibers. This dissertation addresses two important aspects of determining and improving the strength and toughness of CMCs and is comprised of three research papers that have been prepared for journal publication. The first paper, "Transverse Fracture Toughness of Unidirectional Continuous Fiber and Hybrid Ceramic Matrix Composites" provides the results of three-point chevron-notched-beam fracture toughness testing and demonstrates a significant improvement in transverse fracture toughness can be obtained through the use of hybrid fiber reinforcements. The second paper, "A Tensile Testing Method for Ceramic Matrix Composites" presents a novel approach to testing small brittle material specimens using conventional testing equipment with minimal specialized fixture components. The third paper, "Fiber/Matrix Interface Properties of Hybrid Ceramic Matrix Composites", presents a method of determining the characteristics of the fiber/matrix interface of a continuous fiber reinforced CMC and a related hybrid CMC reinforced by both continuous fibers and finely dispersed whiskers using a multiple fiber pullout technique.

  12. Engineering of Metal Organic Framework Catalysts

    NARCIS (Netherlands)

    Juan-Alcaniz, J.

    2013-01-01

    The last few decades have witnessed the unprecedented explosion of a new research field built around Metal-Organic Frameworks (MOFs). MOFs are crystalline porous solids consisting of metal ions (also named clusters) coordinated to often rigid organic molecules (also called ligands) to form one-

  13. Superhydrophobic perfluorinated metal-organic frameworks.

    Science.gov (United States)

    Chen, Teng-Hao; Popov, Ilya; Zenasni, Oussama; Daugulis, Olafs; Miljanić, Ognjen Š

    2013-08-07

    Three perfluorinated Cu-based metal-organic frameworks (MOFs) were prepared starting from extensively fluorinated biphenyl-based ligands accessed via C-H functionalization. These new materials are highly hydrophobic: with water contact angles of up to 151 ± 1°, they are among the most water-repellent MOFs ever reported.

  14. Engineering of Metal Organic Framework Catalysts

    NARCIS (Netherlands)

    Juan-Alcaniz, J.

    2013-01-01

    The last few decades have witnessed the unprecedented explosion of a new research field built around Metal-Organic Frameworks (MOFs). MOFs are crystalline porous solids consisting of metal ions (also named clusters) coordinated to often rigid organic molecules (also called ligands) to form one- two-

  15. Chemically crosslinked isoreticular metal-organic frameworks.

    Science.gov (United States)

    Allen, Corinne A; Boissonnault, Jake A; Cirera, Jordi; Gulland, Ryan; Paesani, Francesco; Cohen, Seth M

    2013-04-21

    Herein we report the synthesis of canonical isoreticular metal-organic frameworks (IRMOFs) containing interligand crosslinks. Chemically crosslinking two molecules of 2-amino-1,4-benzene dicarboxylic acid (NH2-BDC) gives ligands that readily form IRMOF-1 analogs, producing crosslinked MOFs that may be designed to have novel properties.

  16. Nets, tiles, and metal-organic frameworks

    Directory of Open Access Journals (Sweden)

    Michael O’Keeffe

    2014-12-01

    Full Text Available An account is given of the basic nets that are important in the description and design of metal-organic framework (MOF structures. These are generally of minimal transitivity, a concept which is explained. Derived nets are defined and the advantages of using derived nets to describe the topology of MOF frameworks with multiple branch points are emphasized.

  17. Composition and doping control for metal-organic chemical vapor deposition of InP-based double heterojunction bipolar transistor with hybrid base structure consisting of GaAsSb contact and InGaAsSb graded layers

    Science.gov (United States)

    Hoshi, Takuya; Kashio, Norihide; Sugiyama, Hiroki; Yokoyama, Haruki; Kurishima, Kenji; Ida, Minoru; Matsuzaki, Hideaki

    2017-07-01

    We report on a method for composition and doping control for metalorganic chemical vapor deposition of a double heterojunction bipolar transistor (DHBT) with a hybrid base structure consisting of a compositionally graded InGaAsSb for boosting an average electron velocity and a heavily doped thin GaAsSb for lowering the base contact resistivity. The GaAsSb contact layer can be formed by simply turning off the supply of In precursor tetramethylindium (TMIn) after the growth of the composition and doping graded InGaAsSb base. Consequently, the solid composition and hole concentration of hybrid base can be properly controlled by just modulating the supply of only TMIn and carbon tetrabromide. Secondary ion mass spectroscopy for the DHBT wafer reveals that the contents of In, Ga, and C inside the base are actually modulated from the collector side to the emitter side as expected. Transmission-line-model measurements were performed for the compositionally graded-InGaAsSb/GaAsSb hybrid base. The contact resistivity is estimated to be 5.3 Ω µm2, which is lower than half the value of a compositionally graded InGaAsSb base without the GaAsSb contact layer. The results indicate that the compositionally-graded-InGaAsSb/GaAsSb-contact hybrid base structure grown by this simple method is very advantageous for obtaining DHBTs with a very high maximum oscillation frequency.

  18. Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface

    KAUST Repository

    Gruenewald, Marco

    2015-02-11

    We investigate the prototypical hybrid interface formed between PTCDA and conductive n-doped ZnO films by means of complementary optical and electronic spectroscopic techniques. We demonstrate that shallow donors in the vicinity of the ZnO surface cause an integer charge transfer to PTCDA, which is clearly restricted to the first monolayer. By means of DFT calculations, we show that the experimental signatures of the anionic PTCDA species can be understood in terms of strong hybridization with localized states (the shallow donors) in the substrate and charge back-donation, resulting in an effectively integer charge transfer across the interface. Charge transfer is thus not merely a question of locating the Fermi level above the PTCDA electron-transport level but requires rather an atomistic understanding of the interfacial interactions. The study reveals that defect sites and dopants can have a significant influence on the specifics of interfacial coupling and thus on carrier injection or extraction.

  19. Decoding of four movement directions using hybrid NIRS-EEG brain-computer interface

    Directory of Open Access Journals (Sweden)

    M. Jawad Khan

    2014-04-01

    Full Text Available The hybrid brain-computer interface (BCI’s multimodal technology enables precision brain-signal classification that can be used in the formulation of control commands. In the present study, an experimental hybrid near-infrared spectroscopy-electroencephalography (NIRS-EEG technique was used to extract and decode four different types of brain signals. The NIRS setup was positioned over the prefrontal brain region, and the EEG over the left and right motor cortex regions. Twelve subjects participating in the experiment were shown four direction symbols, namely, forward, backward, left and right. The control commands for forward and backward movement were estimated by performing arithmetic mental tasks related to oxy-hemoglobin (HbO changes. The left and right directions commands were associated with right and left hand tapping, respectively. The high classification accuracies achieved showed that the four different control signals can be accurately estimated using the hybrid NIRS-EEG technology.

  20. Some recent developments in surface and interface design for photocatalytic and electrocatalytic hybrid structures.

    Science.gov (United States)

    Bai, Song; Xiong, Yujie

    2015-06-28

    The surface and interface are considered as the crucial features that can be engineered to improve the performance of catalysts. The great advancements in both controlled syntheses and catalytic mechanism studies have paved the way for the rational surface and interface design of catalysts. In this feature article, we overview our recent progress in surface and interface design for well-defined hybrid structures mainly toward the photocatalytic and electrocatalytic applications in which charge carriers play an important role. First, we outline the surface parameters of components including exposed facets, compositions, surface areas and crystal phases that have been tailored toward higher surface activation abilities for electrocatalytic and photocatalytic reactions. Second, we summarize the designing rules for the interface between two components to favor the charge transfer for photocatalytic reactions on the surface. Furthermore, we outline the synergistic effects on photocatalysis and electrocatalysis through the simultaneous control of the surface and the interface, which can also be extended to enhance other catalytic reactions (e.g., CO oxidation). Finally, we discuss the challenges and opportunities for further development of surface and interface design toward catalytic performance tuning.

  1. AN ITERATIVE HYBRIDIZED MIXED FINITE ELEMENT METHOD FOR ELLIPTIC INTERFACE PROBLEMS WITH STRONGLY DISCONTINUOUS COEFFICIENTS

    Institute of Scientific and Technical Information of China (English)

    Dao-qi Yang; Jennifer Zhao

    2003-01-01

    An iterative algorithm is proposed and analyzed based on a hybridized mixed finite element method for numerically solving two-phase generalized Stefan interface problems withstrongly discontinuous solutions, conormal derivatives, and coefficients. This algorithmiteratively solves small problems for each single phase with good accuracy and exchangeinformation at the interface to advance the iteration until convergence, following the ideaof Schwarz Alternating Methods. Error estimates are derived to show that this algorithmalways converges provided that relaxation parameters are suitably chosen. Numeric experiments with matching and non-matching grids at the interface from different phases areperformed to show the accuracy of the method for capturing discontinuities in the solutionsand coefficients. In contrast to standard numerical methods, the accuracy of our methoddoes not seem to deteriorate as the coefficient discontinuity increases.

  2. Minerals with metal-organic framework structures

    Science.gov (United States)

    Huskić, Igor; Pekov, Igor V.; Krivovichev, Sergey V.; Friščić, Tomislav

    2016-01-01

    Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals. PMID:27532051

  3. Thermodynamics of Metal-Organic Frameworks

    Science.gov (United States)

    Hughes, James Thomas

    Metal-Organic Frameworks (MOF) are crystalline nanoporous lattices constructed from the combination of cation and multi-dentate organic molecules. MOFs can display both chemical and thermal robustness while having large surface areas and pore volumes. In addition the modular composition of MOFs allows a degree of design and control of MOF structures. These unique physical properties have attracted wide interest and position MOFs to make meaningful contributions towards many applications, such as adsorption, catalysis, separation, and sensing. Despite the extensive investigative work over the last decade on MOF materials, the initial synthesis is still done by trial and error. Of the identified structures some MOFs are robust while others are fragile. It is unclear what role thermodynamics plays in the formation energies of MOFs and guest molecules interactions within the pores. Better understanding of thermochemical properties of MOFs is critical if MOF synthesis is to obtain true predictive design. To address these questions aqueous solution calorimetry was performed on ten different frameworks in both the as-synthesized and activated state. To understand the structural energetics of MOFs, the heat of formation from dense states (metal oxide and protonated organic linkers) to the open MOF framework was measured. Chapter 2 discusses the new aqueous calorimetry methodology developed to measure the enthalpy of solution for hybrid materials. Chapters 3, 4 and 5 detail the enthalpies of formation from their dense states of the frameworks: (MOF-5, ZIF-zni, ZIF-1, ZIF-3, ZIF-4, ZIF-7, ZIF-8, ZIF-9 and Cu-HKUST-1). These chapters also compare the MOF heat of formation energetics to those of zeolites, zeotypes and mesoporous silica materials. Finding that MOFs are metastable with respect to their dense states (metal oxide and protonated organic), following the current destabilization trend of the main group porous materials. The thermochemical effect of solvent on the MOF

  4. Metal Organic Frameworks: From Structure to Property

    OpenAIRE

    Bu, Fei

    2016-01-01

    Porous Materials are an important class of materials due to their large-scale industrial applications in gas adsorption, gas separation, heterogeneous catalysis and so on. Among many kinds of porous materials, metal organic frameworks (MOFs) have emerged as one of the favorites in the past fifteen years. MOFs are crystalline porous materials that are mainly made of inorganic metal containing units (secondary building units, also called SBUs), organic ligands and templates.Compared to commerci...

  5. Prediction of hot spots in protein interfaces using a random forest model with hybrid features.

    Science.gov (United States)

    Wang, Lin; Liu, Zhi-Ping; Zhang, Xiang-Sun; Chen, Luonan

    2012-03-01

    Prediction of hot spots in protein interfaces provides crucial information for the research on protein-protein interaction and drug design. Existing machine learning methods generally judge whether a given residue is likely to be a hot spot by extracting features only from the target residue. However, hot spots usually form a small cluster of residues which are tightly packed together at the center of protein interface. With this in mind, we present a novel method to extract hybrid features which incorporate a wide range of information of the target residue and its spatially neighboring residues, i.e. the nearest contact residue in the other face (mirror-contact residue) and the nearest contact residue in the same face (intra-contact residue). We provide a novel random forest (RF) model to effectively integrate these hybrid features for predicting hot spots in protein interfaces. Our method can achieve accuracy (ACC) of 82.4% and Matthew's correlation coefficient (MCC) of 0.482 in Alanine Scanning Energetics Database, and ACC of 77.6% and MCC of 0.429 in Binding Interface Database. In a comparison study, performance of our RF model exceeds other existing methods, such as Robetta, FOLDEF, KFC, KFC2, MINERVA and HotPoint. Of our hybrid features, three physicochemical features of target residues (mass, polarizability and isoelectric point), the relative side-chain accessible surface area and the average depth index of mirror-contact residues are found to be the main discriminative features in hot spots prediction. We also confirm that hot spots tend to form large contact surface areas between two interacting proteins. Source data and code are available at: http://www.aporc.org/doc/wiki/HotSpot.

  6. CO{sub 2} Adsorption in Metal-organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jun; Kim, Hee-Young; Ahn, Wha-Seung [Inha University, Incheon (Korea, Republic of)

    2013-04-15

    Metal organic frameworks (MOFs) are a class of crystalline organic-inorganic hybrid compounds formed by coordination of metal clusters or ions with organic linkers. MOFs have recently attracted intense research interest due to their permanent porous structures, large surface areas and pore volume, high-dispersed metal species, and potential applications in gas adsorption, separation, and catalysis. CO{sub 2} adsorption in MOFs has been investigated in two areas of CO{sub 2} storage at high pressures and CO{sub 2} adsorption at atmospheric pressure conditions. In this short review, CO{sub 2} adsorption/separation results using MOFs conducted in our laboratory was explained in terms of four contributing effects; (1) coordinatively unsaturated open metal sites, (2) functionalization, (3) interpenetration/catenation, and (4) ion-exchange. Zeolitic imidazolate frameworks (ZIFs) and covalent organic frameworks (COFs) were also considered as a candidate material.

  7. Nanoporous metal organic framework materials for hydrogen storage

    Institute of Scientific and Technical Information of China (English)

    Bo Xiao; Qingchun Yuan

    2009-01-01

    Hydrogen is expected to play an important role in future transportation as a promising alternative clean energy source to carbon-based fuels.One of the key challenges to commercialize hydrogen energy is to develop appropriate onboard hydrogen storage systems,capable of charging and discharging large quantities of hydrogen with fast enough kinetics to meet commercial requirements.Metal organic framework (MOF) is a new type of inorganic and organic hybrid nanoporous particulate materials.Its diverse networks can enhance hydrogen storage through tuning the structure and property of MOFs.The MOF materials so far developed adsorb hydrogen through weak disperston interactions,which allow significant quantity of hydrogen to be stored at cryogenic temperatures with fast kinetics.Novel MOFs are being developed to strengthen the interactions between hydrogen and MOFs in order to store hydrogen under ambient conditions.This review surveys the development of such candidate materials,their performance and future research needs.

  8. Ab initio calculation of pentacene-PbSe hybrid interface for photovoltaic applications.

    Science.gov (United States)

    Roy, P; Nguyen, Thao P

    2016-07-21

    We perform density functional theory (DFT) quantum chemical calculations for the pentacene-PbSe hybrid interface at both molecular and crystal levels. At the interface, the parallel orientation of pentacene on the PbSe surface is found to be the most favorable, analogous to a pentacene-gold interface. The molecule-surface distance and the value of charge transfer from one pentacene molecule to the PbSe surface are estimated at around 4.15 Å and 0.12 e(-) respectively. We found that, standard-LDA/GGA-PBE/hybrid/meta-GGA xc-functionals incorrectly determine the band gaps of both pentacene and PbSe and leads to a failed prediction of the energy alignment in this system. So, we use a relativistic G0W0 functional and accurately model the electronic properties of pentacene and PbSe in both bulk material and near the interface. An energy shift of 0.23 eV, due to the difference in work function at the interface was supplemented after a detailed analysis of the electrostatic potential. The highest occupied molecular orbital level of pentacene is 0.01 eV above PbSe while the lowest unoccupied molecular orbital of pentacene lies 1.70 eV above PbSe, allowing both electrons and holes to transfer along the donor-acceptor junction. Our results provide additional insights into the electronic structure properties of the pentacene-PbSe heterojunction and establish it as a promising and efficient candidate for photovoltaic applications.

  9. Metal-organic frameworks for membrane-based separations

    Science.gov (United States)

    Denny, Michael S.; Moreton, Jessica C.; Benz, Lauren; Cohen, Seth M.

    2016-12-01

    As research into metal-organic frameworks (MOFs) enters its third decade, efforts are naturally shifting from fundamental studies to applications, utilizing the unique features of these materials. Engineered forms of MOFs, such as membranes and films, are being investigated to transform laboratory-synthesized MOF powders to industrially viable products for separations, chemical sensors and catalysts. Following encouraging demonstrations of gas separations using MOF-based membranes, liquid-phase separations are now being explored in an effort to build effective membranes for these settings. In this Review, we highlight MOF applications that are in their nascent stages, specifically liquid-phase separations using MOF-based mixed-matrix membranes. We also highlight the analytical techniques that provide important insights into these materials, particularly at surfaces and interfaces, to better understand MOFs and their interactions with other materials, which will ultimately lead to their use in advanced technologies.

  10. Characteristics of hybrid compact stars with a sharp hadron-quark interface

    Energy Technology Data Exchange (ETDEWEB)

    Alford, Mark G.; Han, Sophia [Washington University, Physics Department, St. Louis, Missouri (United States)

    2016-03-15

    We describe two aspects of the physics of hybrid stars that have a sharp interface between a core of quark matter and a mantle of nuclear matter. Firstly, we analyze the mass-radius relation. We describe a generic ''Constant-Speed-of-Sound'' (CSS) parameterization of the quark matter equation of state (EoS), in which the speed of sound is independent of density. In terms of the three parameters of the CSS EoS we obtain the phase diagram of possible forms of the hybrid star mass-radius relation, and we show how observational constraints on the maximum mass and typical radius of neutron stars can be expressed as constraints on the CSS parameters. Secondly, we propose a mechanism for the damping of density oscillations, including r-modes, in hybrid stars with a sharp interface. The dissipation arises from the periodic conversion between quark matter and nuclear matter induced by the pressure oscillations in the star. We find the damping grows nonlinearly with the amplitude of the oscillation and is powerful enough to saturate an r-mode at very low saturation amplitude, of order 10{sup -10}, which is compatible with currently available observations of neutron star spin frequencies and temperatures. (orig.)

  11. Theory of coupled hybrid inorganic/organic systems: Excitation transfer at semiconductor/molecule interfaces

    Science.gov (United States)

    Specht, Judith; Verdenhalven, Eike; Theuerholz, Sverre; Knorr, Andreas; Richter, Marten

    2016-03-01

    We derive a theoretical framework for describing hybrid organic-inorganic systems consisting of an ordered organic molecular layer coupled to a semiconductor quantum well (e.g., ZnO). A Heisenberg equation of motion technique based on a density matrix formalism is applied to derive dynamical equations for the composite system on a mesoscopic scale. Our theoretical approach focuses on the inuence of nonradiative Förster excitation transfer across the hybrid interface on linear optical absorption spectra. Therefore, the dielectric screening is discussed at the interface of two materials with different dielectric constants. Moreover, the Förster transfer matrix element is calculated in the point-dipole approximation. For a consistent theoretical description of both constituents (i.e., the molecular layer and the semiconductor substrate), the problem is treated in momentum space. Solving the equations of motion for the microscopic polarizations in frequency space directly leads to an equation for the frequency-dependent linear absorption coefficient. Our theoretical approach forms the basis for studying parameter regimes and geometries with optimized excitation transfer efficiency across the semiconductor/ molecule interface.

  12. On the hybrid glassy carbon electrode/OligoThiophene/Ag(NP) interface.

    Science.gov (United States)

    Tassinari, Francesco; Tancini, Erik; Innocenti, Massimo; Schenetti, Luisa; Fontanesi, Claudio

    2012-11-06

    GC/OligoThiophene/Ag(NP) hybrid interfaces are synthesized and characterized: GC is the glassy carbon surface; OligoThiophene stands for both an ultrathin bithiophene grafted film and a 4-Br-Bithiophene grafted polymer; Ag(NP) stands for silver nanoparticles. The hybrid interface preparation involves different steps: first, the electrode surface is functionalized through a combination of electrochemically assisted grafting (under reduction regime) and polymerization (under oxidation regime); then, silver nanoparticles are chemisorbed by dipping. In particular, an ultrathin film of grafted bithiophene can be obtained by applying one cyclic voltammetry reduction cycle (GC/BT surface), while subsequent cyclic voltammetry cycling under oxidation regime yields an immobilized 4Br-Bithiophene polymer (GC/4BrBT surface). AFM and TEM images were recorded to investigate the morphology and chemical composition of the Ag(NP). Fe(II)/Fe(III) cyclic voltammetry, Zn underpotential deposition (UPD), XPS, LA-ICP-MS, and Raman techniques were exploited to characterize both the GC/OligoThiophene and GC/OligoThiophene/Ag(NP) interfaces. Theoretical calculation, at the B3LYP/6-311G** level of the theory, enabled rationalization of the electroreduction mechanism and the Raman results.

  13. Gradient-augmented hybrid interface capturing method for incompressible two-phase flow

    Science.gov (United States)

    Zheng, Fu; Shi-Yu, Wu; Kai-Xin, Liu

    2016-06-01

    Motivated by inconveniences of present hybrid methods, a gradient-augmented hybrid interface capturing method (GAHM) is presented for incompressible two-phase flow. A front tracking method (FTM) is used as the skeleton of the GAHM for low mass loss and resources. Smooth eulerian level set values are calculated from the FTM interface, and are used for a local interface reconstruction. The reconstruction avoids marker particle redistribution and enables an automatic treatment of interfacial topology change. The cubic Hermit interpolation is employed in all steps of the GAHM to capture subgrid structures within a single spacial cell. The performance of the GAHM is carefully evaluated in a benchmark test. Results show significant improvements of mass loss, clear subgrid structures, highly accurate derivatives (normals and curvatures) and low cost. The GAHM is further coupled with an incompressible multiphase flow solver, Super CE/SE, for more complex and practical applications. The updated solver is evaluated through comparison with an early droplet research. Project supported by the National Natural Science Foundation of China (Grant Nos. 10972010, 11028206, 11371069, 11372052, 11402029, and 11472060), the Science and Technology Development Foundation of China Academy of Engineering Physics (CAEP), China (Grant No. 2014B0201030), and the Defense Industrial Technology Development Program of China (Grant No. B1520132012).

  14. Microporous Metal Organic Materials for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    S. G. Sankar; Jing Li; Karl Johnson

    2008-11-30

    We have examined a number of Metal Organic Framework Materials for their potential in hydrogen storage applications. Results obtained in this study may, in general, be summarized as follows: (1) We have identified a new family of porous metal organic framework materials with the compositions M (bdc) (ted){sub 0.5}, {l_brace}M = Zn or Co, bdc = biphenyl dicarboxylate and ted = triethylene diamine{r_brace} that adsorb large quantities of hydrogen ({approx}4.6 wt%) at 77 K and a hydrogen pressure of 50 atm. The modeling performed on these materials agree reasonably well with the experimental results. (2) In some instances, such as in Y{sub 2}(sdba){sub 3}, even though the modeling predicted the possibility of hydrogen adsorption (although only small quantities, {approx}1.2 wt%, 77 K, 50 atm. hydrogen), our experiments indicate that the sample does not adsorb any hydrogen. This may be related to the fact that the pores are extremely small or may be attributed to the lack of proper activation process. (3) Some samples such as Zn (tbip) (tbip = 5-tert butyl isophthalate) exhibit hysteresis characteristics in hydrogen sorption between adsorption and desorption runs. Modeling studies on this sample show good agreement with the desorption behavior. It is necessary to conduct additional studies to fully understand this behavior. (4) Molecular simulations have demonstrated the need to enhance the solid-fluid potential of interaction in order to achieve much higher adsorption amounts at room temperature. We speculate that this may be accomplished through incorporation of light transition metals, such as titanium and scandium, into the metal organic framework materials.

  15. Biomimicry in metal-organic materials

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, MW; Gu, ZY; Bosch, M; Perry, Z; Zhou, HC

    2015-06-15

    Nature has evolved a great number of biological molecules which serve as excellent constructional or functional units for metal-organic materials (MOMs). Even though the study of biomimetic MOMs is still at its embryonic stage, considerable progress has been made in the past few years. In this critical review, we will highlight the recent advances in the design, development and application of biomimetic MOMs, and illustrate how the incorporation of biological components into MOMs could further enrich their structural and functional diversity. More importantly, this review will provide a systematic overview of different methods for rational design of MOMs with biomimetic features. Published by Elsevier B.V.

  16. Hydrogen storage in metal-organic frameworks.

    Science.gov (United States)

    Hu, Yun Hang; Zhang, Lei

    2010-05-25

    Metal-organic frameworks (MOFs) are highly attractive materials because of their ultra-high surface areas, simple preparation approaches, designable structures, and potential applications. In the past several years, MOFs have attracted worldwide attention in the area of hydrogen energy, particularly for hydrogen storage. In this review, the recent progress of hydrogen storage in MOFs is presented. The relationships between hydrogen capacities and structures of MOFs are evaluated, with emphasis on the roles of surface area and pore size. The interaction mechanism between H(2) and MOFs is discussed. The challenges to obtain a high hydrogen capacity at ambient temperature are explored.

  17. Epitaxially grown metal-organic frameworks

    Directory of Open Access Journals (Sweden)

    Hartmut Gliemann

    2012-03-01

    Full Text Available The functionalization of inorganic and organic surfaces is becoming a key issue in a vast number of technical applications. The present review will focus on a particularly attractive route for surface functionalization via the coating of substrates with ordered, highly-porous, self-assembling layers of metal-organic frameworks. Loading the nm-sized pores of these molecular scaffolds with molecules, clusters, and nanoparticles creates many opportunities for using these flexible, three-dimensional shelf systems as storage material, for developing highly specific sensors, catalysts and electronic devices, as well as implementing optical metamaterials.

  18. Metal-organic frameworks in chromatography.

    Science.gov (United States)

    Yusuf, Kareem; Aqel, Ahmad; ALOthman, Zeid

    2014-06-27

    Metal-organic frameworks (MOFs) emerged approximately two decades ago and are the youngest class of porous materials. Despite their short existence, MOFs are finding applications in a variety of fields because of their outstanding chemical and physical properties. This review article focuses on the applications of MOFs in chromatography, including high-performance liquid chromatography (HPLC), gas chromatography (GC), and other chromatographic techniques. The use of MOFs in chromatography has already had a significant impact; however, the utilisation of MOFs in chromatography is still less common than other applications, and the number of MOF materials explored in chromatography applications is limited.

  19. Hybrid EEG-EOG brain-computer interface system for practical machine control.

    Science.gov (United States)

    Punsawad, Yunyong; Wongsawat, Yodchanan; Parnichkun, Manukid

    2010-01-01

    Practical issues such as accuracy with various subjects, number of sensors, and time for training are important problems of existing brain-computer interface (BCI) systems. In this paper, we propose a hybrid framework for the BCI system that can make machine control more practical. The electrooculogram (EOG) is employed to control the machine in the left and right directions while the electroencephalogram (EEG) is employed to control the forword, no action, and complete stop motions of the machine. By using only 2-channel biosignals, the average classification accuracy of more than 95% can be achieved.

  20. Polymer-polymer and hybrid clay-polymer complexes at liquid-liquid interfaces

    Science.gov (United States)

    Wang, Yuhao; Sukhishvili, Svetlana

    2014-03-01

    We report on polymer-polymer and hybrid clay-polymer complex formation at oil-water interfaces. The complexes were composed of poly(methacrylic acid) (PMAA) and poly(N-isopropylacrylamide) (PNIPAM) or PNIPAM modified Laponite (L@PN). Interfacial surface tension, confocal laser scanning microscopy (CLSM) and cryogenic scanning electron microscopy (cryo-SEM) measurements were performed at various ratios of complex components and as a function of solution pH. The results reveal that interfacial PNIPAM/PMAA and L@PN/PMAA complexes are significantly more stable across the pH scale than their solution counterparts, probably because of the suppressed ionization of PMAA at the oil-water interface. In addition, we will discuss the effect of interfacial complex formation on PMAA chain dynamics, as measured by fluorescence-correlation spectroscopy (FCS), and demonstrate the use of these systems to control emulsion stability via changes in solution pH or temperature.

  1. Eye-hand Hybrid Gesture Recognition System for Human Machine Interface

    Directory of Open Access Journals (Sweden)

    N. R. Raajan

    2013-04-01

    Full Text Available Gesture Recognition has become a way for computers to recognise and understand human body language. They bridge the gap between machines and human beings and make the primitive interfaces like keyboards and mice redundant. This paper suggests a hybrid gesture recognition system for computer interface and wireless robot control. The real-time eye-hand gesture recognition system can be used for computer drawing, navigating cursors and simulating mouse clicks, playing games, controlling a wireless robot with commands and more. The robot illustrated in this paper is controlled by RF module. Playing a PING-PONG game has also been demonstrated using the gestures. The Haar cascade classifiers and template matching are used to detect eye gestures and convex hull for finding the defects and counting the number of fingers in the given region.

  2. Topological phase transition and interface states in hybrid plasmonic-photonic systems

    Science.gov (United States)

    Ge, Lixin; Liu, Liang; Xiao, Meng; Du, Guiqiang; Shi, Lei; Han, Dezhuan; Chan, C. T.; Zi, Jian

    2017-06-01

    The geometric phase and topological property for one-dimensional hybrid plasmonic-photonic crystals consisting of a simple lattice of graphene sheets are investigated systematically. For transverse magnetic waves, both plasmonic and photonic modes exist in the momentum space. The accidental degeneracy point of these two kinds of modes is identified to be a diabolic point accompanied with a topological phase transition. For a closed loop around this degeneracy point, the Berry phase is π as a consequence of the discontinuous jump of the geometric Zak phase. The wave impedance is calculated analytically for the semi-infinite system, and the corresponding topological interface states either start from or terminate at the degeneracy point. This type of localized interface state may find potential applications in manipulation of photon emission of quantum dots, optical sensing and enhancement of nonlinear effects, etc.

  3. Cascade reactions catalyzed by metal organic frameworks.

    Science.gov (United States)

    Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo

    2014-09-01

    Cascade or tandem reactions where two or more individual reactions are carried out in one pot constitute a clear example of process intensification, targeting the maximization of spatial and temporal productivity with mobilization of minimum resources. In the case of catalytic reactions, cascade processes require bi-/multifunctional catalysts that contain different classes of active sites. Herein, we show that the features and properties of metal-organic frameworks (MOFs) make these solids very appropriate materials for the development of catalysts for cascade reactions. Due to composition and structure, MOFs can incorporate different types of sites at the metal nodes, organic linkers, or at the empty internal pores, allowing the flexible design and synthesis of multifunctional catalysts. After some introductory sections on the relevance of cascade reactions from the point of view of competitiveness, sustainability, and environmental friendliness, the main part of the text provides a comprehensive review of the literature reporting the use of MOFs as heterogeneous catalysts for cascade reactions including those that combine in different ways acid/base, oxidation/reduction, and metal-organic centers. The final section summarizes the current state of the art, indicating that the development of a first commercial synthesis of a high-added-value fine chemical will be a crucial milestone in this area.

  4. Hierarchical Control of Parallel AC-DC Converter Interfaces for Hybrid Microgrids

    DEFF Research Database (Denmark)

    Lu, Xiaonan; Guerrero, Josep M.; Sun, Kai;

    2014-01-01

    In this paper, a hierarchical control system for parallel power electronics interfaces between ac bus and dc bus in a hybrid microgrid is presented. Both standalone and grid-connected operation modes in the dc side of the microgrid are analyzed. Concretely, a three-level hierarchical control syst...... the three control levels is developed in order to adjust the main control parameters and study the system stability. Experimental results of a 2×2.2 kW parallel ac-dc converter system have shown satisfactory realization of the designed system.......In this paper, a hierarchical control system for parallel power electronics interfaces between ac bus and dc bus in a hybrid microgrid is presented. Both standalone and grid-connected operation modes in the dc side of the microgrid are analyzed. Concretely, a three-level hierarchical control system...... is implemented. In the primary control level, the decentralized control is realized by using the droop method. Local ac current proportional-resonant controller and dc voltage proportional-integral controller are employed. When the local load is connected to the dc bus, dc droop control is applied to obtain...

  5. Hybrid silicon-plasmonics: efficient waveguide interfacing for low-loss integrated switching components

    Science.gov (United States)

    Tsilipakos, Odysseas; Pitilakis, Alexandros; Kriezis, Emmanouil E.

    2012-04-01

    We present a thorough numerical investigation of end-fire coupling between dielectric-loaded surface plasmon polariton (DLSPP) and compact rib/wire silicon-on-insulator (SOI) waveguides. Simulations are based on the three-dimensional vector finite element method. The interface geometrical parameters leading to optimum performance, i.e., maximum coupling efficiency or, equivalently, minimum insertion loss (IL), are identified. We show that coupling efficiencies as high as 85 % are possible. In addition, we quantify the fabrication tolerances about the optimum parameter values. In the same context, we assess the effect of a metallic stripe gap and that of a horizontal offset between waveguides on insertion loss. Finally, we demonstrate that by benefiting form the low-loss coupling between the two waveguides, hybrid silicon-plasmonic 2 x 2 thermo-optic switching elements can outperform their all-plasmonic counterparts in terms of IL. Specifically, we examine two hybrid SOI-DLSPP switching elements, namely, a Mach-Zehnder Interferometer (MZI) and a Multi-Mode-Interference (MMI) switch. In particular, in the MZI case the IL improvement compared to the all-plasmonic counterpart is 4.5 dB. Moreover, the proposed hybrid components maintain the high extinction ratio, small footprint, and efficient tuning traits of plasmonic technology.

  6. Metal-organic frameworks for photocatalysis.

    Science.gov (United States)

    Li, Ying; Xu, Hua; Ouyang, Shuxin; Ye, Jinhua

    2016-03-21

    Photocatalysis is a promising technology to convert solar energy into chemical energy. Recently, metal-organic frameworks (MOFs) have emerged as novel photocatalysts owing to their inherent structural characteristics of a large surface area and a well-ordered porous structure. Most importantly, via modulation of the organic linker/metal clusters or incorporation with metal/complex catalysts, not only the reactant adsorption and light absorption but also the charge separation and reactant activation will be largely promoted, leading to superior photocatalytic performance. In this article, we will first introduce the photophysical/chemical properties of MOFs; then various strategies of modification of MOFs towards better photocatalytic activity will be presented; finally, we will address the challenge and further perspective in MOF-based photocatalysis.

  7. Multifunctional Metal-Organic Frameworks for Photocatalysis.

    Science.gov (United States)

    Wang, Sibo; Wang, Xinchen

    2015-07-01

    Metal-organic frameworks (MOFs) have attracted significant research attention in diverse areas due to their unique physical and chemical characteristics that allow their innovative application in various research fields. Recently, the application of MOFs in heterogeneous photocatalysis for water splitting, CO2 reduction, and organic transformation have emerged, aiming at providing alternative solutions to address the world-wide energy and environmental problems by taking advantage of the unique porous structure together with ample physicochemical properties of the metal centers and organic ligands in MOFs. In this review, the latest progress in MOF-involved solar-to-chemical energy conversion reactions are summarized according to their different roles in the photoredox chemical systems, e.g., photocatalysts, co-catalysts, and hosts. The achieved progress and existing problems are evaluated and proposed, and the opportunities and challenges of MOFs and their related materials for their advanced development in photocatalysis are discussed and anticipated.

  8. Emerging Multifunctional Metal-Organic Framework Materials.

    Science.gov (United States)

    Li, Bin; Wen, Hui-Min; Cui, Yuanjing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2016-10-01

    Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self-assembled through the coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre-designing or post-synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. An Electrically Switchable Metal-Organic Framework

    Science.gov (United States)

    Fernandez, Carlos A.; Martin, Paul C.; Schaef, Todd; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-01

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  10. An Electrically Switchable Metal-Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, Carlos A.; Martin, Paul F.; Schaef, Herbert T.; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem X.; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-19

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ 5 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  11. [Progress in metal-organic frameworks].

    Science.gov (United States)

    Zhai, Rui; Jiao, Fenglong; Lin, Hongjun; Hao, Feiran; Li, Jiabin; Yan, Hui; Li, Nannan; Wang, Huanhuan; Jin, Zuyao; Zhang, Yangjun; Qian, Xiaohong

    2014-02-01

    Metal-organic frameworks (MOFs) are a class of crystalline materials built from organic binding ligands and metal ions through self-assembly. Currently, MOFs have drawn a growing interest among the scientific teams of various fields. Compared with conventional inorganic porous materials, MOFs possess larger specific surface areas, higher porosity and diversity of structures and functions, thus many potential applications have been proposed in the domains of gas adsorption and separation, sensors, drug delivery, catalysis or others. The combinations of MOFs and other materials such as graphene oxide, magnetic nanoparticles have obvious advantages in adsorption and separation. The appearance of novel materials greatly promotes interdisciplinary developments such as organic chemistry, inorganic chemistry, coordination chemistry, materials chemistry, life science and computer science. This article reviews the progress of MOFs in recent years, including the characteristics of MOFs, advances at home and abroad, applications, central issues of compound MOFs and the prospects in the future.

  12. Shape assisted fabrication of fluorescent cages of squarate based metal-organic coordination frameworks.

    Science.gov (United States)

    Jayaramulu, Kolleboyina; Krishna, Katla Sai; George, Subi J; Eswaramoorthy, Muthuswamy; Maji, Tapas Kumar

    2013-05-11

    Micronic cage structures of squarate based metal-organic coordination frameworks (MOCFs) have been fabricated for the first time by specific anion selective etching of metal squarate cubes. Time and stoichiometry dependent synthesis and the corresponding microscopic studies have provided mechanistic insight into the cage formation. Furthermore, a non-covalent post-synthetic strategy has been adopted to functionalize the micronic cubes or cages with chromophores rendering the resulting hybrids green fluorescent.

  13. Hematite(001)-liquid water interface from hybrid density functional-based molecular dynamics

    Science.gov (United States)

    Falk von Rudorff, Guido; Jakobsen, Rasmus; Rosso, Kevin M.; Blumberger, Jochen

    2016-10-01

    The atom-scale characterisation of interfaces between transition metal oxides and liquid water is fundamental to our mechanistic understanding of diverse phenomena ranging from crystal growth to biogeochemical transformations to solar fuel production. Here we report on the results of large-scale hybrid density functional theory-based molecular dynamics simulations for the hematite(001)-liquid water interface. A specific focus is placed on understanding how different terminations of the same surface influence surface solvation. We find that the two dominant terminations for the hematite(001) surface exhibit strong differences both in terms of the active species formed on the surface and the strength of surface solvation. According to present simulations, we find that charged oxyanions (-O-) and doubly protonated oxygens (-OH2+ ) can be formed on the iron terminated layer via autoionization of neutral -OH groups. No such charged species are found for the oxygen terminated surface. In addition, the missing iron sublayer in the iron terminated surface strongly influences the solvation structure, which becomes less well ordered in the vicinity of the interface. These pronounced differences are likely to affect the reactivity of the two surface terminations, and in particular the energetics of excess charge carriers at the surface.

  14. Tuning back contact property via artificial interface dipoles in Si/organic hybrid solar cells

    Science.gov (United States)

    Wang, Dan; Sheng, Jiang; Wu, Sudong; Zhu, Juye; Chen, Shaojie; Gao, Pingqi; Ye, Jichun

    2016-07-01

    Back contact property plays a key role in the charge collection efficiency of c-Si/poly(3,4-ethylthiophene):poly(styrenesulfonate) hybrid solar cells (Si-HSCs), as an alternative for the high-efficiency and low-cost photovoltaic devices. In this letter, we utilize the water soluble poly (ethylene oxide) (PEO) to modify the Al/Si interface to be an Ohmic contact via interface dipole tuning, decreasing the work function of the Al film. This Ohmic contact improves the electron collection efficiency of the rear electrode, increasing the short circuit current density (Jsc). Furthermore, the interface dipoles make the band bending downward to increase the total barrier height of built-in electric field of the solar cell, enhancing the open circuit voltage (Voc). The PEO solar cell exhibits an excellent performance, 12.29% power conversion efficiency, a 25.28% increase from the reference solar cell without a PEO interlayer. The simple and water soluble method as a promising alternative is used to develop the interfacial contact quality of the rear electrode for the high photovoltaic performance of Si-HSCs.

  15. Monitoring DNA hybridization and thermal dissociation at the silica/water interface using resonantly enhanced second harmonic generation spectroscopy.

    Science.gov (United States)

    Azam, Md Shafiul; Gibbs-Davis, Julianne M

    2013-09-03

    The immobilization of oligonucleotide sequences onto glass supports is central to the field of biodiagnostics and molecular biology with the widespread use of DNA microarrays. However, the influence of confinement on the behavior of DNA immobilized on silica is not well understood owing to the difficulties associated with monitoring this buried interface. Second harmonic generation (SHG) is an inherently surface specific technique making it well suited to observe processes at insulator interfaces like silica. Using a universal 3-nitropyrolle nucleotide as an SHG-active label, we monitored the hybridization rate and thermal dissociation of a 15-mer of DNA immobilized at the silica/aqueous interface. The immobilized DNA exhibits hybridization rates on the minute time scale, which is much slower than hybridization kinetics in solution but on par with hybridization behavior observed at electrochemical interfaces. In contrast, the thermal dissociation temperature of the DNA immobilized on silica is on average 12 °C lower than the analogous duplex in solution, which is more significant than that observed on other surfaces like gold. We attribute the destabilizing affect of silica to its negatively charged surface at neutral pH that repels the hybridizing complementary DNA.

  16. High Critical Current in Metal Organic Derived YBCO Films

    Science.gov (United States)

    2010-10-31

    Contract No. FA9550-07-C-0034 “High Critical Current in Metal Organic Derived YBCO Films” Final Report Prepared for: Dr. Harold...Critical Current in Metal Organic Derived YBCO Films 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT...Project focused on optimization of the Metal Organic Deposition (MOD) process for deposition thick, high critical current YBCO films for use in the

  17. Metal-organic framework materials with ultrahigh surface areas

    Energy Technology Data Exchange (ETDEWEB)

    Farha, Omar K.; Hupp, Joseph T.; Wilmer, Christopher E.; Eryazici, Ibrahim; Snurr, Randall Q.; Gomez-Gualdron, Diego A.; Borah, Bhaskarjyoti

    2015-12-22

    A metal organic framework (MOF) material including a Brunauer-Emmett-Teller (BET) surface area greater than 7,010 m.sup.2/g. Also a metal organic framework (MOF) material including hexa-carboxylated linkers including alkyne bond. Also a metal organic framework (MOF) material including three types of cuboctahedron cages fused to provide continuous channels. Also a method of making a metal organic framework (MOF) material including saponifying hexaester precursors having alkyne bonds to form a plurality of hexa-carboxylated linkers including alkyne bonds and performing a solvothermal reaction with the plurality of hexa-carboxylated linkers and one or more metal containing compounds to form the MOF material.

  18. Photonic engineering of hybrid metal-organic chromophores

    CERN Document Server

    Busson, Mickaël P; Stout, Brian; Bonod, Nicolas; Wenger, Jérôme; Bidault, Sébastien; 10.1002/anie.201205995

    2012-01-01

    We experimentally demonstrate control of the absorption and emission properties of individual emitters by photonic antennas in suspension. The method results in a new class of water-soluble chromophores with unprecedented photophysical properties, such as short lifetime, low quantum yield but high brightness.

  19. Self-aligning subatmospheric hybrid liquid junction electrospray interface for capillary electrophoresis.

    Science.gov (United States)

    Krenkova, Jana; Kleparnik, Karel; Grym, Jakub; Luksch, Jaroslav; Foret, Frantisek

    2016-02-01

    We report a construction of a self-aligning subatmospheric hybrid liquid junction electrospray interface for CE eliminating the need for manual adjustment by guiding the capillaries in a microfabricated liquid junction glass chip at a defined angle. Both the ESI and separation capillaries are inserted into the microfabricated part until their ends touch. The distance between the capillary openings is defined by the angle between the capillaries. The microfabricated part contains channels for placement of the capillaries and connection of the external electrode reservoirs. It was fabricated using standard photolithographic/wet chemical etching techniques followed by thermal bonding. The liquid junction is connected to a subatmospheric electrospray chamber inducing the flow inside the ESI needle and helping the ion transport via aerodynamic focusing.

  20. Hybrid bio-organic interfaces with matchable nanoscale topography for durable high extracellular electron transfer activity.

    Science.gov (United States)

    Ding, Chunmei; Liu, Huan; Lv, Meiling; Zhao, Tianyi; Zhu, Ying; Jiang, Lei

    2014-07-21

    Here, we developed a novel hybrid bio-organic interface with matchable nano-scale topography between a polypyrrole nanowire array (PPy-NA) and the bacterium Shewanella, which enabled a remarkably increased extracellular electron transfer (EET) current from genus Shewanella over a rather long period. PPy-NA thus exhibited outstanding performance in mediating bacterial EET, which was superior to normal electrodes such as carbon plates, Au and tin-doped In₂O₃. It was proposed that the combined effect of the inherent electrochemical nature of PPy and the porous structured bacterial network that was generated on the PPy-NA enabled long-term stability, while the high efficiency was attributed to the enhanced electron transfer rate between PPy-NA and microbes caused by the enhanced local topological interactions.

  1. Interface electric properties of Si/organic hybrid solar cells using impedance spectroscopy analysis

    Science.gov (United States)

    Wang, Dan; Zhu, Juye; Ding, Li; Gao, Pingqi; Pan, Xiaoyin; Sheng, Jiang; Ye, Jichun

    2016-05-01

    The internal resistance and capacitance of Si/organic hybrid solar cells (Si-HSC) based on poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) are investigated by electrochemical impedance spectroscopy (EIS). Three types of Nyquist plots in Si-HSC are observed firstly at different bias voltages, while suitable equivalent circuit models are established to evaluate the details of interface carrier transfer and recombination. In particular, the carrier transport property of the PEDOT:PSS film responds at a high frequency (6 × 104-1 × 106 Hz) in three-arc spectra. Therefore, EIS could help us deeply understand the electronic properties of Si-HSC for developing high performance devices.

  2. Hydrogen Storage in Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Long, Jeffrey R. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2016-04-28

    The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing a high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H2 storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H2 at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H2 adsorption measurements, to provide a comprehensive picture of H2 adsorption at all relevant pressures. A

  3. Electrodeposition of WO3 nanoparticles into surface mounted metal-organic framework HKUST-1 thin films

    Science.gov (United States)

    Yoo, Hyeonseok; Welle, Alexander; Guo, Wei; Choi, Jinsub; Redel, Engelbert

    2017-03-01

    We describe a novel procedure to fabricate WO3@surface-mounted metal-organic framework (SURMOF) hybrid materials by electrodeposition of WO3 nanoparticles into HKUST-1, also termed Cu3(BTC)2 SURMOFs. These materials have been characterized using x-ray diffraction, time-of-flight secondary ion mass spectrometry, scanning electron microscopy, x-ray photoelectron spectroscopy as well as linear sweep voltammetry. The WO3 semiconductor/SURMOF heterostructures were further tested as hybrid electrodes in their performance for hydrogen evolution reaction from water.

  4. Feasibility of a Hybrid Brain-Computer Interface for Advanced Functional Electrical Therapy

    Directory of Open Access Journals (Sweden)

    Andrej M. Savić

    2014-01-01

    Full Text Available We present a feasibility study of a novel hybrid brain-computer interface (BCI system for advanced functional electrical therapy (FET of grasp. FET procedure is improved with both automated stimulation pattern selection and stimulation triggering. The proposed hybrid BCI comprises the two BCI control signals: steady-state visual evoked potentials (SSVEP and event-related desynchronization (ERD. The sequence of the two stages, SSVEP-BCI and ERD-BCI, runs in a closed-loop architecture. The first stage, SSVEP-BCI, acts as a selector of electrical stimulation pattern that corresponds to one of the three basic types of grasp: palmar, lateral, or precision. In the second stage, ERD-BCI operates as a brain switch which activates the stimulation pattern selected in the previous stage. The system was tested in 6 healthy subjects who were all able to control the device with accuracy in a range of 0.64–0.96. The results provided the reference data needed for the planned clinical study. This novel BCI may promote further restoration of the impaired motor function by closing the loop between the “will to move” and contingent temporally synchronized sensory feedback.

