Modulating Protein Adsorption on Oxygen Plasma Modified Polysiloxane Surfaces

International Nuclear Information System (INIS)

Marletta, G.

2006-01-01

In the present paper we report the study on the adsorption behaviour of three model globular proteins, Human Serum Albumin, Lactoferrin and Egg Chicken Lysozyme onto both unmodified surfaces of a silicon-based polymer and the corresponding plasma treated surfaces. In particular, thin films of hydrophobic polysiloxane (about 90 degree of static water contact angle, WCA) were converted by oxygen plasma treatment at reduced pressure into very hydrophilic phases of SiOx (WCA less than 5 degree). The kinetics of protein adsorption processes were investigated by QCM-D technique, while the chemical structure and topography of the protein adlayer have been studied by Angular resolved-XPS and AFM respectively. It turned out that Albumin and Lysozyme exhibited the opposite preferential adsorption respectively onto the hydrophobic and hydrophilic surfaces, while Lactoferrin did not exhibit significant differences. The observed protein behaviour are discussed both in terms of surface-dependent parameters, including surface free energy and chemical structure, and in terms of protein-dependent parameters, including charge as well as the average molecular orientation in the adlayers. Finally, some examples of differential adsorption behaviour of the investigated proteins are reported onto nanopatterned polysiloxane surfaces consisting of hydrophobic nanopores surrounded by hydrophilic (plasma-treated) matrix and the reverse

Adsorption of cationic surfactants on silica surface: 1. Adsorption isotherms and surface charge

NARCIS (Netherlands)

Goloub, T.P.; Koopal, L.K.; Sidorova, M.P.

2004-01-01

Adsorption isotherms of cationic surfactant, dodecylpyridinium chloride, on an Aerosil OX50 and isotherms of surface charge against the background of 0.001- and 0.1-M KCl solutions at pH 7 and 9 were measured and analyzed. Different forms of adsorption isotherms of surfactants at low and high

Fibrinogen adsorption on blocked surface of albumin.

Science.gov (United States)

Holmberg, Maria; Hou, Xiaolin

2011-05-01

We have investigated the adsorption of albumin and fibrinogen onto PET (polyethylene terephthalate) and glass surfaces and how pre-adsorption of albumin onto these surfaces can affect the adsorption of later added fibrinogen. For materials and devices being exposed to blood, adsorption of fibrinogen is often a non-wanted event, since fibrinogen is part of the clotting cascade and unspecific adsorption of fibrinogen can have an influence on the activation of platelets. Albumin is often used as blocking agent for avoiding unspecific protein adsorption onto surfaces in devices designed to handle biological samples, including protein solutions. It is based on the assumption that proteins adsorbs as a monolayer on surfaces and that proteins do not adsorb on top of each other. By labelling albumin and fibrinogen with two different radioactive iodine isotopes that emit gamma radiation with different energies, the adsorption of both albumin and fibrinogen has been monitored simultaneously on the same sample. Information about topography and coverage of adsorbed protein layers has been obtained using AFM (Atomic Force Microscopy) analysis in liquid. Our studies show that albumin adsorbs in a multilayer fashion on PET and that fibrinogen adsorbs on top of albumin when albumin is pre-adsorbed on the surfaces. Copyright © 2010 Elsevier B.V. All rights reserved.

Adsorption mechanism of BMP-7 on hydroxyapatite (001) surfaces

International Nuclear Information System (INIS)

Zhou, Hailong; Wu, Tao; Dong, Xiuli; Wang, Qi; Shen, Jiawei

2007-01-01

Many properties and functions of bone-related proteins perform through the interface with the hydroxyapatite. However, the mechanism of difference of proteins adsorbing behaviors caused by the variation of calcium and phosphate ions on hydroxyapatite is still unclear at atomic level. In this work, we investigated the site-selective adhesion and the adsorption mechanism of protein BMP-7 to the hydroxyapatite surfaces in aqueous media during adsorption and desorption processes. Molecular dynamics (MD) and steered molecular dynamics (SMD) simulations combined with trajectory analysis were employed to give insight into the underlying behaviors of BMP-7 binding. The results suggest that the adsorption sites could be divided into two categories: COO - and NH 2 /NH3+. For COO - , the adsorption phenomenon is driven by the electrostatic interaction formed between the negative charged carboxylate groups and the Ca1 cations on the hydroxyapatite surface. While for NH 2 /NH3+, the interaction is through the intermolecular H-bonds between the N-containing groups and the phosphate on the hydroxyapatite surface

Selective adsorption of bovine hemoglobin on functional TiO2 nano-adsorbents: surface physic-chemical properties determined adsorption activity

Science.gov (United States)

Guo, Shiguang; Zhang, Jianghua; Shao, Mingxue; Zhang, Xia; Liu, Yufeng; Xu, Junli; Meng, Hao; Han, Yide

2015-04-01

Surface functionalized nanoparticles are efficient adsorbents which have shown good potential for protein separation. In this work, we chose two different types of organic molecules, oleic acid (OA) and 3-glycidoxypropyltrimethoxy silane (GPTMS), to functionalize the surface of TiO2 nanoparticles, and we studied the effects of this modification on their surface physicochemical properties in correlation with their selective adsorption of proteins. The results showed that the surface zeta potential and the surface water wettability of the modified TiO2 were significantly changed in comparison with the original TiO2 nanoparticles. The adsorption activities of bovine hemoglobin (BHb) and bovine serum albumin (BSA) on these functionalized TiO2 samples were investigated under different conditions, including pH values, contact time, ion strength, and initial protein concentration. In comparison with the non-specific adsorption of original TiO2, however, both the OA-TiO2 and GPTMS-TiO2 exhibited increased BHb adsorption and decreased BSA adsorption at the same time. Using a binary protein mixture as the adsorption object, a higher separation factor (SF) was obtained for OA-TiO2 under optimum conditions. The different adsorption activities of BHb and BSA on the modified TiO2 were correlated with different interactions at the protein/solid interface, and the chemical force as well as the electrostatic force played an important role in the selective adsorption process.

Spectroscopic study of cystine adsorption on pyrite surface: From vacuum to solution conditions

Energy Technology Data Exchange (ETDEWEB)

Sanchez-Arenillas, M.; Mateo-Marti, E., E-mail: mateome@cab.inta-csic.es

2015-09-08

Highlights: • Successful adsorption of cystine on pyrite surface under several conditions. • Detailed XPS spectroscopic characterization of cystine adsorption on pyrite surface. • Spectroscopy evidence, oxidation and anoxic conditions adjust molecular adsorption. • Molecular chemistry on pyrite is driven depending on the surrounding conditions. • The cystine/pyrite(100) model is in good agreement with Wächtershäuser’s theory. - Abstract: We characterized the adsorption of cystine molecules on pyrite surface via X-ray photoelectron spectroscopy. Anoxic conditions were simulated under ultra-high-vacuum conditions. In contrast, to simulate oxidation conditions, the molecules were adsorbed on pyrite surface from solution. A novel comparative analysis revealed remarkable differences with respect to molecular adsorption and surface chemistry induced by environmental conditions. Molecular adsorption under anoxic conditions was observed to be more favorable, concentrating a large number of molecules on the surface and two different chemical species. In contrast, the presence of oxygen induced an autocatalytic oxidation process on the pyrite surface, which facilitated water binding on pyrite surface and partially blocked molecular adsorption. Pyrite is a highly reactive surface and contains two crucial types of surface functional groups that drive molecular chemistry on the surface depending on the surrounding conditions. Therefore, the system explored in this study holds interesting implications for supporting catalyzed prebiotic chemistry reactions.

Spectroscopic study of cystine adsorption on pyrite surface: From vacuum to solution conditions

International Nuclear Information System (INIS)

Sanchez-Arenillas, M.; Mateo-Marti, E.

2015-01-01

Highlights: • Successful adsorption of cystine on pyrite surface under several conditions. • Detailed XPS spectroscopic characterization of cystine adsorption on pyrite surface. • Spectroscopy evidence, oxidation and anoxic conditions adjust molecular adsorption. • Molecular chemistry on pyrite is driven depending on the surrounding conditions. • The cystine/pyrite(100) model is in good agreement with Wächtershäuser’s theory. - Abstract: We characterized the adsorption of cystine molecules on pyrite surface via X-ray photoelectron spectroscopy. Anoxic conditions were simulated under ultra-high-vacuum conditions. In contrast, to simulate oxidation conditions, the molecules were adsorbed on pyrite surface from solution. A novel comparative analysis revealed remarkable differences with respect to molecular adsorption and surface chemistry induced by environmental conditions. Molecular adsorption under anoxic conditions was observed to be more favorable, concentrating a large number of molecules on the surface and two different chemical species. In contrast, the presence of oxygen induced an autocatalytic oxidation process on the pyrite surface, which facilitated water binding on pyrite surface and partially blocked molecular adsorption. Pyrite is a highly reactive surface and contains two crucial types of surface functional groups that drive molecular chemistry on the surface depending on the surrounding conditions. Therefore, the system explored in this study holds interesting implications for supporting catalyzed prebiotic chemistry reactions

Adsorption of antimony onto iron oxyhydroxides: Adsorption behavior and surface structure

Energy Technology Data Exchange (ETDEWEB)

Guo, Xuejun; Wu, Zhijun [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19 Xinjiekouwai Street, Beijing 100875 (China); He, Mengchang, E-mail: hemc@bnu.edu.cn [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19 Xinjiekouwai Street, Beijing 100875 (China); Meng, Xiaoguang [Center for Environmental Systems, Stevens Institute of Technology, Hoboken, NJ 07030 (United States); Jin, Xin [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19 Xinjiekouwai Street, Beijing 100875 (China); Qiu, Nan; Zhang, Jing [Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

2014-07-15

Graphical abstract: - Highlights: • Antimony adsorption depended on the Sb species, pH, and the type of iron oxides. • Sb(V) adsorption favored at acidic pH, Sb(III) adsorption optimized in wider pH. • Antimony was adsorbed onto the iron oxides by the inner-sphere surface complex. • Bidentate mononuclear ({sup 2}E) was the dominant form of Sb incorporated into HFO. • XAFS and XPS indicated Sb(III) adsorbed was slowly oxidized to Sb(V). - Abstract: Antimony is detected in soil and water with elevated concentration due to a variety of industrial applications and mining activities. Though antimony is classified as a pollutant of priority interest by the United States Environmental Protection Agency (USEPA) and Europe Union (EU), very little is known about its environmental behavior and adsorption mechanism. In this study, the adsorption behaviors and surface structure of antimony (III/V) on iron oxides were investigated using batch adsorption techniques, surface complexation modeling (SCM), X-ray photon spectroscopy (XPS) and extended X-ray absorption fine structure spectroscopy (EXAFS). The adsorption isotherms and edges indicated that the affinity of Sb(V) and Sb(III) toward the iron oxides depended on the Sb species, solution pH, and the characteristics of iron oxides. Sb(V) adsorption was favored at acidic pH and decreased dramatically with increasing pH, while Sb(III) adsorption was constant over a broad pH range. When pH is higher than 7, Sb(III) adsorption by goethite and hydrous ferric oxide (HFO) was greater than Sb(V). EXAFS analysis indicated that the majority of Sb(III), either adsorbed onto HFO or co-precipitated by FeCl{sub 3}, was oxidized into Sb(V) probably due to the involvement of O{sub 2} in the long duration of sample preservation. Only one Sb–Fe subshell was filtered in the EXAFS spectra of antimony adsorption onto HFO, with the coordination number of 1.0–1.9 attributed to bidentate mononuclear edge-sharing ({sup 2}E) between Sb and

Adsorption of gas mixtures on heterogeneous solid surfaces

Energy Technology Data Exchange (ETDEWEB)

Jaroniec, M; Rudzinski, W

1977-01-01

A review of theoretical studies on the physical adsorption from gas mixtures on heterogeneous solid surfaces, mainly by Jaroniec and coworkers, covers the vector notation used in the calculations; adsorption isotherms for multicomponent gases; the generalized integral equation for adsorption of gas mixtures, its numerical and analytical solutions, applied, (e.g., to interpret the experimental adsorption isotherms of ethane/ethylene on Nuxit-AL); thermodynamic relations, applied, (e.g., to calculating isosteric adsorption heats from experimental parameters for the adsorption of propylene from propane/propylene mixtures on Nuxit-AL); and the derivation and use of a simplified integral equation for describing the adsorption from gas mixtures on heterogeneous surfaces. 75 references.

Chirality in adsorption on solid surfaces.

Science.gov (United States)

Zaera, Francisco

2017-12-07

In the present review we survey the main advances made in recent years on the understanding of chemical chirality at solid surfaces. Chirality is an important topic, made particularly relevant by the homochiral nature of the biochemistry of life on Earth, and many chiral chemical reactions involve solid surfaces. Here we start our discussion with a description of surface chirality and of the different ways that chirality can be bestowed on solid surfaces. We then expand on the studies carried out to date to understand the adsorption of chiral compounds at a molecular level. We summarize the work published on the adsorption of pure enantiomers, of enantiomeric mixtures, and of prochiral molecules on chiral and achiral model surfaces, especially on well-defined metal single crystals but also on other flat substrates such as highly ordered pyrolytic graphite. Several phenomena are identified, including surface reconstruction and chiral imprinting upon adsorption of chiral agents, and the enhancement or suppression of enantioselectivity seen in some cases upon adsorption of enantiomixtures of chiral compounds. The possibility of enhancing the enantiopurity of adsorbed layers upon the addition of chiral seeds and the so-called "sergeants and soldiers" phenomenon are presented. Examples are provided where the chiral behavior has been associated with either thermodynamic or kinetic driving forces. Two main approaches to the creation of enantioselective surface sites are discussed, namely, via the formation of supramolecular chiral ensembles made out of small chiral adsorbates, and by adsorption of more complex chiral molecules capable of providing suitable chiral environments for reactants by themselves, via the formation of individual adsorbate:modifier adducts on the surface. Finally, a discussion is offered on the additional effects generated by the presence of the liquid phase often required in practical applications such as enantioselective crystallization, chiral

Methyl Butanoate Adsorption on MoS2 Surface: A Density Functional Theory Investigation

Directory of Open Access Journals (Sweden)

Prabowo Wahyu Aji Eko

2018-01-01

Full Text Available Methyl butanoate is one of the compound which is obtained from triglyceride molecule. It has hydrocarbon components and hence may produce hydrocarbon through hydrodeoxygenation (HDO or decarbonylation (DCO processes. The first step to uncover the underlying mechanism of HDO or DCO is to find the active site of methyl butanoate adsorption over the catalyst. This study attempts to investigate the active site of methyl butanoate adsorption on MoS2 surface. Stable bonding configuration for methyl butanoate adsorption on MoS2 is investigated by using density functional theory (DFT. This investigation consists of geometry optimisation and adsorption energy calculations. The stable configuration of methyl butanoate adsorption on MoS2 surface is found to be on top of Mo atom in Mo-edge surface.

Structural determinants for protein adsorption/non-adsorption to silica surface

International Nuclear Information System (INIS)

Mathe, Christelle; Devineau, Stephanie; Aude, Jean-Christophe; Lagniel, Gilles; Chedin, Stephane; Legros, Veronique; Mathon, Marie-Helene; Renault, Jean-Philippe; Pin, Serge; Boulard, Yves; Labarre, Jean

2013-01-01

The understanding of the mechanisms involved in the interaction of proteins with inorganic surfaces is of major interest in both fundamental research and applications such as nano-technology. However, despite intense research, the mechanisms and the structural determinants of protein/surface interactions are still unclear. We developed a strategy consisting in identifying, in a mixture of hundreds of soluble proteins, those proteins that are adsorbed on the surface and those that are not. If the two protein subsets are large enough, their statistical comparative analysis must reveal the physicochemical determinants relevant for adsorption versus non-adsorption. This methodology was tested with silica nanoparticles. We found that the adsorbed proteins contain a higher number of charged amino acids, particularly arginine, which is consistent with involvement of this basic amino acid in electrostatic interactions with silica. The analysis also identified a marked bias toward low aromatic amino acid content (phenylalanine, tryptophan, tyrosine and histidine) in adsorbed proteins. Structural analyses and molecular dynamics simulations of proteins from the two groups indicate that non-adsorbed proteins have twice as many p-p interactions and higher structural rigidity. The data are consistent with the notion that adsorption is correlated with the flexibility of the protein and with its ability to spread on the surface. Our findings led us to propose a refined model of protein adsorption. (authors)

Structural determinants for protein adsorption/non-adsorption to silica surface.

Directory of Open Access Journals (Sweden)

Christelle Mathé

Full Text Available The understanding of the mechanisms involved in the interaction of proteins with inorganic surfaces is of major interest in both fundamental research and applications such as nanotechnology. However, despite intense research, the mechanisms and the structural determinants of protein/surface interactions are still unclear. We developed a strategy consisting in identifying, in a mixture of hundreds of soluble proteins, those proteins that are adsorbed on the surface and those that are not. If the two protein subsets are large enough, their statistical comparative analysis must reveal the physicochemical determinants relevant for adsorption versus non-adsorption. This methodology was tested with silica nanoparticles. We found that the adsorbed proteins contain a higher number of charged amino acids, particularly arginine, which is consistent with involvement of this basic amino acid in electrostatic interactions with silica. The analysis also identified a marked bias toward low aromatic amino acid content (phenylalanine, tryptophan, tyrosine and histidine in adsorbed proteins. Structural analyses and molecular dynamics simulations of proteins from the two groups indicate that non-adsorbed proteins have twice as many π-π interactions and higher structural rigidity. The data are consistent with the notion that adsorption is correlated with the flexibility of the protein and with its ability to spread on the surface. Our findings led us to propose a refined model of protein adsorption.

Risedronate adsorption on bioactive glass surface for applications as bone biomaterial

Energy Technology Data Exchange (ETDEWEB)

Mosbahi, Siwar [University of Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes (France); Orthopaedic and Traumatology Laboratory, Sfax Faculty of Medicine, Sfax (Tunisia); Oudadesse, Hassane, E-mail: hassane.oudadesse@univ-rennes1.fr [University of Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes (France); Lefeuvre, Bertand [University of Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes (France); Barroug, Allal [University Cadi Ayyad, Faculty of Science Semlalia, Marrakech (Morocco); CNRST, Rabat (Morocco); Elfeki, Hafed [Science Materials and Environement Laboratory, Sfax Faculty of Science, Sfax (Tunisia); Elfeki, Abdelfattah [Animal Ecophysiology Laboratory, Sfax Faculty of Science, Department of Life Sciences, Sfax (Tunisia); Roiland, Claire [University of Rennes 1, UMR CNRS 6226, Campus de Beaulieu, 35042 Rennes (France); Keskes, Hassib [Orthopaedic and Traumatology Laboratory, Sfax Faculty of Medicine, Sfax (Tunisia)

2016-03-30

Highlights: • The fixation of risèdronates on the bioactive glass surface has been highlighted. • Scanning electron microscopy shows the new morphology of this composite. • Chemical analyses reveal the stability of adsorption process after 40 min of incubation. - Abstract: The aim of the current work is to study the physicochemical interactions between bisphosphonates molecules, risedronate (RIS) and bioactive glass (46S6) after their association by adsorption phenomenon. To more understand the interaction processes of RIS with the 46S6 surface we have used complementary physicochemical techniques such as infrared (FTIR), Raman and nuclear magnetic resonance (NMR) spectroscopy. The obtained results suggest that risedronate adsorption corresponds to an ion substitution reaction with silicon ions occurring at the bioactive glass surface. Thus, a pure bioactive glass was synthesized and fully characterized comparing the solids after adsorption (46S6-XRIS obtained after the interaction of 46S6 and X% risedronate). Therefore, based on the spectroscopic results FTIR, Raman and MAS-NMR, it can be concluded that strong interactions have been established between RIS ions and 46S6 surface. In fact, FTIR and Raman spectroscopy illustrate the fixation of risedronate on the bioactive glass surface by the appearance of several bands characterizing risedronate. The {sup 31}P MAS-NMR of the composite 46S6-XRIS show the presence of two species at a chemical shift of 15 and 19 ppm demonstrating thus the fixation of the RIS on 46S6 surface.

Adsorption of simple molecules on clean metal surfaces

International Nuclear Information System (INIS)

Na Lamphun, O.-A.

1980-06-01

The adsorption of nitric oxide, oxygen, krypton and xenon on evaporated tungsten, nickel and iron films is studied. The theoretical and experimental aspects of adsorption are reviewed, a preliminary study of adsorption by the volumetric method is presented, surface potential and sticking probability studies of adsorption using ion gauges are investigated and an analysis of residual gases, sticking probability and surface potential studies using quadrupole mass spectrometry, given. (author)

Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics.

Science.gov (United States)

Kusaba, Akira; Li, Guanchen; von Spakovsky, Michael R; Kangawa, Yoshihiro; Kakimoto, Koichi

2017-08-15

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and N ad -H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on N ad -H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches.

Adsorption of plasma proteins : adsorption behaviour on apolar surfaces and effect on colloid stability

NARCIS (Netherlands)

van der Scheer, Albert

1978-01-01

In this thesis the adsorption of some plasma proteins (human albumin (HSA) and fibrinogen (HFb)) on non polar surfaces is studied, together with the influence of these proteins on the stability of polystyrene latices. The aim of these investigations is a better understanding of the processes

Surface modification, characterization and adsorptive properties of a coconut activated carbon

Energy Technology Data Exchange (ETDEWEB)

Lu Xincheng [Institute of Chemical Industry of Forest Products, CAF, National Engineering Lab. for Biomass Chemical Utilization, Key and Open Lab. of Forest Chemical Engineering, SFA, Key Lab. of Biomass Energy and Material, Jiangsu Province, Suojin wucun 16, Nanjing 210042 (China); Jiang Jianchun, E-mail: lhs_ac2011@yahoo.cn [Institute of Chemical Industry of Forest Products, CAF, National Engineering Lab. for Biomass Chemical Utilization, Key and Open Lab. of Forest Chemical Engineering, SFA, Key Lab. of Biomass Energy and Material, Jiangsu Province, Suojin wucun 16, Nanjing 210042 (China); Sun Kang; Xie Xinping; Hu Yiming [Institute of Chemical Industry of Forest Products, CAF, National Engineering Lab. for Biomass Chemical Utilization, Key and Open Lab. of Forest Chemical Engineering, SFA, Key Lab. of Biomass Energy and Material, Jiangsu Province, Suojin wucun 16, Nanjing 210042 (China)

2012-08-01

A coconut activated carbon was modified using chemical methods. Different concentration of nitric acid oxidation of the conventional sample produced samples with weakly acidic functional groups. The oxidized samples were characterized by scanning electron micrograph, nitrogen absorption-desorption, Fourier transform infra red spectroscopy, Bothem method, pH titration, adsorption capacity of sodium and formaldehyde, and the adsorption mechanism of activated carbons was investigated. The results showed that BET surface area and pore volume of activated carbons were decreased after oxidization process, while acidic functional groups were increased. The surface morphology of oxidized carbons looked clean and eroded which was caused by oxidization of nitric acid. The oxidized carbons showed high adsorption capacity of sodium and formaldehyde, and chemical properties of activated carbon played an important role in adsorption of metal ions and organic pollutants.

Insight into the adsorption of chloramphenicol on a vermiculite surface

Science.gov (United States)

Tri, Nguyen Ngoc; Carvalho, A. J. P.; Dordio, A. V.; Nguyen, Minh Tho; Trung, Nguyen Tien

2018-05-01

Four stable configurations were found upon adsorption of the chloramphenicol on a period slab model of the vermiculite surface, using the PBE and C09-vdW functionals in a projector-augmented wave (PAW) method approach. The adsorption is a strong chemisorption process, characterized by an adsorption energy of -106.5 kcal mol-1 at the most stable configuration. Stability of configurations contributed mainly by Mg⋯O/Cl attractive electrostatic interactions and C/Osbnd H⋯O hydrogen bonds. It is remarkable that the vermiculite is found to be a solid material with good potential to be used for adsorption and consequent removal of this type of antibiotic drugs.

Surface Complexation Modeling of Fluoride Adsorption by Soil and the Role of Dissolved Aluminum on Adsorption

Science.gov (United States)

Padhi, S.; Tokunaga, T.

2017-12-01

Adsorption of fluoride (F) on soil can control the mobility of F and subsequent contamination of groundwater. Hence, accurate evaluation of adsorption equilibrium is a prerequisite for understanding transport and fate of F in the subsurface. While there have been studies for the adsorption behavior of F with respect to single mineral constituents based on surface complexation models (SCM), F adsorption to natural soil in the presence of complexing agents needs much investigation. We evaluated the adsorption processes of F on a natural granitic soil from Tsukuba, Japan, as a function of initial F concentration, ionic strength, and initial pH. A SCM was developed to model F adsorption behavior. Four possible surface complexation reactions were postulated with and without including dissolved aluminum (Al) and Al-F complex sorption. Decrease in F adsorption with the increase in initial pH was observed in between the initial pH range of 4 to 9, and a decrease in the rate of the reduction of adsorbed F with respect to the increase in the initial pH was observed in the initial pH range of 5 to 7. Ionic strength variation in the range of 0 to 100mM had insignificant effect on F removal. Changes in solution pH were observed by comparing the solution before and after F adsorption experiments. At acidic pH, the solution pH increased, whereas at alkaline pH, the solution pH decreased after equilibrium. The SCM including dissolved Al and the adsorption of Al-F complex can simulate the experimental results quite successfully. Also, including dissolved Al and the adsorption of Al-F complex to the model explained the change in solution pH after F adsorption.

Adsorption Mechanism of Inhibitor and Guest Molecules on the Surface of Gas Hydrates.

Science.gov (United States)

Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

2015-09-23

The adsorption of guest and kinetic inhibitor molecules on the surface of methane hydrate is investigated by using molecular dynamics simulations. We calculate the free energy profile for transferring a solute molecule from bulk water to the hydrate surface for various molecules. Spherical solutes with a diameter of ∼0.5 nm are significantly stabilized at the hydrate surface, whereas smaller and larger solutes exhibit lower adsorption affinity than the solutes of intermediate size. The range of the attractive force is subnanoscale, implying that this force has no effect on the macroscopic mass transfer of guest molecules in crystal growth processes of gas hydrates. We also examine the adsorption mechanism of a kinetic hydrate inhibitor. It is found that a monomer of the kinetic hydrate inhibitor is strongly adsorbed on the hydrate surface. However, the hydrogen bonding between the amide group of the inhibitor and water molecules on the hydrate surface, which was believed to be the driving force for the adsorption, makes no contribution to the adsorption affinity. The preferential adsorption of both the kinetic inhibitor and the spherical molecules to the surface is mainly due to the entropic stabilization arising from the presence of cavities at the hydrate surface. The dependence of surface affinity on the size of adsorbed molecules is also explained by this mechanism.

Adsorption properties of AlN on Si(111) surface: A density functional study

Science.gov (United States)

Yuan, Yinmei; Zuo, Ran; Mao, Keke; Tang, Binlong; Zhang, Zhou; Liu, Jun; Zhong, Tingting

2018-04-01

In the process of preparing GaN on Si substrate by MOCVD, an AlN buffer layer is very important. In this study, we conducted density functional theory calculations on the adsorption of AlN molecule on Si(111)-(2 × 2) surface, with the AlN molecule located horizontally or vertically above Si(111) surface at different adsorption sites. The calculations revealed that the lowest adsorption energy was at the N-top-Al-bridge site in the horizontal configuration, with the narrowest band gap, indicating that it was the most preferential adsorption growth status of AlN. In the vertical configurations, N adatom was more reactive and convenient to form bonds with the topmost Si atoms than Al adatom. When the N-end of the AlN molecule was located downward, the hollow site was the preferred adsorption site; when the Al-end was located downward, the bridge site was the most energetically favorable. Moreover, we investigated some electronic properties such as partial density of states, electron density difference, Mulliken populations, etc., revealing the microscale mechanism for AlN adsorption on Si(111) surface and providing theoretical support for adjusting the processing parameters during AlN or GaN production.

Surface rheology of saponin adsorption layers.

Science.gov (United States)

Stanimirova, R; Marinova, K; Tcholakova, S; Denkov, N D; Stoyanov, S; Pelan, E

2011-10-18

Extracts of the Quillaja saponaria tree contain natural surfactant molecules called saponins that very efficiently stabilize foams and emulsions. Therefore, such extracts are widely used in several technologies. In addition, saponins have demonstrated nontrivial bioactivity and are currently used as essential ingredients in vaccines, food supplements, and other health products. Previous preliminary studies showed that saponins have some peculiar surface properties, such as a very high surface modulus, that may have an important impact on the mechanisms of foam and emulsion stabilization. Here we present a detailed characterization of the main surface properties of highly purified aqueous extracts of Quillaja saponins. Surface tension isotherms showed that the purified Quillaja saponins behave as nonionic surfactants with a relatively high cmc (0.025 wt %). The saponin adsorption isotherm is described well by the Volmer equation, with an area per molecule of close to 1 nm(2). By comparing this area to the molecular dimensions, we deduce that the hydrophobic triterpenoid rings of the saponin molecules lie parallel to the air-water interface, with the hydrophilic glucoside tails protruding into the aqueous phase. Upon small deformation, the saponin adsorption layers exhibit a very high surface dilatational elasticity (280 ± 30 mN/m), a much lower shear elasticity (26 ± 15 mN/m), and a negligible true dilatational surface viscosity. The measured dilatational elasticity is in very good agreement with the theoretical predictions of the Volmer adsorption model (260 mN/m). The measured characteristic adsorption time of the saponin molecules is 4 to 5 orders of magnitude longer than that predicted theoretically for diffusion-controlled adsorption, which means that the saponin adsorption is barrier-controlled around and above the cmc. The perturbed saponin layers relax toward equilibrium in a complex manner, with several relaxation times, the longest of them being around 3

Oxygen adsorption on the Al0.25Ga0.75N (0001) surface: A first-principles study

Science.gov (United States)

Fu, Jiaqi; Song, Tielei; Liang, Xixia; Zhao, Guojun

2018-04-01

To understand the interaction mechanism for the oxygen adsorption on AlGaN surface, herein, we built the possible models of oxygen adsorption on Al0.25Ga0.75N (0001) surface. For different oxygen coverage, three kinds of adsorption site are considered. Then the favorable adsorption sites are characterized by first principles calculation for (2 × 2) supercell of Al0.25Ga0.75N (0001) surface. On basis of the optimal adsorption structures, our calculated results show that all the adsorption processes are exothermic, indicating that the (0001) surface orientation is active towards the adsorption of oxygen. The doping of Al is advantage to the adsorption of O atom. Additionally, the adsorption energy decreases with reducing the oxygen coverage, and the relationship between them is approximately linear. Owing to the oxygen adsorption, the surface states in the fundamental band gap are significant reduced with respect to the free Al0.25Ga0.75N (0001) surface. Moreover, the optical properties on different oxygen coverage are also discussed.

Irreversible adsorption of particles on heterogeneous surfaces.

Science.gov (United States)

Adamczyk, Zbigniew; Jaszczółt, Katarzyna; Michna, Aneta; Siwek, Barbara; Szyk-Warszyńska, Lilianna; Zembala, Maria

2005-12-30

Methods of theoretical and experimental evaluation of irreversible adsorption of particles, e.g., colloids and globular proteins at heterogeneous surfaces were reviewed. The theoretical models were based on the generalized random sequential adsorption (RSA) approach. Within the scope of these models, localized adsorption of particles occurring as a result of short-ranged attractive interactions with discrete adsorption sites was analyzed. Monte-Carlo type simulations performed according to this model enabled one to determine the initial flux, adsorption kinetics, jamming coverage and the structure of the particle monolayer as a function of the site coverage and the particle/site size ratio, denoted by lambda. It was revealed that the initial flux increased significantly with the site coverage theta(s) and the lambda parameter. This behavior was quantitatively interpreted in terms of the scaled particle theory. It also was demonstrated that particle adsorption kinetics and the jamming coverage increased significantly, at fixed site coverage, when the lambda parameter increased. Practically, for alpha = lambda2theta(s) > 1 the jamming coverage at the heterogeneous surfaces attained the value pertinent to continuous surfaces. The results obtained prove unequivocally that spherically shaped sites were more efficient in binding particles in comparison with disk-shaped sites. It also was predicted that for particle size ratio lambda charge. Particle deposition occurred under diffusion-controlled transport conditions and their coverage was evaluated by direct particle counting using the optical and electron microscopy. Adsorption kinetics was quantitatively interpreted in terms of numerical solutions of the governing diffusion equation with the non-linear boundary condition derived from Monte-Carlo simulations. It was proven that for site coverage as low as a few percent the initial flux at heterogeneous surfaces attained the maximum value pertinent to homogeneous

Early stages of Cs adsorption mechanism for GaAs nanowire surface

Science.gov (United States)

Diao, Yu; Liu, Lei; Xia, Sihao; Feng, Shu

2018-03-01

In this study, the adsorption mechanism of Cs adatoms on the (100) surface of GaAs nanowire with [0001] growth direction is investigated utilizing first principles method based on density function theory. The adsorption energy, work function, atomic structure and electronic property of clean surface and Cs-covered surfaces with different coverage are discussed. Results show that when only one Cs is adsorbed on the surface, the most favorable adsorption site is BGa-As. With increasing Cs coverage, work function gradually decreases and gets its minimum at 0.75 ML, then rises slightly when Cs coverage comes to 1 ML, indicating the existence of 'Cs-kill' phenomenon. According to further analysis, Cs activation process can effectively reduce the work function due to the formation of a downward band bending region and surface dipole moment directing from Cs adatom to the surface. As Cs coverage increases, the conduction band minimum and valence band maximum both shift towards lower energy side, contributed by the orbital hybridization between Cs-5s, Cs-5p states and Ga-4p, As-4s, As-4p states near Fermi level. The theoretical calculations and analysis in this study can improve the Cs activation technology for negative electron affinity optoelectronic devices based on GaAs nanowires, and also provide a reference for the further Cs/O or Cs/NF3 activation process.

Co-adsorption of surfactants and water at inorganic solid surfaces.

Science.gov (United States)

Cooper, Timothy G; de Leeuw, Nora H

2002-07-21

Computer simulations of the co-adsorption of water and methanoic acid at a range of surface features of calcite and fluorite minerals have shown that the relative adsorption energies for the two minerals are reversed when solvent effects are included in the calculations, a finding which is important in the search for effective surfactant reagents in flotation techniques, which are used extensively in the mining and pharmaceutical industries and in environmental remediation processes.

Hydrogen adsorption on bimetallic PdAu(111) surface alloys

DEFF Research Database (Denmark)

Takehiro, Naoki; Liu, Ping; Bergbreiter, Andreas

2014-01-01

The adsorption of hydrogen on structurally well defined PdAu-Pd(111) monolayer surface alloys was investigated in a combined experimental and theoretical study, aiming at a quantitative understanding of the adsorption and desorption properties of individual PdAu nanostructures. Combining...... the structural information obtained by high resolution scanning tunneling microscopy (STM), in particular on the abundance of specific adsorption ensembles at different Pd surface concentrations, with information on the adsorption properties derived from temperature programmed desorption (TPD) spectroscopy...... and high resolution electron energy loss spectroscopy (HREELS) provides conclusions on the minimum ensemble size for dissociative adsorption of hydrogen and on the adsorption energies on different sites active for adsorption. Density functional theory (DFT) based calculations give detailed insight...

Competitive Protein Adsorption on Polysaccharide and Hyaluronate Modified Surfaces

Science.gov (United States)

Ombelli, Michela; Costello, Lauren; Postle, Corinne; Anantharaman, Vinod; Meng, Qing Cheng; Composto, Russell J.; Eckmann, David M.

2011-01-01

We measured adsorption of bovine serum albumin (BSA) and fibrinogen (Fg) onto six distinct bare and dextran- and hyaluronate-modified silicon surfaces created using two dextran grafting densities and three hyaluronic acid (HA) sodium salts derived from human umbilical cord, rooster comb and streptococcus zooepidemicus. Film thickness and surface morphology depended on HA molecular weight and concentration. BSA coverage was enhanced on surfaces upon competitive adsorption of BSA:Fg mixtures. Dextranization differentially reduced protein adsorption onto surfaces based on oxidation state. Hyaluronization was demonstrated to provide the greatest resistance to protein coverage, equivalent to that of the most resistant dextranized surface. Resistance to protein adsorption was independent of the type of hyaluronic acid utilized. With changing bulk protein concentration from 20 to 40 µg ml−1 for each species, Fg coverage on silicon increased by 4×, whereas both BSA and Fg adsorption on dextran and HA were far less dependent of protein bulk concentration. PMID:21623481

First principles study of dissolved oxygen water adsorption on Fe (001 surfaces

Directory of Open Access Journals (Sweden)

Dong ZHANG

2018-02-01

Full Text Available In order to study the mechanism of dissolved oxygen content on the surface corrosion behavior of Fe-based heat transfer, the first principle is used to study the adsorption of O2 monomolecular, H2O monolayer and dissolved oxygen system on Fe-based heat transfer surface. The GGA/PBE approximation is used to calculate the adsorption energy, state density and population change during the adsorption process. Calculations prove that when the dissolved oxygen is adsorbed on the Fe-based surface, the water molecule tends to adsorb at the top sites, and the oxygen molecule tends to adsorb at Griffiths. When the H2O molecule adsorbs and interacts on the Fe (001 surface, the charge distribution of the interfacial double electric layer changes to cause the Fe atoms to lose electrons, resulting in the change of the surface potential. When the O2 molecule adsorbs on the Fe (001 crystal surfaces, the electrons on the Fe (001 surface are lost and the surface potential increases. O2 molecule and the surface of the Fe atoms are prone to electron transfer, in which O atom's 2p orbit for the adsorption of O2 molecule on Fe (001 crystal surface play a major role. With the increase of the proportion of O2 molecule in the dissolved oxygen water, the absolute value of the adsorption energy increases, and the interaction of the Fe-based heat transfer surface is stronger. This study explores the influence law of different dissolved oxygen on the Fe base heat exchange surface corrosion, and the base metal corrosion mechanism for experimental study provides a theoretical reference.

Adsorption of Dyes in Studying the Surface Chemistry of Ultradispersed Diamond

Science.gov (United States)

Khokhlova, T. D.; Yunusova, G. R.; Lanin, S. N.

2018-05-01

The effect the surface chemistry of ultradispersed diamond (UDD) has on the adsorption of watersoluble dyes is considered. A comparison is made to adsorption on graphitized thermal carbon black (GTCB), which has a homogeneous and nonporous surface. The adsorption isotherms of dyes and the dependence of the adsorption on the pH of solutions are measured. It is found that UDD adsorbs acid (anionic) dyes—acid orange (AO) and acid anthraquinone blue (AAB)—but barely adsorbs a basic (cationic) dye, methylene blue (MB), because of the predominance of positively charged basic groups on the surface of UDD. The maximum adsorption of AO is much lower on UDD than on GTCB, while the maximum adsorption of AAB is similar for both surfaces. The adsorption of AO on UDD depends strongly on the pH of the solution, while the adsorption of AAB is independent of this parameter. It is suggested that the adsorption of AAB is determined not only by ionic and hydrophobic interactions but also by coordination interactions with impurity metal ions on a UDD surface. It is concluded that the adsorption of dyes characterizes the chemistry of a UDD surface with high sensitivity.

Adsorption of surface functionalized silica nanoparticles onto mineral surfaces and decane/water interface

International Nuclear Information System (INIS)

Metin, Cigdem O.; Baran, Jimmie R.; Nguyen, Quoc P.

2012-01-01

The adsorption of silica nanoparticles onto representative mineral surfaces and at the decane/water interface was studied. The effects of particle size (the mean diameters from 5 to 75 nm), concentration and surface type on the adsorption were studied in detail. Silica nanoparticles with four different surfaces [unmodified, surface modified with anionic (sulfonate), cationic (quaternary ammonium (quat)) or nonionic (polyethylene glycol (PEG)) surfactant] were used. The zeta potential of these silica nanoparticles ranges from −79.8 to 15.3 mV. The shape of silica particles examined by a Hitachi-S5500 scanning transmission electron microscope (STEM) is quite spherical. The adsorption of all the nanoparticles (unmodified or surface modified) on quartz and calcite surfaces was found to be insignificant. We used interfacial tension (IFT) measurements to investigate the adsorption of silica nanoparticles at the decane/water interface. Unmodified nanoparticles or surface modified ones with sulfonate or quat do not significantly affect the IFT of the decane/water interface. It also does not appear that the particle size or concentration influences the IFT. However, the presence of PEG as a surface modifying material significantly reduces the IFT. The PEG surface modifier alone in an aqueous solution, without the nanoparticles, yields the same IFT reduction for an equivalent PEG concentration as that used for modifying the surface of nanoparticles. Contact angle measurements of a decane droplet on quartz or calcite plate immersed in water (or aqueous nanoparticle dispersion) showed a slight change in the contact angle in the presence of the studied nanoparticles. The results of contact angle measurements are in good agreement with experiments of adsorption of nanoparticles on mineral surfaces or decane/water interface. This study brings new insights into the understanding and modeling of the adsorption of surface-modified silica nanoparticles onto mineral surfaces and

Nitrile versus isonitrile adsorption at interstellar grain surfaces. II. Carbonaceous aromatic surfaces

Science.gov (United States)

Bertin, M.; Doronin, M.; Michaut, X.; Philippe, L.; Markovits, A.; Fillion, J.-H.; Pauzat, F.; Ellinger, Y.; Guillemin, J.-C.

2017-12-01

Context. Almost 20% of the 200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Of these 37 molecules, 30 are nitrile R-CN compounds, the remaining 7 belonging to the isonitrile R-NC family. How these species behave in their interactions with the grain surfaces is still an open question. Aims: In a previous work, we have investigated whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of various nature and morphologies. This study is a follow up of this work, where we focus on the adsorption on carbonaceous aromatic surfaces. Methods: The question is addressed by means of a concerted experimental and theoretical approach of the adsorption energies of CH3CN and CH3NC on the surface of graphite (with and without surface defects). The experimental determination of the molecule and surface interaction energies is carried out using temperature-programmed desorption in an ultra-high vacuum between 70 and 160 K. Theoretically, the question is addressed using first-principle periodic density functional theory to represent the organised solid support. Results: The adsorption energy of each compound is found to be very sensitive to the structural defects of the aromatic carbonaceous surface: these defects, expected to be present in a large numbers and great diversity on a realistic surface, significantly increase the average adsorption energies to more than 50% as compared to adsorption on perfect graphene planes. The most stable isomer (CH3CN) interacts more efficiently with the carbonaceous solid support than the higher energy isomer (CH3NC), however.

First-principle study of Mg adsorption on Si(111) surfaces

International Nuclear Information System (INIS)

Min-Ju, Ying; Ping, Zhang; Xiao-Long, Du

2009-01-01

We have carried out first-principle calculations of Mg adsorption on Si(111) surfaces. Different adsorption sites and coverage effects have been considered. We found that the threefold hollow adsorption is energy-favoured in each coverage considered, while for the clean Si(111) surface of metallic feature, we found that 0.25 and 0.5 ML Mg adsorption leads to a semiconducting surface. The results for the electronic behaviour suggest a polarized covalent bonding between the Mg adatom and Si(111) surface. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Polysiloxane surface modified with bipyrazolic tripodal receptor for quantitative lead adsorption

Energy Technology Data Exchange (ETDEWEB)

Radi, Smaail, E-mail: radi_smaail@yahoo.fr [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Equipe de Chimie Bio-organique et Macromoleculaire, Unite Associee au CNRST URAC 25, Departement de Chimie, Faculte des Sciences, Universite Med I, BP 524, 60 000 Oujda (Morocco); Tighadouini, Said; Toubi, Yahya [Laboratoire de Chimie Organique, Macromoleculaire et Produits Naturels, Equipe de Chimie Bio-organique et Macromoleculaire, Unite Associee au CNRST URAC 25, Departement de Chimie, Faculte des Sciences, Universite Med I, BP 524, 60 000 Oujda (Morocco); Bacquet, Maryse [Universite des Sciences et Technologies de Lille, UMET: Unite Materiaux et Transformations UMR8207, Equipe Ingenierie des Systemes Polymeres, Batiment C6 salle 119-59655 Villeneuve d' Ascq (France)

2011-01-15

A new silica gel compound modified N,N-bis(3,5-dimethylpyrazol-1-ylmethyl) amine (SiN{sub 2}Pz) was synthesized and characterized by elemental analysis, FT-IR, {sup 13}C NMR of the solid state, nitrogen adsorption-desorption isotherm, BET surface area and BJH pore sizes. The new surface exhibits good chemical and thermal stability determined by thermogravimetry curves (TGA). The effect of pH and stirring time on the adsorption of Pb(II) were studied. The process of metal retention was followed by batch method and the optimum pH value for the quantitative adsorption of this toxic metal ion was 7. At this pH value, the new functionalized polysiloxane presents further improvements and shows higher affinity (123 mg of Pb{sup 2+}/g of silica) for the effective adsorption of Pb(II) compared to others described sorbents. The extracted amounts of Pb(II) were determined by atomic absorption measurements.

Gallium adsorption on (0001) GaN surfaces

International Nuclear Information System (INIS)

Adelmann, Christoph; Brault, Julien; Mula, Guido; Daudin, Bruno; Lymperakis, Liverios; Neugebauer, Joerg

2003-01-01

We study the adsorption behavior of Ga on (0001) GaN surfaces combining experimental specular reflection high-energy electron diffraction with theoretical investigations in the framework of a kinetic model for adsorption and ab initio calculations of energy parameters. Based on the experimental results we find that for substrate temperatures and Ga fluxes typically used in molecular-beam epitaxy of GaN, finite equilibrium Ga surface coverages can be obtained. The measurement of a Ga/GaN adsorption isotherm allows the quantification of the equilibrium Ga surface coverage as a function of the impinging Ga flux. In particular, we show that a large range of Ga fluxes exists, where 2.5±0.2 monolayers (in terms of the GaN surface site density) of Ga are adsorbed on the GaN surface. We further demonstrate that the structure of this adsorbed Ga film is in good agreement with the laterally contracted Ga bilayer model predicted to be most stable for strongly Ga-rich surfaces [Northrup et al., Phys. Rev. B 61, 9932 (2000)]. For lower Ga fluxes, a discontinuous transition to Ga monolayer equilibrium coverage is found, followed by a continuous decrease towards zero coverage; for higher Ga fluxes, Ga droplet formation is found, similar to what has been observed during Ga-rich GaN growth. The boundary fluxes limiting the region of 2.5 monolayers equilibrium Ga adsorption have been measured as a function of the GaN substrate temperature giving rise to a Ga/GaN adsorption phase diagram. The temperature dependence is discussed within an ab initio based growth model for adsorption taking into account the nucleation of Ga clusters. This model consistently explains recent contradictory results of the activation energy describing the critical Ga flux for the onset of Ga droplet formation during Ga-rich GaN growth [Heying et al., J. Appl. Phys. 88, 1855 (2000); Adelmann et al., J. Appl. Phys. 91, 9638 (2002).