  5. Detecting awareness in patients with disorders of consciousness using a hybrid brain-computer interface

    Science.gov (United States)

    Pan, Jiahui; Xie, Qiuyou; He, Yanbin; Wang, Fei; Di, Haibo; Laureys, Steven; Yu, Ronghao; Li, Yuanqing

    2014-10-01

    Objective. The bedside detection of potential awareness in patients with disorders of consciousness (DOC) currently relies only on behavioral observations and tests; however, the misdiagnosis rates in this patient group are historically relatively high. In this study, we proposed a visual hybrid brain-computer interface (BCI) combining P300 and steady-state evoked potential (SSVEP) responses to detect awareness in severely brain injured patients. Approach. Four healthy subjects, seven DOC patients who were in a vegetative state (VS, n = 4) or minimally conscious state (MCS, n = 3), and one locked-in syndrome (LIS) patient attempted a command-following experiment. In each experimental trial, two photos were presented to each patient; one was the patient's own photo, and the other photo was unfamiliar. The patients were instructed to focus on their own or the unfamiliar photos. The BCI system determined which photo the patient focused on with both P300 and SSVEP detections. Main results. Four healthy subjects, one of the 4 VS, one of the 3 MCS, and the LIS patient were able to selectively attend to their own or the unfamiliar photos (classification accuracy, 66-100%). Two additional patients (one VS and one MCS) failed to attend the unfamiliar photo (50-52%) but achieved significant accuracies for their own photo (64-68%). All other patients failed to show any significant response to commands (46-55%). Significance. Through the hybrid BCI system, command following was detected in four healthy subjects, two of 7 DOC patients, and one LIS patient. We suggest that the hybrid BCI system could be used as a supportive bedside tool to detect awareness in patients with DOC.

  6. Nanoleakage in Hybrid Layer and Acid-Base Resistant Zone at the Adhesive/Dentin Interface.

    Science.gov (United States)

    Nikaido, Toru; Nurrohman, Hamid; Takagaki, Tomohiro; Sadr, Alireza; Ichinose, Shizuko; Tagami, Junji

    2015-10-01

    The aim of interfacial nanoleakage evaluation is to gain a better understanding of degradation of the adhesive-dentin interface. The acid-base resistant zone (ABRZ) is recognized at the bonded interface under the hybrid layer (HL) in self-etch adhesive systems after an acid-base challenge. The purpose of this study was to evaluate nanoleakage in HL and ABRZ using three self-etch adhesives; Clearfil SE Bond (SEB), Clearfil SE One (SEO), and G-Bond Plus (GBP). One of the three adhesives was applied on the ground dentin surface and light cured. The specimens were longitudinally divided into two halves. One half remained as the control group. The others were immersed in ammoniacal silver nitrate solution, followed by photo developing solution under fluorescent light. Following this, the specimens were subjected to acid-base challenges with an artificial demineralization solution (pH4.5) and sodium hypochlorite, and prepared in accordance with common procedures for transmission electron microscopy (TEM) examination. The TEM images revealed silver depositions in HL and ABRZ due to nanoleakage in all the adhesives; however, the extent of nanoleakage was material dependent. Funnel-shaped erosion beneath the ABRZ was observed only in the all-in-one adhesive systems; SEO and GBP, but not in the two-step self-etch adhesive system; SEB.

  7. Influence of structural fluctuations on lifetimes of adsorbate states at hybrid organic-semiconductor interfaces

    Science.gov (United States)

    Müller, M.; Sánchez-Portal, D.; Lin, H.; Fratesi, G.; Brivio, G. P.; Selloni, A.

    On the road towards a more realistic description of charge transfer processes at hybrid organic-semiconductor interfaces for photovoltaic applications we extend our first-principles scheme for the extraction of elastic linewidths to include the effects of structural fluctuations. Based on snapshots obtained from Car-Parinello molecular dynamics simulations at room temperature, we set up geometries in which dye molecules at interfaces are attached to a semi-infinite TiO2 substrate. The elastic linewidths are computed using a Green's function method. This effectively introduces the coupling to a continuum of states in the substrate. In particular we investigate catechol and isonicotinic acid on rutile(110) and anatase(101) at the level of semi-local density functional theory. We perform multiple calculations of linewidths and peak-positions associated with the adsorbate's frontier orbitals for different geometric configurations to obtain a time-averaged analysis of such physical properties. We compare the results from the considered systems to understand the effects of dynamics onto interfacial charge transfer and systematically assess the dependence of the extracted elastic lifetimes on the relative alignment between adsorbate and substrate states. This project has received funding from the European Union Seventh Framework Programme under Grant Agreement No. 607323 [THINFACE].

  8. sBCI-Headset—Wearable and Modular Device for Hybrid Brain-Computer Interface

    Directory of Open Access Journals (Sweden)

    Tatsiana Malechka

    2015-02-01

    Full Text Available Severely disabled people, like completely paralyzed persons either with tetraplegia or similar disabilities who cannot use their arms and hands, are often considered as a user group of Brain Computer Interfaces (BCI. In order to achieve high acceptance of the BCI by this user group and their supporters, the BCI system has to be integrated into their support infrastructure. Critical disadvantages of a BCI are the time consuming preparation of the user for the electroencephalography (EEG measurements and the low information transfer rate of EEG based BCI. These disadvantages become apparent if a BCI is used to control complex devices. In this paper, a hybrid BCI is described that enables research for a Human Machine Interface (HMI that is optimally adapted to requirements of the user and the tasks to be carried out. The solution is based on the integration of a Steady-state visual evoked potential (SSVEP-BCI, an Event-related (de-synchronization (ERD/ERS-BCI, an eye tracker, an environmental observation camera, and a new EEG head cap for wearing comfort and easy preparation. The design of the new fast multimodal BCI (called sBCI system is described and first test results, obtained in experiments with six healthy subjects, are presented. The sBCI concept may also become useful for healthy people in cases where a “hands-free” handling of devices is necessary.

  9. Lanthanide Metal-Organic Framework Materials

    Science.gov (United States)

    Hsieh, Ping-Yen; Green, Mark A.; Briber, Robert M.

    2009-03-01

    A series of lanthanide metal-organic framework materials (MOF) with variable organic linkages including benzene-dicarboxylic acid (BDC); 1,3,5-benzene-tricarboxylic acid (BTC); and 1,3,5-tris(4-carboxyphenyl)benzene (BTB) have been synthesized. The low density and high porosity of MOFs make them candidates molecular sieve or hydrogen storage materials. The crystal structures have been determined using a combination of single crystal X-ray diffractometer and synchrotron powder X-ray diffraction work. Holmium with the BDC ligand material (Ho-BDC) crystallizes in a monoclinic C2/c space group, with lattice parameters of a = 17.06 å, b = 10.67 å, c = 10.57 å, b = 96.12^o. The crystal structure of Ho-BTC is in tetragonal P 41 2 2 space group and Ho-BTB is in a triclinic P-1 space group. A comprehensive examination of Ho-MOF with different ligands by x-ray and thermogravimetric analysis shows that there is a stable nanoporous structure for dehydrated Ho-BTC up to 250^oC. The same phenomenon is not observed in the Ho-BDC and Ho-BTB materials. The collapsed structure with BDC and BTB indicates the stability of dehydrated samples is strongly related to the interactions between the metal and the organic linkers.

  10. Ultrahigh porosity in metal-organic frameworks.

    Science.gov (United States)

    Furukawa, Hiroyasu; Ko, Nakeun; Go, Yong Bok; Aratani, Naoki; Choi, Sang Beom; Choi, Eunwoo; Yazaydin, A Ozgür; Snurr, Randall Q; O'Keeffe, Michael; Kim, Jaheon; Yaghi, Omar M

    2010-07-23

    Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized that support well-defined pores with internal diameters of up to 48 angstroms. The Zn4O(CO2)6 unit was joined with either one or two kinds of organic link, 4,4',4''-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE), 4,4',44''-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (BBC), 4,4',44''-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and BTE/biphenyl-4,4'-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, -205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas (hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer-Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials.

  11. Metal-Organic Heat Carrier Nanofluids

    Energy Technology Data Exchange (ETDEWEB)

    McGrail, B. Peter; Thallapally, Praveen K.; Blanchard, Jeremy; Nune, Satish K.; Jenks, Jeromy WJ; Dang, Liem X.

    2013-09-01

    Nanofluids, dispersions of metal or oxide nanoparticles in a base working fluid, are being intensively studied due to improvements they offer in thermal properties of the working fluid. However, these benefits have been erratically demonstrated and proven impacts on thermal conductivity are modest and well described from long-established effective medium theory. In this paper, we describe a new class of metal-organic heat carrier (MOHC) nanofluid that offers potential for a larger performance boost in thermal vapor-liquid compression cycles. MOHCs are nanophase porous coordination solids designed to reversibly uptake the working fluid molecules in which the MOHCs are suspended. Additional heat can be extracted in a heat exchanger or solar collector from the endothermic enthalpy of desorption, which is then released as the nanofluid transits through a power generating device such as a turboexpander. Calculations for an R123 MOHC nanofluid indicated potential for up to 15% increase in power output. Capillary tube experiments show that liquid-vapor transitions occur without nanoparticle deposition on the tube walls provided entrance Reynolds number exceeds approximately 100.

  12. Atomistic simulations of thiol-terminated modifiers for hybrid photovoltaic interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Malloci, G. [Istituto Officina dei Materiali (CNR-IOM), Unità di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy); Petrozza, A. [Center for Nano Science and Technology @Polimi, Istituto Italiano di Tecnologia, Via Pascoli 70/3, I-20133 Milano (Italy); Mattoni, A., E-mail: mattoni@iom.cnr.it [Istituto Officina dei Materiali (CNR-IOM), Unità di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy)

    2014-06-02

    Small aromatic molecules such as benzene or pyridine derivatives are often used as interface modifiers (IMs) at polymer/metal oxide hybrid interfaces. We performed a theoretical investigation on prototypical thiol-terminated IMs aimed at improving the photovoltaic performances of poly(3-hexylthiophene)/TiO{sub 2} devices. By means of first-principles calculations in the framework of the density functional theory we investigate 3-furanthiol (3FT), 4-mercaptobenzoicacid (4MB), and 6-isoquinolinethiol (6QT) molecules. We discuss the role of these molecules as modifiers alternative to 4-mercaptopyridine (4MP) which has recently shown to induce a large improvement in the overall power conversion efficiency of mesoporous films of TiO{sub 2} infiltrated by poly(3-hexylthiophene). The IMs investigated are expected to keep the beneficial features of 4MP giving at the same time the possibility to further tune the interlayer properties (e.g., its thickness, stability, and density). Dense interlayers of 6QT turn out to be slightly unstable since the titania substrate induces a compressive strain in the molecular film. On the contrary, we predict very stable films for both 3FT and 4MB molecules, which makes them interesting candidates for future experimental investigations. - Highlights: • We performed a theoretical investigation on thiol-terminated interface modifiers. • We investigate 3-furanthiol (3FT), 4-mercaptobenzoicacid (4MB), and 6-isoquinolinethiol molecules. • We discuss the role of these molecules as modifiers alternative to 4-mercaptopyridine. • Dense interlayers of 6-isoquinolinethiol turn out to be slightly unstable. • We predict very stable self-assembled thin-films for both 3FT and 4MB molecules.

  13. Controlled Growth of Metal-Organic Frameworks on Polymer Brushes.

    Science.gov (United States)

    Hou, Liman; Zhou, Mingdong; Dong, Xiaozhe; Wang, Lei; Xie, Zhigang; Dong, Dewen; Zhang, Ning

    2017-08-17

    Polymer brushes are for the first time used to induce the synthesis of metal-organic frameworks (MOFs). The semi-fixed polymer chains provide a confined environment, which allows a mild growth of MOFs in between polymer chains to give surface-attached spherical MOF nanoparticles, in contrast to the larger MOF cubes/plates formed simultaneously in solution. Polymer brushes bearing carboxylate acid functionalities are indispensable for the formation of surface bound MOFs, while no MOF nanoparticles are observed on neutral polymer brushes. Characterization of the resultant MOF/polymer brushes hybrid film indicates the formation of crystalline MOF structure. The dimension of surface-attached MOFs can be fine-tuned from 20 nm to 1.4 μm simply by varying the structural parameter of polymer brushes and the nucleation duration. The method is not only applicable to the synthesis of MOF-5 and MIL-125, but shows great potential for the preparation of other surface-attached MOFs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Functionalization of silicon nanowire surfaces with metal-organic frameworks

    KAUST Repository

    Liu, Nian

    2011-12-28

    Metal-organic frameworks (MOFs) and silicon nanowires (SiNWs) have been extensively studied due to their unique properties; MOFs have high porosity and specific surface area with well-defined nanoporous structure, while SiNWs have valuable one-dimensional electronic properties. Integration of the two materials into one composite could synergistically combine the advantages of both materials and lead to new applications. We report the first example of a MOF synthesized on surface-modified SiNWs. The synthesis of polycrystalline MOF-199 (also known as HKUST-1) on SiNWs was performed at room temperature using a step-by-step (SBS) approach, and X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy dispersive spectroscopy elemental mapping were used to characterize the material. Matching of the SiNW surface functional groups with the MOF organic linker coordinating groups was found to be critical for the growth. Additionally, the MOF morphology can by tuned by changing the soaking time, synthesis temperature and precursor solution concentration. This SiNW/MOF hybrid structure opens new avenues for rational design of materials with novel functionalities. © 2011 Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

  15. Hydrogen storage by physisorption on Metal Organic Frameworks

    Science.gov (United States)

    Dailly, Anne

    2008-03-01

    Cryo-adsorption systems based on materials with high specific surface areas have the main advantage that they can store and release hydrogen with fast kinetics and high reversibility over multiples cycles. Recently Metal Organic Frameworks (MOFs) have been proposed as promising adsorbents for hydrogen. These crystallographically well organized hybrid solids resulting from the three dimensional connection of inorganic clusters using organic linkers show the largest specific surface areas of all known crystalline solids. The determination of the relationships between physical properties (chemistry, structure, surface area ) of the MOFs and their hydrogen storage behavior is a key step in the characterization of these materials, if they are to be designed for hydrogen storage applications. Excess hydrogen sorption measurements for different MOFs will be presented. We show that maximum hydrogen uptake at high pressure and 77K does not always scale with the specific surface area. A linear correlation trend only apply within a class of specific materials and breaks down when the surface area measurement does not represent the surface sites that are available to H2. The influence of pore size and shape will also be discussed by comparing several MOFs with different structure types. The hydrogen adsorption and binding energy at low pressure are strongly dependent on the metal ions and the pore size.

  16. Metal-organic frameworks as sensory materials and imaging agents.

    Science.gov (United States)

    Liu, Demin; Lu, Kuangda; Poon, Christopher; Lin, Wenbin

    2014-02-17

    Metal-organic frameworks (MOFs) are a class of hybrid materials self-assembled from organic bridging ligands and metal ion/cluster connecting points. The combination of a variety of organic linkers, metal ions/clusters, and structural motifs can lead to an infinite array of new materials with interesting properties for many applications. In this Forum Article, we discuss the design and applications of MOFs in chemical sensing and biological imaging. The first half of this article focuses on the development of MOFs as chemical sensors by highlighting how unique attributes of MOFs can be utilized to enhance sensitivity and selectivity. We also discuss some of the issues that need to be addressed in order to develop practically useful MOF sensors. The second half of this article focuses on the design and applications of nanoscale MOFs (NMOFs) as imaging contrast agents. NMOFs possess several interesting attributes, such as high cargo loading capacity, ease of postmodification, tunable size and shape, and intrinsic biodegradability, to make them excellent candidates as imaging contrast agents. We discuss the use of representative NMOFs in magnetic resonance imaging (MRI), X-ray computed tomography (CT), and optical imaging. Although still in their infancy, we believe that the compositional tunability and mild synthetic conditions of NMOF imaging agents should greatly facilitate their further development for clinical translation.

  17. Zeolite-like metal-organic frameworks (ZMOFs) based on the directed assembly of finite metal-organic cubes (MOCs).

    Science.gov (United States)

    Alkordi, Mohamed H; Brant, Jacilynn A; Wojtas, Lukasz; Kravtsov, Victor Ch; Cairns, Amy J; Eddaoudi, Mohamed

    2009-12-16

    Two zeolite-like metal-organic frameworks (ZMOFs) with lta- and ast- topologies, zeolitic nets that can be interpreted as augmented edge-transitive 8-connected nets, are targeted through directed self-assembly of metal-organic cubes (MOCs) as supermolecular building blocks (SBBs).

  18. Porous metal-organic frameworks for heterogeneous biomimetic catalysis.

    Science.gov (United States)

    Zhao, Min; Ou, Sha; Wu, Chuan-De

    2014-04-15

    Metalloporphyrins are the active sites in monooxygenases that oxidize a variety of substrates efficiently and under mild conditions. Researchers have developed artificial metalloporphyrins, but these structures have had limited catalytic applications. Homogeneous artificial metalloporphyrins can undergo catalytic deactivation via suicidal self-oxidation, which lowers their catalytic activity and sustainability relative to their counterparts in Nature. Heme molecules in protein scaffolds can maintain high efficiency over numerous catalytic cycles. Therefore, we wondered if immobilizing metalloporphyrin moieties within porous metal-organic frameworks (MOFs) could stabilize these structures and facilitate the molecular recognition of substrates and produce highly efficient biomimetic catalysis. In this Account, we describe our research to develop multifunctional porphyrinic frameworks as highly efficient heterogeneous biomimetic catalysts. Our studies indicate that porous porphyrinic frameworks provide an excellent platform for mimicking the activity of biocatalysts and developing new heterogeneous catalysts that effect new chemical transformations under mild conditions. The porous structures and framework topologies of the porphyrinic frameworks depend on the configurations, coordination donors, and porphyrin metal ions of the metalloporphyrin moieties. To improve the activity of porous porphyrinic frameworks, we have developed a two-step synthesis that introduces the functional polyoxometalates (POMs) into POM-porphyrin hybrid materials. To tune the pore structures and the catalytic properties of porphyrinic frameworks, we have designed metalloporphyrin M-H8OCPP ligands with four m-benzenedicarboxylate moieties, and introduced the secondary auxiliary ligands. The porphyrin metal ions and the secondary functional moieties that are incorporated into porous metal-organic frameworks greatly influence the catalytic properties and activities of porphyrinic frameworks in

  19. Stepwise Synthesis of Metal-Organic Frameworks.

    Science.gov (United States)

    Bosch, Mathieu; Yuan, Shuai; Rutledge, William; Zhou, Hong-Cai

    2017-04-18

    Metal-organic frameworks (MOFs) are a category of porous materials that offer unparalleled control over their surface areas (demonstrated as higher than for any other material), pore characteristics, and functionalization. This allows them to be customized for exceptional performance in a wide variety of applications, most commonly including gas storage and separation, drug delivery, luminescence, or heterogeneous catalysis. In order to optimize biomimicry, controlled separations and storage of small molecules, and detailed testing of structure-property relationships, one major goal of MOF research is "rational design" or "pore engineering", or precise control of the placement of multiple functional groups in pores of chosen sizes and shapes. MOF crystal growth can be controlled through judicious design of stepwise synthetic routes, which can also allow functionalization of MOFs in ways that were previously synthetically inaccessible. Organic chemists have developed a library of powerful techniques over the last century, allowing the total synthesis and detailed customization of complex molecules. Our hypothesis is that total synthesis is also possible for customized porous materials, through the development of similar multistep techniques. This will enable the rational design of MOFs, which is a major goal of many researchers in the field. We have begun developing a library of stepwise synthetic techniques for MOFs, allowing the synthesis of ultrastable MOFs with multiple crystallographically ordered and customizable functional groups at controlled locations within the pores. In order to design MOFs with precise control over pore size and shape, stability, and the placement of multiple different functional groups within the pores at tunable distances from one another, we have concentrated on methods which allow us to circumvent the lack of control inherent to one-pot MOF crystallization. Kinetically tuned dimensional augmentation (KTDA) is an approach using

  20. Nanoscale Fluorescent Metal-Organic Framework@Microporous Organic Polymer Composites for Enhanced Intracellular Uptake and Bioimaging.

    Science.gov (United States)

    Wang, Lei; Wang, Weiqi; Zheng, Xiaohua; Li, Zhensheng; Xie, Zhigang

    2017-01-26

    Polymer-modified metal-organic frameworks combine the advantages of both soft polymers and crystalline metal-organic frameworks (MOFs). It is a big challenge to develop simple methods for surface modification of MOFs. In this work, MOF@microporous organic polymer (MOP) hybrid nanoparticles (UNP) have been synthesized by epitaxial growth of luminescent boron-dipyrromethene (BODIPYs)-imine MOPs on the surface of UiO-MOF seeds, which exhibit low cytotoxicity, smaller size distribution, well-retained pore integrity, and available functional sites. After folic acid grafting, the enhanced intracellular uptake and bioimaging was validated.

  1. An Efficient Framework for EEG Analysis with Application to Hybrid Brain Computer Interfaces Based on Motor Imagery and P300

    Directory of Open Access Journals (Sweden)

    Jinyi Long

    2017-01-01

    Full Text Available The hybrid brain computer interface (BCI based on motor imagery (MI and P300 has been a preferred strategy aiming to improve the detection performance through combining the features of each. However, current methods used for combining these two modalities optimize them separately, which does not result in optimal performance. Here, we present an efficient framework to optimize them together by concatenating the features of MI and P300 in a block diagonal form. Then a linear classifier under a dual spectral norm regularizer is applied to the combined features. Under this framework, the hybrid features of MI and P300 can be learned, selected, and combined together directly. Experimental results on the data set of hybrid BCI based on MI and P300 are provided to illustrate competitive performance of the proposed method against other conventional methods. This provides an evidence that the method used here contributes to the discrimination performance of the brain state in hybrid BCI.

  2. An Efficient Framework for EEG Analysis with Application to Hybrid Brain Computer Interfaces Based on Motor Imagery and P300

    Science.gov (United States)

    Wang, Jue; Yu, Tianyou

    2017-01-01

    The hybrid brain computer interface (BCI) based on motor imagery (MI) and P300 has been a preferred strategy aiming to improve the detection performance through combining the features of each. However, current methods used for combining these two modalities optimize them separately, which does not result in optimal performance. Here, we present an efficient framework to optimize them together by concatenating the features of MI and P300 in a block diagonal form. Then a linear classifier under a dual spectral norm regularizer is applied to the combined features. Under this framework, the hybrid features of MI and P300 can be learned, selected, and combined together directly. Experimental results on the data set of hybrid BCI based on MI and P300 are provided to illustrate competitive performance of the proposed method against other conventional methods. This provides an evidence that the method used here contributes to the discrimination performance of the brain state in hybrid BCI. PMID:28316617

  3. Interplay between defects, disorder and flexibility in metal-organic frameworks

    Science.gov (United States)

    Bennett, Thomas D.; Cheetham, Anthony K.; Fuchs, Alain H.; Coudert, François-Xavier

    2017-01-01

    Metal-organic frameworks are a novel family of chemically diverse materials, which are of interest across engineering, physics, chemistry, biology and medicine-based disciplines. Since the development of the field in its current form more than two decades ago, priority has been placed on the synthesis of new structures. However, more recently, a clear trend has emerged in shifting the emphasis from material design to exploring the chemical and physical properties of structures already known. In particular, although such nanoporous materials were traditionally seen as rigid crystalline structures, there is growing evidence that large-scale flexibility, the presence of defects and long-range disorder are not the exception in metal-organic frameworks, but the rule. Here we offer some perspective into how these concepts are perhaps inescapably intertwined, highlight recent advances in our understanding and discuss how a consideration of the interfaces between them may lead to enhancements of the materials' functionalities.

  4. Interface

    DEFF Research Database (Denmark)

    Computerens interface eller grænseflade har spredt sig overalt. Mobiltelefoner, spilkonsoller, pc'er og storskærme indeholder computere – men computere indbygges også i tøj og andre hverdagslige genstande, så vi konstant har adgang til digitale data. Interface retter fokus mod, hvordan den digita...

  5. Gold nanoparticles immobilized on metal-organic frameworks with enhanced catalytic performance for DNA detection.

    Science.gov (United States)

    Liu, Ya Li; Fu, Wen Liang; Li, Chun Mei; Huang, Cheng Zhi; Li, Yuan Fang

    2015-02-25

    In this work, gold nanoparticles (AuNPs) assembled on the surface of iron based metal-organic frameworks (MOFs), Fe-MIL-88, are facilely prepared through electrostatic interactions using polyethyleneimine (PEI) molecules as linker. The resulting hybrid materials possess synergetic peroxidase-like activity. Because iron based metal-organic frameworks, Fe-MIL-88, exhibits highly peroxidase-like activity, and AuNPs has the distinct adsorption property to single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA). The peroxidase-like activity of Au@Fe-MIL-88 exhibit excellent switchable in response to specific DNA, ssDNA is easily adsorbed on the surface of the Au@Fe-MIL-88 hybrids, resulting in the reduce of the peroxidase-like activity of the hybrids. While it is recovered by the addition of target DNA, and the recovery degree is proportional to the target DNA concentration over the range of 30-150 nM with a detection limit of 11.4 nM. Based on these unique properties, we develop a label-free colorimetric method for DNA hybridization detection. In control experiment, base-mismatched DNA cannot induce recovery of the peroxidase-like activity. This detection method is simple, cheap, rapid and colorimetric.

  6. DNA hybridization-induced reorientation of liquid crystal anchoring at the nematic liquid crystal/aqueous interface.

    Science.gov (United States)

    Price, Andrew D; Schwartz, Daniel K

    2008-07-01

    Interactions between DNA and an adsorbed cationic surfactant at the nematic liquid crystal (LC)/aqueous interface were investigated using polarized and fluorescence microscopy. The adsorption of octadecyltrimethylammonium bromide (OTAB) surfactant to the LC/aqueous interface resulted in homeotropic (untilted) LC alignment. Subsequent adsorption of single-stranded DNA (ssDNA) to the surfactant-laden interface modified the interfacial structure, resulting in a reorientation of the LC from homeotropic alignment to an intermediate tilt angle. Exposure of the ssDNA/OTAB interfacial complex to its ssDNA complement induced a second change in the interfacial structure characterized by the nucleation, growth, and coalescence of lateral regions that induced homeotropic LC alignment. Fluorescence microscopy showed explicitly that the complement was colocalized in the same regions as the homeotropic domains. Exposure to noncomplementary ssDNA caused no such response, suggesting that the homeotropic regions were due to DNA hybridization. This hybridization occurred in the vicinity of the interface despite the fact that the conditions in bulk solution were such that hybridization did not occur (high stringency), suggesting that the presence of the cationic surfactant neutralized electrostatic repulsion and allowed for hydrogen bonding between DNA complements. This system has potential for label-less and portable DNA detection. Indeed, LC response to ssDNA target was detected with a lower limit of approximately 50 fmol of complement and was sufficiently selective to differentiate a one-base-pair mismatch in a 16-mer target.

  7. A hybrid three-class brain-computer interface system utilizing SSSEPs and transient ERPs

    Science.gov (United States)

    Breitwieser, Christian; Pokorny, Christoph; Müller-Putz, Gernot R.

    2016-12-01

    Objective. This paper investigates the fusion of steady-state somatosensory evoked potentials (SSSEPs) and transient event-related potentials (tERPs), evoked through tactile simulation on the left and right-hand fingertips, in a three-class EEG based hybrid brain-computer interface. It was hypothesized, that fusing the input signals leads to higher classification rates than classifying tERP and SSSEP individually. Approach. Fourteen subjects participated in the studies, consisting of a screening paradigm to determine person dependent resonance-like frequencies and a subsequent online paradigm. The whole setup of the BCI system was based on open interfaces, following suggestions for a common implementation platform. During the online experiment, subjects were instructed to focus their attention on the stimulated fingertips as indicated by a visual cue. The recorded data were classified during runtime using a multi-class shrinkage LDA classifier and the outputs were fused together applying a posterior probability based fusion. Data were further analyzed offline, involving a combined classification of SSSEP and tERP features as a second fusion principle. The final results were tested for statistical significance applying a repeated measures ANOVA. Main results. A significant classification increase was achieved when fusing the results with a combined classification compared to performing an individual classification. Furthermore, the SSSEP classifier was significantly better in detecting a non-control state, whereas the tERP classifier was significantly better in detecting control states. Subjects who had a higher relative band power increase during the screening session also achieved significantly higher classification results than subjects with lower relative band power increase. Significance. It could be shown that utilizing SSSEP and tERP for hBCIs increases the classification accuracy and also that tERP and SSSEP are not classifying control- and non

  8. Zeolite-like metal-organic frameworks with ana topology

    KAUST Repository

    Eddaoudi, Mohamed

    2017-04-20

    Embodiments of the present disclosure describe a zeolite-like metal-organic framework composition comprising a metal-organic framework composition with ana topology characterized by the formula [MIII(4, 5-imidazole dicarboxylic acid)2X(solvent)a]n wherein MIII comprises a trivalent cation of a rare earth element, X comprises an alkali metal element or alkaline earth metal element, and solvent comprises a guest molecule occupying pores. Embodiments of the present disclosure describe a method of separating paraffins comprising contacting a zeolite-like metal-organic framework with ana topology with a flow of paraffins, and separating the paraffins by size.

  9. Hydrogen Storage in Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Omar M. Yaghi

    2012-04-26

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g L-1) densities to be achieved by 2015. Given that these are system goals, a practical material will need to have higher capacity when the weight of the tank and associated cooling or regeneration system is considered. The size and weight of these components will vary substantially depending on whether the material operates by a chemisorption or physisorption mechanism. In the latter case, metal-organic frameworks (MOFs) have recently been identified as promising adsorbents for hydrogen storage, although little data is available for their sorption behavior. This grant was focused on the study of MOFs with these specific objectives. (1) To examine the effects of functionalization, catenation, and variation of the metal oxide and organic linkers on the low-pressure hydrogen adsorption properties of MOFs. (2) To develop a strategy for producing MOFs with high surface area and porosity to reduce the dead space and increase the hydrogen storage capacity per unit volume. (3) To functionalize MOFs by post synthetic functionalization with metals to improve the adsorption enthalpy of hydrogen for the room temperature hydrogen storage. This effort demonstrated the importance of open metal sites to improve the adsorption enthalpy by the systematic study, and this is also the origin of the new strategy, which termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. Based on our principle to design highly porous MOFs, guest-free MOFs with ultrahigh porosity have been experimentally synthesized. MOF-210, whose BET surface area is 6240 m2 g-1 (the highest among porous solids), takes up

  10. Automatic artefact removal in a self-paced hybrid brain- computer interface system

    Directory of Open Access Journals (Sweden)

    Yong Xinyi

    2012-07-01

    Full Text Available Abstract Background A novel artefact removal algorithm is proposed for a self-paced hybrid brain-computer interface (BCI system. This hybrid system combines a self-paced BCI with an eye-tracker to operate a virtual keyboard. To select a letter, the user must gaze at the target for at least a specific period of time (dwell time and then activate the BCI by performing a mental task. Unfortunately, electroencephalogram (EEG signals are often contaminated with artefacts. Artefacts change the quality of EEG signals and subsequently degrade the BCI’s performance. Methods To remove artefacts in EEG signals, the proposed algorithm uses the stationary wavelet transform combined with a new adaptive thresholding mechanism. To evaluate the performance of the proposed algorithm and other artefact handling/removal methods, semi-simulated EEG signals (i.e., real EEG signals mixed with simulated artefacts and real EEG signals obtained from seven participants are used. For real EEG signals, the hybrid BCI system’s performance is evaluated in an online-like manner, i.e., using the continuous data from the last session as in a real-time environment. Results With semi-simulated EEG signals, we show that the proposed algorithm achieves lower signal distortion in both time and frequency domains. With real EEG signals, we demonstrate that for dwell time of 0.0s, the number of false-positives/minute is 2 and the true positive rate (TPR achieved by the proposed algorithm is 44.7%, which is more than 15.0% higher compared to other state-of-the-art artefact handling methods. As dwell time increases to 1.0s, the TPR increases to 73.1%. Conclusions The proposed artefact removal algorithm greatly improves the BCI’s performance. It also has the following advantages: a it does not require additional electrooculogram/electromyogram channels, long data segments or a large number of EEG channels, b it allows real-time processing, and c it reduces signal distortion.

  11. A novel EOG/EEG hybrid human-machine interface adopting eye movements and ERPs: application to robot control.

    Science.gov (United States)

    Ma, Jiaxin; Zhang, Yu; Cichocki, Andrzej; Matsuno, Fumitoshi

    2015-03-01

    This study presents a novel human-machine interface (HMI) based on both electrooculography (EOG) and electroencephalography (EEG). This hybrid interface works in two modes: an EOG mode recognizes eye movements such as blinks, and an EEG mode detects event related potentials (ERPs) like P300. While both eye movements and ERPs have been separately used for implementing assistive interfaces, which help patients with motor disabilities in performing daily tasks, the proposed hybrid interface integrates them together. In this way, both the eye movements and ERPs complement each other. Therefore, it can provide a better efficiency and a wider scope of application. In this study, we design a threshold algorithm that can recognize four kinds of eye movements including blink, wink, gaze, and frown. In addition, an oddball paradigm with stimuli of inverted faces is used to evoke multiple ERP components including P300, N170, and VPP. To verify the effectiveness of the proposed system, two different online experiments are carried out. One is to control a multifunctional humanoid robot, and the other is to control four mobile robots. In both experiments, the subjects can complete tasks effectively by using the proposed interface, whereas the best completion time is relatively short and very close to the one operated by hand.

  12. Interface

    DEFF Research Database (Denmark)

    Computerens interface eller grænseflade har spredt sig overalt. Mobiltelefoner, spilkonsoller, pc'er og storskærme indeholder computere – men computere indbygges også i tøj og andre hverdagslige genstande, så vi konstant har adgang til digitale data. Interface retter fokus mod, hvordan den digitale...... kunst og kultur skabes, spredes og opleves igennem interfaces. Forfatterne undersøger og diskuterer interfacets æstetik, ideologi og kultur – og analyserer aktuel interfacekunst på tværs af musik, kunst, litteratur og film. Bogen belyser interfacets oprindelse i den kolde krigs laboratorier og dets...

  13. Effect of interface microstructure on the mechanical properties of Pb-free hybrid microcircuit solder joints

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez, C.L.; Vianco, P.T.; Rejent, J.A.

    1998-08-01

    Although Sn-Pb eutectic alloy is widely used as a joining material in the electronics industry, it has well documented environmental and toxicity issues. Sandia National Laboratories is developing alternative solder materials to replace traditional Pb-containing alloys. The alloys are based on the Sn-Ag, Sn-Ag-Bi and Sn-Ag-Bi-Au systems. Prototype hybrid microcircuit (HMC) test vehicles have been developed to evaluate these Pb-free solders, using Au-Pt-Pd thick film metallization. Populated test vehicles with surface mount devices have been designed and fabricated to evaluate the reliability of surface mount solder joints. The test components consist of a variety of dummy chip capacitors and leadless ceramic chip carriers (LCCC`s). Intermetallic compound (IMC) layer reaction products that form at the solder/substrate interface have been characterized and their respective growth kinetics quantified. Thicker IMC layers pose a potential reliability problem with solder joint integrity. Since the IMC layer is brittle, the likelihood of mechanical failure of a joint in service is increased. The effect of microstructure and the response of these different materials to wetting, aging and mechanical testing was also investigated. Solid-state reaction data for intermetallic formation and mechanical properties of the solder joints are reported.

  14. Novel Metal Organic Framework Synthesis for Spacecraft Oxygen Capture Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Busek and University of Utah propose to develop novel metal organic framework (MOF) material to efficiently capture oxygen in spacecraft cabin environment. The...

  15. Porous materials: Lining up metal-organic frameworks

    Science.gov (United States)

    Champness, Neil R.

    2017-03-01

    A new report demonstrates an innovative approach to aligning crystallites of metal-organic frameworks such that thin films are created with oriented channels -- potentially overcoming one of the major barriers to application of these highly topical materials.

  16. Coordinatively unsaturated metal organic frameworks for olefin separations

    OpenAIRE

    Renouf, Catherine Louise

    2013-01-01

    The research presented in this thesis aims to assess the capacity of metal organic frameworks with open metal sites for the separation of olefin mixtures. Chapter 1 provides a background to the field, including industrial separation techniques, metal organic frameworks and their applications and the current state-of-the- art for olefin separation. Chapter 3 describes the experimental techniques used in this research. Ethylene and propylene adsorption and desorption isotherms...

  17. Metal organic frameworks for removal of compounds from a fluid

    KAUST Repository

    Eddaoudi, Mohamed

    2016-03-03

    Embodiments provide a method of compound removal from a fluid. The method includes contacting one or more metal organic framework (MOF) compositions with a fluid and sorbing one or more compounds, such as CO2, H2S and condensable hydrocarbons. One or more of CO2, H2S and condensable hydrocarbons can be sorbed simultaneously or in series. The metal organic framework can be an M-soc-MOF.

  18. Metal-organic framework for the separation of alkane isomers

    Science.gov (United States)

    Long, Jeffrey R.; Herm, Zoey R.; Wiers, Brian M.; Krishna, Rajamani

    2017-01-10

    A metal organic framework Fe.sub.2(bdp).sub.3 (BDP.sup.2-=1,4-benzenedipyrazolate) with triangular channels is particularly suited for C5-C7 separations of alkanes according to the number of branches in the molecule rather than by carbon number. The metal-organic framework can offer pore geometries that is unavailable in zeolites or other porous media, facilitating distinct types of shape-based molecular separations.

  19. Redox-promoted associative assembly of metal-organic materials.

    Science.gov (United States)

    Glavinović, Martin; Qi, Feng; Katsenis, Athanassios D; Friščić, Tomislav; Lumb, Jean-Philip

    2016-01-01

    We develop an associative synthesis of metal-organic materials that combines solid-state metal oxidation and coordination-driven self-assembly into a one-step, waste-free transformation. The methodology hinges on the unique reactivity of ortho-quinones, which we introduce as versatile oxidants for mechanochemical synthesis. Our strategy opens a previously unexplored route to paramagnetic metal-organic materials from elementary metals.

  20. Fuel upgrading and reforming with metal organic framework

    KAUST Repository

    Eddaoudi, Mohamed

    2016-03-31

    Systems and methods for separating hydrocarbons on an internal combustion powered vehicle via one or more metal organic frameworks are disclosed. Systems and methods can further include utilizing separated hydrocarbons and exhaust to generate hydrogen gas for use as fuel. In one aspect, a method for separating hydrocarbons can include contacting a first component containing a first metal organic framework with a flow of hydrocarbons and separating hydrocarbons by size. In certain embodiments, the hydrocarbons can include alkanes.

  1. Fuel upgrading and reforming with metal organic framework

    KAUST Repository

    Eddaoudi, Mohamed

    2016-03-31

    Systems and methods for separating hydrocarbons on an internal combustion powered vehicle via one or more metal organic frameworks are disclosed. Systems and methods can further include utilizing separated hydrocarbons and exhaust to generate hydrogen gas for use as fuel. In one aspect, a method for separating hydrocarbons can include contacting a first component containing a first metal organic framework with a flow of hydrocarbons and separating hydrocarbons by size. In certain embodiments, the hydrocarbons can include alkanes.

  2. Metal-organic framework for the separation of alkane isomers

    Energy Technology Data Exchange (ETDEWEB)

    Long, Jeffrey R.; Herm, Zoey R.; Wiers, Brian M.; Krishna, Rajamani

    2017-01-10

    A metal organic framework Fe.sub.2(bdp).sub.3 (BDP.sup.2-=1,4-benzenedipyrazolate) with triangular channels is particularly suited for C5-C7 separations of alkanes according to the number of branches in the molecule rather than by carbon number. The metal-organic framework can offer pore geometries that is unavailable in zeolites or other porous media, facilitating distinct types of shape-based molecular separations.

  3. Multi-responsive metal-organic lantern cages in solution.

    Science.gov (United States)

    Brega, Valentina; Zeller, Matthias; He, Yufan; Lu, H Peter; Klosterman, Jeremy K

    2015-03-25

    Soluble copper-based M4L4 lantern-type metal-organic cages bearing internal amines were synthesized. The solution state integrity of the paramagnetic metal-organic cages was demonstrated using NMR, DLS, MS, and AFM spectroscopy. 1D supramolecular pillars of pre-formed cages or covalent host-guest complexes selectively formed upon treatment with 4,4'-bipyridine and acetic anhydride, respectively.

  4. A hybrid VOF and PIC multi-material interface treatment method and its application in the penetration

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A hybrid VOF and PIC multi-material interface treatment method for Eulerian method is presented in this study in order to solve the problem that the Eulerian method is not robust enough to treat the dynamic fracture of material. This treatment method is used in the important computational region such as the material interface,large deformation region and fracture region where more particles are added for calculation,while the continuous transport method is used in the other regions. Through this method,a series of penetration problems such as blunt projectile penetration into the steel target and steel projectile penetration into concert target are numerically simulated. The comparison of the numerical result and experimental result shows that the hybrid algorithm can effectively track the deformation in the process of penetration and also insure precision and efficiency.

  5. Biocompatible hybrid nanomaterials involving polymers and hydrogels interfaced with phosphorescent complexes and toxin-free metallic nanoparticles for biomedical applications

    Science.gov (United States)

    Marpu, Sreekar B.

    The major topics discussed are all relevant to interfacing brightly phosphorescent and non-luminescent coinage metal complexes of [Ag(I) and Au(I)] with biopolymers and thermoresponsive gels for making hybrid nanomaterials with an explanation on syntheses, characterization and their significance in biomedical fields. Experimental results and ongoing work on determining outreaching consequences of these hybrid nanomaterials for various biomedical applications like cancer therapy, bio-imaging and antibacterial abilities are described. In vitro and in vivo studies have been performed on majority of the discussed hybrid nanomaterials and determined that the cytotoxicity or antibacterial activity are comparatively superior when compared to analogues in literature. Consequential differences are noticed in photoluminescence enhancement from hybrid phosphorescent hydrogels, phosphorescent complex ability to physically crosslink, Au(I) sulfides tendency to form NIR (near-infrared) absorbing AuNPs compared to any similar work in literature. Syntheses of these hybrid nanomaterials has been thoroughly investigated and it is determined that either metallic nanoparticles syntheses or syntheses of phosphorescent hydrogels can be carried in single step without involving any hazardous reducing agents or crosslinkers or stabilizers that are commonly employed during multiple step syntheses protocols for syntheses of similar materials in literature. These astounding results that have been discovered within studies of hybrid nanomaterials are an asset to applications ranging from materials development to health science and will have striking effect on environmental and green chemistry approaches.

  6. Manipulating the Topological Interface by Molecular Adsorbates: Adsorption of Co-Phthalocyanine on Bi2Se3.

    Science.gov (United States)

    Caputo, Marco; Panighel, Mirko; Lisi, Simone; Khalil, Lama; Santo, Giovanni Di; Papalazarou, Evangelos; Hruban, Andrzej; Konczykowski, Marcin; Krusin-Elbaum, Lia; Aliev, Ziya S; Babanly, Mahammad B; Otrokov, Mikhail M; Politano, Antonio; Chulkov, Evgueni V; Arnau, Andrés; Marinova, Vera; Das, Pranab K; Fujii, Jun; Vobornik, Ivana; Perfetti, Luca; Mugarza, Aitor; Goldoni, Andrea; Marsi, Marino

    2016-06-08

    Topological insulators are a promising class of materials for applications in the field of spintronics. New perspectives in this field can arise from interfacing metal-organic molecules with the topological insulator spin-momentum locked surface states, which can be perturbed enhancing or suppressing spintronics-relevant properties such as spin coherence. Here we show results from an angle-resolved photemission spectroscopy (ARPES) and scanning tunnelling microscopy (STM) study of the prototypical cobalt phthalocyanine (CoPc)/Bi2Se3 interface. We demonstrate that that the hybrid interface can act on the topological protection of the surface and bury the Dirac cone below the first quintuple layer.

  7. A critical review of interfaces with the peripheral nervous system for the control of neuroprostheses and hybrid bionic systems.

    Science.gov (United States)

    Navarro, Xavier; Krueger, Thilo B; Lago, Natalia; Micera, Silvestro; Stieglitz, Thomas; Dario, Paolo

    2005-09-01

    Considerable scientific and technological efforts have been devoted to develop neuroprostheses and hybrid bionic systems that link the human nervous system with electronic or robotic prostheses, with the main aim of restoring motor and sensory functions in disabled patients. A number of neuroprostheses use interfaces with peripheral nerves or muscles for neuromuscular stimulation and signal recording. Herein, we provide a critical overview of the peripheral interfaces available and trace their use from research to clinical application in controlling artificial and robotic prostheses. The first section reviews the different types of non-invasive and invasive electrodes, which include surface and muscular electrodes that can record EMG signals from and stimulate the underlying or implanted muscles. Extraneural electrodes, such as cuff and epineurial electrodes, provide simultaneous interface with many axons in the nerve, whereas intrafascicular, penetrating, and regenerative electrodes may contact small groups of axons within a nerve fascicle. Biological, technological, and material science issues are also reviewed relative to the problems of electrode design and tissue injury. The last section reviews different strategies for the use of information recorded from peripheral interfaces and the current state of control neuroprostheses and hybrid bionic systems.

  8. Application of improved hybrid interface substructural component modal synthesis method in vibration characteristics of mistuned blisk

    Science.gov (United States)

    Bai, Bin; Bai, Guangchen; Li, Chao

    2014-11-01

    The large and complex structures are divided into hundreds of thousands or millions degrees of freedom(DOF) when they are calculated which will spend a lot of time and the efficiency will be extremely low. The classical component modal synthesis method (CMSM) are used extensively, but for many structures in the engineering of high-rise buildings, aerospace systemic engineerings, marine oil platforms etc, a large amount of calculation is still needed. An improved hybrid interface substructural component modal synthesis method(HISCMSM) is proposed. The parametric model of the mistuned blisk is built by the improved HISCMSM. The double coordinating conditions of the displacement and the force are introduced to ensure the computational accuracy. Compared with the overall structure finite element model method(FEMM), the computational time is shortened by 23.86%-31.56% and the modal deviation is 0.002%-0.157% which meets the requirement of the computational accuracy. It is faster 4.46%-10.57% than the classical HISCMSM. So the improved HISCMSM is better than the classical HISCMSM and the overall structure FEMM. Meanwhile, the frequency and the modal shape are researched, considering the factors including rotational speed, gas temperature and geometry size. The strong localization phenomenon of the modal shape's the maximum displacement and the maximum stress is observed in the second frequency band and it is the most sensitive in the frequency veering. But the localization phenomenon is relatively weak in 1st and the 3d frequency band. The localization of the modal shape is more serious under the condition of the geometric dimensioning mistuned. An improved HISCMSM is proposed, the computational efficiency of the mistuned blisk can be increased observably by this method.