A theoretical study of hydrogen atoms adsorption and diffusion on PuO_2 (110) surface

International Nuclear Information System (INIS)

Yu, H.L.; Tang, T.; Zheng, S.T.; Shi, Y.; Qiu, R.Z.; Luo, W.H.; Meng, D.Q.

2016-01-01

The mechanisms of adsorption and diffusion of hydrogen atoms on the PuO_2 (110) surface are investigated by density functional theory corrected for onsite Coulombic interactions (GGA + U). In order to find out the energetically more favorable adsorption site and optimum diffusion path, adsorption energy of atomic H on various sites and the diffusion energy barrier are derived and compared. Our results show that both chemisorption and physisorption exist for H atoms adsorption configurations on PuO_2 (110) surface. Two processes for H diffusion are investigated using the climbing nudged-elastic-band (cNEB) approach. We have identified two diffusion mechanisms, leading to migration of atomic H on the surface and diffusion from surface to subsurface. The energy barriers indicate that it is energetically more favorable for H atom to be on the surface. Hydrogen permeation through purity PuO_2 surface is mainly inhibited from hydrogen atom diffusion from surface to subsurface. - Highlights: • H atoms adsorption on PuO_2 (110) surface are investigated by GGA + U. • Both chemisorption and physisorption exist for H atoms adsorption configurations. • H atoms migration into PuO_2 (100) surface are inhibited with the barrier of 2.15 eV. • H atoms diffusion on PuO_2 (110) surface are difficult at room temperature.

Adsorption of surfactants on sand surface in enhanced oil recovery: Isotherms, kinetics and thermodynamic studies

Energy Technology Data Exchange (ETDEWEB)

Bera, Achinta; Kumar, T.; Ojha, Keka; Mandal, Ajay, E-mail: mandal_ajay@hotmail.com

2013-11-01

Adsorption of surfactants onto reservoir rock surface may result in the loss and reduction of their concentrations in surfactant flooding, which may render them less efficient or ineffective in practical applications of enhanced oil recovery (EOR) techniques. Surfactant flooding for EOR received attraction due to its ability to increase the displacement efficiency by lowering the interfacial tension between oil and water and mobilizing the residual oil. This article highlights the adsorption of surfactants onto sand surface with variation of different influencing factors. It has been experimentally found that adsorption of cationic surfactant on sand surface is more and less for anionic surfactant, while non-ionic surfactant shows intermediate behaviour. X-ray diffraction (XRD) study of clean sand particles has been made to determine the main component present in the sand particles. The interaction between sand particles and surfactant has been studied by Fourier Transform Infrared (FTIR) Spectroscopy of the sand particles before and after aging with surfactant. Salinity plays an important role in adsorption of anionic surfactant. Batch experiments were also performed to understand the effects of pH and adsorbent dose on the sorption efficiency. The sand particles exhibited high adsorption efficiency at low pH for anionic and nonionic surfactants. But opposite trend was found for cationic surfactant. Adsorption data were analyzed by fitting with Langmuir, Freundlich, Redlich-Peterson, and Sips isotherm models. Results show that the Langmuir isotherm and pseudo-second order kinetics models suit the equilibrium and kinetics of adsorption on sand surface. Thermodynamics feasibility of the adsorption process was also studied to verify the spontaneity of the process.

Computational study of cis-oleic acid adsorption on Ni(1 1 1) surface

Energy Technology Data Exchange (ETDEWEB)

Simonetti, S., E-mail: ssimonet@uns.edu.ar [Departamento de Fisica, IFISUR, Universidad Nacional del Sur-CONICET, Av. Alem 1253, 8000 Bahia Blanca (Argentina); Departamentos de Ciencias Basicas e Ingenieria Mecanica, Universidad Tecnologica Nacional, Facultad Regional Bahia Blanca, 11 de Abril 461, 8000 Bahia Blanca (Argentina); Ulacco, S. [Departamentos de Ciencias Basicas e Ingenieria Mecanica, Universidad Tecnologica Nacional, Facultad Regional Bahia Blanca, 11 de Abril 461, 8000 Bahia Blanca (Argentina); Brizuela, G.; Juan, A. [Departamento de Fisica, IFISUR, Universidad Nacional del Sur-CONICET, Av. Alem 1253, 8000 Bahia Blanca (Argentina)

2012-05-15

In the present work, the Atom Superposition and Electron Delocalization method has been applied in order to study the adsorption of cis-oleic acid on Ni(1 1 1) surface. This molecule presents two active functional groups, C=C (in the middle) and -COOH (at one end). Therefore, it is important to explore adsorption on the metal surface through the C=C bond in a geometry parallel to the surface and also in a vertical one with -COOH pointing at Ni atoms. Our results indicate that the parallel geometry is more stable than the vertical one and C=C bond adsorption dominates the process. Energetic results show a strong interaction with the metallic surface. Ni-Ni, C=C, and C-C bonds are weakened upon adsorption because of a bonding interaction between carbons and nickel surface. We found that Ni 5d{sub z}{sup 2} and 5d{sub yz} orbitals play an important role in the bonding between C p{sub x}, p{sub z} orbitals and surface, and the same happens with Ni 6p{sub x} and Ni 6p{sub z}. A small Ni-H interaction is also detected.

Influence of the pore structure and surface chemical properties of activated carbon on the adsorption of mercury from aqueous solutions

International Nuclear Information System (INIS)

Lu, Xincheng; Jiang, Jianchun; Sun, Kang; Wang, Jinbiao; Zhang, Yanping

2014-01-01

Highlights: • Activated carbons with different pore structure and surface chemical properties were prepared by modification process. • HgCl 2 as a pollution target to evaluate the adsorption performance. • Influence of pore structure and surface chemical properties of activated carbon on adsorption of mercury was investigated. -- Abstract: Reactivation and chemical modification were used to obtain modified activated carbons with different pore structure and surface chemical properties. The samples were characterized by nitrogen absorption–desorption, Fourier transform infrared spectroscopy and the Bothem method. Using mercury chloride as the target pollutant, the Hg 2+ adsorption ability of samples was investigated. The results show that the Hg 2+ adsorption capacity of samples increased significantly with increases in micropores and acidic functional groups and that the adsorption process was exothermic. Different models and thermodynamic parameters were evaluated to establish the mechanisms. It was concluded that the adsorption occurred through a monolayer mechanism by a two-speed process involving both rapid adsorption and slow adsorption. The adsorption rate was determined by chemical reaction

Studies of surface adsorption on LiAlO2

International Nuclear Information System (INIS)

Fischer, A.K.; Johnson, C.E.; McDaniel, J.A.

1986-01-01

Computational and experimental approaches are being taken to understanding surface adsorption/desorption effects on tritium inventory and release. The computational survey integrates a thermodynamic treatment of surface adsorption and bulk phase effects such as solubility and gas phase composition. The system T 2 O:T 2 :LiAlO 2 was examined. The calculations indicate that surface adsorption can be expected to contribute most to tritium inventory under the conditions of lower temperatures and higher oxygen activities. Higher temperature and lower oxygen activity favor lower surface inventory. In the experimental work, a high temperature gas chromatograph was constructed in order to measure the H 2 O:H 2 surface adsorption isotherms and the solubility of hydroxide in LiAlO 2 . Preliminary data indicate that at 478 K approximately 15% of the surface is coverred for a partial pressure of H 2 O of approximately 52 Pa. Calculated values can be obtained that are in reasonable agreement with this. (orig.)

Studies of surface adsorption on LiAlO2

International Nuclear Information System (INIS)

Fischer, A.K.; McDaniel, J.A.; Johnson, C.E.

1986-01-01

Computational and experimental approaches are being taken to understanding surface adsorption/desorption effects on tritium inventory and release. The computational survey integrates a thermodynamic treatment of surface adsorption and bulk phase effects such as solubility and gas phase composition. The system T 2 O:T 2 :LiAlO 2 was examined. The calculations indicate that surface adsorption can be expected to contribute most to tritium inventory under the conditions of lower temperatures and higher oxygen activities. Higher temperature and lower oxygen activity favor lower surface inventory. In the experimental work, a high temperature gas chromatograph was constructed in order to measure the H 2 O:H 2 surface adsorption isotherms and the solubility of hydroxide in LiAlO 2 . Preliminary data indicate that at 478K approximately 15% of the surface is covered for a partial pressure of H 2 O of approximately 52 Pa. Calculated values can be obtained that are in reasonable agreement with this

Surfaces of Microparticles in Colloids: Structure and Molecular Adsorption Kinetics

Science.gov (United States)

Dai, Hai-Lung

2002-03-01

Surfaces of micron and sub-micron size particles in liquid solution are probed by second harmonic generation (SHG) facilitated with femtosecond laser pulses. The particles probed include inorganic objects such as carbon black and color pigments, polymeric species like polystyrene beads, and biological systems such as blood cells and ecoli. In the experiments, dye molecules are first adsorbed onto the particle surface to allow generation of second harmonics upon light irradiation. Competition for adsorption between these surface dye molecules and the molecules of interest in the solution is then monitored by the SHG signal to reveal the molecular adsorption kinetics and surface structure. Specifically, surfactant adsorption on polymer surfaces, the structure of carbon black surface, and protein adsorption on biological surfaces, monitored by this technique, will be discussed.

Radiotracer studies of the adsorption of surface active substances at aqueous surfaces, 6

International Nuclear Information System (INIS)

Tajima, Kazuo

1976-01-01

The surface tension and adsorption were observed by the Wilhelmy plate and radiotracer methods at the air-solution interface of an aqueous solution of urea and α-dodecyl-ω-hydroxyhexa(oxyethylene) (D(EO) 6 ). The adsorption of D(EO) 6 was dependent on the concentration of urea below the CMC values, but above the values it was independent of the concentration. Urea adsorption occurs positively for low-surface packing of the poly(oxyethylene) group of D(EO) 6 , but negatively for the closest packing of the group and high concentrations of urea. It was confirmed that D(EO) 6 adsorption took place at the solution surface according to the Gibbs adsorption isotherm, which was taken into account as an activity coefficient in an empirical equation for the interactions of D(EO) 6 and urea in solution. Urea adsorption for the adsorbed monolayer of D(EO) 6 above the CMC value was interpreted assuming that urea, as for the nonionic micelle, was nonpenetrating, which was examined by gel permeation. (auth.)

Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features

Energy Technology Data Exchange (ETDEWEB)

Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu [College of Science, Sichuan Agricultural University, Ya' an 625014 (China); He, Hua [Institute of Animal Genetics and Breeding, Sichuan Agricultural University, Wenjiang, Sichuan 611130 (China); Rao, Hanbing, E-mail: rhbscu@gmail.com [College of Science, Sichuan Agricultural University, Ya' an 625014 (China)

2015-07-01

The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer–Emmett–Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g{sup −1}, respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG < 0) and entropy increasing (ΔS > 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. - Highlights: • A novel protein adsorption studies based on sheet, rod and whisker of HA were designed. • Kinetic and thermodynamics parameters of BMP-2 and HA bonded materials were evaluated. • Surface topographies of the HA effect BMP-2 adsorption • The HA-whisker material had excellent adsorption performance for protein enrichment. • The electrostatic interaction is responsible for the

Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features

International Nuclear Information System (INIS)

Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu; He, Hua; Rao, Hanbing

2015-01-01

The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer–Emmett–Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g −1 , respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG < 0) and entropy increasing (ΔS > 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. - Highlights: • A novel protein adsorption studies based on sheet, rod and whisker of HA were designed. • Kinetic and thermodynamics parameters of BMP-2 and HA bonded materials were evaluated. • Surface topographies of the HA effect BMP-2 adsorption • The HA-whisker material had excellent adsorption performance for protein enrichment. • The electrostatic interaction is responsible for the BMP-2

Nanoscopic characterization of the water vapor-salt interfacial layer reveals a unique biphasic adsorption process

Science.gov (United States)

Yang, Liu; He, Jianfeng; Shen, Yi; Li, Xiaowei; Sun, Jielin; Czajkowsky, Daniel M.; Shao, Zhifeng

2016-08-01

Our quantitative understanding of water adsorption onto salt surfaces under ambient conditions is presently quite poor owing to the difficulties in directly characterizing this interfacial layer under these conditions. Here we determine the thickness of the interfacial layer on NaCl at different relative humidities (RH) based on a novel application of atomic force spectroscopy and capillary condensation theory. In particular, we take advantage of the microsecond-timescale of the capillary condensation process to directly resolve the magnitude of its contribution in the tip-sample interaction, from which the interfacial water thickness is determined. Further, to correlate this thickness with salt dissolution, we also measure surface conductance under similar conditions. We find that below 30% RH, there is essentially only the deposition of water molecules onto this surface, typical of conventional adsorption onto solid surfaces. However, above 30% RH, adsorption is simultaneous with the dissolution of ions, unlike conventional adsorption, leading to a rapid increase of surface conductance. Thus, water adsorption on NaCl is an unconventional biphasic process in which the interfacial layer not only exhibits quantitative differences in thickness but also qualitative differences in composition.

[Adsorption of heavy metals on the surface of birnessite relationship with its Mn average oxidation state and adsorption sites].

Science.gov (United States)

Wang, Yan; Tan, Wen-Feng; Feng, Xiong-Han; Qiu, Guo-Hong; Liu, Fan

2011-10-01

Adsorption characteristics of mineral surface for heavy metal ions are largely determined by the type and amount of surface adsorption sites. However, the effects of substructure variance in manganese oxide on the adsorption sites and adsorption characteristics remain unclear. Adsorption experiments and powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) were combined to examine the adsorption characteristics of Pb2+, Cu2+, Zn2+ and Cd2+ sequestration by birnessites with different Mn average oxidation state (AOS), and the Mn AOS dependent adsorption sites and adsorption characteristics. The results show that the maximum adsorption capacity of Pb2+, Cu2+, Zn2+ and Cd2+ increased with increasing birnessite Mn AOS. The adsorption capacity followed the order of Pb2+ > Cu2+ > Zn2+ > Cd2+. The observations suggest that there exist two sites on the surface of birnessite, i. e., high-binding-energy site (HBE site) and low-binding-energy site (LBE site). With the increase of Mn AOS for birnessites, the amount of HBE sites for heavy metal ions adsorption remarkably increased. On the other hand, variation in the amount of LBE sites was insignificant. The amount of LBE sites is much more than those of HBE sites on the surface of birnessite with low Mn AOS. Nevertheless, both amounts on the surface of birnessite with high Mn AOS are very close to each other. Therefore, the heavy metal ions adsorption capacity on birnessite is largely determined by the amount of HBE sites. On birnessite surface, adsorption of Cu2+, Zn2+, and Cd2+ mostly occurred at HBE sites. In comparison with Zn2+ and Cd2+, more Cu2+ adsorbed on the LBW sites. Pb2+ adsorption maybe occupy at both LBE sites and HBE sites simultaneously.

Prediction of iodide adsorption on oxides by surface complexation modeling with spectroscopic confirmation.

Science.gov (United States)

Nagata, Takahiro; Fukushi, Keisuke; Takahashi, Yoshio

2009-04-15

A deficiency in environmental iodine can cause a number of health problems. Understanding how iodine is sequestered by materials is helpful for evaluating and developing methods for minimizing human health effects related to iodine. In addition, (129)I is considered to be strategically important for safety assessment of underground radioactive waste disposal. To assess the long-term stability of disposed radioactive waste, an understanding of (129)I adsorption on geologic materials is essential. Therefore, the adsorption of I(-) on naturally occurring oxides is of environmental concern. The surface charges of hydrous ferric oxide (HFO) in NaI electrolyte solutions were measured by potentiometric acid-base titration. The surface charge data were analyzed by means of an extended triple-layer model (ETLM) for surface complexation modeling to obtain the I(-) adsorption reaction and its equilibrium constant. The adsorption of I(-) was determined to be an outer-sphere process from ETLM analysis, which was consistent with independent X-ray absorption near-edge structure (XANES) observation of I(-) adsorbed on HFO. The adsorption equilibrium constants for I(-) on beta-TiO(2) and gamma-Al(2)O(3) were also evaluated by analyzing the surface charge data of these oxides in NaI solution as reported in the literature. Comparison of these adsorption equilibrium constants for HFO, beta-TiO(2), and gamma-Al(2)O(3) based on site-occupancy standard states permitted prediction of I(-) adsorption equilibrium constants for all oxides by means of the Born solvation theory. The batch adsorption data for I(-) on HFO and amorphous aluminum oxide were reasonably reproduced by ETLM with the predicted equilibrium constants, confirming the validity of the present approach. Using the predicted adsorption equilibrium constants, we calculated distribution coefficient (K(d)) values for I(-) adsorption on common soil minerals as a function of pH and ionic strength.

Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features.

Science.gov (United States)

Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu; He, Hua; Rao, Hanbing

2015-01-01

The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer-Emmett-Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g(-1), respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. Copyright © 2015 Elsevier B.V. All rights reserved.

A first-principles study of oxygen adsorption on Ir(111) surface

Energy Technology Data Exchange (ETDEWEB)

Gao, Hengjiao, E-mail: gaohengjiao@163.com; Xiong, Yuqing, E-mail: xiongyq@hotmail.com; Liu, Xiaoli, E-mail: shantianzi@126.com; Zhao, Dongcai, E-mail: zhaodongc@163.com; Feng, Yudong, E-mail: yudong_feng@sina.com; Wang, Lanxi, E-mail: wanglanxi@live.com; Wang, Jinxiao, E-mail: coldwind716@gmail.com

2016-12-15

Highlights: • Adsorption of oxygen on Ir(111) surface was studied by density functional theory. • The most stable adsorption site was determined by adsorption energy calculation. • Adsorption of oxygen at bridge and top site on Ir surface was the most stable ones. • Interaction of O 2p and Ir 5d orbits is relatively strong and formed hybridization. - Abstract: In order to understand deposition mechanism of iridium thin film by atomic layer deposition, the adsorption of oxygen on Ir(111) surface was studied by use of density functional theory and a periodical slab model. By calculating the adsorption energy and structure of oxygen at four adsorption sites (top, bridge, fcc-hollow and hcp-hollow) on Ir(111) surface, the most stable adsorption site was determined. On this basis, the banding mechanism of O and Ir atoms was studied by density of states of oxygen and iridium atoms. Oxygen adsorbed at hcp(parallel) site on Ir(111) surface was the most stable one according to the adsorption energy calculation results. Orbital charge analysis indicate that charge transferred from 5p and 5d orbit to 2p orbit of adsorbed O atoms, and 6s orbit of iridium atoms. Meanwhile, density of state study indicated that adsorption of oxygen on Ir(111) surface is mainly due to the interaction between 2p orbit of O atoms and 5d orbit of iridium atoms.

Theoretical and Experimental Analysis of Adsorption in Surface-based Biosensors

DEFF Research Database (Denmark)

Hansen, Rasmus

The present Ph.D. dissertation concerns the application of surface plasmon resonance (SPR) spectroscopy, which is a surface-based biosensor technology, for studies of adsorption dynamics. The thesis contains both experimental and theoretical work. In the theoretical part we develop the theory...... cell of the surface-based biosensor, in addition to the sensor surface, is investigated. In the experimental part of the thesis we use a Biacore SPR sensor to study lipase adsorption on model substrate surfaces, as well as competitive adsorption of lipase and surfactants. A part of the experimental...

Surface modification influencing adsorption of red wine constituents: The role of functional groups

Energy Technology Data Exchange (ETDEWEB)

Mierczynska-Vasilev, Agnieszka, E-mail: agnieszka.mierczynska-vasilev@awri.com.au; Smith, Paul A., E-mail: paul.smith@awri.com.au

2016-11-15

Highlights: • Chemical surface composition affects behaviour of wine adsorption. • SO{sub 3}H and COOH groups adsorb more of the wine nitrogen-containing compounds. • NH{sub 2} and NR{sub 3} groups encourage carbon-containing compounds adsorption. • Red wine constituents after filtration adsorbed more on NR{sub 3} and CHO surfaces. - Abstract: The adsorption of wine constituents at solid surfaces is important in applications such as filtration and membrane fouling, binding to tanks and fittings and interactions with processing aids such as bentonite. The interaction of wine constituents with surfaces is mediated through adsorbed wine components, where the type of constituents, amount, orientation, and conformation are of consequence for the surface response. This study examines the effect of surface chemical functionalities on the adsorption of red wine constituents. Plasma-polymerized films rich in amine, carboxyl, hydroxyl, formyl and methyl functional groups were generated on solid substrates whereas, glycidyltrimethylammonium chloride was covalently attached to allylamine plasma-polymer modified surface and poly(sodium styrenesulfonate) was electrostatically adsorbed to an amine plasma-polymerized surface. The surface chemical functionalities were characterized by X-ray photoelectron spectroscopy. The ability of different substrates to adsorb red wine constituents was evaluated by quartz crystal microbalance and atomic force microscopy. The results showed that substrates modified with −SO{sub 3}H and –COOH groups can adsorb more of the wine nitrogen-containing compounds whereas −NH{sub 2} and −NR{sub 3} groups encourage carbon-containing compounds adsorption. Red wine constituents after filtration were adsorbed in higher extend on −NR{sub 3} and –CHO surfaces. The –OH modified surfaces had the lowest ability to absorb wine components.

Surface modification influencing adsorption of red wine constituents: The role of functional groups

International Nuclear Information System (INIS)

Mierczynska-Vasilev, Agnieszka; Smith, Paul A.

2016-01-01

Highlights: • Chemical surface composition affects behaviour of wine adsorption. • SO_3H and COOH groups adsorb more of the wine nitrogen-containing compounds. • NH_2 and NR_3 groups encourage carbon-containing compounds adsorption. • Red wine constituents after filtration adsorbed more on NR_3 and CHO surfaces. - Abstract: The adsorption of wine constituents at solid surfaces is important in applications such as filtration and membrane fouling, binding to tanks and fittings and interactions with processing aids such as bentonite. The interaction of wine constituents with surfaces is mediated through adsorbed wine components, where the type of constituents, amount, orientation, and conformation are of consequence for the surface response. This study examines the effect of surface chemical functionalities on the adsorption of red wine constituents. Plasma-polymerized films rich in amine, carboxyl, hydroxyl, formyl and methyl functional groups were generated on solid substrates whereas, glycidyltrimethylammonium chloride was covalently attached to allylamine plasma-polymer modified surface and poly(sodium styrenesulfonate) was electrostatically adsorbed to an amine plasma-polymerized surface. The surface chemical functionalities were characterized by X-ray photoelectron spectroscopy. The ability of different substrates to adsorb red wine constituents was evaluated by quartz crystal microbalance and atomic force microscopy. The results showed that substrates modified with −SO_3H and –COOH groups can adsorb more of the wine nitrogen-containing compounds whereas −NH_2 and −NR_3 groups encourage carbon-containing compounds adsorption. Red wine constituents after filtration were adsorbed in higher extend on −NR_3 and –CHO surfaces. The –OH modified surfaces had the lowest ability to absorb wine components.

Preventing protein adsorption from a range of surfaces using an aqueous fish protein extract

DEFF Research Database (Denmark)

Pillai, Saju; Arpanaei, Ayyoob; Meyer, Rikke L.

2009-01-01

We utilize an aqueous extract of fish proteins (FPs) as a coating for minimizing the adsorption of fibrinogen (Fg) and human serum albumin (HSA). The surfaces include stainless steel (SS), gold (Au), silicon dioxide (SiO2), and poly(styrene) (PS). The adsorption processes (kinetics and adsorbed...

Adsorption of lysozyme unto silica and polystyrene surfaces in ...

African Journals Online (AJOL)

user

2011-04-11

Apr 11, 2011 ... surfaces were well fitted by the Langmuir adsorption isotherm model with maximum adsorption .... following reasons: (1) Lysozyme is a globular protein with ... vigorously for 1 h to attain equilibrium adsorption and allowed to.

Study of Cs adsorption on (100) surface of [001]-oriented GaN nanowires: A first principle research

Energy Technology Data Exchange (ETDEWEB)

Xia, Sihao [Department of Optoelectronic Technology, School of Electronic and Optical Engineering, Nanjing University of Science and Technology Nanjing, 210094 (China); Liu, Lei, E-mail: liu1133_cn@sina.com.cn [Department of Optoelectronic Technology, School of Electronic and Optical Engineering, Nanjing University of Science and Technology Nanjing, 210094 (China); Kong, Yike [Department of Optoelectronic Technology, School of Electronic and Optical Engineering, Nanjing University of Science and Technology Nanjing, 210094 (China); Wang, Honggang; Wang, Meishan [School of Information and Electrical Engineering, Ludong University, Yantai 264025 (China)

2016-11-30

Highlights: • B{sub N} is the most stable adsorption site. • Work function is reduced after Cs adsorption. • Surface atomic structures are reconstructed. • Surface states near fermi level is contributed to the hybridization of Cs 5s state with Ga 4p and N 2p state. • NEA surface is demonstrated after Cs adsorption on GaN nanowire surface. - Abstract: Based on first-principle study, the adsorption mechanism of Cs on (100) crystal plane of GaN nanowire surface with coverage of 1/12 monolayer is explored. It is discovered that the most stable adsorption site is B{sub N} because of its lowest adsorption energy. The work function of GaN nanowire surface is reduced by 1.69 eV and will be further reduced with increasing Cs adsorption, which promotes the development of negative electron affinity (NEA) state of the materials. Furthermore, Cs adatom will make a great influence on the surface atomic structure, oppositely, little influence on the center atomic structure. There appears a dipole moment valued −6.93 Debye on the nanowire surface contributed to the formation the heterojunction on the surface, which is beneficial to the photoelectrons liberation. After Cs adsorption, the valence band and conduction band both move to lower energy side. The surface states mainly result from the hybridization of Cs 5s state with Ga 4p state and N 2p state. This study can help us to further experiment on the Cs adsorption processing on GaN nanowire and improve the photoemission performance of GaN nanowire devices.

Study of Cs adsorption on (100) surface of [001]-oriented GaN nanowires: A first principle research

International Nuclear Information System (INIS)

Xia, Sihao; Liu, Lei; Kong, Yike; Wang, Honggang; Wang, Meishan

2016-01-01

Highlights: • B N is the most stable adsorption site. • Work function is reduced after Cs adsorption. • Surface atomic structures are reconstructed. • Surface states near fermi level is contributed to the hybridization of Cs 5s state with Ga 4p and N 2p state. • NEA surface is demonstrated after Cs adsorption on GaN nanowire surface. - Abstract: Based on first-principle study, the adsorption mechanism of Cs on (100) crystal plane of GaN nanowire surface with coverage of 1/12 monolayer is explored. It is discovered that the most stable adsorption site is B N because of its lowest adsorption energy. The work function of GaN nanowire surface is reduced by 1.69 eV and will be further reduced with increasing Cs adsorption, which promotes the development of negative electron affinity (NEA) state of the materials. Furthermore, Cs adatom will make a great influence on the surface atomic structure, oppositely, little influence on the center atomic structure. There appears a dipole moment valued −6.93 Debye on the nanowire surface contributed to the formation the heterojunction on the surface, which is beneficial to the photoelectrons liberation. After Cs adsorption, the valence band and conduction band both move to lower energy side. The surface states mainly result from the hybridization of Cs 5s state with Ga 4p state and N 2p state. This study can help us to further experiment on the Cs adsorption processing on GaN nanowire and improve the photoemission performance of GaN nanowire devices.

Adsorption and migration of single metal atoms on the calcite (10.4) surface

International Nuclear Information System (INIS)

Pinto, H; Haapasilta, V; Lokhandwala, M; Foster, Adam S; Öberg, S

2017-01-01

Transition metal atoms are one of the key ingredients in the formation of functional 2D metal organic coordination networks. Additionally, the co-deposition of metal atoms can play an important role in anchoring the molecular structures to the surface at room temperature. To gain control of such processes requires the understanding of adsorption and diffusion properties of the different transition metals on the target surface. Here, we used density functional theory to investigate the adsorption of 3 d (Ti, Cr, Fe, Ni, Cu), 4 d (Zr, Nb, Mo, Pd, Ag) and 5 d (Hf, W, Ir, Pt, Au) transition metal adatoms on the insulating calcite (10.4) surface. We identified the most stable adsorption sites and calculated binding energies and corresponding ground state structures. We find that the preferential adsorption sites are the Ca–Ca bridge sites. Apart from the Cr, Mo, Cu, Ag and Au all the studied metals bind strongly to the calcite surface. The calculated migration barriers for the representative Ag and Fe atoms indicates that the metal adatoms are mobile on the calcite surface at room temperature. Bader analysis suggests that there is no significant charge transfer between the metal adatoms and the calcite surface. (paper)

Adsorption of ethanol on V2O5 (010) surface for gas-sensing applications: Ab initio investigation

International Nuclear Information System (INIS)

Qin, Yuxiang; Cui, Mengyang; Ye, Zhenhua

2016-01-01

Highlights: • Ethanol adsorbed on V 2 O 5 (010) surface was investigated by ab initio calculations. • Ethanol prefers to adsorb on “Hill”-like surface, rather than“Valley”-like region. • Surface O 1(H) site plays a key role to dominate the ethanol adsorption process. • Sensing mechanism is related with electronic structure and electron redistribution. • Gas sensitivity is reflected by quantitative electron population analysis. - Abstract: The adsorption of ethanol on V 2 O 5 (010) surface was investigated by means of density functional theory (DFT) with a combined generalized gradient approximation (GGA) plus Hubbard U approach to exploit the potential sensing applications. The adsorption configurations were first constructed by considering different orientations of ethanol molecule to V and O sites on the “Hill”- and “Valley”-like regions of corrugated (010) surface. It is found that ethanol molecule can adsorb on whole surface in multiple stable configurations. Nevertheless the molecular adsorption on the “Hill”-like surface is calculated to occur preferentially, and the single coordinated oxygen on “Hill”-like surface (O 1(H) ) acting as the most energetically favorable adsorption site shows the strongest adsorption ability to ethanol molecule. Surface adsorption of ethanol tunes the electronic structure of V 2 O 5 and cause an n-doping effect. As a consequence, the Fermi levels shift toward the conductive bond increasing the charge carrier concentration of electrons in adsorbed V 2 O 5 . The sensitive electronic structure and the multiple stable configurations to ethanol adsorption highlight the high adsorption activity and then the potential of V 2 O 5 (010) surface applied to high sensitive sensor for ethanol vapor detection. Further Mulliken population and Natural bond orbital (NBO) calculations quantify the electron transfer from the adsorbed ethanol to the surface, and correlates the adsorption ability of surface sites

Supramolecular structures on silica surfaces and their adsorptive properties.

Science.gov (United States)

Belyakov, Vladimir N; Belyakova, Lyudmila A; Varvarin, Anatoly M; Khora, Olexandra V; Vasilyuk, Sergei L; Kazdobin, Konstantin A; Maltseva, Tetyana V; Kotvitskyy, Alexey G; Danil de Namor, Angela F

2005-05-01

The study of adsorptive and chemical immobilization of beta-cyclodextrin on a surface of hydroxylated silicas with various porous structure is described. Using IR spectroscopy, thermal gravimetrical analysis with a programmed heating, and chemical analysis of the silica surface, it is shown that the process of adsorption-desorption of beta-cyclodextrin depends on the porous structure of the silica. The reaction of esterification was used for chemical grafting of beta-cyclodextrin on the surface of hydroxylated silicas. Hydrolytic stability of silicas chemically modified by beta-cyclodextrin apparently is explained by simultaneous formation of chemical and hydrogen bonds between surface silanol groups and hydroxyl groups of beta-cyclodextrin. The uptake of the cations Cu(II), Cd(II), and Pb(II) and the anions Cr(VI) and As(V) by silicas modified with beta-cyclodextrin is investigated as a function of equilibrium ion concentrations. The increase of ion uptake and selectivity of ion extraction in comparison with starting silicas is established. It is due to the formation of surface inclusion complexes of the "host-guest" type in which one molecule of beta-cyclodextrin interacts simultaneously with several ions.

Post-adsorption process of Yb phosphate nano-particle formation by Saccharomyces cerevisiae

Science.gov (United States)

Jiang, MingYu; Ohnuki, Toshihiko; Tanaka, Kazuya; Kozai, Naofumi; Kamiishi, Eigo; Utsunomiya, Satoshi

2012-09-01

In this study, we have investigated the post-adsorption process of ytterbium (Yb) phosphate nano-particle formation by Saccharomyces cerevisiae (yeast). The yeast grown in P-rich medium were exposed to 1.44 × 10-4 mol/L Yb(III) solution for 2-120 h, and 2 months at 25 ± 1 °C at an initial pH of 3, 4, or 5, respectively. Ytterbium concentrations in solutions decreased as a function of exposure time. Field-emission scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy (FESEM), transmission electron microscopy (TEM), and synchrotron-based extended X-ray absorption fine structure (EXAFS) analyses revealed that nano-sized blocky Yb phosphate with an amorphous phase formed on the yeast cells surfaces in the solutions with Yb. These nano-sized precipitates that formed on the cell surfaces remained stable even after 2 months of exposure at 25 ± 1 °C around neutral pHs. The EXAFS data revealed that the chemical state of the accumulated Yb on the cell surfaces changed from the adsorption on both phosphate and carboxyl sites at 30 min to Yb phosphate precipitates at 5 days, indicating the Yb-phosphate precipitation as a major post-adsorption process. In addition, the precipitation of Yb phosphate occurred on cell surfaces during 7 days of exposure in Yb-free solution after 2 h of exposure (short-term Yb adsorption) in Yb solution. These results suggest that the released P from the inside of yeast cells reacted with adsorbed Yb on cell surfaces, resulting in the formation of Yb precipitates, even though no P was added to the exposure solution. In an abiotic system, the EXAFS data showed that the speciation of sorbed Yb on the reference materials, carboxymethyl cellulose and Ln resin, did not change even when the Yb was exposed to P solution, without forming Yb phosphate precipitates. This result strongly suggests that the cell surface of the yeast plays an important role in the Yb-phosphate precipitation process, not only as a carrier of the

Adsorption of benzene and toluene from aqueous solutions onto activated carbon and its acid and heat treated forms: influence of surface chemistry on adsorption.

Science.gov (United States)

Wibowo, N; Setyadhi, L; Wibowo, D; Setiawan, J; Ismadji, S

2007-07-19

The influence of surface chemistry and solution pH on the adsorption of benzene and toluene on activated carbon and its acid and heat treated forms were studied. A commercial coal-based activated carbon F-400 was chosen as carbon parent. The carbon samples were obtained by modification of F-400 by means of chemical treatment with HNO3 and thermal treatment under nitrogen flow. The treatment with nitric acid caused the introduction of a significant number of oxygenated acidic surface groups onto the carbon surface, while the heat treatment increases the basicity of carbon. The pore characteristics were not significantly changed after these modifications. The dispersive interactions are the most important factor in this adsorption process. Activated carbon with low oxygenated acidic surface groups (F-400Tox) has the best adsorption capacity.

Response surface modeling of boron adsorption from aqueous solution by vermiculite using different adsorption agents: Box-Behnken experimental design.

Science.gov (United States)

Demirçivi, Pelin; Saygılı, Gülhayat Nasün

2017-07-01

In this study, a different method was applied for boron removal by using vermiculite as the adsorbent. Vermiculite, which was used in the experiments, was not modified with adsorption agents before boron adsorption using a separate process. Hexadecyltrimethylammonium bromide (HDTMA) and Gallic acid (GA) were used as adsorption agents for vermiculite by maintaining the solid/liquid ratio at 12.5 g/L. HDTMA/GA concentration, contact time, pH, initial boron concentration, inert electrolyte and temperature effects on boron adsorption were analyzed. A three-factor, three-level Box-Behnken design model combined with response surface method (RSM) was employed to examine and optimize process variables for boron adsorption from aqueous solution by vermiculite using HDTMA and GA. Solution pH (2-12), temperature (25-60 °C) and initial boron concentration (50-8,000 mg/L) were chosen as independent variables and coded x 1 , x 2 and x 3 at three levels (-1, 0 and 1). Analysis of variance was used to test the significance of variables and their interactions with 95% confidence limit (α = 0.05). According to the regression coefficients, a second-order empirical equation was evaluated between the adsorption capacity (q i ) and the coded variables tested (x i ). Optimum values of the variables were also evaluated for maximum boron adsorption by vermiculite-HDTMA (HDTMA-Verm) and vermiculite-GA (GA-Verm).

Effect of the surface oxygen groups on methane adsorption on coals

Energy Technology Data Exchange (ETDEWEB)

Hao Shixiong [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China); Department of Chemical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Wen Jie [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China); Yu Xiaopeng [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China); Department of Chemical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Chu Wei, E-mail: chuwei1965_scu@yahoo.com [Department of Chemical Engineering, Sichuan University, Chengdu 610065 (China)

2013-01-01

Highlights: Black-Right-Pointing-Pointer We modified one coal with H{sub 2}O{sub 2}, (NH{sub 4}){sub 2}S{sub 2}O{sub 8} and HNO{sub 3} respectively, to prepare coal samples with different surface properties. Black-Right-Pointing-Pointer The oxygen groups on coal surface were characterized by XPS. Black-Right-Pointing-Pointer The textures of the coal samples were investigated by N{sub 2} adsorption at 77 K. Black-Right-Pointing-Pointer The adsorption behaviors were measured by volumetric method. Black-Right-Pointing-Pointer There was a negative correlation between methane saturated adsorption capacity and the O{sub total}/C{sub total}. - Abstract: To investigate the influence of surface oxygen groups on methane adsorption on coals, one bituminous coal was modified with H{sub 2}O{sub 2}, (NH{sub 4}){sub 2}S{sub 2}O{sub 8} and HNO{sub 3} respectively, to prepare coal samples with different surface properties. The oxygen groups on coal surface were characterized by X-ray photoelectron spectroscopy (XPS). The textures of the coal samples were investigated by N{sub 2} adsorption at 77 K. Their surface morphologies were analyzed by scanning electron microscopy (SEM). The methane adsorption behaviors of these coal samples were measured at 303 K in pressure range of 0-5.3 MPa by volumetric method. The adsorption data of methane were fitted to the Langmuir model and Dubinin-Astakhov (D-A) model. The fitting results showed that the D-A model fitted the isotherm data better than the Langmuir model. It was observed that there was, in general, a positive correlation between the methane saturated adsorption capacity and the micropore volume of coals while a negative correlation between methane saturated adsorption capacity and the O{sub total}/C{sub total}. The methane adsorption capacity was determined by the coal surface chemistry when the microporosity parameters of two samples were similar. Coal with a higher amount of oxygen surface groups, and consequently with a less

Adsorption of charged albumin subdomains on a graphite surface.

Science.gov (United States)

Raffaini, Giuseppina; Ganazzoli, Fabio

2006-03-01

We report some new molecular dynamics simulation results about the adsorption on a hydrophobic graphite surface of two albumin subdomains, each formed by three different alpha-helices, considering the correctly charged side groups at pH = 7 instead of the neutral ones as done in our previous exploratory paper (Raffaini and Ganazzoli, Langmuir 2003;19:3403-3412). We find that the presence of charges affects somewhat the initial adsorption stage on the electrostatically neutral surface, but not the final one. Thus, we recover the result that a monolayer of aminoacids is eventually formed, with a rough parallelism of distant strands to optimize both the intramolecular and the surface interactions. This feature is consistent with the adsorption on the hydrophobic surface being driven by dispersion forces only, and with the "soft" nature of albumin. Additional optimizations of the final monolayer carried out at pH = 3 and 11 do not modify appreciably this picture, suggesting that adsorption on graphite is basically independent of pH. The enhanced hydration of the final adsorption state due to the (delocalized) charges of the side groups is also discussed in comparison with similar results of the neutralized subdomains. (c) 2005 Wiley Periodicals, Inc.

Influence of Surface Charge/Potential of a Gold Electrode on the Adsorptive/Desorptive Behaviour of Fibrinogen

International Nuclear Information System (INIS)

Dargahi, Mahdi; Konkov, Evgeny; Omanovic, Sasha

2015-01-01

. It was suggested that the driving force for the adsorption of FG on a negatively charged surface represents a positive gain in the entropy of the system, whereas the adsorption on a positively charged gold surface was found to be controlled by electrostatic forces. FG desorption measurements revealed that when the gold surface is polarized within the electrochemical double-layer region during the desorption process, the protein desorption kinetics is rather slow. However, within the regions of hydrogen and oxygen evolution, the FG desorption kinetics accelerates significantly, due to the physical removal of the adsorbed protein layer by gas bubbles evolving from the substrate surface, which enables a complete removal of the pre-adsorbed FG layer. The latter could potentially be employed for electrochemical cleaning of electrically-conducting surfaces fouled by adsorbed protein layers (heat exchangers, filtration membranes, etc.)

Acid-base properties and surface complexation modeling of phosphate anion adsorption by wasted low grade iron ore with high phosphorus.

Science.gov (United States)

Yuan, Xiaoli; Bai, Chenguang; Xia, Wentang; An, Juan

2014-08-15

The adsorption phenomena and specific reaction processes of phosphate onto wasted low grade iron ore with high phosphorus (WLGIOWHP) were studied in this work. Zeta potential and Fourier transform infrared spectroscopy (FTIR) analyses were used to elucidate the interaction mechanism between WLGIOWHP and aqueous solution. The results implied that the main adsorption mechanism was the replacement of surface hydroxyl groups by phosphate via the formation of inner-sphere complex. The adsorption process was characterized by chemical adsorption onto WLGIOWHP. The non-electrostatic model (NEM) was used to simulate the surface adsorption of phosphate onto WLGIOWHP. The total surface site density and protonation constants for NEM (N(T)=1.6×10(-4) mol/g, K(a1)=2.2×10(-4), K(a2)=6.82×10(-9)) were obtained by non-linear data fitting of acid-base titrations. In addition, the NEM was used to establish the surface adsorption complexation modeling of phosphate onto WLGIOWHP. The model successfully predicted the adsorption of phosphate onto WLGIOWHP from municipal wastewater. Copyright © 2014 Elsevier Inc. All rights reserved.

Effect of the selective adsorption on the reactive scattering process of molecular beams from stepped surfaces

International Nuclear Information System (INIS)

Garcia, N.

1977-01-01

An indicative proposal which may explain the diffusion of incident atomic beams scattered by a crystal surface is made in terms of the selective adsorption mechanism. In this sense, the stepped metallic surfaces present characteristics which enhance the displacements and the lifetimes of the beams on the surface. This may be important for increasing the exchange reactive scattering of molecules from crystal surfaces

Phosphorus removal from aqueous solution in parent and aluminum-modified eggshells: thermodynamics and kinetics, adsorption mechanism, and diffusion process.

Science.gov (United States)

Guo, Ziyan; Li, Jiuhai; Guo, Zhaobing; Guo, Qingjun; Zhu, Bin

2017-06-01

Parent and aluminum-modified eggshells were prepared and characterized with X-ray diffraction, specific surface area measurements, infrared spectroscopy, zeta potential, and scanning electron microscope, respectively. Besides, phosphorus adsorptions in these two eggshells at different temperatures and solution pH were carried out to study adsorption thermodynamics and kinetics as well as the mechanisms of phosphorus adsorption and diffusion. The results indicated that high temperature was favorable for phosphorus adsorption in parent and aluminum-modified eggshells. Alkaline solution prompted phosphorus adsorption in parent eggshell, while the maximum adsorption amount was achievable at pH 4 in aluminum-modified eggshell. Adsorption isotherms of phosphorus in these eggshells could be well described by Langmuir and Freundlich models. Phosphorus adsorption amounts in aluminum-modified eggshell were markedly higher compared to those in parent eggshell. Adsorption heat indicated that phosphorus adsorption in parent eggshell was a typically physical adsorption process, while chemical adsorption mechanism of ion exchange between phosphorus and hydroxyl groups on the surface of eggshells was dominated in aluminum-modified eggshell. The time-resolved uptake curves showed phosphorus adsorption in aluminum-modified eggshell was significantly faster than that in parent eggshell. Moreover, there existed two clear steps in time-resolved uptake curves of phosphorus in parent eggshell. Based on pseudo-second order kinetic model and intraparticle diffusion model, we inferred more than one process affected phosphorus adsorption. The first process was the diffusion of phosphorus through water to external surface and the opening of pore channel in the eggshells, and the second process was mainly related to intraparticle diffusion.

Atomistic simulation of the coupled adsorption and unfolding of protein GB1 on the polystyrenes nanoparticle surface

Science.gov (United States)

Xiao, HuiFang; Huang, Bin; Yao, Ge; Kang, WenBin; Gong, Sheng; Pan, Hai; Cao, Yi; Wang, Jun; Zhang, Jian; Wang, Wei

2018-03-01

Understanding the processes of protein adsorption/desorption on nanoparticles' surfaces is important for the development of new nanotechnology involving biomaterials; however, an atomistic resolution picture for these processes and for the simultaneous protein conformational change is missing. Here, we report the adsorption of protein GB1 on a polystyrene nanoparticle surface using atomistic molecular dynamic simulations. Enabled by metadynamics, we explored the relevant phase space and identified three protein states, each involving both the adsorbed and desorbed modes. We also studied the change of the secondary and tertiary structures of GB1 during adsorption and the dominant interactions between the protein and surface in different adsorption stages. The results we obtained from simulation were found to be more adequate and complete than the previous one. We believe the model presented in this paper, in comparison with the previous ones, is a better theoretical model to understand and explain the experimental results.

Immunoglobulin adsorption on modified surfaces

NARCIS (Netherlands)

Bremer, M.G.E.G.

2001-01-01

Preservation of biological functioning of proteins during immobilisation is of special interest in various biomedical and biotechnical applications. In industry physical adsorption of immunoglobulins (IgGs) onto solid surfaces is still the predominant immobilisation procedure because it is

A Density Functional Theory Study of the Adsorption of Benzene on Hematite (α-Fe2O3 Surfaces

Directory of Open Access Journals (Sweden)

Nelson Y. Dzade

2014-02-01

Full Text Available The reactivity of mineral surfaces in the fundamental processes of adsorption, dissolution or growth, and electron transfer is directly tied to their atomic structure. However, unraveling the relationship between the atomic surface structure and other physical and chemical properties of complex metal oxides is challenging due to the mixed ionic and covalent bonding that can occur in these minerals. Nonetheless, with the rapid increase in computer processing speed and memory, computer simulations using different theoretical techniques can now probe the nature of matter at both the atomic and sub-atomic levels and are rapidly becoming an effective and quantitatively accurate method for successfully predicting structures, properties and processes occurring at mineral surfaces. In this study, we have used Density Functional Theory calculations to study the adsorption of benzene on hematite (α-Fe2O3 surfaces. The strong electron correlation effects of the Fe 3d-electrons in α-Fe2O3 were described by a Hubbard-type on-site Coulomb repulsion (the DFT+U approach, which was found to provide an accurate description of the electronic and magnetic properties of hematite. For the adsorption of benzene on the hematite surfaces, we show that the adsorption geometries parallel to the surface are energetically more stable than the vertical ones. The benzene molecule interacts with the hematite surfaces through π-bonding in the parallel adsorption geometries and through weak hydrogen bonds in the vertical geometries. Van der Waals interactions are found to play a significant role in stabilizing the absorbed benzene molecule. Analyses of the electronic structures reveal that upon benzene adsorption, the conduction band edge of the surface atoms is shifted towards the valence bands, thereby considerably reducing the band gap and the magnetic moments of the surface Fe atoms.

Nitrogen adsorption on Fe(111), (100), and (110) surfaces

DEFF Research Database (Denmark)

Mortensen, Jens Jørgen; Ganduglia-Pirovano, Veronica; Hansen, Lars Bruno

1999-01-01

Adsorption energies and structures for N atoms on three low-index surfaces of Fe have been calculated using density functional theory (DFT) and the generalized gradient approximation (GGA). At low N coverage the adsorption energy on Fe(100) is found to be similar to 0.7 eV higher than on the (111......) and (110) surfaces - particularly the c(2 x 2)-N/Fe(100) structure with the N atoms in four-fold sites is very stable. We attribute the differences in adsorption energy to the lack of four-fold sites on the (111) and (110) surfaces, We suggest that at higher N coverages, islands with a structure similar...

Adsorption of oxazole and isoxazole on BNNT surface: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Kaur, Jasleen, E-mail: jasleen.chem@gmail.com; Singla, Preeti, E-mail: preetisingla21@gmail.com; Goel, Neetu, E-mail: neetugoel@pu.ac.in

2015-02-15

Highlights: • The adsorption of oxazole and isoxazole over (6,0) and (5,5) BNNTs is studied. • The adsorption energies and structural changes are inductive of covalent adsorption. • The solvent plays an important role in improving the adsorption properties. • The adsorption witnesses substantial changes in electronic properties of the BNNT. • The functionalization of the BNNTs open up their applicability as drug carrier. - Abstract: The adsorption behavior of oxazole and isoxazole heterocycles over the (6,0) zigzag and (5,5) armchair boron nitride nanotube (BNNT) has been studied within the formalism of density functional theory (DFT). The adsorption energies, the frontier molecular orbital (FMO) analysis and the structural changes at the adsorption site are indicative of covalent adsorption on the zigzag BNNT surface, while the adsorption is physical in nature on the armchair BNNT surface. The role of solvent in improving the adsorption properties over the BNNT surface is elucidated by reoptimizing the structures in aqueous phase. The solvation energy is indicative of remarkable increase in the solubility of BNNTs after adsorption of heterocyclic rings. The Density of states (DOS) Plots, natural bond orbital (NBO) analysis and the quantum molecular descriptors (QMD) are witness to the substantial changes in the electronic properties of the BNNT systems following the attachment of these heterocycles with the tube surface. The study envisages the functionalization of the BNNT as well as its applicability as carrier of the drugs containing heterocyclic rings oxazole and isoxazole with marked sensitivity to the type of adsorbate and the adsorbent.

Adsorptive removal of residual catalyst from palm biodiesel: Application of response surface methodology

Directory of Open Access Journals (Sweden)

Mjalli Sabri Farouq

2012-01-01

Full Text Available In this work, the residual potassium hydroxide catalyst was removed from palm oil-based methyl esters using an adsorption technique. The produced biodiesel was initially purified through a water washing process. To produce a biodiesel with a better quality and also to meet standard specifications (EN 14214 and ASTM D6751, batch adsorption on palm shell activated carbon was used for further catalyst removal. The Central Composite Design (CCD of the Response Surface Methodology (RSM was used to study the influence of adsorbent amount, time and temperature on the adsorption of potassium species. The maximum catalyst removal was achieved at 40°C using 0.9 g activated carbon for 20 h adsorption time. The results from the Response Surface Methodology are in a good agreement with the measured values. The absolute error in prediction at the optimum condition was 3.7%, which is reasonably accurate. This study proves that adsorption post-treatment techniques can be successfully employed to improve the quality of biodiesel fuel for its effective use on diesel engines and to minimize the usage of water.

Dopant Adsorption and Incorporation at Irradiated GaN Surfaces

Science.gov (United States)

Sun, Qiang; Selloni, Annabella; Myers, Thomas; Doolittle, W. Alan

2006-03-01

Mg and O are two of the common dopants in GaN, but, in spite of extensive investigation, the atomic scale understanding of their adsorption and incorporation is still incomplete. In particular, high-energy electron irradiation, such as occurring during RHEED, has been reported to have an important effect on the incorporation of these impurities, but no study has addressed the detailed mechanisms of this effect yet. Here we use DFT calculations to study the adsorption and incorporation of Mg and O at the Ga- and N-polar GaN surfaces under various Ga, Mg and O coverage conditions as well as in presence of light or electron beam-induced electronic excitation. We find that the adsorption and incorporation of the two impurities have opposite surface polarity dependence: substitutional Mg prefers to incorporate at the GaN(0001) surface, while O prefers to adsorb and incorporate at the N-polar surface. In addition, our results indicate that in presence of light irradiation the tendency of Mg to surface-segregate is reduced. The O adsorption energy on the N-polar surface is also significantly reduced, consistent with the experimental observation of a much smaller concentration of oxygen in the irradiated samples.

Surface modification influencing adsorption of red wine constituents: The role of functional groups

Science.gov (United States)

Mierczynska-Vasilev, Agnieszka; Smith, Paul A.

2016-11-01

The adsorption of wine constituents at solid surfaces is important in applications such as filtration and membrane fouling, binding to tanks and fittings and interactions with processing aids such as bentonite. The interaction of wine constituents with surfaces is mediated through adsorbed wine components, where the type of constituents, amount, orientation, and conformation are of consequence for the surface response. This study examines the effect of surface chemical functionalities on the adsorption of red wine constituents. Plasma-polymerized films rich in amine, carboxyl, hydroxyl, formyl and methyl functional groups were generated on solid substrates whereas, glycidyltrimethylammonium chloride was covalently attached to allylamine plasma-polymer modified surface and poly(sodium styrenesulfonate) was electrostatically adsorbed to an amine plasma-polymerized surface. The surface chemical functionalities were characterized by X-ray photoelectron spectroscopy. The ability of different substrates to adsorb red wine constituents was evaluated by quartz crystal microbalance and atomic force microscopy. The results showed that substrates modified with -SO3H and -COOH groups can adsorb more of the wine nitrogen-containing compounds whereas -NH2 and -NR3 groups encourage carbon-containing compounds adsorption. Red wine constituents after filtration were adsorbed in higher extend on -NR3 and -CHO surfaces. The -OH modified surfaces had the lowest ability to absorb wine components.

Adsorption of iodide and iodate on colloidal silver surface

International Nuclear Information System (INIS)

Zhang Aiping; Tie Xiaoyun; Zhang Jinzhi; An Yanwei; Li Lingjie

2008-01-01

'Chemically pure' silver colloids were prepared by laser ablated method to investigate their adsorption-induced spectral and morphologic changes, using UV-visible absorption, Raman and transmission electron microscopy (TEM) techniques, when nucleophilic different anions (IO 3 - and I - ) were added into sols. It reveals that the adsorption of nucleophiles on silver surfaces leads to an excess negative charge in the metal interior and modifies both surface charge density and the Fermi levels of metal, which is responsible for the colloidal aggregation, reconstruction and appearance of new resonance absorption bands or with wavelength shift. In addition, two models regarding different adsorption effects of these two anions on silver surfaces were proposed to explain their variant spectral and TEM phenomena.

SeO2 adsorption on CaO surface: DFT and experimental study on the adsorption of multiple SeO2 molecules

Science.gov (United States)

Fan, Yaming; Zhuo, Yuqun; Li, Liangliang

2017-10-01

SeO2 adsorption mechanisms on CaO surface were firstly investigated by both density functional theory (DFT) calculations and adsorption experiments. Adsorption of multiple SeO2 on the CaO (001) surface was investigated using slab model. Based on the results of adsorption energy and surface property, a double-layer adsorption mechanisms were proposed. In experiments, the SeO2 adsorption products were prepared in a U-shaped quartz reactor at 200 °C. The surface morphology was investigated by field emission scanning electron microscopy (FE-SEM). The superficial and total SeO2 mass fractions were measured by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), respectively. The surface valence state and bulk structure are determined by XPS and X-Ray Diffraction (XRD). The experimental results are in good agreement with the DFT results. In conclusion, the fundamental SeO2 chemisorption mechanisms on CaO surface were suggested.

Multifaceted adsorption of α-cyano-4-hydroxycinnamic acid on silver colloidal and island surfaces

Science.gov (United States)

Jung, Dawoon; Jeon, Kooknam; Yeo, Juhyun; Hussain, Shafqat; Pang, Yoonsoo

2017-12-01

The surface adsorption of organic nitrile compounds on the silver colloidal and island surfaces has been studied using surface-enhanced Raman scattering (SERS). α-Cyano-4-hydroxycinnamic acid (CHCA) with nitrile and carboxyl groups shows various surface adsorption on the silver surfaces. In acidic conditions, the surface adsorption of CHCA via the nitrile group with a more or less tilted geometry to the surface was found. When the solution pH increases, the carboxylate and nitrile groups of deprotonated CHCA participate in the surface adsorption, whereas the molecular plane of CHCA becomes more parallel to the surface. The ν(Ctbnd N) band in SERS of CHCA is the indicator of the surface adsorption geometry. The strongly red-shifted and broadened ν(Ctbnd N) band in SERS represents the surface adsorption via π-electrons of the Ctbnd N bond (side-on geometry; π-coordination). Nitriles adsorbed on the surface via the nonbonding electron pair of the nitrogen atom (end-on geometry; σ-coordination) often cause the blue-shifts and small band broadening in ν(Ctbnd N) in SERS. The surface adsorption geometry of organic nitriles based on many previous experimental results was further confirmed by the surface adsorption of CHCA on the silver island surfaces and dinitrile compounds on the silver colloidal surfaces.

Surface and Adsorption Properties of Activated Carbon Fabric Prepared from Cellulosic Polymer: Mixed Activation Method

Energy Technology Data Exchange (ETDEWEB)

Bhati, Surendra; Mahur, J. S.; Choubey, O. N. [Barkatullah Univ., Bhopal (India); Dixit, Mahur Savita [Maulana Azad National Institute of Technology, Bhopla (India)

2013-02-15

In this study, activated carbon fabric was prepared from a cellulose-based polymer (viscose rayon) via a combination of physical and chemical activation (mixed activation) processes by means of CO{sub 2} as a gasifying agent and surface and adsorption properties were evaluated. Experiments were performed to investigate the consequence of activation temperature (750, 800, 850 and 925 .deg. C), activation time (15, 30, 45 and 60 minutes) and CO{sub 2} flow rate (100, 200, 300 and 400 mL/min) on the surface and adsorption properties of ACF. The nitrogen adsorption isotherm at 77 K was measured and used for the determination of surface area, total pore volume, micropore volume, mesopore volume and pore size distribution using BET, t-plot, DR, BJH and DFT methods, respectively. It was observed that BET surface area and TPV increase with rising activation temperature and time due to the formation of new pores and the alteration of micropores into mesopores. It was also found that activation temperature dominantly affects the surface properties of ACF. The adsorption of iodine and CCl{sub 4} onto ACF was investigated and both were found to correlate with surface area.

Surface and Adsorption Properties of Activated Carbon Fabric Prepared from Cellulosic Polymer: Mixed Activation Method

International Nuclear Information System (INIS)

Bhati, Surendra; Mahur, J. S.; Choubey, O. N.; Dixit, Mahur Savita

2013-01-01

In this study, activated carbon fabric was prepared from a cellulose-based polymer (viscose rayon) via a combination of physical and chemical activation (mixed activation) processes by means of CO 2 as a gasifying agent and surface and adsorption properties were evaluated. Experiments were performed to investigate the consequence of activation temperature (750, 800, 850 and 925 .deg. C), activation time (15, 30, 45 and 60 minutes) and CO 2 flow rate (100, 200, 300 and 400 mL/min) on the surface and adsorption properties of ACF. The nitrogen adsorption isotherm at 77 K was measured and used for the determination of surface area, total pore volume, micropore volume, mesopore volume and pore size distribution using BET, t-plot, DR, BJH and DFT methods, respectively. It was observed that BET surface area and TPV increase with rising activation temperature and time due to the formation of new pores and the alteration of micropores into mesopores. It was also found that activation temperature dominantly affects the surface properties of ACF. The adsorption of iodine and CCl 4 onto ACF was investigated and both were found to correlate with surface area

Adsorption of ibuprofen from aqueous solution on chemically surface-modified activated carbon cloths

Directory of Open Access Journals (Sweden)

Hanen Guedidi

2017-05-01

Full Text Available This study aims to investigate the performance of an activated carbon cloth for adsorption of ibuprofen. The cloth was oxidized by a NaOCl solution (0.13 mol L−1 or thermally treated under N2 (700 °C for 1 hour. The raw and modified cloths were characterized by N2 adsorption–desorption measurement at 77 K, CO2 adsorption at 273 K, Boehm titrations, pHPZC measurements, X-ray Photoelectron Spectroscopy analysis, and by infrared spectroscopy. The NaOCl treatment increases the acidic sites, mostly creating phenolic and carboxylic groups and decreases both the specific surface area and slightly the micropore volume. However, the thermal treatment at 700 °C under N2 induced a slight increase in the BET specific surface area and yielded to the only increase in the carbonyl group content. Ibuprofen adsorption studies of kinetics and isotherms were carried out at pH = 3 and 7. The adsorption properties were correlated to the cloth porous textures, surface chemistry and pH conditions. The isotherms of adsorption were better reproduced by Langmuir–Freundlich models at 298, 313 and 328 K. The adsorption of ibuprofen on the studied activated carbon cloths at pH 3 was an endothermic process. The pore size distributions of all studied ibuprofen-loaded fabrics were determined by DFT method to investigate the accessible porosity of the adsorbate. Both treatments do not influence the kind of micropores where the adsorption of ibuprofen occurred.

Evaluation of adsorption and Fenton-adsorption processes for landfill leachate treatment

OpenAIRE

San Pedro-Cedillo, L.; Méndez-Novelo, R.I.; Rojas-Valencia, M.N.; Barceló-Quintal, M.; Castillo-Borges, E.R.; Sauri-Riancho, M.R.; Marrufo-Gómez, J.M.

2015-01-01

The objective of this research was to compare the adsorption and Fenton-adsorption treatments for the removal of contaminants in leachate from landfills and thus determine the most efficient one. The adsorption process with granular activated carbon was tested in two types of samples: raw leachate and leachate treated by Fenton. The results showed color, chemical oxygen demand (COD), total nitrogen and total organic carbon (TOC) removal rates higher than 99% through the Fenton-adsorption proc...

Adsorption of methane and CO2 onto olivine surfaces in Martian dust conditions

Science.gov (United States)

Escamilla-Roa, Elizabeth; Martin-Torres, Javier; Sainz-Díaz, C. Ignacio

2018-04-01

Methane has been detected on all planets of our Solar System, and most of the larger moons, as well as in dwarf-planets like Pluto and Eric. The presence of this molecule in rocky planets is very interesting because its presence in the Earth's atmosphere is mainly related to biotic processes. Space instrumentation in orbiters around Mars has detected olivine on the Martian soil and dust. On the other hand the measurements of methane from the Curiosity rover report detection of background levels of atmospheric methane with abundance that is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, elevated levels of methane about this background have been observed implying that Mars is episodically producing methane from an additional unknown source, making the reasons of these temporal fluctuations of methane a hot topic in planetary research. The goal of this study is to investigate at atomic level the interactions during the adsorption processes of methane and other Mars atmospheric species (CO2, H2O) on forsterite surfaces, through electronic structure calculations based on the Density Functional Theory (DFT). We propose two models to simulate the interaction of adsorbates with the surface of dust mineral, such as binary mixtures (5CH4+5H2O/5CH4+5CO2) and as a semi-clathrate adsorption. We have obtained interesting results of the adsorption process in the mixture 5CH4+5CO2. Associative and dissociative adsorptions were observed for water and CO2 molecules. The methane molecules were only trapped and held by water or CO2 molecules. In the dipolar surface, the adsorption of CO2 molecules produced new species: one CO from a CO2 dissociation, and, two CO2 molecules chemisorbed to mineral surface forming in one case a carbonate group. Our results suggest that CO2 has a strong interaction with the mineral surface when methane is present. These results could be confirmed after the

Use of activated carbon adsorption in conjunction with radiation treatment processes

International Nuclear Information System (INIS)

Dickson, L.W.; Lopata, V.J.; Toft-Hall, A.; Kremers, W.; Singh, A.

1988-01-01

This report presents the results of an assessment of the potential applications of combined adsorption-irradiation treatment processes. The rationale for the study was to determine whether the cost of radiation treatment could be reduced by concentrating target species on an adsorbent in the radiation field. Several different studies on adsorption-irradiation treatment were identified in the literature, and experimental work was done on both the conversion of sulphur dioxide to elemental sulphur, and the removal of trihalomethanes from water by adsorption on activated carbon and subsequent irradiation. Adsorption-irradiation treatment would appear to be less costly than irradiation alone for radiolytic decomposition of target species at low concentration in liquid streams, in the presence of high-surface-area, electrically insulating adsorbents. 116 refs

Controlled adsorption of cytochrome c to nanostructured gold surfaces

International Nuclear Information System (INIS)

Gomes, Inês; Feio, Maria J.; Santos, Nuno C.; Eaton, Peter; Serro, Ana Paula; Saramago, Benilde; Pereira, Eulália; Franco, Ricardo

2012-01-01

Controlled electrostatic physisorption of horse heart cytochrome c (Cyt c) onto nanostructured gold surfaces was investigated using Quartz-Crystal Microbalance measurements in planar gold surfaces with or without functionalization using a self-assembled monolayer (SAM) of the alkanethiol mercaptoundecanoic acid (MUA). MUA is a useful functionalization ligand for gold surfaces, shedding adsorbed biomolecules from the excessive electron density of the metal. A parallel analysis was conducted in the corresponding curved surfaces of 15 nm gold nanoparticles (AuNPs), using zeta-potential and UV– visible spectroscopy. Atomic Force Microscopy of both types of functionalized gold surfaces with a MUA SAM, allowed for visualization of Cyt c deposits on the nanostructured gold surface. The amount of Cyt c adsorbed onto the gold surface could be controlled by the solution pH. For the assays conducted at pH 4.5, when MUA SAM- functionalized planar gold surfaces are positive or neutral, and Cyt c has a positive net charge, only 13 % of the planar gold surface area was coated with protein. In contrast, at pH 7.4, when MUA SAM-functionalized planar gold surfaces and Cyt c have opposite charges, a protein coverage of 28 % could be observed implying an adsorption process strongly governed by electrostatic forces. Cyt c adsorption on planar and curved gold surfaces are found to be greatly favored by the presence of a MUA-capping layer. In particular, on the AuNPs, the binding constant is three times larger than the binding constant obtained for the original citrate-capped AuNPs.

Controlled adsorption of cytochrome c to nanostructured gold surfaces

Energy Technology Data Exchange (ETDEWEB)

Gomes, Ines [Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisboa, REQUIMTE, Departamento de Quimica (Portugal); Feio, Maria J. [Faculdade de Ciencias da Universidade do Porto, REQUIMTE, Departamento de Quimica e Bioquimica (Portugal); Santos, Nuno C. [Faculdade de Medicina da Universidade de Lisboa, Instituto de Medicina Molecular (Portugal); Eaton, Peter [Faculdade de Ciencias da Universidade do Porto, REQUIMTE, Departamento de Quimica e Bioquimica (Portugal); Serro, Ana Paula; Saramago, Benilde [Centro de Quimica Estrutural, Instituto Superior Tecnico (Portugal); Pereira, Eulalia [Faculdade de Ciencias da Universidade do Porto, REQUIMTE, Departamento de Quimica e Bioquimica (Portugal); Franco, Ricardo, E-mail: ricardo.franco@fct.unl.pt [Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisboa, REQUIMTE, Departamento de Quimica (Portugal)

2012-12-15

Controlled electrostatic physisorption of horse heart cytochrome c (Cyt c) onto nanostructured gold surfaces was investigated using Quartz-Crystal Microbalance measurements in planar gold surfaces with or without functionalization using a self-assembled monolayer (SAM) of the alkanethiol mercaptoundecanoic acid (MUA). MUA is a useful functionalization ligand for gold surfaces, shedding adsorbed biomolecules from the excessive electron density of the metal. A parallel analysis was conducted in the corresponding curved surfaces of 15 nm gold nanoparticles (AuNPs), using zeta-potential and UV- visible spectroscopy. Atomic Force Microscopy of both types of functionalized gold surfaces with a MUA SAM, allowed for visualization of Cyt c deposits on the nanostructured gold surface. The amount of Cyt c adsorbed onto the gold surface could be controlled by the solution pH. For the assays conducted at pH 4.5, when MUA SAM- functionalized planar gold surfaces are positive or neutral, and Cyt c has a positive net charge, only 13 % of the planar gold surface area was coated with protein. In contrast, at pH 7.4, when MUA SAM-functionalized planar gold surfaces and Cyt c have opposite charges, a protein coverage of 28 % could be observed implying an adsorption process strongly governed by electrostatic forces. Cyt c adsorption on planar and curved gold surfaces are found to be greatly favored by the presence of a MUA-capping layer. In particular, on the AuNPs, the binding constant is three times larger than the binding constant obtained for the original citrate-capped AuNPs.

Comparative study on the copper activation and xanthate adsorption on sphalerite and marmatite surfaces

Science.gov (United States)

Liu, Jian; Wang, Yu; Luo, Deqiang; Chen, Luzheng; Deng, Jiushuai

2018-05-01

The copper activation and potassium butyl xanthate (PBX) adsorption on sphalerite and marmatite surfaces were comparatively investigated using in situ local electrochemical impedance spectroscopy (LEIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and surface adsorption tests. Comparing the LEIS and surface adsorption results, it was found that the activation time is a key factor influencing the copper activation and PBX adsorption on marmatite surface, but it has a negligible influence on sphalerite. For a short activation time within 10 min, the Fe impurity in marmatite shows an adverse influence on the speed of Cu adsorption and ion exchange as well as on the subsequent PBX adsorption. For a long activation time of 30 min, the LEIS, ToF-SIMS and surface adsorption results suggested that the Fe impurity in marmatite enhances the copper adsorption, whereas such enhanced copper adsorption of marmatite cannot result in corresponding enhancing of PBX adsorption. DFT result showed that the Fe impurity in marmatite has harmful influence on the PBX interaction with the Cu-activated surface by increasing the interaction energy. ToF-SIMS result further indicated that the Cu distribution in the outermost surface of marmatite is less than that of the sphalerite, which also results in the less PBX adsorption for the marmatite.

Adsorption of metals and protons on Gloeocapsa sp. cyanobacteria: A surface speciation approach

Energy Technology Data Exchange (ETDEWEB)

Pokrovsky, O.S. [Geochimie et Biogeochimie Experimentale, LMTG, Universite de Toulouse, CNRS-IRD-OMP, 14 Avenue Edouard Belin, 31400 Toulouse (France)], E-mail: oleg@lmtg.obs-mip.fr; Martinez, R.E.; Golubev, S.V. [Geochimie et Biogeochimie Experimentale, LMTG, Universite de Toulouse, CNRS-IRD-OMP, 14 Avenue Edouard Belin, 31400 Toulouse (France); Kompantseva, E.I. [Winogradsky Institute of Microbiology, Russian Academy of Science, Moscow (Russian Federation); Shirokova, L.S. [Institute of Ecological Problems of the Northern Regions, Russian Academy of Science, 29 Naberezhnaja Sev. Dviny, Arkhangelsk (Russian Federation)

2008-09-15

The purpose of the present work is to extend our knowledge of metal-cyanobacteria interactions and to contribute to the database on adsorption parameters of aquatic microorganisms with respect to metal pollutants. To this end, the surface properties of the cyanobacteria (Gloeocapsa sp. f-6gl) were studied using potentiometric acid-base titration methods and ATR-FTIR (attenuated total reflection infrared) spectroscopy. The electrophoretic mobility of viable cells was measured as a function of pH and ionic strength (0.01 and 0.1 M). Surface titrations at 0.01-1.0 M NaCl were performed using limited residence time reactors (discontinuous titration) with analysis of Ca, Mg and dissolved organic C for each titration point in order to account for alkali-earth metal-proton exchange and cell degradation, respectively. Results demonstrate that the cell-wall bound Ca and Mg from the culture media contribute to the total proton uptake via surface ion-exchange reactions. This has been explicitly taken into account for net proton balance calculations. Adsorption of Zn, Cd, Pb and Cu was studied at 25 deg. C in 0.01 M NaNO{sub 3} as a function of pH and metal concentration. The proportion of adsorbed metal increases as a function of culture age with cells of 44 days old having the largest adsorption capacities. A competitive Langmuir sorption isotherm in conjunction with a linear programming method (LPM) was used to fit experimental data and assess the number of surface sites and adsorption reaction constants involved in the binding of metals to the cyanobacteria surface. These observations allowed the determination of the identity and concentration of the major surface functional groups (carboxylate, amine, phosphoryl/phosphodiester and hydroxyl) responsible for the amphoteric behavior of cyanobacterial cell surfaces in aqueous solutions and for metal adsorption. Results of this work should allow better optimizing of metal bioremediation/biosequestration processes as they help

Adsorption of metals and protons on Gloeocapsa sp. cyanobacteria: A surface speciation approach

International Nuclear Information System (INIS)

Pokrovsky, O.S.; Martinez, R.E.; Golubev, S.V.; Kompantseva, E.I.; Shirokova, L.S.

2008-01-01

The purpose of the present work is to extend our knowledge of metal-cyanobacteria interactions and to contribute to the database on adsorption parameters of aquatic microorganisms with respect to metal pollutants. To this end, the surface properties of the cyanobacteria (Gloeocapsa sp. f-6gl) were studied using potentiometric acid-base titration methods and ATR-FTIR (attenuated total reflection infrared) spectroscopy. The electrophoretic mobility of viable cells was measured as a function of pH and ionic strength (0.01 and 0.1 M). Surface titrations at 0.01-1.0 M NaCl were performed using limited residence time reactors (discontinuous titration) with analysis of Ca, Mg and dissolved organic C for each titration point in order to account for alkali-earth metal-proton exchange and cell degradation, respectively. Results demonstrate that the cell-wall bound Ca and Mg from the culture media contribute to the total proton uptake via surface ion-exchange reactions. This has been explicitly taken into account for net proton balance calculations. Adsorption of Zn, Cd, Pb and Cu was studied at 25 deg. C in 0.01 M NaNO 3 as a function of pH and metal concentration. The proportion of adsorbed metal increases as a function of culture age with cells of 44 days old having the largest adsorption capacities. A competitive Langmuir sorption isotherm in conjunction with a linear programming method (LPM) was used to fit experimental data and assess the number of surface sites and adsorption reaction constants involved in the binding of metals to the cyanobacteria surface. These observations allowed the determination of the identity and concentration of the major surface functional groups (carboxylate, amine, phosphoryl/phosphodiester and hydroxyl) responsible for the amphoteric behavior of cyanobacterial cell surfaces in aqueous solutions and for metal adsorption. Results of this work should allow better optimizing of metal bioremediation/biosequestration processes as they help to

[Adsorption of Cu on Core-shell Structured Magnetic Particles: Relationship Between Adsorption Performance and Surface Properties].

Science.gov (United States)

Li, Qiu-mei; Chen, Jing; Li, Hai-ning; Zhang, Xiao-lei; Zhang, Gao-sheng

2015-12-01

In order to reveal the relationship between the adsorption performance of adsorbents and their compositions, structure, and surface properties, the core-shell structured Fe₃O₄/MnO2 and Fe-Mn/Mn₂2 magnetic particles were systematically characterized using multiple techniques and their Cu adsorption behaviors as well as mechanism were also investigated in details. It was found that both Fe₃O4 and Fe-Mn had spinel structure and no obvious crystalline phase change was observed after coating with MnO₂. The introduction of Mn might improve the affinity between the core and the shell, and therefore enhanced the amount and distribution uniformity of the MnO₂ coated. Consequently, Fe-Mn/MnO₂ exhibited a higher BET specific surface area and a lower isoelectric point. The results of sorption experiments showed that Fe-Mn had a higher maximal Cu adsorption capacity of 33.7 mg · g⁻¹ at pH 5.5, compared with 17.5 mg · g⁻¹ of Fe₃O4. After coating, the maximal adsorption capacity of Fe-Mn/MnO₂ was increased to 58.2 mg · g⁻¹, which was 2.6 times as high as that of Fe₃O₄/MnO₂ and outperformed the majority of magnetic adsorbents reported in literature. In addition, a specific adsorption of Cu occurred at the surface of Fe₃O₄/MnO₂ or Fe-Mn/MnO₂ through the formation of inner-sphere complexes. In conclusion, the adsorption performance of the magnetic particles was positively related to their compositions, structure, and surface properties.

Theoretical studies of arsenite adsorption and its oxidation mechanism on a perfect TiO 2 anatase (1 0 1) surface

Science.gov (United States)

Wei, Zhigang; Zhang, Shaowen; Pan, Zhanchang; Liu, Yue

2011-11-01

There are many areas in the world where the ground water has been contaminated by arsenic. TiO2 is one of the most promising materials that can remove arsenic from groundwater supplies by the adsorption-based processes. The TiO2 surface is capable of photo-catalytic oxidation (PCO) changing the arsenite [As(III)] to arsenate [As(V)] which is more easily absorbed by the surface, increasing the efficiency of the process. In this paper, a density functional theory calculation has been performed to investigate the adsorption of As(III) on a perfect TiO2 anatase (1 0 1) surface. All the As(III) solution species such as H3AsO3, H2AsO3-, HAsO32- and AsO33- are put onto the surface with many different possible attitudes to obtain the adsorption energy. Based on the adsorption energy and the concentration of H3AsO3, H2AsO3-, HAsO32- and AsO33- in an aqueous solution, the bidentate binuclear (BB) adsorption configurations of H2AsO3- on the surface are more favorable at low As(III) concentrations, whereas BB form and monodentate mononuclear (MM) form may coexist at higher concentrations. By calculating H2AsO3- co-adsorption with water and oxygen, we can confirm the deep acceptor character of an adsorbed O2 molecule which implies that surface superoxide (or hydroperoxyl radical) plays an important role during the PCO process of As(III) on TiO2 surface.

Highly efficient fluoride adsorption from aqueous solution by nepheline prepared from kaolinite through alkali-hydrothermal process.

Science.gov (United States)

Wang, Hao; Feng, Qiming; Liu, Kun; Li, Zishun; Tang, Xuekun; Li, Guangze

2017-07-01

A direct alkali-hydrothermal induced transformation process was adopted to prepare nepheline from raw kaolinite (shortened form RK in this paper) and NaOH solution in this paper. Structure and morphology characterizations of the synthetic product showed that the nepheline possessed high degree of crystallinity and uniform surface morphology. Specific surface area of nepheline is 18 m 2 /g, with a point of zero charge at around pH 5.0-5.5. The fluoride (F - ions) adsorption by the synthetic nepheline (shortened form SN in this paper) from aqueous solution was also investigated under different experimental conditions. The adsorption process well matched the Langmuir isotherm model with an amazing maximum adsorption capacity of 183 mg/g at 323 K. The thermodynamic parameters (ΔG 0 , ΔH 0 , and ΔS 0 ) for adsorption on SN were also determined from the temperature dependence. The adsorption capacities of fluoride on SN increased with increasing of temperature and initial concentration. Initial pH value also had influence on adsorption process. Adsorption of fluoride was rapidly increased in 5-60 min and thereafter increased slowly to reach the equilibrium in about 90-180 min under all conditions. The adsorption followed a pseudo-second order rate law. Copyright © 2017 Elsevier Ltd. All rights reserved.

A DFT study on benzene adsorption over tungsten sulfides: surface model and adsorption geometries

NARCIS (Netherlands)

Koide, R.; Hensen, E.J.M.; Paul, J.F.; Cristol, S.; Payen, E.; Nakamura, H.; Santen, van R.A.

2007-01-01

Benzene adsorption on a WS2(100) surface was studied by ab initio periodic DFT computations. Benzene adsorption is facile on the bridge site of the bare W edge via ¿2 or ¿3 coordination. Taking into account the stable configuration at the W edge under typical hydrotreating reaction conditions (623

Gold nanoparticles: role of size and surface chemistry on blood protein adsorption

Energy Technology Data Exchange (ETDEWEB)

Benetti, F., E-mail: filippo.benetti@unitn.it; Fedel, M. [BIOtech Research Centre (Italy); Minati, L.; Speranza, G. [Fondazione Bruno Kessler (Italy); Migliaresi, C. [BIOtech Research Centre (Italy)

2013-06-15

Material interaction with blood proteins is a critical issue, since it could influence the biological processes taking place in the body following implantation/injection. This is particularly important in the case of nanoparticles, where innovative properties, such as size and high surface to volume ratio can lead to a behavioral change with respect to bulk macroscopic materials and could be responsible for a potential risk for human health. The aim of this work was to compare gold nanoparticles (AuNP) and planar surfaces to study the role of surface curvature moving from the macro- to the nano-size in the process of blood protein adsorption. In the course of the study, different protocols were tested to optimize the analysis of protein adsorption on gold nanoparticles. AuNP with different size (10, 60 and 200 nm diameter) and surface coatings (citrate and polyethylene glycol) were carefully characterized. The stabilizing action of blood proteins adsorbed on AuNP was studied measuring the variation of size and solubility of the nanoparticles following incubation with single protein solutions (human serum albumin and fibrinogen) and whole blood plasma. In addition, we developed a method to elute proteins from AuNP to study the propensity of gold materials to adsorb plasma proteins in function of dimensional characteristics and surface chemistry. We showed a different efficacy of the various eluting media tested, proving that even the most aggressive agent cannot provide a complete detachment of the protein corona. Enhanced protein adsorption was evidenced on AuNP if compared to gold laminae (bare and PEGylated) used as macroscopic control, probably due to the superior AuNP surface reactivity.

Surface complexation models for uranium adsorption in the sub-surface environment

International Nuclear Information System (INIS)

Payne, T.E.

2007-01-01

Adsorption experiments with soil component minerals under a range of conditions are being used to develop models of uranium(VI) uptake in the sub-surface environment. The results show that adsorption of U on iron oxides and clay minerals is influenced by chemical factors including the pH, partial pressure of CO 2 , and the presence of ligands such as phosphate. Surface complexation models (SCMs) can be used to simulate U adsorption on these minerals. The SCMs are based on plausible mechanistic assumptions and describe the experimental data more adequately than Kd values or sorption isotherms. It is conceptually possible to simulate U sorption data on complex natural samples by combining SCMs for individual component minerals. This approach was used to develop a SCM for U adsorption to mineral assemblages from Koongarra (Australia), and produced a reasonable description of U uptake. In order to assess the applicability of experimental data to the field situation, in-situ measurements of U distributions between solid and liquid phases were undertaken at the Koongarra U deposit. This field partitioning data showed a satisfactory agreement with laboratory sorption data obtained under comparable conditions. (author)

Theoretical investigation of lead vapor adsorption on kaolinite surfaces with DFT calculations

Energy Technology Data Exchange (ETDEWEB)

Wang, Xinye [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China); Huang, Yaji, E-mail: heyyj@seu.edu.cn [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China); Pan, Zhigang [College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009 (China); Wang, Yongxing; Liu, Changqi [Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096 (China)

2015-09-15

Highlights: • Al surface after dehydroxylation is active while Si surface is inert. • The active sites are the unsaturated Al atoms and O atoms losing H atom. • PbO is the most suitable species for adsorption. • Increasing the activities of Al atoms can enhance the performance of kaolinite. • Produce of amorphous silica is a potential path to enhance the performance of kaolinite. - Abstract: Kaolinite can be used as the in-furnace sorbent/additive to adsorb lead (Pb) vapor at high temperature. In this paper, the adsorptions of Pb atom, PbO molecule and PbCl{sub 2} molecule on kaolinie surfaces were investigated by density functional theory (DFT) calculation. Si surface is inert to Pb vapor adsorption while Al surfaces with dehydroxylation are active for the unsaturated Al atoms and the O atoms losing H atoms. The adsorption energy of PbO is much higher than that of Pb atom and PbCl{sub 2}. Considering the energy barriers, it is easy for PbO and PbCl{sub 2} to adsorb on Al surfaces but difficult to escape. The high energy barriers of de–HCl process cause the difficulties of PbCl{sub 2} to form PbO·Al{sub 2}O{sub 3}·2SiO{sub 2} with kaolinite. Considering the inertia of Si atoms and the activity of Al atoms after dehydroxylation, calcination, acid/alkali treatment and some other treatment aiming at amorphous silica producing and Al activity enhancement can be used as the modification measures to improve the performance of kaolinite as the in-furnace metal capture sorbent.

Adsorption characteristics of N-nitrosodimethylamine from aqueous solution on surface-modified activated carbons

Energy Technology Data Exchange (ETDEWEB)

Xiaodong, Dai [Chemistry and Chemical Engineering School, China University of Petroleum, Dongying 257061, Shandong (China); Institute for Sustainability and Innovation, Victoria University, Melbourne, VIC 8001 (Australia); Zou, Linda [SA Water Centre for Water Management and Reuse, University of South Australia, Adelaide, SA5095 (Australia); Zifeng, Yan [Chemistry and Chemical Engineering School, China University of Petroleum, Dongying 257061, Shandong (China); Millikan, Mary [Institute for Sustainability and Innovation, Victoria University, Melbourne, VIC 8001 (Australia)

2009-08-30

This study investigated the removal of N-nitrosodimethylamine (NDMA) by an adsorption mechanism using commercially available activated carbons and surface-modified activated carbons. The effects of the modification on the properties of the activated carbon were studied by N{sub 2} adsorption/desorption, Diffuse Reflectance Infrared Fourier Transmission (DRIFT) analysis and X-Ray Photoelectron Spectroscopy (XPS). Adsorption experiments revealed that the activated carbons demonstrated a greater capacity for NDMA adsorption capacity than can be achieved using zeolite. The equilibrium data was fitted to the Freundlich equation and it was found that the adsorption capacity was significantly influenced by the micropore size, relative pore volume and surface characteristics. Adsorption experiments were conducted using unmodified and modified activated carbons. The results indicated that the adsorption capacity of NDMA can be significantly improved by heat treatment and doping of TiO{sub 2} particles. This was because the surface treatments yielded more hydrophobic sites and fewer oxygen-containing surface functional groups, and consequently an increased capacity for NDMA adsorption.

Adsorption characteristics of N-nitrosodimethylamine from aqueous solution on surface-modified activated carbons

International Nuclear Information System (INIS)

Dai Xiaodong; Zou, Linda; Yan Zifeng; Millikan, Mary

2009-01-01

This study investigated the removal of N-nitrosodimethylamine (NDMA) by an adsorption mechanism using commercially available activated carbons and surface-modified activated carbons. The effects of the modification on the properties of the activated carbon were studied by N 2 adsorption/desorption, Diffuse Reflectance Infrared Fourier Transmission (DRIFT) analysis and X-Ray Photoelectron Spectroscopy (XPS). Adsorption experiments revealed that the activated carbons demonstrated a greater capacity for NDMA adsorption capacity than can be achieved using zeolite. The equilibrium data was fitted to the Freundlich equation and it was found that the adsorption capacity was significantly influenced by the micropore size, relative pore volume and surface characteristics. Adsorption experiments were conducted using unmodified and modified activated carbons. The results indicated that the adsorption capacity of NDMA can be significantly improved by heat treatment and doping of TiO 2 particles. This was because the surface treatments yielded more hydrophobic sites and fewer oxygen-containing surface functional groups, and consequently an increased capacity for NDMA adsorption.

Adsorption of H atoms on cubic Er2O3 (0 0 1) surface: A DFT study

International Nuclear Information System (INIS)

Mao, Wei; Chikada, Takumi; Shimura, Kenichiro; Suzuki, Akihiro; Yamaguchi, Kenji; Terai, Takayuki

2013-01-01

First-principles plane wave calculations based on spin-polarized density functional theory (DFT) and generalized gradient approximation (GGA) have been used to study the adsorption of H atoms on cubic Er 2 O 3 (0 0 1) surface. We identify stable adsorption positions and find that H preferentially adsorbs on top of fourfold-hollow sites and transfers electrons to the surface, resulting in the formations of covalent bonds to the nearest neighboring four oxygen atoms. In the most energetically favorable adsorption sites, It was found that H bonds with O atoms at the cubic Er 2 O 3 (0 0 1) surface with an adsorption energy of −295.68 kJ mol −1 at coverage 1/8 ML, and the adsorption energy is inclined to decrease with the increase of H coverage (>1/4 ML). In addition, our calculations indicate that the dissociative H atom configurations have adsorption energies that are at least 152.64 kJ mol −1 greater than the H 2 molecule configurations on the surface. These results discussed in the context of erbium oxide slabs are employed to rationalize some processes regarding to the hydrogen isotope permeation behavior of tritium permeation barrier

Effects of Surface Treatment of Activated Carbon on Its Surface and Cr(VI) Adsorption Characteristics

Energy Technology Data Exchange (ETDEWEB)

Park, Soo Jin; Jang, Yu Sin [Advanced Materials Division., Korea Research Institute of Chimical Technology, Taejon (Korea)

2001-04-01

In this work, the effect of surface treatments on activated carbons (ACs) has been studied in the context of gas and liquid adsorption behaviors. The chemical solutions used in this experiment were 35% sodium hydroxide, and these were used for the acidic and basic treatments, respectively. The surface properties have been determined by pH, acid-base values, and FT-IR. The adsorption isotherms of Cr(VI) ion on activated carbons have been studied with the 5 mg/l concentration at ambient temperature. N{sub 2} adsorption isotherm characteristics, which include the specific surface area, micro pore volume, and microporosity, were determined by BET and Boer's-plot methods. In case of the acidic treatment of activated carbons, it was observed that the adsorption of Cr(VI) ion was more effective due to the increase acid value (or acidic functional group) of activated carbon surfaces. However, the basic treatment on activated carbons was caused no significant effects, probably due to the decreased specific surface area and total pore volume. 27 refs., 7 figs., 4 tabs.

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

Science.gov (United States)

Arai, Y.; McBeath, M.; Bargar, J.R.; Joye, J.; Davis, J.A.

2006-01-01

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in

Surface modification of pitch-based spherical activated carbon by CVD of NH3 to improve its adsorption to uric acid

International Nuclear Information System (INIS)

Liu Chaojun; Liang Xiaoyi; Liu Xiaojun; Wang Qin; Zhan Liang; Zhang Rui; Qiao Wenming; Ling Licheng

2008-01-01

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH 3 (NH 3 -CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N 2 adsorption, pH PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH 3 -CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH 3 -CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH PZC , surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature

Surface modification of pitch-based spherical activated carbon by CVD of NH 3 to improve its adsorption to uric acid

Science.gov (United States)

Liu, Chaojun; Liang, Xiaoyi; Liu, Xiaojun; Wang, Qin; Zhan, Liang; Zhang, Rui; Qiao, Wenming; Ling, Licheng

2008-08-01

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH 3 (NH 3-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N 2 adsorption, pH PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH 3-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH 3-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH PZC, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.

Chromate adsorption on selected soil minerals: Surface complexation modeling coupled with spectroscopic investigation

Energy Technology Data Exchange (ETDEWEB)

Veselská, Veronika, E-mail: veselskav@fzp.czu.cz [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Fajgar, Radek [Department of Analytical and Material Chemistry, Institute of Chemical Process Fundamentals of the CAS, v.v.i., Rozvojová 135/1, CZ-16502, Prague (Czech Republic); Číhalová, Sylva [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Bolanz, Ralph M. [Institute of Geosciences, Friedrich-Schiller-University Jena, Carl-Zeiss-Promenade 10, DE-07745, Jena (Germany); Göttlicher, Jörg; Steininger, Ralph [ANKA Synchrotron Radiation Facility, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, DE-76344, Eggenstein-Leopoldshafen (Germany); Siddique, Jamal A.; Komárek, Michael [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic)

2016-11-15

Highlights: • Study of Cr(VI) adsorption on soil minerals over a large range of conditions. • Combined surface complexation modeling and spectroscopic techniques. • Diffuse-layer and triple-layer models used to obtain fits to experimental data. • Speciation of Cr(VI) and Cr(III) was assessed. - Abstract: This study investigates the mechanisms of Cr(VI) adsorption on natural clay (illite and kaolinite) and synthetic (birnessite and ferrihydrite) minerals, including its speciation changes, and combining quantitative thermodynamically based mechanistic surface complexation models (SCMs) with spectroscopic measurements. Series of adsorption experiments have been performed at different pH values (3–10), ionic strengths (0.001–0.1 M KNO{sub 3}), sorbate concentrations (10{sup −4}, 10{sup −5}, and 10{sup −6} M Cr(VI)), and sorbate/sorbent ratios (50–500). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy were used to determine the surface complexes, including surface reactions. Adsorption of Cr(VI) is strongly ionic strength dependent. For ferrihydrite at pH <7, a simple diffuse-layer model provides a reasonable prediction of adsorption. For birnessite, bidentate inner-sphere complexes of chromate and dichromate resulted in a better diffuse-layer model fit. For kaolinite, outer-sphere complexation prevails mainly at lower Cr(VI) loadings. Dissolution of solid phases needs to be considered for better SCMs fits. The coupled SCM and spectroscopic approach is thus useful for investigating individual minerals responsible for Cr(VI) retention in soils, and improving the handling and remediation processes.