  9. Improvement of antimony sulfide photo absorber performance by interface modification in Sb2S3-ZnO hybrid nanostructures

    Science.gov (United States)

    Ali, Asad; Hasanain, Syed Khurshid; Ali, Tahir; Sultan, Muhammad

    2017-03-01

    Metal-oxide chalcogenide nanostructures as part of hybrid systems are very important for photovoltaic and optoelectronic applications. It is however known that the various interfaces within the hybrid structures play a crucial role in limiting the efficiency of these devices. Here we report on the improvement of Sb2S3 structure through modification of interface between Zn-oxide nanostructures and chalcogenides. ZnO nanorods were grown on fluorine doped tin oxide (FTO) substrate by chemical bath deposition (CBD) method. X-ray diffraction (XRD) and SEM analysis confirmed the single phase wurtzite structure and c-axis orientation of the ZnO nanorod arrays. Antimony tri-sulfide (Sb2S3) was deposited on ZnO nanords by CBD and subsequently annealed at 300 °C in argon environment for 30 min. XRD and the XPS analysis of ZnO-Sb2S3 system showed the dominant presence of Sb2O3 rather than Sb2S3. Since oxidation of Sb2S3 is understood to proceed mainly from the ZnO-Sb2S3 interface, a ZnS interlayer was introduced between ZnO nanorods and Sb2S3 by chemical route. The subsequent structural and optical properties of the ZnO-ZnS-Sb2S3 system are analyzed in detail. The introduction of sulfide interlayer prevents the oxidation of Sb2S3 which is evident from reduced oxide phase in Sb2S3. Significant improvement in the structural and optical properties of Sb2S3 are reported as compared to the parent ZnO-Sb2S3 system. This gain in the optical properties of hybrid ZnO-ZnS-Sb2S3 nanostructures is explained as being related to successful prevention of Sb2O3 formation at the Sb-ZnO interface and stabilization of the desired Sb2S3.

  10. interfaces

    Directory of Open Access Journals (Sweden)

    Dipayan Sanyal

    2005-01-01

    macroscopic conservation equations with an order parameter which can account for the solid, liquid, and the mushy zones with the help of a phase function defined on the basis of the liquid fraction, the Gibbs relation, and the phase diagram with local approximations. Using the above formalism for alloy solidification, the width of the diffuse interface (mushy zone was computed rather accurately for iron-carbon and ammonium chloride-water binary alloys and validated against experimental data from literature.

  11. Hybrid plasma bonding for void-free strong bonded interface of silicon/glass at 200 degrees C.

    Science.gov (United States)

    Howlader, M M R; Kibria, M G; Zhang, F; Kim, M J

    2010-07-15

    A novel hybrid plasma bonding (HPB) that combines sequential plasma activation (reactive ion etching followed by microwave radicals) with anodic bonding has been developed to achieve void-free and strong silicon/glass bonding at low temperature. The interfacial voids were observed at the silicon/glass interface both in the anodic bonding and in the plasma activated anodic bonding, but the voids were completely disappeared in the HPB method at 200 degrees C. The bonding strength of the silicon/glass in the HPB was as high as 30 MPa at 200 degrees C, which was higher than that in the individual treatment of anodic and plasma activated bonding methods. The improved characteristic behavior of the interface in the HPB is attributed to the higher hydrophilicity and smooth surfaces of silicon and glass after sequential plasma activation. These highly reactive and clean surfaces enhance the mobility of alkaline cations from the glass surface across the interface toward the bulk of glass in the HPB. This transportation resulted in a approximately 353 nm thick alkaline depletion layer in the glass and enlarged the amorphous SiO(2) across the interface. The void-free strong bonding is attributed to the clean hydrophilic surfaces and the amorphous SiO(2) layer across the interface. Copyright 2010 Elsevier B.V. All rights reserved.

  12. Heteroepitaxial growth of 3-5 semiconductor compounds by metal-organic chemical vapor deposition for device applications

    Science.gov (United States)

    Collis, Ward J.; Abul-Fadl, Ali

    1988-01-01

    The purpose of this research is to design, install and operate a metal-organic chemical vapor deposition system which is to be used for the epitaxial growth of 3-5 semiconductor binary compounds, and ternary and quaternary alloys. The long-term goal is to utilize this vapor phase deposition in conjunction with existing current controlled liquid phase epitaxy facilities to perform hybrid growth sequences for fabricating integrated optoelectronic devices.

  13. Bi2O3 nanoparticles encapsulated in surface mounted metal-organic framework thin films

    Science.gov (United States)

    Guo, Wei; Chen, Zhi; Yang, Chengwu; Neumann, Tobias; Kübel, Christian; Wenzel, Wolfgang; Welle, Alexander; Pfleging, Wilhelm; Shekhah, Osama; Wöll, Christof; Redel, Engelbert

    2016-03-01

    We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye.We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00532b

  14. Reconfigurable electronics using conducting metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Talin, Albert Alec; Leonard, Francois; Stavila, Vitalie

    2017-07-18

    A device including a porous metal organic framework (MOF) disposed between two terminals, the device including a first state wherein the MOF is infiltrated by a guest species to form an electrical path between the terminals and a second state wherein the electrical conductivity of the MOF is less than the electrical conductivity in the first state. A method including switching a porous metal organic framework (MOF) between two terminals from a first state wherein a metal site in the MOF is infiltrated by a guest species that is capable of charge transfer to a second state wherein the MOF is less electrically conductive than in the first state.

  15. Plasmonic nanopatch array with integrated metal-organic framework for enhanced infrared absorption gas sensing

    Science.gov (United States)

    Chong, Xinyuan; Kim, Ki-joong; Zhang, Yujing; Li, Erwen; Ohodnicki, Paul R.; Chang, Chih-Hung; Wang, Alan X.

    2017-06-01

    In this letter, we present a nanophotonic device consisting of plasmonic nanopatch array (NPA) with integrated metal-organic framework (MOF) for enhanced infrared absorption gas sensing. By designing a gold NPA on a sapphire substrate, we are able to achieve enhanced optical field that spatially overlaps with the MOF layer, which can adsorb carbon dioxide (CO2) with high capacity. Experimental results show that this hybrid plasmonic-MOF device can effectively increase the infrared absorption path of on-chip gas sensors by more than 1100-fold. The demonstration of infrared absorption spectroscopy of CO2 using the hybrid plasmonic-MOF device proves a promising strategy for future on-chip gas sensing with ultra-compact size.

  16. Alkali Metal Halide Salts as Interface Additives to Fabricate Hysteresis-Free Hybrid Perovskite-Based Photovoltaic Devices.

    Science.gov (United States)

    Wang, Lili; Moghe, Dhanashree; Hafezian, Soroush; Chen, Pei; Young, Margaret; Elinski, Mark; Martinu, Ludvik; Kéna-Cohen, Stéphane; Lunt, Richard R

    2016-09-07

    A new method was developed for doping and fabricating hysteresis-free hybrid perovskite-based photovoltaic devices by using alkali metal halide salts as interface layer additives. Such salt layers introduced at the perovskite interface can provide excessive halide ions to fill vacancies formed during the deposition and annealing process. A range of solution-processed halide salts were investigated. The highest performance of methylammonium lead mixed-halide perovskite device was achieved with a NaI interlayer and showed a power conversion efficiency of 12.6% and a hysteresis of less than 2%. This represents a 90% improvement compared to control devices without this salt layer. Through depth-resolved mass spectrometry, optical modeling, and photoluminescence spectroscopy, this enhancement is attributed to the reduction of iodide vacancies, passivation of grain boundaries, and improved hole extraction. Our approach ultimately provides an alternative and facile route to high-performance and hysteresis-free perovskite solar cells.

  17. Hybrid solvation models for bulk, interface, and membrane: Reference interaction site methods coupled with density functional theory

    Science.gov (United States)

    Nishihara, S.; Otani, M.

    2017-09-01

    We present two hybrid solvation models for the calculation of the solvation structure with model 1 in a confined nanospace in bulk materials and model 2 at solid/liquid interfaces where an electrode is in contact with an electrolyte and a membrane is immersed into a solution. The hybrid theory is based on the reference interaction site method (RISM) for the solvent region. The electronic structure of a bulk material, an electrode, and a membrane is treated by density functional theory with the plane-wave basis and pseudopotentials technique. For model 1, we use the three-dimensional RISM (3D-RISM) by imposing a 3D periodic boundary condition on the system. However, for model 2, we reformulate the RISM by means of a two-dimensional boundary condition parallel to the surface and an open boundary condition normal to the surface. Four benchmark calculations are performed for the formaldehyde-water system, water packed into a zeolite framework, a NaCl solution in contact with an Al electrode, and an Al thin film immersed in a NaCl solution with different concentrations. The calculations are shown to be efficient and stable. Because of the flexibility of the RISM theory, the models are considered to be applicable to a wide range of solid/liquid interfaces.

  18. Rational design, synthesis, purification, and activation of metal-organic framework materials.

    Science.gov (United States)

    Farha, Omar K; Hupp, Joseph T

    2010-08-17

    The emergence of metal-organic frameworks (MOFs) as functional ultrahigh surface area materials is one of the most exciting recent developments in solid-state chemistry. Now constituting thousands of distinct examples, MOFs are an intriguing class of hybrid materials that exist as infinite crystalline lattices with inorganic vertices and molecular-scale organic connectors. Useful properties such as large internal surface areas, ultralow densities, and the availability of uniformly structured cavities and portals of molecular dimensions characterize functional MOFs. Researchers have effectively exploited these unusual properties in applications such as hydrogen and methane storage, chemical separations, and selective chemical catalysis. In principle, one of the most attractive features of MOFs is the simplicity of their synthesis. Typically they are obtained via one-pot solvothermal preparations. However, with the simplicity come challenges. In particular, MOF materials, especially more complex ones, can be difficult to obtain in pure form and with the optimal degree of catenation, the interpenetration or interweaving of identical independent networks. Once these two issues are satisfied, the removal of the guest molecules (solvent from synthesis) without damaging the structural integrity of the material is often an additional challenge. In this Account, we review recent advances in the synthetic design, purification, and activation of metal-organic framework materials. We describe the rational design of a series of organic struts to limit framework catenation and thereby produce large pores. In addition, we demonstrate the rapid separation of desired MOFs from crystalline and amorphous contaminants cogenerated during synthesis based on their different densities. Finally, we discuss the mild and efficient activation of initially solvent-filled pores with supercritical carbon dioxide, yielding usable channels and high internal surface areas. We expect that the

  19. Bipolar resistive switching properties of Ti-CuO/(hexafluoro-hexa-peri-hexabenzocoronene)-Cu hybrid interface device: Influence of electronic nature of organic layer

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Bharti; Mehta, B. R.; Varandani, Deepak [Thin Film Laboratory, Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016 (India); Govind [Surface Physics Group, National Physical Laboratory (CSIR), New Delhi-110012 (India); Narita, A.; Feng, X.; Muellen, K. [Max-Planck Institute for Polymer Research, D-55128 Mainz (Germany)

    2013-05-28

    This study reports the change in the structural and junction properties of Ti-CuO-Cu structure on incorporation of a 2-dimensional (2D) organic layer comprising of n-type hexafluoro-hexa-peri-hexabenzocoronene (6F-HBC). A bipolar resistive switching is observed in the device having interface between sputter deposited copper oxide (CuO) and vacuum sublimated 6F-HBC hybrid interface. The CuO/6F-HBC hybrid interface exhibits rectifying I-V characteristics in complete contrast to the ohmic and rectifying characteristics of junctions based on individual 6F-HBC and CuO layers. Large change in resistive switching property from unipolar resistive switching in CuO/HBC to bipolar resistive switching in CuO/6F-HBC interface was observed. At the CuO/6F-HBC interface, C1s peak corresponding to fluorinated carbon is shifted by 0.68 eV towards higher binding energy (BE) side and O1s peak due to non-lattice oxygen is shifted by 0.6 eV towards lower BE, confirming the interaction of O{sup 2-} ion in CuO with fluorinated carbon atoms in 6F-HBC at the hybrid interface. Correlation between conductive atomic force microscopy images and atomic force microscopy topography images, I-V characteristics in conducting, non-conducting, and pristine regions along with x-ray photoelectron spectroscopy results establishes the important role of hybrid interface to determining the resistive switching properties. This study demonstrates that the resistive switching and interface properties of a hybrid device based on inorganic and organic 2D materials can be modified by changing the electronic properties of organic layer by attaching suitable functional groups.

  20. Hybrid Brain–Computer Interface Techniques for Improved Classification Accuracy and Increased Number of Commands: A Review

    Directory of Open Access Journals (Sweden)

    Keum-Shik Hong

    2017-07-01

    Full Text Available In this article, non-invasive hybrid brain–computer interface (hBCI technologies for improving classification accuracy and increasing the number of commands are reviewed. Hybridization combining more than two modalities is a new trend in brain imaging and prosthesis control. Electroencephalography (EEG, due to its easy use and fast temporal resolution, is most widely utilized in combination with other brain/non-brain signal acquisition modalities, for instance, functional near infrared spectroscopy (fNIRS, electromyography (EMG, electrooculography (EOG, and eye tracker. Three main purposes of hybridization are to increase the number of control commands, improve classification accuracy and reduce the signal detection time. Currently, such combinations of EEG + fNIRS and EEG + EOG are most commonly employed. Four principal components (i.e., hardware, paradigm, classifiers, and features relevant to accuracy improvement are discussed. In the case of brain signals, motor imagination/movement tasks are combined with cognitive tasks to increase active brain–computer interface (BCI accuracy. Active and reactive tasks sometimes are combined: motor imagination with steady-state evoked visual potentials (SSVEP and motor imagination with P300. In the case of reactive tasks, SSVEP is most widely combined with P300 to increase the number of commands. Passive BCIs, however, are rare. After discussing the hardware and strategies involved in the development of hBCI, the second part examines the approaches used to increase the number of control commands and to enhance classification accuracy. The future prospects and the extension of hBCI in real-time applications for daily life scenarios are provided.

  1. Functionally graded scaffolds for the engineering of interface tissues using hybrid twin screw extrusion/electrospinning technology

    Science.gov (United States)

    Erisken, Cevat

    Tissue engineering is the application of the principles of engineering and life sciences for the development of biological alternatives for improvement or regeneration of native tissues. Native tissues are complex structures with functions and properties changing spatially and temporally, and engineering of such structures requires functionally graded scaffolds with composition and properties changing systematically along various directions. Utilization of a new hybrid technology integrating the controlled feeding, compounding, dispersion, deaeration, and pressurization capabilities of extrusion process with electrospinning allows incorporation of liquids and solid particles/nanoparticles into polymeric fibers/nanofibers for fabrication of functionally graded non-woven meshes to be used as scaffolds in engineering of tissues. The capabilities of the hybrid technology were demonstrated with a series of scaffold fabrication and cell culturing studies along with characterization of biomechanical properties. In the first study, the hybrid technology was employed to generate concentration gradations of beta-tricalcium phosphate (beta-TCP) nanoparticles in a polycaprolactone (PCL) binder, between two surfaces of nanofibrous scaffolds. These scaffolds were seeded with pre-osteoblastic cell line (MC3T3-E1) to attempt to engineer cartilage-bone interface, and after four weeks, the tissue constructs revealed formation of continuous gradations in extracellular matrix akin to cartilage-bone interface in terms of distributions of mineral concentrations and biomechanical properties. In a second demonstration of the hybrid technology, graded differentiation of stem cells was attempted by using insulin, a known stimulator of chondrogenic differentiation, and beta-glycerol phosphate (beta-GP), for mineralization. Concentrations of insulin and beta-GP in PCL were controlled to monotonically increase and decrease, respectively, along the length of scaffolds, which were then seeded

  2. A hybrid grid method in an auxiliary coordinate system for irregular fluid-solid interface modelling

    Science.gov (United States)

    Qu, Yingming; Huang, Jianping; Li, Zhenchun; Li, Jinli

    2017-03-01

    Seismic wave propagation in a fluid-solid environment cannot be simulated with a single wave equation, but can be described by use of the acoustic and viscoelastic wave equations for their respective fluid and solid parts. Proper boundary conditions at the fluid-solid interface based on the relationship between pressure and stress are crucial when combining the two different wave equations. Traditional finite difference methods have had difficulties in dealing with the irregular fluid-solid interface topography. The Cartesian grids discretization leads to artificial reflections and diffractions during the conversion between acoustic wave and elastic waves. We propose a variable coordinate transformation methodology to simulate seismic waves in a fluid-solid environment. An irregular fluid-solid interface can be transformed into a horizontal interface, so that pressure and stress can be well converted. We also introduce a multiblock coordinate transformation (MCT) method which meshes each layer with curvilinear grids to transform the interface topography into a horizontal one, thereby allocating vertical sampling points adaptively. The grid size is determined adaptively based on the shape and the parameters of the target area, which reduces in size in when the layers are thin or exhibit low velocities. A Lebedev-standard staggered grid scheme is applied to the MCT method to reduce both the computational cost associated with the Lebedev grid scheme and the instability in the auxiliary coordinate system when using a standard staggered grid scheme.

  3. Helical nanostructure of tubular metal-organic complex synthesized by sonochemical process

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Tubular metal-organic complex (C2H9N2)2(C2H10N2)0.5[MoO2(OC6H4O)2] has been synthesized. The title complex crystallizes in the tetragonal system, space group P4(2)/n with a = 25.214(8), c = 7.484(4) ?, and Z = 8. The X-ray structural analysis of the complex reveals tube-like framework which is stabilized by hydrogen bond. Chiral anions [Mo(V)O2(OC6H4O)2]3? of the complex have two types of isomers(λ /δ configuration). Helical nanostructure of this metal-organic complex was formed using a sonochemical method. Sonocation may lead to the transformation from the bulk tubular complex to the helical nanostructure. The as-synthesized nanohelices were all double-stranded and left- and right-handed nanohelices were both formed. The helical nanostructure is a new morphology of inorganic-organic hybrid materials on the nanoscale level and the exact formation mechanism of these helices still needs further investigation.

  4. Effects of ultrasound on properties of ni-metal organic framework nanostructures

    Directory of Open Access Journals (Sweden)

    Abbas Pardakhty

    2016-10-01

    Full Text Available Objective(s: According to the unique properties of magnetic nanoparticles, Nickel Metal-Organic Frameworks (MOF was synthesized successfully by ultrasound irradiation. Metal-organic frameworks (MOFs are organic–inorganic hybrid extended networks that are constructed via covalent linkages between metal ions/metal clusters and organic ligands called a linker. Materials and Methods: The nanoparticles were synthesized by Ultrasound  Method Under a synthesis conditions, All chemicals were used as received without further purification. Scanning electron microscopy (SEM images were obtained on LEO- 1455VP equipped with an energy dispersive X-ray spectroscopy at university of Kashan in Iran. Transition electron microscopy (TEM images were obtained on EM208 Philips transmission electron microscope with an accelerating voltage of 200 kV. Results: Results showed that Ni-MOF synthesized by this method, had smaller particle size distribution and It was found that the different kinds of ligand leads to preparation products with different morphologies and textural properties. Moreover, ultrasound irradiation method has significant effect on microstructures of as-synthesized MOFs and can improve their textural properties compared to method without using hydrothermal route.The XRD patterns of the samples obtained from ultrasound irradiation was well matched with that of as-prepared Ni-MOF by solvothermal method. Conclusion: This rapid method of ultrasonic radiation as compared to the classical solvothermal synthesis, showed promising results in terms of size distribution, surface area, pore diameter and pore volume.

  5. A series of isoreticular chiral metal-organic frameworks as a tunable platform for asymmetric catalysis.

    Science.gov (United States)

    Ma, Liqing; Falkowski, Joseph M; Abney, Carter; Lin, Wenbin

    2010-10-01

    Metal-organic frameworks, built by bridging metal ions with organic linkers, represent a new class of porous hybrid materials with attractive tunability in compositions, structures and functions. In particular, the mild conditions typically employed for their synthesis allow for the functionalization of their building blocks, and thus the rational design of novel materials. Here we demonstrate the systematic design of eight mesoporous chiral metal-organic frameworks, with the framework formula [LCu2(solvent)2] (where L is a chiral tetracarboxylate ligand derived from 1,1'-bi-2-naphthol), that have the same structures but channels of different sizes. Chiral Lewis acid catalysts were generated by postsynthesis functionalization with Ti(OiPr)4, and the resulting materials proved to be highly active asymmetric catalysts for diethylzinc and alkynylzinc additions, which converted aromatic aldehydes into chiral secondary alcohols. The enantioselectivities of these reactions can be modified by tuning the size of the channels, which alters the diffusion rates of the organic substrates.

  6. Homochiral metal-organic frameworks and their application in chromatography enantioseparations.

    Science.gov (United States)

    Peluso, Paola; Mamane, Victor; Cossu, Sergio

    2014-10-10

    The last frontier in the chiral stationary phases (CSPs) field for chromatography enantioseparations is represented by homochiral metal-organic frameworks (MOFs), a class of organic-inorganic hybrid materials built from metal-connecting nodes and organic-bridging ligands. The modular nature of these materials allows to design focused structures by combining properly metal, organic ligands and rigid polytopic spacers. Intriguingly, chiral ligands introduce molecular chirality in the MOF-network as well as homochirality in the secondary structure of materials (such as homohelicity) producing homochiral nets in a manner mimicking biopolymers (proteins, polysaccharides) which are characterized by a definite helical sense associated with the chirality of their building blocks (amino acids or sugars). Nowadays, robust and flexible materials characterized by high porosity and surface area became available by using preparative procedures typical of the so-called reticular synthesis. This review focuses on recent developments in the synthesis and applications of homochiral MOFs as supports for chromatography enantioseparations. Indeed, despite this field is in its infancy, interesting results have been produced and a critical overview of the 12 reported applications for gas chromatography (GC) and high-performance liquid chromatography (HPLC) can orient the reader approaching the field. Mechanistic aspects are shortly discussed and a view regarding future trends in this field is provided.

  7. A low-cost EEG system-based hybrid brain-computer interface for humanoid robot navigation and recognition.

    Science.gov (United States)

    Choi, Bongjae; Jo, Sungho

    2013-01-01

    This paper describes a hybrid brain-computer interface (BCI) technique that combines the P300 potential, the steady state visually evoked potential (SSVEP), and event related de-synchronization (ERD) to solve a complicated multi-task problem consisting of humanoid robot navigation and control along with object recognition using a low-cost BCI system. Our approach enables subjects to control the navigation and exploration of a humanoid robot and recognize a desired object among candidates. This study aims to demonstrate the possibility of a hybrid BCI based on a low-cost system for a realistic and complex task. It also shows that the use of a simple image processing technique, combined with BCI, can further aid in making these complex tasks simpler. An experimental scenario is proposed in which a subject remotely controls a humanoid robot in a properly sized maze. The subject sees what the surrogate robot sees through visual feedback and can navigate the surrogate robot. While navigating, the robot encounters objects located in the maze. It then recognizes if the encountered object is of interest to the subject. The subject communicates with the robot through SSVEP and ERD-based BCIs to navigate and explore with the robot, and P300-based BCI to allow the surrogate robot recognize their favorites. Using several evaluation metrics, the performances of five subjects navigating the robot were quite comparable to manual keyboard control. During object recognition mode, favorite objects were successfully selected from two to four choices. Subjects conducted humanoid navigation and recognition tasks as if they embodied the robot. Analysis of the data supports the potential usefulness of the proposed hybrid BCI system for extended applications. This work presents an important implication for the future work that a hybridization of simple BCI protocols provide extended controllability to carry out complicated tasks even with a low-cost system.

  8. An Ising model for metal-organic frameworks

    Science.gov (United States)

    Höft, Nicolas; Horbach, Jürgen; Martín-Mayor, Victor; Seoane, Beatriz

    2017-08-01

    We present a three-dimensional Ising model where lines of equal spins are frozen such that they form an ordered framework structure. The frame spins impose an external field on the rest of the spins (active spins). We demonstrate that this "porous Ising model" can be seen as a minimal model for condensation transitions of gas molecules in metal-organic frameworks. Using Monte Carlo simulation techniques, we compare the phase behavior of a porous Ising model with that of a particle-based model for the condensation of methane (CH4) in the isoreticular metal-organic framework IRMOF-16. For both models, we find a line of first-order phase transitions that end in a critical point. We show that the critical behavior in both cases belongs to the 3D Ising universality class, in contrast to other phase transitions in confinement such as capillary condensation.

  9. Applications of metal-organic frameworks in heterogeneous supramolecular catalysis.

    Science.gov (United States)

    Liu, Jiewei; Chen, Lianfen; Cui, Hao; Zhang, Jianyong; Zhang, Li; Su, Cheng-Yong

    2014-08-21

    This review summarizes the use of metal-organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal-organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.

  10. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids

    Science.gov (United States)

    Nandasiri, Manjula I.; Liu, Jian; McGrail, B. Peter; Jenks, Jeromy; Schaef, Herbert T.; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F.; Nune, Satish K.

    2016-06-01

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model.

  11. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids.

    Science.gov (United States)

    Nandasiri, Manjula I; Liu, Jian; McGrail, B Peter; Jenks, Jeromy; Schaef, Herbert T; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F; Nune, Satish K

    2016-06-15

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model.

  12. Metallacarboranes: Towards promising hydrogen storage metal organic framework

    Science.gov (United States)

    Singh, Abhishek; Sadrzadeh, Arta; Yakobson, Boris

    2011-03-01

    Using first principles calculations we show the high hydrogen storage capacity of metallacarboranes, where the transition metal (TM) atoms bind hydrogen via Kubas interaction. The average binding energy of ~ 0.3 eV/H favorably lies within the reversible adsorption range The Sc and Ti are found to be the optimum metal atoms maximizing the number of stored H2 molecules. Depending upon the structure, metallacarboranes can adsorb up to 8 wt% of hydrogen, which exceeds DOE goal for 2015. Being integral part of the cage, TMs do not suffer from the aggregation problem. Furthermore, the presence of carbon atom in the cages permits linking the metallacarboranes to form metal organic frameworks (MOF), thus able to adsorb hydrogen via Kubas interaction, in addition to van der Waals physisorption. A. K. Singh, A. Sadrzadeh, and B. I. Yakobson, Metallacarboranes: Toward Promising Hydrogen Storage Metal Organic Frameworks, JACS 132,14126 (2010).

  13. Hydrogen Storage in Microporous Metal-Organic Frameworks

    Science.gov (United States)

    Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed; Vodak, David T.; Kim, Jaheon; O'Keeffe, Michael; Yaghi, Omar M.

    2003-05-01

    Metal-organic framework-5 (MOF-5) of composition Zn4O(BDC)3 (BDC = 1,4-benzenedicarboxylate) with a cubic three-dimensional extended porous structure adsorbed hydrogen up to 4.5 weight percent (17.2 hydrogen molecules per formula unit) at 78 kelvin and 1.0 weight percent at room temperature and pressure of 20 bar. Inelastic neutron scattering spectroscopy of the rotational transitions of the adsorbed hydrogen molecules indicates the presence of two well-defined binding sites (termed I and II), which we associate with hydrogen binding to zinc and the BDC linker, respectively. Preliminary studies on topologically similar isoreticular metal-organic framework-6 and -8 (IRMOF-6 and -8) having cyclobutylbenzene and naphthalene linkers, respectively, gave approximately double and quadruple (2.0 weight percent) the uptake found for MOF-5 at room temperature and 10 bar.

  14. Hydrogen storage in Li-doped metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Himsl, D.; Hartmann, M. [Erlangen-Nuernberg Univ., Erlangen (Germany). Erlangen Catalysis Resource Center

    2010-12-30

    Porous Metal-Organic Frameworks have been considered as potential materials for solid state hydrogen storage in recent times. In this context their properties like high permanent porosity, large surface area and the ease of chemical modification due their modular assembly are highly attractive. Unfortunately these materials suffer from low physisorption interaction energies with hydrogen and consequently the need for low adsorption temperatures (77 K) to achieve sufficient hydrogen loadings. One possible approach to overcome the outlined problem is the introduction of unsaturated metal sites within the interior MOF surface to strengthen the adsorbate-adsorbent interaction. We established the functionalization with lithiumalkoxide groups via a post-synthetic transformation of pendant hydroxyl groups with a suitable lithium base. Our results show a significant increase of the isosteric heat of adsorption for hydrogen within the lithium-containing material, thus showing that our approach is a promising strategy to make hydrogen storage in Metal-Organic Frameworks more efficient. (orig.)

  15. Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

    Science.gov (United States)

    Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

    2013-04-10

    Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

  16. A multistimuli-responsive photochromic metal-organic gel.

    Science.gov (United States)

    Wei, Shi-Chao; Pan, Mei; Li, Kang; Wang, Sujuan; Zhang, Jianyong; Su, Cheng-Yong

    2014-04-02

    A photochromic metal-organic gel with thermo-, photo-, and anion-responsive behavior is obtained. Unusually, heating of the Al-ligand solution leads to gel formation and cooling to room temperature reverses the process to reform the solution. The gel is sensitive to weakly coordinating anions. Additionally, reversible photochromic transformations take place both in the solution and gel states, accompanied by reversibly switched luminescence.

  17. Metal-Organic Frameworks for Thin-Layer Chromatographic Applications.

    Science.gov (United States)

    Schenk, Claudia; Kutzscher, Christel; Drache, Franziska; Helten, Stella; Senkovska, Irena; Kaskel, Stefan

    2017-01-25

    Preparation of thin-layer chromatographic (TLC) plates based on metal-organic frameworks (MOFs) as porous stationary phases is described. DUT-67 (DUT = Dresden University of Technology), a zirconium based MOF, was used in combination with a fluorescent indicator as stationary phase for analyzing a small selection of a wide spectrum of relevant analytes. The successful separation of benzaldehyde from trans-cinnamaldehyde and 4-aminophenol from 2-aminotoluene is reported as a model system using optimized eluent mixtures containing acetic acid.

  18. Molecularly Imprinted Polymer/Metal Organic Framework Based Chemical Sensors

    Directory of Open Access Journals (Sweden)

    Zhenzhong Guo

    2016-10-01

    Full Text Available The present review describes recent advances in the concept of molecular imprinting using metal organic frameworks (MOF for development of chemical sensors. Two main strategies regarding the fabrication, performance and applications of recent sensors based on molecularly imprinted polymers associated with MOF are presented: molecularly imprinted MOF films and molecularly imprinted core-shell nanoparticles using MOF as core. The associated transduction modes are also discussed. A brief conclusion and future expectations are described herein.

  19. Molecularly Imprinted Polymer/Metal Organic Framework Based Chemical Sensors

    OpenAIRE

    Zhenzhong Guo; Anca Florea; Mengjuan Jiang; Yong Mei; Weiying Zhang; Aidong Zhang; Robert Săndulescu; Nicole Jaffrezic-Renault

    2016-01-01

    The present review describes recent advances in the concept of molecular imprinting using metal organic frameworks (MOF) for development of chemical sensors. Two main strategies regarding the fabrication, performance and applications of recent sensors based on molecularly imprinted polymers associated with MOF are presented: molecularly imprinted MOF films and molecularly imprinted core-shell nanoparticles using MOF as core. The associated transduction modes are also discussed. A brief conclu...

  20. Cadmium and Zinc Thiolate and Selenolate Metal-Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Turner, D.; Stone, K; Stephens, P; Vaid, T

    2010-01-01

    Metal-organic frameworks based on metal-sulfur or metal-selenium bonds are relatively rare; herein we describe the synthesis and structural characterization of several examples, including, for example, [Cd(en){sub 3}][Cd(SC{sub 6}H{sub 4}S){sub 2}], which contains the anionic two-dimensional square-grid network [Cd(SC{sub 6}H{sub 4}S){sub 2}]{sub n}{sup 2n-}.

  1. Cadmium and zinc thiolate and selenolate metal-organic frameworks.

    Science.gov (United States)

    Turner, Dayna L; Stone, Kevin H; Stephens, Peter W; Vaid, Thomas P

    2010-06-07

    Metal-organic frameworks based on metal-sulfur or metal-selenium bonds are relatively rare; herein we describe the synthesis and structural characterization of several examples, including, for example, [Cd(en)3][Cd(SC6H4S)2], which contains the anionic two-dimensional square-grid network [Cd(SC6H4S)2]n(2n-).

  2. Nano-architecture of metal-organic frameworks

    Science.gov (United States)

    Milichko, Valentin A.; Zalogina, Anastasiia; Mingabudinova, Leila R.; Vinogradov, Alexander V.; Ubyivovk, Evgeniy; Krasilin, Andrei A.; Mukhin, Ivan; Zuev, Dmitry A.; Makarov, Sergey V.; Pidko, Evgeny A.

    2017-09-01

    Change the shape and size of materials supports new functionalities never found in the sources. This strategy has been recently applied for porous crystalline materials - metal-organic frameworks (MOFs) to create hollow nanoscale structures or mesostructures with improved functional properties. However, such structures are characterized by amorphous state or polycrystallinity which limits their applicability. Here we follow this strategy to create such nano- and mesostructures with perfect crystallinity and new photonics functionalities by laser or focused ion beam fabrication.

  3. Liquid Metal-Organic Frameworks: Formation Mechanism, Structure and Properties

    OpenAIRE

    Gaillac, Romain; Pullumbi, Pluton; Beyer, Kevin A.; Chapman, Karena W.; Keen, David A.; Bennett, Thomas D.; Coudert, François-Xavier

    2017-01-01

    Metal--organic frameworks are a novel family of chemically diverse materials, with applications in a wide field covering engineering, physics, chemistry, biology and medicine. Research so far has focused almost entirely on crystalline structures, yet a clear trend has emerged shifting the emphasis onto disordered states of MOFs, including "defective by design" crystals, as well as amorphous phases such as glasses and gels. Here we introduce a MOF liquid, a strongly associated liquid obtained ...

  4. Metal organic framework MIL-101 for radioiodine capture and storage

    Science.gov (United States)

    Assaad, Thaer; Assfour, Bassem

    2017-09-01

    we report on the use of metal organic frameworks(MOFs) for radioiodine recovery and storage. One MOF (namely MIL-101) was prepared and investigated in detail to demonstrate the iodine removal efficiency and capacity of MOFs. The typical sorption kinetics and uptake isotherms were measured using radioactive iodine (123 I) for the first time. Our measurements indicate that MOFs can capture and store radioiodine in very high efficiency and fast kinetics.

  5. Perspective: Metal-organic frameworks—Opportunities and challenges

    OpenAIRE

    Rosseinsky, M.J.

    2014-01-01

    The interplay of metal-ligand coordination chemistry with the diverse organic chemistry of the molecular linkers in metal-organic frameworks offers exciting new directions not only in the important area of porous materials, but more generally as a route to control of function by the integration of organic and inorganic components. This makes the current APL Materials issue particularly timely. This Perspective summarises some important aspects of the current state of play.

  6. Perspective: Metal-organic frameworks—Opportunities and challenges

    Directory of Open Access Journals (Sweden)

    M. J. Rosseinsky

    2014-12-01

    Full Text Available The interplay of metal-ligand coordination chemistry with the diverse organic chemistry of the molecular linkers in metal-organic frameworks offers exciting new directions not only in the important area of porous materials, but more generally as a route to control of function by the integration of organic and inorganic components. This makes the current APL Materials issue particularly timely. This Perspective summarises some important aspects of the current state of play.

  7. Evolution of form in metal-organic frameworks

    Science.gov (United States)

    Lee, Jiyoung; Kwak, Ja Hun; Choe, Wonyoung

    2017-01-01

    Self-assembly has proven to be a widely successful synthetic strategy for functional materials, especially for metal-organic materials (MOMs), an emerging class of porous materials consisting of metal-organic frameworks (MOFs) and metal-organic polyhedra (MOPs). However, there are areas in MOM synthesis in which such self-assembly has not been fully utilized, such as controlling the interior of MOM crystals. Here we demonstrate sequential self-assembly strategy for synthesizing various forms of MOM crystals, including double-shell hollow MOMs, based on single-crystal to single-crystal transformation from MOP to MOF. Moreover, this synthetic strategy also yields other forms, such as solid, core-shell, double and triple matryoshka, and single-shell hollow MOMs, thereby exhibiting form evolution in MOMs. We anticipate that this synthetic approach might open up a new direction for the development of diverse forms in MOMs, with highly advanced areas such as sequential drug delivery/release and heterogeneous cascade catalysis targeted in the foreseeable future.

  8. Refined Sulfur Nanoparticles Immobilized in Metal-Organic Polyhedron as Stable Cathodes for Li-S Battery.

    Science.gov (United States)

    Bai, Linyi; Chao, Dongliang; Xing, Pengyao; Tou, Li Juan; Chen, Zhen; Jana, Avijit; Shen, Ze Xiang; Zhao, Yanli

    2016-06-15

    The lithium-sulfur (Li-S) battery presents a promising rechargeable energy storage technology for the increasing energy demand in a worldwide range. However, current main challenges in Li-S battery are structural degradation and instability of the solid-electrolyte interphase caused by the dissolution of polysulfides during cycling, resulting in the corrosion and loss of active materials. Herein, we developed novel hybrids by employing metal-organic polyhedron (MOP) encapsulated PVP-functionalized sulfur nanoparticles (S@MOP), where the active sulfur component was efficiently encapsulated within the core of MOP and PVP as a surfactant was helpful to stabilize the sulfur nanoparticles and control the size and shape of corresponding hybrids during their syntheses. The amount of sulfur embedded into MOP could be controlled according to requirements. By using the S@MOP hybrids as cathodes, an obvious enhancement in the performance of Li-S battery was achieved, including high specific capacity with good cycling stability. The MOP encapsulation could enhance the utilization efficiency of sulfur. Importantly, the structure of the S@MOP hybrids was very stable, and they could last for almost 1000 cycles as cathodes in Li-S battery. Such high performance has rarely been obtained using metal-organic framework systems. The present approach opens up a promising route for further applications of MOP as host materials in electrochemical and energy storage fields.

  9. Nanoarchitectured Design of Porous Materials and Nanocomposites from Metal-Organic Frameworks.

    Science.gov (United States)

    Kaneti, Yusuf Valentino; Tang, Jing; Salunkhe, Rahul R; Jiang, Xuchuan; Yu, Aibing; Wu, Kevin C-W; Yamauchi, Yusuke

    2017-03-01

    The emergence of metal-organic frameworks (MOFs) as a new class of crystalline porous materials is attracting considerable attention in many fields such as catalysis, energy storage and conversion, sensors, and environmental remediation due to their controllable composition, structure and pore size. MOFs are versatile precursors for the preparation of various forms of nanomaterials as well as new multifunctional nanocomposites/hybrids, which exhibit superior functional properties compared to the individual components assembling the composites. This review provides an overview of recent developments achieved in the fabrication of porous MOF-derived nanostructures including carbons, metal oxides, metal chalcogenides (metal sulfides and selenides), metal carbides, metal phosphides and their composites. Finally, the challenges and future trends and prospects associated with the development of MOF-derived nanomaterials are also examined. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Stimuli-Responsive Metal-Organic Frameworks with Photoswitchable Azobenzene Side Groups.

    Science.gov (United States)

    Kanj, Anemar Bruno; Müller, Kai; Heinke, Lars

    2017-07-31

    Metal-organic frameworks (MOFs) are nanoporous, crystalline hybrid materials, which enable various functionalities by incorporating functional organic molecules. By using organic linker molecules that possess photoswitchable azobenzene side groups, the remote control over certain properties was introduced to MOFs. Different MOF materials in the form of powders and thin films have been used to demonstrate the photoswitching. The applications of these stimuli-responsive nanoporous solids range from switching the adsorption capacity of various gases over remote-controlled release of guest molecules to continuously tunable membrane separation of molecular mixtures. A particular focus of this review is the effect of the azobenzene photoswitching on the host-guest interaction, enabling smart applications of the material. Steric hindrance, which may suppress the photoswitching in some MOF structures, is also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Separation of C2 Hydrocarbons by Porous Materials: Metal Organic Frameworks as Platform

    Energy Technology Data Exchange (ETDEWEB)

    Banerjee, Debasis; Liu, Jun; Thallapally, Praveen K.

    2014-12-22

    The effective separation of small hydrocarbon molecules (C1 – C4) is an important process for petroleum industry, determining the end price of many essential commodities in our daily lives. Current technologies for separation of these molecules rely on energy intensive fractional distillation processes at cryogenic temperature, which is particularly difficult because of their similar volatility. In retrospect, adsorptive separation using solid state adsorbents might be a cost effective alternative. Several types of solid state adsorbents (e.g. zeolite molecular sieves) were tested for separation of small hydrocarbon molecules as a function of pressure, temperature or vacuum. Among different types of plausible adsorbents, metal organic frameworks (MOFs), a class of porous, crystalline, inorganic-organic hybrid materials, is particularly promising. In this brief comment article, we discuss the separation properties of different types of solid state adsorbents, with a particular emphasis on MOF based adsorbents for separation of C2 hydrocarbon molecules.

  12. Efficient photocatalytic degradation of rhodamine 6G with a quantum dot-metal organic framework nanocomposite.

    Science.gov (United States)

    Kaur, Rajnish; Vellingiri, Kowsalya; Kim, Ki-Hyun; Paul, A K; Deep, Akash

    2016-07-01

    The hybrid structures of metal organic frameworks (MOFs) and nanoparticles may offer the realization of effective photocatalytic materials due to combined benefits of the porous and molecular sieving properties of MOF matrix and the functional characteristics of encapsulated nanoparticles. In this study, cadmium telluride (CdTe) quantum dots (QD) are conjugated with a europium-MOF for the synthesis of a novel nanocomposite material with photocatalytic properties. Successful synthesis of a QD/Eu-MOF nanocomposite was characterized with various spectroscopic and microscopic techniques. This QD/Eu-MOF is found to be an effective catalyst to complete the degradation of Rhodamine 6G dye within 50 min. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Metal-organic frameworks for electronics: emerging second order nonlinear optical and dielectric materials.

    Science.gov (United States)

    Mendiratta, Shruti; Lee, Cheng-Hua; Usman, Muhammad; Lu, Kuang-Lieh

    2015-10-01

    Metal-organic frameworks (MOFs) have been intensively studied over the past decade because they represent a new category of hybrid inorganic-organic materials with extensive surface areas, ultrahigh porosity, along with the extraordinary tailorability of structure, shape and dimensions. In this highlight, we summarize the current state of MOF research and report on structure-property relationships for nonlinear optical (NLO) and dielectric applications. We focus on the design principles and structural elements needed to develop potential NLO and low dielectric (low-κ) MOFs with an emphasis on enhancing material performance. In addition, we highlight experimental evidence for the design of devices for low-dielectric applications. These results motivate us to develop better low-dielectric and NLO materials and to perform in-depth studies related to deposition techniques, patterning and the mechanical performance of these materials in the future.

  14. Rear interface engineering of hybrid organic-silicon nanowire solar cells via blade coating.

    Science.gov (United States)

    Lai, Yi-Chun; Chang, Yu-Fan; Tsai, Pei-Ting; Chang, Jan-kai; Tseng, Wei-Hsuan; Lin, Yi-Cheng; Hsiao, Chu-Yen; Zan, Hsiao-Wen; Wu, Chih-I; Chi, Gou-Chung; Meng, Hsin-Fei; Yu, Peichen

    2016-01-25

    In this work, we investigate blade-coated organic interlayers at the rear surface of hybrid organic-silicon photovoltaics based on two small molecules: Tris(8-hydroxyquinolinato) aluminium (Alq(3)) and 1,3-bis(2-(4-tert-butylphenyl)-1,3,4-oxadiazol-5-yl) benzene (OXD-7). In particular, soluble Alq(3) resulting in a uniform thin film with a root-mean-square roughness organic-silicon photovoltaics.

  15. Optical determination of Shockley-Read-Hall and interface recombination currents in hybrid perovskites

    Science.gov (United States)

    Sarritzu, Valerio; Sestu, Nicola; Marongiu, Daniela; Chang, Xueqing; Masi, Sofia; Rizzo, Aurora; Colella, Silvia; Quochi, Francesco; Saba, Michele; Mura, Andrea; Bongiovanni, Giovanni

    2017-03-01

    Metal-halide perovskite solar cells rival the best inorganic solar cells in power conversion efficiency, providing the outlook for efficient, cheap devices. In order for the technology to mature and approach the ideal Shockley-Queissier efficiency, experimental tools are needed to diagnose what processes limit performances, beyond simply measuring electrical characteristics often affected by parasitic effects and difficult to interpret. Here we study the microscopic origin of recombination currents causing photoconversion losses with an all-optical technique, measuring the electron-hole free energy as a function of the exciting light intensity. Our method allows assessing the ideality factor and breaks down the electron-hole recombination current into bulk defect and interface contributions, providing an estimate of the limit photoconversion efficiency, without any real charge current flowing through the device. We identify Shockley-Read-Hall recombination as the main decay process in insulated perovskite layers and quantify the additional performance degradation due to interface recombination in heterojunctions.

  16. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  17. Driving electrocatalytic activity by interface electronic structure control in a metalloprotein hybrid catalyst for efficient hydrogen evolution.

    Science.gov (United States)

    Behera, Sushant Kumar; Deb, Pritam; Ghosh, Arghya

    2016-08-17

    The rational design of metalloprotein hybrid structures and precise calculations for understanding the role of the interfacial electronic structure in regulating the HER activity of water splitting sites and their microscopic effect for obtaining robust hydrogen evolution possess great promise for developing highly efficient nano-bio hybrid HER catalysts. Here, we employ high-accuracy linear-scaling density functional theory calculations using a near-complete basis set and a minimal parameter implicit solvent model within the self-consistent calculations, on silver (Ag) ions assimilated on bacteriorhodopsin (bR) at specific binding sites. Geometry optimization indicates the formation of active sites at the interface of the metalloprotein complex and the density of states reflects the metallic nature of the active sites. The reduced value of the canonical orbital gap indicates the state of dynamic nature after Ag ion assimilation on active sites and smooth electron transfer. These incorporated active protein sites are more efficient in electrolytic splitting of water than pristine sites due to their low value of Gibbs free energy for the HER in terms of hydrogen coverages. Volcano plot analysis and the free energy diagram are compared for understanding the hydrogen evolution efficiency. Moreover, the essential role of the interfacial electronic properties in regulating the HER catalytic activity of water splitting sites and enhancing the efficiency is elucidated.

  18. Hybrid brain-computer interface for biomedical cyber-physical system application using wireless embedded EEG systems.

    Science.gov (United States)

    Chai, Rifai; Naik, Ganesh R; Ling, Sai Ho; Nguyen, Hung T

    2017-01-07

    One of the key challenges of the biomedical cyber-physical system is to combine cognitive neuroscience with the integration of physical systems to assist people with disabilities. Electroencephalography (EEG) has been explored as a non-invasive method of providing assistive technology by using brain electrical signals. This paper presents a unique prototype of a hybrid brain computer interface (BCI) which senses a combination classification of mental task, steady state visual evoked potential (SSVEP) and eyes closed detection using only two EEG channels. In addition, a microcontroller based head-mounted battery-operated wireless EEG sensor combined with a separate embedded system is used to enhance portability, convenience and cost effectiveness. This experiment has been conducted with five healthy participants and five patients with tetraplegia. Generally, the results show comparable classification accuracies between healthy subjects and tetraplegia patients. For the offline artificial neural network classification for the target group of patients with tetraplegia, the hybrid BCI system combines three mental tasks, three SSVEP frequencies and eyes closed, with average classification accuracy at 74% and average information transfer rate (ITR) of the system of 27 bits/min. For the real-time testing of the intentional signal on patients with tetraplegia, the average success rate of detection is 70% and the speed of detection varies from 2 to 4 s.

  19. Interface design recommendations for computerised clinical audit and feedback: Hybrid usability evidence from a research-led system.

    Science.gov (United States)

    Brown, Benjamin; Balatsoukas, Panos; Williams, Richard; Sperrin, Matthew; Buchan, Iain

    2016-10-01

    Audit and Feedback (A&F) is a widely used quality improvement technique that measures clinicians' clinical performance and reports it back to them. Computerised A&F (e-A&F) system interfaces may consist of four key components: (1) Summaries of clinical performance; (2) Patient lists; (3) Patient-level data; (4) Recommended actions. There is a lack of evidence regarding how to best design e-A&F interfaces; establishing such evidence is key to maximising usability, and in turn improving patient safety. To evaluate the usability of a novel theoretically-informed and research-led e-A&F system for primary care (the Performance Improvement plaN GeneratoR: PINGR). (1) Describe PINGR's design, rationale and theoretical basis; (2) Identify usability issues with PINGR; (3) Understand how these issues may interfere with the cognitive goals of end-users; (4) Translate the issues into recommendations for the user-centred design of e-A&F systems. Eight experienced health system evaluators performed a usability inspection using an innovative hybrid approach consisting of five stages: (1) Development of representative user tasks, Goals, and Actions; (2) Combining Heuristic Evaluation and Cognitive Walkthrough methods into a single protocol to identify usability issues; (3) Consolidation of issues; (4) Severity rating of consolidated issues; (5) Analysis of issues according to usability heuristics, interface components, and Goal-Action structure. A final list of 47 issues were categorised into 8 heuristic themes. The most error-prone heuristics were 'Consistency and standards' (13 usability issues; 28% of the total) and 'Match between system and real world' (n=10, 21%). The recommended actions component of the PINGR interface had the most usability issues (n=21, 45%), followed by patient-level data (n=5, 11%), patient lists (n=4, 9%), and summaries of clinical performance (n=4, 9%). The most error-prone Actions across all user Goals were: (1) Patient selection from a list; (2) Data

  20. Towards Organized Hybrid Nanomaterials at the Air/Water Interface Based on Liquid-Crystal/ZnO Nanocrystals.

    Science.gov (United States)

    Paczesny, Jan; Wolska-Pietkiewicz, Małgorzata; Binkiewicz, Ilona; Wróbel, Zbigniew; Wadowska, Monika; Matuła, Kinga; Dzięcielewski, Igor; Pociecha, Damian; Smalc-Koziorowska, Julita; Lewiński, Janusz; Hołyst, Robert

    2015-11-16

    The ability to self-assemble nanosized ligand-stabilized metal oxide or semiconductor materials offers an intriguing route to engineer nanomaterials with new tailored properties from the disparate components. We describe a novel one-pot two-step organometallic approach to prepare ZnO nanocrystals (NCs) coated with deprotonated 4-(dodecyloxy)benzoic acid (i.e., an X-type liquid-crystalline ligand) as a model LC system (termed ZnO-LC1 NCs). Langmuir and Langmuir-Blodgett films of the resulting hybrids are investigated. The observed behavior of the ZnO NCs at the air/water interface is rationalized by invoking a ZnO-interdigitation process mediated by the anchored liquid-crystalline shell. The ordered superstructures form according to mechanism based on a ZnO-interdigitation process mediated by liquid crystals (termed ZIP-LC). The external and directed force applied upon compression at the air/water interface and the packing of the ligands that stabilize the ZnO cores drives the formation of nanorods of ordered internal structure. To study the process in detail, we follow a nontraditional protocol of thin-film investigation. We collect the films from the air/water interface in powder form (ZnO-LC1 LB), resuspend the powder in organic solvents and utilize otherwise unavailable experimental techniques. The structural and physical properties of the resulting superlattices were studied by using electron microscopy, atomic force microscopy, X-ray studies, dynamic light scattering, thermogravimetric analysis, UV/Vis absorption, and photoluminescence spectroscopy.

  1. Interplay of Nanoscale, Hybrid P3HT/ZTO Interface on Optoelectronics and Photovoltaic Cells.

    Science.gov (United States)

    Lai, Jian-Jhong; Li, Yu-Hsun; Feng, Bo-Rui; Tang, Shiow-Jing; Jian, Wen-Bin; Fu, Chuan-Min; Chen, Jiun-Tai; Wang, Xu; Lee, Pooi-See

    2017-09-05

    Photovoltaic effects in poly(3-hexylthiophene-2,5-diyl) (P3HT) attract much attention recently. Here natively p-type doped P3HT nanofibers and n-type doped zinc tin oxide (ZTO) nanowires are used for making not only field-effect transistors but also p-n nanoscale diodes. The hybrid P3HT/ZTO p-n heterojunction shows applications in many directions and it also facilitates the investigation of photoelectrons and photovoltaic effects at the nanoscale. As for applications, the heterojunction device shows simultaneously high on/off ratio of n- and p-type field-effect transistors, gatable p-n junction diodes, tri-state buffer device, gatable photodetectors, and gatable solar cells. On the other hand, P3HT nanofibers are taken as a photoactive layer and the role of p-n heterojunction playing on the photoelectric and photovoltaic effects is investigated. It is found that the hybrid P3HT/ZTO p-n heterojunction assists to increase photocurrents and to enhance photovoltaic effects. Through the controllable gating of the heterojunction, we can discuss the background mechanisms of photocurrent generation and photovoltaic energy harvest.

  2. Hybrid Spaces in Art and Science Fiction from cyberspace to mobile interfaces

    Directory of Open Access Journals (Sweden)

    Adriana de Souza e Silva

    2003-01-01

    Full Text Available The concept of real changes due to the emergence of ubiquitous computing and nomadic technology devices, which are responsible for creating a hybrid reality that merges physical and digital spaces, and creating a new articulation between real and imaginary. This paper addresses the evolution of virtual space from the perspective of arts and science fiction. The first section shows how the concept of virtual space as a mindspace has been developed. Also it presents how computers as simulation machines have played an important role in the construcion of digital space. Second, the paper argues that the concept of virtual space is changing, since it can no longer be considered disjoint from physical space. Finally, the movies The Thirteenth Floor (Rusnak, 1999 and The Matrix (Wachowski, 1999 are case studies that illustrate how the idea of inhabiting a virtual space changes to a hybrid space that is part of our lives. As a result, it amplifies the notion of what the real can be.

  3. Hybrid brain-computer interfaces and hybrid neuroprostheses for restoration of upper limb functions in individuals with high-level spinal cord injury.

    Science.gov (United States)

    Rohm, Martin; Schneiders, Matthias; Müller, Constantin; Kreilinger, Alex; Kaiser, Vera; Müller-Putz, Gernot R; Rupp, Rüdiger

    2013-10-01

    The bilateral loss of the grasp function associated with a lesion of the cervical spinal cord severely limits the affected individuals' ability to live independently and return to gainful employment after sustaining a spinal cord injury (SCI). Any improvement in lost or limited grasp function is highly desirable. With current neuroprostheses, relevant improvements can be achieved in end users with preserved shoulder and elbow, but missing hand function. The aim of this single case study is to show that (1) with the support of hybrid neuroprostheses combining functional electrical stimulation (FES) with orthoses, restoration of hand, finger and elbow function is possible in users with high-level SCI and (2) shared control principles can be effectively used to allow for a brain-computer interface (BCI) control, even if only moderate BCI performance is achieved after extensive training. The individual in this study is a right-handed 41-year-old man who sustained a traumatic SCI in 2009 and has a complete motor and sensory lesion at the level of C4. He is unable to generate functionally relevant movements of the elbow, hand and fingers on either side. He underwent extensive FES training (30-45min, 2-3 times per week for 6 months) and motor imagery (MI) BCI training (415 runs in 43 sessions over 12 months). To meet individual needs, the system was designed in a modular fashion including an intelligent control approach encompassing two input modalities, namely an MI-BCI and shoulder movements. After one year of training, the end user's MI-BCI performance ranged from 50% to 93% (average: 70.5%). The performance of the hybrid system was evaluated with different functional assessments. The user was able to transfer objects of the grasp-and-release-test and he succeeded in eating a pretzel stick, signing a document and eating an ice cream cone, which he was unable to do without the system. This proof-of-concept study has demonstrated that with the support of hybrid FES

  4. Transient and modulated charge separation at CuInSe2/C60 and CuInSe2/ZnPc hybrid interfaces

    Science.gov (United States)

    von Morzé, Natascha; Dittrich, Thomas; Calvet, Wolfram; Lauermann, Iver; Rusu, Marin

    2017-02-01

    Spectral dependent charge transfer and exciton dissociation have been investigated at hybrid interfaces between inorganic polycrystalline CuInSe2 (untreated and Na-conditioned) thin films and organic C60 as well as zinc phthalocyanine (ZnPc) layers by transient and modulated surface photovoltage measurements. The stoichiometry and electronic properties of the bare CuInSe2 surface were characterized by photoelectron spectroscopy which revealed a Cu-poor phase with n-type features. After the deposition of the C60 layer, a strong band bending at the CuInSe2 surface was observed. Evidence for dissociation of excitons followed by charge separation was found at the CuInSe2/ZnPc interface. The Cu-poor layer at the CuInSe2 surface was found to be crucial for transient and modulated charge separation at CuInSe2/organic hybrid interfaces.

  5. Metal-Organic Frameworks for Highly Selective Separations

    Energy Technology Data Exchange (ETDEWEB)

    Omar M. Yaghi

    2009-09-28

    This grant was focused on the study of metal-organic frameworks with these specific objectives. (1) To examine the use of MOFs with well-defined open metal sites for binding of gases and small organics. (2) To develop a strategy for producing MOFs that combine large pore size with high surface area for their use in gas adsorption and separation of polycyclic organic compounds. (3) To functionalize MOFs for the storage of inert gases such as methane. A brief outline of our progress towards these objectives is presented here as it forms part of the basis for the ideas to be developed under the present proposal.

  6. Boron Trifluoride Gas Adsorption in Metal-Organic Frameworks.

    Science.gov (United States)

    Siu, Paul W; Siegfried, John P; Weston, Mitchell H; Fuller, Patrick E; Morris, William; Murdock, Christopher R; Hoover, William J; Richardson, Rachelle K; Rodriguez, Stephanie; Farha, Omar K

    2016-12-05

    Coordinatively unsaturated metal-organic frameworks (MOFs) were studied for boron trifluoride (BF3) sorption. MOF-74-Mg, MOF-74-Mn, and MOF-74-Co show high initial uptake (below 6.7 × 10(-3) bar) with negligible deliverable capacity. The BF3 isotherm of MOF-74-Cu exhibits gradual uptake up to 0.9 bar and has a deliverable gravimetric capacity that is more than 100% higher than activated carbon. Two other Cu(2+) MOFs, MOF-505 and HKUST-1, have slightly lower deliverable capacities compared to MOF-74-Cu.

  7. Nanostructure and hydrogen spillover of bridged metal-organic frameworks.

    Science.gov (United States)

    Tsao, Cheng-Si; Yu, Ming-Sheng; Wang, Cheng-Yu; Liao, Pin-Yen; Chen, Hsin-Lung; Jeng, U-Ser; Tzeng, Yi-Ren; Chung, Tsui-Yun; Wu, Hsiu-Chu

    2009-02-04

    The metal-organic frameworks (MOF) with low and medium specific surface areas (SSA) were shown to be able to adsorb hydrogen via bridged spillover at room temperature (RT) up to an amount of full coverage of hydrogen in the MOF. Anomalous small-angle X-ray scattering was employed to investigate the key relationship between the structures and storage properties of the involved materials. It was found that the tunable imperfect lattice defects and the 3D pore network in the MOF crystal are the most critical structures for RT hydrogen uptake rather than the known micropores in the crystal, SSA, and Pt catalyst structure.

  8. Site characteristics in metal organic frameworks for gas adsorption

    Science.gov (United States)

    Uzun, Alper; Keskin, Seda

    2014-02-01

    Metal organic frameworks (MOFs) are a new class of nanoporous materials that have many potential advantages over traditional nanoporous materials for several chemical technologies including gas adsorption, catalysis, membrane-based gas separation, sensing, and biomedical devices. Knowledge on the interaction of guest molecules with the MOF surface is required to design and develop these MOF-based processes. In this review, we examine the importance of identification of gas adsorption sites in MOFs using the current state-of-the-art in experiments and computational modeling. This review provides guidelines to design new MOFs with useful surface properties that exhibit desired performances, such as high gas storage capacity, and high gas selectivity.

  9. A hybrid microfluidic-vacuum device for direct interfacing with conventional cell culture methods.

    Science.gov (United States)

    Chung, Bong Geun; Park, Jeong Won; Hu, Jia Sheng; Huang, Carlos; Monuki, Edwin S; Jeon, Noo Li

    2007-09-20

    Microfluidics is an enabling technology with a number of advantages over traditional tissue culture methods when precise control of cellular microenvironment is required. However, there are a number of practical and technical limitations that impede wider implementation in routine biomedical research. Specialized equipment and protocols required for fabrication and setting up microfluidic experiments present hurdles for routine use by most biology laboratories. We have developed and validated a novel microfluidic device that can directly interface with conventional tissue culture methods to generate and maintain controlled soluble environments in a Petri dish. It incorporates separate sets of fluidic channels and vacuum networks on a single device that allows reversible application of microfluidic gradients onto wet cell culture surfaces. Stable, precise concentration gradients of soluble factors were generated using simple microfluidic channels that were attached to a perfusion system. We successfully demonstrated real-time optical live/dead cell imaging of neural stem cells exposed to a hydrogen peroxide gradient and chemotaxis of metastatic breast cancer cells in a growth factor gradient. This paper describes the design and application of a versatile microfluidic device that can directly interface with conventional cell culture methods. This platform provides a simple yet versatile tool for incorporating the advantages of a microfluidic approach to biological assays without changing established tissue culture protocols.

  10. Ionic charging by local imbalance at interfaces in hybrid lead halide perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Almora, Osbel; Guerrero, Antonio; Garcia-Belmonte, Germà, E-mail: garciag@uji.es [Institute of Advanced Materials (INAM), Universitat Jaume I, 12071 Castelló (Spain)

    2016-01-25

    Identification of specific operating mechanisms becomes particularly challenging when mixed ionic-electronic conductors are used in optoelectronic devices. Ionic effects in perovskite solar cells are believed to distort operation curves and possess serious doubts about their long term stability. Current hysteresis and switchable photovoltaic characteristics have been connected to the kinetics of ion migration. However, the nature of the specific ionic mechanism (or mechanisms) able to explain the operation distortions is still poorly understood. It is observed here that the local rearrangement of ions at the electrode interfaces gives rise to commonly observed capacitive effects. Charging transients in response to step voltage stimuli using thick CH{sub 3}NH{sub 3}PbI{sub 3} samples show two main polarization processes and reveal the structure of the ionic double-layer at the interface with the non-reacting contacts. It is observed that ionic charging, with a typical response time of 10 s, is a local effect confined in the vicinity of the electrode, which entails absence of net mobile ionic concentration (space-charge) in the material bulk.

  11. Optical determination of Shockley-Read-Hall and interface recombination currents in hybrid perovskites

    Science.gov (United States)

    Sarritzu, Valerio; Sestu, Nicola; Marongiu, Daniela; Chang, Xueqing; Masi, Sofia; Rizzo, Aurora; Colella, Silvia; Quochi, Francesco; Saba, Michele; Mura, Andrea; Bongiovanni, Giovanni

    2017-01-01

    Metal-halide perovskite solar cells rival the best inorganic solar cells in power conversion efficiency, providing the outlook for efficient, cheap devices. In order for the technology to mature and approach the ideal Shockley-Queissier efficiency, experimental tools are needed to diagnose what processes limit performances, beyond simply measuring electrical characteristics often affected by parasitic effects and difficult to interpret. Here we study the microscopic origin of recombination currents causing photoconversion losses with an all-optical technique, measuring the electron-hole free energy as a function of the exciting light intensity. Our method allows assessing the ideality factor and breaks down the electron-hole recombination current into bulk defect and interface contributions, providing an estimate of the limit photoconversion efficiency, without any real charge current flowing through the device. We identify Shockley-Read-Hall recombination as the main decay process in insulated perovskite layers and quantify the additional performance degradation due to interface recombination in heterojunctions. PMID:28317883

  12. A hybrid microfluidic-vacuum device for direct interfacing with conventional cell culture methods

    Directory of Open Access Journals (Sweden)

    Monuki Edwin S

    2007-09-01

    Full Text Available Abstract Background Microfluidics is an enabling technology with a number of advantages over traditional tissue culture methods when precise control of cellular microenvironment is required. However, there are a number of practical and technical limitations that impede wider implementation in routine biomedical research. Specialized equipment and protocols required for fabrication and setting up microfluidic experiments present hurdles for routine use by most biology laboratories. Results We have developed and validated a novel microfluidic device that can directly interface with conventional tissue culture methods to generate and maintain controlled soluble environments in a Petri dish. It incorporates separate sets of fluidic channels and vacuum networks on a single device that allows reversible application of microfluidic gradients onto wet cell culture surfaces. Stable, precise concentration gradients of soluble factors were generated using simple microfluidic channels that were attached to a perfusion system. We successfully demonstrated real-time optical live/dead cell imaging of neural stem cells exposed to a hydrogen peroxide gradient and chemotaxis of metastatic breast cancer cells in a growth factor gradient. Conclusion This paper describes the design and application of a versatile microfluidic device that can directly interface with conventional cell culture methods. This platform provides a simple yet versatile tool for incorporating the advantages of a microfluidic approach to biological assays without changing established tissue culture protocols.

  13. Solution growth of metal-organic complex CuTCNQ in small dimension interconnect structures

    Science.gov (United States)

    Demolliens, A.; Muller, Ch.; Müller, R.; Turquat, Ch.; Goux, L.; Deleruyelle, D.; Wouters, D. J.

    2010-11-01

    In this paper, we report two different elaboration routes to grow metal-organic complex CuTCNQ in liquid phase within small interconnect structures (i.e. via holes opened in SiO 2/SiC stack). The basic common idea relies on the formation of CuTCNQ material from the partial corrosion of a Cu bottom electrode by a TCNQ-based solution. The two solution growth methods are compared in terms of (i) via holes filling; (ii) local microstructure of CuTCNQ complex and (iii) quality of interface between CuTCNQ and copper metallic electrode. In the first route, in the reaction of the substrate with a TCNQ/copper salt solution in acetonitrile/toluene, a rapid formation of porous CuTCNQ complex is observed with an over-growth outside interconnect structures and many voids within via holes and at the interface with Cu layer. In contrast to this "mushroom-like" growth, the reaction of the substrate with a TCNQ solution in acetonitrile/2-butanone results in a "crystal-like" dense CuTCNQ complex within via holes and a CuTCNQ/Cu interface free of voids. In the latter case, satisfactory electrical performances are expected for future resistive switching memory devices.

  14. Adaptive multi-rate interface: development and experimental verification for real-time hybrid simulation

    DEFF Research Database (Denmark)

    Maghareh, Amin; Waldbjørn, Jacob Paamand; Dyke, Shirley J.;

    2016-01-01

    Real-time hybrid simulation (RTHS) is a powerful cyber-physical technique that is a relatively cost-effective method to perform global/local system evaluation of structural systems. A major factor that determines the ability of an RTHS to represent true system-level behavior is the fidelity...... it employs different time steps in the numerical and the physical substructures while including rate-transitioning to link the components appropriately. Typically, a higher-order numerical substructure model is solved at larger time intervals, and is coupled with a physical substructure that is driven...... frequency between the numerical and physical substructures and for input signals with high-frequency content. Further, it does not induce signal chattering at the coupling frequency. The effectiveness of AMRI is also verified experimentally....

  15. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids

    Energy Technology Data Exchange (ETDEWEB)

    Nandasiri, Manjula I.; Liu, Jian; McGrail, B. Peter; Jenks, Jeromy WJ; Schaef, Herbert T.; Shutthanandan, V.; Nie, Zimin; Martin, Paul F.; Nune, Satish K.

    2016-06-15

    Metal organic heat carriers (MOHCs) are recently developed nanofluids containing metal organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. MOHCs utilize the MOF properties to improve the thermo-physical properties of base fluids. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC containing MIL-101(Cr)/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nano MIL-101(Cr) and the properties depend on the amount of GO added. Powder X-ray diffraction (PXRD) confirmed the preserved crystallinity of MIL-101(Cr) in all nanocomposites with the absence of any unreacted GO. Scanning electron microscopy images confirmed the presence of near spherical MIL-101(Cr) nanoparticles in the range of 40-80 nm in diameter. MOHC nanofluids containing MIL-101(Cr)/GO in methanol exhibited significant enhancement in the thermal conductivity (by approxi-mately 50%) relative to that of the intrinsic nano MIL-101(Cr) in methanol. The thermal conductivity of base fluid (methanol) was enhanced by about 20 %. The enhancement in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to graphene oxide functionalization is explained using a classical Maxwell model.

  16. Optimizing the performance of neural interface devices with hybrid poly(3,4-ethylene dioxythiophene) (PEDOT)

    Science.gov (United States)

    Kuo, Chin-chen

    This thesis describes methods for improving the performance of poly(3,4-ethylenedioxythiophene) (PEDOT) as a direct neural interfacing material. The chronic foreign body response is always a challenge for implanted bionic devices. After long-term implantation (typically 2-4 weeks), insulating glial scars form around the devices, inhibiting signal transmission, which ultimately leads to device failure. The mechanical mismatch at the device-tissue interface is one of the issues that has been associated with chronic foreign body response. Another challenge for using PEDOT as a neural interface material is its mechanical failure after implantation. We observed cracking and delamination of PEDOT coatings on devices after extended implantations. In the first part of this thesis, we present a novel method for directly measuring the mechanical properties of a PEDOT thin film. Before investigating methods to improve the mechanical behavior of PEDOT, a comprehensive understanding of the mechanical properties of PEDOT thin film is required. A PEDOT thin film was machined into a dog-bone shape specimen with a dual beam FIB-SEM. With an OmniProbe, this PEDOT specimen could be attached onto a force sensor, while the other side was attached to OmniProbe. By moving the OmniProbe, the specimen could be deformed in tension, and a force sensor recorded the applied load on the sample simultaneously. Mechanical tensile tests were conducted in the FIB-SEM chamber along with in situ observation. With precise force measurement from the force sensor and the corresponding high resolution SEM images, we were able to convert the data to a stress-strain curve for further analysis. By analyzing these stress-strain curves, we were able to obtain information about PEDOT including the Young's modulus, strength of failure, strain to failure, and toughness (energy to failure). This information should be useful for future material selection and molecular design for specific applications. The second

  17. Towards a naturalistic brain-machine interface: hybrid torque and position control allows generalization to novel dynamics.

    Directory of Open Access Journals (Sweden)

    Pratik Y Chhatbar

    Full Text Available Realization of reaching and grasping movements by a paralytic person or an amputee would greatly facilitate her/his activities of daily living. Towards this goal, control of a computer cursor or robotic arm using neural signals has been demonstrated in rodents, non-human primates and humans. This technology is commonly referred to as a Brain-Machine Interface (BMI and is achieved by predictions of kinematic parameters, e.g. position or velocity. However, execution of natural movements, such as swinging baseball bats of different weights at the same speed, requires advanced planning for necessary context-specific forces in addition to kinematic control. Here we show, for the first time, the control of a virtual arm with representative inertial parameters using real-time neural control of torques in non-human primates (M. radiata. We found that neural control of torques leads to ballistic, possibly more naturalistic movements than position control alone, and that adding the influence of position in a hybrid torque-position control changes the feedforward behavior of these BMI movements. In addition, this level of control was achievable utilizing the neural recordings from either contralateral or ipsilateral M1. We also observed changed behavior of hybrid torque-position control under novel external dynamic environments that was comparable to natural movements. Our results demonstrate that inclusion of torque control to drive a neuroprosthetic device gives the user a more direct handle on the movement execution, especially when dealing with novel or changing dynamic environments. We anticipate our results to be a starting point of more sophisticated algorithms for sensorimotor neuroprostheses, eliminating the need of fully automatic kinematic-to-dynamic transformations as currently used by traditional kinematic-based decoders. Thus, we propose that direct control of torques, or other force related variables, should allow for more natural

  18. Dislocation structure in interfaces between Si wafers with hybrid crystal orientation

    Energy Technology Data Exchange (ETDEWEB)

    Vdovin, Vladimir [Institute for Chemical Problems of Microelectronics, Moscow (Russian Federation); Zakharov, Nikolai; Pippel, Eckhard; Werner, Peter [Max-Planck-Institut fuer Mikrostrukturphysik, Halle (Saale) (Germany); Milvidskii, Mikhail [Institute of Rare Metals ' Giredmet' , Moscow (Russian Federation); Ries, Mike; Seacrist, Mike [MEMC Inc., 501 Pearl Drive, St. Peters, MO (United States); Falster, Robert [MEMC Electronic Materials SpA, Novara (Italy)

    2009-08-15

    Dislocation structure in Si(110)/Si(001) wafer bonding (WB) structures have been studied by transmission electron microscopy (TEM). The behavior of intermediate native oxide layers during high temperature annealing, the nature of interfacial dislocations and dislocation generation mechanisms are the main issues of this work. Samples were fabricated by direct hydrophilic WB of 200 mm wafers with native oxide. The as-bonded structures containing 140-nm thick layers were thermally annealed in the temperature range 1150 to 1200 C. The dislocation structure composed of a pattern of unidirectional parallel but broken dislocation arrays is formed in the structures with partial or entire dissolution of the oxide layer. The contrast of broken dark lines usually observed in TEM bright field micrographs is supposed to be caused by integral effect of steps compensating twist misorientation and arrays of 60-degree dislocations. We suggest that nucleation of dislocation loops at the interface due to the agglomeration of intrinsic point defects is a plausible mechanism of dislocation generation. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  19. Hybrid EEG-fNIRS Asynchronous Brain-Computer Interface for Multiple Motor Tasks.

    Directory of Open Access Journals (Sweden)

    Alessio Paolo Buccino

    Full Text Available Non-invasive Brain-Computer Interfaces (BCI have demonstrated great promise for neuroprosthetics and assistive devices. Here we aim to investigate methods to combine Electroencephalography (EEG and functional Near-Infrared Spectroscopy (fNIRS in an asynchronous Sensory Motor rhythm (SMR-based BCI. We attempted to classify 4 different executed movements, namely, Right-Arm-Left-Arm-Right-Hand-Left-Hand tasks. Previous studies demonstrated the benefit of EEG-fNIRS combination. However, since normally fNIRS hemodynamic response shows a long delay, we investigated new features, involving slope indicators, in order to immediately detect changes in the signals. Moreover, Common Spatial Patterns (CSPs have been applied to both EEG and fNIRS signals. 15 healthy subjects took part in the experiments and since 25 trials per class were available, CSPs have been regularized with information from the entire population of participants and optimized using genetic algorithms. The different features have been compared in terms of performance and the dynamic accuracy over trials shows that the introduced methods diminish the fNIRS delay in the detection of changes.

  20. Electronic Interfacing Between a Living Cell and a Nanodevice: A Bio-Nano Hybrid System

    Energy Technology Data Exchange (ETDEWEB)

    Saraf, Ravi F. [Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemical and Biomolecular Engineering

    2013-12-31

    The primary goal of this program was to couple physical electronics with live cells to leverage the highly sophisticated functions of a biological system to ultimately create advanced functionality. The study was built on a unique self-assembled architecture of nanoparticles that exhibits transport properties that are sensitive to single-electron charge modulation. At room temperature, the energy of switching due to single-electron charge modulation was in the range of 4 to 100 kT. The structure invented in the principal investigator’s lab is a two-dimensional (2D) network of one-dimensional (1D) necklaces of 10 nm Au nanoparticles. The electron transport through the necklace network is regulated by quantum mechanical single-electron traps. As a result of the single electron traps, the all metal nanoparticle network array displays a conduction band gap. Fundamental studies on the transport properties of the network in air and water were studied to regulate the band gap by tailoring the network structure to demonstrate the first electrochemical single electron transistor operating in water. Cells were interfaced with the network to observe electrochemical activity in a cell during photosynthesis and single viral infection.

  1. Nanoscale interfaces in hybrid materials for exciton fission and fusion (Conference Presentation)

    Science.gov (United States)

    Bardeen, Christopher J.

    2016-09-01

    The ability to downconvert (1 photon to 2 photons) and upconvert (2 photons to 1 photon) energy can have applications in many fields, including solar energy. Singlet fission provides a way to convert one photon into a pair of triplet excitons. It occurs efficiently in organic semiconductors, but the question remains how to extract the triplet excitons in a useful form. In this talk, we will describe efforts to transform triplet excitons into other forms through energy transfer into inorganic semiconductors like silicon. Heterogeneous solid-liquid approaches to use spin-orbit coupling to enhance the triplet excitons' oscillator strength so they can emit photons will also be described. The solid-solid and solid-liquid interface appears to be critical for these schemes to succeed. Upconversion occurs via the reverse process, where a pair of triplet excitons fuse into a high-energy singlet state. A new approach to triplet state sensitization involves absorption of low energy photons by the semiconductor nanocrystals followed by energy transfer to the molecular triplet states. These states can then undergo triplet-triplet annihilation to create high energy singlet states that emit upconverted light in the visible and ultraviolet regions. By using conjugated organic ligands to form an energy cascade, the upconversion can be enhanced by up to three orders of magnitude. The mechanism of the nanocrystal-to-triplet energy transfer is investigated using time-resolved spectroscopy. Again, the role of organic ligand-inorganic surface interactions is important for determining the ultimate efficiency.

  2. Metal-Organic Nanosheets Formed via Defect-Mediated Transformation of a Hafnium Metal-Organic Framework.

    Science.gov (United States)

    Cliffe, Matthew J; Castillo-Martínez, Elizabeth; Wu, Yue; Lee, Jeongjae; Forse, Alexander C; Firth, Francesca C N; Moghadam, Peyman Z; Fairen-Jimenez, David; Gaultois, Michael W; Hill, Joshua A; Magdysyuk, Oxana V; Slater, Ben; Goodwin, Andrew L; Grey, Clare P

    2017-04-19

    We report a hafnium-containing MOF, hcp UiO-67(Hf), which is a ligand-deficient layered analogue of the face-centered cubic fcu UiO-67(Hf). hcp UiO-67 accommodates its lower ligand:metal ratio compared to fcu UiO-67 through a new structural mechanism: the formation of a condensed "double cluster" (Hf12O8(OH)14), analogous to the condensation of coordination polyhedra in oxide frameworks. In oxide frameworks, variable stoichiometry can lead to more complex defect structures, e.g., crystallographic shear planes or modules with differing compositions, which can be the source of further chemical reactivity; likewise, the layered hcp UiO-67 can react further to reversibly form a two-dimensional metal-organic framework, hxl UiO-67. Both three-dimensional hcp UiO-67 and two-dimensional hxl UiO-67 can be delaminated to form metal-organic nanosheets. Delamination of hcp UiO-67 occurs through the cleavage of strong hafnium-carboxylate bonds and is effected under mild conditions, suggesting that defect-ordered MOFs could be a productive route to porous two-dimensional materials.

  3. Design of Multi-Decker Incorporated Metal Organic Frameworks for Hydrogen Storage

    Science.gov (United States)

    Boggavarapu, Kiran; Kandalam, Anil

    2009-03-01

    Metal Organic Frameworks (MOFs) are a new class of rationally designed microporous hybrid (organic-inorganic) materials. They have recently gained attention as potential hydrogen storage systems with gravimetric density meeting the DOE 2015 targets of 9 wt%. However, due to weak interaction between the molecular hydrogen and the host MOF (see figure), high pressures are required to reach the target storage levels. Recently, multi-decker organometallic complexes are shown to exhibit the ideal thermodynamics and kinetics for hydrogen storage. However, it is not clear if these multi-decker complexes can retain their hydrogen storage capability when assembled into a bulk-material. In this presentation, we investigate the hydrogen storage capability of a new class of materials by combining the strengths of MOFs and decker complexes. An ideal way to integrate these two systems is to incorporate the multi-deckers into the structural framework of MOFs. In these hybrid materials, the multi-decker units are expected to maintain their structural integrity and there by retaining the hydrogen storage capacity with an added advantage of being a part of stable porous MOF back-bone.

  4. Electronic properties and chemistry of metal / organic semiconductor/ S-GaAs(100) heterosructures

    Energy Technology Data Exchange (ETDEWEB)

    Gavrila, G.N.

    2005-10-21

    in the framework of this thesis three perylene derivates are applied as interlayers in metal/organic layer/S-GaAs(100) heterostructures. The aim of this thesis is to prove the influence of different chemical end-groups on the electronic and chemical properties of the interfaces, as well as the molecular orientation in the organic layers. The molecules 3,4,9,10-perylene tetracarbonic acid dianhydride (PTCDA), 3,4,9,10-perylene tetracarbonic acid diimide (PTCDI), and dimethyl-3,4,9,10-perylene tetracarbonic acid diimide (DiMe-PTCDI) were evaporated by organic molecular beam deposition (OMBD) in the ultrahigh vacuum on sulfur-passivated GaAs(001):2 x 1 substrates. Surface-sensitive characterization procedures as photoemission spectroscopy (PES), inverse photoemission spectroscopy (IPES), and near-edge X-ray fine-structure measurements (NEXAFS) were applied for the characterization. Theoretical calculations by means of the density-functional methods were performed, in order to allow an assignment of different components in core-level spectra. The NEXAFS spectra allow a precise determination of the molecule orientation in relation to the substrate. So it can be proved that a small change of chemical end-groups for instance in DiMe-PTCDI compared with PTCDI causes a dramatic change of the molecule orientation. The valence-band spectra of DiMe-PTCDI show an energetic dispersion of 0.2 eV, which can be assigned to a {pi}-orbital overlap and covers the formation of valence bands. The energy-level fitting to the organic-layer/S-GaAs interface as well as the transport band gap of PTCDI, DiMe-PTCDI, and PTCDA were deteminde by means of PES and IPES. The electronic, chemical, and structural properties of metal/organic-layer interfaces were studied by means of core-level spectroscopy and NEXAFS. Mg reacts strongly with the end-groups of PTCDA AND ptcdi, while the In atoms contribute to a charge-transfer process with the perylene cores of all three molecules, whereby the

  5. The nature of electronic excitations at the metal-bioorganic interface illustrated on histidine-silver hybrids.

    Science.gov (United States)

    Sanader, Željka; Mitrić, Roland; Bonačić-Koutecký, Vlasta; Bellina, Bruno; Antoine, Rodolphe; Dugourd, Philippe

    2014-01-21

    We present a joint theoretical and experimental study of the structure selective optical properties of cationic and anionic histidine-silver complexes with Ag and Ag3 which were prepared in the gas phase using mass spectroscopy coupled to electrospray ion source. Our TDDFT calculations provide general insight into the nature of electronic excitations at the metal-bioorganic interface that involve π-π* excitation within bioorganic subunits, charge transfer between two subunits and intrametallic excitations. The binding of silver to histidine, one of the most important amino acids, induces red shift in the optical absorption of protonated histidine particularly for anionic species. The presence of the smallest metallic subunit Ag3 increases the intensity of low energy transitions of histidine illustrating a metal cluster-induced enhancement of absorption of biomolecules in hybrid systems. Comparison of calculated absorption spectra with experimental photofragmentation yield provides structural assignment of the measured spectroscopic patterns. Our findings may serve to establish silver-labeling as the tool for the detection of histidine or histidine-tagged proteins.

  6. Designing Kitaev Spin Liquids in Metal-Organic Frameworks

    Science.gov (United States)

    Yamada, Masahiko G.; Fujita, Hiroyuki; Oshikawa, Masaki

    2017-08-01

    Kitaev's honeycomb lattice spin model is a remarkable exactly solvable model, which has a particular type of spin liquid (Kitaev spin liquid) as the ground state. Although its possible realization in iridates and α -RuCl3 has been vigorously discussed recently, these materials have substantial non-Kitaev direct exchange interactions and do not have a spin liquid ground state. We propose metal-organic frameworks (MOFs) with Ru3 + (or Os3 + ), forming the honeycomb lattice as promising candidates for a more ideal realization of Kitaev-type spin models, where the direct exchange interaction is strongly suppressed. The great flexibility of MOFs allows generalization to other three-dimensional lattices for the potential realization of a variety of spin liquids, such as a Weyl spin liquid.

  7. Semiconductor Metal-Organic Frameworks: Future Low-Bandgap Materials.

    Science.gov (United States)

    Usman, Muhammad; Mendiratta, Shruti; Lu, Kuang-Lieh

    2017-02-01

    Metal-organic frameworks (MOFs) with low density, high porosity, and easy tunability of functionality and structural properties, represent potential candidates for use as semiconductor materials. The rapid development of the semiconductor industry and the continuous miniaturization of feature sizes of integrated circuits toward the nanometer (nm) scale require novel semiconductor materials instead of traditional materials like silicon, germanium, and gallium arsenide etc. MOFs with advantageous properties of both the inorganic and the organic components promise to serve as the next generation of semiconductor materials for the microelectronics industry with the potential to be extremely stable, cheap, and mechanically flexible. Here, a perspective of recent research is provided, regarding the semiconducting properties of MOFs, bandgap studies, and their potential in microelectronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Metal-Organic Frameworks for CO2 Chemical Transformations.

    Science.gov (United States)

    He, Hongming; Perman, Jason A; Zhu, Guangshan; Ma, Shengqian

    2016-12-01

    Carbon dioxide (CO2 ), as the primary greenhouse gas in the atmosphere, triggers a series of environmental and energy related problems in the world. Therefore, there is an urgent need to develop multiple methods to capture and convert CO2 into useful chemical products, which can significantly improve the environment and promote sustainable development. Over the past several decades, metal-organic frameworks (MOFs) have shown outstanding heterogeneous catalytic activity due in part to their high internal surface area and chemical functionalities. These properties and the ability to synthesize MOF platforms allow experiments to test structure-function relationships for transforming CO2 into useful chemicals. Herein, recent developments are highlighted for MOFs participating as catalysts for the chemical fixation and photochemical reduction of CO2 . Finally, opportunities and challenges facing MOF catalysts are discussed in this ongoing research area. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Multi-Photon Absorption in Metal-Organic Frameworks.

    Science.gov (United States)

    Medishetty, Raghavender; Nemec, Lydia; Nalla, Venkatram; Henke, Sebastian; Samoc, Marek; Reuter, Karsten; Fischer, Roland A

    2017-09-12

    Multi-photon absorption (MPA) is among the most prominent nonlinear optical (NLO) effects and has applications, for example in telecommunications, defense, photonics and bio-medicines. Established MPA materials include dyes, quantum dots, organometallics and conjugated polymers, most often dispersed in solution. We demonstrate how metal-organic frameworks (MOFs), a novel NLO solid-state materials class, can be designed for exceptionally strong MPA behavior. MOFs consisting of zirconium- and hafnium-oxo-clusters and featuring a chromophore linker based on the tetraphenylethene (TPE) molecule exhibit record high two-photon absorption (2PA) cross section values, up to 3600 GM. The unique modular building-block principle of MOFs allows enhancing and optimizing their MPA properties in a theory guided approach by combining tailored charge polarization, conformational strain, three-dimensional arrangement and alignment of the chromophore linkers in the crystal. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Structure and Properties of an Amorphous Metal-Organic Framework

    Science.gov (United States)

    Bennett, Thomas D.; Goodwin, Andrew L.; Dove, Martin T.; Keen, David A.; Tucker, Matthew G.; Barney, Emma R.; Soper, Alan K.; Bithell, Erica G.; Tan, Jin-Chong; Cheetham, Anthony K.

    2010-03-01

    ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300°C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400°C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

  11. Structural diversity in serine derived homochiral metal organic frameworks

    Indian Academy of Sciences (India)

    Tanay Kundu; Rahul Banerjee

    2014-09-01

    Two new Zn(II) and Cd(II) based homochiral metal-organic frameworks (MOFs) [SerCdOAc and Zn(Ser)2] have been synthesized using pyridyl functionalized amino acid, viz., serine, as an organic linker. The SerCdOAc structure is three dimensional, while that of the Zn(Ser)2 is two dimensional. The polar voids of the corresponding MOFs are filled with solvent molecules (water in the case of SerCdOAc and methanol in the case of Zn(Ser)2). In both cases, metal centres, i.e., Zn(II) and Cd(II), are hexacoordinated. However, with a change in the solvent for synthesis, ligand coordinationmode and incorporation of additional coordinated anion resulted in a great change in the final MOF architecture. Herein, for the first time, we could achieve structural variety and synthesize MOFs composed of only metal ion and pyridyl functionalized amino acid linker.

  12. Transformation of metal-organic frameworks for molecular sieving membranes

    Science.gov (United States)

    Li, Wanbin; Zhang, Yufan; Zhang, Congyang; Meng, Qin; Xu, Zehai; Su, Pengcheng; Li, Qingbiao; Shen, Chong; Fan, Zheng; Qin, Lei; Zhang, Guoliang

    2016-04-01

    The development of simple, versatile strategies for the synthesis of metal-organic framework (MOF)-derived membranes are of increasing scientific interest, but challenges exist in understanding suitable fabrication mechanisms. Here we report a route for the complete transformation of a series of MOF membranes and particles, based on multivalent cation substitution. Through our approach, the effective pore size can be reduced through the immobilization of metal salt residues in the cavities, and appropriate MOF crystal facets can be exposed, to achieve competitive molecular sieving capabilities. The method can also be used more generally for the synthesis of a variety of MOF membranes and particles. Importantly, we design and synthesize promising MOF membranes candidates that are hard to achieve through conventional methods. For example, our CuBTC/MIL-100 membrane exhibits 89, 171, 241 and 336 times higher H2 permeance than that of CO2, O2, N2 and CH4, respectively.

  13. Seed-Mediated Synthesis of Metal-Organic Frameworks.

    Science.gov (United States)

    Xu, Hai-Qun; Wang, Kecheng; Ding, Meili; Feng, Dawei; Jiang, Hai-Long; Zhou, Hong-Cai

    2016-04-27

    The synthesis of phase-pure metal-organic frameworks (MOFs) is of prime importance but remains a significant challenge because of the flexible and diversified coordination modes between metal ions and organic linkers. In this work, we report the synthesis of phase-pure MOFs via a facile seed-mediated approach. For several "accompanying" pairs of Zr-porphyrinic MOFs that are prone to yield mixtures, by fixing all reaction parameters except introducing seed crystals, MOFs in phase-pure forms have been obtained because the stage of MOF nucleation, which generates mixed nuclei, is bypassed. In addition, phase-pure MOF isomers with distinct pore structures have also been prepared through such an approach, revealing its versatility. To the best of our knowledge, this is an initial report on seed-assisted synthesis of phase-pure MOFs.

  14. Metal-organic frameworks for Xe/Kr separation

    Science.gov (United States)

    Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

    2014-07-22

    Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

  15. Diffusion of Small Molecules in Metal Organic Framework Materials

    Science.gov (United States)

    Canepa, Pieremanuele; Nijem, Nour; Chabal, Yves J.; Thonhauser, T.

    2013-01-01

    Ab initio simulations are combined with in situ infrared spectroscopy to unveil the molecular transport of H2, CO2, and H2O in the metal organic framework MOF-74-Mg. Our study uncovers—at the atomistic level—the major factors governing the transport mechanism of these small molecules. In particular, we identify four key diffusion mechanisms and calculate the corresponding diffusion barriers, which are nicely confirmed by time-resolved infrared experiments. We also answer a long-standing question about the existence of secondary adsorption sites for the guest molecules, and we show how those sites affect the macroscopic diffusion properties. Our findings are important to gain a fundamental understanding of the diffusion processes in these nanoporous materials, with direct implications for the usability of MOFs in gas sequestration and storage applications.

  16. Storage of electrical information in metal-organic-framework memristors.

    Science.gov (United States)

    Yoon, Seok Min; Warren, Scott C; Grzybowski, Bartosz A

    2014-04-22

    Single crystals of a cyclodextrin-based metal-organic framework (MOF) infused with an ionic electrolyte and flanked by silver electrodes act as memristors. They can be electrically switched between low and high conductivity states that persist even in the absence of an applied voltage. In this way, these small blocks of nanoporous sugar function as a non-volatile RRAM memory elements that can be repeatedly read, erased, and re-written. These properties derive from ionic current within the MOF and the deposition of nanometer-thin passivating layers at the anode flanking the MOF crystal. The observed phenomena are crucially dependent on the sub-nanometer widths of the channels in the MOF, allowing the passage of only smaller ions. Conversely, with the electrolyte present but no MOF, there are no memristance or memory effects. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Correlated defect nanoregions in a metal-organic framework

    Science.gov (United States)

    Cliffe, Matthew J.; Wan, Wei; Zou, Xiaodong; Chater, Philip A.; Kleppe, Annette K.; Tucker, Matthew G.; Wilhelm, Heribert; Funnell, Nicholas P.; Coudert, François-Xavier; Goodwin, Andrew L.

    2014-06-01

    Throughout much of condensed matter science, correlated disorder is a key to material function. While structural and compositional defects are known to exist within a variety of metal-organic frameworks (MOFs), the prevailing understanding is that these defects are only ever included in a random manner. Here we show—using a combination of diffuse scattering, electron microscopy, anomalous X-ray scattering and pair distribution function measurements—that correlations between defects can in fact be introduced and controlled within a hafnium terephthalate MOF. The nanoscale defect structures that emerge are an analogue of correlated Schottky vacancies in rocksalt-structured transition metal monoxides and have implications for storage, transport, optical and mechanical responses. Our results suggest how the diffraction behaviour of some MOFs might be reinterpreted, and establish a strategy of exploiting correlated nanoscale disorder as a targetable and desirable motif in MOF design.

  18. High methane storage capacity in aluminum metal-organic frameworks.

    Science.gov (United States)

    Gándara, Felipe; Furukawa, Hiroyasu; Lee, Seungkyu; Yaghi, Omar M

    2014-04-09

    The use of porous materials to store natural gas in vehicles requires large amounts of methane per unit of volume. Here we report the synthesis, crystal structure and methane adsorption properties of two new aluminum metal-organic frameworks, MOF-519 and MOF-520. Both materials exhibit permanent porosity and high methane volumetric storage capacity: MOF-519 has a volumetric capacity of 200 and 279 cm(3) cm(-3) at 298 K and 35 and 80 bar, respectively, and MOF-520 has a volumetric capacity of 162 and 231 cm(3) cm(-3) under the same conditions. Furthermore, MOF-519 exhibits an exceptional working capacity, being able to deliver a large amount of methane at pressures between 5 and 35 bar, 151 cm(3) cm(-3), and between 5 and 80 bar, 230 cm(3) cm(-3).

  19. Metal-organic frameworks for lithium ion batteries and supercapacitors

    Science.gov (United States)

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang

    2015-03-01

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100-1000 m2 g-1) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m2 g-1), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs.

  20. Chemical, thermal and mechanical stabilities of metal-organic frameworks

    Science.gov (United States)

    Howarth, Ashlee J.; Liu, Yangyang; Li, Peng; Li, Zhanyong; Wang, Timothy C.; Hupp, Joseph T.; Farha, Omar K.

    2016-03-01

    The construction of thousands of well-defined, porous, metal-organic framework (MOF) structures, spanning a broad range of topologies and an even broader range of pore sizes and chemical functionalities, has fuelled the exploration of many applications. Accompanying this applied focus has been a recognition of the need to engender MOFs with mechanical, thermal and/or chemical stability. Chemical stability in acidic, basic and neutral aqueous solutions is important. Advances over recent years have made it possible to design MOFs that possess different combinations of mechanical, thermal and chemical stability. Here, we review these advances and the associated design principles and synthesis strategies. We focus on how these advances may render MOFs effective as heterogeneous catalysts, both in chemically harsh condensed phases and in thermally challenging conditions relevant to gas-phase reactions. Finally, we briefly discuss future directions of study for the production of highly stable MOFs.

  1. Metal-organic frameworks for artificial photosynthesis and photocatalysis.

    Science.gov (United States)

    Zhang, Teng; Lin, Wenbin

    2014-08-21

    Solar energy is an alternative, sustainable energy source for mankind. Finding a convenient way to convert sunlight energy into chemical energy is a key step towards realizing large-scale solar energy utilization. Owing to their structural regularity and synthetic tunability, metal-organic frameworks (MOFs) provide an interesting platform to hierarchically organize light-harvesting antennae and catalytic centers to achieve solar energy conversion. Such photo-driven catalytic processes not only play a critical role in the solar to chemical energy conversion scheme, but also provide a novel methodology for the synthesis of fine chemicals. In this review, we summarize the fundamental principles of energy transfer and photocatalysis and provide an overview of the latest progress in energy transfer, light-harvesting, photocatalytic proton and CO2 reduction, and water oxidation using MOFs. The applications of MOFs in organic photocatalysis and degradation of model organic pollutants are also discussed.