Mechanisms and energetics of surface atomic processes

International Nuclear Information System (INIS)

Tsong, T.T.

1991-01-01

The energies involved in various surface atomic processes such as surface diffusion, the binding of small atomic clusters on the surface, the interaction between two adsorbed atoms, the dissociation of an atom from a small cluster or from a surface layer, the binding of kink size atoms or atoms at different adsorption sites to the surface etc., can be derived from an analysis of atomically resolved field ion microscope images and a kinetic energy measurement of low temperature field desorbed ions using the time-of-flight atom-probe field ion microscope. These energies can be used to compare with theories and to understand the transport of atoms on the surface in atomic reconstructions, epitaxial growth of surface layers and crystal growth, adsorption layer superstructure formation, and also why an atomic ordering or atomic reconstruction at the surface is energetically favored. Mechanisms of some of the surface atomic processes are also clarified from these quantitative, atomic resolution studies. In this paper work in this area is bris briefly reviewed

Adsorption of sulfide ions on cerussite surfaces and implications for flotation

International Nuclear Information System (INIS)

Feng, Qicheng; Wen, Shuming; Zhao, Wenjuan; Deng, Jiushuai; Xian, Yongjun

2016-01-01

Highlights: • A new discussion on the lead sulfide species is introduced. • The Na_2S concentration determines cerussite sulfidization. • The activity of lead sulfide species also determines cerussite sulfidization. • Disulfide and polysulfide in lead sulfide species affect its activity. - Abstract: The adsorption of sulfide ions on cerussite surfaces and implications for flotation were studied by X-ray photoelectron spectroscopy (XPS) analysis, micro-flotation tests, and surface adsorption experiments. The XPS analysis results indicated that lead sulfide species formed on the mineral surface after treatment by Na_2S, and the increase in the Na_2S concentration was beneficial for sulfidization. In addition to the content of lead sulfide species, its activity, which was determined by the proportion of sulfide, disulfide and polysulfide, also played an important role in cerussite sulfidization. Micro-flotation tests results demonstrated that insufficient or excessive addition of Na_2S in pulp solutions has detrimental effects on flotation performance, which was attributed to the dosage of Na_2S and the activity of lead sulfide species formed on the mineral surface. Surface adsorption experiments of sulfide ions determined the residual S concentrations in pulp solutions and provided a quantitative illustration for the inhibition of cerussite flotation by excessive sulfide ions. Moreover, it also revealed that sulfide ions in the pulp solution were transformed onto the mineral surface and formed lead sulfide species. These results showed that both of lead sulfide species and its activity acted as an important role in sulfidization flotation process of cerussite.

Adsorption of sulfide ions on cerussite surfaces and implications for flotation

Energy Technology Data Exchange (ETDEWEB)

Feng, Qicheng [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093 (China); Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093 (China); Wen, Shuming, E-mail: fqckmust@126.com [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093 (China); Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093 (China); Zhao, Wenjuan [Kunming Metallurgical Research Institute, Kunming 650031 (China); Deng, Jiushuai; Xian, Yongjun [State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093 (China); Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming 650093 (China)

2016-01-01

Highlights: • A new discussion on the lead sulfide species is introduced. • The Na{sub 2}S concentration determines cerussite sulfidization. • The activity of lead sulfide species also determines cerussite sulfidization. • Disulfide and polysulfide in lead sulfide species affect its activity. - Abstract: The adsorption of sulfide ions on cerussite surfaces and implications for flotation were studied by X-ray photoelectron spectroscopy (XPS) analysis, micro-flotation tests, and surface adsorption experiments. The XPS analysis results indicated that lead sulfide species formed on the mineral surface after treatment by Na{sub 2}S, and the increase in the Na{sub 2}S concentration was beneficial for sulfidization. In addition to the content of lead sulfide species, its activity, which was determined by the proportion of sulfide, disulfide and polysulfide, also played an important role in cerussite sulfidization. Micro-flotation tests results demonstrated that insufficient or excessive addition of Na{sub 2}S in pulp solutions has detrimental effects on flotation performance, which was attributed to the dosage of Na{sub 2}S and the activity of lead sulfide species formed on the mineral surface. Surface adsorption experiments of sulfide ions determined the residual S concentrations in pulp solutions and provided a quantitative illustration for the inhibition of cerussite flotation by excessive sulfide ions. Moreover, it also revealed that sulfide ions in the pulp solution were transformed onto the mineral surface and formed lead sulfide species. These results showed that both of lead sulfide species and its activity acted as an important role in sulfidization flotation process of cerussite.

Adsorption of ammonia at GaN(0001) surface in the mixed ammonia/hydrogen ambient - a summary of ab initio data

International Nuclear Information System (INIS)

Kempisty, Paweł; Krukowski, Stanisław

2014-01-01

Adsorption of ammonia at NH 3 /NH 2 /H-covered GaN(0001) surface was analyzed using results of ab initio calculations. The whole configuration space of partially NH 3 /NH 2 /H-covered GaN(0001) surface was divided into zones of differently pinned Fermi level: at the Ga broken bond state for dominantly bare surface (region I), at the valence band maximum (VBM) for NH 2 and H-covered surface (region II), and at the conduction band minimum (CBM) for NH 3 -covered surface (region III). The electron counting rule (ECR) extension was formulated for the case of adsorbed molecules. The extensive ab intio calculations show the validity of the ECR in case of all mixed H-NH 2 -NH 3 coverages for the determination of the borders between the three regions. The adsorption was analyzed using the recently identified dependence of the adsorption energy on the charge transfer at the surface. For region I ammonia adsorbs dissociatively, disintegrating into a H adatom and a HN 2 radical for a large fraction of vacant sites, while for region II adsorption of ammonia is molecular. The dissociative adsorption energy strongly depends on the Fermi level at the surface (pinned) and in the bulk (unpinned) while the molecular adsorption energy is determined by bonding to surface only, in accordance to the recently published theory. Adsorption of Ammonia in region III (Fermi level pinned at CBM) leads to an unstable configuration both molecular and dissociative, which is explained by the fact that broken Ga-bonds are doubly occupied by electrons. The adsorbing ammonia brings 8 electrons to the surface, necessitating the transfer of these two electrons from the Ga broken bond state to the Fermi level. This is an energetically costly process. Adsorption of ammonia at H-covered site leads to the creation of a NH 2 radical at the surface and escape of H 2 molecule. The process energy is close to 0.12 eV, thus not large, but the direct inverse process is not possible due to the escape of the

Gas-phase formaldehyde adsorption isotherm studies on activated carbon: correlations of adsorption capacity to surface functional group density.

Science.gov (United States)

Carter, Ellison M; Katz, Lynn E; Speitel, Gerald E; Ramirez, David

2011-08-01

Formaldehyde (HCHO) adsorption isotherms were developed for the first time on three activated carbons representing one activated carbon fiber (ACF) cloth, one all-purpose granular activated carbon (GAC), and one GAC commercially promoted for gas-phase HCHO removal. The three activated carbons were evaluated for HCHO removal in the low-ppm(v) range and for water vapor adsorption from relative pressures of 0.1-0.9 at 26 °C where, according to the IUPAC isotherm classification system, the adsorption isotherms observed exhibited Type V behavior. A Type V adsorption isotherm model recently proposed by Qi and LeVan (Q-L) was selected to model the observed adsorption behavior because it reduces to a finite, nonzero limit at low partial pressures and it describes the entire range of adsorption considered in this study. The Q-L model was applied to a polar organic adsorbate to fit HCHO adsorption isotherms for the three activated carbons. The physical and chemical characteristics of the activated carbon surfaces were characterized using nitrogen adsorption isotherms, X-ray photoelectron spectroscopy (XPS), and Boehm titrations. At low concentrations, HCHO adsorption capacity was most strongly related to the density of basic surface functional groups (SFGs), while water vapor adsorption was most strongly influenced by the density of acidic SFGs.

Computational study of ethanol adsorption and reaction over rutile TiO2 (110) surfaces

KAUST Repository

Muir, J. N.

2012-01-01

Studies of the modes of adsorption and the associated changes in electronic structures of renewable organic compounds are needed in order to understand the fundamentals behind surface reactions of catalysts for future energies. Using planewave density functional theory (DFT) calculations, the adsorption of ethanol on perfect and O-defected TiO 2 rutile (110) surfaces was examined. On both surfaces the dissociative adsorption mode on five-fold coordinated Ti cations (Ti 4+ 5c) was found to be more favourable than the molecular adsorption mode. On the stoichiometric surface E ads was found to be equal to 0.85 eV for the ethoxide mode and equal to 0.76 eV for the molecular mode. These energies slightly increased when adsorption occurred on the Ti 4+ 5c closest to the O-defected site. However, both considerably increased when adsorption occurred at the removed bridging surface O; interacting with Ti 3+ cations. In this case the dissociative adsorption becomes strongly favoured (E ads = 1.28 eV for molecular adsorption and 2.27 eV for dissociative adsorption). Geometry and electronic structures of adsorbed ethanol were analysed in detail on the stoichiometric surface. Ethanol does not undergo major changes in its structure upon adsorption with its C-O bond rotating nearly freely on the surface. Bonding to surface Ti atoms is a σ type transfer from the O2p of the ethanol-ethoxide species. Both ethanol and ethoxide present potential hole traps on O lone pairs. Charge density and work function analyses also suggest charge transfer from the adsorbate to the surface, in which the dissociative adsorptions show a larger charge transfer than the molecular adsorption mode. This journal is © 2012 the Owner Societies.

Adsorptive removal of crystal violet dye by a local clay and process optimization by response surface methodology

Science.gov (United States)

Loqman, Amal; El Bali, Brahim; Lützenkirchen, Johannes; Weidler, Peter G.; Kherbeche, Abdelhak

2017-11-01

The current study relates to the removal of a dye [crystal violet (CV)] from aqueous solutions through batch adsorption experiment onto a local clay from Morocco. The clay was characterized by X-ray diffraction, IR spectroscopy, X-ray fluorescence, scanning electron microscope, Brunauer-Emmett-Teller analysis and Fraunhofer diffraction method. The influence of independent variables on the removal efficiency was determined and optimized by response surface methodology using the Box-Behnken surface statistical design. The model predicted maximum adsorption of 81.62% under the optimum conditions of operational parameters (125 mg L-1 initial dye concentration, 2.5 g L-1 adsorbent dose and time of 43 min). Practically, the removal ranges in 27.4-95.3%.

Theoretical study of adsorption of organic phosphines on transition metal surfaces

Science.gov (United States)

Lou, Shujie; Jiang, Hong

2018-04-01

The adsorption properties of organic phosphines on transition metal (TM) surfaces (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) have been studied to explore the possibility of building novel heterogeneous chiral catalytic systems based on organic phosphines. Preferred adsorption sites, adsorption energies and surface electronic structures of a selected set of typical organic phosphines adsorbed on TM surfaces are calculated with density-functional theory to obtain a systematic understanding on the nature of adsorption interactions. All organic phosphines considered are found to chemically adsorb on these TM surfaces with the atop site as the most preferred one, and the TM-P bond is formed via the lone-pair electrons of the P atom and the directly contacted TM atom. These findings imply that it is indeed possible to build heterogeneous chiral catalytic systems based on organic phosphines adsorbed on TM surfaces, which, however, requires a careful design of molecular structure of organic phosphines.

Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

International Nuclear Information System (INIS)

Stout, R B

2001-01-01

one of the two models developed, the propagation velocity of the solid-liquid dissolution interface is assumed proportional to configurational entropy discontinuity across the interface. Based on this assumption, the derived functional forms for non-equilibrium rate-thermodynamic force relationships are different from the near-equilibrium, linear rate-thermodynamic force relationships derived from the non-negative entropy dissipation requirement used in the classical approach of Onsager. These analyses of non-equilibrium thermodynamic processes across a propagating discontinuity, along with other idealized dissolution processes that depend on surface adsorption and radiolysis kinetics, provide generic dissolution response functions for empirical and/or regression analysis of data

Investigation of adsorption performance deterioration in silica gel–water adsorption refrigeration

International Nuclear Information System (INIS)

Wang Dechang; Zhang Jipeng; Xia Yanzhi; Han Yanpei; Wang Shuwei

2012-01-01

Highlights: ► Adsorption deterioration of silica gel in refrigeration systems is verified. ► Possible factors to cause such deterioration are analyzed. ► Specific surface area, silanol content and adsorption capacity are tested. ► The pollution is the primary factor to decline the adsorption capacity. ► Deteriorated samples are partly restored after being processed by acid solution. - Abstract: Silica gel acts as a key role in adsorption refrigeration systems. The adsorption deterioration must greatly impact the performance of the silica gel–water adsorption refrigeration system. In order to investigate the adsorption deterioration of silica gel, many different silica gel samples were prepared according to the application surroundings of silica gel in adsorption refrigeration systems after the likely factors to cause such deterioration were analyzed. The specific surface area, silanol content, adsorption capacity and pore size distribution of those samples were tested and the corresponding adsorption isotherms were achieved. In terms of the experimental data comparisons, it could be found that there are many factors to affect the adsorption performance of silica gel, but the pollution was the primary one to decline the adsorption capacity. In addition, the adsorption performance of the deteriorated samples after being processed by acid solution was explored in order to find the possible methods to restore its adsorption performance.

Adsorption and pathways of single atomistic processes on NbN (0 0 1) and (1 1 1) surfaces: A first-principle study

International Nuclear Information System (INIS)

Ren, Yuan; Liu, Xuejie; Tan, Xin; Sun, Shiyang; Wei, Huai; Lu, Feng

2014-01-01

Highlights: • We investigate the behaviors of Nb, Si, N atom on NbN(0 0 1) and (1 1 1) surfaces. • The adsorption and diffusion of single atom on NbN(0 0 1) and (1 1 1) were calculated by DFT. • The potential energy surface of single atom on NbN(0 0 1) and (1 1 1) surfaces were investigated. • The diffusion process of single on NbN(0 0 1) and (1 1 1) were calculated by nudged elastic band. - Abstract: The adsorption and pathway processes of atomistic Nb, Si, and N at high-symmetry sites on NbN (0 0 1) and (1 1 1) surfaces were studied using first-principle method, which is based on the density functional theory. This investigation presents some of the results obtained. The potential energy surface (PES) was obtained by calculating the adsorption of Nb, Si, and N atoms on NbN (0 0 1). The most energetic site for the Nb atom adsorbed on NbN(0 0 1) was the site ‘on-top of face–center cubic’ (HL), whereas those for N and Si were both at the site ‘between TopN and HL’ (TopN-HL). The minimum energy paths of the single atom on NbN (0 0 1) surface diffusion were obtained using the PES calculation results. The Nb and Si atoms were diffused from the TopN to the HL position. The N atom was diffused from the TopNb, whereas the TopN–HL to HL position. The diffusion energies of the Nb, Si, and N atoms on the NbN (0 0 1) surface were 0.32, 0.69, and 1.32 eV, respectively. The pathways of the atomistic diffusion involved the diffusion of atoms from the FCC to the HCP site on the NbN (1 1 1) surface. The results showed that the diffusion energy of Si on the Nb layer was smaller than that on the N layer. Si and N can easily form stable structures while bonding on the N layer. Moreover, Si atoms can stabilize the activity of N atoms while promoting the spread of Nb atoms during deposition

Adsorption Behavior of Uranium and Mechanism Analysis on Banyan Leaves

International Nuclear Information System (INIS)

Xia Liangshu; Tan Kaixuan; Wang Xiao; Zheng Weina

2010-01-01

The adsorption behavior of uranium on banyan leaves was studied with static experiments. The adsorption process was analyzed in terms of thermodynamics and kinetics, and the adsorption mechanism was analyzed with FTIR and SEM. In the studied condition, the equilibrium adsorption data fit to Freundlich isotherms, with a relation coefficient greater than 0.99. The adsorption of uranium on banyan leaves is an endothermic process. Kinetic analysis shows that the adsorption rate is mainly controlled by surface adsorption. The process of adsorption can be described by an equation of Pseudo 2nd-order model. The calculation data are in good agreement with the experimental data,and the relation coefficient is 0.9998. The thermodynamic data indicate that the synergistic uranium biosorption by banyan leaves is a spontaneous and endothermal adsorption process. The adsorption of uranium on banyan leaves changes the cell's surface form of banyan leaves.In the adsorption process, UO 2 2+ mainly chelates with -OH,C=O,P-O and Si=O etc. on the cell's surface and forms the complexes. The adsorption of uranium should be of surface coordination. (authors)

General framework for adsorption processes on dynamic interfaces

International Nuclear Information System (INIS)

Schmuck, Markus; Kalliadasis, Serafim

2016-01-01

We propose a novel and general variational framework modelling particle adsorption mechanisms on evolving immiscible fluid interfaces. A by-product of our thermodynamic approach is that we systematically obtain analytic adsorption isotherms for given equilibrium interfacial geometries. We validate computationally our mathematical methodology by demonstrating the fundamental properties of decreasing interfacial free energies by increasing interfacial particle densities and of decreasing surface pressure with increasing surface area. (paper)

Competitive Adsorption between Nanoparticles and Surface Active Ions for the Oil-Water Interface.

Science.gov (United States)

Hua, Xiaoqing; Bevan, Michael A; Frechette, Joelle

2018-04-24

Nanoparticles (NPs) can add functionality (e.g., catalytic, optical, rheological) to an oil-water interface. Adsorption of ∼10 nm NPs can be reversible; however, the mechanisms for adsorption and its effects on surface pressure remain poorly understood. Here we demonstrate how the competitive reversible adsorption of NPs and surfactants at fluid interfaces can lead to independent control of both the adsorbed amount and surface pressure. In contrast to prior work, both species investigated (NPs and surfactants) interact reversibly with the interface and without the surface active species binding to NPs. Independent measurements of the adsorption and surface pressure isotherms allow determination of the equation of state (EOS) of the interface under conditions where the NPs and surfactants are both in dynamic equilibrium with the bulk phase. The adsorption and surface pressure measurements are performed with gold NPs of two different sizes (5 and 10 nm), at two pH values, and across a wide concentration range of surfactant (tetrapentylammonium, TPeA + ) and NPs. We show that free surface active ions compete with NPs for the interface and give rise to larger surface pressures upon the adsorption of NPs. Through a competitive adsorption model, we decouple the contributions of NPs wetting at the interface and their surface activity on the measured surface pressure. We also demonstrate reversible control of adsorbed amount via changes in the surfactant concentration or the aqueous phase pH.

Adsorption of ethanol on V{sub 2}O{sub 5} (010) surface for gas-sensing applications: Ab initio investigation

Energy Technology Data Exchange (ETDEWEB)

Qin, Yuxiang, E-mail: qinyuxiang@tju.edu.cn [School of Electronics and Information Engineering, Tianjin University, Tianjin 300072 (China); Key Laboratory for Advanced Ceramics and Machining Technology, Ministry of Education, School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Cui, Mengyang; Ye, Zhenhua [School of Electronics and Information Engineering, Tianjin University, Tianjin 300072 (China)

2016-08-30

Highlights: • Ethanol adsorbed on V{sub 2}O{sub 5} (010) surface was investigated by ab initio calculations. • Ethanol prefers to adsorb on “Hill”-like surface, rather than“Valley”-like region. • Surface O{sub 1(H)} site plays a key role to dominate the ethanol adsorption process. • Sensing mechanism is related with electronic structure and electron redistribution. • Gas sensitivity is reflected by quantitative electron population analysis. - Abstract: The adsorption of ethanol on V{sub 2}O{sub 5} (010) surface was investigated by means of density functional theory (DFT) with a combined generalized gradient approximation (GGA) plus Hubbard U approach to exploit the potential sensing applications. The adsorption configurations were first constructed by considering different orientations of ethanol molecule to V and O sites on the “Hill”- and “Valley”-like regions of corrugated (010) surface. It is found that ethanol molecule can adsorb on whole surface in multiple stable configurations. Nevertheless the molecular adsorption on the “Hill”-like surface is calculated to occur preferentially, and the single coordinated oxygen on “Hill”-like surface (O{sub 1(H)}) acting as the most energetically favorable adsorption site shows the strongest adsorption ability to ethanol molecule. Surface adsorption of ethanol tunes the electronic structure of V{sub 2}O{sub 5} and cause an n-doping effect. As a consequence, the Fermi levels shift toward the conductive bond increasing the charge carrier concentration of electrons in adsorbed V{sub 2}O{sub 5}. The sensitive electronic structure and the multiple stable configurations to ethanol adsorption highlight the high adsorption activity and then the potential of V{sub 2}O{sub 5} (010) surface applied to high sensitive sensor for ethanol vapor detection. Further Mulliken population and Natural bond orbital (NBO) calculations quantify the electron transfer from the adsorbed ethanol to the surface, and

Surface modification of poly (styrene-b-(ethylene-co-butylene)-b-styrene) elastomer and its plasma protein adsorption by QCM-D

Energy Technology Data Exchange (ETDEWEB)

Li, Rui [Northeast Normal University, School of Physics, Changchun 130022 (China); Jin, Jing, E-mail: jjin@ciac.ac.cn [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Sun, Yingchun, E-mail: sunyc149@nenu.edu.cn [Northeast Normal University, School of Physics, Changchun 130022 (China)

2014-05-01

Graphical abstract: - Highlights: • Grafting concentration of PEG was defined by the peak-area ratio of [C–O]/[C]. • Quantitatively investigated the adsorption processes of BSA and fibrinogen using QCM-D. • The inactivated BSA on SEBS surface could induce the subsequent fibrinogen adsorption. • SEBS-g-PEG with graft concentration of 0.207 has excellent protein resistance. - Abstract: Protein adsorption is a dynamic process and plays a major role in determining the hemocompatibility of biomaterials. We have obtained different poly (ethylene glycol) (PEG) graft concentrations of SEBS-g-PEG and the surface chemical compositions are confirmed by X-ray photoelectron spectroscopy (XPS). Graft concentration is defined by peak-area ratio of [C-O]/[C] on modified SEBS surface. With increasing graft concentration, water contact angles of the modified SEBS have significantly decreased. The platelet adhesion and static protein adsorption demonstrate that the hemocompatibility of copolymers films are improved effectively and SEBS-g-PEG-2 with larger graft concentration has more superior anticoagulation than that of SEBS-g-PEG-1. Moreover, we have quantitatively investigated the adsorption process of bovine serum albumin (BSA) and fibrinogen (Fib) on the surfaces of pristine SEBS and modified SEBS using quartz crystal microbalance with dissipation (QCM-D) in real time. The results indicate that the inactivated BSA on the pristine SEBS can continuously induce the subsequent Fib adsorption. The hemocompatibility of SEBS-g-PEG-2 with the graft concentration of 0.207 has excellent anti-protein property and the bio-inert BSA layer on the film can resist the subsequent Fib adsorption.

Selective adsorption of a supramolecular structure on flat and stepped gold surfaces

Science.gov (United States)

Peköz, Rengin; Donadio, Davide

2018-04-01

Halogenated aromatic molecules assemble on surfaces forming both hydrogen and halogen bonds. Even though these systems have been intensively studied on flat metal surfaces, high-index vicinal surfaces remain challenging, as they may induce complex adsorbate structures. The adsorption of 2,6-dibromoanthraquinone (2,6-DBAQ) on flat and stepped gold surfaces is studied by means of van der Waals corrected density functional theory. Equilibrium geometries and corresponding adsorption energies are systematically investigated for various different adsorption configurations. It is shown that bridge sites and step edges are the preferred adsorption sites for single molecules on flat and stepped surfaces, respectively. The role of van der Waals interactions, halogen bonds and hydrogen bonds are explored for a monolayer coverage of 2,6-DBAQ molecules, revealing that molecular flexibility and intermolecular interactions stabilize two-dimensional networks on both flat and stepped surfaces. Our results provide a rationale for experimental observation of molecular carpeting on high-index vicinal surfaces of transition metals.

Adsorption of trace thorium(IV) from aqueous solution by mono-modified β-cyclodextrin polyrotaxane using response surface methodology (RSM)

International Nuclear Information System (INIS)

Huijun Liu; Caixia Qi; Zhiyuan Feng; Lanlin Lei; Shanxia Deng

2017-01-01

The adsorption of thorium(IV) was studied using a novel supramolecular polyrotaxane based on β-cyclodextrin derivatives. The effects of pH, contact time, Th(IV) initial concentration and adsorbents dosage on the adsorption of thorium(IV) by polyrotaxane were optimized using Box-Behnken design of response surface methodology. Analysis of variance and correlation coefficients showed that the predicted model was consistent with the experimental data well. The adsorption best fitted to the Langmuir model indicated that the adsorption process happened on homogeneous surface. The thermodynamic parameters (∆G 0 < 0, ∆H 0 > 0, ∆S 0 > 0) demonstrated that the adsorption of Th(IV) ions onto polyrotaxane was spontaneous and endothermic. (author)

p-Chlorophenol adsorption on activated carbons with basic surface properties

Science.gov (United States)

Lorenc-Grabowska, Ewa; Gryglewicz, Grażyna; Machnikowski, Jacek

2010-05-01

The adsorption of p-chlorophenol (PCP) from aqueous solution on activated carbons (ACs) with basic surface properties has been studied. The ACs were prepared by two methods. The first method was based on the modification of a commercial CWZ AC by high temperature treatment in an atmosphere of ammonia, nitrogen and hydrogen. The second approach comprised the carbonization followed by activation of N-enriched polymers and coal tar pitch using CO 2 and steam as activation agent. The resultant ACs were characterized in terms of porous structure, elemental composition and surface chemistry (pH PZC, acid/base titration, XPS). The adsorption of PCP was carried out from an aqueous solution in static conditions. Equilibrium adsorption isotherm was of L2 type for polymer-based ACs, whereas L3-type isotherm was observed for CWZ ACs series. The Langmuir monolayer adsorption capacity was related to the porous structure and the amount of basic sites. A good correlation was found between the adsorption capacity and the volume of micropores with a width water molecule adsorption on the PCP uptake is discussed.

Adsorption of 1-naphthyl methyl carbamate in water by utilizing a surface molecularly imprinted polymer

Science.gov (United States)

So, Juhyok; Pang, Cholho; Dong, Hongxing; Jang, Paeksan; U, Juhyok; Ri, Kumchol; Yun, Cholyong

2018-05-01

Surface molecularly imprinting polymer (SMIP) was utilized in the removal of a residual pesticide (carbaryl (CBL)) in water and simulated fruit juice. Being the crosslinking agent, ethylene glycol dimethacrylate (EGDMA) was copolymerized with the monomer, methacrylic acid (MAA) and CBL as the template molecules on the surface of the silica gel particles to produce the SMIP adsorbents. The SMIP adsorbents showed good selectivity and good adsorption capacity for CBL in the competitive adsorptions with two structurally related carbamate pesticides. The effect of the pretreatment solvents on the adsorption capacity of the SMIP adsorbent was investigated with the results of the numerical simulations. The adsorption isotherms and the adsorption kinetics were well described by the Freundlich equilibrium model and the pseudo-second-order kinetic model, respectively. Scatchard plot analysis revealed that there were two classes of binding sites populated in the SMIP adsorbents. In addition, the good selective adsorption of CBL by the SMIP adsorbent in a simulated fruit juice containing vitamin C and fructose indicated the great potential of the SMIP adsorbents to remove residual pesticide in food industry and processing industry for agricultural products.

Transient Convection, Diffusion, and Adsorption in Surface-Based Biosensors

DEFF Research Database (Denmark)

Hansen, Rasmus; Bruus, Henrik; Callisen, Thomas H.

2012-01-01

This paper presents a theoretical and computational investigation of convection, diffusion, and adsorption in surface-based biosensors. In particular, we study the transport dynamics in a model geometry of a surface plasmon resonance (SPR) sensor. The work, however, is equally relevant for other...... microfluidic surface-based biosensors, operating under flow conditions. A widely adopted approximate quasi-steady theory to capture convective and diffusive mass transport is reviewed, and an analytical solution is presented. An expression of the Damköhler number is derived in terms of the nondimensional...... concentration to the maximum surface capacity is critical for reliable use of the quasi-steady theory. Finally, our results provide users of surface-based biosensors with a tool for correcting experimentally obtained adsorption rate constants....

Response mechanism for surface acoustic wave gas sensors based on surface-adsorption.

Science.gov (United States)

Liu, Jiansheng; Lu, Yanyan

2014-04-16

A theoretical model is established to describe the response mechanism of surface acoustic wave (SAW) gas sensors based on physical adsorption on the detector surface. Wohljent's method is utilized to describe the relationship of sensor output (frequency shift of SAW oscillator) and the mass loaded on the detector surface. The Brunauer-Emmett-Teller (BET) formula and its improved form are introduced to depict the adsorption behavior of gas on the detector surface. By combining the two methods, we obtain a theoretical model for the response mechanism of SAW gas sensors. By using a commercial SAW gas chromatography (GC) analyzer, an experiment is performed to measure the frequency shifts caused by different concentration of dimethyl methylphosphonate (DMMP). The parameters in the model are given by fitting the experimental results and the theoretical curve agrees well with the experimental data.

The role of mineral surface chemistry in modified dextrin adsorption.

Science.gov (United States)

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka M; Harmer, Sarah L; Beattie, David A

2011-05-15

The adsorption of two modified dextrins (phenyl succinate dextrin--PS Dextrin; styrene oxide dextrin--SO Dextrin) on four different mineral surfaces has been studied using X-ray photoelectron spectroscopy (XPS), in situ atomic force microscopy (AFM) imaging, and captive bubble contact angle measurements. The four surfaces include highly orientated pyrolytic graphite (HOPG), freshly cleaved synthetic sphalerite (ZnS), and two surfaces produced through surface reactions of sphalerite: one oxidized in alkaline solution (pH 9, 1 h immersion); and one subjected to metal ion exchange between copper and zinc (i.e. copper activation: exposed to 1×10(-3) M CuSO(4) solution for 1 h). XPS measurements indicate that the different sphalerite surfaces contain varying amounts of sulfur, zinc, oxygen, and copper, producing substrates for polymer adsorption with a range of possible binding sites. AFM imaging has shown that the two polymers adsorb to a similar extent on HOPG, and that the two polymers display very different propensities for adsorption on the three sphalerite surface types, with freshly cleaved sphalerite encouraging the least adsorption, and copper activated and oxidized sphalerite encouraging significantly more adsorption. Contact angle measurements of the four surfaces indicate that synthetic sphalerite has a low contact angle upon fracture, and that oxidation on the timescale of one hour substantially alters the hydrophobicity. HOPG and copper-activated sphalerite were the most hydrophobic, as expected due to the carbon and di/poly-sulfide rich surfaces of the two samples, respectively. SO Dextrin is seen to have a significant impact on the wettability of HOPG and the surface reacted sphalerite samples, highlighting the difficulty in selectively separating sphalerite from carbonaceous unwanted minerals in flotation. PS Dextrin has the least effect on the hydrophobicity of the reacted sphalerite surfaces, whilst still significantly increasing the wettability of

Surface charge effects in protein adsorption on nanodiamonds

Science.gov (United States)

Aramesh, M.; Shimoni, O.; Ostrikov, K.; Prawer, S.; Cervenka, J.

2015-03-01

Understanding the interaction of proteins with charged diamond nanoparticles is of fundamental importance for diverse biomedical applications. Here we present a thorough study of protein binding, adsorption kinetics and structure on strongly positively (hydrogen-terminated) and negatively (oxygen-terminated) charged nanodiamond particles using a quartz crystal microbalance by dissipation and infrared spectroscopy. By using two model proteins (bovine serum albumin and lysozyme) of different properties (charge, molecular weight and rigidity), the main driving mechanism responsible for the protein binding to the charged nanoparticles was identified. Electrostatic interactions were found to dominate the protein adsorption dynamics, attachment and conformation. We developed a simple electrostatic model that can qualitatively explain the observed adsorption behaviour based on charge-induced pH modifications near the charged nanoparticle surfaces. Under neutral conditions, the local pH around the positively and negatively charged nanodiamonds becomes very high (11-12) and low (1-3) respectively, which has a profound impact on the protein charge, hydration and affinity to the nanodiamonds. Small proteins (lysozyme) were found to form multilayers with significant conformational changes to screen the surface charge, while larger proteins (albumin) formed monolayers with minor conformational changes. The findings of this study provide a step forward toward understanding and eventually predicting nanoparticle interactions with biofluids.Understanding the interaction of proteins with charged diamond nanoparticles is of fundamental importance for diverse biomedical applications. Here we present a thorough study of protein binding, adsorption kinetics and structure on strongly positively (hydrogen-terminated) and negatively (oxygen-terminated) charged nanodiamond particles using a quartz crystal microbalance by dissipation and infrared spectroscopy. By using two model proteins

Surface stoichiometry of zinc sulfide and its effect on the adsorption behaviors of xanthate

Directory of Open Access Journals (Sweden)

Wang Meng

2011-11-01

Full Text Available Abstract In this paper, the surface stoichiometry, acid-base properties as well as the adsorption of xanthate at ZnS surfaces were studied by means of potentiometric titration, adsorption and solution speciation modeling. The surface proton binding site was determined by using Gran plot to evaluate the potentiometric titration data. Testing results implied that for stoichiometric surfaces of zinc sulfide, the proton and hydroxide determine the surface charge. For the nonstoichiometric surfaces, the surface charge is controlled by proton, hydroxide, zinc and sulfide ions depending on specific conditions. The xanthate adsorption decreases with increasing solution pH, which indicates an ion exchange reaction at the surfaces. Based on experimental results, the surface protonation, deprotonation, stoichiometry and xanthate adsorption mechanism were discussed.

Adsorption energies of poly(ethylene oxide)-based surfactants and nanoparticles on an air-water surface.

Science.gov (United States)

Zell, Zachary A; Isa, Lucio; Ilg, Patrick; Leal, L Gary; Squires, Todd M

2014-01-14

The self-assembly of polymer-based surfactants and nanoparticles on fluid-fluid interfaces is central to many applications, including dispersion stabilization, creation of novel 2D materials, and surface patterning. Very often these processes involve compressing interfacial monolayers of particles or polymers to obtain a desired material microstructure. At high surface pressures, however, even highly interfacially active objects can desorb from the interface. Methods of directly measuring the energy which keeps the polymer or particles bound to the interface (adsorption/desorption energies) are therefore of high interest for these processes. Moreover, though a geometric description linking adsorption energy and wetting properties through the definition of a contact angle can be established for rigid nano- or microparticles, such a description breaks down for deformable or aggregating objects. Here, we demonstrate a technique to quantify desorption energies directly, by comparing surface pressure-density compression measurements using a Wilhelmy plate and a custom-microfabricated deflection tensiometer. We focus on poly(ethylene oxide)-based polymers and nanoparticles. For PEO-based homo- and copolymers, the adsorption energy of PEO chains scales linearly with molecular weight and can be tuned by changing the subphase composition. Moreover, the desorption surface pressure of PEO-stabilized nanoparticles corresponds to the saturation surface pressure for spontaneously adsorbed monolayers, yielding trapping energies of ∼10(3) k(B)T.

Adsorption Mechanisms of NH3 on Chlorinated Si(100)-2 x 1 Surface

International Nuclear Information System (INIS)

Lee, Hee Soon; Choi, Cheol Ho

2012-01-01

The potential energy surfaces of ammonia molecule adsorptions on the symmetrically chlorinated Si(100)- 2 x 1 surface were explored with SIMOMM:MP2/6-31G(d). It was found that the initial nucleophilic attack by ammonia nitrogen to the surface Si forms a S N 2 type transition state, which eventually leads to an HCl molecular desorption. The second ammonia molecule adsorption requires much less reaction barrier, which can be rationalized by the surface cooperative effect. In general, it was shown that the surface Si-Cl bonds can be easily subjected to the substitution reactions by ammonia molecules yielding symmetric surface Si-NH 2 bonds, which can be a good initial template for subsequent surface chemical modifications. The ammonia adsorptions are in general more facile than the corresponding water adsorption, since ammonia is better nucleophile

Insights on finite size effects in ab initio study of CO adsorption and dissociation on Fe 110 surface

International Nuclear Information System (INIS)

Chakrabarty, Aurab; Bouhali, Othmane; Mousseau, Normand; Becquart, Charlotte S.; El-Mellouhi, Fedwa

2016-01-01

Adsorption and dissociation of hydrocarbons on metallic surfaces represent crucial steps on the path to carburization, eventually leading to dusting corrosion. While adsorption of CO molecules on Fe surface is a barrier-less exothermic process, this is not the case for the dissociation of CO into C and O adatoms and the diffusion of C beneath the surface that are found to be associated with large energy barriers. In practice, these barriers can be affected by numerous factors that combine to favour the CO-Fe reaction such as the abundance of CO and other hydrocarbons as well as the presence of structural defects. From a numerical point of view, studying these factors is challenging and a step-by-step approach is necessary to assess, in particular, the influence of the finite box size on the reaction parameters for adsorption and dissociation of CO on metal surfaces. Here, we use density functional theory (DFT) total energy calculations with the climbing-image nudged elastic band method to estimate the adsorption energies and dissociation barriers for different CO coverages with surface supercells of different sizes. We further compute the effect of periodic boundary condition for DFT calculations and find that the contribution from van der Waals interaction in the computation of adsorption parameters is important as they contribute to correcting the finite-size error in small systems. The dissociation process involves carbon insertion into the Fe surface causing a lattice deformation that requires a larger surface system for unrestricted relaxation. We show that, in the larger surface systems associated with dilute CO-coverages, C-insertion is energetically more favourable, leading to a significant decrease in the dissociation barrier. This observation suggests that a large surface system with dilute coverage is necessary for all similar metal-hydrocarbon reactions in order to study their fundamental electronic mechanisms, as an isolated phenomenon, free from

Insights on finite size effects in ab initio study of CO adsorption and dissociation on Fe 110 surface

Energy Technology Data Exchange (ETDEWEB)

Chakrabarty, Aurab, E-mail: aurab.chakrabarty@qatar.tamu.edu; Bouhali, Othmane [Texas A& M University at Qatar, P.O. Box 23874, Doha (Qatar); Mousseau, Normand [Département de Physique and RQMP, Université de Montréal, Case Postale 6128, Succursale Centre-ville, Montréal, Québec H3C 3J7 (Canada); Becquart, Charlotte S. [UMET, UMR CNRS 8207, ENSCL, Université Lille I, 59655 Villeneuve d' Ascq Cédex (France); El-Mellouhi, Fedwa [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, P.O. Box 5825, Doha (Qatar)

2016-08-07

Adsorption and dissociation of hydrocarbons on metallic surfaces represent crucial steps on the path to carburization, eventually leading to dusting corrosion. While adsorption of CO molecules on Fe surface is a barrier-less exothermic process, this is not the case for the dissociation of CO into C and O adatoms and the diffusion of C beneath the surface that are found to be associated with large energy barriers. In practice, these barriers can be affected by numerous factors that combine to favour the CO-Fe reaction such as the abundance of CO and other hydrocarbons as well as the presence of structural defects. From a numerical point of view, studying these factors is challenging and a step-by-step approach is necessary to assess, in particular, the influence of the finite box size on the reaction parameters for adsorption and dissociation of CO on metal surfaces. Here, we use density functional theory (DFT) total energy calculations with the climbing-image nudged elastic band method to estimate the adsorption energies and dissociation barriers for different CO coverages with surface supercells of different sizes. We further compute the effect of periodic boundary condition for DFT calculations and find that the contribution from van der Waals interaction in the computation of adsorption parameters is important as they contribute to correcting the finite-size error in small systems. The dissociation process involves carbon insertion into the Fe surface causing a lattice deformation that requires a larger surface system for unrestricted relaxation. We show that, in the larger surface systems associated with dilute CO-coverages, C-insertion is energetically more favourable, leading to a significant decrease in the dissociation barrier. This observation suggests that a large surface system with dilute coverage is necessary for all similar metal-hydrocarbon reactions in order to study their fundamental electronic mechanisms, as an isolated phenomenon, free from

Insights into the superhydrophobicity of metallic surfaces prepared by electrodeposition involving spontaneous adsorption of airborne hydrocarbons

International Nuclear Information System (INIS)

Liu, Peng; Cao, Ling; Zhao, Wei; Xia, Yue; Huang, Wei; Li, Zelin

2015-01-01

Graphical abstract: - Highlights: • Several superhydrophobic metallic surfaces were fabricated by fast electrodeposition. • Both micro/nanostructures and adsorption of airborne hydrocarbons make contributions. • XPS analyses confirm presence of airborne hydrocarbons on these metallic surfaces. • The adsorption of airborne hydrocarbons on the clean metal Au surface was very quick. • UV-O 3 treatment oxidized the hydrocarbons to hydrophilic oxygen-containing organics. - Abstract: Electrochemical fabrication of micro/nanostructured metallic surfaces with superhydrophobicity has recently aroused great attention. However, the origin still remains unclear why smooth hydrophilic metal surfaces become superhydrophobic by making micro/nanostructures without additional surface modifications. In this work, several superhydrophobic micro/nanostructured metal surfaces were prepared by a facile one-step electrodeposition process, including non-noble and noble metals such as copper, nickel, cadmium, zinc, gold, and palladium with (e.g. Cu) or without (e.g. Au) surface oxide films. We demonstrated by SEM and XPS that both hierarchical micro/nanostructures and spontaneous adsorption of airborne hydrocarbons endowed these surfaces with excellent superhydrophobicity. We revealed by XPS that the adsorption of airborne hydrocarbons at the Ar + -etched clean Au surface was rather quick, such that organic contamination can hardly be prevented in practical operation of surface wetting investigation. We also confirmed by XPS that ultraviolet-O 3 treatment of the superhydrophobic metal surfaces did not remove the adsorbed hydrocarbons completely, but mainly oxidized them into hydrophilic oxygen-containing organic substances. We hope our findings here shed new light on deeper understanding of superhydrophobicity for micro/nanostructured metal surfaces with and without surface oxide films

Mercury adsorption to gold nanoparticle and thin film surfaces

Science.gov (United States)

Morris, Todd Ashley

Mercury adsorption to gold nanoparticle and thin film surfaces was monitored by spectroscopic techniques. Adsorption of elemental mercury to colloidal gold nanoparticles causes a color change from wine-red to orange that was quantified by UV-Vis absorption spectroscopy. The wavelength of the surface plasmon mode of 5, 12, and 31 nm gold particles blue-shifts 17, 14, and 7.5 nm, respectively, after a saturation exposure of mercury vapor. Colorimetric detection of inorganic mercury was demonstrated by employing 2.5 nm gold nanoparticles. The addition of low microgram quantities of Hg 2+ to these nanoparticles induces a color change from yellow to peach or blue. It is postulated that Hg2+ is reduced to elemental mercury by SCN- before and/or during adsorption to the nanoparticle surface. It has been demonstrated that surface plasmon resonance spectroscopy (SPRS) is sensitive to mercury adsorption to gold and silver surfaces. By monitoring the maximum change in reflectivity as a function of amount of mercury adsorbed to the surface, 50 nm Ag films were shown to be 2--3 times more sensitive than 50 nm Au films and bimetallic 15 nm Au/35 nm Ag films. In addition, a surface coverage of ˜40 ng Hg/cm2 on the gold surface results in a 0.03° decrease in the SPR angle of minimum reflectivity. SPRS was employed to follow Hg exposure to self-assembled monolayers (SAMs) on Au. The data indicate that the hydrophilic or hydrophobic character of the SAM has a significant effect on the efficiency of Hg penetration. Water adsorbed to carboxylic acid end group of the hydrophilic SAMs is believed to slow the penetration of Hg compared to methyl terminated SAMs. Finally, two protocols were followed to remove mercury from gold films: immersion in concentrated nitric acid and thermal annealing up to 200°C. The latter protocol is preferred because it removes all of the adsorbed mercury from the gold surface and does not affect the morphology of the gold surface.

Load-dependent surface diffusion model for analyzing the kinetics of protein adsorption onto mesoporous materials.

Science.gov (United States)

Marbán, Gregorio; Ramírez-Montoya, Luis A; García, Héctor; Menéndez, J Ángel; Arenillas, Ana; Montes-Morán, Miguel A

2018-02-01

The adsorption of cytochrome c in water onto organic and carbon xerogels with narrow pore size distributions has been studied by carrying out transient and equilibrium batch adsorption experiments. It was found that equilibrium adsorption exhibits a quasi-Langmuirian behavior (a g coefficient in the Redlich-Peterson isotherms of over 0.95) involving the formation of a monolayer of cyt c with a depth of ∼4nm on the surface of all xerogels for a packing density of the protein inside the pores of 0.29gcm -3 . A load-dependent surface diffusion model (LDSDM) has been developed and numerically solved to fit the experimental kinetic adsorption curves. The results of the LDSDM show better fittings than the standard homogeneous surface diffusion model. The value of the external mass transfer coefficient obtained by numerical optimization confirms that the process is controlled by the intraparticle surface diffusion of cyt c. The surface diffusion coefficients decrease with increasing protein load down to zero for the maximum possible load. The decrease is steeper in the case of the xerogels with the smallest average pore diameter (∼15nm), the limit at which the zero-load diffusion coefficient of cyt c also begins to be negatively affected by interactions with the opposite wall of the pore. Copyright © 2017 Elsevier Inc. All rights reserved.

First-principles calculation of adsorption of shale gas on CaCO3 (100) surfaces.