  2. Metal-Organic Frameworks as Catalysts for Oxidation Reactions.

    Science.gov (United States)

    Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; Garcia, Hermenegildo

    2016-06-01

    This Concept is aimed at describing the current state of the art in metal-organic frameworks (MOFs) as heterogeneous catalysts for liquid-phase oxidations, focusing on three important substrates, namely, alkenes, alkanes and alcohols. Emphases are on the nature of active sites that have been incorporated within MOFs and on future targets to be set in this area. Thus, selective alkene epoxidation with peroxides or oxygen catalyzed by constitutional metal nodes of MOFs as active sites are still to be developed. Moreover, no noble metal-free MOF has been reported to date that can act as a general catalyst for the aerobic oxidation of primary and secondary aliphatic alcohols. In contrast, in the case of alkanes, a target should be to tune the polarity of MOF internal pores to control the outcome of the autooxidation process, resulting in the selective formation of alcohol/ketone mixtures at high conversion.

  3. Metal-organic frameworks: A new hydrogen storage system

    Science.gov (United States)

    Yaghi, Omar

    2004-03-01

    Metal-organic framework-5 (MOF-5) of composition Zn4O(BDC)3 (BDC = 1,4-benzenedi-carboxylate) with a cubic 3-D extended porous structure was found to be capable of adsorbing hydrogen up to 4.5 weight percent (17.2 hydrogen molecules per formula unit) at 78 K. At room temperature and pressures up to 20 bar this material has a hydrogen storage capacity which increases linearly as a function of the applied pressure up to 1.0 percent by weight at 20 bar. Inelastic Neutron Scattering spectroscopy of the rotational transitions of the adsorbed hydrogen molecules was performed on hydrogen loaded MOF-5 using doses equivalent to four, eight and twenty-four hydrogen molecules per formula unit at 10 K. The spectra show peaks at 10.3 and 12.3 meV that are sharper than those observed for hydrogen in other porous materials, indicating the presence of two well-defined binding sites (termed I and II), which we associate with hydrogen binding to zinc and the BDC linker, respectively. At the highest dose (twenty-four hydrogen molecules), the peak corresponding to site II splits into four peaks, suggesting that higher capacity for hydrogen may be achieved by the use of larger linkers. Indeed, preliminary studies on isoreticular (of the same topology) metal-organic framework-6 and 8 having cyclobutyl and benzene moieties respectively fused to the benzene of MOF-5 gave approximately double and quadruple (2.0 weight percent) the uptake found for MOF-5 at room temperature and 10 bar.

  4. Adsorption of Gases on Graphene and Metal Organic Frameworks

    Science.gov (United States)

    Maiga, Sidi Mohamed

    Separation and adsorption of harmful gases from the environment are of great importance to industry and society. For this purpose, several materials are being explored. A large active surface area in the solid state candidates is an important requirement for efficient removal of gases. Owing to their large surface areas, Metal organic frameworks ( 2900 m2/g) and graphene ( 2600 m2/g), have emerged as two promising candidates for gas adsorption, separation and storage. The goal of this research is to investigate the capability of Metal Organic Frameworks and graphene for gas adsorption and separation; also to understand the properties of the molecules adsorbed on these two materials. We explore the adsorption of noble gases on graphene using Grand Canonical Monte Carlo simulations and also investigate the behavior of the monolayers on graphene. We obtain the phase diagrams of argon, krypton and xenon. We study the adsorption of carbon dioxide and methane molecules on graphene. Using Monte Carlo simulations and the Ideal Adsorb Solution Theory, we explore the selectivity of a binary mixture of CO2 and CH4 on graphene and estimate how the selectivity varies with temperature. We found high selectivity for CO2 at low temperature. At room temperature however the selectivity is low. We investigate the adsorption of CO2 and CH4 on a simplified model of the MOF-5 with systematic variations in the charge distribution, size and Lennard Jones parameters. We then test the selectivity of CO2 over CH4 and how it varies when we insert dipoles or quadrupole moments at the corners of the MOF-5. Our finding shows that the selectivity can be improved with adding dipoles or compressing the cell of the MOFs.

  5. Controlling the magnetism of adsorbed metal-organic molecules

    Science.gov (United States)

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-01

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule’s magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  6. Metal-Organic Framework Synthesis System Based on Fuzzy Predictive Control via Network Transmission

    Directory of Open Access Journals (Sweden)

    Jui-Ho Chen

    2014-01-01

    Full Text Available The purpose of this study is to construct metal-organic framework (MOF synthesis heating systems based on fuzzy method for monitoring and automatic control. In this study, the temperature sensing module for measurements sensed values that it through a wireless ZigBee chips and wired DAQ device for real-time data transmission. Because MOF synthesis, often due to different modes of heating or heating instability caused by its nucleation and crystal growth rate, is an important influence, leading to different crystallinity, the use of fuzzy theory to predict the temperature parameter and instant heating MOF synthesis parameters can be adjusted to improve the accuracy of the system. The research system to RS-232 interface module for infrared emission control packets issued and automated control of the furnace through the infrared receiver module. This study is based on a terminal interface window of Visual Basic programming and LabView graphical diagram for control system design. Finally, this research, through a number of experiments to validate the use of fuzzy system development methods and networks, can improve the accuracy of the reaction efficiency MOF sensing and control the heating system.

  7. Metal-Organic Framework Composites%金属-有机骨架复合材料

    Institute of Scientific and Technical Information of China (English)

    付艳艳; 严秀平

    2013-01-01

    金属-有机骨架(metal-organic frameworks,MOFs)是一种新型的有机-无机杂化材料,因具有易于制备、比表面积大、孔隙度高、结构多样性及孔道表面可修饰等特点而广泛应用于气体存储、催化、传感、分离以及生物医学等领域.然而,由于MOFs机械强度低,固体呈粉末状等缺陷,使其在某些领域中的应用受到一定限制.由基体和增强体组成的MOFs复合材料因具有原组成材料的综合性能而成为融合MOFs优点并弥补其缺陷的一种新型材料.本文综述近年来MOFs复合材料的研究进展,与MOFs复合的基体或增强体包括聚合物整体、微球、纤维、金属、磁性纳米粒子、氧化石墨、碳纳米管、量子点、光子晶体以及MOFs,并对其今后的发展进行了展望.%Metal-organic frameworks ( MOFs) , a new class of organic-inorganic hybrids, have attracted tremendous attention and intriguing potential applications in gas storage, catalysis, sensing, separation and biomedical research because of their large surface area, high adsorption affinity, diverse structures and pore topologies, accessible functionalization of tunnels. However, the low mechanical stability and fine powder of MOFs obtained from traditional MOFs synthesis reactions ( e. g. solvothermal methods) are not necessarily the best configuration for the applications outlined above. As a developing research area, metal-organic framework composites ( MOF composites) can overcome the drawbacks of MOFs and give improved properties. MOF composites, composed by continuous phase ( or matrix) and dispersed phase ( or enhancesome) , combine the excellent properties of MOFs and balance the shortcomings. In this review, recent advances in MOF composites are highlighted. The continuous phase or dispersed phase combined with MOFs include polymer monoliths, beads, fibers, metal, magnetic nanoparticles (MNPs) , graphite oxide (GO) , carbon nanotubes (CNTs) , quantum dots (QDs

  8. Modelling of Hybrid Materials and Interface Defects through Homogenization Approach for the Prediction of Effective Thermal Conductivity of FRP Composites Using Finite Element Method

    Directory of Open Access Journals (Sweden)

    C. Mahesh

    2013-01-01

    Full Text Available Finite element method is effectively used to homogenize the thermal conductivity of FRP composites consisting of hybrid materials and fibre-matrix debonds at some of the fibres. The homogenized result at microlevel is used to determine the property of the layer using macromechanics principles; thereby, it is possible to minimize the computational efforts required to solve the problem as in state through only micromechanics approach. The working of the proposed procedure is verified for three different problems: (i hybrid composite having two different fibres in alternate layers, (ii fibre-matrix interface debond in alternate layers, and (iii fibre-matrix interface debond at one fibre in a group of four fibres in one unit cell. It is observed that the results are in good agreement with those obtained through pure micro-mechanics approach.

  9. Interface-directed self-assembly of gold nanoparticles and fabrication of hybrid hollow capsules by interfacial cross-linking polymerization.

    Science.gov (United States)

    Tian, Jia; Yuan, Liang; Zhang, Mingming; Zheng, Fan; Xiong, Qingqing; Zhao, Hanying

    2012-06-26

    Amphiphilic gold nanoparticles (AuNPs) were produced at liquid-liquid interface via ligand exchange between hydrophilic AuNPs and disulfide-containing polymer chains. By using oil droplets as templates, hybrid hollow capsules with AuNPs on the surfaces were obtained after interfacial cross-linking polymerization. The volume ratio of toluene to water exerts an important effect on the size of capsules. The average size of the capsules increases with the volume ratio. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were used to characterize the hollow structures. In this research, not only one-component but also multicomponent hollow capsules were prepared by copolymerization of acrylamide and hybrid AuNPs at liquid-liquid interface. Because of the improvement in hydrophilicity of the hollow capsules, the average size of multicomponent capsules is bigger than one-component ones in aqueous solution.

  10. Fabrication of highly co2 selective metal organic framework membrane using liquid phase epitaxy approach

    KAUST Repository

    Eddaoudi, Mohamed

    2016-01-28

    Embodiments include a method of making a metal organic framework membrane comprising contacting a substrate with a solution including a metal ion and contacting the substrate with a solution including an organic ligand, sufficient to form one or more layers of a metal organic framework on a substrate. Embodiments further include a defect-free metal organic framework membrane comprising MSiF6(pyz)2, wherein M is a metal, wherein the thickness of the membrane is less than 1,000 µm, and wherein the metal organic has a growth orientation along the [110] plane relative to a substrate.

  11. Insight into the construction of metal-organic polyhedra: Metal-organic cubes as a case study

    KAUST Repository

    Al Kordi, Mohamed

    2011-01-01

    Systematic studies were conducted to gain a better understanding of the metal-organic cubes (MOCs) directed assembly and their crystallization under predetermined reaction conditions, i.e. charge and size of metal ions, solvent type, counter anions, pH, and temperature. Four novel metal-organic materials are constructed via solvothermal reactions of different metal ions and 2,2′-(1H-imidazole-4,5-diyl)di-1,4,5,6-tetrahydropyrimidine, namely [Co8(C11N6H15)12]Cl 12·4H2O (1), [Ni4(C11N 6H15)4](NO3)4· 4DMF (2), {Cd(C11N6H15)(NO3) ·DMF}n (3), and [In8(C11N 6H15)12](NO3)12· 4H2O (4). In addition, syntheses and crystal structures for compounds 1(a-f), constructed under deliberately modified reaction conditions of 1, are reported. In compounds 1(a-f), the CoIII-based cationic MOCs crystallize in various packing arrangements in the presence of different counter-ions. Discrete MOCs retain their structural integrity, when crystalline solid was dissolved in water, under various pH (2.03-8.07) and temperatures (298-333 K), as confirmed by solution NMR studies. The assembly of the discrete MOC, from its basic molecular building blocks under mild reaction conditions, is demonstrated and monitored through solution NMR and UV-vis studies. © The Royal Society of Chemistry 2011.

  12. Combining a hybrid robotic system with a bain-machine interface for the rehabilitation of reaching movements: A case study with a stroke patient.

    Science.gov (United States)

    Resquin, F; Ibañez, J; Gonzalez-Vargas, J; Brunetti, F; Dimbwadyo, I; Alves, S; Carrasco, L; Torres, L; Pons, Jose Luis

    2016-08-01

    Reaching and grasping are two of the most affected functions after stroke. Hybrid rehabilitation systems combining Functional Electrical Stimulation with Robotic devices have been proposed in the literature to improve rehabilitation outcomes. In this work, we present the combined use of a hybrid robotic system with an EEG-based Brain-Machine Interface to detect the user's movement intentions to trigger the assistance. The platform has been tested in a single session with a stroke patient. The results show how the patient could successfully interact with the BMI and command the assistance of the hybrid system with low latencies. Also, the Feedback Error Learning controller implemented in this system could adjust the required FES intensity to perform the task.

  13. Lung segmentation refinement based on optimal surface finding utilizing a hybrid desktop/virtual reality user interface.

    Science.gov (United States)

    Sun, Shanhui; Sonka, Milan; Beichel, Reinhard R

    2013-01-01

    Recently, the optimal surface finding (OSF) and layered optimal graph image segmentation of multiple objects and surfaces (LOGISMOS) approaches have been reported with applications to medical image segmentation tasks. While providing high levels of performance, these approaches may locally fail in the presence of pathology or other local challenges. Due to the image data variability, finding a suitable cost function that would be applicable to all image locations may not be feasible. This paper presents a new interactive refinement approach for correcting local segmentation errors in the automated OSF-based segmentation. A hybrid desktop/virtual reality user interface was developed for efficient interaction with the segmentations utilizing state-of-the-art stereoscopic visualization technology and advanced interaction techniques. The user interface allows a natural and interactive manipulation of 3-D surfaces. The approach was evaluated on 30 test cases from 18 CT lung datasets, which showed local segmentation errors after employing an automated OSF-based lung segmentation. The performed experiments exhibited significant increase in performance in terms of mean absolute surface distance errors (2.54±0.75 mm prior to refinement vs. 1.11±0.43 mm post-refinement, p≪0.001). Speed of the interactions is one of the most important aspects leading to the acceptance or rejection of the approach by users expecting real-time interaction experience. The average algorithm computing time per refinement iteration was 150 ms, and the average total user interaction time required for reaching complete operator satisfaction was about 2 min per case. This time was mostly spent on human-controlled manipulation of the object to identify whether additional refinement was necessary and to approve the final segmentation result. The reported principle is generally applicable to segmentation problems beyond lung segmentation in CT scans as long as the underlying segmentation utilizes the

  14. Application of Improved Hybrid Interface Substructural Component Modal Synthesis Method inVibration Characteristics of Mistuned Blisk

    Institute of Scientific and Technical Information of China (English)

    BAI Bin,BAI Guangchen,; LI Chao

    2014-01-01

    The large and complex structures are divided into hundreds of thousands or millions degrees of freedom(DOF) when they are calculated which will spend a lot of time and the efficiency will be extremely low. The classical component modal synthesis method (CMSM) are used extensively, but for many structures in the engineering of high-rise buildings, aerospace systemic engineerings, marine oil platforms etc, a large amount of calculation is still needed. An improved hybrid interface substructural component modal synthesis method(HISCMSM) is proposed. The parametric model of the mistuned blisk is built by the improved HISCMSM. The double coordinating conditions of the displacement and the force are introduced to ensure the computational accuracy. Compared with the overall structure finite element model method(FEMM), the computational time is shortened by23.86%–31.56%and the modal deviation is 0.002%–0.157% which meets the requirement of the computational accuracy. It is faster 4.46%–10.57% than the classical HISCMSM. So the improved HISCMSM is better than the classical HISCMSM and the overall structure FEMM. Meanwhile, the frequency and the modal shape are researched, considering the factors including rotational speed, gas temperature and geometry size. The strong localization phenomenon of the modal shape’s the maximum displacement and the maximum stress is observed in the second frequency band and it is the most sensitive in the frequency veering. But the localization phenomenon is relatively weak in 1st and the 3d frequency band. The localization of the modal shape is more serious under the condition of the geometric dimensioning mistuned. An improved HISCMSM is proposed, the computational efficiency of the mistuned blisk can be increased observably by this method.

  15. Layered inorganic-organic hybrid with talc-like structure for cation removal at the solid/liquid interface

    Energy Technology Data Exchange (ETDEWEB)

    Badshah, Syed [Institute of Chemistry, University of Campinas, UNICAMP, P.O. Box 6154, 13084-971 Campinas, SP (Brazil); Airoldi, Claudio, E-mail: airoldi@iqm.unicamp.br [Institute of Chemistry, University of Campinas, UNICAMP, P.O. Box 6154, 13084-971 Campinas, SP (Brazil)

    2013-01-20

    Graphical abstract: A lamellar inorganic-organic hybrid with talc-like structure has been synthesized through a single sol-gel step. Highlights: Black-Right-Pointing-Pointer New silylating agent isolated from acrylamide includes basic centers attached to enlarged chain. Black-Right-Pointing-Pointer Lamellar inorganic-organic talc-like structure has been synthesized through a single sol-gel step. Black-Right-Pointing-Pointer High basal distance accommodates the pendant chain in the cavities only in inclined disposition. Black-Right-Pointing-Pointer The pendant chain sorbs spontaneously and favorable cations as demonstrated by thermodynamic data. - Abstract: A new silylating agent N-((3-(3-(trimethoxysilyl)propylthio)propanamido)methyl)acrylamide synthesized from the reaction of N,N-methylenebisacrylamide and 3-mercaptopropyltrimethoxysilane yielded layered inorganic-organic talc-like magnesium phyllosilicate through the sol-gel process. Elemental analysis data based on sulfur demonstrated incorporation of 2.70 mmol g{sup -1} of organic moiety inside the lamellar cavities and the X-ray diffraction patterns confirmed the talc-like structure with a basal distance of 2.11 nm. Infrared spectroscopy, {sup 13}C and {sup 29}Si NMR in the solid state are in agreement with the presence of organic chains covalently bonded to the inorganic lamellar framework, as also supported by the presence of T{sup n} silicon species. Nitrogen, oxygen and sulfur basic centers sorb divalent lead, copper and cobalt cations with maximum capacity of 5.30, 3.82 and 1.60 mmol g{sup -1}. The thermodynamic data for cation/basic center interactions at the solid/liquid interface were determined through calorimetric titration with exothermic enthalpy, negative Gibbs energy and positive entropy, as expected for spontaneous and favorable reaction conditions.

  16. Controlling Thermal Expansion: A Metal-Organic Frameworks Route.

    Science.gov (United States)

    Balestra, Salvador R G; Bueno-Perez, Rocio; Hamad, Said; Dubbeldam, David; Ruiz-Salvador, A Rabdel; Calero, Sofia

    2016-11-22

    Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal-organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model material, along with three molecules of similar size and known differences in terms of the nature of host-guest interactions. It has been shown that adsorbate molecules can control, in a colligative way, the thermal expansion of the solid, so that changing the adsorbate molecules induces the solid to display positive, zero, or negative thermal expansion. We analyze in depth the distortion mechanisms, beyond the ligand metal junction, to cover the ligand distortions, and the energetic and entropic effect on the thermo-structural behavior. We provide an unprecedented atomistic insight on the effect of adsorbates on the thermal expansion of MOFs as a basic tool toward controlling the thermal expansion.

  17. Recent Advances in Carbon Capture with Metal-Organic Frameworks.

    Science.gov (United States)

    Stylianou, Kyriakos C; Queen, Wendy L

    2015-01-01

    The escalating level of CO(2) in the atmosphere is one of the most critical environmental issues of our age. The carbon capture and storage from pilot test plants represents an option for reducing CO(2) emissions, however, the energy cost associated with post-combustion carbon capture process alone is ∼30% of the total energy generated by the power plant. Thus, the generation of carbon capture adsorbents with high uptake capacities, great separation performance and low cost is of paramount importance. Metal-organic frameworks are infinite networks of metal-containing nodes bridged by organic ligands through coordination bonds into porous extended structures and several reports have revealed that they are ideal candidates for the selective capture of CO(2). In this review we summarize recent advances related to the synthesis of porous MOFs and the latest strategies to enhance the CO(2) adsorption enthalpies and capacities at low-pressures, increase hydrolytic and mechanical stabilities, and improve the ease of regeneration. Although they show great promise for post-combustion carbon capture, there are still major challenges that must be overcome before they can be used for such a large-scale application.

  18. Multi-shelled Hollow Metal-Organic Frameworks.

    Science.gov (United States)

    Liu, Wenxian; Huang, Jijiang; Yang, Qiu; Wang, Shiji; Sun, Xiaoming; Zhang, Weina; Liu, Junfeng; Huo, Fengwei

    2017-05-08

    Hollow metal-organic frameworks (MOFs) are promising materials with sophisticated structures, such as multiple shells, that cannot only enhance the properties of MOFs but also endow them with new functions. Herein, we show a rational strategy to fabricate multi-shelled hollow chromium (III) terephthalate MOFs (MIL-101) with single-crystalline shells through step-by-step crystal growth and subsequent etching processes. This strategy relies on the creation of inhomogeneous MOF crystals in which the outer layer is chemically more robust than the inner layer and can be selectively etched by acetic acid. The regulation of MOF nucleation and crystallization allows the tailoring of the cavity size and shell thickness of each layer. The resultant multi-shelled hollow MIL-101 crystals show significantly enhanced catalytic activity during styrene oxidation. The insight gained from this systematic study will aid in the rational design and synthesis of other multi-shelled hollow structures and the further expansion of their applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Xenon Recovery at Room Temperature using Metal-Organic Frameworks.

    Science.gov (United States)

    Elsaidi, Sameh K; Ongari, Daniele; Xu, Wenqian; Mohamed, Mona H; Haranczyk, Maciej; Thallapally, Praveen K

    2017-08-10

    Xenon is known to be a very efficient anesthetic gas, but its cost prohibits the wider use in medical industry and other potential applications. It has been shown that Xe recovery and recycling from anesthetic gas mixtures can significantly reduce its cost as anesthetic. The current technology uses series of adsorbent columns followed by low-temperature distillation to recover Xe; this method is expensive to use in medical facilities. Herein, we propose a much simpler and more efficient system to recover and recycle Xe from exhaled anesthetic gas mixtures at room temperature using metal-organic frameworks (MOFs). Among the MOFs tested, PCN-12 exhibits unprecedented performance with high Xe capacity and Xe/O2 , Xe/N2 and Xe/CO2 selectivity at room temperature. The in situ synchrotron measurements suggest that Xe is occupies the small pockets of PCN-12 compared to unsaturated metal centers (UMCs). Computational modeling of adsorption further supports our experimental observation of Xe binding sites in PCN-12. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Increasing the Stability of Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Mathieu Bosch

    2014-01-01

    Full Text Available Metal-organic frameworks (MOFs are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapse upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.

  1. Structural versatility of Metal-organic frameworks: Synthesis and Characterization

    KAUST Repository

    Alsadun, Norah S.

    2017-05-01

    Metal-Organic Frameworks (MOFs), an emerging class of porous crystalline materials, have shown promising properties for diverse applications such as catalysis, gas storage and separation. The high degree of tunability of MOFs vs other solid materials enable the assembly of advanced materials with fascinating properties for specific applications. Nevertheless, the precise control in the construction of MOFs at the molecular level remains challenging. Particularly, the formation of pre-targeted multi-nuclear Molecular Building Block (MBB) precursors to unveil materials with targeted structural characteristics is captivating. The aim of my master project in the continuous quest of the group of Prof. Eddaoudi in exploring different synthetic pathways to control the assembly of Rare Earth (RE) based MOF. After giving a general overview about MOFs, I will discuss in this thesis the results of my work on the use of tri-topic oriented organic carboxylate building units with the aim to explore the assembly/construction of new porous RE based MOFs. In chapter 2 will discuss the assembly of 3-c linkers with RE metals was then evaluated based on symmetry and angularity of the three connected linkers. The focus of chapter 3 is cerium based MOFs and heterometallic system, based on 3-c ligands with different length and symmetry. Overall, the incompatibility of 3-c ligands with the 12-c cuo MBB did not allow to any formation of higher neuclearity (˃6), but it has resulted in affecting the connectivity of the cluster.

  2. Metal-organic frameworks for lithium ion batteries and supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang, E-mail: hdeng@whu.edu.cn

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.

  3. Synthesis and Characterization of Functionalized Metal-organic Frameworks

    Science.gov (United States)

    Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A.; Hupp, Joseph T.; Farha, Omar K.

    2014-01-01

    Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy. PMID:25225784

  4. Humidity Detection Using Metal Organic Framework Coated on QCM

    KAUST Repository

    Kosuru, Lakshmoji

    2016-06-28

    Quartz crystal microbalance (QCM) coated with poly-4-vinylpyridine (PVP) and metal organic framework HKUST-1 are investigated and compared for humidity sensing. Drop casting method is employed to coat the PVP and HKUST-1 solutions onto the surface of a quartz crystal microbalance. The resonance frequencies of these sensors with varying relative humidity (RH) from 22% RH to 69% RH are measured using impedance analysis method. The sensitivity, humidity hysteresis, response, and recovery times of these sensors are studied. The sensitivities of uncoated, PVP, and HKUST-1 coated QCM sensors are 7 Hz, 48 Hz, and 720 Hz, respectively, in the range of 22% RH–69% RH. The extraction of desorption rate and adsorption energy associated with the adsorption and desorption of water molecules on these surfaces reveals that HKUST-1 has better sensing properties than PVP and uncoated QCM sensors. In this work, the HKUST-1 coated QCM is shown to be a promising material for moisture detection.

  5. Molecular Transport in Metal Organic Framework Ma- terials

    Science.gov (United States)

    Canepa, P.; Nijem, N.; Chabal, Y. J.; Thonhauser, T.

    2013-03-01

    Metal organic frameworks (MOF) materials are a class of porous materials well suited for hydrogen storage and gas separation. While current work on MOFs focuses mostly on the adsorption properties of small molecules, their diffusion is still poorly understood. To elucidate the diffusion process, we study the diffusion of H2, CO2, and H2O in the nano-pores of MOF-74-Mg by combining ab initio simulations with infrared (IR) spectroscopy. We present computed adsorption energies and changes in the IR frequencies upon adsorption. We also discuss several diffusion mechanisms and their calculated barriers. We further verify the existence of the debated secondary binding sites for guest molecules and we discuss the role played by H2O. We find that H2O is much more likely to adsorb in the MOF than H2 and CO2, leading to a significant reduction of the adsorption capabilities of the MOF towards these target molecules, and hence resulting in limitations for practical applications. Overall, our computational findings are in very good agreement with experiment and they provide a fundamental understanding of the diffusion processes of small molecules in these nano-porous materials, with implication for the usability of MOFs in gas separation and storage applications.

  6. Infrared spectroscopy of trapped hydrogen in metal-organic-frameworks

    Science.gov (United States)

    Fitzgerald, Stephen; Allen, Kelty; Landerman, Patrick; Rowsell, Jesse

    2007-03-01

    We present a novel use of diffuse reflectance infrared spectroscopy to study the quantum dynamics of molecular hydrogen trapped within metal-organic-framework (MOF) hosts. This technique is particularly useful in the context of hydrogen storage since it provides detailed information about the intermolecular potential at the binding site. The spectra consist of quite sharp bands associated with the quantized vibrational and rotational motion of the trapped hydrogen. The vibrational bands are redshifted relative to the gas phase while the rotational sidebands contain an additional fine structure due to the orientational dependence of the binding potential. Results on MOF-5 reveal the presence of two primary binding sites. The first saturates at a loading concentration on the order of 4 H2 per Zn ion and has a binding energy of roughly 4 kJ/mole. The second has a somewhat lower binding energy. Both site produce an ortho to para conversion rate on the order of 30-50 % per hour.

  7. Large-scale screening of hypothetical metal-organic frameworks

    Science.gov (United States)

    Wilmer, Christopher E.; Leaf, Michael; Lee, Chang Yeon; Farha, Omar K.; Hauser, Brad G.; Hupp, Joseph T.; Snurr, Randall Q.

    2012-02-01

    Metal-organic frameworks (MOFs) are porous materials constructed from modular molecular building blocks, typically metal clusters and organic linkers. These can, in principle, be assembled to form an almost unlimited number of MOFs, yet materials reported to date represent only a tiny fraction of the possible combinations. Here, we demonstrate a computational approach to generate all conceivable MOFs from a given chemical library of building blocks (based on the structures of known MOFs) and rapidly screen them to find the best candidates for a specific application. From a library of 102 building blocks we generated 137,953 hypothetical MOFs and for each one calculated the pore-size distribution, surface area and methane-storage capacity. We identified over 300 MOFs with a predicted methane-storage capacity better than that of any known material, and this approach also revealed structure-property relationships. Methyl-functionalized MOFs were frequently top performers, so we selected one such promising MOF and experimentally confirmed its predicted capacity.

  8. Metal-organic framework composites: from fundamentals to applications

    Science.gov (United States)

    Li, Shaozhou; Huo, Fengwei

    2015-04-01

    Metal-organic frameworks (MOFs) are a class of crystallized porous polymeric materials consisting of metal ions or clusters linked together by organic bridging ligands. Due to their permanent porosity, rich surface chemistry and tuneable pore sizes, MOFs have emerged as one type of important porous solid and have attracted intensive interests in catalysis, gas adsorption, separation and storage over the past two decades. When compared with pure MOFs, the combination of MOFs with functional species or matrix materials not only shows enhanced properties, but also broadens the applications of MOFs in new fields, such as bio-imaging, drug delivery and electrical catalysis, owing to the interactions of the functional species/matrix with the MOF structures. Although the synthesis, chemical modification and potential applications of MOFs have been reviewed previously, there is an increasing awareness on the synthesis and applications of their composites, which have rarely been reviewed. This review aims to fill this gap and discuss the fabrication, properties, and applications of MOF composites. The remaining challenges and future opportunities in this field, in terms of processing techniques, maximizing composite properties, and prospects for applications, have also been indicated.

  9. Alkali-metal azides interacting with metal-organic frameworks.

    Science.gov (United States)

    Armata, Nerina; Cortese, Remedios; Duca, Dario; Triolo, Roberto

    2013-01-14

    Interactions between alkali-metal azides and metal-organic framework (MOF) derivatives, namely, the first and third members of the isoreticular MOF (IRMOF) family, IRMOF-1 and IRMOF-3, are studied within the density functional theory (DFT) paradigm. The investigations take into account different models of the selected IRMOFs. The mutual influence between the alkali-metal azides and the π rings or Zn centers of the involved MOF derivatives are studied by considering the interactions both of the alkali-metal cations with model aromatic centers and of the alkali-metal azides with distinct sites of differently sized models of IRMOF-1 and IRMOF-3. Several exchange and correlation functionals are employed to calculate the corresponding interaction energies. Remarkably, it is found that, with increasing alkali-metal atom size, the latter decrease for cations interacting with the π-ring systems and increase for the azides interacting with the MOF fragments. The opposite behavior is explained by stabilization effects on the azide moieties and determined by the Zn atoms, which constitute the inorganic vertices of the IRMOF species. Larger cations can, in fact, coordinate more efficiently to both the aromatic center and the azide anion, and thus stabilizing bridging arrangements of the azide between one alkali-metal and two Zn atoms in an η(2) coordination mode are more favored.

  10. Selective gas adsorption and separation in metal-organic frameworks.

    Science.gov (United States)

    Li, Jian-Rong; Kuppler, Ryan J; Zhou, Hong-Cai

    2009-05-01

    Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal-organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

  11. Unusual adsorption behavior on metal-organic frameworks.

    Science.gov (United States)

    Fairen-Jimenez, David; Seaton, Nigel A; Düren, Tina

    2010-09-21

    Metal-organic frameworks (MOFs) have shown adsorption behavior that is not observed in other microporous materials such as zeolites or activated carbons. This study used grand canonical Monte Carlo simulation to evaluate a particular form of behavior, which corresponds to the presence of unusual type V adsorption isotherms. Study of a series of MOFs in the IRMOF family, containing chemically similar linkers of different length, showed that the presence of type V adsorption depends on a fine balance between the strength of the fluid-fluid and fluid-solid interactions, which in turn is a strong function of the length of the linker and therefore the pore size. A transition from type V behavior to the more common type I behavior is observed as the temperature increases. The temperature at which this transition occurs increases, and the transition becomes more diffuse, as the length of the linker increases. This type V behavior leads to an interesting possibility in the design of MOF adsorbents for use in gas separation and gas storage applications.

  12. Separation of chemical reaction intermediates by metal-organic frameworks.

    Science.gov (United States)

    Centrone, Andrea; Santiso, Erik E; Hatton, T Alan

    2011-08-22

    HPLC columns custom-packed with metal-organic framework (MOF) materials are used for the separation of four small intermediates and byproducts found in the commercial synthesis of an important active pharmaceutical ingredient in methanol. In particular, two closely related amines can be separated in the methanol reaction medium using MOFs, but not with traditional C18 columns using an optimized aqueous mobile phase. Infrared spectroscopy, UV-vis spectroscopy, X-ray diffraction, and thermogravimetric analysis are used in combination with molecular dynamic simulations to study the separation mechanism for the best-performing MOF materials. It is found that separation with ZIF-8 is the result of an interplay between the thermodynamic driving force for solute adsorption within the framework pores and the kinetics of solute diffusion into the material pores, while the separation with Basolite F300 is achieved because of the specific interactions between the solutes and Fe(3+) sites. This work, and the exceptional ability to tailor the porous properties of MOF materials, points to prospects for using MOF materials for the continuous separation and synthesis of pharmaceutical compounds.

  13. Atomistic Simulation of Protein Encapsulation in Metal-Organic Frameworks.

    Science.gov (United States)

    Zhang, Haiyang; Lv, Yongqin; Tan, Tianwei; van der Spoel, David

    2016-01-28

    Fabrication of metal-organic frameworks (MOFs) with large apertures triggers a brand-new research area for selective encapsulation of biomolecules within MOF nanopores. The underlying inclusion mechanism is yet to be clarified however. Here we report a molecular dynamics study on the mechanism of protein encapsulation in MOFs. Evaluation for the binding of amino acid side chain analogues reveals that van der Waals interaction is the main driving force for the binding and that guest size acts as a key factor predicting protein binding with MOFs. Analysis on the conformation and thermodynamic stability of the miniprotein Trp-cage encapsulated in a series of MOFs with varying pore apertures and surface chemistries indicates that protein encapsulation can be achieved via maintaining a polar/nonpolar balance in the MOF surface through tunable modification of organic linkers and Mg-O chelating moieties. Such modifications endow MOFs with a more biocompatible confinement. This work provides guidelines for selective inclusion of biomolecules within MOFs and facilitates MOF functions as a new class of host materials and molecular chaperones.

  14. Governing metal-organic frameworks towards high stability.

    Science.gov (United States)

    Li, Na; Xu, Jian; Feng, Rui; Hu, Tong-Liang; Bu, Xian-He

    2016-06-30

    Metal-organic frameworks (MOFs) constructed with metal ions/clusters and organic ligands have emerged as an important family of porous materials for various applications. However, the stability of this class of materials is crucial for their practical applications, which might be improved by varying their chemical composition and/or structurally tuning them. To fabricate MOFs with high stability, several strategies for enhancing the stability of MOFs have been developed, in which the strength of metal-ligand bonds is especially considered: the use of highly charged cations and higher pKa ligands, and varying the chemical functionality of linkers. On the other hand, the regulation of their structural architectures is also investigated: interpenetrated frameworks, multi-walled frameworks, and self-strengthening of the frameworks. In addition, the surface modification can also improve the stability of the materials. In this review, we introduce and summarize these strategies from the viewpoint of structural tuning and component choosing, providing useful instructions for the further design and synthesis of MOFs with high-level stability.

  15. Large-scale screening of hypothetical metal-organic frameworks.

    Science.gov (United States)

    Wilmer, Christopher E; Leaf, Michael; Lee, Chang Yeon; Farha, Omar K; Hauser, Brad G; Hupp, Joseph T; Snurr, Randall Q

    2011-11-06

    Metal-organic frameworks (MOFs) are porous materials constructed from modular molecular building blocks, typically metal clusters and organic linkers. These can, in principle, be assembled to form an almost unlimited number of MOFs, yet materials reported to date represent only a tiny fraction of the possible combinations. Here, we demonstrate a computational approach to generate all conceivable MOFs from a given chemical library of building blocks (based on the structures of known MOFs) and rapidly screen them to find the best candidates for a specific application. From a library of 102 building blocks we generated 137,953 hypothetical MOFs and for each one calculated the pore-size distribution, surface area and methane-storage capacity. We identified over 300 MOFs with a predicted methane-storage capacity better than that of any known material, and this approach also revealed structure-property relationships. Methyl-functionalized MOFs were frequently top performers, so we selected one such promising MOF and experimentally confirmed its predicted capacity.

  16. Green methods for preparing highly co2 selective and h2s tolerant metal organic frameworks

    KAUST Repository

    Eddaoudi, Mohamed

    2015-12-23

    A green route for preparing a metal organic framework include mixing metal precursor with a ligand precursor to form a solvent-free mixture; adding droplets of water to the mixture; heating the mixture at a first temperature after adding the water; and isolating the metal organic framework material including the metal and the ligand.

  17. Metal-organic frameworks for adsorption and separation of noble gases

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Greathouse, Jeffery A.; Staiger, Chad

    2017-05-30

    A method including exposing a gas mixture comprising a noble gas to a metal organic framework (MOF), including an organic electron donor and an adsorbent bed operable to adsorb a noble gas from a mixture of gases, the adsorbent bed including a metal organic framework (MOF) including an organic electron donor.

  18. Metal organic frameworks for the catalytic detoxification of chemical warfare nerve agents

    Energy Technology Data Exchange (ETDEWEB)

    Hupp, Joseph T.; Farha, Omar K.; Katz, Michael J.; Mondloch, Joseph E.

    2017-04-18

    A method of using a metal organic framework (MOF) comprising a metal ion and an at least bidendate organic ligand to catalytically detoxify chemical warfare nerve agents including exposing the metal-organic-framework (MOF) to the chemical warfare nerve agent and catalytically decomposing the nerve agent with the MOF.

  19. Redox-Active Metal-Organic Composites for Highly Selective Oxygen Separation Applications

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Wen [Physical & Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Banerjee, Debasis [Physical & Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Liu, Jian [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Schaef, Herbert T. [Physical & Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Crum, Jarrod V. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Fernandez, Carlos A. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Kukkadapu, Ravi K. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Nie, Zimin [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Nune, Satish K. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Motkuri, Radha K. [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Chapman, Karena W. [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA; Hayes, James C. [National Security Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Silvers, Kurt L. [National Security Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; Krishna, Rajamani [Van' t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904 1098 XH Amsterdam The Netherlands; McGrail, B. Peter [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Liu, Jun [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA; Thallapally, Praveen K. [Physical & Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA

    2016-03-08

    A redox-active metal-organic composite material shows improved and selective O-2 adsorption over N-2 with respect to individual components (MIL-101 and ferrocene). The O-2 sensitivity of the composite material arises due to the formation of maghemite nanoparticles with the pore of the metal-organic framework material.

  20. Molecular Level Characterization of the Structure and Interactions in Peptide-Functionalized Metal-Organic Frameworks.

    Science.gov (United States)

    Todorova, Tanya K; Rozanska, Xavier; Gervais, Christel; Legrand, Alexandre; Ho, Linh N; Berruyer, Pierrick; Lesage, Anne; Emsley, Lyndon; Farrusseng, David; Canivet, Jérôme; Mellot-Draznieks, Caroline

    2016-11-07

    We use density functional theory, newly parameterized molecular dynamics simulations, and last generation (15) N dynamic nuclear polarization surface enhanced solid-state NMR spectroscopy (DNP SENS) to understand graft-host interactions and effects imposed by the metal-organic framework (MOF) host on peptide conformations in a peptide-functionalized MOF. Focusing on two grafts typified by MIL-68-proline (-Pro) and MIL-68-glycine-proline (-Gly-Pro), we identified the most likely peptide conformations adopted in the functionalized hybrid frameworks. We found that hydrogen bond interactions between the graft and the surface hydroxyl groups of the MOF are essential in determining the peptides conformation(s). DNP SENS methodology shows unprecedented signal enhancements when applied to these peptide-functionalized MOFs. The calculated chemical shifts of selected MIL-68-NH-Pro and MIL-68-NH-Gly-Pro conformations are in a good agreement with the experimentally obtained (15) N NMR signals. The study shows that the conformations of peptides when grafted in a MOF host are unlikely to be freely distributed, and conformational selection is directed by strong host-guest interactions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Modeling Ferro- and Antiferromagnetic Interactions in Metal-Organic Coordination Networks

    CERN Document Server

    Faraggi, Marisa N; Stepanow, Sebastian; Tseng, Tzu-Chun; Abdurakhmanova, Nasiba; Kley, Christopher Seiji; Langner, Alexander; Sessi, Violetta; Kern, Klaus; Arnau, Andres

    2014-01-01

    Magnetization curves of two rectangular metal-organic coordination networks formed by the organic ligand TCNQ (7,7,8,8-tetracyanoquinodimethane) and two different (Mn and Ni) 3d transition metal atoms [M(3d)] show marked differences that are explained using first principles density functional theory and model calculations. We find that the existence of a weakly dispersive hybrid band with M(3d) and TCNQ character crossing the Fermi level is determinant for the appearance of ferromagnetic coupling between metal centers, as it is the case of the metallic system Ni-TCNQ but not of the insulating system Mn-TCNQ. The spin magnetic moment localized at the Ni atoms induces a significant spin polarization in the organic molecule; the corresponding spin density being delocalized along the whole system. The exchange interaction between localized spins at Ni centers and the itinerant spin density is ferromagnetic. Based on two different model Hamiltonians, we estimate the strength of exchange couplings between magnetic ...

  2. Porous metal-organic-framework nanoscale carriers as a potential platform for drug delivery and imaging

    Science.gov (United States)

    Horcajada, Patricia; Chalati, Tamim; Serre, Christian; Gillet, Brigitte; Sebrie, Catherine; Baati, Tarek; Eubank, Jarrod F.; Heurtaux, Daniela; Clayette, Pascal; Kreuz, Christine; Chang, Jong-San; Hwang, Young Kyu; Marsaud, Veronique; Bories, Phuong-Nhi; Cynober, Luc; Gil, Sophie; Férey, Gérard; Couvreur, Patrick; Gref, Ruxandra

    2010-02-01

    In the domain of health, one important challenge is the efficient delivery of drugs in the body using non-toxic nanocarriers. Most of the existing carrier materials show poor drug loading (usually less than 5wt% of the transported drug versus the carrier material) and/or rapid release of the proportion of the drug that is simply adsorbed (or anchored) at the external surface of the nanocarrier. In this context, porous hybrid solids, with the ability to tune their structures and porosities for better drug interactions and high loadings, are well suited to serve as nanocarriers for delivery and imaging applications. Here we show that specific non-toxic porous iron(III)-based metal-organic frameworks with engineered cores and surfaces, as well as imaging properties, function as superior nanocarriers for efficient controlled delivery of challenging antitumoural and retroviral drugs (that is, busulfan, azidothymidine triphosphate, doxorubicin or cidofovir) against cancer and AIDS. In addition to their high loadings, they also potentially associate therapeutics and diagnostics, thus opening the way for theranostics, or personalized patient treatments.

  3. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    Science.gov (United States)

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

    2015-09-01

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm-2. Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

  4. Water-Based Assembly of Polymer-Metal Organic Framework (MOF) Functional Coatings

    Energy Technology Data Exchange (ETDEWEB)

    De, Souvik [Artie McFerrin Department of Chemical Engineering, Texas A& M University, 77843-3122 TAMU College Station TX 77843-3122 USA; Nandasiri, Manjula I. [Environmental Molecular Sciences Laboratory (EMSL), Pacific Northwest National Laboratory, Richland WA 99352 USA; Schaef, Herbert T. [Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA; McGrail, Benard Peter [Energy & Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99352 USA; Nune, Satish K. [Energy & Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99352 USA; Lutkenhaus, Jodie L. [Artie McFerrin Department of Chemical Engineering, Texas A& M University, 77843-3122 TAMU College Station TX 77843-3122 USA; Department of Materials Science & Engineering, Texas A& M University, 3122 TAMU College Station TX 77843-3122 USA

    2016-12-27

    Metal organic frameworks (MOFs) have gained tremendous attention for their porosity, size selectivity, and structural diversity. There is a need for MOF-based coatings, particularly in applications such as separations, electronics and energy; yet forming thin, functional, conformal coatings is prohibitive because MOFs exist as a powder. Layer-by- layer assembly, a versatile thin film coating approach, offers a unique solution to this problem, but this approach requires MOFs that are water-dispersible and bear a surface charge. Here, we address these issues by examining water-based dispersions of MIL-101(Cr) that facilitate the formation of robust polymer-MOF hybrid coatings. Specifically, the substrate to be coated is alternately exposed to an aqueous solution of poly(styrene sulfonate) and dispersion MIL-101(Cr), yielding linear film growth and coatings with a MOF content as high as 77 wt%.This approach is surface-agnostic, in which the coating is successfully applied to silicon, glass, flexible plastic, and even cotton fabric, conformally coating individual fibers. In contrast, prior attempts at forming MOF-coatings were severely limited to a handful of surfaces, required harsh chemical treatment, and were not conformal. The approach presented here unambiguously confirms that MOFs can be conformally coated onto complex and unusual surfaces, opening the door for a wide variety of applications.

  5. Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Best, James P., E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu; Michler, Johann; Maeder, Xavier [Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Mechanics of Materials and Nanostructures, Feuerwerkerstrasse 39, CH-3602 Thun (Switzerland); Liu, Jianxi; Wang, Zhengbang; Tsotsalas, Manuel; Liu, Jinxuan; Gliemann, Hartmut; Weidler, Peter G.; Redel, Engelbert, E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu; Wöll, Christof, E-mail: james.best@empa.ch, E-mail: engelbert.redel@kit.edu, E-mail: christof.woell@kit.edu [Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Röse, Silvana [Preparative Macromolecular Chemistry, Institute for Chemical Technology and Polymer Chemistry (ICTP), Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76128 Karlsruhe (Germany); Institute for Biological Interfaces (IBG), Karlsruhe Institute of Technology (KIT), Herrmann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Oberst, Vanessa [Institute of Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany); Walheim, Stefan [Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

    2015-09-07

    Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (E{sub ITO} ≈ 96.7 GPa, E{sub HKUST−1} ≈ 22.0 GPa). For indentation of multilayer stacks, it was found that as the layer thicknesses were increased, while holding the relative thickness of ITO and HKUST-1 constant, the resistance to deformation was significantly altered. Such an observation is likely due to small, albeit significant, changes in film texture, interfacial roughness, size effects, and controlling deformation mechanism as a result of increasing material deposition during processing. Such effects may have consequences regarding the rational mechanical design and utilization of MOF-based hybrid thin-film devices.

  6. Functionalization of plasmonic metamaterials utilizing metal-organic framework thin films

    Science.gov (United States)

    Jakšić, Zoran; Popović, Zora; Djerdj, Igor; Jaćimović, Željko K.; Radulović, Katarina

    2012-05-01

    We considered theoretically and experimentally a strategy to functionalize plasmonic metamaterials utilizing either a metal-organic framework (MOF) or inorganic-organic hybrids for application in adsorption-based gas sensing. MOFs are one-dimensional (1D), 2D or 3D crystalline compounds that simultaneously contain metal ions or ion clusters and organic moieties, forming thus porous networks ensuring an increased effective surface for adsorption. Metamaterials can enhance plasmonic sensor performance through metal-dielectric nanocompositing that simultaneously tailors the electromagnetic response and boosts adsorption of the targeted analyte through the use of nanopores. To perform functionalization, it is necessary to integrate one or several layers of MOF nanocrystals with the metamaterial scaffold. The simplest approach is to use dip or drop coating or the layer-by-layer technique. The scaffolds that we considered included freestanding, ultrathin membranes and sandwich structures with nanoaperture arrays. For this investigation, we used a non-aqueous sol-gel route to synthesize vanadium oxyanthracene carboxylate, a novel material with 1D crystal structure. Our results suggest that preferential concentration of analyte within the MOF pores may ensure improved adsorption and thus sensor sensitivity enhancement. Also, one may increase selectivity by introducing nanoparticle fillers or by utilizing other functionalizing materials such as catalysts or ligands.