Science.gov (United States)

Luo, Qiang; Pan, Yikun; Guo, Ping; Wang, Zhouhua; Wei, Na; Sun, Pengfei; Liu, Yuxiao

2017-06-16

To demonstrate the adsorption strength of shale gas to calcium carbonate in shale matrix, the adsorption of shale gas on CaCO3 (100) surfaces was studied using the first-principles method, which is based on the density functional theory (DFT). The structures and electronic properties of CH4, C2H6, CO2 and N2 molecules were calculated by the generalized gradient approximation (GGA), for a coverage of 1 monolayer (ML). Under the same conditions, the density of states (DOS) of CaCO3 (100) surfaces before and after the adsorption of shale gas molecules at high-symmetry adsorption sites were compared. The results showed that the adsorption energies of CH4, C2H6, CO2 and N2 on CaCO3 (100) surfaces were between 0.2683 eV and -0.7388 eV. When a CH4 molecule was adsorbed at a hollow site and its 2 hydrogen atoms were parallel to the long diagonal (H3) on the CaCO3 (100) surface, it had the most stable adsorption, and the adsorption energy was only -0.4160 eV. The change of adsorption energy of CH4 was no more than 0.0535 eV. Compared with the DOS distribution of CH4 before adsorption, it shifted to the left overall after adsorption. At the same time, the partial density of states (PDOS) curves of CaCO3 (100) surfaces before and after adsorption basically overlapped. This work showed that the adsorption effect of shale gas on calcium carbonate is very weak, and the adsorption is physisorption at the molecular level.

Surface complexation modeling calculation of Pb(II) adsorption onto the calcined diatomite

Science.gov (United States)

Ma, Shu-Cui; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

2015-12-01

Removal of noxious heavy metal ions (e.g. Pb(II)) by surface adsorption of minerals (e.g. diatomite) is an important means in the environmental aqueous pollution control. Thus, it is very essential to understand the surface adsorptive behavior and mechanism. In this work, the Pb(II) apparent surface complexation reaction equilibrium constants on the calcined diatomite and distributions of Pb(II) surface species were investigated through modeling calculations of Pb(II) based on diffuse double layer model (DLM) with three amphoteric sites. Batch experiments were used to study the adsorption of Pb(II) onto the calcined diatomite as a function of pH (3.0-7.0) and different ionic strengths (0.05 and 0.1 mol L-1 NaCl) under ambient atmosphere. Adsorption of Pb(II) can be well described by Freundlich isotherm models. The apparent surface complexation equilibrium constants (log K) were obtained by fitting the batch experimental data using the PEST 13.0 together with PHREEQC 3.1.2 codes and there is good agreement between measured and predicted data. Distribution of Pb(II) surface species on the diatomite calculated by PHREEQC 3.1.2 program indicates that the impurity cations (e.g. Al3+, Fe3+, etc.) in the diatomite play a leading role in the Pb(II) adsorption and dominant formation of complexes and additional electrostatic interaction are the main adsorption mechanism of Pb(II) on the diatomite under weak acidic conditions.

Effects of chemical functional groups on elemental mercury adsorption on carbonaceous surfaces

Energy Technology Data Exchange (ETDEWEB)

Liu Jing, E-mail: liujing27@mail.hust.edu.cn [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074 (China); Cheney, Marcos A. [Department of Natural Sciences, University of Maryland Eastern Shore, Princess Anne, MD 21853 (United States); Wu Fan; Li Meng [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074 (China)

2011-02-15

A systematic theoretical study using density functional theory is performed to provide molecular-level understanding of the effects of chemical functional groups on mercury adsorption on carbonaceous surfaces. The zigzag and armchair edges were used in modeling the carbonaceous surfaces to simulate different adsorption sites. The edge atoms on the upper side of the models are unsaturated to simulate active sites. All calculations (optimizations, energies, and frequencies) were made at B3PW91 density functional theory level, using RCEP60VDZ basis set for mercury and 6-31G(d) pople basis set for other atoms. The results indicate that the embedding of halogen atom can increase the activity of its neighboring site which in turn increases the adsorption capacity of the carbonaceous surface for Hg{sup 0}. The adsorption belongs to chemisorptions, which is in good agreement with the experimental results. For the effects of oxygen functional groups, lactone, carbonyl and semiquinone favor Hg{sup 0} adsorption because they increase the neighboring site's activity for mercury adsorption. On the contrary, phenol and carboxyl functional groups show a physisorption of Hg{sup 0}, and reduce Hg capture. This result can explain the seemingly conflicting experimental results reported in the literature concerning the influence of oxygen functional groups on mercury adsorption on carbonaceous surface.

Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics

OpenAIRE

Kusaba, Akira; Li, Guanchen; von Spakovsky, Michael R.; Kangawa, Yoshihiro; Kakimoto, Koichi

2017-01-01

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and Nad-H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict...

MONTE CARLO SIMULATIONS OF THE ADSORPTION OF DIMERS ON STRUCTURED HETEROGENEOUS SURFACES

Directory of Open Access Journals (Sweden)

Abreu C.R.A.

2001-01-01

Full Text Available The effect of surface topography upon the adsorption of dimer molecules is analyzed by means of grand canonical ensemble Monte Carlo simulations. Heterogeneous surfaces were assumed to consist of a square lattice containing active sites with two different energies. These were distributed in three different configurations: a random distribution of isolated sites; a random distribution of grains with four high-energy sites; and a random distribution of grains with nine high-energy sites. For the random distribution of isolated sites, the results are in good agreement with the molecular simulations performed by Nitta et al. (1997. In general, the comparison with theoretical models shows that the Nitta et al. (1984 isotherm presents good predictions of dimer adsorption both on homogeneous and heterogeneous surfaces with sites having small differences in characteristic energies. The molecular simulation results also show that the energy topology of the solid surfaces plays an important role in the adsorption of dimers on solids with large differences in site energies. For these cases, the Nitta et al. model does not describe well the data on dimer adsorption on random heterogeneous surfaces (grains with one acid site, but does describe reasonably well the adsorption of dimers on more patchwise heterogeneous surfaces (grains with nine acid sites.

A new analytical potential energy surface for the adsorption systemk CO/Cu(100)

NARCIS (Netherlands)

Marquardt, R.; Cuvelier, F.; Olsen, R.A.; Baerends, E.J.; Tremblay, J.C.; Saalfrank, P.

2010-01-01

Electronic structure data and analytical representations of the potential energy surface for the adsorption of carbon monoxide on a crystalline copper Cu(100) substrate are reviewed. It is found that a previously published and widely used analytical hypersurface for this process [J. C. Tully, M.

Adsorption energy of iron-phthalocyanine on crystal surfaces

International Nuclear Information System (INIS)

Struzzi, C.; Scardamaglia, M.; Angelucci, M; Massimi, L.; Mariani, C.; Betti, G.

2013-01-01

The adsorption energy of iron-phthalocyanine (FePc) deposited on different crystal surfaces is studied by thermal desorption spectroscopy. A thin film of molecules has been absorbed on highly oriented pyrolytic graphite (HOPG), on graphene epitaxially grown on Ir(111), and on Au(110). Activation energies for the desorption of a molecular thin film and for the FePc single layer are determined at the three surfaces. The desorption temperature measured for the thin films is only slightly dependent on the substrate, since it is mostly dominated by molecule-molecule interactions. A definitely different desorption temperature is found at the single-layer coverage: we find an increasing desorption temperature going from HOPG, to graphene/Ir, to the Au(110) surface. The different adsorption energies of the first FePc layer in contact with the substrate surface are discussed taking into account the interaction and the growth morphology.

Effects of textural and surface characteristics of microporous activated carbons on the methane adsorption capacity at high pressures

International Nuclear Information System (INIS)

Bastos-Neto, M.; Canabrava, D.V.; Torres, A.E.B.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.; Azevedo, D.C.S.; Cavalcante, C.L.

2007-01-01

The objective of this study is to relate textural and surface characteristics of selected microporous activated carbons to their methane storage capacity. In this work, a magnetic suspension balance (Rubotherm, Germany) was used to measure methane adsorption isotherms of several activated carbon samples. Textural characteristics were assessed by nitrogen adsorption on a regular surface area analyzer (Autosorb-MP, by Quantachrome, USA). N 2 adsorption was analysed by conventional models (BET, DR, HK) and by Monte Carlo molecular simulations. Elemental and surface analyses were performed by X-ray photoelectronic spectroscopy (XPS) for the selected samples. A comparative analysis was then carried out with the purpose of defining some correlation among the variables under study. For the system under study, pore size distribution and micropore volume seem to be a determining factor as long as the solid surface is perfectly hydrophobic. It was concluded that the textural parameters per se do not unequivocally determine natural gas storage capacities. Surface chemistry and methane adsorption equilibria must be taken into account in the decision-making process of choosing an adsorbent for gas storage

Surface modification of pitch-based spherical activated carbon by CVD of NH{sub 3} to improve its adsorption to uric acid

Energy Technology Data Exchange (ETDEWEB)

Liu Chaojun [State Key Laboratory of Chemical Engineering, East China University of Science and Technology (ECUST), Shanghai 200237 (China); Liang Xiaoyi [State Key Laboratory of Chemical Engineering, East China University of Science and Technology (ECUST), Shanghai 200237 (China)], E-mail: xyliang@ecust.edu.cn; Liu Xiaojun; Wang Qin; Zhan Liang; Zhang Rui; Qiao Wenming; Ling Licheng [State Key Laboratory of Chemical Engineering, East China University of Science and Technology (ECUST), Shanghai 200237 (China)

2008-08-30

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH{sub 3} (NH{sub 3}-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N{sub 2} adsorption, pH{sub PZC} (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH{sub 3}-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH{sub 3}-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH{sub PZC}, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.

Ions-induced nanostructuration: effect of specific ionic adsorption on hydrophobic polymer surfaces.

Science.gov (United States)

Siretanu, Igor; Chapel, Jean-Paul; Bastos-González, Delfi; Drummond, Carlos

2013-06-06

The effect of surface charges on the ionic distribution in close proximity to an interface has been extensively studied. On the contrary, the influence of ions (from dissolved salts) on deformable interfaces has been barely investigated. Ions can adsorb from aqueous solutions on hydrophobic surfaces, generating forces that can induce long-lasting deformation of glassy polymer films, a process called ion-induced polymer nanostructuration, IPN. We have found that this process is ion-specific; larger surface modifications are observed in the presence of water ions and hydrophobic and amphiphilic ions. Surface structuration is also observed in the presence of certain salts of lithium. We have used streaming potential and atomic force microscopy to study the effect of dissolved ions on the surface properties of polystyrene films, finding a good correlation between ionic adsorption and IPN. Our results also suggest that the presence of strongly hydrated lithium promotes the interaction of anions with polystyrene surfaces and more generally with hydrophobic polymer surfaces, triggering then the IPN process.

On modeling biomolecular–surface nonbonded interactions: application to nucleobase adsorption on single-wall carbon nanotube surfaces

International Nuclear Information System (INIS)

Akdim, B; Pachter, R; Day, P N; Kim, S S; Naik, R R

2012-01-01

In this work we explored the selectivity of single nucleobases towards adsorption on chiral single-wall carbon nanotubes (SWCNTs) by density functional theory calculations. Specifically, the adsorption of molecular models of guanine (G), adenine (A), thymine (T), and cytosine (C), as well as of AT and GC Watson–Crick (WC) base pairs on chiral SWCNT C(6, 5), C(9, 1) and C(8, 3) model structures, was analyzed in detail. The importance of correcting the exchange–correlation functional for London dispersion was clearly demonstrated, yet limitations in modeling such interactions by considering the SWCNT as a molecular model may mask subtle effects in a molecular–macroscopic material system. The trend in the calculated adsorption energies of the nucleobases on same diameter C(6, 5) and C(9, 1) SWCNT surfaces, i.e. G > A > T > C, was consistent with related computations and experimental work on graphitic surfaces, however contradicting experimental data on the adsorption of single-strand short homo-oligonucleotides on SWCNTs that demonstrated a trend of G > C > A > T (Albertorio et al 2009 Nanotechnology 20 395101). A possible role of electrostatic interactions in this case was partially captured by applying the effective fragment potential method, emphasizing that the interplay of the various contributions in modeling nonbonded interactions is complicated by theoretical limitations. Finally, because the calculated adsorption energies for Watson–Crick base pairs have shown little effect upon adsorption of the base pair farther from the surface, the results on SWCNT sorting by salmon genomic DNA could be indicative of partial unfolding of the double helix upon adsorption on the SWCNT surface. (paper)

Role of the oxidation state of cerium on the ceria surfaces for silicate adsorption

Energy Technology Data Exchange (ETDEWEB)

Seo, Jihoon [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Moon, Jinok [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Clean/CMP Technology Team, Memory, Samsung Electronics, Hwaseong (Korea, Republic of); Kim, Joo Hyun; Lee, Kangchun [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Hwang, Junha [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Materials R& D Center, K.C.Tech, Anseong (Korea, Republic of); Yoon, Heesung [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Yi, Dong Kee, E-mail: vitalis@mju.ac.kr [Department of Chemistry, Myongji University, Yongin (Korea, Republic of); Paik, Ungyu, E-mail: upaik@hanyang.ac.kr [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of)

2016-12-15

Highlights: • We investigated the role of Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for the silicate adsorption. • As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. • The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. - Abstract: In this study, we have investigated the role of the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for silicate adsorption. In aqueous medium, the Ce{sup 3+} sites lead to the formation of −OH groups at the CeO{sub 2} surface through H{sub 2}O dissociation. Silicate ions can adsorb onto the CeO{sub 2} surface through interaction with the −OH groups (−Ce−OH− + −Si−O{sup −} ↔ −Ce−O−Si− + OH{sup −}). As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. To evaluate the adsorption behaviors of silicate ions onto CeO{sub 2} NPs, we carried out an adsorption isothermal analysis, and the adsorption isotherm data followed the Freundlich model. The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. As a result, we have demonstrated that the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surface can have a significant influence on the silicate adsorption.

First-principles studies on the adsorption of molecular oxygen on Ba(110) surface

International Nuclear Information System (INIS)

Li, S.F.; Xue Xinlian; Li Pinglin; Li Xinjian; Jia Yu

2006-01-01

The adsorption of O 2 on Ba(110) surface is studied with first-principles calculations based on density functional theory. Our calculations predict that O 2 may prefer to dissociative adsorption on Ba(110) surface without obvious barrier. Also our results do not support the model of charge transfer from the surface to the molecule as a bond breaking mechanism. Instead, the increasing hybridization between O 2 orbitals and the d states of Ba(110) surface may play an important role in the dissociation adsorption

A novel film-pore-surface diffusion model to explain the enhanced enzyme adsorption of corn stover pretreated by ultrafine grinding.

Science.gov (United States)

Zhang, Haiyan; Chen, Longjian; Lu, Minsheng; Li, Junbao; Han, Lujia

2016-01-01

Ultrafine grinding is an environmentally friendly pretreatment that can alter the degree of polymerization, the porosity and the specific surface area of lignocellulosic biomass and can, thus, enhance cellulose hydrolysis. Enzyme adsorption onto the substrate is a prerequisite for the enzymatic hydrolysis process. Therefore, it is necessary to investigate the enzyme adsorption properties of corn stover pretreated by ultrafine grinding. The ultrafine grinding pretreatment was executed on corn stover. The results showed that ultrafine grinding pretreatment can significantly decrease particle size [from 218.50 μm of sieve-based grinding corn stover (SGCS) to 17.45 μm of ultrafine grinding corn stover (UGCS)] and increase the specific surface area (SSA), pore volume (PV) and surface composition (SSA: from 1.71 m(2)/g of SGCS to 2.63 m(2)/g of UGCS, PV: from 0.009 cm(3)/g of SGCS to 0.024 m(3)/g of UGCS, cellulose surface area: from 168.69 m(2)/g of SGCS to 290.76 m(2)/g of UGCS, lignin surface area: from 91.46 m(2)/g of SGCS to 106.70 m(2)/g of UGCS). The structure and surface composition changes induced by ultrafine grinding increase the enzyme adsorption capacity from 2.83 mg/g substrate of SGCS to 5.61 mg/g substrate of UGCS. A film-pore-surface diffusion model was developed to simultaneously predict the enzyme adsorption kinetics of both the SGCS and UGCS. Satisfactory predictions could be made with the model based on high R (2) and low RMSE values (R (2) = 0.95 and RMSE = 0.16 mg/g for the UGCS, R (2) = 0.93 and RMSE = 0.09 mg/g for the SGCS). The model was further employed to analyze the rate-limiting steps in the enzyme adsorption process. Although both the external-film and internal-pore mass transfer are important for enzyme adsorption on the SGCS and UGCS, the UGCS has a lower internal-pore resistance compared to the SGCS. Ultrafine grinding pretreatment can enhance the enzyme adsorption onto corn stover by altering structure and

A computational investigation of adsorption of organics on mineral surfaces: Implications for organics delivery in the early solar system

Science.gov (United States)

Asaduzzaman, A. M.; Zega, T. J.; Laref, Slimane; Runge, K.; Deymier, P. A.; Muralidharan, Krishna

2014-12-01

The adsorption of simple organic compounds onto minerals that are known to occur in the early solar nebula such as olivine, spinel and water-ice, is examined using first-principles density functional theory. The calculations show that electron-rich organics and organics containing cyanide, amine and carboxylic functional groups can strongly bind to low-index surfaces of olivine and spinel. Based on the surface coverage as obtained from these calculations, it can be inferred that an estimated amount of 1013 kg of organics could have been delivered to early Earth via direct adsorption mechanisms, thereby providing an endogenous source of planetary organics. In addition, adsorption of organic compounds on magnesite, a carbonate phase believed to have formed via aqueous processes on asteroidal bodies, is also studied. The adsorption behavior of the organics is observed to be similar in both cases, i.e., for minerals that formed during the earliest stages of nebular evolution through condensation (spinel and olivine) or other processes and for those that formed via hydration processes on asteroidal bodies (magnesite). These results suggest that direct incorporation via adsorption is an important delivery mechanism of organics to both asteroidal bodies and terrestrial planets.

Study of Cs adsorption on Ga(Mg)0.75Al0.25N (0 0 0 1) surface: A first principle calculation

International Nuclear Information System (INIS)

Yang, Mingzhu; Chang, Benkang; Hao, Guanghui; Guo, Jing; Wang, Honggang; Wang, Meishan

2013-01-01

In order to study the activation process of Ga 1−x Al x N photocathodes theoretically, models of Cs adsorption on Ga(Mg) 0.75 Al 0.25 N (0 0 0 1) surface are built, then the atomic structure, electronic structure, adsorption energy, work function, dipole moment and optical properties of the models are calculated. All calculations are carried out using Cambridge Serial Total Energy Package (CASTEP) based on first principle. Results show that Cs adsorption on Mg doping Ga 1−x Al x N (0 0 0 1) surface can reduce work function of the surface, and the favorite adsorption site is on the top of p-type impurity. Cs adsorption on p-type Ga 1−x Al x N (0 0 0 1) surface can produce the structure of p-type bulk with n-type surface, which is helpful to surface band bend downward and decrease electron affinity seriously. The absorption coefficient of Cs adsorption system is less than that of the clean surface. Theoretical study of Cs adsorption on Ga 1−x Al x N (0 0 0 1) surface can help to improve activation technology of Ga 1−x Al x N photocathodes.

Oxygen adsorption on the Al9Co2(001) surface: first-principles and STM study

International Nuclear Information System (INIS)

Villaseca, S Alarcón; Loli, L N Serkovic; Ledieu, J; Fournée, V; Dubois, J-M; Gaudry, É; Gille, P

2013-01-01

Atomic oxygen adsorption on a pure aluminum terminated Al 9 Co 2 (001) surface is studied by first-principle calculations coupled with STM measurements. Relative adsorption energies of oxygen atoms have been calculated on different surface sites along with the associated STM images. The local electronic structure of the most favourable adsorption site is described. The preferential adsorption site is identified as a ‘bridge’ type site between the cluster entities exposed at the (001) surface termination. The Al–O bonding between the adsorbate and the substrate presents a covalent character, with s–p hybridization occurring between the states of the adsorbed oxygen atom and the aluminum atoms of the surface. The simulated STM image of the preferential adsorption site is in agreement with experimental observations. This work shows that oxygen adsorption generates important atomic relaxations of the topmost surface layer and that sub-surface cobalt atoms strongly influence the values of the adsorption energies. The calculated Al–O distances are in agreement with those reported in Al 2 O and Al 2 O 3 oxides and for oxygen adsorption on Al(111). (paper)

Adsorption of water, sulfates and chloride on arsenopyrite surface

Science.gov (United States)

Silva, Juliana C. M.; dos Santos, Egon C.; de Oliveira, Aline; Heine, Thomas; De Abreu, Heitor A.; Duarte, Hélio A.

2018-03-01

Arsenopyrite is one of the sulfide minerals responsible for acid rock drainage (ARD) and is one of the most hazardous in regions affected by mining activities. This phenomenon involves complex reaction mechanism. Although it is intensely investigated, there is a lack of consensus concerning the reaction mechanisms and more information is still necessary. In this work, the adsorption of water, hydrochloric acid, and sulfuric acid on arsenopyrite (001) surface was investigated by means of Density Functional calculations and the results compared to other sulfides aiming to understand the mineral/water interface. The interaction of the chemical species with the (001) FeAsS surface is the first step to understand the intricate oxidation mechanism of arsenopyrite. Molecular water adsorption on (001) FeAsS is more favored than the adsorption of sulfate favoring the dissolution of sulfates and enhancing its oxidation. The estimated adsorption energies of water, sulfates and chloride on other sulfide minerals are compared with the estimated values for arsenopyrite and the chemical reactivity differences discussed in detail.

Adsorption and surface reaction of bis-diethylaminosilane as a Si precursor on an OH-terminated Si (0 0 1) surface

International Nuclear Information System (INIS)

Baek, Seung-Bin; Kim, Dae-Hee; Kim, Yeong-Cheol

2012-01-01

The adsorption and the surface reaction of bis-diethylaminosilane (SiH 2 [N(C 2 H 5 ) 2 ] 2 , BDEAS) as a Si precursor on an OH-terminated Si (0 0 1) surface were investigated to understand the initial reaction mechanism of the atomic layer deposition (ALD) process using density functional theory. The bond dissociation energies between two atoms in BDEAS increased in the order of Si-H, Si-N, and the rest of the bonds. Therefore, the relatively weak Si-H and Si-N bonds were considered for bond breaking during the surface reaction. Optimum locations of BDEAS for the Si-H and Si-N bond breaking were determined on the surface, and adsorption energies of 0.43 and 0.60 eV, respectively, were obtained. The Si-H bond dissociation energy of the adsorbed BDEAS on the surface did not decrease, so that a high reaction energy barrier of 1.60 eV was required. On the other hand, the Si-N bond dissociation energy did decrease, so that a relatively low reaction energy barrier of 0.52 eV was required. When the surface reaction energy barrier was higher than the adsorption energy, BDEAS would be desorbed from the surface instead of being reacted. Therefore, the Si-N bond breaking would be dominantly involved during the surface reaction, and the result is in good agreement with the experimental data in the literature.

H2S adsorption and decomposition on the gradually reduced α-Fe2O3(001) surface: A DFT study

Science.gov (United States)

Lin, Changfeng; Qin, Wu; Dong, Changqing

2016-11-01

Reduction of iron based desulfurizer occurs during hot gas desulfurization process, which will affect the interaction between H2S and the desulfurizer surface. In this work, a detailed adsorption behavior and dissociation mechanism of H2S on the perfect and reduced α-Fe2O3(001) surfaces, as well as the correlation between the interaction characteristic and reduction degree of iron oxide, have been studied by using periodic density functional theory (DFT) calculations. Results demonstrate that H2S firstly chemisorbs on surface at relatively higher oxidation state (reduction degree χ 33%. Reduction of iron oxide benefits the H2S adsorption. Further, dissociation processes of H2S via molecular and dissociative adsorption were investigated. Results show that after reduction of Fe2O3 into the oxidation state around FeO and Fe, the reduced surface exhibits very strong catalytic capacity for H2S decomposition into S species. Meanwhile, the overall dissociation process on all surfaces is exothermic. These results provide a fundamental understanding of reduction effect of iron oxide on the interaction mechanism between H2S and desulfurizer surface, and indicate that rational control of reduction degree of desulfurizer is essential for optimizing the hot gas desulfurization process.

Sputter deposited bioceramic coatings: surface characterisation and initial protein adsorption studies using surface-MALDI-MS

DEFF Research Database (Denmark)

Boyd, A. R.; Burke, G. A.; Duffy, H.

2011-01-01

Protein adsorption onto calcium phosphate (Ca–P) bioceramics utilised in hard tissue implant applications has been highlighted as one of the key events that influences the subsequent biological response, in vivo. This work reports on the use of surface-matrix assisted laser desorption ionisation...... to a combination of growth factors and lipoproteins present in serum. From the data obtained here it is evident that surface-MALDI-MS has significant utility as a tool for studying the dynamic nature of protein adsorption onto the surfaces of bioceramic coatings, which most likely plays a significant role...

In Situ Investigation of the Adsorption of Styrene Phosphonic Acid on Cassiterite (110 Surface by Molecular Modeling

Directory of Open Access Journals (Sweden)

Guichen Gong

2017-09-01

Full Text Available Abstract: The flotation, adsorption and bonding mechanisms of styrene phosphonic acid (SPA to cassiterite were studied using microflotation tests, zeta potential measurements, solution chemistry analysis and density functional theory (DFT calculations in this paper. Flotation results demonstrated SPA was an excellent collector for cassiterite which could recover over 85% cassiterite particles with the pH range 4.3–6.06 and 40 mg/L SPA. Zeta potential measurements and solution chemistry analysis revealed the adsorption of SPA was mainly contributed by the chemisorption of the monoanions on cassiterite surfaces. Frontier molecular orbital theory analysis and adsorption energy calculation results proved the monoanion of SPA was able to replace the OH− on cassiterite surfaces. The adsorption structure optimization results confirmed the binuclear complex was the most favorable adsorption configuration of SPA on cassiterite (110 surface. Mulliken population calculations and density of states analysis indicated during the bonding process the Sn3 atom lost electrons to O3 atom, and the bonding interaction between O3 and Sn3 atoms was mainly from the contribution of the 2p orbital of O3 atom and the 5s and 5p orbitals of Sn3 atom.

Tuning the work function of VO_2(1 0 0) surface by Ag adsorption and incorporation: Insights from first-principles calculations

International Nuclear Information System (INIS)

Chen, Lanli; Wang, Xiaofang; Shi, Siqi; Cui, Yuanyuan; Luo, Hongjie; Gao, Yanfeng

2016-01-01

Graphical abstract: - Highlights: • After adsorption, there is a charge transfer from Ag to VO_2(1 0 0) surface, which thus increases the electron concentration in VO_2 thin film. • Ag adsorption on VO_2(1 0 0) surface process is an exothermic chemical process, and the adsorption system is stable. • The work function can be tuned by Ag adsorption on and incorporation into the VO_2(1 0 0) surface, which in turn regulates the phase transition temperature of VO_2. - Abstract: VO_2 is an attractive material for application to thermochromic optoelectronic devices such as smart windows, and Ag/VO_2 double-layered structure can effectively decrease the phase transition temperature (T_c) of VO_2 thin film, which is very important for practical application of VO_2. Previous works has shown that the decrease in phase transition temperature (T_c) seems to be relevant with the work function of VO_2 in Ag/VO_2 double-layered thin film, although the underlying mechanism of tuning its T_c by Ag incorporation and adsorption on the VO_2(1 0 0) surface has been rarely investigated. Our first-principles calculations reveal that the adsorption of Ag atoms on the VO_2(1 0 0) surface rather than incorporation of Ag exhibits a lower work function, which is ascribed to an integrated effect of charge transfer from Ag to VO_2(1 0 0) surface and enhanced surface dipole moment. The results suggest that the decrease in work function of VO_2 with Ag adsorption favors the reduction in T_c. The current findings are helpful to understand the fundamental mechanism for yielding high-efficiency VO_2-based optoelectronic devices.

A First Principles Study of H2 Adsorption on LaNiO3(001 Surfaces

Directory of Open Access Journals (Sweden)

Changchang Pan

2017-01-01

Full Text Available The adsorption of H2 on LaNiO3 was investigated using density functional theory (DFT calculations. The adsorption sites, adsorption energy, and electronic structure of LaNiO3(001/H2 systems were calculated and indicated through the calculated surface energy that the (001 surface was the most stable surface. By looking at optimized structure, adsorption energy and dissociation energy, we found that there were three types of adsorption on the surface. First, H2 molecules completely dissociate and then tend to bind with the O atoms, forming two –OH bonds. Second, H2 molecules partially dissociate with the H atoms bonding to the same O atom to form one H2O molecule. These two types are chemical adsorption modes; however, the physical adsorption of H2 molecules can also occur. When analyzing the electron structure of the H2O molecule formed by the partial dissociation of the H2 molecule and the surface O atom, we found that the interaction between H2O and the (001 surface was weaker, thus, H2O was easier to separate from the surface to create an O vacancy. On the (001 surface, a supercell was constructed to accurately study the most stable adsorption site. The results from analyses of the charge population; electron localization function; and density of the states indicated that the dissociated H and O atoms form a typical covalent bond and that the interaction between the H2 molecule and surface is mainly due to the overlap-hybridization among the H 1s, O 2s, and O 2p states. Therefore, the conductivity of LaNiO3(001/H2 is stronger after adsorption and furthermore, the conductivity of the LaNiO3 surface is better than that of the LaFeO3 surface.

Adsorption of carbon monoxide on the Si(111)-7 × 7 surface

Energy Technology Data Exchange (ETDEWEB)

Shong, Bonggeun, E-mail: bshong@cnu.ac.kr

2017-05-31

Highlights: • Detailed chemistry of CO with the Si(111)-7 × 7 surface is computationally studied. • On-top on rest-atoms and back-bond insertion on adatoms are suggested geometries. • The two structures exhibit no activation barrier for adsorption and significant stability. • Geometrical and spectroscopic properties of CO adsorbates are predicted. • Direction of the interfacial charge transfer depends on the bonding configuration. - Abstract: The adsorption of CO and surface chemistry of Si are well-understood topics in surface science. However, research into the adsorption of CO on the Si(111)-7 × 7 surface is deficient. In this study, the adsorption of CO on Si(111)-7 × 7 is investigated via high-level density functional theory calculations using cluster model. Two adsorption configurations are found to be kinetically and thermodynamically viable: on-top on rest-atoms and back-bond insertion on adatoms, both binding to the surface via C atom. Structural, electronic, and spectroscopic properties of the adsorbates indicate a σ-donating/π-accepting nature of the CO−Si bonds in both configurations. The domination of σ-donation in the on-top configuration results in a net positive charge on the on-top adsorbate, and the opposite situation yields a net negative charge on the back-bond insertion adsorbates. Our study provides a detailed understanding of the previous experimental observations of fundamental surface chemical phenomena, suggesting possible applications of Si surface functionalization using CO.

First principles study of NH3 molecular adsorption on LiH (100) surfaces

International Nuclear Information System (INIS)

Lu Xiaoxia; Chen Yuhong; Dong Xiao

2012-01-01

The adsorption of NH 3 on LiH (100) crystal surfaces was studied by first principles method. The preferred adsorption sites, adsorption energy, dissociation energy and electronic structure of the LiH (100)/NH 3 systems were calculated separately. It is found that chemical adsorption happened mainly when NH 3 molecules are on the LiH (100) crystal surfaces. When NH 3 is adsorbed on the Li top site, NH 2 is formed on the LiH (100) crystal surfaces after loss of H atom, the calculated adsorption energy, 0.511 eV, belongs to strong chemical adsorption, then the interaction is strongest. The interaction between NH 2 and the neighboring Li, H are ionic. The covalent bonds are formed between N and H atoms in NH 2 . One H 2 molecule is formed by another H atom in NH 3 and H atom from LiH (100) crystal sur- faces. The covalent bonds are formed between H and H atoms in H 2 . (authors)

DFT study of the adsorption of the corrosion inhibitor 2-mercaptoimidazole onto Fe(1 0 0) surface

International Nuclear Information System (INIS)

Radilla, Juan; Negrón-Silva, Guillermo E.; Palomar-Pardavé, Manuel; Romero-Romo, Mario; Galván, Marcelo

2013-01-01

Graphical abstract: - Highlights: • Work functions and surface energies for a set of iron surfaces were obtained by DFT. • Fe(1 0 0) surface was chosen to address the adsorption study of 2-mercaptoimidazole. • 2-Mercaptoimidazole adsorbs planarly onto Fe(1 0 0) with −1.26 eV as adsorption energy. • Deprotonation of the thiol group and dropping of the entire thiol group were found too. • 2-Mercaptoimidazole received 0.88 of an electron mainly through its aromatic ring. - Abstract: From quantum mechanical calculations, based on density functional theory and using the pseudopotentials plane-wave method, in the first part of this work, a set of iron surfaces namely: (1 1 0), (1 0 0), (1 1 1) and (3 1 1) have been modeled and their work functions and surface energies calculated. It was found that the Fe(1 0 0) surface displayed the highest surface energy (2.43 J m −2 ), the lowest work function (3.95 eV) and the lowest coordination number too, thus furnishing the conditions for the interaction with the organic molecule. In the second part, the bonding structure for 2-mercaptoimidazole, 2MI, adsorbed onto Fe(1 0 0) surface has been studied and the geometry optimized; the adsorption energy (−1.26 eV), the Bader analysis and the bonding structure are presented and discussed. In these calculations, different adsorption sites of the Fe(1 0 0) surface, such as top, bridge and hollow were considered. The energetically most favored adsorption geometry shows the aromatic 2MI ring in a parallel position with respect to the surface, the charge transfer flows from the metallic surface to the inhibitor mainly through the adsorbate's carbon and sulfur atoms. Two dissociation processes were found: one related to deprotonation of the thiol group, and the other to releasing the entire thiol group. They were lower in energy by about 0.33 eV and 1.42 eV, respectively, than the adsorption energy of the molecule as a whole

Adsorption of malachite green by magnetic litchi pericarps: A response surface methodology investigation.

Science.gov (United States)

Zheng, Hao; Qi, Jinqiu; Jiang, Ruixue; Gao, Yan; Li, Xiaochen

2015-10-01

In this work, we synthesized a novel magnetic adsorbent containing litchi pericarps, denoted as MLP, for the removal of malachite green (MG) from solution. The factors influencing MG adsorption, such as contact time, adsorbent dosage, and initial dye concentration, were optimized using the Box-Behnken response surface methodology (RSM). The adsorption isotherms as well as the kinetics and thermodynamics of the adsorption of MG onto MLP are discussed. The results showed that MLP has a maximum adsorption efficiency of 99.5% when the temperature, pH, contact time, adsorbent dosage, and initial MG concentration were optimally set as 25 °C, 6.0, 66.69 min, 5.14 g/L, and 150 mg/L, respectively. The best model to describe this process is the Langmuir isotherm, with the maximum adsorption capacity being 70.42 mg/g. In addition, the kinetics of MG adsorption onto MLP followed a pseudo-second-order model; moreover, thermodynamic analysis suggested that MG adsorption onto MLP is spontaneous and endothermic. Finally, it was found that the new magnetic adsorbent can be separated easily and rapidly from mixed solutions in the presence of an external magnetic field. Copyright © 2015 Elsevier Ltd. All rights reserved.

Direct measurement of the adsorption kinetics of 2-Mercaptobenzothiazole on a microcrystalline copper surface

Energy Technology Data Exchange (ETDEWEB)

Ramirez-Cano, J. A.; Veleva, L.

2016-05-01

The adsorption on copper of 2-Mercaptobenzothiazole (2-MBT), a heterocyclic compound member of the tiazole family, has been investigated at different concentrations (1x10{sup -}1 to 1x10{sup -}6 M) in water, employing the Electrochemical Quartz Crystal Microbalance (EQCM). The frequency response over time was obtained for each concentration, showing a defined exponential behavior at higher concentrations (1x10{sup -}1, 1x10{sup -}2 and 1x10{sup -}3 M), which was filed to the Langmuir adsorption isotherm with a good correlation coefficients (R{sup 2}=0.91 to 0.98) Surface coverage (θ) was calculated and found to be in the order of 0.50 to 0.01 for 2-MBT high concentrations. The free energy of adsorption was ΔG{sub a}ds=-5.59 kJ mol{sup -}1, corresponding to physisorption process, probably of electrostatic nature of the interaction between 2-MBT and copper surface in aqueous solution. (Author)

Effect of solution chemistry on the adsorption of perfluorooctane sulfonate onto mineral surfaces.

Science.gov (United States)

Tang, Chuyang Y; Shiang Fu, Q; Gao, Dawen; Criddle, Craig S; Leckie, James O

2010-04-01

Perfluorooctane sulfonate (PFOS) is an emergent contaminant of substantial environmental concerns, yet very limited information has been available on PFOS adsorption onto mineral surfaces. PFOS adsorption onto goethite and silica was investigated by batch adsorption experiments under various solution compositions. Adsorption onto silica was only marginally affected by pH, ionic strength, and calcium concentration, likely due to the dominance of non-electrostatic interactions. In contrast, PFOS uptake by goethite increased significantly at high [H+] and [Ca2+], which was likely due to enhanced electrostatic attraction between the negatively charged PFOS molecules and positively charged goethite surface. The effect of pH was less significant at high ionic strength, likely due to electrical double layer compression. PFOS uptake was reduced at higher ionic strength for a strongly positively charged goethite surface (pH 3), while it increased for a weakly charged surface (pH 7 and 9), which could be attributed to the competition between PFOS-surface electrostatic attraction and PFOS-PFOS electrostatic repulsion. A conceptual model that captures PFOS-surface and PFOS-PFOS electrostatic interactions as well as non-electrostatic interaction was also formulated to understand the effect of solution chemistry on PFOS adsorption onto goethite and silica surfaces. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

The surface characteristics of hyperbranched polyamide modified corncob and its adsorption property for Cr(VI)

Energy Technology Data Exchange (ETDEWEB)

Lin, Hai, E-mail: linhai@ces.ustb.edu.cn [School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory on Resource-oriented Treatment of Industrial Pollutants, Beijing 100083 (China); Han, Shaoke; Dong, Yingbo; He, Yinhai [School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory on Resource-oriented Treatment of Industrial Pollutants, Beijing 100083 (China)

2017-08-01

Highlights: • An anion adsorbent was synthesized by hyperbranched polyamide modified corncob (HPMC). • The surface characteristics of samples (RCC, HPMC, HPMC-Cr) were studied. • Langmuir isotherm provided more fit and maximum adsorption capacity was 131.6 mg/g. • The adsorption process was chemisorption, controlled by intra-particle diffusion and film diffusion. • Adsorption is fast, stable, spontaneous and endothermic. - Abstract: A low-cost anion adsorbent for Cr(VI) effectively removing was synthesized by hyperbranched polyamide modified corncob (HPMC). Samples were characterized by Brunauer–Emmett–Teller (BET) surface area analysis, field-emission scanning electron microscopy (FE-SEM) with energy-dispersive X-ray spectroscopy, Fourier transform infrared (FTIR) and zeta potential analysis. Kinetics, isotherms and thermodynamics studies of HPMC for Cr(VI) adsorption were investigated in batch static experiments, in the temperature range of 25–45 °C, pH = 2.0. Results showed that the adsorption was rapid and stable, with the uptake capacity higher than 80% after 30 min. Adsorption behavior and rate-controlling mechanisms were analyzed using three kinetic models (pseudo-first order, pseudo-second order, intra-particle kinetic model). Kinetic studies showed that the adsorption of HPMC to Cr(VI) relied the pseudo-second-order model, and controlled both by the intra-particle diffusion and film diffusion. Equilibrium data was tested by Langmuir and Freundlich adsorption isotherm models. Langmuir model was more suitable to indicate a homogeneous distribution of active sites on HPMC and monolayer adsorption. The maximum adsorption capacity from the Langmuir model, q{sub max}, was 131.6 mg/g at pH 2.0 and 45 °C for HPMC. Thermodynamic parameters revealed spontaneous and endothermic nature of the Cr(VI) adsorption onto HPMC.

Fluoride adsorption on goethite in relation to different types of surface sites

NARCIS (Netherlands)

Hiemstra, T.; Riemsdijk, van W.H.

2000-01-01

Metal (hydr)oxides have different types of surface groups. Fluoride ions have been used as a probe to assess the number of surface sites. We have studied the F− adsorption on goethite by measuring the F− and H interaction and F− adsorption isotherms. Fluoride ions exchange against singly coordinated

Adsorption of asymmetric rigid rods or heteronuclear diatomic moleculeson homogeneous surfaces

Science.gov (United States)

Engl, W.; Courbin, L.; Panizza, P.

2004-10-01

We treat the adsorption on homogeneous surfaces of asymmetric rigid rods (like for instance heteronuclear diatomic molecules). We show that the n→0 vector spin formalism is well suited to describe such a problem. We establish an isomorphism between the coupling constants of the magnetic Hamiltonian and the adsorption parameters of the rigid rods. By solving this Hamiltonian within a mean-field approximation, we obtain analytical expressions for the densities of the different rod’s configurations, both isotherm and isobar adsorptions curves. The most probable configurations of the molecules (normal or parallel to the surface) which depends on temperature and energy parameters are summarized in a diagram. We derive that the variation of Qv , the heat of adsorption at constant volume, with the temperature is a direct signature of the adsorbed molecules configuration change. We show that this formalism can be generalized to more complicated problems such as for instance the adsorption of symmetric and asymmetric rigid rods mixtures in the presence or not of interactions.

Research progress of novel adsorption processes in water purification:A review

Institute of Scientific and Technical Information of China (English)

无

2008-01-01

As an effective, efficient, and economic approach for water purification, adsorbents and adsorption processes have been widely studied and applied in different aspects for a long time. In the recent years, a lot of novel adsorption processes have been developed for enhancing the efficiency of removing the organic and inorganic contaminants from water. This article reviews some new adsorbents and advanced adsorption methods that specialize in their compositions, structures, functions, and characteristics used in water treatment. The review emphasizes adsorption/catalytic oxidation process, adsorption/catalytic reduction process, adsorption coupled with redox process, biomimetic sorbent and its sorption behaviors of POPs, and modified adsorbents and their water purification efficiency.

Protein Adsorption in Three Dimensions

Science.gov (United States)

Vogler, Erwin A.

2011-01-01

Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and

Hydrophilic crosslinked-polymeric surface capable of effective suppression of protein adsorption

Energy Technology Data Exchange (ETDEWEB)

Kamon, Yuri; Inoue, Naoko; Mihara, Erika; Kitayama, Yukiya; Ooya, Tooru; Takeuchi, Toshifumi, E-mail: takeuchi@gold.kobe-u.ac.jp

2016-08-15

Highlights: • Three hydrophilic crosslinked polymers were examined for protein adsorption. • All polymers showed low nonspecific adsorption of negatively charged proteins. • Poly(MMPC) showed the lowest adsorption for positively charged proteins. • Poly(MMPC) is able to reduce nonspecific adsorption of a wide range of proteins. - Abstract: We investigated the nonspecific adsorption of proteins towards three hydrophilic crosslinked-polymeric thin layers prepared by surface-initiated atom transfer radical polymerization using N,N′-methylenebisacrylamide, 2-(methacryloyloxy)ethyl-[N-(2-methacryloyloxy)ethyl]phosphorylcholine (MMPC), or 6,6′-diacryloyl-trehalose crosslinkers. Protein binding experiments were performed by surface plasmon resonance with six proteins of different pI values including α-lactalbumin, bovine serum albumin (BSA), myoglobin, ribonuclease A, cytochrome C, and lysozyme in buffer solution at pH 7.4. All of the obtained crosslinked-polymeric thin layers showed low nonspecific adsorption of negatively charged proteins at pH 7.4 such as α-lactalbumin, BSA, and myoglobin. Nonspecific adsorption of positively charged proteins including ribonuclease A, cytochrome C, and lysozyme was the lowest for poly(MMPC). These results suggest poly(MMPC) can effectively reduce nonspecific adsorption of a wide range of proteins that are negatively or positively charged at pH 7.4. MMPC is a promising crosslinker for a wide range of polymeric materials requiring low nonspecific protein binding.

Adsorption, desorption, and removal of polymeric nanomedicine on and from cellulose surfaces: effect of size.

Science.gov (United States)

Zhang, Ming; Akbulut, Mustafa

2011-10-18

The increased production and commercial use of nanoparticulate drug delivery systems combined with a lack of regulation to govern their disposal may result in their introduction to soils and ultimately into groundwater systems. To better understand how such particles interact with environmentally significant interfaces, we study the adsorption, desorption, and removal behavior of poly(ethylene glycol)-based nanoparticulate drug delivery systems on and from cellulose, which is the most common organic compound on Earth. It is shown that such an adsorption process is only partially reversible, and most of the adsorbate particles do not desorb from the cellulose surface even upon rinsing with a large amount of water. The rate constant of adsorption decreases with increasing particle size. Furthermore, hydrodynamic forces acting parallel to the surfaces are found to be of great importance in the context of particle dynamics near the cellulose surface, and ultimately responsible for the removal of some fraction of particles via rolling or sliding. As the particle size increases, the removal rates of the particles increase for a given hydrodynamical condition. © 2011 American Chemical Society

Langmuir and Freundlich Isotherm Adsorption Equations for Chromium (VI) Waste Adsorption by Zeolite

International Nuclear Information System (INIS)

Murni Handayani; Eko Sulistiyono

2009-01-01

The research of chromium (VI) waste adsorption by zeolite has done. Wastes which are produced by Industries, both radioactive waste and heavy metal waste need done more processing so that they are not endanger environment and human health. Zeolite has very well-ordered crystal form with cavity each other to way entirely so that cause surface wide of zeolite become very big and very good as adsorbents. This research intends to know appropriate isotherm adsorption method to determine maximum capacity of zeolite to chromium (VI) waste. The equations which used in adsorption process are Langmuir and Freundlich isotherm Adsorption equations. The instrument was used in adsorption process by using Atomic Adsorption Spectroscopy (AAS). The experiment result showed that the biggest mass of chromium (VI) metal ion which was absorb by zeolite in 20 ppm concentration was 7.71 mg/gram zeolite. Adsorption process of Chromium (VI) waste by zeolite followed Langmuir and Freundlich isotherm equations with R 2 >0,9 . Appropriate equation to determine maximum adsorption capacity of zeolite for chromium (VI) waste adsorption is Langmuir equation. The maximum adsorption capacity of zeolite is 52.25 mg/gram. (author)

Surface and adsorptive properties of Moringa oleifera bark for removal of V(V) from aqueous solutions.