  7. A fine-tuned Metal-Organic Framework for Autonomous Indoor Moisture Control .

    KAUST Repository

    Abdul Halim, Racha Ghassan

    2017-06-29

    Conventional adsorbents, namely zeolites and silica gel, are often used to control humidity by adsorbing water; however, adsorbents capable of dual functionality of humidification and dehumidification, offering the desired control of the moisture level at room temperature, has yet to be explored. Here we report Y-shp-MOF-5, a hybrid microporous highly-connected Rare-Earth based metal-organic framework (MOF), with dual functionality for moisture control within the recommended range of relative humidity (45% to 65% RH) set by the American Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASHRAE). Y-shp-MOF-5 exhibits exceptional structural integrity, robustness and unique humidity-control performance as confirmed by the large number (thousand) of conducted water vapor adsorption-desorption cycles. The retained structural integrity and the mechanism of water sorption were corroborated using in situ single crystal X-ray diffraction (SCXRD) studies. The resultant working water uptake of 0.45 g.g-1 is solely regulated by a simple adjustment of the relative humidity, positioning this hydrolytically stable MOF as a prospective adsorbent for humidity control in confined spaces such as space shuttles, aircraft cabins and air-conditioned buildings.

  8. Metal-Organic Frameworks (MOFs) as Sandwich Coating Cushion for Silicon Anode in Lithium Ion Batteries.

    Science.gov (United States)

    Han, Yuzhen; Qi, Pengfei; Zhou, Junwen; Feng, Xiao; Li, Siwu; Fu, Xiaotao; Zhao, Jingshu; Yu, Danni; Wang, Bo

    2015-12-09

    A novel metal-organic framework (MOF) sandwich coating method (denoted as MOF-SC) is developed for hybrid Li ion battery electrode preparation, in which the MOF films are casted on the surface of a silicon layer and sandwiched between the active silicon and the separator. The obtained electrodes show improved cycling performance. The areal capacity of the cheap and readily available microsized Si treated with MOF-SC can reach 1700 μAh cm(-2) at 265 μA cm(-2) and maintain at 850 μAh cm(-2) after 50 cycles. Beyond the above, the commercial nanosized Si treated by MOF-SC also shows greatly enhanced areal capacity and outstanding cycle stability, 600 μAh cm(-2) for 100 cycles without any apparent fading. By virtue of the novel structure prepared by the MOFs, this new MOF-SC structure serves as an efficient protection cushion for the drastic volume change of silicon during charge/discharge cycles. Furthermore, this MOF layer, with large pore volume and high surface area, can adsorb electrolyte and allow faster diffusion of Li(+) as evidenced by decreased impedance and improved rate performance.

  9. Complex Nanostructures from Materials based on Metal-Organic Frameworks for Electrochemical Energy Storage and Conversion.

    Science.gov (United States)

    Guan, Bu Yuan; Yu, Xin Yao; Wu, Hao Bin; Lou, Xiong Wen David

    2017-09-27

    Metal-organic frameworks (MOFs) have drawn tremendous attention because of their abundant diversity in structure and composition. Recently, there has been growing research interest in deriving advanced nanomaterials with complex architectures and tailored chemical compositions from MOF-based precursors for electrochemical energy storage and conversion. Here, a comprehensive overview of the synthesis and energy-related applications of complex nanostructures derived from MOF-based precursors is provided. After a brief summary of synthetic methods of MOF-based templates and their conversion to desirable nanostructures, delicate designs and preparation of complex architectures from MOFs or their composites are described in detail, including porous structures, single-shelled hollow structures, and multishelled hollow structures, as well as other unusual complex structures. Afterward, their applications are discussed as electrode materials or catalysts for lithium-ion batteries, hybrid supercapacitors, water-splitting devices, and fuel cells. Lastly, the research challenges and possible development directions of complex nanostructures derived from MOF-based-templates for electrochemical energy storage and conversion applications are outlined. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. A Fine-Tuned Metal-Organic Framework for Autonomous Indoor Moisture Control.

    Science.gov (United States)

    AbdulHalim, Rasha G; Bhatt, Prashant M; Belmabkhout, Youssef; Shkurenko, Aleksander; Adil, Karim; Barbour, Leonard J; Eddaoudi, Mohamed

    2017-08-09

    Conventional adsorbents, namely zeolites and silica gel, are often used to control humidity by adsorbing water; however, adsorbents capable of the dual functionality of humidification and dehumidification, offering the desired control of the moisture level at room temperature, have yet to be explored. Here we report Y-shp-MOF-5, a hybrid microporous highly connected rare-earth-based metal-organic framework (MOF), with dual functionality for moisture control within the recommended range of relative humidity (45%-65% RH) set by the American Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASHRAE). Y-shp-MOF-5 exhibits exceptional structural integrity, robustness, and unique humidity-control performance, as confirmed by the large number (thousand) of conducted water vapor adsorption-desorption cycles. The retained structural integrity and the mechanism of water sorption were corroborated using in situ single-crystal X-ray diffraction (SCXRD) studies. The resultant working water uptake of 0.45 g·g(-1) is solely regulated by a simple adjustment of the relative humidity, positioning this hydrolytically stable MOF as a prospective adsorbent for humidity control in confined spaces, such as space shuttles, aircraft cabins, and air-conditioned buildings.

  11. Chemical Reactions Catalyzed by Metalloporphyrin-Based Metal-Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Kelly Aparecida Dias de Freitas Castro

    2013-06-01

    Full Text Available The synthetic versatility and the potential application of metalloporphyrins (MP in different fields have aroused researchers’ interest in studying these complexes, in an attempt to mimic biological systems such as cytochrome P-450. Over the last 40 years, synthetic MPs have been mainly used as catalysts for homogeneous or heterogeneous chemical reactions. To employ them in heterogeneous catalysis, chemists have prepared new MP-based solids by immobilizing MP onto rigid inorganic supports, a strategy that affords hybrid inorganic-organic materials. More recently, materials obtained by supramolecular assembly processes and containing MPs as building blocks have been applied in a variety of areas, like gas storage, photonic devices, separation, molecular sensing, magnets, and heterogeneous catalysis, among others. These coordination polymers, known as metal-organic frameworks (MOFs, contain organic ligands or complexes connected by metal ions or clusters, which give rise to a 1-, 2- or 3-D network. These kinds of materials presents large surface areas, Brønsted or redox sites, and high porosity, all of which are desirable features in catalysts with potential use in heterogeneous phases. Building MOFs based on MP is a good way to obtain solid catalysts that offer the advantages of bioinspired systems and zeolitic materials. In this mini review, we will adopt a historical approach to present the most relevant MP-based MOFs applicable to catalytic reactions such as oxidation, reduction, insertion of functional groups, and exchange of organic functions.

  12. Chemical reactions catalyzed by metalloporphyrin-based metal-organic frameworks.

    Science.gov (United States)

    Nakagaki, Shirley; Ferreira, Gabriel Kaetan Baio; Ucoski, Geani Maria; Dias de Freitas Castro, Kelly Aparecida

    2013-06-21

    The synthetic versatility and the potential application of metalloporphyrins (MP) in different fields have aroused researchers' interest in studying these complexes, in an attempt to mimic biological systems such as cytochrome P-450. Over the last 40 years, synthetic MPs have been mainly used as catalysts for homogeneous or heterogeneous chemical reactions. To employ them in heterogeneous catalysis, chemists have prepared new MP-based solids by immobilizing MP onto rigid inorganic supports, a strategy that affords hybrid inorganic-organic materials. More recently, materials obtained by supramolecular assembly processes and containing MPs as building blocks have been applied in a variety of areas, like gas storage, photonic devices, separation, molecular sensing, magnets, and heterogeneous catalysis, among others. These coordination polymers, known as metal-organic frameworks (MOFs), contain organic ligands or complexes connected by metal ions or clusters, which give rise to a 1-, 2- or 3-D network. These kinds of materials presents large surface areas, Brønsted or redox sites, and high porosity, all of which are desirable features in catalysts with potential use in heterogeneous phases. Building MOFs based on MP is a good way to obtain solid catalysts that offer the advantages of bioinspired systems and zeolitic materials. In this mini review, we will adopt a historical approach to present the most relevant MP-based MOFs applicable to catalytic reactions such as oxidation, reduction, insertion of functional groups, and exchange of organic functions.

  13. Automatic In-Syringe Dispersive Microsolid Phase Extraction Using Magnetic Metal-Organic Frameworks.

    Science.gov (United States)

    Maya, Fernando; Palomino Cabello, Carlos; Estela, Jose Manuel; Cerdà, Víctor; Turnes Palomino, Gemma

    2015-08-04

    A novel automatic strategy for the use of micro- and nanomaterials as sorbents for dispersive microsolid phase extraction (D-μ-SPE) based on the lab-in-syringe concept is reported. Using the developed technique, the implementation of magnetic metal-organic framework (MOF) materials for automatic solid-phase extraction has been achieved for the first time. A hybrid material based on submicrometric MOF crystals containing Fe3O4 nanoparticles was prepared and retained in the surface of a miniature magnetic bar. The magnetic bar was placed inside the syringe of an automatic bidirectional syringe pump, enabling dispersion and subsequent magnetic retrieval of the MOF hybrid material by automatic activation/deactivation of magnetic stirring. Using malachite green (MG) as a model adsorption analyte, a limit of detection of 0.012 mg/L and a linear working range of 0.04-2 mg/L were obtained for a sample volume equal to the syringe volume (5 mL). MG preconcentration was linear up to a volume of 40 mL, obtaining an enrichment factor of 120. The analysis throughput is 18 h(-1), and up to 3000 extractions/g of material can be performed. Recoveries ranging between 95 and 107% were obtained for the analysis of MG in different types of water and trout fish samples. The developed automatic D-μ-SPE technique is a safe alternative for the use of small-sized materials for sample preparation and is readily implementable to other magnetic materials independent of their size and shape and can be easily hyphenated to the majority of detectors and separation techniques.

  14. Functionalized Metal-organic Frameworks for Applications in Gas Storage and Catalysis

    Science.gov (United States)

    Dau, Phuong Viet

    Metal-organic frameworks (MOFs) are 3-dimensional (3D) inorganic-organic hybrid materials. Due to their hybrid structures, MOFs have been increasingly become attractive materials for energy related applications. In recent years, many methods have been investigated and utilized to functionalize MOFs with a variety of chemical groups to enhance its properties. Among these methods, prefunctionalization and postsynthetic modification methods (PSM) have been proven to be versatile and accessible pathways to incorporate functional groups into MOFs. In this dissertation, the use of prefunctionalization and PSM methods to decorate MOFs with functionalities, and an overview of functionalized MOFs for applications in gas storage and catalysis will be highlighted and investigated. In the first part of the dissertation, a series of free phenylpyridine functionalized MOFs are synthesized and characterized. These MOFs are further decorated with Ir(I) and Rh(I) via cyclometalation reactions using PSM method. Amazingly, a selective PSM on an interpenetrated MOF is unprecedentedly observed. The selective outcome of the PSM is the result of the spatial difference between of chemically modifiable sites within the interpenetrated framework. In the second haft of this dissertation, Ir(I)phenylpyrdine functionalized MOFs are showed to be effective, stable, and reusable heterogeneous catalysts for allylic N-alkylation of amines. Furthermore, the use of prefunctionalization and PSM methods are utilized for the rational synthesis of a bifunctional, site-isolated MOF that has both organocatalytic -NH2 and organometallic Ir(I)phenylpyridine. The bifunctional MOF is further investigated as a tandem catalyst for one-pot condensation and alkylation reactions. Lastly, the synthesis of the first pair of isomeric MOFs is realized via prefunctionalization and PSM methods. More importantly, these cubic isoreticular MOFs with disordered ordered phenyl amide substituents displayed drastic differences

  15. Theoretical Discovery of a Superconducting Two-Dimensional Metal-Organic Framework.

    Science.gov (United States)

    Zhang, Xiaoming; Zhou, Yinong; Cui, Bin; Zhao, Mingwen; Liu, Feng

    2017-09-15

    Superconductivity is a fascinating quantum phenomenon characterized by zero electrical resistance and the Meissner effect. To date, several distinct families of superconductors (SCs) have been discovered. These include three-dimensional (3D) bulk SCs in both inorganic and organic materials as well as two-dimensional (2D) thin film SCs but only in inorganic materials. Here we predict superconductivity in 2D and 3D organic metal-organic frameworks by using first-principles calculations. We show that the highly conductive and recently synthesized Cu-benzenehexathial (BHT) is a Bardeen-Cooper-Schrieffer SC. Remarkably, the monolayer Cu-BHT has a critical temperature (Tc) of 4.43 K, while Tc of bulk Cu-BHT is 1.58 K. Different from the enhanced Tc in 2D inorganic SCs which is induced by interfacial effects, the Tc enhancement in this 2D organic SC is revealed to be the out-of-plane soft-mode vibrations, analogous to surface mode enhancement originally proposed by Ginzburg. Our findings not only shed new light on better understanding 2D superconductivity but also open a new direction to search for SCs by interface engineering with organic materials.

  16. Synthesis of metal-organic framework films by pore diffusion method

    Science.gov (United States)

    Murayama, Naohiro; Nishimura, Yuki; Kajiro, Hiroshi; Kishida, Satoru; Kinoshita, Kentaro; Tottori Univ Team; Nippon Steel; Sumitomo Metal Co. Collaboration; Tottori Integrated Frontier Resaerch Center (Tifrec) Collaboration; Tottori University Electronic Display Resaerch Center (Tedrec) Collaboration

    Metal-organic frameworks (MOFs) presents high controllability in designing the nano-scale pore, and this enable molecular storages, catalysts, gas sensors, gas separation membranes, and electronic devices for next-generation. Therefore, a simple method for film synthesis of MOFs compared with conventional methods [1] is strongly required. In this paper, we provide pore diffusion method, in which a substrate containing constituent metals of MOF is inserted in solution that includes only linker molecules of MOF. As a result, 2D growth of MOF was effectively enhanced, and the formation of flat and dense MOF films was attained. The growth time, t, dependence of film thickness, d, can be expressed by the relation of d = Aln(t + 1) + B, where A and B are constants. It means that ionized coppers diffuse through the pores of MOFs and the synthesis reaction proceeds at the MOF/solvent interface. We demonstrated the fabrication of a HKUST-1/Cu-TPA hetero structure by synthesizing a Cu-TPA film continuously after the growth of a HKUST-1 film on the CuOx substrate.

  17. 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.

  18. Self-assembly of one-dimensional metal-organic nanoarchitectures on a surface

    Science.gov (United States)

    Capsoni, Martina; Schiffrin, Agustin; Shaw, Adam; Burke, Sarah

    2014-03-01

    Supramolecular chemistry holds promise for designing low-dimensional nanostructures with predefined functionalities. In particular, the interface between metal-organic complexes and surfaces is relevant in applications such as photovoltaics, photocatalysis, molecular electronics, etc. The structural, chemical and electronic properties of these systems can be dramatically altered by the interaction with the underlying surface. It is therefore of great relevance to achieve morphological control of functional nano-assemblies on a substrate at the single molecule and atom level. Here, we investigate the in situ coordination of bisterpyridine molecules with transition metal adatoms on Ag(111), by means of low-temperature scanning tunneling microscopy. The bare ligand adsorbs following specific orientations with respect to the substrate atomic lattice. Ordered supramolecular domains emerge via parallel adjacent non-covalent binding of the molecules. Coordination between deposited iron adatoms and terpyridine ligands is activated at room temperature, likely mediated by an intramolecular conformational change of the pyridine groups. The resulting self-assembled one-dimensional nanostructures are described.

  19. Investigation of metal hydride nanoparticles templated in metal organic frameworks.

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, Benjamin W.; Herberg, Julie L. (Lawrence Livermore National Laboratory, Livermore, CA); Highley, Aaron M.; Grossman, Jeffrey (MIT, Cambridge, MA); Wagner, Lucas (MIT, Cambridge, MA); Bhakta, Raghu; Peaslee, D. (University of Missouri, St. Louis, MO); Allendorf, Mark D.; Liu, X. (University of Missouri, St. Louis, MO); Behrens, Richard, Jr.; Majzoub, Eric H. (University of Missouri, St. Louis, MO)

    2010-11-01

    Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorption kinetics and limited reversibility. One method for enhancing reaction kinetics is to reduce the size of the metal hydrides to nano scale. This method exploits the short diffusion distances and constrained environment that exist in nanoscale hydride materials. In order to reduce the particle size of metal hydrides, mechanical ball milling is widely used. However, microscopic mechanisms responsible for the changes in kinetics resulting from ball milling are still being investigated. The objective of this work is to use metal organic frameworks (MOFs) as templates for the synthesis of nano-scale NaAlH4 particles, to measure the H2 desorption kinetics and thermodynamics, and to determine quantitative differences from corresponding bulk properties. Metal-organic frameworks (MOFs) offer an attractive alternative to traditional scaffolds because their ordered crystalline lattice provides a highly controlled and understandable environment. The present work demonstrates that MOFs are stable hosts for metal hydrides and their reactive precursors and that they can be used as templates to form metal hydride nanoclusters on the scale of their pores (1-2 nm). We find that using the MOF HKUST-1 as template, NaAlH4 nanoclusters as small as 8 formula units can be synthesized inside the pores. A detailed picture of

  20. Toxic effect of zinc nanoscale metal-organic frameworks on rat pheochromocytoma (PC12) cells in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Fei, E-mail: paper_mail@126.com [Department of Pharmacy, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Yang, Baochun; Cai, Jing [Department of Pharmacy, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Jiang, Yaodong [Department of Urology, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Xu, Jun [Department of Health Economy Administration, Nanfang Hospital, Southern Medical University, Guangzhou 510515 (China); Wang, Shan [Department of Pharmacy, Winthrop University Hospital, Mineola, NY 11501 (United States)

    2014-04-01

    Highlights: • Metal-organic frameworks (MOFs) represent a newborn family of hybrid materials. • MOFs have already shown promise in a number of biological applications. • The biological applications of MOFs raise concerns for potential cytotoxicity. • Substantial information about MOF's neurotoxicity is still quite scarce. • This study reveals for the first time the interaction of MOFs with neural cells. - Abstract: Metal-organic frameworks (MOFs) possess unique properties desirable for delivery of drugs and gaseous therapeutics, but their uncharacterized interactions with cells raise increasing concerns of their safety in such biomedical applications. We evaluated the adverse effects of zinc nanoscale MOFs on the cell morphology, cytoskeleton, cell viability and expression of neurotrophin signaling pathway-associated GAP-43 protein in rat pheochromocytoma PC12 cells. At the concentration of 25 μg/ml, zinc MOFs did not significantly affect morphology, viability and membrane integrity of the cells. But at higher concentrations (over 100 μg/ml), MOFs exhibited a time- and concentration-dependent cytotoxicity, indicating their entry into the cells via endocytosis where they release Zn{sup 2+} into the cytosol to cause increased intracellular concentration of Zn{sup 2+}. We demonstrated that the toxicity of MOFs was associated with a disrupted cellular zinc homeostasis and down-regulation of GAP-43 protein, which might be the underlying mechanism for the improved differentiation in PC12 cells. These findings highlight the importance of cytotoxic evaluation of the MOFs before their biomedical application.

  1. Flue-gas and direct-air capture of CO2 by porous metal-organic materials.

    Science.gov (United States)

    Madden, David G; Scott, Hayley S; Kumar, Amrit; Chen, Kai-Jie; Sanii, Rana; Bajpai, Alankriti; Lusi, Matteo; Curtin, Teresa; Perry, John J; Zaworotko, Michael J

    2017-01-13

    Sequestration of CO2, either from gas mixtures or directly from air (direct air capture), is a technological goal important to large-scale industrial processes such as gas purification and the mitigation of carbon emissions. Previously, we investigated five porous materials, three porous metal-organic materials (MOMs), a benchmark inorganic material, ZEOLITE 13X: and a chemisorbent, TEPA-SBA-15: , for their ability to adsorb CO2 directly from air and from simulated flue-gas. In this contribution, a further 10 physisorbent materials that exhibit strong interactions with CO2 have been evaluated by temperature-programmed desorption for their potential utility in carbon capture applications: four hybrid ultramicroporous materials, SIFSIX-3-CU: , DICRO-3-NI-I: , SIFSIX-2-CU-I: and MOOFOUR-1-NI: ; five microporous MOMs, DMOF-1: , ZIF-8: , MIL-101: , UIO-66: and UIO-66-NH2: ; an ultramicroporous MOM, NI-4-PYC: The performance of these MOMs was found to be negatively impacted by moisture. Overall, we demonstrate that the incorporation of strong electrostatics from inorganic moieties combined with ultramicropores offers improved CO2 capture performance from even moist gas mixtures but not enough to compete with chemisorbents.This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  2. Flue-gas and direct-air capture of CO2 by porous metal-organic materials

    Science.gov (United States)

    Madden, David G.; Scott, Hayley S.; Kumar, Amrit; Chen, Kai-Jie; Sanii, Rana; Bajpai, Alankriti; Lusi, Matteo; Curtin, Teresa; Perry, John J.; Zaworotko, Michael J.

    2017-01-01

    Sequestration of CO2, either from gas mixtures or directly from air (direct air capture), is a technological goal important to large-scale industrial processes such as gas purification and the mitigation of carbon emissions. Previously, we investigated five porous materials, three porous metal-organic materials (MOMs), a benchmark inorganic material, Zeolite 13X and a chemisorbent, TEPA-SBA-15, for their ability to adsorb CO2 directly from air and from simulated flue-gas. In this contribution, a further 10 physisorbent materials that exhibit strong interactions with CO2 have been evaluated by temperature-programmed desorption for their potential utility in carbon capture applications: four hybrid ultramicroporous materials, SIFSIX-3-Cu, DICRO-3-Ni-i, SIFSIX-2-Cu-i and MOOFOUR-1-Ni; five microporous MOMs, DMOF-1, ZIF-8, MIL-101, UiO-66 and UiO-66-NH2; an ultramicroporous MOM, Ni-4-PyC. The performance of these MOMs was found to be negatively impacted by moisture. Overall, we demonstrate that the incorporation of strong electrostatics from inorganic moieties combined with ultramicropores offers improved CO2 capture performance from even moist gas mixtures but not enough to compete with chemisorbents. This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  3. Metal-organic frameworks as selectivity regulators for hydrogenation reactions

    Science.gov (United States)

    Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

    2016-11-01

    Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design

  4. Anisotropic thermal expansion in a metal-organic framework.

    Science.gov (United States)

    Madsen, Solveig Røgild; Lock, Nina; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2014-06-01

    Ionothermal reaction between Mn(II)(acetate)2·4H2O and 1,3,5-benzenetricarboxylic acid (H3BTC) in either of the two ionic liquids 1-ethyl-3-methylimidazolium bromide (EMIMBr) and 1-ethyl-3-methylimidazolium tosylate (EMIMOTs) resulted in the formation of the new metal-organic framework (MOF) EMIM[Mn(II)BTC] (BTC = 1,3,5-benzenetricarboxylate). The compound crystallizes in the orthorhombic space group Pbca with unit-cell parameters of a = 14.66658 (12), b = 12.39497 (9), c = 16.63509 (14) Å at 100 K. Multi-temperature single-crystal (15-340 K) and powder X-ray diffraction studies (100-400 K) reveal strongly anisotropic thermal expansion properties. The linear thermal expansion coefficients, αL(l), attain maximum values at 400 K along the a- and b-axis, with αL(a) = 115 × 10(-6) K(-1) and αL(b) = 75 × 10(-6) K(-1). At 400 K a negative thermal expansion coefficient of -40 × 10(-6) K(-1) is observed along the c-axis. The thermal expansion is coupled to a continuous deformation of the framework, which causes the structure to expand in two directions. Due to the rigidity of the linker, the expansion in the ab plane causes the network to contract along the c-axis. Hirshfeld surface analysis has been used to describe the interaction between the framework structure and the EMIM cation that resides within the channel. This reveals a number of rather weak interactions and one governing hydrogen-bonding interactions.

  5. Anion separation by selective crystallization of metal-organic frameworks.

    Science.gov (United States)

    Custelcean, Radu; Haverlock, Tamara J; Moyer, Bruce A

    2006-08-07

    A novel approach for the separation of anions from aqueous mixtures was demonstrated, which involves their selective crystallization with metal-organic frameworks (MOFs) containing urea functional groups. Self-assembly of Zn2+ with the N,N'-bis(m-pyridyl)urea (BPU) linker results in the formation of one-dimensional MOFs including various anions for charge balance, which interact to different extents with the zinc nodes and the urea hydrogen-bonding groups, depending on their coordinating abilities. Thus, Cl-, Br-, I-, and SO4(2-), in the presence of BPU and Zn2+, form MOFs from water, in which the anions coordinate the zinc and are hydrogen-bonded to the urea groups, whereas NO3- and ClO4- anions either do not form MOFs or form water-soluble discrete coordination complexes under the same conditions. X-ray diffraction, FTIR, and elemental analysis of the coordination polymers precipitated from aqueous mixtures containing equivalent amounts of these anions indicated total exclusion of the oxoanions and selective crystallization of the halides in the form of solid solutions with the general composition ZnCl(x)Br(y)I(z).BPU (x + y + z = 2), with an anti-Hofmeister selectivity. The concomitant inclusion of the halides in the same structural frameworks facilitates the rationalization of the observed selectivity on the basis of the diminishing interactions with the zinc and urea acidic centers in the MOFs when going from Cl- to I-, which correlates with decreasing anionic charge density in the same order. The overall crystal packing efficiency of the coordination frameworks, which ultimately determines their solubility, also plays an important role in the anion crystallization selectivity under thermodynamic equilibration.

  6. Adsorptive desulfurization and denitrogenation using metal-organic frameworks.

    Science.gov (United States)

    Ahmed, Imteaz; Jhung, Sung Hwa

    2016-01-15

    With the increasing worldwide demand for energy, utilization of fossil fuels is increasing proportionally. Additionally, new and unconventional energy sources are also being utilized at an increasing rate day-by-day. These sources, along with some industrial processes, result in the exposal of several sulfur- and nitrogen-containing compounds (SCCs and NCCs, respectively) to the environment, and the exposure is one of the greatest environmental threats in the recent years. Although, several methods were established for the removal of these pollutants during the last few decades, recent advancements in adsorptive desulfurization and denitrogenation (ADS and ADN, respectively) with metal-organic frameworks (MOFs) make this the most promising and remarkable method. Therefore, many research groups are currently involved with ADS and ADN with MOFs, and the results are improving gradually by modifying the MOF adsorbents according to several specific adsorption mechanisms. In this review, ADS and ADN studies are thoroughly discussed for both liquid-phase and gas-phase adsorption. The MOF modification procedures, which are important for improved adsorption, are also described. To improve the knowledge among the scientific community, it is very important to understand the detailed chemistry and mechanism involved in a chemical process, which also creates the possibility and pathway for further developments in research and applications. Therefore, the mechanisms related to the adsorption procedures are also discussed in detail. From this review, it can be expected that the scientific community will obtain an understanding of the current state of ADS and ADN, their importance, and some encouragement and insight to take the research knowledge base to a higher level.

  7. Multifunctional metal-organic frameworks: from academia to industrial applications.

    Science.gov (United States)

    Silva, Patrícia; Vilela, Sérgio M F; Tomé, João P C; Almeida Paz, Filipe A

    2015-10-01

    After three decades of intense and fundamental research on metal-organic frameworks (MOFs), is there anything left to say or to explain? The synthesis and properties of MOFs have already been comprehensively described elsewhere. It is time, however, to prove the nature of their true usability: technological applications based on these extended materials require development and implementation as a natural consequence of the up-to-known intensive research focused on their design and preparation. The current large number of reviews on MOFs emphasizes practical strategies to develop novel networks with varied crystal size, shape and topology, being mainly devoted to academic concerns. The present survey intends to push the boundaries and summarise the state-of-the-art on the preparation of promising (multi)functional MOFs in worldwide laboratories and their use as materials for industrial implementation. This review starts, on the one hand, to describe several tools and striking examples of remarkable and recent (multi)functional MOFs exhibiting outstanding properties (e.g., in gas adsorption and separation, selective sorption of harmful compounds, heterogeneous catalysis, luminescent and corrosion protectants). On the other hand, and in a second part, it intends to use these examples of MOFs to incite scientists to move towards the transference of knowledge from the laboratories to the industry. Within this context, we exhaustively review the many efforts of several worldwide commercial companies to bring functional MOFs towards the daily use, analysing the various patents and applications reported to date. Overall, this review goes from the very basic concepts of functional MOF engineering and preparation ending up in their industrial production on a large scale and direct applications in society.

  8. Research Progress of Metal-Organic Frameworks%金属有机框架的研究进展

    Institute of Scientific and Technical Information of China (English)

    李玮; 蒙斌芳; 刘宇奇

    2016-01-01

    金属有机框架(Metal-Organic Frameworks即MOFs)是一类具有拓扑结构的有机-无机杂化材料,由金属离子或金属团簇和有机配体通过自发自组装的方式合成得到。这种材料具有高孔隙率、比表面积大、骨架孔径尺寸的可调节性及结构的可裁性和多样性等优点,在气体吸附与分离、传感器、药物缓释、发光及催化等领域有着广泛的应用。本文主要介绍了MOFs材料的合成方法及优缺点,讨论了近十年来金属有机框架(MOFs)在气体存储、吸附与分离、靶向催化以及分子筛等方面的应用,并列举了计算化学在设计MOFs材料中的一些应用实例。此外,对今后MOFs的研究方向与应用前景进行了展望。%Metal organic frameworks are organic -inorganic hybrid materials with topological structure,formed by metal ions or metal clusters that are connected by organic ligands through self-assembly.Due to their high porosity,large specific surface area,the adjustable pore size of the skeleton and the tailorable structure,they have been applied to many fields such as diversity,gas adsorption,separation,sensor,drug delivery,lumines-cence and catalysis.In this review paper,the recent applications of metal organic frameworks(MOFs)especially to the fields of storage of gas,adsorption and separation,targeted catalysis and molecular sieves during the last ten years are reviewed and thoroughly discussed.Some application examples are adopted to introduce how com-putational chemistry can help to design the metal organic frameworks.In addition,the prospect of new applica-tion areas of metal organic frameworks is also presented.

  9. Palladium Nanoparticles Supported on Ce-Metal-Organic Framework for Efficient CO Oxidation and Low-Temperature CO2 Capture.

    Science.gov (United States)

    Lin, Andrew; Ibrahim, Amr Awad; Arab, Pezhman; El-Kaderi, Hani M; El-Shall, M Samy

    2017-05-31

    In this article, we report the lowest-temperature CO oxidation catalyst supported on metal-organic frameworks (MOFs). We have developed a facile, general, and effective approach based on microwave irradiation for the incorporation of Pd nanoparticle catalyst within Ce-MOF. The resulting Pd/Ce-MOF material is a unique catalyst that is capable of CO oxidation at modest temperatures and also of efficient uptake of the product CO2 gas at low temperatures. The observed catalytic activity of this material toward CO oxidation is significantly higher than those of other reported metal nanoparticles supported on MOFs. The high activity of the Pd/Ce-MOF catalyst is due to the presence of Ce(III) and Ce(IV) ions within the metal-organic framework support. The Pd nanoparticles supported on the Ce-MOF store oxygen in the form of a thin palladium oxide layer at the particle-support interface, in addition to the oxygen stored on the Ce(III)/Ce(IV) centers. Oxygen from these reservoirs can be released during CO oxidation at 373 K. At lower temperatures (273 K), the Pd/Ce-MOF has a significant CO2 uptake of 3.5 mmol/g.

  10. Demonstration of a semi-autonomous hybrid brain-machine interface using human intracranial EEG, eye tracking, and computer vision to control a robotic upper limb prosthetic.

    Science.gov (United States)

    McMullen, David P; Hotson, Guy; Katyal, Kapil D; Wester, Brock A; Fifer, Matthew S; McGee, Timothy G; Harris, Andrew; Johannes, Matthew S; Vogelstein, R Jacob; Ravitz, Alan D; Anderson, William S; Thakor, Nitish V; Crone, Nathan E

    2014-07-01

    To increase the ability of brain-machine interfaces (BMIs) to control advanced prostheses such as the modular prosthetic limb (MPL), we are developing a novel system: the Hybrid Augmented Reality Multimodal Operation Neural Integration Environment (HARMONIE). This system utilizes hybrid input, supervisory control, and intelligent robotics to allow users to identify an object (via eye tracking and computer vision) and initiate (via brain-control) a semi-autonomous reach-grasp-and-drop of the object by the MPL. Sequential iterations of HARMONIE were tested in two pilot subjects implanted with electrocorticographic (ECoG) and depth electrodes within motor areas. The subjects performed the complex task in 71.4% (20/28) and 67.7% (21/31) of trials after minimal training. Balanced accuracy for detecting movements was 91.1% and 92.9%, significantly greater than chance accuracies (p system improvements implemented for the second subject. Our hybrid-BMI design prevented all but one baseline false positive from initiating the system. The novel approach demonstrated in this proof-of-principle study, using hybrid input, supervisory control, and intelligent robotics, addresses limitations of current BMIs.

  11. Metal-insulator transition at the LaAlO3/SrTiO3 interface revisited: A hybrid functional study

    KAUST Repository

    Cossu, Fabrizio

    2013-07-17

    We investigate the electronic properties of the LaAlO3/SrTiO3 interface using density functional theory. In contrast to previous studies, which relied on (semi-)local functionals and the GGA+U method, we here use a recently developed hybrid functional to determine the electronic structure. This approach offers the distinct advantage of accessing both the metallic and insulating multilayers on a parameter-free equal footing. As compared to calculations based on semilocal GGA functionals, our hybrid functional calculations lead to a considerably increased band gap for the insulating systems. The details of the electronic structure show substantial deviations from those obtained by GGA calculations. This casts severe doubts on all previous results based on semilocal functionals. In particular, corrections using rigid band shifts (“scissors operator”) cannot lead to valid results.

  12. Ionic liquid accelerates the crystallization of Zr-based metal-organic frameworks.

    Science.gov (United States)

    Sang, Xinxin; Zhang, Jianling; Xiang, Junfeng; Cui, Jie; Zheng, Lirong; Zhang, Jing; Wu, Zhonghua; Li, Zhihong; Mo, Guang; Xu, Yuan; Song, Jinliang; Liu, Chengcheng; Tan, Xiuniang; Luo, Tian; Zhang, Bingxing; Han, Buxing

    2017-08-02

    The Zr-based metal-organic frameworks are generally prepared by solvothermal procedure. To overcome the slow kinetics of nucleation and crystallization of Zr-based metal-organic frameworks is of great interest and challenging. Here, we find that an ionic liquid as solvent can significantly accelerate the formation of Zr-based metal-organic frameworks at room temperature. For example, the reaction time is shortened to 0.5 h in 1-hexyl-3-methylimidazolium chloride for Zr-based metal-organic framework formation, while that in the conventional solvent N,N-dimethylformamide needs at least 120 h. The reaction mechanism was investigated in situ by (1)H nuclear magnetic resonance, spectroscopy synchrotron small angle X-ray scattering and X-ray absorption fine structure. This rapid, low-energy, and facile route produces Zr-based metal-organic framework nanoparticles with small particle size, missing-linker defects and large surface area, which can be used as heterogeneous catalysts for Meerwein-Ponndorf-Verley reaction.Crystallization kinetics of metal-organic frameworks in conventional organic solvents are usually very slow. Here, the authors show that an ionic liquid medium accelerates considerably the formation of Zr-based metal-organic frameworks that are active catalysts in the Meerwein-Ponndorf-Verley reaction.

  13. Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy

    Energy Technology Data Exchange (ETDEWEB)

    McGrail, B. Peter; Brown, Daryl R.; Thallapally, Praveen K.

    2016-08-02

    Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

  14. Metal-organic-framework-derived two-dimensional ultrathin mesoporous hetero-ZnFe2O4/ZnO nanosheets with enhanced lithium storage properties for Li-ion batteries

    Science.gov (United States)

    Cao, Hui; Zhu, Siqi; Yang, Chao; Bao, Ruiqi; Tong, Liuniu; Hou, Linrui; Zhang, Xiaogang; Yuan, Changzhou

    2016-11-01

    Mesoporous hetero-structures have drawn tremendous attention due to their unprecedented inherent advantages in advanced Li-ion batteries (LIBs). In this study, we developed a facile metal-organic-framework-engaged synthetic methodology for large-scale fabrication of two-dimensional (2D) mesoporous hetero-ZnFe2O4/ZnO nanosheets (ZFOZ NSs) with homogeneously dispersed hetero-nanodomains of spinel ZnFe2O4 and ZnO. When evaluated as a promising anode for LIB applications, the resultant 2D ultrathin mesoporous hetero-ZFOZ NSs exhibited extraordinary electrochemical Li storage performance with long-cycle behavior and large reversible capacities for next-generation LIB applications, thanks to the attractive synergetic contributions from ultrathin mesoporous architecture and electroactive bi-component hetero-interfaces at the nanoscale. Even more encouragingly, the electrode concept we developed here can be easily generalized to rational design and synthesis of other mesoporous hetero-hybrids with remarkable lithium storage capacities for LIBs.

  15. Highly sensitive and selective fluoride detection in water through fluorophore release from a metal-organic framework.

    Science.gov (United States)

    Hinterholzinger, Florian M; Rühle, Bastian; Wuttke, Stefan; Karaghiosoff, Konstantin; Bein, Thomas

    2013-01-01

    The detection, differentiation and visualization of compounds such as gases, liquids or ions are key challenges for the design of selective optical chemosensors. Optical chemical sensors employ a transduction mechanism that converts a specific analyte recognition event into an optical signal. Here we report a novel concept for fluoride ion sensing where a porous crystalline framework serves as a host for a fluorescent reporter molecule. The detection is based on the decomposition of the host scaffold which induces the release of the fluorescent dye molecule. Specifically, the hybrid composite of the metal-organic framework NH2-MIL-101(Al) and fluorescein acting as reporter shows an exceptional turn-on fluorescence in aqueous fluoride-containing solutions. Using this novel strategy, the optical detection of fluoride is extremely sensitive and highly selective in the presence of many other anions.

  16. [Metal-Organic Frameworks: A New Class of Mesoporous Materials and Potential Possibilities of Their Use in Pharmaceutical Technology].

    Science.gov (United States)

    Wyszogrodzka, Gabriela; Dorożyński, Przemysław

    2015-01-01

    Metal-organic frameworks (MOFs) belong to the new class of mesoporous, hybrid materials composed of metal ions and organic binding ligands. Their unique features: wide range of chemical building components, which enables obtaining biocompatible materials, and high surface area and loading capacity, make them promising drug delivery vehicles for therapeutic agents. The ability to tune their structures and porosities provides better adjustment for adsorbed drug molecule. Moreover, MOFs functionalized with ligands or antibodies can be used in cancer targeted therapy. Through the incorporation of paramagnetic metal ions into the structure, MOFs are suited to serve as magnetic resonance imaging (MRI) contrast agents. Combining drug delivery ability with imaging properties of MOFs indicates their potential use as theranostic agents and makes possible monitoring drug delivery within the body after administration in the real time. The aim of the present study is to characterize a new class of compounds and to present potential possibilities of their use as excipients in pharmaceutical technology .

  17. Polymer-Metal-Organic Frameworks (polyMOFs) as Water Tolerant Materials for Selective Carbon Dioxide Separations.

    Science.gov (United States)

    Zhang, Zhenjie; Nguyen, Ha Thi Hoang; Miller, Stephen A; Ploskonka, Ann M; DeCoste, Jared B; Cohen, Seth M

    2016-01-27

    Recently, polymer-metal-organic frameworks (polyMOFs) were reported as a new class of hybrid porous materials that combine advantages of both organic polymers and crystalline MOFs. Herein, we report a bridging coligand strategy to prepare new types of polyMOFs, demonstrating that polyMOFs are compatible with additional MOF architectures besides that of the earlier reported IRMOF-1 type polyMOF. Gas sorption studies revealed that these polyMOF materials exhibited relatively high CO2 sorption but very low N2 sorption, making them promising materials for CO2/N2 separations. Moreover, these polyMOFs demonstrated exceptional water stability attributed to the hydrophobicity of polymer ligands as well as the cross-linking of the polymer chains within the MOF.

  18. Metal organic frameworks/macroporous carbon composites with enhanced stability properties and good electrocatalytic ability for ascorbic acid and hemoglobin.

    Science.gov (United States)

    Zhang, Yufan; Nsabimana, Anaclet; Zhu, Liande; Bo, Xiangjie; Han, Ce; Li, Mian; Guo, Liping

    2014-11-01

    The thermal, water and electrochemical stability of Cu-based metal organic frameworks (Cu-MOFs) confined in macroporous carbon (MPC) hybrids has been investigated. Thermogravimetric analyses, X-Ray diffraction, scanning electron microscopy, and cyclic voltammetry were employed to confirm the stability of pure Cu-MOFs, MPC, and Cu-MOFs-MPC. As compared to pure Cu-MOFs, the porous composite materials of MPC and Cu-MOFs interact and seem to form new materials having homogenous structure and chemistry, which show structural stability in aqueous media and electrochemical stability in phosphate buffer solution (PBS pH 7.4). The detection of ascorbic acid and hemoglobin is performed as an electrochemical probe, indicating Cu-MOFs-MPC holds great promise for the design of electrochemical sensors.

  19. Separation of Industrially-Relevant Gas Mixtures With Metal-Organic Frameworks

    Science.gov (United States)

    Herm, Zoey Rose

    The work herein describes the investigation of metal-organic frameworks for industrial applications, specifically gas phase separations of mixtures. Metal-organic frameworks are crystalline molecular scaffolds built from cationic metal vertices and organic bridging ligands. They are porous on a molecular scale and can separate gas mixtures when one component interacts more strongly with the pore walls than others. The near-infinite combination of metals and ligands allows for optimization of metal-organic framework structures for specific separations. (Abstract shortened by UMI.)

  20. In Situ Characterization of the Initial Effect of Water on Molecular Interactions at the Interface of Organic/Inorganic Hybrid Systems

    Science.gov (United States)

    Pletincx, Sven; Trotochaud, Lena; Fockaert, Laura-Lynn; Mol, Johannes M. C.; Head, Ashley R.; Karslıoğlu, Osman; Bluhm, Hendrik; Terryn, Herman; Hauffman, Tom

    2017-01-01

    Probing initial interactions at the interface of hybrid systems under humid conditions has the potential to reveal the local chemical environment at solid/solid interfaces under real-world, technologically relevant conditions. Here, we show that ambient pressure X-ray photoelectron spectroscopy (APXPS) with a conventional X-ray source can be used to study the effects of water exposure on the interaction of a nanometer-thin polyacrylic acid (PAA) layer with a native aluminum oxide surface. The formation of a carboxylate ionic bond at the interface is characterized both with APXPS and in situ attenuated total reflectance Fourier transform infrared spectroscopy in the Kretschmann geometry (ATR-FTIR Kretschmann). When water is dosed in the APXPS chamber up to 5 Torr (~28% relative humidity), an increase in the amount of ionic bonds at the interface is observed. To confirm our APXPS interpretation, complementary ATR-FTIR Kretschmann experiments on a similar model system, which is exposed to an aqueous electrolyte, are conducted. These spectra demonstrate that water leads to an increased wet adhesion through increased ionic bond formation. PMID:28327587

  1. In Situ Characterization of the Initial Effect of Water on Molecular Interactions at the Interface of Organic/Inorganic Hybrid Systems

    Science.gov (United States)

    Pletincx, Sven; Trotochaud, Lena; Fockaert, Laura-Lynn; Mol, Johannes M. C.; Head, Ashley R.; Karslıoğlu, Osman; Bluhm, Hendrik; Terryn, Herman; Hauffman, Tom

    2017-03-01

    Probing initial interactions at the interface of hybrid systems under humid conditions has the potential to reveal the local chemical environment at solid/solid interfaces under real-world, technologically relevant conditions. Here, we show that ambient pressure X-ray photoelectron spectroscopy (APXPS) with a conventional X-ray source can be used to study the effects of water exposure on the interaction of a nanometer-thin polyacrylic acid (PAA) layer with a native aluminum oxide surface. The formation of a carboxylate ionic bond at the interface is characterized both with APXPS and in situ attenuated total reflectance Fourier transform infrared spectroscopy in the Kretschmann geometry (ATR-FTIR Kretschmann). When water is dosed in the APXPS chamber up to 5 Torr (~28% relative humidity), an increase in the amount of ionic bonds at the interface is observed. To confirm our APXPS interpretation, complementary ATR-FTIR Kretschmann experiments on a similar model system, which is exposed to an aqueous electrolyte, are conducted. These spectra demonstrate that water leads to an increased wet adhesion through increased ionic bond formation.