Science.gov (United States)

Mnisi, Robert Londi; Ndibewu, Peter Papoh

2017-11-04

The bark of Moringa oleifera, a cheap and readily available natural biopolymeric resource material, found to significantly reduce coliform load and turbidity in contaminated water is investigated in this paper. Its surface and adsorptive properties are investigated to explore its adsorptive potential in removing V(V) from aqueous solutions. Surface properties were investigated using FTIR, HRSEM/EDS, IC, and BET-N 2 adsorption techniques. Adsorptive properties were investigated by optimizing adsorption parameters such as pH, temperature, initial metal concentration, and adsorbent dosage, using V(V) as an adsorbate. The adsorption-desorption isotherms are typical of type II with a H3 hysteresis loop and is characteristic of a largely macroporous material. Bottle ink pores are observed, which can provide good accessibility of the active sites, even though the internal BET surface area is typically low (1.79 g/m 2 ). Solution pH significantly influences the adsorptive potential of the material. The low surface area negatively impacts on the adsorption capacity, but is compensated for by the exchangeable anions (Cl - , F - , PO 4 3- , NO 3 - , and SO 4 2- ) and cations (Ca 2+ , K + , Mg 2+ , and Al 3+ ) at the surface and the accessibility of the active sites. Adsorption isotherm modeling show that the surface is largely heterogeneous with complex multiple sites and adsorption is not limited to monolayer.

A semiflexible alternating copolymer chain adsorption on a flat and a fluctuating surface

International Nuclear Information System (INIS)

Mishra, Pramod Kumar

2010-01-01

A lattice model of a directed self-avoiding walk is used to investigate adsorption properties of a semiflexible alternating copolymer chain on an impenetrable flat and fluctuating surface in two (square, hexagonal and rectangular lattice) and three dimensions (cubic lattice). In the cubic lattice case the surface is two-dimensional impenetrable flat and in two dimensions the surface is a fluctuating impenetrable line (hexagonal lattice) and also flat impenetrable line (square and rectangular lattice). Walks of the copolymer chains are directed perpendicular to the plane of the surface and at a suitable value of monomer surface attraction, the copolymer chain gets adsorbed on the surface. To calculate the exact value of the monomer surface attraction, the directed walk model has been solved analytically using the generating function method to discuss results when one type of monomer of the copolymer chain has attractive, repulsive or no interaction with the surface. Results obtained in the flat surface case show that, for a stiffer copolymer chain, adsorption transition occurs at a smaller value of monomer surface attraction than a flexible copolymer chain while in the case of a fluctuating surface, the adsorption transition point is independent of bending energy of the copolymer chain. These features are similar to that of a semiflexible homopolymer chain adsorption.

A semiflexible alternating copolymer chain adsorption on a flat and a fluctuating surface.

Science.gov (United States)

Mishra, Pramod Kumar

2010-04-21

A lattice model of a directed self-avoiding walk is used to investigate adsorption properties of a semiflexible alternating copolymer chain on an impenetrable flat and fluctuating surface in two (square, hexagonal and rectangular lattice) and three dimensions (cubic lattice). In the cubic lattice case the surface is two-dimensional impenetrable flat and in two dimensions the surface is a fluctuating impenetrable line (hexagonal lattice) and also flat impenetrable line (square and rectangular lattice). Walks of the copolymer chains are directed perpendicular to the plane of the surface and at a suitable value of monomer surface attraction, the copolymer chain gets adsorbed on the surface. To calculate the exact value of the monomer surface attraction, the directed walk model has been solved analytically using the generating function method to discuss results when one type of monomer of the copolymer chain has attractive, repulsive or no interaction with the surface. Results obtained in the flat surface case show that, for a stiffer copolymer chain, adsorption transition occurs at a smaller value of monomer surface attraction than a flexible copolymer chain while in the case of a fluctuating surface, the adsorption transition point is independent of bending energy of the copolymer chain. These features are similar to that of a semiflexible homopolymer chain adsorption.

Adsorption behavior and mechanism of uranium on wood fiber

International Nuclear Information System (INIS)

Wang Zhe; Yi Facheng; Feng Yuan

2015-01-01

The adsorption performance of uranium on wood fiber was studied with static experiment. The influence factors on the U(Ⅵ) removal rate such as wood fiber particle size, adsorption time, dosage, temperature, pH and initial concentration were researched, and the adsorption process was analyzed in terms of thermodynamics and kinetics. The results show that the adsorption equilibrium time is 4 hours. When the pH reaches 3 for uranium-containing wastewater, uranium can be removed with the decrease of the size of adsorbent and with the increase of adsorbent dosage and temperature. The equilibrium adsorption data fit to Langmuir isotherms. The kinetic analysis shows that the adsorption rate is mainly controlled by chemical adsorption. The adsorption process can be described by an equation of pseudo 2nd-order model. The thermodynamic data indicate that the synergistic uranium bio-sorption by wood fiber is a spontaneous and endothermal adsorption process. The adsorption mechanism was analyzed with SEM, FT-IR and EDS. The results show that the surface form of wood fiber is changed and uranium mainly chelates with active groups on the fiber-s surface and forms the complexes. These indicate that the adsorption of uranium should be of surface coordination. The analyses of EDS before and after adsorption of uranium prove that the behavior of adsorption is ion exchange. The above results indicate that the adsorption mechanism is mainly surface coordination and ion exchange adsorption, followed by physical absorption. (authors)

Ice-surface adsorption enhanced colligative effect of antifreeze proteins in ice growth inhibition

Science.gov (United States)

Mao, Yougang; Ba, Yong

2006-09-01

This Communication describes a mechanism to explain antifreeze protein's function to inhibit the growth of ice crystals. We propose that the adsorption of antifreeze protein (AFP) molecules on an ice surface induces a dense AFP-water layer, which can significantly decrease the mole fraction of the interfacial water and, thus, lower the temperature for a seed ice crystal to grow in a super-cooled AFP solution. This mechanism can also explain the nearly unchanged melting point for the ice crystal due to the AFP's ice-surface adsorption. A mathematical model combining the Langmuir theory of adsorption and the colligative effect of thermodynamics has been proposed to find the equilibrium constants of the ice-surface adsorptions, and the interfacial concentrations of AFPs through fitting the theoretical curves to the experimental thermal hysteresis data. This model has been demonstrated by using the experimental data of serial size-mutated beetle Tenebrio molitor (Tm) AFPs. It was found that the AFP's ice-surface adsorptions could increase the interfacial AFP's concentrations by 3 to 4 orders compared with those in the bulk AFP solutions.

A review of the surface features and properties, surfactant adsorption and floatability of four key minerals of diasporic bauxite resources.

Science.gov (United States)

Zhang, Ningning; Nguyen, Anh V; Zhou, Changchun

2018-04-01

Diasporic bauxite represents one of the major aluminum resources. Its upgrading for further processing involves a separation of diaspore (the valuable mineral) from aluminosilicates (the gangue minerals) such as kaolinite, illite, and pyrophyllite. Flotation is one of the most effective ways to realize the upgrading. Since flotation is a physicochemical process based on the difference in the surface hydrophobicity of different components, determining the adsorption characteristics of various flotation surfactants on the mineral surfaces is critical. The surfactant adsorption properties of the minerals, in turn, are controlled by the surface chemistry of the minerals, while the latter is related to the mineral crystal structures. In this paper, we first discuss the crystal structures of the four key minerals of diaspore, kaolinite, illite, and pyrophyllite as well as the broken bonds on their exposed surfaces after grinding. Next, we summarize the surface chemistry properties such as surface wettability and surface electrical properties of the four minerals, and the differences in these properties are explained from the perspective of mineral crystal structures. Then we review the adsorption mechanism and adsorption characteristics of surfactants such as collectors (cationic, anionic, and mixed surfactants), depressants (inorganic and organic), dispersants, and flocculants on these mineral surfaces. The separation of diaspore and aluminosilicates by direct flotation and reverse flotation are reviewed, and the collecting properties of different types of collectors are compared. Furthermore, the abnormal behavior of the cationic flotation of kaolinite is also explained in this section. This review provides a strong theoretical support for the optimization of the upgrading of diaspore bauxite ore by flotation and the early industrialization of the reverse flotation process. Copyright © 2018 Elsevier B.V. All rights reserved.

Adsorption of metals on metal surfaces and the possibilities of its application in nuclear chemistry

International Nuclear Information System (INIS)

Roesch, F.; Eichler, B.

1986-01-01

Starting with values of differential enthalpies of adsorption ΔH-bar/sub a/ the desorption temperatures of 65 adsorptive metals as to 40 adsorbens metals have been obtained according to a model calculation. With regard to their potential separation by means of selective desorption from solid metal surfaces the desorption behaviour of combinations of radionuclides Me 1 (proton number Z)/Me 2 (proton number Z+1) and Me 1 (proton number Z)/Me 2 (proton number Z+2) was calculated. Basing on the parameters of the model assumptions, the results of the calculations allow estimations about the desorption temperatures of the adsorptive Me 1 as well as the temperature differences to the desorption of the adsorptive Me 2 and about the efficiency of the potential separation process. (author)

Tuning the work function of VO{sub 2}(1 0 0) surface by Ag adsorption and incorporation: Insights from first-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Chen, Lanli; Wang, Xiaofang [School of Materials Science and Engineering, Shanghai University, Shanghai 200444 (China); Shi, Siqi, E-mail: sqshi@shu.edu.cn [School of Materials Science and Engineering, Shanghai University, Shanghai 200444 (China); Materials Genome Institute, Shanghai University, Shanghai 200444 (China); Cui, Yuanyuan [School of Materials Science and Engineering, Shanghai University, Shanghai 200444 (China); Luo, Hongjie [School of Materials Science and Engineering, Shanghai University, Shanghai 200444 (China); Materials Genome Institute, Shanghai University, Shanghai 200444 (China); Gao, Yanfeng, E-mail: yfgao@shu.edu.cn [School of Materials Science and Engineering, Shanghai University, Shanghai 200444 (China)

2016-03-30

Graphical abstract: - Highlights: • After adsorption, there is a charge transfer from Ag to VO{sub 2}(1 0 0) surface, which thus increases the electron concentration in VO{sub 2} thin film. • Ag adsorption on VO{sub 2}(1 0 0) surface process is an exothermic chemical process, and the adsorption system is stable. • The work function can be tuned by Ag adsorption on and incorporation into the VO{sub 2}(1 0 0) surface, which in turn regulates the phase transition temperature of VO{sub 2}. - Abstract: VO{sub 2} is an attractive material for application to thermochromic optoelectronic devices such as smart windows, and Ag/VO{sub 2} double-layered structure can effectively decrease the phase transition temperature (T{sub c}) of VO{sub 2} thin film, which is very important for practical application of VO{sub 2}. Previous works has shown that the decrease in phase transition temperature (T{sub c}) seems to be relevant with the work function of VO{sub 2} in Ag/VO{sub 2} double-layered thin film, although the underlying mechanism of tuning its T{sub c} by Ag incorporation and adsorption on the VO{sub 2}(1 0 0) surface has been rarely investigated. Our first-principles calculations reveal that the adsorption of Ag atoms on the VO{sub 2}(1 0 0) surface rather than incorporation of Ag exhibits a lower work function, which is ascribed to an integrated effect of charge transfer from Ag to VO{sub 2}(1 0 0) surface and enhanced surface dipole moment. The results suggest that the decrease in work function of VO{sub 2} with Ag adsorption favors the reduction in T{sub c}. The current findings are helpful to understand the fundamental mechanism for yielding high-efficiency VO{sub 2}-based optoelectronic devices.

Effect of surface acidic oxides of activated carbon on adsorption of ammonia.

Science.gov (United States)

Huang, Chen-Chia; Li, Hong-Song; Chen, Chien-Hung

2008-11-30

The influence of surface acidity of activated carbon (AC) was experimentally studied on adsorption of ammonia (NH(3)). Coconut shell-based AC was modified by various acids at different concentrations. There were five different acids employed to modified AC, which included nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and acetic acid. Acidic functional groups on the surface of ACs were determined by a Fourier transform infrared spectrograph (FTIR) and by the Boehm titration method. Specific surface area and pore volume of the ACs were measured by a nitrogen adsorption apparatus. Adsorption amounts of NH(3) onto the ACs were measured by a dynamic adsorption system at room temperature according to the principle of the ASTM standard test method. The concentration of NH(3) in the effluent stream was monitored by a gas-detecting tube technique. Experimental results showed that adsorption amounts of NH(3) on the modified ACs were all enhanced. The ammonia adsorption amounts on various activated carbons modified by different acids are in the following order: nitric acid>sulfuric acid>acetic acid approximately phosphoric acid>hydrochloric acid. It is worth to note that the breakthrough capacity of NH(3) is linearly proportional to the amount of acidic functional groups of the ACs.

Adsorption-Driven Surface Segregation of the Less Reactive Alloy Component

DEFF Research Database (Denmark)

Andersson, Klas Jerker; Calle Vallejo, Federico; Rossmeisl, Jan

2009-01-01

Counterintuitive to expectations and all prior observations of adsorbate-induced surface segregation of the more reactive alloy component (the one forming the stronger bond with the adsorbate), we show that CO adsorption at elevated pressures and temperatures pulls the less reactive Cu to the sur......Counterintuitive to expectations and all prior observations of adsorbate-induced surface segregation of the more reactive alloy component (the one forming the stronger bond with the adsorbate), we show that CO adsorption at elevated pressures and temperatures pulls the less reactive Cu...... to the surface of a CuPt near-surface alloy. The Cu surface segregation is driven by the formation of a stable self-organized CO/CuPt surface alloy structure and is rationalized in terms of the radically stronger Pt−CO bond when Cu is present in the first surface layer of Pt. The results, which are expected...

Competitive Adsorption of Plasma Proteins on Polysaccharide-Modified Silicon Surfaces

National Research Council Canada - National Science Library

Ombelli, Michela; Costello, Lauren B; Meng, Qing C; Composto, Russell J; Eckmann, David M

2005-01-01

.... Competitive protein adsorption plays a key role in the hemocompatibility of the surface. The synthesis of nonfouling surfaces is therefore one of the major prerequisites for devices for biomedical applications...

Ab initio-based approach to reconstruction, adsorption and incorporation on GaN surfaces

International Nuclear Information System (INIS)

Ito, T; Akiyama, T; Nakamura, K

2012-01-01

Reconstruction, adsorption and incorporation on various GaN surfaces are systematically investigated using an ab initio-based approach that predicts the surface phase diagram as functions of temperature and beam-equivalent pressure (BEP). The calculated results for GaN surface reconstructions with polar (0 0 0 1), nonpolar (1 1 −2 0), semipolar (1 −1 0 1) and semipolar (1 1 −2 2) orientations imply that reconstructions on GaN surfaces with Ga adlayers generally appear on the polar and the semipolar surfaces, while the stable ideal surface without Ga adsorption is found on the nonpolar GaN(1 1 −2 0) surface because it satisfies the electron counting rule. The hydrogen adsorption on GaN(0 0 0 1) and GaN(1 1 −2 0) realizes several surface structures forming N–H and Ga–NH 2 bonds on their surfaces that depend on temperature and Ga BEP during metal-organic vapor-phase epitaxy (MOVPE). In contrast, the stable structures due to hydrogen adsorption on the semipolar GaN(1 −1 0 1) and GaN(1 1 −2 2) surfaces are not varied over the wide range of temperature and Ga BEP. This implies that the hydrogen adsorbed stable structures are expected to emerge on the semipolar surfaces during MOVPE regardless of the growth conditions. Furthermore, we clarify that Mg incorporation on GaN(1 −1 0 1) surfaces is enhanced by hydrogen adsorption consistent with experimental findings

Goethite surface reactivity: III. Unifying arsenate adsorption behavior through a variable crystal face - Site density model

Science.gov (United States)

Salazar-Camacho, Carlos; Villalobos, Mario

2010-04-01

goethite, may be performed for each preparation either by experimental determination of site saturation by an index ion (e.g., chromate), or by achieving congruency of proton adsorption data with those of ideal goethites when plotted as percentage of proton-reactive ( lbond2 FeOH + lbond2 Fe 3OH) sites occupied. The surface arsenate complexes proposed additionally explained: (1) the higher affinity of goethite for As(V) than for Cr(VI) at high pH, and thus the gentle slope of the arsenate pH adsorption edges; and (2) the lower adsorption capacity for As(V) than for Cr(VI) at low pH on low-surface area goethites, through incomplete lbond2 FeOH site occupancy of As(V). The model is very promising as a practical means of predicting the adsorption behavior of arsenate on any goethite preparation, and may extend to predictive capabilities for adsorption behavior of many other relevant oxyanions, as well as for explaining differences in ligand-promoted surface transformation processes on goethite as a function of particle size.

Inter-row Adsorption Configuration and Stability of Threonine Adsorbed on the Ge(100) Surfaces

International Nuclear Information System (INIS)

Lee, Myungjin; Park, Youngchan; Jeong, Hyuk; Lee, Hangil

2013-01-01

The adsorption structures of threonine on the Ge(100) surface were investigated using core-level photoemission spectroscopy (CLPES) in conjunction with density functional theory (DFT) calculations. CLPES measurements were performed to identify the experimentally preferred adsorption structure. The preferred structure indicated the relative reactivities of the carboxyl and hydroxymethyl groups as electron donors to the Ge(100) surface during adsorption. The core-level C 1s, N 1s, and O 1s CLPES spectra indicated that the carboxyl oxygen competed more strongly with the hydroxymethyl oxygen during the adsorption reaction. Three among six possible adsorption structures were identified as energetically favorable using DFT calculation methods that considered the inter- and intra-bonding configurations upon adsorption onto the Ge(100) surface. These structures were O-H dissociated N dative inter bonding, O-H dissociated N dative intra bonding, O-H dissociation bonding. One of the adsorption structures: O-H dissociated N dative inter bonding was predicted to be stable in light of the transition state energies. We thus confirmed that the most favorable adsorption structure is the O-H dissociated N dative-inter bonding structure using CLPES and DFT calculation

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

Science.gov (United States)

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

Surface complexation modeling of the effects of phosphate on uranium(VI) adsorption

Energy Technology Data Exchange (ETDEWEB)

Romero-Gonzalez, M.R.; Cheng, T.; Barnett, M.O. [Auburn Univ., AL (United States). Dept. of Civil Engeneering; Roden, E.E. [Wisconsin Univ., Madison, WI (United States). Dept. of Geology and Geophysics

2007-07-01

Previous published data for the adsorption of U(VI) and/or phosphate onto amorphous Fe(III) oxides (hydrous ferric oxide, HFO) and crystalline Fe(III) oxides (goethite) was examined. These data were then used to test the ability of a commonly-used surface complexation model (SCM) to describe the adsorption of U(VI) and phosphate onto pure amorphous and crystalline Fe(III) oxides and synthetic goethite-coated sand, a surrogate for a natural Fe(III)-coated material, using the component additivity (CA) approach. Our modeling results show that this model was able to describe U(VI) adsorption onto both amorphous and crystalline Fe(III) oxides and also goethite-coated sand quite well in the absence of phosphate. However, because phosphate adsorption exhibits a stronger dependence on Fe(III) oxide type than U(VI) adsorption, we could not use this model to consistently describe phosphate adsorption onto both amorphous and crystalline Fe(III) oxides and goethite-coated sand. However, the effects of phosphate on U(VI) adsorption could be incorporated into the model to describe U(VI) adsorption to both amorphous and crystalline Fe(III) oxides and goethite-coated sand, at least for an initial approximation. These results illustrate both the potential and limitations of using surface complexation models developed from pure systems to describe metal/radionuclide adsorption under more complex conditions. (orig.)

Surface complexation modeling of the effects of phosphate on uranium(VI) adsorption

International Nuclear Information System (INIS)

Romero-Gonzalez, M.R.; Cheng, T.; Barnett, M.O.; Roden, E.E.

2007-01-01

Previous published data for the adsorption of U(VI) and/or phosphate onto amorphous Fe(III) oxides (hydrous ferric oxide, HFO) and crystalline Fe(III) oxides (goethite) was examined. These data were then used to test the ability of a commonly-used surface complexation model (SCM) to describe the adsorption of U(VI) and phosphate onto pure amorphous and crystalline Fe(III) oxides and synthetic goethite-coated sand, a surrogate for a natural Fe(III)-coated material, using the component additivity (CA) approach. Our modeling results show that this model was able to describe U(VI) adsorption onto both amorphous and crystalline Fe(III) oxides and also goethite-coated sand quite well in the absence of phosphate. However, because phosphate adsorption exhibits a stronger dependence on Fe(III) oxide type than U(VI) adsorption, we could not use this model to consistently describe phosphate adsorption onto both amorphous and crystalline Fe(III) oxides and goethite-coated sand. However, the effects of phosphate on U(VI) adsorption could be incorporated into the model to describe U(VI) adsorption to both amorphous and crystalline Fe(III) oxides and goethite-coated sand, at least for an initial approximation. These results illustrate both the potential and limitations of using surface complexation models developed from pure systems to describe metal/radionuclide adsorption under more complex conditions. (orig.)

[Adsorption characteristics of proteins on membrane surface and effect of protein solution environment on permeation behavior of berberine].

Science.gov (United States)

Li, Yi-Qun; Xu, Li; Zhu, Hua-Xu; Tang, Zhi-Shu; Li, Bo; Pan, Yong-Lan; Yao, Wei-Wei; Fu, Ting-Ming; Guo, Li-Wei

2017-10-01

In order to explore the adsorption characteristics of proteins on the membrane surface and the effect of protein solution environment on the permeation behavior of berberine, berberine and proteins were used as the research object to prepare simulated solution. Low field NMR, static adsorption experiment and membrane separation experiment were used to study the interaction between the proteins and ceramic membrane or between the proteins and berberine. The static adsorption capacity of proteins, membrane relative flux, rejection rate of proteins, transmittance rate of berberine and the adsorption rate of proteins and berberine were used as the evaluation index. Meanwhile, the membrane resistance distribution, the particle size distribution and the scanning electron microscope (SEM) were determined to investigate the adsorption characteristics of proteins on ceramic membrane and the effect on membrane separation process of berberine. The results showed that the ceramic membrane could adsorb the proteins and the adsorption model was consistent with Langmuir adsorption model. In simulating the membrane separation process, proteins were the main factor to cause membrane fouling. However, when the concentration of proteins was 1 g•L⁻¹, the proteins had no significant effect on membrane separation process of berberine. Copyright© by the Chinese Pharmaceutical Association.

Intensify dodecylamine adsorption on magnesite and dolomite surfaces by monohydric alcohols

Science.gov (United States)

Zhang, Hao; Liu, Wengang; Han, Cong; Wei, Dezhou

2018-06-01

The flotation of magnesite and dolomite were investigated with the presence of single dodecylamine (DDA) and combined mixtures of DDA and monohydric alcohols, respectively. The adsorption behavior of DDA, butanol, hexanol and octanol on the surface of the two minerals were shown by molecular dynamics simulation, and the results were corresponding with the analysis of zeta potential, measurements of the contact angle and adsorption. Flotation results indicated that part of DDA could be replaced by the three alcohols (butanol, hexanol, octanol) to get better flotation results. Molecular dynamics simulation and the results of zeta potential and contact angle measurements indicated that adsorption of DDA on mineral surfaces could be strengthened by monohydric alcohols.

Effective NH2-grafting on attapulgite surfaces for adsorption of reactive dyes

International Nuclear Information System (INIS)

Xue, Ailian; Zhou, Shouyong; Zhao, Yijiang; Lu, Xiaoping; Han, Pingfang

2011-01-01

Highlights: → We prepared a new amine functionalized adsorbent derived from clay-based material. → Attapulgite surface was modified with 3-aminopropyltriethoxysilane. → Some modification parameters affecting the adsorption potential were investigated. → Enhance the attapulgite adsorptive capacity for reactive dyes from aqueous solutions. - Abstract: The amine moiety has an important function in many applications, including, adsorption, catalysis, electrochemistry, chromatography, and nanocomposite materials. We developed an effective adsorbent for aqueous reactive dye removal by modifying attapulgite with an amino-terminated organosilicon (3-aminopropyltriethoxysilane, APTES). Surface properties of the APTES-modified attapulgite were characterized by the Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption. We evaluated the impact of solvent, APTES concentration, water volume, reaction time, and temperature on the surface modification. NH 2 -attapulgite was used to remove reactive dyes in aqueous solution and showed very high adsorption rates of 99.32%, 99.67%, and 96.42% for Reactive Red 3BS, Reactive Blue KE-R and Reactive Black GR, respectively. These powerful dye removal effects were attributed to strong electrostatic interactions between reactive dyes and the grafted NH 2 groups.

Anisotropic surface chemistry properties and adsorption behavior of silicate mineral crystals.

Science.gov (United States)

Xu, Longhua; Tian, Jia; Wu, Houqin; Fang, Shuai; Lu, Zhongyuan; Ma, Caifeng; Sun, Wei; Hu, Yuehua

2018-03-07

Anisotropic surface properties of minerals play an important role in a variety of fields. With a focus on the two most intensively investigated silicate minerals (i.e., phyllosilicate minerals and pegmatite aluminosilicate minerals), this review highlights the research on their anisotropic surface properties based on their crystal structures. Four surface features comprise the anisotropic surface chemistry of minerals: broken bonds, energy, wettability, and charge. Analysis of surface broken bond and energy anisotropy helps to explain the cleavage and growth properties of mineral crystals, and understanding surface wettability and charge anisotropy is critical to the analysis of minerals' solution behavior, such as their flotation performance and rheological properties. In a specific reaction, the anisotropic surface properties of minerals are reflected in the adsorption strengths of reagents on different mineral surfaces. Combined with the knowledge of mineral crushing and grinding, a thorough understanding of the anisotropic surface chemistry properties and the anisotropic adsorption behavior of minerals will lead to the development of effective relational models comprising their crystal structure, surface chemistry properties, and targeted reagent adsorption. Overall, such a comprehensive approach is expected to firmly establish the connection between selective cleavage of mineral crystals for desired surfaces and designing novel reagents selectively adsorbed on the mineral surfaces. As tools to characterize the anisotropic surface chemistry properties of minerals, DLVO theory, atomic force microscopy (AFM), and molecular dynamics (MD) simulations are also reviewed. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of activated carbon characteristics on toluene and hexane adsorption: Application of surface response methodology

Science.gov (United States)

Izquierdo, Mª Teresa; de Yuso, Alicia Martínez; Valenciano, Raquel; Rubio, Begoña; Pino, Mª Rosa

2013-01-01

The objective of this study was to evaluate the adsorption capacity of toluene and hexane over activated carbons prepared according an experimental design, considering as variables the activation temperature, the impregnation ratio and the activation time. The response surface methodology was applied to optimize the adsorption capacity of the carbons regarding the preparation conditions that determine the physicochemical characteristics of the activated carbons. The methodology of preparation produced activated carbons with surface areas and micropore volumes as high as 1128 m2/g and 0.52 cm3/g, respectively. Moreover, the activated carbons exhibit mesoporosity, ranging from 64.6% to 89.1% the percentage of microporosity. The surface chemistry was characterized by TPD, FTIR and acid-base titration obtaining different values of surface groups from the different techniques because the limitation of each technique, but obtaining similar trends for the activated carbons studied. The exhaustive characterization of the activated carbons allows to state that the measured surface area does not explain the adsorption capacity for either toluene or n-hexane. On the other hand, the surface chemistry does not explain the adsorption results either. A compromise between physical and chemical characteristics can be obtained from the appropriate activation conditions, and the response surface methodology gives the optimal activated carbon to maximize adsorption capacity. Low activation temperature, intermediate impregnation ratio lead to high toluene and n-hexane adsorption capacities depending on the activation time, which a determining factor to maximize toluene adsorption.

Optical luminescence studies of the ethyl xanthate adsorption layer on the surface of sphalerite minerals.

Science.gov (United States)

Todoran, R; Todoran, D; Szakács, Zs

2016-01-05

In this work we propose optical luminescence measurements as a method to evaluate the kinetics of adsorption processes. Measurement of the intensity of the integral optical radiation obtained from the mineral-xanthate interface layer, stimulated with a monochromatic pulsating optical signal, as a function of time were made. The luminescence radiation was obtained from the thin interface layer formed at the separation surface between the sphalerite natural mineral and potassium ethyl xanthate solution, for different solution concentrations and pH-es at the constant industry standard temperature. This method enabled us to determine the time to achieve dynamic equilibrium in the formation of the interface layer of approximately 20min, gaining information on the adsorption kinetics in the case of xanthate on mineral surface and leading to the optimization of the industrial froth flotation process. Copyright © 2015 Elsevier B.V. All rights reserved.

Combined quantum chemistry and Monte Carlo simulation of competitive adsorption of O{sub 2} and OH on Pt surfaces

Energy Technology Data Exchange (ETDEWEB)

Li, Rui, E-mail: ruililcu@gmail.com [Department of Chemistry, Liaocheng University, Liaocheng 252059 (China); Li, Haibo; Xu, Shuling [Department of Chemistry, Liaocheng University, Liaocheng 252059 (China); Liu, Jifeng, E-mail: liujifeng111@gmail.com [Key Laboratory of Food Nutrition and Safety, Ministry of Education of China, Tianjin University of Science and Technology, Tianjin 300457 (China)

2017-07-15

Highlights: • Competitive adsorption of O{sub 2} and OH on different Pt surfaces was theoretically studied. • The adsorption energies of O{sub 2} and OH depend on the Pt surfaces and the adsorption sites. • The order of O{sub 2} adsorption efficiency was characterized. - Abstract: To obtain a microscopic explanation on the difference of oxygen reduction reaction activity on different Pt low index surfaces, we simulated competitive adsorptions of O{sub 2} and OH on four Pt low index surfaces. Firstly, all possible chemical adsorption configurations of the O{sub 2} and OH molecules on the three surfaces were acquired through density functional theory. The distribution of these configurations on the different surfaces was collected from Monte Carlo simulations. Our results demonstrated that the adsorption energy order of O{sub 2} on different surfaces was (110)(1 × 2) > (110) > (100) > (111) and that the adsorption energy order of the OH molecules on Pt surfaces was the same. Considering the competitive adsorption of O{sub 2} and OH on Pt surfaces, the final O{sub 2} adsorption efficiencies order of three surfaces was (111) > (110) > (100) > (110)(1 × 2), which was consistent with the experimental activities of oxygen reduction. Our study provided theoretical references for previous experimental studies and had important significance for the understanding of oxygen adsorption on Pt surfaces.

Surface enhanced spectroscopic investigations of adsorption of cations on electrochemical interfaces.

Science.gov (United States)

Dunwell, M; Wang, Junhua; Yan, Y; Xu, B

2017-01-04

The adsorption of alkali and tetraalkylammonium cations on Pt is investigated using surface enhanced infrared absorption spectroscopy and carbon monoxide as a probe molecule. Alkali cations exhibit a stronger adsorption than organic cations, with potassium showing the strongest effect, followed by sodium and lithium.

Adsorption of crystal violet with diatomite earth&carbon by a modification of hydrothermal carbonization process.

Science.gov (United States)

Zhang, Yanzhuo; Li, Jun; Chen, Guanghui; Bian, Wei; Lu, Yun; Li, Wenjing; Zheng, Zhaoming; Cheng, Xiaojie

2016-01-01

The high colority and difficulty of decolorization are the most important tasks on printing and dyeing wastewater. This study investigates the ability of diatomite earth&carbon (DE&C) as an adsorbent to removal crystal violet (CV) from aqueous solutions. Fourier transform infrared spectroscopy results indicate the importance of functional groups during the adsorption of CV. The obtained N2 adsorption-desorption isotherm values accord with well IUPAC type II. Our calculations determined a surface area of 73.15 m(2) g(-1) for DE&C and an average pore diameter of 10.56 nm. Equilibrium data of the adsorption process fitted very well to the Langmuir model (R(2) > 0.99). The results of kinetics study showed that the pseudo-second-order model fitted to the experimental data well. The thermodynamic parameters were also evaluated. ΔH° 0 and ΔG° < 0 demonstrated that the adsorption process was spontaneous and exothermic for dye. Furthermore the positive value of ΔS° reflected good affinity of the CV dye.

Surface modification of chitin using ultrasound-assisted and supercritical CO{sub 2} technologies for cobalt adsorption

Energy Technology Data Exchange (ETDEWEB)

Dotto, Guilherme L., E-mail: guilherme_dotto@yahoo.com.br; Cunha, Jeanine M., E-mail: jeaninecunha@gmail.com; Calgaro, Camila O., E-mail: camila.itepjr@gmail.com; Tanabe, Eduardo H., E-mail: edutanabe@yahoo.com.br; Bertuol, Daniel A., E-mail: dbertuol@gmail.com

2015-09-15

Highlights: • Chitin was modified by ultrasound-assisted (UA) and supercritical (SCO{sub 2}) technologies. • Chitin, UA-chitin and SCO{sub 2}-chitin were used as adsorbents for Co(II). • UA and SCO{sub 2} treatments provided increase of 20 and 3 times in chitin surface area. • The Co(II) adsorption capacity increased until 67.8%, using UA-chitin. - Abstract: Ultrasound-assisted (UA) and supercritical CO{sub 2} technologies (SCO{sub 2}) were used to modify the chitin surface and, improve its adsorption characteristics regarding to cobalt. Chitin, before and after the treatments, was characterized by N{sub 2} adsorption isotherms (BET), infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Unmodified and surface modified chitins were used as adsorbents to remove cobalt from aqueous solutions. The adsorption study was performed by equilibrium isotherms and kinetic curves. The chitin particle characteristics, such as, surface area, pore volume and porosity were improved by the UA and SCO{sub 2} treatments. The crystallinity index decreased after the UA and SCO{sub 2} treatments, and also, intense surface modifications were observed. Langmuir and Freundlich models were adequate to represent the adsorption equilibrium. The maximum adsorption capacities were 50.03, 83.94 and 63.08 mg g{sup −1} for unmodified chitin, UA surface modified chitin and SCO{sub 2} surface modified chitin. The adsorption kinetic curves were well represented by the pseudo-second order model. UA and SCO{sub 2} technologies are alternatives to modify the chitin surface and improve its adsorption characteristics.

Preparation and characterization of high-surface-area activated carbon fibers from silkworm cocoon waste for congo red adsorption

International Nuclear Information System (INIS)

Li, Jia; Ng, Dickon H.L.; Song, Peng; Kong, Chao; Song, Yi; Yang, Ping

2015-01-01

Herein, we report the preparation of activated carbon fibers from silkworm cocoon waste via the combination of (NH 4 ) 2 HPO 4 -pretreatment and KOH activation. The morphology, phase structure and surface chemistry constitute of the obtained ACFs were characterized by X-ray diffraction, IR spectroscopy, Micro Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, thermal analysis and N 2 adsorption–desorption isotherm. The effects of various factors such as the concentration of (NH 4 ) 2 HPO 4 and the activation time of KOH were also evaluated. These results demonstrated that the synthesized ACFs retained the fibrous morphology of silkworm cocoon waste, and exhibited highly defective graphite layer structure. A large amount of surface oxygen-containing functional groups were found on the ACFs surface. The obtained samples exhibited high BET surface areas ranging from 1153 to 2797 m 2  g −1 , total pore volumes of 0.64–1.74 cm 3  g −1 with micropore volume fractions between 75.2 and 93.6%. In addition, we also evaluated the congo red (CR) adsorption performance of the obtained ACFs. The CR adsorption fitted well to the pseudo-second-order kinetic model. Adsorption isotherm data indicated that the adsorption of CR onto ACFs was monolayer adsorption which followed well the Langmuir isotherm model. The maximum adsorption capacity of CR was 512 g kg −1 . The mechanism of the adsorption process was also described from the intraparticle diffusion model. - Highlights: • A new biomass fibroin precursor for activated carbon fibers (ACFs) was proposed. • High specific surface area (2797 m 2  g −1 ) and total pore volume (1.74 cm 3  g −1 ) were obtained. • The original fibrous structure of raw silkworm cocoons was retained in the ACF product. • Congo red maximum monolayer adsorption capacity of our ACF product was up to 1100 g kg −1

Site competition on metal surfaces: an electron spectroscopic study of sequential adsorption on W(110)

International Nuclear Information System (INIS)

Steinkilberg, M.; Menzel, D.

1977-01-01

Using UPS and XPS, the sequential adsorption of hydrogen + carbon monoxide, and of hydrogen + oxygen, on W(110) has been studied at room temperature. Adsorption of CO on a H-covered surface is rapid and leads to total displacement of hydrogen. The resulting CO layer however, is different from that formed on the clean surface under identical conditions, in that it consists of a higher percentage of virgin CO, while considerably more β-CO forms on the clean surface. Oxygen does not adsorb on a H-covered surface, nor displace hydrogen. It is concluded that hydrogen most probably occupies the same sites utilized by dissociative adsorption of CO and oxygen, while virgin CO can also occupy different sites; its adsorption can thus lead to interactional weakening of the H-surface bond. (Auth.)

Effects of topology on the adsorption of singly tethered ring polymers to attractive surfaces.

Science.gov (United States)

Li, Bing; Sun, Zhao-Yan; An, Li-Jia

2015-07-14

We investigate the effect of topology on the equilibrium behavior of singly tethered ring polymers adsorbed on an attractive surface. We focus on the change of square radius of gyration Rg(2), the perpendicular component Rg⊥(2) and the parallel component Rg‖(2) to the adsorbing surface, the mean contacting number of monomers with the surface , and the monomer distribution along z-direction during transition from desorption to adsorption. We find that both of the critical point of adsorption εc and the crossover exponent ϕ depend on the knot type when the chain length of ring ranges from 48 to 400. The behaviors of Rg(2), Rg⊥(2), and Rg‖(2) are found to be dependent on the topology and the monomer-surface attractive strength. At weak adsorption, the polymer chains with more complex topology are more adsorbable than those with simple topology. However, at strong adsorption, the polymer chains with complex topology are less adsorbable. By analyzing the distribution of monomer along z-direction, we give a possible mechanism for the effect of topology on the adsorption behavior.

AFM study of adsorption of protein A on a poly(dimethylsiloxane) surface

International Nuclear Information System (INIS)

Yu Ling; Lu Zhisong; Gan Ye; Liu Yingshuai; Li, C M

2009-01-01

In this paper, the morphology and kinetics of adsorption of protein A on a PDMS surface is studied by AFM. The results of effects of pH, protein concentration and contact time of the adsorption reveal that the morphology of adsorbed protein A is significantly affected by pH and adsorbed surface concentration, in which the pH away from the isoelectric point (IEP) of protein A could produce electrical repulsion to change the protein conformation, while the high adsorbed surface protein volume results in molecular networks. Protein A can form an adsorbed protein film on PDMS with a maximum volume of 2.45 x 10 -3 μm 3 . This work enhances our fundamental understanding of protein A adsorption on PDMS, a frequently used substrate component in miniaturized immunoassay devices.

Surface charge effects in protein adsorption on nanodiamonds.

Science.gov (United States)

Aramesh, M; Shimoni, O; Ostrikov, K; Prawer, S; Cervenka, J

2015-03-19

Understanding the interaction of proteins with charged diamond nanoparticles is of fundamental importance for diverse biomedical applications. Here we present a thorough study of protein binding, adsorption kinetics and structure on strongly positively (hydrogen-terminated) and negatively (oxygen-terminated) charged nanodiamond particles using a quartz crystal microbalance by dissipation and infrared spectroscopy. By using two model proteins (bovine serum albumin and lysozyme) of different properties (charge, molecular weight and rigidity), the main driving mechanism responsible for the protein binding to the charged nanoparticles was identified. Electrostatic interactions were found to dominate the protein adsorption dynamics, attachment and conformation. We developed a simple electrostatic model that can qualitatively explain the observed adsorption behaviour based on charge-induced pH modifications near the charged nanoparticle surfaces. Under neutral conditions, the local pH around the positively and negatively charged nanodiamonds becomes very high (11-12) and low (1-3) respectively, which has a profound impact on the protein charge, hydration and affinity to the nanodiamonds. Small proteins (lysozyme) were found to form multilayers with significant conformational changes to screen the surface charge, while larger proteins (albumin) formed monolayers with minor conformational changes. The findings of this study provide a step forward toward understanding and eventually predicting nanoparticle interactions with biofluids.

The adsorption and dissociation of water molecule on goethite (010) surface: A DFT approach

Energy Technology Data Exchange (ETDEWEB)

Zhou, Long, E-mail: shuweixia@ouc.edu.cn [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, College of Chemistry and Chemical Engineering (China); Xiu, Fangyuan [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, College of Chemistry and Chemical Engineering (China); Qiu, Meng [Qingdao Institute of Bioenergy and Bioprocess Technology (China); Xia, Shuwei; Yu, Liangmin [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, College of Chemistry and Chemical Engineering (China)

2017-01-15

Graphical abstract: The optimized structure of hydrated goethite (010) surface with medium water coverage (water density about 6.7 H{sub 2}O/nm{sup 2}). - Highlights: • Stable adsorption and dissociation structure of H{sub 2}O on goethite (010) surface was investigated by DFT. • Reasonable path for water dissociation was proposed by transitional state analysis. • The mechanism of water adsorption on goethite and binding nature were revealed by PDOS. - Abstract: Using density functional theory (DFT) calculation, we investigate the configuration, stability and electronic properties of fresh cleaved (010) goethite surface (Pnma) and this surface exposed to water monolayer at low, medium and high coverage. Water is predicted to be chemisorbed to the surface, together with the surface reconstruction. The interaction energy of the most stable configuration of both low and medium coverage per water molecule is almost the same (−1.17 eV), while that of high coverage is much lower (less than 1.03 eV). It indicates that highly hydrated surface is less stable. PDOS analysis reveals the adsorption of H{sub 2}O is due to the formation of Fe−O bond, caused by overlapping of Fe's 3d and O's 2p orbitals. Dissociation processes at low and medium water coverage are non-spontaneous; while at high coverage, it can undertake spontaneously both thermodynamically and dynamically. The dissociation paths of all three water coverage are the similar. The proton from one adsorbed water is likely to dissociate to bind to the vicinal surface μ{sub 3}−O as an intermediate product; the proton belonged to μ{sub 3}−O transferred to the neighbor surface μ{sub 2}−O as the dissociative configuration.

Iodide adsorption on the surface of chemically pretreated clinoptilolite

International Nuclear Information System (INIS)

Chmielewska-Horvatova, E.; Lesny, J.

1995-01-01

The possibility to use the monoionic Ag +- form (eventually Hg +- and Hg 2+ -forms) of clinoptilolite of domestic origin for radioactive iodide elimination from waters has been studied. The capacity of the monoforms of clinoptilolite towards iodide exceeds many times that of the capacity of clinoptilolite in natural form. Due to the low solubility product of AgI, Hg 2 I 2 and HgI 2 iodides generate precipitates on the zeolite surface. Rtg analyses of the silver form of clinoptilolite after sorption of iodide demonstrate the formation of new crystals on the zeolite surface. The influence of interfering anions on the adsorption capacity of silver clinoptilolite towards iodide was investigated, too. Kinetic curves of iodide desorption from the surface of silver and mercury clinoptilolite were compared. Simultaneously, adsorption isotherms for the systems aqueous iodide solution/Ag-, Hg-clinoptilolite were determined. (author) 6 refs.; 7 figs.; 4 tabs

A Tire-Sulfur Hybrid Adsorption Denitrification (T-SHAD) process for decentralized wastewater treatment.

Science.gov (United States)

Krayzelova, Lucie; Lynn, Thomas J; Banihani, Qais; Bartacek, Jan; Jenicek, Pavel; Ergas, Sarina J

2014-09-15

Nitrogen discharges from decentralized wastewater treatment (DWT) systems contribute to surface and groundwater contamination. However, the high variability in loading rates, long idle periods and lack of regular maintenance presents a challenge for biological nitrogen removal in DWT. A Tire-Sulfur Hybrid Adsorption Denitrification (T-SHAD) process was developed that combines nitrate (NO3(-)) adsorption to scrap tire chips with sulfur-oxidizing denitrification. This allows the tire chips to adsorb NO3(-) when the influent loading exceeds the denitrification capacity of the biofilm and release it when NO3(-) loading rates are low (e.g. at night). Three waste products, scrap tire chips, elemental sulfur pellets and crushed oyster shells, were used as a medium in adsorption, leaching, microcosm and up-flow packed bed bioreactor studies of NO3(-) removal from synthetic nitrified DWT wastewater. Adsorption isotherms showed that scrap tire chips have an adsorption capacity of 0.66 g NO3(-)-N kg(-1) of scrap tires. Leaching and microcosm studies showed that scrap tires leach bioavailable organic carbon that can support mixotrophic metabolism, resulting in lower effluent SO4(2-) concentrations than sulfur oxidizing denitrification alone. In column studies, the T-SHAD process achieved high NO3(-)-N removal efficiencies under steady state (90%), variable flow (89%) and variable concentration (94%) conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

The adsorption of Run (n = 1-4) on γ-Al2O3 Surface: A DFT study

Science.gov (United States)

Liu, Zhe; Guo, Yafei; Chen, Yu; Shen, Rong

2018-05-01

The density functional theory (DFT) was adopted to study the adsorption and growth of Run (n = 1-4) clusters on γ-Al2O3 surface, which is of great significances for the design of many important catalysts, especially for carbon dioxide methanation. It is found that both the Rusbnd Ru bond length and adsorption energy Eads of Ru clusters with the surface increase with the Run clusters increasing. The growth ability of the supported Run cluster is weaker than the gas phase Run clusters through comparing their respective growth process, which ascribes to the stabilization of γ-Al2O3 support. An interesting discovery is that the basin structure was supposed to be the most favorable adsorption geometry for Run clusters. Additionally, the distances between Ru atoms in the adsorbed clusters are longer than that in their isolated counterparts. Bader charge analysis was conducted for the most stable configurations of Run (n = 1-4) clusters on γ-Al2O3 surface as well. And the results suggest that Run (n = 1-4) clusters serve as the electron donators. The result of projected density of states (PDOS) shows that strong adsorption of Ru atom on the γ-Al2O3 surface correlates with strong interaction between d orbital of Ru atom and p orbital of Al or O atom of the Al2O3 support.

A new theoretical approach to adsorption desorption behavior of Ga on GaAs surfaces

Science.gov (United States)

Kangawa, Y.; Ito, T.; Taguchi, A.; Shiraishi, K.; Ohachi, T.

2001-11-01

We propose a new theoretical approach for studying adsorption-desorption behavior of atoms on semiconductor surfaces. The new theoretical approach based on the ab initio calculations incorporates the free energy of gas phase; therefore we can calculate how adsorption and desorption depends on growth temperature and beam equivalent pressure (BEP). The versatility of the new theoretical approach was confirmed by the calculation of Ga adsorption-desorption transition temperatures and transition BEPs on the GaAs(0 0 1)-(4×2)β2 Ga-rich surface. This new approach is feasible to predict how adsorption and desorption depend on the growth conditions.

Studies on adsorption-desorption of xenon on surface of BC-404 plastic scintillator based on soaking method

Energy Technology Data Exchange (ETDEWEB)

Yongchun, Xiang [Institute of Nuclear Physics and Chemistry, China and Academy of Engineer Physics, Mianyang 621900 (China); School of Physics, Peking University, Beijing 100080 (China); Tieshuan, Fan [School of Physics, Peking University, Beijing 100080 (China); Chuanfei, Zhang; Fei, Luo; Qian, Wang; Rende, Ze [Institute of Nuclear Physics and Chemistry, China and Academy of Engineer Physics, Mianyang 621900 (China); Qingpei, Xiang, E-mail: xiangqingpei@163.com [Institute of Nuclear Physics and Chemistry, China and Academy of Engineer Physics, Mianyang 621900 (China)

2017-03-01

The phoswich coincidence detector is used to verify the CTBT treaty by measuring radioxenon and as such needs to possess high detection sensitivity. However, residual xenon adsorbed onto the surface of β detectors greatly influences subsequent measurements of weak samples. In this study, we investigate the adsorption-desorption behavior of xenon on BC-404 scintillator surfaces with different coating thicknesses using the soaking method. The results present the desorption behavior of xenon on a BC-404 surface for the first time. The calculated adsorption capacity for an uncoated surface is consistent with that from previous studies. However, due to factors such as limitations in coating technology, the effectiveness of coating on reducing the “memory effect” of the detector was poor. The proposed method is suitable for studying the adsorption-desorption behavior of gases on solid surfaces due to its simplicity and flexibility. - Highlights: • We investigate the adsorption-desorption of xenon on coated BC-404 surfaces. • The calculated adsorption capacity on an uncoated surface agrees with other results. • The method can be used to simulate xenon adsorption in phoswich detectors.

Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

Energy Technology Data Exchange (ETDEWEB)

Park, Sang-Won; Leckie, J.O. [Stanford Univ., CA (United States); Siegel, M.D. [Sandia National Labs., Albuquerque, NM (United States)

1995-09-01

Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption.

Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

International Nuclear Information System (INIS)

Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

1995-09-01

Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption

The Adsorption of Cu Species onto Pyrite Surface and Its Effect on Pyrite Flotation

Directory of Open Access Journals (Sweden)

Bo Yang

2016-01-01

Full Text Available The adsorption of Cu species onto pyrite surface and its effect on flotation were investigated by using microflotation tests, first-principle calculations, and XPS surface analysis. The results indicated that the flotation of pyrite appears to be activated with CuSO4 only at alkaline pH, while being depressed at acidic and neutral pH. The adsorption of copper ions on pyrite surface was pH-dependent, and the adsorption magnitude of copper ions at alkaline pH is higher than that at acidic and neutral pH due to a strong interaction between O atom in Cu(OH2 and surface Fe atom except for the interaction between Cu atom and surface S atom. At acidic and neutral pH, there is only an interaction between Cu atom and surface S atom. The adsorption was relatively weak, and more copper ions in solution precipitated the collector and depressed the flotation of pyrite. XPS analysis confirmed that more copper ionic species (Cu(I and Cu(II are adsorbed on the pyrite surface at alkaline pH than that at acidic and neutral pH.

Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

Science.gov (United States)

Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

2015-12-01

This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. Copyright © 2015 Elsevier Inc. All rights reserved.

Krypton Adsorption on Zeolite-Templated Carbon and Anomalous Surface Thermodynamics.

Science.gov (United States)

Murialdo, Maxwell; Stadie, Nicholas P; Ahn, Channing C; Fultz, Brent

2015-07-28

Krypton adsorption was measured at eight temperatures between 253 and 433 K on a zeolite-templated carbon and two commercial carbons. The data were fitted using a generalized Langmuir isotherm model and thermodynamic properties were extracted. Differing from that on commercial carbons, krypton adsorption on the zeolite-templated carbon is accompanied by an increasing isosteric enthalpy of adsorption, rising by up to 1.4 kJ mol(-1) as a function of coverage. This increase is a result of enhanced adsorbate-adsorbate interactions promoted by the ordered, nanostructured surface of the adsorbent. An assessment of the strength and nature of these adsorbate-adsorbate interactions is made by comparing the measured isosteric enthalpies of adsorption (and other thermodynamic quantities) to fundamental metrics of intermolecular interactions of krypton and other common gases.

Finite Element Modeling of Adsorption Processes for Gas Separation and Purification

International Nuclear Information System (INIS)

Humble, Paul H.; Williams, Richard M.; Hayes, James C.

2009-01-01

Pacific Northwest National Laboratory (PNNL) has expertise in the design and fabrication of automated radioxenon collection systems for nuclear explosion monitoring. In developing new systems there is an ever present need to reduce size, power consumption and complexity. Most of these systems have used adsorption based techniques for gas collection and/or concentration and purification. These processes include pressure swing adsorption, vacuum swing adsorption, temperature swing adsorption, gas chromatography and hybrid processes that combine elements of these techniques. To better understand these processes, and help with the development of improved hardware, a finite element software package (COMSOL Multiphysics) has been used to develop complex models of these adsorption based operations. The partial differential equations used include a mass balance for each gas species and adsorbed species along with a convection conduction energy balance equation. These equations in conjunction with multicomponent temperature dependent isotherm models are capable of simulating separation processes ranging from complex multibed PSA processes, and multicomponent temperature programmed gas chromatography, to simple two component temperature swing adsorption. These numerical simulations have been a valuable tool for assessing the capability of proposed processes and optimizing hardware and process parameters.

High coverage hydrogen adsorption on the Fe{sub 3}O{sub 4}(1 1 0) surface

Energy Technology Data Exchange (ETDEWEB)

Yu, Xiaohu, E-mail: yuxiaohu950203@126.com [College of Physics and Electrical Engineering, Anyang Normal University, Anyang, Henan 455000 (China); State Key laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001 (China); Zhang, Xuemei [College of Physics and Electrical Engineering, Anyang Normal University, Anyang, Henan 455000 (China); Wang, Shengguang [State Key laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001 (China); Synfuels China Co., Ltd., Huairou, Beijing 101407 (China)

2015-10-30

Graphical abstract: - Highlights: • Hydrogen adsorption on the A and B termination layers of the Fe{sub 3}O{sub 4}(1 1 0) surface at different coverage has been studied by DFT + U method. • The adsorption of hydrogen prefers surface oxygen atoms on both Fe{sub 3}O{sub 4}(1 1 0) surface layers. • The more stable A layer has stronger adsorption energy than the less stable B layer. • The saturation coverage has two dissociatively adsorbed H{sub 2} on the A layer, and one dissociatively adsorbed H{sub 2} on the B layer. - Abstract: Hydrogen adsorption on the A and B termination layers of the Fe{sub 3}O{sub 4}(1 1 0) surface at different coverage has been systematically studied by density functional theory calculations including an on-site Hubbard term (GGA + U). The adsorption of hydrogen prefers surface oxygen atoms on both layers. The more stable A layer has stronger adsorption energy than the less stable B layer. The saturation coverage has two dissociatively adsorbed H{sub 2} on the A layer, and one dissociatively adsorbed H{sub 2} on the B layer. The adsorption mechanism has been analyzed on the basis of projected density of states (PDOS).

First-principles study of the adsorption of methanol at the α-Al2O3(0001) surface

International Nuclear Information System (INIS)

Borck, Oeyvind; Schroeder, Elsebeth

2006-01-01

We present density functional theory calculations of methanol molecular adsorption at the (0001) surface of α-Al 2 O 3 , for methanol coverages of 1/4 to 1 monolayer (ML). Adsorption energies, adsorption-induced restructuring of the surface, and induced changes to the electronic structure are calculated. We find that methanol bonds with its O atom to Al atoms at the α-Al 2 O 3 (0001) surface with an adsorption energy of 1.23 eV at coverage 1/4 ML, decreasing with coverage to 1.03 eV at 1 ML coverage. From calculations of the relaxed adsorption geometry and the angular dependence of the total energy, we predict an orientation of the adsorbed methanol molecule that has the molecular COH plane tilted away from the surface normal. The adsorption of methanol significantly restructures α-Al 2 O 3 (0001), especially for the outermost Al layer. Upon adsorption a small charge transfer from the molecule to the substrate takes place

First principles study of halogens adsorption on intermetallic surfaces

International Nuclear Information System (INIS)

Zhu, Quanxi; Wang, Shao-qing

2016-01-01

Graphical abstract: - Highlights: • The linear relation between adsorbates induced work function change and dipole moment change also exists for intermetallic surfaces. • It is just a common linear relationship rather than a directly proportion. • A new weight parameter β is proposed to describe different factors effect on work function shift. - Abstract: Halides are often present at electrochemical environment, they can directly influence the electrode potential or zero charge potential through the induced work-function change. In this work, we focused in particular on the halogen-induced work function change as a function of the coverage of fluorine, chlorine, bromine and iodine on Al_2Au and Al_2Pt (110) surfaces. Results show that the real relation between work function change and dipole moment change for halogens adsorption on intermetallic surfaces is just a common linear relationship rather than a directly proportion. Besides, the different slopes between fitted lines and the theoretical slope employed in pure metal surfaces demonstrating that the halogens adsorption on intermetallic surfaces are more complicated. We also present a weight parameter β to describe different factors effect on work function shift and finally qualify which factor dominates the shift direction.

Rapid and selective adsorption of cationic dyes by a unique metal-organic framework with decorated pore surface

Science.gov (United States)

Zhang, Jie; Li, Fan; Sun, Qian

2018-05-01

Organic dye pollutants become a big headache due to their toxic nature to the environment, and it should be one of the best solutions if we can remove and separate them. Here, a metal-organic framework (MOF) (denoted as Zn-MOF) with carbonyl group based on fluorenone-2,7-dicarboxylate ligand, was directly synthesized without post-synthesis method and applied to selectively absorb cationic dyes such as MB, CV, RhB from aqueous solution, while anionic or neutral dyes were excluded. Characterization of the Zn-MOF was achieved by X-ray diffraction, scanning electron microscope, Fourier transform infrared spectrometry and elemental analysis. The Zn-MOF mainly possesses open pore channels, high surface area, big pore volume, and most important, the pore surface is furnished with carbonyl groups arising from the ligand and pointing toward the centers of the large chambers of the framework, which are benefit for the adsorption of the cationic dyes. The MB maximum adsorption capacities can attain 326 mg g-1, which is probably due to the suitable pore size, higher solvent-accessible void, and the prominent adsorption capacity of the mesoporous material. The dye adsorption process for the material is proven to be charge-selective and size-selective, and the adsorption isotherms, as well as kinetics characteristic of dye adsorption onto the Zn-MOF were also investigated.

Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations.

Science.gov (United States)

Greathouse, Jeffery A; Cygan, Randall T

2006-06-15

Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water

Adsorption on smooth electrodes: A radiotracer study

International Nuclear Information System (INIS)

Rice-Jackson, L.M.

1990-01-01

Adsorption on solids is a complicated process and in most cases, occurs as the early stage of other more complicated processes, i.e. chemical reactions, electrooxidation, electroreduction. The research reported here combines the electroanalytical method, cyclic voltammetry, and the use of radio-labeled isotopes, soft beta emitters, to study adsorption processes at smooth electrodes. The in-situ radiotracer method is highly anion (molecule) specific and provides information on the structure and composition of the electric double layer. The emphasis of this research was on studying adsorption processes at smooth electrodes of copper, gold, and platinum. The application of the radiotracer method to these smooth surfaces have led to direct in-situ measurements from which surface coverage was determined; anions and molecules were identified; and weak interactions of adsorbates with the surface of the electrodes were readily monitored. 179 refs

Controlled surface chemistry of diamond/β-SiC composite films for preferential protein adsorption.

Science.gov (United States)

Wang, Tao; Handschuh-Wang, Stephan; Yang, Yang; Zhuang, Hao; Schlemper, Christoph; Wesner, Daniel; Schönherr, Holger; Zhang, Wenjun; Jiang, Xin

2014-02-04

Diamond and SiC both process extraordinary biocompatible, electronic, and chemical properties. A combination of diamond and SiC may lead to highly stable materials, e.g., for implants or biosensors with excellent sensing properties. Here we report on the controllable surface chemistry of diamond/β-SiC composite films and its effect on protein adsorption. For systematic and high-throughput investigations, novel diamond/β-SiC composite films with gradient composition have been synthesized using the hot filament chemical vapor deposition (HFCVD) technique. As revealed by scanning electron microscopy (SEM), the diamond/β-SiC ratio of the composite films shows a continuous change from pure diamond to β-SiC over a length of ∼ 10 mm on the surface. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) was employed to unveil the surface termination of chemically oxidized and hydrogen treated surfaces. The surface chemistry of the composite films was found to depend on diamond/β-SiC ratio and the surface treatment. As observed by confocal fluorescence microscopy, albumin and fibrinogen were preferentially adsorbed from buffer: after surface oxidation, the proteins preferred to adsorb on diamond rather than on β-SiC, resulting in an increasing amount of proteins adsorbed to the gradient surfaces with increasing diamond/β-SiC ratio. By contrast, for hydrogen-treated surfaces, the proteins preferentially adsorbed on β-SiC, leading to a decreasing amount of albumin adsorbed on the gradient surfaces with increasing diamond/β-SiC ratio. The mechanism of preferential protein adsorption is discussed by considering the hydrogen bonding of the water self-association network to OH-terminated surfaces and the change of the polar surface energy component, which was determined according to the van Oss method. These results suggest that the diamond/β-SiC gradient film can be a promising material for biomedical applications which

Surface metal adsorption on zooplankton carapaces: implications for exposure and effects in consumer organisms

International Nuclear Information System (INIS)

Robinson, K.A.; Baird, D.J.; Wrona, F.J.

2003-01-01

Metals adsorbed to prey surfaces may be a mechanism of exposure in predators. - The current study aimed to determine the potential of two important aquatic invertebrate crustacean species, Daphnia magna and Ceriodaphnia dubia, to adsorb cadmium on to their carapaces from aqueous solution. Using the Langmuir equation to model data outputs, it was shown that cadmium readily became associated with the carapace surfaces of both species, with uptake being dependent on exposure time and concentration. Maximum carapace-adsorption potential was found to be directly related to surface area, so that at predicted carapace saturation, D. magna neonates bound approximately five times more cadmium than the smaller C. dubia neonates. However, adsorption per unit surface area was found to be similar under the same exposure conditions. Results of surface metal adsorption studies in C. dubia suggested that short term exposures to high concentrations of aqueous cadmium would lead to similar levels of adsorption as obtained with long-term exposures to low concentrations. The study illustrates that contaminants adsorbed to prey surfaces may be an important mechanism of exposure to predators, and highlights some potential problems of feeding organisms during long-term toxicity tests

Evaluation of protein adsorption onto a polyurethane nanofiber surface having different segment distributions

Energy Technology Data Exchange (ETDEWEB)

Morita, Yuko; Koizumi, Gaku [Frontier Fiber Technology and Science, Graduate School of Engineering, University of Fukui (Japan); Sakamoto, Hiroaki, E-mail: hi-saka@u-fukui.ac.jp [Tenure-Track Program for Innovative Research, University of Fukui (Japan); Suye, Shin-ichiro [Frontier Fiber Technology and Science, Graduate School of Engineering, University of Fukui (Japan)

2017-02-01

Electrospinning is well known to be an effective method for fabricating polymeric nanofibers with a diameter of several hundred nanometers. Recently, the molecular-level orientation within nanofibers has attracted particular attention. Previously, we used atomic force microscopy to visualize the phase separation between soft and hard segments of a polyurethane (PU) nanofiber surface prepared by electrospinning. The unstretched PU nanofibers exhibited irregularly distributed hard segments, whereas hard segments of stretched nanofibers prepared with a high-speed collector exhibited periodic structures along the long-axis direction. PU was originally used to inhibit protein adsorption, but because the surface segment distribution was changed in the stretched nanofiber, here, we hypothesized that the protein adsorption property on the stretched nanofiber might be affected. We investigated protein adsorption onto PU nanofibers to elucidate the effects of segment distribution on the surface properties of PU nanofibers. The amount of adsorbed protein on stretched PU nanofibers was increased compared with that of unstretched nanofibers. These results indicate that the hard segment alignment on stretched PU nanofibers mediated protein adsorption. It is therefore expected that the amount of protein adsorption can be controlled by rotation of the collector. - Highlights: • The hard segments of stretched PU nanofibers exhibit periodic structures. • The adsorbed protein on stretched PU nanofibers was increased compared with PU film. • The hard segment alignment on stretched PU nanofibers mediated protein adsorption.

Adsorption mechanisms of carboxymethyl cellulose on mineral surfaces.

NARCIS (Netherlands)

Hoogendam, C.W.; Keizer, de A.; Cohen Stuart, M.A.; Bijsterbosch, B.H.; Batelaan, J.G.; Horst, van der P.M.

1998-01-01

The adsorption behavior of carboxymethyl cellulose (CMC) on inorganic surfaces (TiO2 and -Fe2O3) in aqueous solution has been studied systematically. The general trends are that the adsorbed amount decreases with increasing pH, whereas increasing the electrolyte (NaCl) concentration causes the

Time scale of random sequential adsorption.

Science.gov (United States)

Erban, Radek; Chapman, S Jonathan

2007-04-01

A simple multiscale approach to the diffusion-driven adsorption from a solution to a solid surface is presented. The model combines two important features of the adsorption process: (i) The kinetics of the chemical reaction between adsorbing molecules and the surface and (ii) geometrical constraints on the surface made by molecules which are already adsorbed. The process (i) is modeled in a diffusion-driven context, i.e., the conditional probability of adsorbing a molecule provided that the molecule hits the surface is related to the macroscopic surface reaction rate. The geometrical constraint (ii) is modeled using random sequential adsorption (RSA), which is the sequential addition of molecules at random positions on a surface; one attempt to attach a molecule is made per one RSA simulation time step. By coupling RSA with the diffusion of molecules in the solution above the surface the RSA simulation time step is related to the real physical time. The method is illustrated on a model of chemisorption of reactive polymers to a virus surface.

In silico approach to investigating the adsorption mechanisms of short chain perfluorinated sulfonic acids and perfluorooctane sulfonic acid on hydrated hematite surface.

Science.gov (United States)

Feng, Hongru; Lin, Yuan; Sun, Yuzhen; Cao, Huiming; Fu, Jianjie; Gao, Ke; Zhang, Aiqian

2017-05-01

Short chain perfluorinated sulfonic acids (PFSAs) that were introduced as alternatives for perfluorooctane sulfonic acid (PFOS) have been widely produced and used. However, few studies have investigated the environmental process of short chain PFSAs, and the related adsorption mechanisms still need to be uncovered. The water-oxide interface is one of the major environmental interfaces that plays an important role in affecting the adsorption behaviour and transport potential of the environmental pollutant. In this study, we performed molecular dynamics simulations and quantum chemistry calculations to investigate the adsorption mechanisms of five PFSAs and their adsorption on hydrated hematite surface as well. Different to the vertical configuration reported for PFOS on titanium oxide, all PFSAs share the same adsorption configuration as the long carbon chains parallel to the surface. The formation of hydrogen bonds between F and inter-surface H helps to stabilize the unique configuration. As a result, the sorption capacity increases with increasing C-F chain length. Moreover, both calculated adsorption energy and partial density of states (PDOS) analysis demonstrate a PFSAs adsorption mechanism in between physical and chemical adsorption because the hydrogen bonds formed by the overlap of F (p) orbital and H (s) orbital are weak intermolecular interactions while the physical adsorption are mainly ascribed to the electrostatic interactions. This massive calculation provides a new insight into the pollutant adsorption behaviour, and in particular, may help to evaluate the environmental influence of pollutants. Copyright © 2017. Published by Elsevier Ltd.

Effect of softening precipitate composition and surface characteristics on natural organic matter adsorption.

Science.gov (United States)

Russell, Caroline G; Lawler, Desmond F; Speitel, Gerald E; Katz, Lynn E

2009-10-15

Natural organic matter (NOM) removal during water softening is thought to occur through adsorption onto or coprecipitation with calcium and magnesium solids. However, details of precipitate composition and surface chemistry and subsequent interactions with NOM are relatively unknown. In this study, zeta potentiometry analyses of precipitates formed from inorganic solutions under varying conditions (e.g., Ca-only, Mg-only, Ca + Mg, increasing lime or NaOH dose) indicated that both CaCO3 and Mg(OH)2 were positively charged at higher lime (Ca(OH)2) and NaOH doses (associated with pH values above 11.5), potentially yielding a greater affinity for adsorbing negatively charged organic molecules. Environmental scanning electron microscopy (ESEM) images of CaCO3 solids illustrated the rhombohedral shape characteristic of calcite. In the presence of increasing concentrations of magnesium, the CaCO3 rhombs shifted to more elongated crystals. The CaCO3 solids also exhibited increasingly positive surface charge from Mg incorporation into the crystal lattice, potentially creating more favorable conditions for adsorption of organic matter. NOM adsorption experiments using humic substances extracted from Lake Austin and Missouri River water elucidated the role of surface charge and surface area on adsorption.

Combined DFT and XPS investigation of iodine anions adsorption on the sulfur terminated (001) chalcopyrite surface

Energy Technology Data Exchange (ETDEWEB)

Li, Kui, E-mail: likui9606@stu.xjtu.edu.cn [School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Zhao, Yaolin, E-mail: zhaoyaolin@mail.xjtu.edu.cn [School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Zhang, Peng, E-mail: zp32@qq.com [Sino Shaanxi Nuclear Industry Group, Xi’an 710100 (China); He, Chaohui, E-mail: hechaohui@mail.xjtu.edu.cn [School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Deng, Jia, E-mail: djkokocase@stu.xjtu.edu.cn [School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049 (China); Ding, Shujiang, E-mail: dingsj@mail.xjtu.edu.cn [Department of Applied Chemistry, School of Science, Xi’an Jiaotong University, Xi’an 710049 (China); Shi, Weiqun, E-mail: shiwq@ihep.ac.cn [Key Laboratory of Nuclear Radiation and Nuclear Energy Technology and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

2016-12-30

Highlights: • Metal surface sites of (001)-S surface of chalcopyrite show significant chemical affinity to iodide and iodate. • The energetically favorable active site is copper for iodide adsorption and iron for iodate adsorption, respectively. • Iodate undergoes a dissociative adsorption on the copper site of chalcopyrite surface. - Abstract: The adsorption of iodine anions (iodide and iodate) on the sulfur terminated (001) chalcopyrite surface has been systematically investigated combining first-principles calculations based on density functional theory (DFT) with X-ray photoelectron spectroscopy (XPS) measurements. Based on the total energy calculations and geometric optimization, the thermodynamically preferred site was copper atom for iodide adsorption and iron atom for iodate adsorption, respectively. In the case of Cu site mode, the iodate underwent a dissociative adsorption, where one I−O bond of iodate ion was broken and the dissociative oxygen atom adsorbed on the adjacent sulphur site. Projected density of states (PDOS) analysis further clarified the interaction mechanism between active sites of chalcopyrite surface and adsorbates. In addition, full-range XPS spectra qualitatively revealed the presence of iodine on chalcopyrite surface. High resolution XPS spectra of the I 3d peaks after adsorption verified the chemical environment of iodine. The binding energies of 618.8 eV and 623.5 eV for I 3d{sub 5/2} peaks unveiled that the adsorption of iodide and iodate ions on copper-iron sulfide minerals was the result of formation of low solubility metal iodides precipitate. Also two I 3d peaks with low intensity around 618 eV and 630 eV might be related to the inorganic reduction of iodate to iodide by reducing S{sup 2−} ion of chalcopyrite.

Adsorption of pesticides onto granular activated carbon in water treatment process

OpenAIRE

Kopecká, Ivana

2010-01-01

The diploma thesis is aimed at adsorption processes during the removal of pesticides onto granular activated carbon (GAC) in the process of drinking water treatment. Adsorption onto GAC represents an efficient method for pesticides removal. High adsorption efficiency can be significantly reduced due to the occurrence of natural organic matter (NOM) in raw water, which involves AOM (Algal Organic Matter) produced by phytoplankton. Analogous to NOM, AOM probably affects adsorption of pesticides...

Adsorption of Different Fractions of Organic Matter on the Surface of Metal Oxide

KAUST Repository

Zaouri, Noor A

2013-05-18

The adsorption of different fractions of organic matter on the surface of Al2O3 and ZrO2 were investigated. The aim was to study the affinity of these fractions on the surface of metal oxide and the effect of several factors. Batch adsorption experiments were conducted with Low molecular weight oxygenated compounds. These chemical compound have been chosen to investigate:1) the aliphatic and aromatic structurer;2)contribution of hydroxyl group and; 3) the number of carboxyl group. HPLC and IC analysis used for determent the concentration of these chemical in the working solution. ATR-FTIR used to distinguish the type of coordination structure with the surface of metal oxide. The results fitted with Langmuir equation. The results showed that the chemical structure and the type and number of attached functional have an impact on the adsorption. Which it was proved via ATR-FTIR where the result showed that each chemical have different coordination structure on the surface of ZrO2 and Al2O3. Different fractions and sources of NOM were used (hydrophobic fraction of Suwannee and Colorado River, biopolymers extracted for the exuded of 2 species of algae, and low molecular acids that do not adsorb in XAD-8 resin). Results showed that these different fractions have different affinity with the surface of Al2O3 and ZrO2. These adsorption behaviors were varying according to the difference in the component of each NOM. Biopolymers showed significant adsorption at acidic pH. These biopolymers are mainly comprised of polysaccharides and this result proved that polysaccharide adsorb on the surface of ZrO2 more than Al2O3.

Adsorption and recognition characteristics of surface molecularly imprinted polymethacrylic acid/silica toward genistein.

Science.gov (United States)

Zhang, Yanyan; Gao, Baojiao; An, Fuqiang; Xu, Zeqing; Zhang, Tingting

2014-09-12

In this paper, on the basis of surface-initiated graft polymerization, a new surface molecular imprinting technique is established by molecular design. And molecularly imprinted polymer MIP-PMAA/SiO2 is successfully prepared with genistein as template. The adsorption and recognition characteristics of MIP-PMAA/SiO2 for genistein are studied in depth by using static method, dynamic method and competitive adsorption experiment. The experimental results show that MIP-PMAA/SiO2 possesses very strong adsorption affinity and specific recognition for genistein. The saturated adsorption capacity could reach to 0.36mmolg(-1). The selectivity coefficients relative to quercetin and rutin are 5.4 and 11.8, respectively. Besides, MIP-PMAA/SiO2 is regenerated easily and exhibits excellent reusability. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation of H2TiO3-lithium adsorbent by the sol–gel process and its adsorption performance

International Nuclear Information System (INIS)

Zhang, Liyuan; Zhou, Dali; Yao, Qianqian; Zhou, Jiabei

2016-01-01

Graphical abstract: - Highlights: • Nano-Li 2 TiO 3 was synthesized with CH 3 COOLi and Ti(OC 4 H 9 ) 4 by the sol–gel process. • H 2 TiO 3 -lithium adsorbent was obtained by treating Li 2 TiO 3 with HCl. • Langmuir and Freundlich models were used to analyze the adsorption process. • The adsorption performance of the obtained adsorbent was studied. - Abstract: CH 3 COOLi and Ti(OC 4 H 9 ) 4 were employed as lithium and titanium sources, respectively to synthesize Li 2 TiO 3 by the sol–gel process, followed by treating with hydrochloric acid to yield H 2 TiO 3 -lithium adsorbent. Various concentrations of LiOH and lithium sources were used as adsorption liquid to carry out adsorption experiment, the data from which were analyzed by Langmuir and Freundlich models. The results indicate that the optimal calcination temperature is 650 °C, and Li 2 TiO 3 with particle size 60–80 nm is observed. The Li + drawn out ratio from Li 2 TiO 3 reaches 78.9%, and the dissolution of titanium ions can be as low as 0.07%. The protonated sample obtained has a lower basal spacing, while the crystal morphology is retained. The main factors affecting the adsorptive capacity are the Li + concentration and pH in the liquid. The adsorption process of H 2 TiO 3 -lithium adsorbent can be seen as a process including surface adsorption and ion exchange. Compared with Langmuir model, Freundlich model is more suitable for describing the actual adsorption process.

4He adsorption and third-sound propagation on rough CaF2 surfaces

International Nuclear Information System (INIS)

Herrmann, J.C.; Hallock, R.B.

2003-01-01

We have investigated the propagation of third sound on well characterized rough CaF 2 surfaces as a function of 4 He film thickness. In addition we have measured the adsorption of 4 He to the CaF 2 surfaces using quartz crystal microbalances. We report values for the superfluid depletion thickness D for the three surfaces examined here. A model for the reduction of the third-sound speed due to the increased helium adsorption on rough CaF 2 is explored

Adsorption of aromatic hydrocarbons and ozone at environmental aqueous surfaces.

Science.gov (United States)

Vácha, Robert; Cwiklik, Lukasz; Rezác, Jan; Hobza, Pavel; Jungwirth, Pavel; Valsaraj, Kalliat; Bahr, Stephan; Kempter, Volker

2008-06-05

Adsorption of environmentally important aromatic molecules on a water surface is studied by means of classical and ab initio molecular dynamics simulations and by reflection-absorption infrared spectroscopy. Both techniques show strong activity and orientational preference of these molecules at the surface. Benzene and naphthalene, which bind weakly to water surface with a significant contribution of dispersion interactions, prefer to lie flat on water but retain a large degree of orientational flexibility. Pyridine is more rigid at the surface. It is tilted with the nitrogen end having strong hydrogen bonding interactions with water molecules. The degree of adsorption and orientation of aromatic molecules on aqueous droplets has atmospheric implications for heterogeneous ozonolysis, for which the Langmuir-Hinshelwood kinetics mechanism is discussed. At higher coverages of aromatic molecules the incoming ozone almost does not come into contact with the underlying aqueous phase. This may rationalize the experimental insensitivity of the ozonolysis on the chemical nature of the substrate on which the aromatic molecules adsorb.

Influence of surface treatments on micropore structure and hydrogen adsorption behavior of nanoporous carbons.

Science.gov (United States)

Kim, Byung-Joo; Park, Soo-Jin

2007-07-15

The scope of this work was to control the pore sizes of porous carbons by various surface treatments and to investigate the relation between pore structures and hydrogen adsorption capacity. The effects of various surface treatments (i.e., gas-phase ozone, anodic oxidation, fluorination, and oxygen plasma) on the micropore structures of porous carbons were investigated by N(2)/77 K isothermal adsorption. The hydrogen adsorption capacity was measured by H(2) isothermal adsorption at 77 K. In the result, the specific surface area and micropore volume of all of the treated samples were slightly decreased due to the micropore filling or pore collapsing behaviors. It was also found that in F(2)-treated carbons the center of the pore size distribution was shifted to left side, meaning that the average size of the micropores decreased. The F(2)- and plasma-treated samples showed higher hydrogen storage capacities than did the other samples, the F(2)-treated one being the best, indicating that the micropore size of the porous carbons played a key role in the hydrogen adsorption at 77 K.

Adsorption of Cr(III) on ozonised activated carbon. Importance of Cpi-cation interactions.

Science.gov (United States)

Rivera-Utrilla, J; Sánchez-Polo, M

2003-08-01

The adsorption of Cr(III) in aqueous solution was investigated on a series of ozonised activated carbons, analysing the effect of oxygenated surface groups on the adsorption process. A study was carried out to determine the adsorption isotherms and the influence of the pH on the adsorption of this metal. The adsorption capacity and affinity of the adsorbent for Cr(III) increased with the increase in oxygenated acid groups on the surface of the activated carbon. These findings imply that electrostatic-type interactions predominate in the adsorption process, although the adsorption of Cr(III) on the original (basic) carbon indicates that other forces also participate in the adsorption process. Thus, the ionic exchange of protons in the -Cpi-H3O(+) interaction for Cr(III) accounts for the adsorption of cationic species in basic carbons with positive charge density. Study of the influence of pH on the adsorption of Cr(III) showed that, in each system, the maximum adsorption occurred when the charge of the carbon surface was opposite that of the species of Cr(III) present at the pH of the experiment. These results confirmed that electrostatic interactions predominate in the adsorption process.

Cell surface engineering of microorganisms towards adsorption of heavy metals.

Science.gov (United States)

Li, Peng-Song; Tao, Hu-Chun

2015-06-01

Heavy metal contamination has become a worldwide environmental concern due to its toxicity, non-degradability and food-chain bioaccumulation. Conventional physical and chemical treatment methods for heavy metal removal have disadvantages such as cost-intensiveness, incomplete removal, secondary pollution and the lack of metal specificity. Microbial biomass-based biosorption is one of the approaches gaining increasing attention because it is effective, cheap, and environmental friendly and can work well at low concentrations. To enhance the adsorption properties of microbial cells to heavy metal ions, the cell surface display of various metal-binding proteins/peptides have been performed using a cell surface engineering approach. The surface engineering of Gram-negative bacteria, Gram-positive bacteria and yeast towards the adsorption of heavy metals are reviewed in this article. The problems and future perspectives of this technology are discussed.

Ab initio modeling of Al adsorption on CaF2 surfaces

International Nuclear Information System (INIS)

Barzilai, S.; Argaman, N.; Froumin, N.; Fuks, D.; Frage, N.

2008-01-01

Ab initio simulations of the adsorption of Al atoms on CaF 2 (0 0 1) and (1 1 1) surfaces have been performed for supercells with 7 different atomic configurations, using density functional theory. For (1 1 1) surfaces, a repulsive interaction was observed for most configurations, while a weak attraction was obtained when the Al atom was placed above F atoms. For the Ca-terminated (0 0 1) surface, the adsorption energy was about 5 times larger, whereas for the F-terminated (0 0 1) surface it was about 20 times greater. The comparative analysis indicates that the (0 0 1) surfaces are reactive and have a strong Al adatom bonding (chemisorption), especially for the F-terminated substrate. On the contrary, the (1 1 1) plane may be considered as non-reactive (physisorption), having a weak bonding of the Al adatom above the F site

Adsorption on metal surfaces: Final report

International Nuclear Information System (INIS)

Einstein, T.L.; Glover, R.E. III; Park, R.L.

1987-01-01

This report discusses the progress at the University of Maryland Department of Physics on the adsorption of atoms or molecules on the surfaces of metals. Also discussed are: Phase transformation studies; the use of transfer matrices to study the 2-d, 3-state chiral Potts model; electron-induced ionization of core electrons of atoms; the reflected electron energy loss fine structure above the M/sub 2,3/ core excitation edge of Cu; and other research in atomic and solid state physics

Modification process optimization, characterization and adsorption property of granular fir-based activated carbon

International Nuclear Information System (INIS)

Chen, Congjin; Li, Xin; Tong, Zhangfa; Li, Yue; Li, Mingfei

2014-01-01

Highlights: • Granular fir-based activated carbon (GFAC) was modified with H 2 O 2 . • Orthogonal array design method was used to optimize the modification process. • Optimized parameters were: aqueous H 2 O 2 concentration 1.0 mol l −1 , modification temperature and time 30.0 °C and 4.0 h. • Adsorption capacity of the modified GFAC increased by 500.0% (caramel), 59.7% (methylene blue), 32.5% (phenol), and 15.1% (I 2 ). • The pore structure parameters and surface oxygen groups changed in the modified GFAC. - Abstract: Granular fir-based activated carbon (GFAC) was modified with H 2 O 2 , and orthogonal array experimental design method was used to optimize the process. The properties of the original and modified GFAC were characterized by N 2 adsorption–desorption isotherms, Brunauer–Emmett–Teller (BET) equation, Barett–Joyner–Halenda (BJH) equation, field emission scanning electron microscopy (FESEM), and Fourier transform infrared spectroscopy (FT-IR) analysis, etc. When 10.00 g of GFAC with particle size of 0.25–0.85 mm was modified by 150.0 ml of aqueous H 2 O 2 solution, the optimized conditions were found to be as follows: aqueous H 2 O 2 solution concentration 1.0 mol·l −1 , modification temperature 30.0 °C, modification time 4.0 h. Modified under the optimized conditions, decolonization of caramel, methylene blue adsorption, phenol adsorption and iodine number of the modified GFAC increased by 500.0%, 59.7%, 32.5%, and 15.1%, respectively. The original and optimally modified GFAC exhibited adsorption isotherms of hybrid Type I–IV isotherms with H4 hysteresis. BET surface area, micropore area, total pore volume, micropore volume, and microporosity of the modified GFAC increased by 7.33%, 11.25%, 3.89%, 14.23%, 9.91%, respectively. Whereas the average pore width decreased by 3.16%. In addition, the amount of surface oxygen groups (such as carbonyl or carboxyl) increased in the modified GFAC

Adsorption characteristics of brilliant green dye on kaolin

International Nuclear Information System (INIS)

Nandi, B.K.; Goswami, A.; Purkait, M.K.

2009-01-01

Experimental investigations were carried out to adsorb toxic brilliant green dye from aqueous medium using kaolin as an adsorbent. Characterization of kaolin is done by measuring: (i) particle size distribution using particle size analyzer, (ii) BET surface area using BET surface analyzer, and (iii) structural analysis using X-ray diffractometer. The effects of initial dye concentration, contact time, kaolin dose, stirring speed, pH and temperature were studied for the adsorption of brilliant green in batch mode. Adsorption experiments indicate that the extent of adsorption is strongly dependent on pH of solution. Free energy of adsorption (ΔG 0 ), enthalpy (ΔH 0 ) and entropy (ΔS 0 ) changes are calculated to know the nature of adsorption. The calculated values of ΔG 0 at 299 K and 323 K indicate that the adsorption process is spontaneous. The estimated values of ΔH 0 and ΔS 0 both show the negative sign, which indicate that the adsorption process is exothermic and the dye molecules are organized on the kaolin surface in less randomly fashion than in solution. The adsorption kinetic has been described by first-order, pseudo-second-order and intra-particle-diffusion models. It was observed that the rate of dye adsorption follows pseudo-second-order model for the dye concentration range studied in the present case. Standard adsorption isotherms were used to fit the experimental equilibrium data. It was found that the adsorption of brilliant green on kaolin follows the Langmuir adsorption isotherm

Thermogravimetric determination of the enthalpy of astatine and radon adsorption on palladium surfaces

International Nuclear Information System (INIS)

Eichler, B.; Son Chun, K.

1985-01-01

In order to investigate the adsorption of astatine and radon on a palladium surface some on- and off-line thermochromatographic experiments were carried out with 210 At and 220 Rn tracers. The partial molar adsorption enthalpy for zero covering was found to be ΔH/sub a//sup 0, loc./(At) = -(15S +- 10) kJ mole -1 and ΔH/sub a//sup 0, mob./(Rn) = -(37 +- 4) kJ mole -1 . The results are compared with theoretical and experimental values for other elements of the sixth period. The adsorption behaviour of At is in conformity with that of the p-metals on a palladium surface. (author)

Adsorption and oxidation of oxalic acid on anatase TiO2 (001) surface: A density functional theory study.

Science.gov (United States)

Sun, Tao; Wang, Yun; Zhang, Haimin; Liu, Porun; Zhao, Huijun

2015-09-15

Anatase TiO2 (001) surfaces have attracted great interest for photo-degradation of organic species recently due to their high reactivity. In this work, adsorption properties and oxidation mechanisms of oxalic acid on the anatase TiO2 (001) surface have been theoretically investigated using the first-principles density functional theory. Various possible adsorption configurations are considered by diversifying the connectivity of carboxylic groups with the surface. It is found that the adsorption of oxalic acid on the anatase (001) surface prefer the dissociative states. A novel double-bidentate configuration has been found due to the structural match between oxalic acid and the (001) surface. More charge is transferred from the adsorbed oxalic acid to the surface with the double-bidentate configuration when comparing with other adsorption structures. Thus, there is a positive correlation relationship between the transferred charge amount and the interfacial bond numbers when oxalic acid adsorbs on the anatase TiO2 (001) surface. The adsorption energies with dispersion corrections have demonstrated that the van der Waals interactions play an important role in the adsorption, especially when adsorbates are close to the surface. Copyright © 2015 Elsevier Inc. All rights reserved.

A first principles kinetic Monte Carlo investigation of the adsorption and mobility of gadolinium on the (100) surface of tungsten

International Nuclear Information System (INIS)

Samin, Adib J.; Zhang, Jinsuo

2017-01-01

An accurate characterization of lanthanide adsorption and mobility on tungsten surfaces is important for pyroprocessing. In the present study, the adsorption and diffusion of gadolinium on the (100) surface of tungsten was investigated. It was found that the hollow sites were the most energetically favorable for the adsorption. It was further observed that a magnetic moment was induced following the adsorption of gadolinium on the tungsten surface and that the system with adsorbed hollow sites had the largest magnetization. A pathway for the surface diffusion of gadolinium was determined to occur by hopping between the nearest neighbor hollow sites via the bridge site and the activation energy for the hop was calculated to be 0.75 eV. The surface diffusion process was further assessed using two distinct kinetic Monte Carlo models; one that accounted for lateral adsorbate interactions up to the second nearest neighbor and one that did not account for such interatomic interactions in the adlayer. When the lateral interactions were included in the simulations, the diffusivity was observed to have a strong dependence on coverage (for the coverage values being studied). The effects of lateral interactions were further observed in a one-dimensional simulation of the diffusion equation where the asymmetry in the surface coverage profile upon its approach to a steady state distribution was clear in comparison with the simulations which did not account for those interactions.

A first principles kinetic Monte Carlo investigation of the adsorption and mobility of gadolinium on the (100) surface of tungsten

Energy Technology Data Exchange (ETDEWEB)

Samin, Adib J., E-mail: samin.2@osu.edu; Zhang, Jinsuo

2017-05-15

An accurate characterization of lanthanide adsorption and mobility on tungsten surfaces is important for pyroprocessing. In the present study, the adsorption and diffusion of gadolinium on the (100) surface of tungsten was investigated. It was found that the hollow sites were the most energetically favorable for the adsorption. It was further observed that a magnetic moment was induced following the adsorption of gadolinium on the tungsten surface and that the system with adsorbed hollow sites had the largest magnetization. A pathway for the surface diffusion of gadolinium was determined to occur by hopping between the nearest neighbor hollow sites via the bridge site and the activation energy for the hop was calculated to be 0.75 eV. The surface diffusion process was further assessed using two distinct kinetic Monte Carlo models; one that accounted for lateral adsorbate interactions up to the second nearest neighbor and one that did not account for such interatomic interactions in the adlayer. When the lateral interactions were included in the simulations, the diffusivity was observed to have a strong dependence on coverage (for the coverage values being studied). The effects of lateral interactions were further observed in a one-dimensional simulation of the diffusion equation where the asymmetry in the surface coverage profile upon its approach to a steady state distribution was clear in comparison with the simulations which did not account for those interactions.

Development of a nondestructive testing method and facility for investigation of surface reactions appearing in damage, corrosion, adsorption and catalytic processes encountered in the heat transfer systems of nuclear power plants and the energy storage problems

International Nuclear Information System (INIS)

Gumhalter, G.

1986-08-01

Studies of corrosion, oxide layer growth, etc., necessitate the investigation of processes which take place at surfaces: adsorption and desorption. Two problems are of major importance: i) initial stages of oxidative attack, e.g. the adsorptive properties of oxygen for a given system and possible synergetic effects of coadsorbed species like CO, H 2 O, OH, H 2 , SH 2 , impurities, and ii) the influence of surface conditions (crystalography, defects, pores, impurities, segregates) on the oxidative attack. An apparatus has been developed with three surface sensitive techniques: a) quartzcrystal micro-balance as a method for measuring the kinetics of deposition of thin metal films and gas adsorption, b) diode probe for the measurement of work function change caused by gas adsorption at metallic surfaces, and c) thermal desorption spectroscopy (TDS) which gives information on adsorption/desorption properties of a system studied: activation energy, preexponential factors for desorption, coverage, precursor states, lateral interaction, etc. The system investigated was oxygen/palladium foil (polycrystalline) by means of TDS and the following conclusions have been drawn: 1. Oxygen adsorbs on Pd foil both dissociatively and nondissociatively - depending on the adsorption temperature. 2. Certain amounts of oxygen penetrates into the surface and subsurface region, giving rise to a desorption peak around 1350K. 3. There are two groups of desorption peaks corresponding to atomically adsorbed oxygen (730K and 800K). The analysis of these peaks show the existence of strong lateral interactions between oxygen atoms at high coverages, which is not the case for low coverages. The position of the peaks and the dynamics of their evolution is consistent with the data obtained for Pd(111) and Pd(100) single crystal surfaces

Initial heats of H{sub 2}S adsorption on activated carbons: Effect of surface features

Energy Technology Data Exchange (ETDEWEB)

Bagreev, A.; Adib, F.; Bandosz, T.J.

1999-11-15

The sorption of hydrogen sulfide was studied on activated carbons of various origins by means of inverse gas chromatography at infinite dilution. The conditions of the experiment were dry and anaerobic. Prior to the experiments the surface of some carbon samples was oxidized using either nitric acid or ammonium persulfate. Then the structural parameters of carbons were evaluated from the sorption of nitrogen. From the IGC experiments at various temperatures, heats of adsorption were calculated. The results showed that the heat of H{sub 2}S adsorption under dry anaerobic conditions does not depend on surface chemistry. The dependence of the heat of adsorption on the characteristic energy of nitrogen adsorption calculated from the Dubinin-Raduskevich equation was found. This correlation can be used to predict the heat of H{sub 2}S adsorption based on the results obtained from nitrogen adsorption.