  2. Reaction Engineering with Metal-Organic Framework Catalysts

    Science.gov (United States)

    Melkonian, Arek Viken

    To date, there has been no comprehensive attempt to perform and/or describe catalytic reactions in the gas phase that utilize metal-organic frameworks (MOFs) as catalysts. In addition, there has been no attempt to reaction engineer these MOF catalysts in order to determine their regimes of optimal catalytic activity and possible limitations to their use. A zinc-based MOF that has been post-synthetically modified with a homogeneous palladium catalyst, Pd(CH 3CN)2Cl2, is used to catalyze the hydrogenation of propylene. The catalyst is assembled in a packed-bed reactor under a continuous flow of reactants. The reaction is optimized with respect to isoreticular metalation, reactant flow rate, and reactor temperature. Maximum catalytic conversion is found at intermediate metalations of 40% and 60%, high hydrogen flow of 50 ccm, and intermediate reactor temperatures of 100 °C and 150 °C. The MOF-60 catalyst is exposed to a traditional catalyst poison, carbon monoxide (CO). It is found that the MOF is reversibly poisoned upon introduction of CO. Upon poisoning, catalytic conversions rates of 90%-100% are dramatically reduced to less than 10%-30%, depending on the CO flow rate and the reactor temperature. The CO poisoning is shown to be reversible, a similar effect as found with palladium on carbon (Pd/C). The time scale of poisoning and recovery is very fast for both the MOF catalyst and Pd/C (approximately 10-30 seconds). Other effects of temperature on the MOF-40 are also investigated. At fixed reactant flow, the temperature grid is partitioned into finer steps of 10 °C to determine the temperature that yields the highest catalytic conversion. It is found that conversion is nearly uniform in the range between the highest conversions, i.e., conversion plateaus between the optimum temperatures. The catalyst also exhibits a weak thermal hysteresis. There is no significant improvement in conversion with thermal cycling after alternating the reactor temperature between

  3. Metal Organic Frameworks: Explorations and Design Strategies for MOF Synthesis

    KAUST Repository

    AbdulHalim, Rasha

    2016-11-27

    Metal-Organic Frameworks (MOFs) represent an emerging new class of functional crystalline solid-state materials. In the early discovery of this now rapidly growing class of materials significant challenges were often encountered. However, MOFs today, with its vast structural modularity, reflected by the huge library of the available chemical building blocks, and exceptional controlled porosity, stand as the most promising candidate to address many of the overbearing societal challenges pertaining to energy and environmental sustainability. A variety of design strategies have been enumerated in the literature which rely on the use of predesigned building blocks paving the way towards potentially more predictable structures. The two major design strategies presented in this work are the molecular building block (MBB) and supermolecular building block (SBB) -based approaches for the rationale assembly of functional MOF materials with the desired structural features. In this context, we targeted two highly connected MOF platforms, namely rht-MOF and shp-MOF. These two MOF platforms are classified based on their topology, defined as the underlying connectivity of their respective net, as edge transitive binodal nets; shp being (4,12)-connected net and rht being (3,24)-connected net. These highly connected nets were deliberately targeted due to the limited number of possible nets for connecting their associated basic building units. Two highly porous materials were designed and successfully constructed; namely Y-shp-MOF-5 and rht-MOF-10. The Y-shp-MOF-5 features a phenomenal water stability with an exquisite behavior when exposed to water, positioning this microporous material as the best adsorbent for moisture control applications. The shp-MOF platform proved to be modular to ligand functionalization and thus imparting significant behavioral changes when hydrophilic and hydrophobic functionalized ligands were introduced on the resultant MOF. On the other hand, rht

  4. Metal organic frameworks as a drug delivery system for flurbiprofen

    Directory of Open Access Journals (Sweden)

    AL Haydar M

    2017-09-01

    Full Text Available Muder AL Haydar,1,2 Hussein Rasool Abid,3,4 Bruce Sunderland,2 Shaobin Wang5,6 1Pharmaceutics Department, College of the Pharmacy, University of Kerbala, Kerbala, Iraq; 2Pharmaceutics Department, School of Pharmacy, Faculty of Health Sciences, Curtin University, Perth, WA, Australia; 3Department of Chemical Engineering, Curtin University, Perth, WA, Australia; 4College of Applied Medical Sciences, University of Kerbala, Kerbala, Iraq; 5School of Pharmacy, Faculty of Health Sciences, Curtin University, Perth, WA, Australia; 6Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Faculty of Science and Engineering, Curtin University, Perth, WA, Australia Background: Metal organic frameworks (MOFs have attracted more attention in the last decade because of a suitable pore size, large surface area, and high pore volume. Developing biocompatible MOFs such as the MIL family as a drug delivery system is possible. Purpose: Flurbiprofen (FBP, a nonsteroidal anti-inflammatory agent, is practically insoluble in aqueous solution, and, therefore, needs suitable drug delivery systems. Different biocompatible MOFs such as Ca-MOF and Fe-MILs (53, 100, and 101 were synthesized and employed for FBP delivery. Patients and methods: A sample of 50 mg of each MOF was mixed and stirred for 24 h with 10 mL of 5 mg FBP in acetonitrile (40% in a sealed container. The supernatant of the mixture after centrifuging was analyzed by high-performance liquid chromatography to determine the loaded quantity of FBP on the MOF. The overnight-dried solid material after centrifuging the mixture was analyzed for loading percent using X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, nuclear magnetic resonance, and FBP release profile. Results: The loading values of FBP were achieved at 10.0%±1%, 20%±0.8%, 37%±2.3%, and 46%±3.1% on Ca-MOF, Fe-MIL-53, Fe-MIL-101, and Fe-MIL-100, respectively. The FBP release

  5. Carbon Dioxide Separation with Novel Microporous Metal Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Richard Willis; Annabelle Benin; John Low; Ganesh Venimadhavan; Syed Faheem; David Lesch; Adam Matzger; Randy Snurr

    2008-02-04

    The goal of this program was to develop a low cost novel sorbent to remove carbon dioxide from flue gas and gasification streams in electric utilities. Porous materials named metal-organic frameworks (MOFs) were found to have good capacity and selectivity for the capture of carbon dioxide. Several materials from the initial set of reference MOFs showed extremely high CO{sub 2} adsorption capacities and very desirable linear isotherm shapes. Sample preparation occurred at a high level, with a new family of materials suitable for intellectual property protection prepared and characterized. Raman spectroscopy was shown to be useful for the facile characterization of MOF materials during adsorption and especially, desorption. Further, the development of a Raman spectroscopic-based method of determining binary adsorption isotherms was initiated. It was discovered that a stronger base functionality will need to be added to MOF linkers in order to enhance CO{sub 2} selectivity over other gases via a chemisorption mechanism. A concentrated effort was expended on being able to accurately predict CO{sub 2} selectivities and on the calculation of predicted MOF surface area values from first principles. A method of modeling hydrolysis on MOF materials that correlates with experimental data was developed and refined. Complimentary experimental data were recorded via utilization of a combinatorial chemistry heat treatment unit and high-throughput X-ray diffractometer. The three main Deliverables for the project, namely (a) a MOF for pre-combustion (e.g., IGCC) CO{sub 2} capture, (b) a MOF for post-combustion (flue gas) CO{sub 2} capture, and (c) an assessment of commercial potential for a MOF in the IGCC application, were completed. The key properties for MOFs to work in this application - high CO{sub 2} capacity, good adsorption/desorption rates, high adsorption selectivity for CO{sub 2} over other gases such as methane and nitrogen, high stability to contaminants, namely

  6. Flexible and hydrophobic Zn-based metal-organic framework.

    Science.gov (United States)

    Hauptvogel, Ines Maria; Biedermann, Ralf; Klein, Nicole; Senkovska, Irena; Cadiau, Amandine; Wallacher, Dirk; Feyerherm, Ralf; Kaskel, Stefan

    2011-09-05

    A zinc-based metal-organic framework Zn(2)(adb)(2)(dabco)·4.5 DMF (K) (DUT-30(Zn), DUT = Dresden University of Technology, adb = 9,10-anthracene dibenzoate, dabco =1,4-diazabicyclo[2.2.2]octane, DMF = N,N-dimethylformamide) was synthesized using a solvothermal route. This MOF exhibits six crystallographic guest dependent phases. Two of them were characterized via single crystal X-ray analysis. The as-synthesized phase K crystallizes in the orthorhombic space group Fmmm, with a = 9.6349(9), b = 26.235(3), and c = 28.821(4) Å and consists of two interpenetrated pillar-layer networks with pcu topology. When the substance loses 0.5 DMF molecules per formula unit, a phase transition from the kinetic phase K to a thermodynamic phase T occurs. Zn(2)(adb)(2)(dabco)·4 DMF (T) crystallizes in the tetragonal space group I4/mmm, with a = 19.5316(8) and c = 9.6779(3) Å. During the evacuation the DUT-30(Zn) undergoes again the structural transformation to A. The activated compound A shows the gate pressure effect in the low pressure region of nitrogen physisorption isotherm and has a BET surface area of 960 m(2 )g(-1) and a specific pore volume of 0.43 cm(3) g(-1). Furthermore, DUT-30(Zn) exhibits a hydrogen storage capacity of 1.12 wt % at 1 bar, a CO(2) uptake of 200 cm(3) g(-1) at -78 °C and 0.9 bar, and a n-butane uptake of 3.0 mmol·g(-1) at 20 °C. The N(2) adsorption process was monitored in situ via X-ray powder diffraction using synchrotron radiation. A low temperature induced transformation of phase A to phase V could be observed if the compound was cooled under vacuum to -196 °C. A further crystalline phase N could be identified if the framework was filled with nitrogen at -196 °C. Additionally, the treatment of activated phase A with water leads to the new phase W.

  7. A generic and facile strategy to fabricate metal-organic framework films on TiO2 substrates for photocatalysis.

    Science.gov (United States)

    Yang, Huimin; Fei, Honghan

    2017-02-28

    We present a facile and compelling method for the synthesis of metal-organic framework (MOF) thin films on TiO2-coated conductive glass substrates. This generic deposition approach is extended to five representative MOF films (e.g. UiO, MIL, IRMOF, and NU series) with high crystallinity and excellent surface coverage, achieving a MOF/TiO2 heterostructure interface. The tunable thickness and functionality of MOF films as well as the preferred orientation of MOF microcrystallites are described. After the incorporation of [Ru(bpy)3](2+) functionality via postsynthetic ligand exchange, the resultant MOF films serve as a robust and efficient catalyst for photo-oxidation of thioanisole. Importantly, our deposition technique avoids the direct contact between solid MOF catalysts and magnetic stirring, thus overcoming the problem that the vast majority of MOF powder catalysts are subject to defragmentation or decomposition under the physical treatment methods.

  8. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks

    National Research Council Canada - National Science Library

    Feng, Dawei; Wang, Kecheng; Wei, Zhangwen; Chen, Ying-Pin; Simon, Cory M; Arvapally, Ravi K; Martin, Richard L; Bosch, Mathieu; Liu, Tian-Fu; Fordham, Stephen; Yuan, Daqiang; Omary, Mohammad A; Haranczyk, Maciej; Smit, Berend; Zhou, Hong-Cai

    2014-01-01

    .... Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core...

  9. Metal-organic Materials (moms) For Co2 Adsorption And Methods Of Using Moms

    KAUST Repository

    Eddaoudi, Mohamed

    2015-06-11

    Embodiments of the present disclosure provide for metal-organic materials (MOMs), systems that exhibit permanent porosity and using hydrophobic MOMs to separate components in a gas, methods of separating CO.sub.2 from a gas, and the like.

  10. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks

    Science.gov (United States)

    Feng, Dawei; Wang, Kecheng; Wei, Zhangwen; Chen, Ying-Pin; Simon, Cory M.; Arvapally, Ravi K.; Martin, Richard L.; Bosch, Mathieu; Liu, Tian-Fu; Fordham, Stephen; Yuan, Daqiang; Omary, Mohammad A.; Haranczyk, Maciej; Smit, Berend; Zhou, Hong-Cai

    2014-12-01

    Metal-organic frameworks with high stability have been pursued for many years due to the sustainability requirement for practical applications. However, researchers have had great difficulty synthesizing chemically ultra-stable, highly porous metal-organic frameworks in the form of crystalline solids, especially as single crystals. Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core. Through this versatile synthetic route, we obtain large single crystals of 34 different iron-containing metal-organic frameworks. Among them, PCN-250(Fe2Co) exhibits high volumetric uptake of hydrogen and methane, and is also stable in water and aqueous solutions with a wide range of pH values.

  11. A highly stable dynamic fluorescent metal-organic framework for selective sensing of nitroaromatic explosives.

    Science.gov (United States)

    Gong, Yun-Nan; Jiang, Long; Lu, Tong-Bu

    2013-12-07

    A dynamic fluorescent metal-organic framework has been constructed using triphenylene-2,6,10-tricarboxylate and Tb(3+) as building blocks, which exhibits guest-responsive structural dynamism and selective sensing of nitroaromatic explosives.

  12. Synthesis of Metal-Organic Zeolites with Homochirality and High Porosity for Enantioselective Separation.

    Science.gov (United States)

    Xu, Zhong-Xuan; Liu, Liyang; Zhang, Jian

    2016-07-01

    Using lactic acid derivatives as chiral ligands, a pair of unprecedented homochiral metal-organic zeolites have been synthesized that feature zeotype CAN topology and have high porosity for enantioselective separation of racemates.

  13. Metal-organic materials (MOMs) for adsorption of polarizable gases and methods of using MOMs

    Energy Technology Data Exchange (ETDEWEB)

    Zaworotko, Michael; Mohamed, Mona H.; Elsaidi, Sameh

    2017-06-14

    Embodiments of the present disclosure provide for multi-component metal-organic materials (MOMs), systems including the MOM, systems for separating components in a gas, methods of separating polarizable gases from a gas mixture, and the like.

  14. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks.

    Science.gov (United States)

    Feng, Dawei; Wang, Kecheng; Wei, Zhangwen; Chen, Ying-Pin; Simon, Cory M; Arvapally, Ravi K; Martin, Richard L; Bosch, Mathieu; Liu, Tian-Fu; Fordham, Stephen; Yuan, Daqiang; Omary, Mohammad A; Haranczyk, Maciej; Smit, Berend; Zhou, Hong-Cai

    2014-12-04

    Metal-organic frameworks with high stability have been pursued for many years due to the sustainability requirement for practical applications. However, researchers have had great difficulty synthesizing chemically ultra-stable, highly porous metal-organic frameworks in the form of crystalline solids, especially as single crystals. Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core. Through this versatile synthetic route, we obtain large single crystals of 34 different iron-containing metal-organic frameworks. Among them, PCN-250(Fe2Co) exhibits high volumetric uptake of hydrogen and methane, and is also stable in water and aqueous solutions with a wide range of pH values.

  15. Stimuli-Responsive DNA-Functionalized Metal-Organic Frameworks (MOFs).

    Science.gov (United States)

    Kahn, Jason S; Freage, Lina; Enkin, Natalie; Garcia, Miguel Angel Aleman; Willner, Itamar

    2017-02-01

    The synthesis of nucleic acid-functionalized metal-organic frameworks (MOFs) is described. The metal-organic frameworks are loaded with a dye being locked in the structures by means of stimuli-responsive nucleic acid caps. The pH and K(+) -ion-triggered release, and switchable release, are demonstrated. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Clean and Efficient Synthesis Using Mechanochemistry: Coordination Polymers, Metal-Organic Frameworks and Metallodrugs

    OpenAIRE

    Friščić, Tomislav; Halasz, Ivan; Štrukil, Vjekoslav; Maksić, Mirjana; Dinnebier, Robert E

    2012-01-01

    This review briefly discusses recent advances and future prospects in the mechanochemical synthesis of coordination compounds by ball milling and grinding, and highlights our contributions to the mechanosynthesis of porous metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs), metal-organic pharmaceutical derivatives and metallodrugs using the recently developed mechanochemical methods of liquid-assisted grinding (LAG) and ion- and liquid-assisted grinding (ILAG). The...

  17. Assembly of metal-organic polyhedra into highly porous frameworks for ethene delivery.

    Science.gov (United States)

    Stoeck, Ulrich; Senkovska, Irena; Bon, Volodymyr; Krause, Simon; Kaskel, Stefan

    2015-01-21

    Two new mesoporous metal-organic frameworks (DUT-75 and DUT-76) with exceptional ethene uptake were obtained using carbazole dicarboxylate based metal-organic polyhedra as supermolecular building blocks. The compounds have a total pore volume of 1.84 and 3.25 cm(3) g(-1) and a specific BET surface area of 4081 and 6344 m(2) g(-1), respectively, and high gas uptake at room temperature and high pressure.

  18. Metal organic frameworks for enzyme immobilization in biofuel cells

    Science.gov (United States)

    Bodell, JaDee

    Interest in biofuel cells has been rapidly expanding as an ever-growing segment of the population gains access to electronic devices. The largest areas of growth for new populations using electronic devices are often in communities without electrical infrastructure. This lack of infrastructure in remote environments is one of the key driving factors behind the development of biofuel cells. Biofuel cells employ biological catalysts such as enzymes to catalyze oxidation and reduction reactions of select fuels to generate power. There are several benefits to using enzymes to catalyze reactions as compared to traditional fuel cells which use metal catalysts. First, enzymes are able to catalyze reactions at or near room temperature, whereas traditional metal catalysts are only efficient at very high temperatures. Second, biofuel cells can operate under mild pH conditions which is important for the eventual design of safe, commercially viable devices. Also, biofuel cells allow for implantable and flexible technologies. Finally, enzymes exhibit high selectivity and can be combined to fully oxidize or reduce the fuel which can generate several electrons from a single molecule of fuel, increasing the overall device efficiency. One of the main challenges which persist in biofuel cells is the instability of enzymes over time which tend to denature after hours or days. For a viable commercial biofuel cell to be produced, the stability of enzymes must be extended to months or years. Enzymes have been shown to have improved stability after being immobilized. The focus of this research was to find a metal organic framework (MOF) structure which could successfully immobilize enzymes while still allowing for electron transport to occur between the catalytic center of the enzyme and the electrode surface within a biofuel cell for power generation. Four MOF structures were successfully synthesized and were subsequently tested to determine the MOF's ability to immobilize the following

  19. Homochiral helical metal-organic frameworks of group 1 metals.

    Science.gov (United States)

    Reger, Daniel L; Leitner, Andrew; Smith, Mark D; Tran, T Thao; Halasyamani, P Shiv

    2013-09-01

    The reactions of (S)-2-(1,8-naphthalimido)propanoic acid (HL(ala)) and (S)-2-(1,8-naphthalimido)-3-hydroxypropanoic acid (HL(ser)), protonated forms of ligands that contain a carboxylate donor group, an enantiopure chiral center, and a 1,8-naphthalimide π···π stacking supramolecular tecton and in the case of HL(ser) an alcohol functional group, with the appropriate alkali metal hydroxide followed by a variety of crystallization methods leads to the formation of crystalline K(L(ala))(MeOH) (1), K(L(ala))(H2O) (2), Na(L(ala))(H2O) (3), KL(ser) (4), CsL(ser) (5), and CsL(ala) (6). Each of these new complexes has a solid state structure based on six-coordinate metals linked into homochiral helical rod secondary building unit (SBU) central cores. In addition to the bonding of the carboxylate and solvent (in the case of L(ser) the ligand alcohol) to the metals, both oxygens on the 1,8-naphthalimide act as donor groups. One naphthalimide oxygen bonds to the same helical rod SBU as the carboxylate group of that ligand forming a chelate ring. The other naphthalimide oxygen bonds to adjacent SBUs. In complexes 1-3, this inter-rod link has a square arrangement bonding four other rods forming a three-dimensional enantiopure metal-organic framework (MOF) structure, whereas in 4-6 this link has a linear arrangement bonding two other rods forming a two-dimensional, sheet structure. In the latter case, the third dimension is supported exclusively by interdigitated π···π stacking interactions of the naphthalimide supramolecular tecton, forming enantiopure supramolecular MOF solids. Compounds 1-3 lose the coordinated solvent when heating above 100 °C. For 1, the polycrystalline powder reverts to 1 only by recrystallization from methanol, whereas compounds 2 and 3 undergo gas/solid, single-crystal to single-crystal transformations to form dehydrated compounds 2* and 3*, and rehydration occurs when crystals of these new complexes are left out in air. The reversible single

  20. Visible Light Induced Organic Transformations Using Metal-Organic-Frameworks (MOFs).

    Science.gov (United States)

    Deng, Xiaoyu; Li, Zhaohui; García, Hermenegildo

    2017-08-22

    With the aim of developing renewable energy based processes, researchers are paying increasing interest to light induced organic transformations. Metal-organic frameworks (MOFs), a class of micro-/mesoporous hybrid materials, are recently emerging as a new type of photoactive materials for organic syntheses due to their unique structural characteristics. In this Review, we summarized the recent applications of MOFs as photocatalysts for light induced organic transformations, including (1) oxidation of alcohols, amines, alkene, alkanes and sulfides; (2) hydroxylation of aromatic compounds like benzene; (3) activation of the C-H bonds to construct new C-C or C-X bonds; (4) atom-transfer radical polymerization (ATRP). This Review starts with general background information of using MOFs in photocatalysis, followed by a description of light induced organic transformations promoted by photoactive inorganic nodes and photocatalytic active ligands in MOFs, respectively. Thereafter, the use of MOFs as multifunctional catalysts for light induced organic transformations via an efficient merge of the metal/ligand/guest based catalysis where the photocatalytic activity of MOFs plays a key role are discussed. Finally, the limitations, challenges and the future perspective of the application of MOFs for light induced organic transformations were addressed. The objective of this Review is to serve as a starting point for other researchers to get into this largely unexplored field. It is also our goal to stimulate intensive research in this field for rational designing of MOF materials to overcome their current limitations in photocatalysis, which can lead to more creative visible-light-induced organic transformations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Keggin-Type Polyoxometalate-Based Metal-Organic Networks for Photocatalytic Dye Degradation.

    Science.gov (United States)

    Hao, Hong-Fang; Zhou, Wen-Zhe; Zang, Hong-Ying; Tan, Hua-Qiao; Qi, Yan-Fei; Wang, Yong-Hui; Li, Yang-Guang

    2015-08-01

    The reaction of Keggin-type polyoxometalate (POM) units, transition-metal (TM) ions, and a rigid bis(imidazole) ligand (1,4-bis(1-imidazolyl)benzene (bimb)) in a hydrothermal environment led to the isolation of four new POM-based metal-organic networks, [H2 L][CuL][SiW12 O40 ]⋅2 H2 O (1), [H2 L]2 [Co(H2 O)3 L][SiW11 CoO39 ]⋅6 H2 O (2), KH[CuL]2 [SiW11 CoO39 (H2 O)]⋅2 H2 O (3), and [CuL]4 [GeW12 O40 ]⋅H2 O (4; L=bimb). All four compounds were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Compounds 1 and 3 are new 3D networks with 1D channels. Compounds 2 and 4 contain 2D networks, which further stack into 3D supramolecular networks. The contributions of pH value, the negative charge of the POM, and the TM coordination modes to the construction of 3D networks were elucidated by comparing the synthetic conditions and structures of compounds 1-4. The photocatalytic properties of compounds 1-4 were investigated using methylene blue (MB) degradation under UV light. All compounds showed good catalytic activity and structural stability. The possible catalytic mechanism was discussed on the basis of active-species trapping experiments. The different photocatalytic activities of compounds 1-4 were explained by comparison of the band gaps of different POM species and different packing modes of POM units in these hybrid compounds.

  2. Synthesis and gas adsorption study of porous metal-organic framework materials

    Science.gov (United States)

    Mu, Bin

    Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) have become the focus of intense study over the past decade due to their potential for advancing a variety of applications including air purification, gas storage, adsorption separations, catalysis, gas sensing, drug delivery, and so on. These materials have some distinct advantages over traditional porous materials such as the well-defined structures, uniform pore sizes, chemically functionalized sorption sites, and potential for postsynthetic modification, etc. Thus, synthesis and adsorption studies of porous MOFs have increased substantially in recent years. Among various prospective applications, air purification is one of the most immediate concerns, which has urgent requirements to improve current nuclear, biological, and chemical (NBC) filters involving commercial and military purposes. Thus, the major goal of this funded project is to search, synthesize, and test these novel hybrid porous materials for adsorptive removal of toxic industrial chemicals (TICs) and chemical warfare agents (CWAs), and to install the benchmark for new-generation NBC filters. The objective of this study is three-fold: (i) Advance our understanding of coordination chemistry by synthesizing novel MOFs and characterizing these porous coordination polymers; (ii) Evaluate porous MOF materials for gasadsorption applications including CO2 capture, CH4 storage, other light gas adsorption and separations, and examine the chemical and physical properties of these solid adsorbents including thermal stability and heat capacity of MOFs; (iii) Evaluate porous MOF materials for next-generation NBC filter media by adsorption breakthrough measurements of TICs on MOFs, and advance our understanding about structureproperty relationships of these novel adsorbents.

  3. Highly mesoporous metal-organic framework assembled in a switchable solvent

    Science.gov (United States)

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-01

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  4. Synthesis of a metal-organic framework confined in periodic mesoporous silica with enhanced hydrostability as a novel fiber coating for solid-phase microextraction.

    Science.gov (United States)

    Abolghasemi, Mir Mahdi; Yousefi, Vahid; Piryaei, Marzieh

    2015-04-01

    A metal-organic framework/periodic mesoporous silica (MOF-5@SBA-15) hybrid material has been prepared by using SBA-15 as a matrix. The prepared MOF-5@SBA-15 hybrid material was then deposited on a stainless-steel wire to obtain the fiber for the solid-phase microextraction of phenolic compounds. Modifications in the metal-organic framework structure have proven to improve the extraction performance of MOF/SBA-15 hybrid materials, compared to pure MOF-5 and SBA-15. Optimum conditions include an extraction temperature of 75°C, a desorption temperature of 260°C, and a salt concentration of 20% w/v. The dynamic linear range and limit of detection range from 0.1-500 and from 0.01-3.12 ng/mL, respectively. The repeatability for one fiber (n = 3), expressed as relative standard deviation, is between 4.3 and 9.6%. The method offers the advantage of being simple to use, rapid, and low cost, the thermal stability of the fiber, and high relative recovery (compared to conventional methods) represent additional attractive features.

  5. Investigation of cracks in GaN films grown by combined hydride and metal organic vapor-phase epitaxial method

    Directory of Open Access Journals (Sweden)

    Yang Tieying

    2011-01-01

    Full Text Available Abstract Cracks appeared in GaN epitaxial layers which were grown by a novel method combining metal organic vapor-phase epitaxy (MOCVD and hydride vapor-phase epitaxy (HVPE in one chamber. The origin of cracks in a 22-μm thick GaN film was fully investigated by high-resolution X-ray diffraction (XRD, micro-Raman spectra, and scanning electron microscopy (SEM. Many cracks under the surface were first observed by SEM after etching for 10 min. By investigating the cross section of the sample with high-resolution micro-Raman spectra, the distribution of the stress along the depth was determined. From the interface of the film/substrate to the top surface of the film, several turnings were found. A large compressive stress existed at the interface. The stress went down as the detecting area was moved up from the interface to the overlayer, and it was maintained at a large value for a long depth area. Then it went down again, and it finally increased near the top surface. The cross-section of the film was observed after cleaving and etching for 2 min. It was found that the crystal quality of the healed part was nearly the same as the uncracked region. This indicated that cracking occurred in the growth, when the tensile stress accumulated and reached the critical value. Moreover, the cracks would heal because of high lateral growth rate.

  6. An Investigation on the Use of a Laser Ablation Treatment on Metallic Surfaces and the Influence of Temperature on Fracture Toughness of Hybrid Co-Cured Metal-PMC Interfaces

    Science.gov (United States)

    Connell, John; Palmieri, Frank; Truong, Hieu; Ochoa, Ozden; Lagoudas, Dimitris

    2015-01-01

    Hybrid composite laminates that contain alternating layers of titanium alloys and carbon fabric reinforced polyimide matrix composites (PMC) are excellent candidates for light-weight, high-temperature structural materials for high-speed aerospace vehicles. The delamination resistance of the hybrid titanium-PMC interface is of crucial consideration for structural integrity during service. Here, we report the first investigations on the use of laser ablation in combination with sol-gel treatment technique on Ti/NiTi foil surfaces in co-cured hybrid polyimide matrix composite laminates. Mode-I and mode-II fracture toughness of the hybrid Ti/NiTi-PMC interface as a function of temperature were determined via experimental testing and finite element analysis.

  7. Photoelectron spectroscopic study on monolayer pentacene thin-film/polar ZnO single-crystal hybrid interface

    Science.gov (United States)

    Nagata, Takahiro; Nakamura, Tatsuru; Hayakawa, Ryoma; Yoshimura, Takeshi; Oh, Seungjun; Hiroshiba, Nobuya; Chikyow, Toyohiro; Fujimura, Norifumi; Wakayama, Yutaka

    2017-02-01

    The polarity effects of ZnO on the electronic state of a monolayer pentacene/ZnO interface were investigated by X-ray photoelectron spectroscopy (XPS). XPS revealed that the Zn-polar ZnO (Zn-ZnO) strongly depleted electrons in pentacene at the interface. The O-polar ZnO showed greater electron transfer from ZnO to pentacene than Zn-ZnO. The surface potential of pentacene on ZnO was larger than that of bulk pentacene regardless of the ZnO polarity. These findings indicate that the polarity of ZnO has the potential to control the electronic state of the organic/inorganic semiconductor interface.

  8. Studies of gas adsorption in flexible Metal-Organic frameworks

    Science.gov (United States)

    Sircar, Sarmishtha

    Flexible Metal-Organic frameworks that exhibit a gate-opening (GO) adsorption mechanism have potential for gas separations and gas storage. The GO phenomenon occurs when molecular gates in the structure expand/contract in response to the activation/de-activation of a system variable e.g. temperature, pressure or gas. Sharp discontinuities in the isotherm leading to S-shapes and large adsorption-desorption hysteresis are typical of this phenomenon. This study investigates the kinetics and thermodynamics of the GO behavior by combining adsorption measurements and analytical modeling of adsorption kinetics and capacity as a function of adsorbate, GO pressure, and temperature. Basic understanding of GO mechanism will help harness GO-MOF's as adsorbents for gas separations and storage. Experiments were performed on two precharacterized MOFs with verified GO behavior. These are (1) Zn2(bpdc)2(bpee), which expands from a relative amorphous to crystalline structure and (2) Cu[(dhbc) 2(4,4f-bpy)]H2O, a mutually interdigitated 2-D structure (bpdc = biphenyldicarboxylate, bpee = 1,2]bipyridylethene; DMF = N,N-dimethyl formamide, dhbc= 2,5-dihydroxybenzoic acid, bpy=bipyridine). Both sub- and super-critical adsorption data were collected using three adsorption units: a standard low-pressure volumetric adsorption unit, a commercial high-pressure gravimetric analyzer and a custom-built high-pressure differential volumetric unit. Collected laboratory data were combined with published adsorption rate and isotherm data for analysis to broaden the range of data collection. The accuracy of the high-pressure differential unit was improved by over 300-fold by changing analytical methods of processing data to establish a reliable null correction. A pronounced effect of the allowed experimental time was found at cryogenic temperatures on (1). Tightening the stability criteria used by the adsorption equipment to determine equilibration increased the experimental time from the order of

  9. In situ growth of CdS nanoparticles on UiO-66 metal-organic framework octahedrons for enhanced photocatalytic hydrogen production under visible light irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Jian-Jian; Wang, Rong; Liu, Xin-Ling; Peng, Fu-Min [School of Chemistry and Chemical Engineering and Innovation Lab for Clean Energy & Green Catalysis, Anhui University, Hefei 230601 (China); Li, Chuan-Hao, E-mail: chuanhao.li@yale.edu [School of Chemistry and Chemical Engineering and Innovation Lab for Clean Energy & Green Catalysis, Anhui University, Hefei 230601 (China); Department of Chemical & Environmental Engineering, Yale University, New Haven 06511 (United States); Teng, Fei [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Sciences and Engineering, Nanjing University of Information Science and Technology, Nanjing 210044 (China); Yuan, Yu-Peng, E-mail: yupengyuan@ahu.edu.cn [School of Chemistry and Chemical Engineering and Innovation Lab for Clean Energy & Green Catalysis, Anhui University, Hefei 230601 (China); Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Sciences and Engineering, Nanjing University of Information Science and Technology, Nanjing 210044 (China)

    2015-08-15

    Graphical abstract: Enhanced photocatalytic hydrogen generation was achieved though constructing the CdS/UiO-66 MOF hybrids. In addition, the resultant hybrids show excellent photostability for hydrogen generation. - Highlights: • CdS nanoparticles were hydrothermally grown on UiO-66 octahedrons. • The resultant CdS/UiO-66 hybrids show enhanced photocatalytic H{sub 2} generation under visible light irradiation. • CdS/UiO-66 hybrids possess excellent photostability for long-term hydrogen generation. - Abstract: CdS nanoparticles acting as photosensitizer was grown in situ upon UiO-66 metal-organic framework octahedrons through a hydrothermal process. The resultant CdS/UiO-66 hybrid photocatalysts show remarkably active hydrogen evolution under visible light irradiation as compared to CdS and UiO-66 alone. The optimum hybrid with 16 wt% CdS loading shows a hydrogen production rate of 235 μmol h{sup −1}, corresponding to 1.2% quantum efficiency at 420 nm. The improved photocatalytic hydrogen production over hybrid CdS/UiO-66 is ascribed to the efficient interfacial charge transfer from CdS to UiO-66, which effectively suppresses the recombination of photogenerated electron-hole pairs and thereby enhancing the photocatalytic efficiency.

  10. Nanoscale metal-organic frameworks for biomedical imaging and drug delivery.

    Science.gov (United States)

    Della Rocca, Joseph; Liu, Demin; Lin, Wenbin

    2011-10-18

    Metal-organic frameworks (MOFs), a class of hybrid materials formed by the self-assembly of polydentate bridging ligands and metal-connecting points, have been studied for a variety of applications. Recently, these materials have been scaled down to nanometer sizes, and this Account details the development of nanoscale metal-organic frameworks (NMOFs) for biomedical applications. NMOFs possess several potential advantages over conventional nanomedicines such as their structural and chemical diversity, their high loading capacity, and their intrinsic biodegradability. Under relatively mild conditions, NMOFs can be obtained as either crystalline or amorphous materials. The particle composition, size, and morphology can be easily tuned to optimize the final particle properties. Researchers have employed two general strategies to deliver active agents using NMOFs: by incorporating active agents into the frameworks or by loading active agents into the pores and channels of the NMOFs. The modification of NMOF surfaces with either silica coatings or organic polymers improves NMOF stability, fine-tunes their properties, and imparts additional functionality. Preliminary biomedical applications of NMOFs have focused on their use as delivery vehicles for imaging contrast agents and molecular therapeutics. Because NMOFs can carry large amounts of paramagnetic metal ions, they have been extensively explored as magnetic resonance imaging (MRI) contrast agents. Both Gd(3+)- and Mn(2+)-containing NMOFs have shown excellent efficacy as T(1)-weighted contrast agents with large per metal- and per particle-based MR relaxivities. Fe(3+)-containing NMOFs have demonstrated excellent T(2)-weighted contrast enhancement. Upon intravenous injection of iron carboxylate NMOFs in Wistar rats, researchers observed negative signal enhancement in the liver and spleen, which dissipated over time, indicating the degradation and clearance of the NMOF. Through the incorporation of luminescent or high

  11. Symbiosis of zeolite-like metal-organic frameworks (rho-ZMOF) and hydrogels: Composites for controlled drug release

    KAUST Repository

    Ananthoji, Ramakanth

    2011-01-01

    The design and synthesis of new finely tunable porous materials has spurred interest in developing novel uses in a variety of systems. Zeolites, inorganic materials with high thermal and mechanical stability, in particular, have been widely examined for use in applications such as catalysis, ion exchange and separation. A relatively new class of inorganic-organic hybrid materials known as metal-organic frameworks (MOFs) have recently surfaced, and many have exhibited their efficiency in potential applications such as ion exchange and drug delivery. A more recent development is the design and synthesis of a subclass of MOFs based on zeolite topologies (i.e. ZMOFs), which often exhibit traits of both zeolites and MOFs. Bio-compatible hydrogels already play an important role in drug delivery systems, but are often limited by stability issues. Thus, the addition of ZMOFs to hydrogel formulations is expected to enhance the hydrogel mechanical properties, and the ZMOF-hydrogel composites should present improved, symbiotic drug storage and release for delivery applications. Herein we present the novel composites of a hydrogel with a zeolite-like metal-organic framework, rho-ZMOF, using 2-hydroxyethyl methacrylate (HEMA), 2,3-dihydroxypropyl methacrylate (DHPMA), N-vinyl-2-pyrolidinone (VP) and ethylene glycol dimethacrylate (EGDMA), and the corresponding drug release. An ultraviolet (UV) polymerization method is employed to synthesize the hydrogels, VP 0, VP 15, VP 30, VP 45 and the ZMOF-VP 30 composite, by varying the VP content (mol%). The rho-ZMOF, VP 30, and ZMOF-VP 30 composite are all tested for the controlled release of procainamide (protonated, PH), an anti-arrhythmic drug, in phosphate buffer solution (PBS) using UV spectroscopy. © 2011 The Royal Society of Chemistry.

  12. Cluster-induced desorption from metal organic surfaces: Structural effects

    Energy Technology Data Exchange (ETDEWEB)

    Delcorte, A., E-mail: arnaud.delcorte@uclouvain.be [Institute of Condensed Matter and Nanosciences, Université catholique de Louvain, 1 Croix du Sud, B-1348 Louvain-la-Neuve (Belgium); Hoecke, E. van; Restrepo, O.A. [Institute of Condensed Matter and Nanosciences, Université catholique de Louvain, 1 Croix du Sud, B-1348 Louvain-la-Neuve (Belgium)

    2013-05-15

    Molecular dynamics (MD) simulations are used to model the 10 keV bombardment of Au-nanoparticle (NP)-covered polymeric samples by Ga, C{sub 60} and Au{sub 400} projectiles, at normal incidence. While the presence of the Au-NPs tends to enhance the organic material emission upon Ga and Au{sub 400} bombardment, as a result of increased projectile stopping, it strongly reduces the organic emission upon C{sub 60} bombardment because of the projectile reflection. Our results show that these trends are valid for kDa polymers (which can be emitted intact) as well as for virtually infinite length chains (which require fragmentation), but that the polymer sputtered mass is consistently >3 times larger in the case of the kDa molecules for all impact points and projectiles. Using a series of samples, it is also shown that embedding the Au-NPs in the organic material leads to completely different results, with, upon C{sub 60} bombardment, the largest sputtered masses observed for impacts above the NPs. For Au{sub 400} bombardment, the burial of the Au-NPs leads to comparatively lower sputtered masses. These new results demonstrate the complexity of the sputtering of nanostructured hybrid materials by cluster projectiles and suggest various artifacts that should complicate the analysis and depth profiling of such materials.

  13. Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production

    Science.gov (United States)

    Tian, Jia; Xu, Zi-Yue; Zhang, Dan-Wei; Wang, Hui; Xie, Song-Hai; Xu, Da-Wen; Ren, Yuan-Hang; Wang, Hao; Liu, Yi; Li, Zhan-Ting

    2016-05-01

    Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy)3]2+-based precursor and cucurbit[8]uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells-Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy)3]2+ units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.

  14. Interplay of Internal Structure and Interfaces on the Emitting Properties of Hybrid ZnO Hierarchical Particles.

    Science.gov (United States)

    Distaso, Monica; Bertoni, Giovanni; Todisco, Stefano; Marras, Sergio; Gallo, Vito; Manna, Liberato; Peukert, Wolfgang

    2017-05-03

    The design of hybrid organic/inorganic nanostructures with controlled assembly drives the development of materials with new or improved properties and superior performances. In this paper, the surface and internal structure of hybrid ZnO poly-N-vinylpyrrolidone (ZnO/PVP) mesocrystals are investigated in detail and correlated with their emitting properties. A photoluminescence study at room temperature reveals that the as-synthesized particles show a remarkable ultraviolet (UV) emission, whereas an emission from defects in the visible region is not observed. On the other hand, a visible emission is achieved upon calcination of the hybrid ZnO/PVP particles in air, and its intensity is found to increase with the calcination temperature and, in some cases, to overwhelm the UV emission. A molecular description is proposed for the absence of a visible emission from defects in the as-synthesized ZnO/PVP mesocrystals on the basis of Fourier transform infrared (FTIR) and solid-state (13)C NMR (SSNMR) spectroscopy. An in-depth electron microscopy study sheds light on the internal organization of mesocrystals and reveals the formation of nanoreactors, that is, particles with enclosed porosity, upon thermal treatment.

  15. ZnO Nanorods on a LaAlO 3 -SrTiO 3 Interface: Hybrid 1D-2D Diodes with Engineered Electronic Properties

    KAUST Repository

    Bera, Ashok

    2015-12-28

    Integrating nanomaterials with different dimensionalities and properties is a versatile approach toward realizing new functionalities in advanced devices. Here, a novel diode-type heterostructure is reported consisting of 1D semiconducting ZnO nanorods and 2D metallic LaAlO3-SrTiO3 interface. Tunable insulator-to-metal transitions, absent in the individual components, are observed as a result of the competing temperature-dependent conduction mechanisms. Detailed transport analysis reveals direct tunneling at low bias, Fowler-Nordheim tunneling at high forward bias, and Zener breakdown at high reverse bias. Our results highlight the rich electronic properties of such artificial diodes with hybrid dimensionalities, and the design principle may be generalized to other nanomaterials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. ZnO Nanorods on a LaAlO3 -SrTiO3 Interface: Hybrid 1D-2D Diodes with Engineered Electronic Properties.

    Science.gov (United States)

    Bera, Ashok; Lin, Weinan; Yao, Yingbang; Ding, Junfeng; Lourembam, James; Wu, Tom

    2016-02-10

    Integrating nanomaterials with different dimensionalities and properties is a versatile approach toward realizing new functionalities in advanced devices. Here, a novel diode-type heterostructure is reported consisting of 1D semiconducting ZnO nanorods and 2D metallic LaAlO3-SrTiO3 interface. Tunable insulator-to-metal transitions, absent in the individual components, are observed as a result of the competing temperature-dependent conduction mechanisms. Detailed transport analysis reveals direct tunneling at low bias, Fowler-Nordheim tunneling at high forward bias, and Zener breakdown at high reverse bias. Our results highlight the rich electronic properties of such artificial diodes with hybrid dimensionalities, and the design principle may be generalized to other nanomaterials.

  17. Bio-hybrid interfaces to study neuromorphic functionalities: New multidisciplinary evidences of cell viability on poly(anyline) (PANI), a semiconductor polymer with memristive properties.

    Science.gov (United States)

    Juarez-Hernandez, Leon J; Cornella, Nicola; Pasquardini, Laura; Battistoni, Silvia; Vidalino, Laura; Vanzetti, Lia; Caponi, Silvia; Dalla Serra, Mauro; Iannotta, Salvatore; Pederzolli, Cecilia; Macchi, Paolo; Musio, Carlo

    2016-01-01

    The interfacing of artificial devices with biological systems is a challenging field that crosses several disciplines ranging from fundamental research (biophysical chemistry, neurobiology, material and surface science) to frontier technological application (nanotechnology, bioelectronics). The memristor is the fourth fundamental circuit element, whose electrical properties favor applications in signal processing, neural networks, and brain-computer interactions and it represents a new frontier for technological applications in many fields including the nanotechnologies, bioelectronics and the biosensors. Using multidisciplinary approaches, covering surface science, cell biology and electrophysiology, we successfully implemented a living bio-hybrid system constituted by cells adhering to films of poly(aniline) (PANI), a semiconductor polymer having memristive properties assembled with polyelectrolytes. Here we tested whether the PANI devices could support survivor, adhesion and differentiation of several cell lines, including the neuron-like SHSY5Y cells. Moreover, we performed electrophysiology on these cells showing that the biophysical properties are retained with differences occurring in the recorded ion currents. Taken together, the cell viability here reported is the key requirement to design and develop a reliable functional memristor-based bio-hybrid able to mimic neuronal activity and plasticity.

  18. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries

    Science.gov (United States)

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-03-01

    Lithium-sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium-sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density.

  19. Homochiral metal-organic framework used as a stationary phase for high-performance liquid chromatography.

    Science.gov (United States)

    Kong, Jiao; Zhang, Mei; Duan, Ai-Hong; Zhang, Jun-Hui; Yang, Rui; Yuan, Li-Ming

    2015-02-01

    Metal-organic frameworks are promising porous materials. Chiral metal-organic frameworks have attracted considerable attention in controlling enantioselectivity. In this study, a homochiral metal-organic framework [Co(2) (D-cam)(2) (TMDPy)] (D-cam = D-camphorates, TMDPy = 4,4'-trimethylenedipyridine) with a non-interpenetrating primitive cubic net has been used as a chiral stationary phase in high-performance liquid chromatography. It has allowed the successful separation of six positional isomers and six chiral compounds. The good selectivity and baseline separation, or at least 60% valley separation, confirmed its excellent molecular recognition characteristics. The relative standard deviations for the retention time of run-to-run and column-to-column were less than 1.8 and 3.1%, respectively. These results demonstrate that [Co(2) (D-cam)(2) (TMDPy)] may represent a promising chiral stationary phase for use in high-performance liquid chromatography.

  20. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries.

    Science.gov (United States)

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-03-06

    Lithium-sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium-sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density.

  1. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium–sulfur batteries

    Science.gov (United States)

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-01-01

    Lithium–sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium–sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density. PMID:28262801

  2. Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules

    Science.gov (United States)

    Liang, Kang; Ricco, Raffaele; Doherty, Cara M.; Styles, Mark J.; Bell, Stephen; Kirby, Nigel; Mudie, Stephen; Haylock, David; Hill, Anita J.; Doonan, Christian J.; Falcaro, Paolo

    2015-06-01

    Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules.

  3. Effect of organic substituents on the adsorption of carbon dioxide on a metal-organic framework

    Science.gov (United States)

    Thu Ha, Nguyen Thi; Lefedova, O. V.; Ha, Nguyen Ngoc

    2017-01-01

    The adsorption of carbon dioxide on the MOF-5 metal-organic framework and modifications of it obtained by replacing the hydrogen atoms in the organic ligands with electron donor (-CH3,-OCH3) or electron acceptor groups (-CN,-NO2) is investigated using the grand canonical Monte Carlo (GCMC) method and density functional theory (DFT). It is shown that the adsorption of carbon dioxide molecules on the structures of metal-organic frameworks is most likely on Zn4O clusters, and that the adsorption of carbon dioxide is of a physical nature. The presence of substituents-CH3,-OCH3,-CN in metal-organic frameworks increases their capacity to adsorb carbon dioxide, while that of nitro groups (-NO2) has the opposite effect.

  4. Selective anion exchange with nanogated isoreticular positive metal-organic frameworks.

    Science.gov (United States)

    Zhao, Xiang; Bu, Xianhui; Wu, Tao; Zheng, Shou-Tian; Wang, Le; Feng, Pingyun

    2013-01-01

    Crystalline porous materials, especially inorganic porous solids such as zeolites, usually have negative frameworks with extra-framework mobile cations and are widely used for cation exchange. It is highly desirable to develop new materials with positive frameworks for selective anion exchange and separation or storage and delivery. Recent advances in metal-organic framework synthesis have created new opportunities in this direction. Here we report the synthesis of a series of positive indium metal-organic frameworks and their utilization as a platform for the anion exchange-based separation process. This process is capable of size- or charge-selective ion-exchange of organic dyes and may form the basis for size-selective ion chromatography. Ion-exchange dynamics of a series of organic dyes and their selective encapsulation and release are also studied, highlighting the advantages of metal-organic framework compositions for designing host materials tailored for applications in anion separation and purification.

  5. Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules.

    Science.gov (United States)

    Liang, Kang; Ricco, Raffaele; Doherty, Cara M; Styles, Mark J; Bell, Stephen; Kirby, Nigel; Mudie, Stephen; Haylock, David; Hill, Anita J; Doonan, Christian J; Falcaro, Paolo

    2015-06-04

    Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules.

  6. A Combined Experimental and Computational Study on the Stability of Nanofluids Containing Metal Organic Frameworks.

    Science.gov (United States)

    Annapureddy, Harsha V R; Nune, Satish K; Motkuri, Radha Kishan; McGrail, B Peter; Dang, Liem X

    2015-07-23

    Computational studies on nanofluids composed of metal organic frameworks were performed using molecular modeling techniques. Grand Canonical Monte Carlo simulations were used to study the adsorption behavior of 1,1,1,3,3-pentafluoropropane (R-245fa) in a MIL-101 metal organic frameworks at various temperatures. To understand the stability of the nanofluid composed of MIL-101 particles, we performed molecular dynamics simulations to compute potentials of mean force between hypothetical MIL-101 fragments terminated with two different kinds of modulators in R-245fa and water. Our computed potentials of mean force results indicate that the metal organic frameworks particles tend to disperse better in water than in R-245fa. The reasons for this difference in dispersion were analyzed and are discussed in the paper. Our results agree with experimental results indicating that the potential models employed and modeling approaches provide good descriptions of molecular interactions and the reliabilities.

  7. Metal-organic Kagome lattices M3(2,3,6,7,10,11-hexaiminotriphenylene)2 (M = Ni and Cu): from semiconducting to metallic by metal substitution.

    Science.gov (United States)

    Chen, Shuang; Dai, Jun; Zeng, Xiao Cheng

    2015-02-28

    Motivated by recent experimental synthesis of a semiconducting metal-organic graphene analogue (J. Am. Chem. Soc., 2014, 136, 8859), i.e., Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 [Ni3(HITP)2], a new Kagome lattice, Cu3(HITP)2, is designed by substituting the coordination of Ni by Cu. Such substitution results in interesting changes in electronic properties of the M3(HITP)2 bulk and two-dimensional (2D) sheets. In Ni3(HITP)2, each Ni atom adopts the dsp(2) hybridization, forming a perfect 2D conjugation, whereas in Cu3(HITP)2, each Cu atom adopts the sp(3) hybridization, resulting in a distorted 2D sheet. The M3(HITP)2 bulks, assembled from M3(HITP)2 sheets via both strong π-π interaction and weak metal-metal interaction, are metallic. However, the 2D Ni3(HITP)2 sheet is a semiconductor with a narrow band gap whereas the 2D Cu3(HITP)2 sheet is a metal. Remarkably, both the 2D M3(HITP)2 Kagome lattices possess Dirac bands in the vicinity of the Fermi level. Additional ab initio molecular dynamics simulations show that both sheets exhibit high thermal stability at elevated temperatures. Our theoretical study offers new insights into tunability of electronic properties for the 2D metal-organic frameworks (MOFs).

  8. Preparation and applications of monolithic structures containing metal-organic frameworks.

    Science.gov (United States)

    Lv, Yongqin; Tan, Xinyi; Svec, Frantisek

    2017-01-01

    Metal-organic frameworks are a new category of advanced porous materials with large surface areas and porosities, uniform pore sizes, tunable surface chemistry, and structural diversity. In combination with monoliths, they allow the fine tuning of desired interactions required in a variety of applications. This review article summarizes results of recent studies focused on synthetic strategies enabling incorporation of metal-organic frameworks in monolithic structures. A diverse array of applications including chromatographic separation, solid-phase microextraction, sample enrichment, heterogeneous catalysis, and enzymatic catalysis are also described. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Highly oriented surface-growth and covalent dye labeling of mesoporous metal-organic frameworks.

    Science.gov (United States)

    Hinterholzinger, Florian M; Wuttke, Stefan; Roy, Pascal; Preusse, Thomas; Schaate, Andreas; Behrens, Peter; Godt, Adelheid; Bein, Thomas

    2012-04-14

    Mesoporous amino-functionalized metal-organic framework thin films with the UiO-68 topology were grown in a highly oriented fashion on two different self-assembled monolayers on gold. The oriented MOF films were covalently modified with the fluorescent dye Rhodamine B inside the pore system, as demonstrated with size-selective fluorescence quenching studies. Our study suggests that mesoporous metal-organic frameworks are promising hosts for the covalent attachment of numerous functional moieties in a molecularly designed crystalline environment.

  10. The relevance of metal organic frameworks (MOFs) in inorganic materials chemistry

    Indian Academy of Sciences (India)

    Srinivasan Natarajan; Partha Mahata; Debajit Sarma

    2012-03-01

    The metal organic frameworks (MOFs) have evolved to be an important family and a corner stone for research in the area of inorganic chemistry. The progress made since 2000 has attracted researchers from other disciplines to actively engage themselves in this area. This cooperative synergy of different scientific believes have provided important edge and spread to the chemistry of metal-organic frameworks. The ease of synthesis coupled with the observation of properties in the areas of catalysis, sorption, separation, luminescence, bioactivity, magnetism, etc., are a proof of this synergism. In this article, we present the recent developments in this area.

  11. Multirate delivery of multiple therapeutic agents from metal-organic frameworks

    Science.gov (United States)

    McKinlay, Alistair C.; Allan, Phoebe K.; Renouf, Catherine L.; Duncan, Morven J.; Wheatley, Paul S.; Warrender, Stewart J.; Dawson, Daniel; Ashbrook, Sharon E.; Gil, Barbara; Marszalek, Bartosz; Düren, Tina; Williams, Jennifer J.; Charrier, Cedric; Mercer, Derry K.; Teat, Simon J.; Morris, Russell E.

    2014-12-01

    The highly porous nature of metal-organic frameworks (MOFs) offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-organic frameworks can be used to deliver multiple therapeutic agents—a biologically active gas, an antibiotic drug molecule, and an active metal ion—simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria.

  12. Tunable electrical conductivity in metal-organic framework thin film devices

    Energy Technology Data Exchange (ETDEWEB)

    Talin, Albert Alec; Allendorf, Mark D.; Stavila, Vitalie; Leonard, Francois

    2016-08-30

    A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal site, wherein the composition is electrically conductive. A method including infiltrating a porous metal organic framework (MOF) including an open metal site with a guest species that is capable of charge transfer; and coordinating the guest species to the open metal site to form a composition including an electrical conductivity greater than an electrical conductivity of the MOF.

  13. Tunable electrical conductivity in metal-organic framework thin film devices

    Energy Technology Data Exchange (ETDEWEB)

    Talin, Albert Alec; Allendorf, Mark D.; Stavila, Vitalie; Leonard, Francois

    2016-05-24

    A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal site, wherein the composition is electrically conductive. A method including infiltrating a porous metal organic framework (MOF) including an open metal site with a guest species that is capable of charge transfer; and coordinating the guest species to the open metal site to form a composition including an electrical conductivity greater than an electrical conductivity of the MOF.

  14. Lamellar metal-organic complex and its rod-like nanoparticles prepared with ultrasonic technique

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Metal-organic complex (H3NCH2CH2NH2)3[MoO2(OC6H4O)2] with a lamellar morphology has been syn- thesized. Its crystal structure was confirmed by single-crystal X-ray diffraction. The morphology of the crystal was observed by scanning electron microscopy (SEM). The metal-organic nanoparticles have been prepared by using an ultrasonic method. The morphology of the as-prepared nanoparticles was observed by transmission electron microscopy (TEM). The possible formation mechanism has also been proposed.

  15. Neutron powder diffraction of metal-organic frameworks for hydrogen storage

    Indian Academy of Sciences (India)

    Craig M Brown; Yun Liu; Dan A Neumann

    2008-10-01

    We review recent structural studies that we have undertaken aimed at elucidating the fundamental properties of metal-organic framework materials and their interactions with hydrogen. We have shown that exposing coordinatively unsaturated metal centers can greatly enhance the hydrogen binding energy and that they result in a significant increase of the surface packing density of adsorbed hydrogen molecules on materials' surface. We will review some of the structural aspects of these materials, especially the adsorbed hydrogen molecule surface packing density in one type of metal-organic framework, MOF-74, which can be packed even denser than that in solid hydrogen.

  16. Multirate delivery of multiple therapeutic agents from metal-organic frameworks

    Directory of Open Access Journals (Sweden)

    Alistair C. McKinlay

    2014-12-01

    Full Text Available The highly porous nature of metal-organic frameworks (MOFs offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-organic frameworks can be used to deliver multiple therapeutic agents—a biologically active gas, an antibiotic drug molecule, and an active metal ion—simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria.

  17. SM and ND Substiturions in YBCO Films Produced through Metal Organic Deposition (Postprint)

    Science.gov (United States)

    2012-02-01

    AFRL-RZ-WP-TP-2012-0122 SM AND ND SUBSTITUTIONS IN YBCO FILMS PRODUCED THROUGH METAL ORGANIC DEPOSITION (POSTPRINT) B.C. Harrison, J...Paper Postprint 01 January 2004 – 01 January 2006 4. TITLE AND SUBTITLE SM AND ND SUBSTITUTIONS IN YBCO FILMS PRODUCED THROUGH METAL ORGANIC...0223; Clearance Date: 06 Dec 2006. 14. ABSTRACT Epitaxial YBa2Cu3O7-x ( YBCO ) films were produced on non-buffered (100) single crystal LaAlO3 using

  18. Poly(isophthalic acid)(ethylene oxide) as a Macromolecular Modulator for Metal-Organic Polyhedra.

    Science.gov (United States)

    Chen, Teng-Hao; Wang, Le; Trueblood, Jonathan V; Grassian, Vicki H; Cohen, Seth M

    2016-08-03

    A new strategy was developed by using a polymer ligand, poly(isophthalic acid)(ethylene oxide), to modulate the growth of metal-organic polyhedra (MOP) crystals. This macromolecular modulator can effectively control the crystal habit of several different Cu24L24 (L = isophthalic acid derivatives) MOPs. The polymer also directed the formation of MOP structures under reaction conditions that only produce metal-organic frameworks in the absence of modulator. Moreover, the polymer also enabled the deposition of MOP crystals on glass surfaces. This macromolecular modulator strategy provides an innovative approach to control the morphology and assembly of MOP particles.

  19. Metal-organic frameworks as host materials of confined supercooled liquids.

    Science.gov (United States)

    Fischer, J K H; Sippel, P; Denysenko, D; Lunkenheimer, P; Volkmer, D; Loidl, A

    2015-10-21

    In this work, we examine the use of metal-organic framework (MOF) systems as host materials for the investigation of glassy dynamics in confined geometry. We investigate the confinement of the molecular glass former glycerol in three MFU-type MOFs with different pore sizes (MFU stands for "Metal-Organic Framework Ulm-University") and study the dynamics of the confined liquid via dielectric spectroscopy. In accord with previous reports on confined glass formers, we find different degrees of deviations from bulk behavior depending on pore size, demonstrating that MOFs are well-suited host systems for confinement investigations.

  20. Ab-initio Study of Known and Hypothetical Metal-Organic Frameworks

    Science.gov (United States)

    Fuentes-Cabrera, Miguel; Nicholson, Don M.

    2004-03-01

    Rosi et al. [1] have found that microporous Metal-Organic Frameworks (MOF) materials are candidates for hydrogen storage applications. In particular, MOF-5 was found to adsorb hydrogen up to 4.5 weight percent at 78 kelvin and 1.0 weight percent at room temperature and pressure of 20 bar. We use ab-initio techniques to investigate hydrogen adsorption, stability, and the electronic properties of known and hypothetical Metal-Organic Frameworks. [1] N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O'Keeffe, and O.M. Yaghi

  1. Targeted manipulation of metal-organic frameworks to direct sorption properties.

    Science.gov (United States)

    Schneemann, Andreas; Henke, Sebastian; Schwedler, Inke; Fischer, Roland A

    2014-04-01

    Metal-organic frameworks are promising materials for manifold applications. This Minireview highlights approaches for the fine-tuning of specific sorption properties (e.g. capacity, selectivity, and breathing behavior) of this interesting class of materials. Central aspects covered are the control over the crystal morphology, the targeted tuning of sorption properties by judicious choice of metal centers and linkers, and the preparation of host-guest systems. We want to introduce the reader to these topics on the basis of the manipulation of a handful of outstanding prototypical metal-organic frameworks.

  2. Tuning the topology and functionality of metal-organic frameworks by ligand design.

    Science.gov (United States)

    Zhao, Dan; Timmons, Daren J; Yuan, Daqiang; Zhou, Hong-Cai

    2011-02-15

    Metal-organic frameworks (MOFs)-highly crystalline hybrid materials that combine metal ions with rigid organic ligands-have emerged as an important class of porous materials. The organic ligands add flexibility and diversity to the chemical structures and functions of these materials. In this Account, we summarize our laboratory's experience in tuning the topology and functionality of MOFs by ligand design. These investigations have led to new materials with interesting properties. By using a ligand that can adopt different symmetry conformations through free internal bond rotation, we have obtained two MOFs that are supramolecular stereoisomers of each other at different reaction temperatures. In another case, where the dimerized ligands function as a D(3)-Piedfort unit spacer, we achieve chiral (10,3)-a networks. In the design of MOF-based materials for hydrogen and methane storage, we focused on increasing the gas affinity of frameworks by using ligands with different geometries to control the pore size and effectively introduce unsaturated metal centers (UMCs) into the framework. Framework interpenetration in PCN-6 (PCN stands for porous coordination network) can lead to higher hydrogen uptake. Because of the proper alignment of the UMCs, PCN-12 holds the record for uptake of hydrogen at 77 K/760 Torr. In the case of methane storage, PCN-14 with anthracene-derived ligand achieves breakthrough storage capacity, at a level 28% higher than the U.S. Department of Energy target. Selective gas adsorption requires a pore size comparable to that of the target gas molecules; therefore, we use bulky ligands and network interpenetration to reduce the pore size. In addition, with the help of an amphiphilic ligand, we were able to use temperature to continuously change pore size in a 2D layer MOF. Adding charge to an organic ligand can also stabilize frameworks. By ionizing the amine group within mesoMOF-1, the resulting electronic repulsion keeps the network from

  3. Synthesis and Characterization of Metal-Organic Frameworks (MOFs) That Are Difficult to Access De Novo

    Science.gov (United States)

    Karagiaridi, Olga

    Metal-organic frameworks (MOFs) are a class of intriguing hybrid materials, comprised of metal-based nodes joined by organic linkers into a crystalline, porous, three-dimensional lattice. Their signature properties (well-defined surfaces, tailorability and ultra-high porosity) render them promising candidates for many applications, including, but not limited to, gas storage, gas separation, catalysis and sensing. One of the greatest challenges associated with MOF synthesis lies in the fact that obtaining a desired MOF structure that is tailored to perform a specific application is often not trivial. Traditional synthetic pathways termed "de novo synthesis" (typically one-pot reactions between the MOF structural building blocks under solvothermal conditions) often give rise to side products that do not possess the desired structure. To circumvent this problem, we have studied in depth two powerful MOF synthetic techniques -- solvent-assisted linker exchange (SALE) and transmetalation. These are heterogeneous reactions of parent MOF crystals with concentrated solutions of organic linkers and inorganic metal salts, respectively, that lead to the replacement of the linkers or metal nodes within the parent MOFs by the desired components, while the overall framework topology is preserved. The projects described in this dissertation have aimed to apply these techniques to transform simple (unfunctionalized) and easy to synthesize representative materials from various MOF systems to structurally and functionally interesting daughter products. Examples include synthesis of MOFs that are energetically "unfavorable", extension of MOF cages by longer linker incorporation, functionalization of MOF pores and endowment of MOFs with permanent and persistent porosity. Through these projects, we have been able to formulate a set of rules that can be applied to predict the successful outcome of SALE. Since the allure of MOFs lies in their applications, expanding the range of

  4. Requirements for Hybrid Cosimulation

    Science.gov (United States)

    2014-08-16

    hybrid cosimulation version of the Functional Mockup Interface (FMI) standard. A cosimulation standard de nes interfaces that enable diverse simulation...cosimulation standards, and specifically provides guidance for development of a hybrid cosimulation version of the Functional Mockup Interface (FMI) standard...V. Peetz, and S. Wolf. The functional mockup interface for tool independent exchange of simulation models. In Proc. of the 8-th International

  5. Rational material, interface, and device engineering for high-performance polymer and perovskite solar cells (Presentation Recording)

    Science.gov (United States)

    Jen, Alex K.

    2015-10-01

    The performance of polymer and hybrid solar cells is also strongly dependent on their efficiency in harvesting light, exciton dissociation, charge transport, and charge collection at the metal/organic/metal oxide or the metal/perovskite/metal oxide interfaces. Our laboratory employs a molecular engineering approach to develop processible low band-gap polymers with high charge carrier mobility that can enhance power conversion efficiency of the single junction solar cells to values as high as ~11%. We have also developed several innovative strategies to modify the interface of bulk-heterojunction devices and create new device architectures to fully explore their potential for solar applications. In this talk, the integrated approach of combining material design, interface, and device engineering to significantly improve the performance of polymer and hybrid perovskite photovoltaic cells will be discussed. Specific emphasis will be placed on the development of low band-gap polymers with reduced reorganizational energy and proper energy levels, formation of optimized morphology of active layer, and minimized interfacial energy barriers using functional conductive surfactants. At the end, several new device architectures and optical engineering strategies to make tandem cells and semitransparent solar cells will be discussed to explore the full promise of polymer and perovskite hybrid solar cells.

  6. Gas Phase Sensing of Alcohols by Metal Organic Framework–Polymer Composite Materials

    Science.gov (United States)

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in a Matrimid polymer matrix with different weight ratios (0–100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH2-MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ0.5) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH2-MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing

  7. Metal-Organic Frameworks at the Biointerface: Synthetic Strategies and Applications.

    Science.gov (United States)

    Doonan, Christian; Riccò, Raffaele; Liang, Kang; Bradshaw, Darren; Falcaro, Paolo

    2017-06-20

    Many living organisms are capable of producing inorganic materials of precisely controlled structure and morphology. This ubiquitous process is termed biomineralization and is observed in nature from the macroscale (e.g., formation of exoskeletons) down to the nanoscale (e.g., mineral storage and transportation in proteins). Extensive research efforts have pursued replicating this chemistry with the overarching aims of synthesizing new materials of unprecedented physical properties and understanding the complex mechanisms that occur at the biological-inorganic interface. Recently, we demonstrated that a class of porous materials termed metal-organic frameworks (MOFs) can spontaneously form on protein-based hydrogels via a process analogous to natural matrix-mediated biomineralization. Subsequently, this strategy was extended to functional biomacromolecules, including proteins and DNA, which have been shown to seed and accelerate crystallization of MOFs. Alternative strategies exploit co-precipitating agents such as polymers to induce MOF particle formation thus facilitating protein encapsulation within the porous crystals. In these examples the rigid molecular architecture of the MOF was found to form a protective coating around the biomacromolecule offering improved stability to external environments that would normally lead to its degradation. In this way, the MOF shell mimics the protective function of a biomineralized exoskeleton. Other methodologies have also been explored to encapsulate enzymes within MOF structures, including the fabrication of polycrystalline hollow MOF microcapsules that preserve the original enzyme functionality over several batch reaction cycles. The potential to design MOFs of varied pore size and chemical functionality has underpinned studies describing the postsynthesis infiltration of enzymes into MOF pore networks and bioconjugation strategies for the decoration of the MOF outer surface, respectively. These methods and

  8. Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions

    NARCIS (Netherlands)

    Xiang, S.C.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B.

    2012-01-01

    Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve s

  9. Lanthanide-Based Metal Organic Frameworks: Synthetic Strategies and Catalytic Applications

    NARCIS (Netherlands)

    Pagis, C.; Ferbinteanu, M.; Rothenberg, G.; Grecea, S.

    2016-01-01

    This short critical review outlines the main synthetic strategies used in the designed synthesis of lanthanide-based metal organic frameworks (Ln-MOFs). It explains the impact of the choice of organic linker on the final network topology, and it highlights the applications of Ln-MOFs in the

  10. Porphyrin-Based Metal-Organic Frameworks as Heterogeneous Catalysts in Oxidation Reactions.

    Science.gov (United States)

    Pereira, Carla F; Simões, Mário M Q; Tomé, João P C; Almeida Paz, Filipe A

    2016-10-12

    Porphyrin-based Metal-Organic Frameworks (Por-MOFs) constitute a special branch of the wide MOF family that has proven its own value and high potential in different applications. In this mini-review the application of these materials as catalysts in oxidation reactions is highlighted.

  11. Exploiting large-pore metal-organic frameworks for separations through entropic molecular mechanisms

    NARCIS (Netherlands)

    Torres-Knoop, A.; Dubbeldam, D.

    2015-01-01

    We review the molecular mechanisms behind adsorption and the separations of mixtures in metal-organic frameworks and zeolites. Separation mechanisms can be based on differences in the affinity of the adsorbate with the framework and on entropic effects. To develop next-generation adsorbents, the

  12. Metal-Organic Frameworks as Active Materials in Electronic Sensor Devices.

    Science.gov (United States)

    Campbell, Michael G; Dincă, Mircea

    2017-05-12

    In the past decade, advances in electrically conductive metal-organic frameworks (MOFs) and MOF-based electronic devices have created new opportunities for the development of next-generation sensors. Here we review this rapidly-growing field, with a focus on the different types of device configurations that have allowed for the use of MOFs as active components of electronic sensor devices.

  13. Metal-Organic Frameworks with d-f Cyanide Bridges: Structural Diversity, Bonding Regime, and Magnetism

    NARCIS (Netherlands)

    Ferbinteanu, M.; Cimpoesu, F.; Tanase, S.; Cheng, P.

    2015-01-01

    We present a selection of metal-organic frameworks based on d-f and f-f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the

  14. Metal-organic framework catalysts for selective cleavage of aryl-ether bonds

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Stavila, Vitalie

    2017-08-01

    The present invention relates to methods of employing a metal-organic framework (MOF) as a catalyst for cleaving chemical bonds. In particular instances, the MOF results in selective bond cleavage that results in hydrogenolyzis. Furthermore, the MOF catalyst can be reused in multiple cycles. Such MOF-based catalysts can be useful, e.g., to convert biomass components.

  15. Properties of alumina films by atmospheric pressure metal-organic chemical vapour deposition

    NARCIS (Netherlands)

    Haanappel, V.A.C.; Corbach, van H.D.; Fransen, T.; Gellings, P.J.

    1994-01-01

    Thin alumina films were deposited at low temperatures (290–420°C) on stainless steel, type AISI 304. The deposition process was carried out in nitrogen by metal-organic chemical vapour deposition using aluminum tri-sec-butoxide. The film properties including the protection of the underlying substrat

  16. The mechanical properties of thin alumina film deposited by metal-organic chemical vapour deposition

    NARCIS (Netherlands)

    Haanappel, V.A.C.; Gellings, P.J.; Vendel, van de D.; Metselaar, H.S.C.; Corbach, van H.D.; Fransen, T.

    1995-01-01

    Amorphous alumina films were deposited by metal-organic chemical vapour deposition (MOCVD) on stainless steel, type AISI 304. The MOCVD experiments were performed in nitrogen at low and atmospheric pressures. The effects of deposition temperature, growth rate and film thickness on the mechanical pro

  17. Modulated synthesis of zirconium-metal organic framework (Zr-MOF) for hydrogen storage applications

    CSIR Research Space (South Africa)

    Ren, Jianwei

    2014-01-01

    Full Text Available A modulated synthesis of Zr-metal organic framework (Zr-MOF) with improved ease of handling and decreased reaction time is reported to yield highly crystalline Zr-MOF with well-defined octahedral shaped crystals for practical hydrogen storage...

  18. Luminescent metal-organic framework films as highly sensitive and fast-response oxygen sensors.

    Science.gov (United States)

    Dou, Zhongshang; Yu, Jiancan; Cui, Yuanjing; Yang, Yu; Wang, Zhiyu; Yang, Deren; Qian, Guodong

    2014-04-16

    Luminescent metal-organic framework films, CPM-5⊃Tb(3+) and MIL-100(In)⊃Tb(3+), have been constructed by postfunctionalization of two porous indium-organic frameworks with different structures, respectively. The MIL-100(In)⊃Tb(3+) film shows high oxygen sensitivity (KSV = 7.59) and short response/recovery time (6 s/53 s).

  19. Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

    Science.gov (United States)

    2013-01-01

    NMR , HR -MS, elemental analysis), and crystallographic information files (CIF) for LH4, LEt4, and NU-135; PXRD, adsorption excess isotherms, BET...boron, MOF, metal?organic framework, coordination polymer , porous, hydrogen, methane Vaiva Krungleviciute, Daniel J. Clingerman, Joseph E. Mondloch...framework, coordination polymer , porous, hydrogen, methane ■ INTRODUCTION Nanoporous materials such as metal−organic frameworks (MOFs) with tailorable pore

  20. In silico screening of metal-organic frameworks in separation applications

    NARCIS (Netherlands)

    R. Krishna; J.M. van Baten

    2011-01-01

    Porous materials such as metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) offer considerable potential for separating a variety of mixtures such as those relevant for CO2 capture (CO2/H2, CO2/CH4, CO2/N2), CH4/H2, alkanes/alkenes, and hydrocarbon isomers. There are basicall

  1. Elucidating steric effects on enantioselective epoxidation catalyzed by (salen)Mn in metal-organic frameworks

    NARCIS (Netherlands)

    Oxford, G.A.E.; Dubbeldam, D.; Broadbelt, L.J.; Snurr, R.Q.

    2011-01-01

    The steric effects of a metal-organic framework (MOF) on the enantioselectivity of a (salen)Mn were studied using classical atomistic modeling. Rotational energy profiles for the approach of 2,2-dimethyl-2H-chromene to the active site of (salen)Mn were mapped for the homogeneous catalyst and the cat

  2. Evaluating metal-organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption

    NARCIS (Netherlands)

    Mason, J.A.; Sumida, K.; Herm, Z.R.; Krishna, R.; Long, J.R.

    2011-01-01

    Two representative metal-organic frameworks, Zn4O(BTB)2 (BTB3− = 1,3,5-benzenetribenzoate; MOF-177) and Mg2(dobdc) (dobdc4− = 1,4-dioxido-2,5-benzenedicarboxylate; Mg-MOF-74, CPO-27-Mg), are evaluated in detail for their potential use in post-combustion CO2 capture via temperature swing adsorption

  3. Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels

    NARCIS (Netherlands)

    Herm, Z.R.; Wiers, B.M.; Mason, J.A.; van Baten, J.M.; Hudson, M.R.; Zajdel, P.; Brown, C.M.; Masciocchi, N.; Krishna, R.; Long, J.R.

    2013-01-01

    Metal-organic frameworks can offer pore geometries that are not available in zeolites or other porous media, facilitating distinct types of shape-based molecular separations. Here, we report Fe-2(BDP)(3) (BDP2- = 1,4-benzenedipyrazotate), a highly stable framework with triangular channels that effec

  4. Metal-Organic Frameworks For Adsorption Driven Energy Transformation: From Fundamentals To Applications

    NARCIS (Netherlands)

    De Lange, M.F.

    2015-01-01

    A novel class of materials, i.e. Metal-Organic Frameworks (MOFs), has successfully been developed that is extremely suited for application in heat pumps and chillers. They have a superior performance over commercial sorbents and may potentially contribute to considerable energy savings

  5. Highly Selective Water Adsorption in a Lanthanum Metal-Organic Framework

    NARCIS (Netherlands)

    Plessius, R.; Kromhout, R.; Dantas Ramos, A.L.; Ferbinteanu, M.; Mittelmeijer-Hazeleger, M.C.; Krishna, R.; Rothenberg, G.; Tanase, S.

    2014-01-01

    We present a new metal-organic framework (MOF) built from lanthanum and pyrazine-2,5-dicarboxylate (pyzdc) ions. This MOF, [La(pyzdc)(1.5)(H2O)(2)]center dot 2H(2)O, is microporous, with 1D channels that easily accommodate water molecules. Its framework is highly robust to dehydration/hydration

  6. Molecular Mechanisms for Adsorption in Cu-BTC Metal Organic Framework

    NARCIS (Netherlands)

    Gutiérrez Sevillano, J.J.; Vicent-Luna, J.M.; Dubbeldam, D.; Calero, S.

    2013-01-01

    We use molecular simulations to analyze the preferential adsorption sites of molecules that differ in size, shape, and polarizability in Cu-BTC metal organic framework. The cage system of the framework can be exploited to enhance adsorption of small gases. We find that nonpolar molecules adsorb

  7. Elucidating steric effects on enantioselective epoxidation catalyzed by (salen)Mn in metal-organic frameworks

    NARCIS (Netherlands)

    Oxford, G.A.E.; Dubbeldam, D.; Broadbelt, L.J.; Snurr, R.Q.

    2011-01-01

    The steric effects of a metal-organic framework (MOF) on the enantioselectivity of a (salen)Mn were studied using classical atomistic modeling. Rotational energy profiles for the approach of 2,2-dimethyl-2H-chromene to the active site of (salen)Mn were mapped for the homogeneous catalyst and the

  8. From metal-organic squares to porous zeolite-like supramolecular assemblies

    KAUST Repository

    Wang, Shuang

    2010-12-29

    We report the synthesis, structure, and characterization of two novel porous zeolite-like supramolecular assemblies, ZSA-1 and ZSA-2, having zeolite gis and rho topologies, respectively. The two compounds were assembled from functional metal-organic squares (MOSs) via directional hydrogen-bonding interactions and exhibited permanent microporosity and thermal stability up to 300 °C. © 2010 American Chemical Society.

  9. Controlling embedment and surface chemistry of nanoclusters in metal-organic frameworks.

    Science.gov (United States)

    Coupry, D E; Butson, J; Petkov, P S; Saunders, M; O'Donnell, K; Kim, H; Buckley, C; Addicoat, M; Heine, T; Szilágyi, P Á

    2016-04-14

    A combined theoretical and experimental approach demonstrates that nanocluster embedment into the pores of metal-organic frameworks (MOF) may be influenced by the chemical functionalisation of the MOF. Furthermore, this results in the surface functionalisation of the embedded nanoclusters, highlighting the potential of MOF scaffolds for the design and synthesis of novel functional materials.

  10. A highly porous metal-organic framework for large organic molecule capture and chromatographic separation.

    Science.gov (United States)

    Li, Pei-Zhou; Su, Jie; Liang, Jie; Liu, Jia; Zhang, Yuanyuan; Chen, Hongzhong; Zhao, Yanli

    2017-03-25

    A highly porous metal-organic framework (MOF) with large pores was successfully obtained via solvothermal assembly of a "click"-extended tricarboxylate ligand and Zn(ii) ions. The inherent feature of large-molecule accessible pores endows the MOF with a unique property for utilization toward large guest molecules.

  11. Metal-Organic Frameworks For Adsorption Driven Energy Transformation: From Fundamentals To Applications

    NARCIS (Netherlands)

    De Lange, M.F.

    2015-01-01

    A novel class of materials, i.e. Metal-Organic Frameworks (MOFs), has successfully been developed that is extremely suited for application in heat pumps and chillers. They have a superior performance over commercial sorbents and may potentially contribute to considerable energy savings worldwide. Gl

  12. Channeling and electromagnetic radiation of relativistic charged particles in metal-organic frameworks

    Science.gov (United States)

    Zhevago, N. K.; Glebov, V. I.

    2017-06-01

    We have developed the theory of electromagnetic interaction of relativistic charged particles with metal-organic frameworks (MOFs). The electrostatic potential and electron number density distribution in MOFs were calculated using the most accurate data for the atomic form factors. Peculiarities of axial channeling of fast charged particles and various types of electromagnetic radiation from relativistic particles has been discussed.

  13. Tuning of gate adsorption: modification of a flexible metal-organic framework by secondary organic ligands.

    Science.gov (United States)

    Kondo, Atsushi; Fujii, Takuro; Maeda, Kazuyuki

    2014-06-14

    For realizing selective adsorption of targeted molecules, a flexible metal-organic framework (MOF) was modified with monodentate secondary ligands. Although the modified MOF retains CO2 adsorptivities with a vertical adsorption uptake, the material also shows gate adsorptivities of a specific gas molecule that the pristine MOF does not adsorb.

  14. Lithium-Ion-Battery Anode Materials with Improved Capacity from a Metal-Organic Framework.

    Science.gov (United States)

    Lin, Xiao-Ming; Niu, Ji-Liang; Lin, Jia; Wei, Lei-Ming; Hu, Lei; Zhang, Gang; Cai, Yue-Peng

    2016-09-06

    We present a porous metal-organic framework (MOF) with remarkable thermal stability that exhibits a discharge capacity of 300 mAh g(-1) as an anode material for a lithium-ion battery. Pyrolysis of the obtained MOF gives an anode material with improved capacity (741 mAh g(-1)) and superior cyclic stability.

  15. Shape Controlled Hierarchical Porous Hydrophobic/Oleophilic Metal-Organic Nanofibrous Gel Composites for Oil Adsorption.

    Science.gov (United States)

    Jayaramulu, Kolleboyina; Geyer, Florian; Petr, Martin; Zboril, Radek; Vollmer, Doris; Fischer, Roland A

    2017-03-01

    A versatile and facile synthetic route toward a ultralight hierarchical poroushybrid composed of metal-organic gels and fluorinated graphene oxide is reported. The composite gels show excellent absorbency of oil and various organic solvents due to their prominent meso/macropores, notable hydrophobicity, and superoleophilicity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Gas Phase Sensing of Alcohols by Metal Organic Framework-Polymer Composite Materials

    NARCIS (Netherlands)

    Sachdeva, Sumit; Koper, Sander J.H.; Sabetghadam, Anahid; Soccol, Dimitri; Gravesteijn, Dirk J.; Kapteijn, Freek; Sudhölter, Ernst J.R.; Gascon, Jorge; Smet, De Louis C.P.M.

    2017-01-01

    Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in

  17. Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions

    NARCIS (Netherlands)

    Xiang, S.C.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B.

    2012-01-01

    Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve

  18. Thermodynamics of Pore Filling Metal Clusters in Metal Organic Frameworks: Pd in UiO-66

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Sholl, David S.

    2012-01-01

    Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory calcu...

  19. In silico screening of metal-organic frameworks in separation applications

    NARCIS (Netherlands)

    Krishna, R.; van Baten, J.M.

    2011-01-01

    Porous materials such as metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) offer considerable potential for separating a variety of mixtures such as those relevant for CO2 capture (CO2/H2, CO2/CH4, CO2/N2), CH4/H2, alkanes/alkenes, and hydrocarbon isomers. There are

  20. Metal organic framework synthesis in the presence of surfactants: towards hierarchical MOFs?

    NARCIS (Netherlands)

    Seoane, B.; Dikhtiarenko, A.; Mayoral, A.; Tellez, C.; Coronas,J.; Kapteijn, F.; Gascon, J.

    2015-01-01

    The effect of synthesis pH and H2O/EtOH molar ratio on the textural properties of different aluminium trimesate metal organic frameworks (MOFs) prepared in the presence of the well-known cationic surfactant cetyltrimethylammonium bromide (CTAB) at 120 °C was studied with the purpose of obtaining a

  1. Capturing neon - the first experimental structure of neon trapped within a metal-organic environment.

    Science.gov (United States)

    Wood, Peter A; Sarjeant, Amy A; Yakovenko, Andrey A; Ward, Suzanna C; Groom, Colin R

    2016-08-21

    Despite being the fifth most abundant element in the atmosphere, neon has never been observed in an organic or metal-organic environment. This study shows the adsorption of this highly unreactive element within such an environment and reveals the first crystallographic observation of an interaction between neon and a transition metal.

  2. Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions

    NARCIS (Netherlands)

    Xiang, S.C.; He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B.

    2012-01-01

    Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve s

  3. Lipase-supported metal-organic framework bioreactor catalyzes warfarin synthesis.

    Science.gov (United States)

    Liu, Wan-Ling; Yang, Ni-Shin; Chen, Ya-Ting; Lirio, Stephen; Wu, Cheng-You; Lin, Chia-Her; Huang, Hsi-Ya

    2015-01-02

    A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase-supported metal-organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. High-throughput synthesis and characterization of nanocrystalline porphyrinic zirconium metal-organic frameworks.

    Science.gov (United States)

    Kelty, M L; Morris, W; Gallagher, A T; Anderson, J S; Brown, K A; Mirkin, C A; Harris, T D

    2016-06-14

    We describe and employ a high-throughput screening method to accelerate the synthesis and identification of pure-phase, nanocrystalline metal-organic frameworks (MOFs). We demonstrate the efficacy of this method through its application to a series of porphyrinic zirconium MOFs, resulting in the isolation of MOF-525, MOF-545, and PCN-223 on the nanoscale.

  5. Metal-organic scintillator crystals for X-ray, gamma ray, and neutron detection

    Science.gov (United States)

    Boatner, Lynn A [Oak Ridge, TN; Kolopus, James A [Clinton, TN; Neal, John S [Knoxville, TN; Ramey, Joanne Oxendine [Knoxville, TN; Wisniewski, Dariusz J [Torun, PL

    2012-01-03

    New metal-organic materials are useful as scintillators and have the chemical formula LX.sub.3(CH.sub.3OH).sub.4 where L is Y, Sc, or a lanthanide element, and X is a halogen element. An example of the scintillator materials is CeCl.sub.3(CH.sub.3OH).sub.4.

  6. Thermodynamics of Pore Filling Metal Clusters in Metal Organic Frameworks: Pd in UiO-66

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Sholl, David S.

    2012-01-01

    Metal organic frameworks (MOFs) have experimentally been demonstrated to be capable of supporting isolated transition-metal clusters, but the stability of these clusters with respect to aggregation is unclear. In this letter we use a genetic algorithm together with density functional theory...

  7. Surface functionalization of metal-organic polyhedron for homogeneous cyclopropanation catalysis.

    Science.gov (United States)

    Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey; Zhou, Hong-Cai

    2011-05-01

    A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

  8. Exploiting large-pore metal-organic frameworks for separations through entropic molecular mechanisms

    NARCIS (Netherlands)

    A. Torres-Knoop; D. Dubbeldam

    2015-01-01

    We review the molecular mechanisms behind adsorption and the separations of mixtures in metal-organic frameworks and zeolites. Separation mechanisms can be based on differences in the affinity of the adsorbate with the framework and on entropic effects. To develop next-generation adsorbents, the sep

  9. Porphyrin-Based Metal-Organic Frameworks as Heterogeneous Catalysts in Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Carla F. Pereira

    2016-10-01

    Full Text Available Porphyrin-based Metal-Organic Frameworks (Por-MOFs constitute a special branch of the wide MOF family that has proven its own value and high potential in different applications. In this mini-review the application of these materials as catalysts in oxidation reactions is highlighted.

  10. Metal-Organic Frameworks with d-f Cyanide Bridges: Structural Diversity, Bonding Regime, and Magnetism

    NARCIS (Netherlands)

    M. Ferbinteanu; F. Cimpoesu; S. Tanase

    2015-01-01

    We present a selection of metal-organic frameworks based on d-f and f-f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the interdisciplinar

  11. Lanthanide-Based Metal Organic Frameworks: Synthetic Strategies and Catalytic Applications

    NARCIS (Netherlands)

    C. Pagis; M. Ferbinteanu; G. Rothenberg; S. Grecea

    2016-01-01

    This short critical review outlines the main synthetic strategies used in the designed synthesis of lanthanide-based metal organic frameworks (Ln-MOFs). It explains the impact of the choice of organic linker on the final network topology, and it highlights the applications of Ln-MOFs in the catalysi

  12. Metal-Organic Frameworks: Bimetallic Metal-Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion (Small 17/2016).

    Science.gov (United States)

    Zou, Ruyi; Li, Pei-Zhou; Zeng, Yong-Fei; Liu, Jia; Zhao, Ruo; Duan, Hui; Luo, Zhong; Wang, Jin-Gui; Zou, Ruqiang; Zhao, Yanli

    2016-05-01

    On page 2334, R. Q. Zou, Y. L. Zhao, and co-workers present a porous metal-organic framework (MOF) that serves as a platform for studying the metal exchange effect on both CO2 adsorption and catalytic fixation. The effect is demonstrated by catalytic CO2 cycloaddition with propylene oxide to produce propylene carbonate. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange could influence the intrinsic properties of MOFs.

  13. Ionic Liquid Hybrid Electrolytes for Lithium-Ion Batteries: A Key Role of the Separator-Electrolyte Interface in Battery Electrochemistry.

    Science.gov (United States)

    Huie, Matthew M; DiLeo, Roberta A; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

    2015-06-10

    Batteries are multicomponent systems where the theoretical voltage and stoichiometric electron transfer are defined by the electrochemically active anode and cathode materials. While the electrolyte may not be considered in stoichiometric electron-transfer calculations, it can be a critical factor determining the deliverable energy content of a battery, depending also on the use conditions. The development of ionic liquid (IL)-based electrolytes has been a research area of recent reports by other researchers, due, in part, to opportunities for an expanded high-voltage operating window and improved safety through the reduction of flammable solvent content. The study reported here encompasses a systematic investigation of the physical properties of IL-based hybrid electrolytes including quantitative characterization of the electrolyte-separator interface via contact-angle measurements. An inverse trend in the conductivity and wetting properties was observed for a series of IL-based electrolyte candidates. Test-cell measurements were undertaken to evaluate the electrolyte performance in the presence of functioning anode and cathode materials, where several promising IL-based hybrid electrolytes with performance comparable to that of conventional carbonate electrolytes were identified. The study revealed that the contact angle influenced the performance more significantly than the conductivity because the cells containing IL-tetrafluoroborate-based electrolytes with higher conductivity but poorer wetting showed significantly decreased performance relative to the cells containing IL-bis(trifluoromethanesulfonyl)imide electrolytes with lower conductivity but improved wetting properties. This work contributes to the development of new IL battery-based electrolyte systems with the potential to improve the deliverable energy content as well as safety of lithium-ion battery systems.

  14. Hybrid Quantum Mechanics/Molecular Mechanics Solvation Scheme for Computing Free Energies of Reactions at Metal-Water Interfaces.

    Science.gov (United States)

    Faheem, Muhammad; Heyden, Andreas

    2014-08-12

    We report the development of a quantum mechanics/molecular mechanics free energy perturbation (QM/MM-FEP) method for modeling chemical reactions at metal-water interfaces. This novel solvation scheme combines planewave density function theory (DFT), periodic electrostatic embedded cluster method (PEECM) calculations using Gaussian-type orbitals, and classical molecular dynamics (MD) simulations to obtain a free energy description of a complex metal-water system. We derive a potential of mean force (PMF) of the reaction system within the QM/MM framework. A fixed-size, finite ensemble of MM conformations is used to permit precise evaluation of the PMF of QM coordinates and its gradient defined within this ensemble. Local conformations of adsorbed reaction moieties are optimized using sequential MD-sampling and QM-optimization steps. An approximate reaction coordinate is constructed using a number of interpolated states and the free energy difference between adjacent states is calculated using the QM/MM-FEP method. By avoiding on-the-fly QM calculations and by circumventing the challenges associated with statistical averaging during MD sampling, a computational speedup of multiple orders of magnitude is realized. The method is systematically validated against the results of ab initio QM calculations and demonstrated for C-C cleavage in double-dehydrogenated ethylene glycol on a Pt (111) model surface.

  15. Synthesis of hierarchical porous carbon monoliths with incorporated metal-organic frameworks for enhancing volumetric based CO₂ capture capability.

    Science.gov (United States)

    Qian, Dan; Lei, Cheng; Hao, Guang-Ping; Li, Wen-Cui; Lu, An-Hui

    2012-11-01

    This work aims to optimize the structural features of hierarchical porous carbon monolith (HCM) by incorporating the advantages of metal-organic frameworks (MOFs) (Cu₃(BTC)₂) to maximize the volumetric based CO₂ capture capability (CO₂ capacity in cm³ per cm³ adsorbent), which is seriously required for the practical application of CO₂ capture. The monolithic HCM was used as a matrix, in which Cu₃(BTC)₂ was in situ synthesized, to form HCM-Cu₃(BTC)₂ composites by a step-by-step impregnation and crystallization method. The resulted HCM-Cu₃(BTC)₂ composites, which retain the monolithic shape and exhibit unique hybrid structure features of both HCM and Cu₃(BTC)₂, show high CO₂ uptake of 22.7 cm³ cm⁻³ on a volumetric basis. This value is nearly as twice as the uptake of original HCM. The dynamic gas separation measurement of HCM-Cu₃(BTC)₂, using 16% (v/v) CO₂ in N₂ as feedstock, illustrates that CO₂ can be easily separated from N₂ under the ambient conditions and achieves a high separation factor for CO₂ over N₂, ranging from 67 to 100, reflecting a strongly competitive CO₂ adsorption by the composite. A facile CO₂ release can be realized by purging an argon flow through the fixed-bed adsorber at 25 °C, indicating the good regeneration ability.

  16. Conetronics in 2D metal-organic frameworks: double/half Dirac cones and quantum anomalous Hall effect

    Science.gov (United States)

    Wu, Menghao; Wang, Zhijun; Liu, Junwei; Li, Wenbin; Fu, Huahua; Sun, Lei; Liu, Xin; Pan, Minghu; Weng, Hongming; Dincă, Mircea; Fu, Liang; Li, Ju

    2017-03-01

    Bandstructure with Dirac cones gives rise to massless Dirac fermions with rich physics, and here we predict rich cone properties in M 3C12S12 and M 3C12O12, where M = Zn, Cd, Hg, Be, or Mg based on recently synthesized Ni3C12S12—class 2D metal-organic frameworks (MOFs). For M 3C12S12, their band structures exhibit double Dirac cones with different Fermi velocities that are n (electron) and p (hole) type, respectively, which are switchable by few-percent strain. The crossing of two cones are symmetry-protected to be non-hybridizing, leading to two independent channels at the same k-point akin to spin-channels in spintronics, rendering ‘conetronics’ device possible. For M 3C12O12, together with conjugated metal-tricatecholate polymers M 3(HHTP)2, the spin-polarized slow Dirac cone center is pinned precisely at the Fermi level, making the systems conducting in only one spin/cone channel. Quantum anomalous Hall effect can arise in MOFs with non-negligible spin-orbit coupling like Cu3C12O12. Compounds of M 3C12S12 and M 3C12O12 with different M, can be used to build spin/cone-selecting heterostructure devices tunable by strain or electrostatic gating, suggesting their potential applications in spintroincs/conetronics.

  17. Are metal-organic frameworks able to provide a new generation of solid-phase microextraction coatings? - A review.

    Science.gov (United States)

    Rocío-Bautista, Priscilla; Pacheco-Fernández, Idaira; Pasán, Jorge; Pino, Verónica

    2016-10-05

    Solid-phase microextraction (SPME) is a powerful technique commonly used in sample preparation for extraction/preconcentration of analytes from a wide variety of samples. Among the trends in improving SPME applications, current investigations are focused on the development of novel coatings able to improve the extraction efficiency, sensitivity, and thermal and mechanical stability, within other properties, of current commercial SPME fibers. Metal-organic frameworks (MOFs) merit to be highlighted as promising sorbent materials in SPME schemes. MOFs are porous hybrid materials composed by metal ions and organic linkers, presenting the highest surface areas known, with ease synthesis and high tuneability, together with adequate chemical and thermal stability. For MOF based-SPME fibers, it results important to pretreat adequately the SPME supports to ensure the correct formation of the MOF onto the fiber or the attachment MOF-support. This, in turn, will increase the final stability of the fiber while generating uniform coatings. This review provides a critical overview of the current state of the use of MOFs as SPME coatings, not only highlighting the advantages of these materials versus commercial SPME coatings in terms of stability, selectivity, and sensitivity; but also insightfully describing the current methods to obtain reproducible MOF-based SPME coatings. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Observing the Growth of Metal-Organic Frameworks by In-Situ Liquid Cell Transmission Electron Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Patterson, Joseph P.; Abellan Baeza, Patricia; Denny, Michael S.; Park, Chiwoo; Browning, Nigel D.; Cohen, Seth M.; Evans, James E.; Gianneschi, Nathan C.

    2015-06-17

    Liquid Cell Transmission Electron Microscopy (LCTEM) can provide direct observations of solution phase nanoscale materials, and holds great promise as a tool for monitoring dynamic self assembly processes. Control over particle behavior within the liquid cell, and under electron beam irradiation, is of paramount importance for this technique to contribute to our understanding of chemistry and materials science at the nanoscale. However, this type of control has not been demonstrated for complex, organic macromolecular materials, which form the basis for all biological systems, all of polymer science, and encompass important classes of advanced porous materials. Here we show that by controlling the liquid cell surface chemistry and electron beam effects, the dynamics and self-assembly of metal-organic frameworks (MOFs) can be observed. Our results demonstrate that hybrid organic/inorganic beam sensitive materials can be analyzed with LCTEM and at least in the case of Zif-8 dynamics, the results correlate with observations from bulk growth or other standard synthetic conditions. We anticipate that direct, nanoscale imaging by LCTEM of MOF nucleation and growth mechanisms, may provide insight into controlled MOF crystal morphology, domain composition, and processes influencing defect formation.

  19. Metal-organic framework preparation using magnetic graphene oxide-β-cyclodextrin for neonicotinoid pesticide adsorption and removal.

    Science.gov (United States)

    Liu, Guangyang; Li, Lingyun; Xu, Donghui; Huang, Xiaodong; Xu, Xiaomin; Zheng, Shuning; Zhang, Yanguo; Lin, Huan

    2017-11-01

    A novel magnetic copper-based metal-organic framework (M-MOF) was prepared using a Fe4O3-graphene oxide (GO)-β-cyclodextrin (β-CD) nanocomposite as the magnetic core and support, and used for adsorption and removal of neonicotinoid insecticide pollutants from aqueous solution. M-MOF characterization suggested that (1)Fe4O3-GO-β-CD consisted of a thin single layer with anchored Fe3O4. The M-MOF was coated on the Fe4O3-GO-β-CD surface. The M-MOF had a large Brunauer-Emmett-Teller surface area (250.33m(2)g(-1)) and high super-paramagnetism with saturation magnetization of 10.47emug(-1). Adsorption model analysis showed that the equilibrium data for thiacloprid fitted Langmuir monolayer adsorption and the other insecticides tested showed Freundlich bimolecular layer adsorption. The results show that M-MOF is a promising hybrid adsorbent for rapid removal of neonicotinoid insecticide pollutants from environmental waters. Copyright © 2017. Published by Elsevier Ltd.

  20. Synthesis,structure and luminescence properties of metal-organic frameworks based on benzo-bis(imidazole)

    Institute of Scientific and Technical Information of China (English)

    YIN XinBo; SONG YuNa; WANG Yang; ZHANG LiJuan; LI QiaoWei

    2014-01-01

    Metal-organic frameworks(MOFs)constructed from conjugated organic ligands are candidates for hybrid photoactive materials with potential applications.Compared to that from the ligands only,the intensity and wavelength of the luminescence could be tuned after they were incorporated in extended framework.In this report,by using an organic ligand with azolate moiety,benzo-bis(imidazole)(H2BBI),we synthesized two new MOF structures.Framework 1([Co(H2BBI)(DMSO)2Cl2]n,DMSO=dimethyl sulfoxide),constructed from tetrahedral Co(II)and H2BBI,exhibits zigzag 1D structure.Meanwhile,framework 2([Cu2(H2BBI)3(DMSO)6(NO3)4]n),a layered structure with hcb topology,was assembled from tetragonal pyramidal Cu(II)and H2BBI.Furthermore,2 exhibits strong luminescence emission(ex=280 nm).A blue shift of 40 nm(from 359 nm to 319 nm)was observed in framework 2 compared to the free ligand,which could be explained by the ligand-to-metal charge transfer in the network.