Methane adsorption on the surface of a model of shale: A density functional theory study

International Nuclear Information System (INIS)

Zhu, Yuan-qiang; Su, Hong; Jing, Ya; Guo, Jianchun; Tang, Junlei

2016-01-01

Highlights: • The adsorption of methane on kerogen was investigated by DFT method with D3 dispersion correction. • Methane prefers to be adsorbed on the sites directly above the carbon atoms of the kerogen. • The interaction energy with BSSE corrections is around 14 kJ mol −1 . • RDG gradient isosurface depicted the van der Waals interactions between methane and kerogen. • The adsorption of methane on kerogen slightly depends upon the adsorption sites on kerogen as well as the orientations of methane. - Abstract: As a model of shale, one part of polycyclic aromatic ring was used to represent the kerogen surface with the structural heterogeneity. The adsorption mechanisms of methane on the surface of the kerogen were investigated by M06-2× functional with D3 dispersion correction. Nine stable adsorption sites and the orientations of methane (CH 4 ) on the surface of the kerogen were systematically considered. Information from different methods lead to the same conclusion that methane prefers to be adsorbed on the sites directly above the carbon atoms of the kerogen rather than above the center of the six-membered rings. The interactions between methane and the surface of the kerogen are the van der Waals interactions. The interaction energies with the basis set superposition error (BSSE) corrections are around 14 kJ mol −1 at the M06-2×-D3/Jun-cc-pVDZ level. The RDG scatter graphs and the RDG gradient isosurface further illustrate that the interactions between methane and the surface of the kerogen belong to the van der Waals interactions. The weak interactions indicate that the adsorption of methane on the surface of the kerogen is physical adsorption and it slightly depends upon the adsorption sites on kerogen as well as the orientations of methane. These results are helpful for the understanding of the microcosmic mechanism of methane–shale interactions and for the exploitation of shale gas.

Methane adsorption on the surface of a model of shale: A density functional theory study

Energy Technology Data Exchange (ETDEWEB)

Zhu, Yuan-qiang, E-mail: zhuline518@163.com [School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500 (China); State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500 (China); Su, Hong; Jing, Ya [School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500 (China); Guo, Jianchun [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500 (China); Tang, Junlei [School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500 (China)

2016-11-30

Highlights: • The adsorption of methane on kerogen was investigated by DFT method with D3 dispersion correction. • Methane prefers to be adsorbed on the sites directly above the carbon atoms of the kerogen. • The interaction energy with BSSE corrections is around 14 kJ mol{sup −1}. • RDG gradient isosurface depicted the van der Waals interactions between methane and kerogen. • The adsorption of methane on kerogen slightly depends upon the adsorption sites on kerogen as well as the orientations of methane. - Abstract: As a model of shale, one part of polycyclic aromatic ring was used to represent the kerogen surface with the structural heterogeneity. The adsorption mechanisms of methane on the surface of the kerogen were investigated by M06-2× functional with D3 dispersion correction. Nine stable adsorption sites and the orientations of methane (CH{sub 4}) on the surface of the kerogen were systematically considered. Information from different methods lead to the same conclusion that methane prefers to be adsorbed on the sites directly above the carbon atoms of the kerogen rather than above the center of the six-membered rings. The interactions between methane and the surface of the kerogen are the van der Waals interactions. The interaction energies with the basis set superposition error (BSSE) corrections are around 14 kJ mol{sup −1} at the M06-2×-D3/Jun-cc-pVDZ level. The RDG scatter graphs and the RDG gradient isosurface further illustrate that the interactions between methane and the surface of the kerogen belong to the van der Waals interactions. The weak interactions indicate that the adsorption of methane on the surface of the kerogen is physical adsorption and it slightly depends upon the adsorption sites on kerogen as well as the orientations of methane. These results are helpful for the understanding of the microcosmic mechanism of methane–shale interactions and for the exploitation of shale gas.

Adsorption effectiveness of β-lactoglobulin onto gold surface determined by quartz crystal microbalance.

Science.gov (United States)

Jachimska, B; Świątek, S; Loch, J I; Lewiński, K; Luxbacher, T

2018-06-01

Bovine β-lactoglobulin (LGB) is a transport protein that can bind to its structure hydrophobic bioactive molecules. Due to the lack of toxicity, high stability and pH-dependent molecular binding mechanism, lactoglobulin can be used as a carrier of sparingly soluble drugs. Dynamic light scattering has confirmed LGB's tendency to create oligomeric forms. The hydrodynamic diameter of LGB molecules varies from 4 nm to 6 nm in the pH range of 2-10 and ionic strength I = 0.001-0.15 M, which corresponds to the presence of mono or dimeric LGB forms. The LGB zeta potential varies from 26.5 mV to -33.3 mV for I = 0.01 M and from 13.3 mV to -16 mV for I = 0.15 M in the pH range of 2-10. The isoelectric point is at pH 4.8. As a result of strong surface charge compensation, the maximum effective ionization degree of the LGB molecule is 35% for ionic strength I = 0.01 M and 22% for I = 0.15 M. The effectiveness of adsorption is linked with the properties of the protein, as well as those of the adsorption surface. The functionalization of gold surfaces with β-lactoglobulin (LGB) was studied using a quartz crystal microbalance with energy dissipation monitoring (QCM-D). The effectiveness of LGB adsorption correlates strongly with a charge of gold surface and the zeta potential of the molecule. The greatest value of the adsorbed mass was observed in the pH range in which LGB has a positive zeta potential values, below pH 4.8. This observation shows that electrostatic interactions play a dominant role in LGB adsorption on gold surfaces. Based on the adsorbed mass, protein orientation on gold surfaces was determined. The preferential side-on orientation of LGB molecules observed in the adsorption layer is consistent with the direction of the molecule dipole momentum determined by molecular dynamics simulations of the protein (MD). The use of the QCM-D method also allowed us to determine the effectiveness of adsorption of LGB on gold

Americium adsorption on the surface of macrophytic algae

Energy Technology Data Exchange (ETDEWEB)

Carvalho, F.P.; Fowler, S.W.

1985-01-01

Data are presented on the rates at which americium (Am) deposits upon blade surfaces of three benthic algal species (Ulva rigida, Fucus vesiculosus and Gigartina stellata) following short-term exposures (1-6 h). Am is taken up in direct proportion to the ambient radionuclide concentration in sea water. Uptake by the green alga was 3 to 5 times greater than that for the brown and red species. Experimental evidence indicated that Am accumulation is a passive process and that adsorption takes place mainly on the thin outer organic coating of the seaweed. The Am transport coefficients are quite similar to that previously found for the naturally occurring ..cap alpha..-emitter /sup 210/Po, but are an order of magnitude lower than a plutonium transport coefficient reported in the literature. Release of labelled extracellular products associated with the algal surface coating is considered to be responsible for the rapid loss of Am observed previously in macroalgae and may in fact serve as a mechanism for transferring Am to filter feeding zooplankton. (author).

Americium adsorption on the surface of macrophytic algae

International Nuclear Information System (INIS)

Carvalho, F.P.; Fowler, S.W.

1985-01-01

Data are presented on the rates at which americium (Am) deposits upon blade surfaces of three benthic algal species (Ulva rigida, Fucus vesiculosus and Gigartina stellata) following short-term exposures (1-6 h). Am is taken up in direct proportion to the ambient radionuclide concentration in sea water. Uptake by the green alga was 3 to 5 times greater than that for the brown and red species. Experimental evidence indicated that Am accumulation is a passive process and that adsorption takes place mainly on the thin outer organic coating of the seaweed. The Am transport coefficients are quite similar to that previously found for the naturally occurring α-emitter 210 Po, but are an order of magnitude lower than a plutonium transport coefficient reported in the literature. Release of labelled extracellular products associated with the algal surface coating is considered to be responsible for the rapid loss of Am observed previously in macroalgae and may in fact serve as a mechanism for transferring Am to filter feeding zooplankton. (author)

Incorporating classic adsorption isotherms into modern surface complexation models: implications for sorption of radionuclides

International Nuclear Information System (INIS)

Kulik, D.A.

2005-01-01

Full text of publication follows: Computer-aided surface complexation models (SCM) tend to replace the classic adsorption isotherm (AI) analysis in describing mineral-water interface reactions such as radionuclide sorption onto (hydr) oxides and clays. Any site-binding SCM based on the mole balance of surface sites, in fact, reproduces the (competitive) Langmuir isotherm, optionally amended with electrostatic Coulomb's non-ideal term. In most SCM implementations, it is difficult to incorporate real-surface phenomena (site heterogeneity, lateral interactions, surface condensation) described in classic AI approaches other than Langmuir's. Thermodynamic relations between SCMs and AIs that remained obscure in the past have been recently clarified using new definitions of standard and reference states of surface species [1,2]. On this basis, a method for separating the Langmuir AI into ideal (linear) and non-ideal parts [2] was applied to multi-dentate Langmuir, Frumkin, and BET isotherms. The aim of this work was to obtain the surface activity coefficient terms that make the SCM site mole balance constraints obsolete and, in this way, extend thermodynamic SCMs to cover sorption phenomena described by the respective AIs. The multi-dentate Langmuir term accounts for the site saturation with n-dentate surface species, as illustrated on modeling bi-dentate U VI complexes on goethite or SiO 2 surfaces. The Frumkin term corrects for the lateral interactions of the mono-dentate surface species; in particular, it has the same form as the Coulombic term of the constant-capacitance EDL combined with the Langmuir term. The BET term (three parameters) accounts for more than a monolayer adsorption up to the surface condensation; it can potentially describe the surface precipitation of nickel and other cations on hydroxides and clay minerals. All three non-ideal terms (in GEM SCMs implementation [1,2]) by now are used for non-competing surface species only. Upon 'surface dilution

Adsorption and structure of water on kaolinite surfaces: possible insight into ice nucleation from grand canonical monte carlo calculations.

Science.gov (United States)

Croteau, T; Bertram, A K; Patey, G N

2008-10-30

Grand canonical Monte Carlo calculations are used to determine water adsorption and structure on defect-free kaolinite surfaces as a function of relative humidity at 235 K. This information is then used to gain insight into ice nucleation on kaolinite surfaces. Results for both the SPC/E and TIP5P-E water models are compared and demonstrate that the Al-surface [(001) plane] and both protonated and unprotonated edges [(100) plane] strongly adsorb at atmospherically relevant relative humidities. Adsorption on the Al-surface exhibits properties of a first-order process with evidence of collective behavior, whereas adsorption on the edges is essentially continuous and appears dominated by strong water lattice interactions. For the protonated and unprotonated edges no structure that matches hexagonal ice is observed. For the Al-surface some of the water molecules formed hexagonal rings. However, the a o lattice parameter for these rings is significantly different from the corresponding constant for hexagonal ice ( Ih). A misfit strain of 14.0% is calculated between the hexagonal pattern of water adsorbed on the Al-surface and the basal plane of ice Ih. Hence, the ring structures that form on the Al-surface are not expected to be good building-blocks for ice nucleation due to the large misfit strain.

The Adsorption Mechanism of Modified Activated Carbon on Phenol

Directory of Open Access Journals (Sweden)

Lin J. Q.

2016-01-01

Full Text Available Modified activated carbon was prepared by thermal treatment at high temperature under nitrogen flow. The surface properties of the activated carbon were characterized by Boehm titration, BET and point of zero charge determination. The adsorption mechanism of phenol on modified activated carbon was explained and the adsorption capacity of modified activated carbon for phenol when compared to plain activated carbon was evaluated through the analysis of adsorption isotherms, thermodynamic and kinetic properties. Results shows that after modification the surface alkaline property and pHpzc value of the activated carbon increase and the surface oxygen-containing functional groups decrease. The adsorption processes of the plain and modified carbon fit with Langmuir isotherm equation well, and the maximum adsorption capacity increase from 123.46, 111.11, 103.09mg/g to 192.31, 178.57, 163,93mg/g under 15, 25 and 35°C after modification, respectively. Thermodynamic parameters show that the adsorption of phenol on activated carbon is a spontaneously exothermic process of entropy reduction, implying that the adsorption is a physical adsorption. The adsorption of phenol on activated carbon follows the pseudo-second-order kinetics (R2>0.99. The optimum pH of adsorption is 6~8.

Adsorption of branched and dendritic polymers onto flat surfaces: A Monte Carlo study

Science.gov (United States)

Sommer, J.-U.; Kłos, J. S.; Mironova, O. N.

2013-12-01

Using Monte Carlo simulations based on the bond fluctuation model we study the adsorption of starburst dendrimers with flexible spacers onto a flat surface. The calculations are performed for various generation number G and spacer length S in a wide range of the reduced temperature τ as the measure of the interaction strength between the monomers and the surface. Our simulations indicate a two-step adsorption scenario. Below the critical point of adsorption, τc, a weakly adsorbed state of the dendrimer is found. Here, the dendrimer retains its shape but sticks to the surface by adsorbed spacers. By lowering the temperature below a spacer-length dependent value, τ*(S) model of a dendrimer in two dimensions. We also performed simulations of star-polymers which display a simple crossover-behavior in full analogy to linear chains. By analyzing the order parameter of the adsorption transition, we determine the critical point of adsorption of the dendrimers which is located close to the critical point of adsorption for star-polymers. While the order parameter for the adsorbed spacers displays a critical crossover scaling, the overall order parameter, which combines both critical and discontinuous transition effects, does not display simple scaling. The step-like transition from the weak into the strong adsorbed regime is confirmed by analyzing the shape-anisotropy of the dendrimers. We present a mean-field model based on the concept of spacer adsorption which predicts a discontinuous transition of dendrimers due to an excluded volume barrier. The latter results from an increased density of the dendrimer in the flatly adsorbed state which has to be overcome before this state is thermodynamically stable.

Protein adsorption at nanopatterned surfaces studied by QCM-D and SPR

DEFF Research Database (Denmark)

Kristensen, Stine; Pedersen, Gitte Albinus; Nejsum, Lene Niemann

2013-01-01

This paper presents the use of the quartz microbalance with dissipation combined with surface plasmon resonance to probe protein adsorption at nanopatterned surfaces. Three different types of adsorbing materials, representing rigid discrete nanoparticles, dense protein films and soft low density ...

A density functional study on adsorption and dissociation of O 2 on Ir(1 0 0) surface

Science.gov (United States)

Erikat, I. A.; Hamad, B. A.; Khalifeh, J. M.

2011-06-01

The adsorption and the reaction barrier for the dissociation of O 2 on Ir(1 0 0) surface are studied using periodic self-consistent density functional theory (DFT) calculations. Dissociative adsorption is found to be energetically more favorable compared to molecular adsorption. Parallel approaches Prl1 and Prl2 on a hollow site with the same adsorption energy of -3.93 eV for both of them are found to have the most energetically preferred sites of adsorptions among all the studied cases. Hybridization between p-O 2 and d-metal orbitals is responsible for the dissociative adsorption. The minimum energy path is determined by using the nudge elastic band method (NEB). We found that the dissociation occurs immediately and very early in the dissociation path with a small activation barrier (0.26 eV), which means that molecular adsorption of O 2 on Ir(1 0 0) surface occurs at very low temperatures; this is consistent with previous experimental and theoretical studies on Ir surfaces.

Uranyl adsorption at clay mineral surfaces

Energy Technology Data Exchange (ETDEWEB)

Roesch, N. [Technische Univ. Muenchen (Germany). Fachgebiet Theoretische Chemie

2016-11-01

This first systematic survey of actinide adsorption at complex clay mineral surfaces, which provided new insights at the atomic level, is currently being extended to neptunyl NpO{sub 2}{sup +} and more complex minerals, like iron-substituted phyllosilicates. In this way we examine if the concepts developed so far can be applied more generally to support the interpretation of pertinent experiments. A further facet of these studies is to account also for the dynamic nature of the mineral/water interface by means of exemplary dynamic simulations.

Adsorption of ions by colloids in electrolyte solutions

International Nuclear Information System (INIS)

Kallay, N.

1977-01-01

The adsorption isotherm for ionic adsorption by colloid particles was evaluated. The adsorption process was treated as the reaction between colloid particles and ions. The colloid particle has been here considered as a reaction entity. The possibility of the surface potential determination was presented. The analyses of the experimental data showed, that (at electrolyte concentration higher than the critical coagulation one) the surface potential reaches its zero value

Pd adsorption on Si(1 1 3) surface: STM and XPS study

International Nuclear Information System (INIS)

Hara, Shinsuke; Yoshimura, Masamichi; Ueda, Kazuyuki

2008-01-01

Pd-induced surface structures on Si(1 1 3) have been studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). In the initial process of the Pd adsorption below 0.10 ML, Pd silicide (Pd 2 Si) clusters are observed to form randomly on the surface. By increasing the Pd coverage to 0.10 ML, the clusters cover the entire surface, and an amorphous layer is formed. After annealing the Si(1 1 3)-Pd surface at 600 deg. C, various types of islands and chain protrusions appears. The agglomeration, coalescence and crystallization of these islands are observed by using high temperature (HT-) STM. It is also found by XPS that the islands correspond to Pd 2 Si structure. On the basis of these results, evolution of Pd-induced structures at high temperatures is in detail discussed

Modification process optimization, characterization and adsorption property of granular fir-based activated carbon

Science.gov (United States)

Chen, Congjin; Li, Xin; Tong, Zhangfa; Li, Yue; Li, Mingfei

2014-10-01

Granular fir-based activated carbon (GFAC) was modified with H2O2, and orthogonal array experimental design method was used to optimize the process. The properties of the original and modified GFAC were characterized by N2 adsorption-desorption isotherms, Brunauer-Emmett-Teller (BET) equation, Barett-Joyner-Halenda (BJH) equation, field emission scanning electron microscopy (FESEM), and Fourier transform infrared spectroscopy (FT-IR) analysis, etc. When 10.00 g of GFAC with particle size of 0.25-0.85 mm was modified by 150.0 ml of aqueous H2O2 solution, the optimized conditions were found to be as follows: aqueous H2O2 solution concentration 1.0 mol·l-1, modification temperature 30.0 °C, modification time 4.0 h. Modified under the optimized conditions, decolonization of caramel, methylene blue adsorption, phenol adsorption and iodine number of the modified GFAC increased by 500.0%, 59.7%, 32.5%, and 15.1%, respectively. The original and optimally modified GFAC exhibited adsorption isotherms of hybrid Type I-IV isotherms with H4 hysteresis. BET surface area, micropore area, total pore volume, micropore volume, and microporosity of the modified GFAC increased by 7.33%, 11.25%, 3.89%, 14.23%, 9.91%, respectively. Whereas the average pore width decreased by 3.16%. In addition, the amount of surface oxygen groups (such as carbonyl or carboxyl) increased in the modified GFAC.

Adsorption of sugars on Al- and Ga-doped boron nitride surfaces: A computational study

Energy Technology Data Exchange (ETDEWEB)

Darwish, Ahmed A. [Center for Nanotechnology, Zewail City of Science and Technology, Giza 12588 (Egypt); Department of Nuclear and Radiation Engineering, Faculty of Engineering, Alexandria University, Alexandria (Egypt); Fadlallah, Mohamed M. [Center for Fundamental Physics, Zewail City of Science and Technology, Giza 12588 (Egypt); Department of Physics, Faculty of Science, Benha University, Benha (Egypt); Badawi, Ashraf [Center for Nanotechnology, Zewail City of Science and Technology, Giza 12588 (Egypt); Maarouf, Ahmed A., E-mail: ahmed.maarouf@egnc.gov.eg [Center for Fundamental Physics, Zewail City of Science and Technology, Giza 12588 (Egypt); Egypt Nanotechnology Center & Department of Physics, Faculty of Science, Cairo University, Giza 12613 (Egypt)

2016-07-30

Highlights: • Doping boron nitride sheets with aluminum or gallium atoms significantly enhances their molecular adsorption properties. • Adsorption of glucose or glucosamine on Al- and Ga-doped boron nitride sheets changes the band gap. • Doping concentration changes the bad gap, but has a minor effect on the adsorption energy. - Abstract: Molecular adsorption on surfaces is a key element for many applications, including sensing and catalysis. Non-invasive sugar sensing has been an active area of research due to its importance to diabetes care. The adsorption of sugars on a template surface study is at the heart of matter. Here, we study doped hexagonal boron nitride sheets (h-BNNs) as adsorbing and sensing template for glucose and glucosamine. Using first principles calculations, we find that the adsorption of glucose and glucosamine on h-BNNs is significantly enhanced by the substitutional doping of the sheet with Al and Ga. Including long range van der Waals corrections gives adsorption energies of about 2 eV. In addition to the charge transfer occurring between glucose and the Al/Ga-doped BN sheets, the adsorption alters the size of the band gap, allowing for optical detection of adsorption. We also find that Al-doped boron nitride sheet is better than Ga-doped boron nitride sheet to enhance the adsorption energy of glucose and glucosamine. The results of our work can be potentially utilized when designing support templates for glucose and glucosamine.

Adsorption of arsenic(III) into modified lamellar Na-magadiite in aqueous medium—Thermodynamic of adsorption process

Science.gov (United States)

Guerra, Denis Lima; Pinto, Alane Azevedo; Airoldi, Claudio; Viana, Rúbia Ribeiro

2008-12-01

Synthetic Na-magadiite sample was used for organofunctionalization process with N-propyldiethylenetrimethoxysilane and bis[3-(triethoxysilyl)propyl]tetrasulfide, after expanding the interlayer distance with polar organic solvents such as dimethylsulfoxide (DMSO). The resulted materials were submitted to process of adsorption with arsenic solution at pH 2.0 and 298±1 K. The adsorption isotherms were adjusted using a modified Langmuir equation with regression nonlinear; the net thermal effects obtained from calorimetric titration measurements were adjusted to a modified Langmuir equation. The adsorption process was exothermic (Δ intH=-4.15-5.98 kJ mol -1) accompanied by increase in entropy (Δ intS=41.32-62.20 J k -1 mol -1) and Gibbs energy (Δ intG=-22.44-24.56 kJ mol -1). The favorable values corroborate with the arsenic (III)/basic reactive centers interaction at the solid-liquid interface in the spontaneous process.

DFT, NBO and molecular docking studies of the adsorption of fluoxetine into and on the surface of simple and sulfur-doped carbon nanotubes

Science.gov (United States)

Shahabi, Dana; Tavakol, Hossein

2017-10-01

In this study, noncovalent interactions between Fluoxetine (FX) and different carbon nanotubes (CNTs) or sulfur doped carbon nanotubes (SCNTs) were fully considered using DFT, natural bond orbital (NBO) and molecular docking calculations. Two different CNTs (and SCNTs) with 7,7 and 8,8 chiralities were considered as the adsorbents and the adsorption of FX by these adsorbents were studied in two cases: into the nanotubes and on their surfaces. The results of DFT and NBO calculations proposed that the 8,8 nanotubes are more suitable adsorbents for FX because the energies of their adsorptions are minimum. Population: analyses were also proposed that the adsorption of FX by SCNTs lead to more changes in electronic and sensing properties than the adsorption by CNTs. Moreover, the adsorption energies, obtained from molecular docking calculations (using 94 different models), proposed that the adsorption of FX into (versus out of) the nanotubes, adsorption processes by double-walled or triple-walled (versus single-walled) nanotubes and the adsorption by nanotubes with 8,8 chiralities are the most favorable adsorption processes.

Adsorption, Desorption, Surface Diffusion, Lattice Defect Formation, and Kink Incorporation Processes of Particles on Growth Interfaces of Colloidal Crystals with Attractive Interactions

Directory of Open Access Journals (Sweden)

Yoshihisa Suzuki

2016-07-01

Full Text Available Good model systems are required in order to understand crystal growth processes because, in many cases, precise incorporation processes of atoms or molecules cannot be visualized easily at the atomic or molecular level. Using a transmission-type optical microscope, we have successfully observed in situ adsorption, desorption, surface diffusion, lattice defect formation, and kink incorporation of particles on growth interfaces of colloidal crystals of polystyrene particles in aqueous sodium polyacrylate solutions. Precise surface transportation and kink incorporation processes of the particles into the colloidal crystals with attractive interactions were observed in situ at the particle level. In particular, contrary to the conventional expectations, the diffusion of particles along steps around a two-dimensional island of the growth interface was not the main route for kink incorporation. This is probably due to the number of bonds between adsorbed particles and particles in a crystal; the number exceeds the limit at which a particle easily exchanges its position to the adjacent one along the step. We also found novel desorption processes of particles from steps to terraces, attributing them to the assistance of attractive forces from additionally adsorbing particles to the particles on the steps.

Enhanced fluoride adsorption using Al (III) modified calcium hydroxyapatite

International Nuclear Information System (INIS)

Nie, Yulun; Hu, Chun; Kong, Chuipeng

2012-01-01

Highlights: ► Al modified hydroxyapatite possessed a higher defluoridation capacity of 32.57 mg/g. ► Hydroxyl groups on the surface of Al-HAP was the adsorption sites for F − removal. ► Enhanced F − removal over Al-HAP was attributed to the modification with aluminum. - Abstract: Aluminum-modified hydroxyapatite (Al-HAP) was prepared and characterized using XRD and BET analyses. Al-HAP possessed higher defluoridation capacity (DC) of 32.57 mgF − /g than unmodified hydroxyapatite (HAP) which showed a DC of 16.38 mgF − /g. The effect of Al/Ca atomic ratio in Al-HAP, solution pH and co-existing anions was further studied. The results indicated that the adsorption data could be well described by the Langmuir isotherm model and the adsorption kinetic followed the pseudo-second-order model. The pH changes during the adsorption process suggested that the -OH on the surface of Al-HAP was the adsorption sites. The more adsorption sites were formed on Al modified HAP, which possessed abundant surface hydroxyl groups, resulting in higher efficiency of F − removal. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated in order to understand the nature of adsorption process. The results revealed that the adsorption reaction was a spontaneous and endothermic process.

Surface-water interface induces conformational changes critical for protein adsorption: Implications for monolayer formation of EAS hydrophobin

Directory of Open Access Journals (Sweden)

Kamron eLey

2015-11-01

Full Text Available The class I hydrophobin EAS is part of a family of small, amphiphilic fungal proteins best known for their ability to self-assemble into stable monolayers that modify the hydrophobicity of a surface to facilitate further microbial growth. These proteins have attracted increasing attention for industrial and biomedical applications, with the aim of designing surfaces that have the potential to maintain their clean state by resisting non-specific protein binding. To gain a better understanding of this process, we have employed all-atom molecular dynamics to study initial stages of the spontaneous adsorption of monomeric EAS hydrophobin on fully hydroxylated silica, a commonly used industrial and biomedical substrate. Particular interest has been paid to the Cys3-Cys4 loop, which has been shown to exhibit disruptive behavior in solution, and the Cys7-Cys8 loop, which is believed to be involved in the aggregation of EAS hydrophobin at interfaces. Specific and water mediated interactions with the surface were also analyzed. We have identified two possible binding motifs, one which allows unfolding of the Cys7-Cys8 loop due to the surfactant-like behavior of the Cys3-Cys4 loop, and another which has limited unfolding due to the Cys3-Cys4 loop remaining disordered in solution. We have also identified intermittent interactions with water which mediate the protein adsorption to the surface, as well as longer lasting interactions which control the diffusion of water around the adsorption site. These results have shown that EAS behaves in a similar way at the air-water and surface-water interfaces, and have also highlighted the need for hydrophilic ligand functionalization of the silica surface in order to prevent the adsorption of EAS hydrophobin.

Dynamic surface tension and adsorption mechanism of surfactin biosurfactant at the air-water interface.

Science.gov (United States)

Onaizi, Sagheer A

2018-03-01

The dynamic adsorption of the anionic biosurfactant, surfactin, at the air-water interface has been investigated in this work and compared to those of two synthetic surfactants: the anionic sodium dodecylbenzenesulfonate (SDBS) and the nonionic octaethylene glycol monotetradecyl ether (C 14 E 8 ). The results revealed that surfactin adsorption at the air-water interface is purely controlled by diffusion mechanism at the initial stage of the adsorption process (i.e., [Formula: see text]), but shifts towards a mixed diffusion-barrier mechanism when surface tension approaches equilibrium (i.e., [Formula: see text]) due to the development of an energy barrier for adsorption. Such energy barrier has been found to be a function of the surfactin bulk concentration (increases with increasing surfactin concentration) and it is estimated to be in the range of 1.8-9.5 kJ/mol. Interestingly, such a trend (pure diffusion-controlled mechanism at [Formula: see text] and mixed diffusion-barrier mechanism at [Formula: see text]) has been also observed for the nonionic C 14 E 8 surfactant. Unlike the pure diffusion-controlled mechanism of the initial surfactin adsorption, which was the case in the presence and the absence of the sodium ion (Na + ), SDBS showed a mixed diffusion-barrier controlled at both short and long time, with an energy barrier of 3.0-9.0 and 3.8-18.0 kJ/mol, respectively. Such finding highlights the nonionic-like adsorption mechanism of surfactin despite its negative charge.

Enhancing phosphate adsorption capacity of SDS-based magnetite by surface modification of citric acid

International Nuclear Information System (INIS)

Yu, Zhigang; Zhang, Chang; Zheng, Zuhong; Hu, Liang; Li, Xuemei; Yang, Zhongzhu; Ma, Chi; Zeng, Guangming

2017-01-01

Highlights: • Citric acid (CA) was used to modify the surface structures of SDS-based magnetite. • Dosage of CA, pH values, ion strength, isotherms and dynamics were analyzed. • High CA dissolved anionic SDS and Fe n+ but increased the stability of magnetite. • 0.05 and 0.1 M CA-modified iron oxide removed about 100% phosphorus. • Precipitation of phosphate and Fe n+ was the main removal mechanism. - Abstract: In this study, citric acid (CA) was employed as a low-molecule organic acid to influence the adsorption performance of phosphorus by as-obtained magnetite. The factors including initial phosphate concentrations, dosage of citric acid, pH value, ion strength, contact time and temperature were examined in detail. Results indicated that the dissolution of anion sodium dodecyl sulfate (SDS) covering on surface of magnetite, a slight decrease of Fe level and a superior structure of magnetite after CA modification occurred. The pH-dependence of phosphate adsorption was impeded and the surface potential of magnetite positively increased at pH > 5.0 when CA was added. Non-linear regression Langmuir-Freundlich model was fitted well in thermodynamics, and the opposite adsorption process as a function of temperatures with or without CA addition was due to the decrease of active energy and active mobility of phosphate ion. Finally, the declining adsorption efficiency with increasing cycles was observed while phosphate removal was approximately finished and had small change with 0.05 and 0.1 M of CA addition. Those improvements of removal efficiency of phosphorus by modified iron oxide were because of the removal of anionic SDS that increased the surface positive charge, and especially the dissolution of element Fe into solution to form precipitate with phosphorus ions. The enhanced stability of magnetite by CA also promoted the high removal efficiency of phosphorus. These implications of CA on phosphate removal can be extended to the field where phosphate

Enhancing phosphate adsorption capacity of SDS-based magnetite by surface modification of citric acid

Energy Technology Data Exchange (ETDEWEB)

Yu, Zhigang [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Zhang, Chang, E-mail: zhangchang@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Zheng, Zuhong [College of Life Science and Technology, Hubei Engineering University, Xiaogan 432000, Hubei Province (China); Hu, Liang; Li, Xuemei; Yang, Zhongzhu; Ma, Chi; Zeng, Guangming [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China)

2017-05-01

Highlights: • Citric acid (CA) was used to modify the surface structures of SDS-based magnetite. • Dosage of CA, pH values, ion strength, isotherms and dynamics were analyzed. • High CA dissolved anionic SDS and Fe{sup n+} but increased the stability of magnetite. • 0.05 and 0.1 M CA-modified iron oxide removed about 100% phosphorus. • Precipitation of phosphate and Fe {sup n+} was the main removal mechanism. - Abstract: In this study, citric acid (CA) was employed as a low-molecule organic acid to influence the adsorption performance of phosphorus by as-obtained magnetite. The factors including initial phosphate concentrations, dosage of citric acid, pH value, ion strength, contact time and temperature were examined in detail. Results indicated that the dissolution of anion sodium dodecyl sulfate (SDS) covering on surface of magnetite, a slight decrease of Fe level and a superior structure of magnetite after CA modification occurred. The pH-dependence of phosphate adsorption was impeded and the surface potential of magnetite positively increased at pH > 5.0 when CA was added. Non-linear regression Langmuir-Freundlich model was fitted well in thermodynamics, and the opposite adsorption process as a function of temperatures with or without CA addition was due to the decrease of active energy and active mobility of phosphate ion. Finally, the declining adsorption efficiency with increasing cycles was observed while phosphate removal was approximately finished and had small change with 0.05 and 0.1 M of CA addition. Those improvements of removal efficiency of phosphorus by modified iron oxide were because of the removal of anionic SDS that increased the surface positive charge, and especially the dissolution of element Fe into solution to form precipitate with phosphorus ions. The enhanced stability of magnetite by CA also promoted the high removal efficiency of phosphorus. These implications of CA on phosphate removal can be extended to the field where

Influences of H on the Adsorption of a Single Ag Atom on Si(111-7 × 7 Surface

Directory of Open Access Journals (Sweden)

Lin Xiu-Zhu

2009-01-01

Full Text Available Abstract The adsorption of a single Ag atom on both clear Si(111-7 × 7 and 19 hydrogen terminated Si(111-7 × 7 (hereafter referred as 19H-Si(111-7 × 7 surfaces has been investigated using first-principles calculations. The results indicated that the pre-adsorbed H on Si surface altered the surface electronic properties of Si and influenced the adsorption properties of Ag atom on the H terminated Si surface (e.g., adsorption site and bonding properties. Difference charge density data indicated that covalent bond is formed between adsorbed Ag and H atoms on 19H-Si(111-7 × 7 surface, which increases the adsorption energy of Ag atom on Si surface.

Nonlinear optical probe of biopolymer adsorption on colloidal particle surface: poly-L-lysine on polystyrene sulfate microspheres.

Science.gov (United States)

Eckenrode, Heather M; Dai, Hai-Lung

2004-10-12

A nonlinear optical technique--second harmonic generation (SHG)--has been applied to characterize the adsorption of poly-L-lysine on micrometer size polystyrene particles, whose surface is covered with negatively charged sulfonate groups, in aqueous solutions. Adsorption behavior of the biopolymer with two chain lengths (14 and 75 amino acid units; PL14 and PL75) has been examined. Centrifugation experiments were also performed to support the adsorption measurements made using SHG. The adsorption free energies of the two polymers PL75 and PL14 are determined as -16.57 and -14.40 kcal/mol, respectively. The small difference in the adsorption free energies of the two chain lengths, however, leads to dramatic difference in the concentration needed for saturated surface coverage: nearly 50 times higher concentration is needed for the smaller polymer. Under acidic colloidal conditions, polylysine is found to adsorb in a relatively flat conformation on the surface. The surface area that each polylysine molecule occupies is nearly 1 order of magnitude larger than the size of the molecule in its extended form. The low adsorption density is likely a result from Coulombic repulsion between the positive charges on the amino acid units of PL. The measurements demonstrate the utility of SHG as an efficient and sensitive experimental approach for measuring adsorption characteristics of bio/macromolecules on colloidal particles and define surface and colloidal conditions for achieving maximum surface coverage of a widely used biopolymer. Copyright 2004 American Chemical Society

An Analytical Model for Adsorption and Diffusion of Atoms/Ions on Graphene Surface

Directory of Open Access Journals (Sweden)

Yan-Zi Yu

2015-01-01

Full Text Available Theoretical investigations are made on adsorption and diffusion of atoms/ions on graphene surface based on an analytical continuous model. An atom/ion interacts with every carbon atom of graphene through a pairwise potential which can be approximated by the Lennard-Jones (L-J potential. Using the Fourier expansion of the interaction potential, the total interaction energy between the adsorption atom/ion and a monolayer graphene is derived. The energy-distance relationships in the normal and lateral directions for varied atoms/ions, including gold atom (Au, platinum atom (Pt, manganese ion (Mn2+, sodium ion (Na1+, and lithium-ion (Li1+, on monolayer graphene surface are analyzed. The equilibrium position and binding energy of the atoms/ions at three particular adsorption sites (hollow, bridge, and top are calculated, and the adsorption stability is discussed. The results show that H-site is the most stable adsorption site, which is in agreement with the results of other literatures. What is more, the periodic interaction energy and interaction forces of lithium-ion diffusing along specific paths on graphene surface are also obtained and analyzed. The minimum energy barrier for diffusion is calculated. The possible applications of present study include drug delivery system (DDS, atomic scale friction, rechargeable lithium-ion graphene battery, and energy storage in carbon materials.

Adsorption of ethyl xanthate on ZnS(110) surface in the presence of water molecules: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Long, Xianhao [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Chen, Jianhua, E-mail: jhchen@gxu.edu.cn [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Guangxi Colleges and University Key Laboratory of Minerals Engineering, 530004 (China); Chen, Ye, E-mail: fby18@126.com [College of Resources and Metallurgy, Guangxi University, Nanning 530004 (China)

2016-05-01

Graphical abstract: - Highlights: • Adsorption of water molecules decreases the reactivity of surface Zn atom. • Copper impurities decrease the band gap of ZnS surface. • Copper impurities enhance the adsorption of xanthate on the ZnS surface. • Water molecules have little influence on the properties of Cu-substituted ZnS surface. • The xanthate S atom can interact with the surface S atom of Cu-substituted ZnS surface. - Abstracts: The interaction of collector with the mineral surface plays a very important role in the froth flotation of sphalerite. The adsorptions occurred at the interface between the mineral surface and waters; however most of DFT simulations are performed in vacuum, without consideration of water effect. Semiconductor surface has an obvious proximity effect, which will greatly influence the surface reactivity. To understand the mechanism of xanthate interacting with sphalerite surface in the presence of water molecules, the ethyl xanthate molecule adsorption on un-activated and Cu-activated ZnS(110) surface in the absence and presence of water molecules were performed using the density functional theory (DFT) method. The calculated results show that the adsorption of water molecules dramatically changes the properties of ZnS surface, resulting in decreasing the reactivity of surface Zn atoms with xanthate. Copper activation of ZnS surface changes the surface properties, leading to the totally different adsorption behaviors of xanthate. The presence of waters has little influence on the properties of Cu-activated ZnS surface. The xanthate S atom can interact with the surface S atom of Cu-substituted ZnS surface, which would result in the formation of dixanthogen.

Adsorption of branched and dendritic polymers onto flat surfaces: A Monte Carlo study

International Nuclear Information System (INIS)

Sommer, J.-U.; Kłos, J. S.; Mironova, O. N.

2013-01-01

Using Monte Carlo simulations based on the bond fluctuation model we study the adsorption of starburst dendrimers with flexible spacers onto a flat surface. The calculations are performed for various generation number G and spacer length S in a wide range of the reduced temperature τ as the measure of the interaction strength between the monomers and the surface. Our simulations indicate a two-step adsorption scenario. Below the critical point of adsorption, τ c , a weakly adsorbed state of the dendrimer is found. Here, the dendrimer retains its shape but sticks to the surface by adsorbed spacers. By lowering the temperature below a spacer-length dependent value, τ*(S) c , a step-like transition into a strongly adsorbed state takes place. In the flatly adsorbed state the shape of the dendrimer is well described by a mean field model of a dendrimer in two dimensions. We also performed simulations of star-polymers which display a simple crossover-behavior in full analogy to linear chains. By analyzing the order parameter of the adsorption transition, we determine the critical point of adsorption of the dendrimers which is located close to the critical point of adsorption for star-polymers. While the order parameter for the adsorbed spacers displays a critical crossover scaling, the overall order parameter, which combines both critical and discontinuous transition effects, does not display simple scaling. The step-like transition from the weak into the strong adsorbed regime is confirmed by analyzing the shape-anisotropy of the dendrimers. We present a mean-field model based on the concept of spacer adsorption which predicts a discontinuous transition of dendrimers due to an excluded volume barrier. The latter results from an increased density of the dendrimer in the flatly adsorbed state which has to be overcome before this state is thermodynamically stable

Adsorption of branched and dendritic polymers onto flat surfaces: A Monte Carlo study

Energy Technology Data Exchange (ETDEWEB)

Sommer, J.-U. [Leibniz Institute of Polymer Research Dresden e. V., 01069 Dresden (Germany); Institute for Theoretical Physics, Technische Universität Dresden, 01069 Dresden (Germany); Kłos, J. S. [Leibniz Institute of Polymer Research Dresden e. V., 01069 Dresden (Germany); Faculty of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Mironova, O. N. [Leibniz Institute of Polymer Research Dresden e. V., 01069 Dresden (Germany)

2013-12-28

Using Monte Carlo simulations based on the bond fluctuation model we study the adsorption of starburst dendrimers with flexible spacers onto a flat surface. The calculations are performed for various generation number G and spacer length S in a wide range of the reduced temperature τ as the measure of the interaction strength between the monomers and the surface. Our simulations indicate a two-step adsorption scenario. Below the critical point of adsorption, τ{sub c}, a weakly adsorbed state of the dendrimer is found. Here, the dendrimer retains its shape but sticks to the surface by adsorbed spacers. By lowering the temperature below a spacer-length dependent value, τ*(S) < τ{sub c}, a step-like transition into a strongly adsorbed state takes place. In the flatly adsorbed state the shape of the dendrimer is well described by a mean field model of a dendrimer in two dimensions. We also performed simulations of star-polymers which display a simple crossover-behavior in full analogy to linear chains. By analyzing the order parameter of the adsorption transition, we determine the critical point of adsorption of the dendrimers which is located close to the critical point of adsorption for star-polymers. While the order parameter for the adsorbed spacers displays a critical crossover scaling, the overall order parameter, which combines both critical and discontinuous transition effects, does not display simple scaling. The step-like transition from the weak into the strong adsorbed regime is confirmed by analyzing the shape-anisotropy of the dendrimers. We present a mean-field model based on the concept of spacer adsorption which predicts a discontinuous transition of dendrimers due to an excluded volume barrier. The latter results from an increased density of the dendrimer in the flatly adsorbed state which has to be overcome before this state is thermodynamically stable.

Certain patterns of IgG adsorption by polystyrene bead surfaces

Energy Technology Data Exchange (ETDEWEB)

Mamedov, M K

1985-01-01

The article reports on tests of domestic Soviet polystyrene beads that permit a simplified modification of the enzyme-adsorption method to identify the alpha hepatitis virus and its antibody in nonspecialized, general laboratories. Only patterns of Ig immunoglobulin adsorption were studied. Human IgG was conjugated with the radioactive isotope /sup 125/I by a chloramine method, with mean radioactivity and protein concentration measured frequently. Bovine serum albumin (BSA) and an anionic detergent Tween-20, and a phosphate-salt buffer with pH 5.8-8.2, were used to produce m-Ig and Ig. Adsorption involved incubation of the beads in various solutions, followed by measurement of their radioactivity. Results of several series of tests were subjected to Student-Fisher evaluation. This suggested that the presence of albumin in physiological concentrations in the solution had no important impact on m-Ig adsorption on the bead surface, which effectively adsorbed Ig from solutions without additional proteins, but also from Ig solutions containing serum albumin in physiological concentrations. Thus, it was possible to coat the beads with alpha Ig hepatitis virus. The Tween-20 weak detergent was effective for eliminating unwanted protein adsorption. 9 references, 3 figures.

CO-induced Pd segregation and the effect of subsurface Pd on CO adsorption on CuPd surfaces

International Nuclear Information System (INIS)

Padama, A A B; Villaos, R A B; Albia, J R; Diño, W A; Nakanishi, H; Kasai, H

2017-01-01

We report results of our study on the adsorption of CO on CuPd surfaces with bulk stoichiometric and nonstoichiometric layers using density functional theory (DFT). We found that the presence of Pd atoms in the subsurface layer promotes the adsorption of CO. We also observed CO-induced Pd segregation on the CuPd surface and we attribute this to the strong CO–Pd interaction. Lastly, we showed that the adsorption of CO promotes Pd–Pd interaction as compared to the pristine surface which promotes strong Cu–Pd interaction. These results indicate that CO adsorption on CuPd surfaces can be tuned by taking advantage of the CO-induced segregation and by considering the role of subsurface Pd atoms. (paper)

Spectroscopic link between adsorption site occupation and local surface chemical reactivity

DEFF Research Database (Denmark)

Baraldi, A.; Lizzit, S.; Comelli, G.

2004-01-01

rules, from which adsorption sites are directly determined. Theoretical calculations rationalize the results for transition metal surfaces in terms of the energy shift of the d-band center of mass and this proves that adsorbate-induced SCL shifts provide a spectroscopic measure of local surface...

Analysis of adsorption behavior of cations onto quartz surface by electrical double-layer model

International Nuclear Information System (INIS)

Kitamura, Akira; Yamamoto, Tadashi; Fujiwara, Kenso; Nishikawa, Sataro; Moriyama, Hirotake

1999-01-01

In a study of the adsorption behavior of cations onto quartz, the distribution coefficient of a variety of cations was determined using the batch method, and using the titration method, the surface charge densities of quartz in a number of electrolyte solutions. The two values thus determined were analyzed applying the electrical double-layer model, from which optimum parameter values were derived for double-layer electrostatics and intrinsic adsorption equilibrium constants. Based on these parameter values, the mechanism of cation adsorption is discussed: A key factor governing this mechanism proved to be the hydration behavior of cations. Consideration of the Coulomb interaction between the adsorbate ions and adsorbent surface led to the finding of a simple rule governing in common the adsorption equilibrium constants of different metal ions. (author)

Modeling adsorption: Investigating adsorbate and adsorbent properties

Science.gov (United States)

Webster, Charles Edwin

1999-12-01

Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

Enhanced Hydrophilicity and Protein Adsorption of Titanium Surface by Sodium Bicarbonate Solution

Directory of Open Access Journals (Sweden)

Shengnan Jia

2015-01-01

Full Text Available The aim of this study was to investigate a novel and convenient method of chemical treatment to modify the hydrophilicity of titanium surfaces. Sand-blasted and acid-etched (SLA titanium surfaces and machined titanium surfaces were treated with sodium bicarbonate (NaHCO3 solution. The wetting behavior of both kinds of surfaces was measured by water contact angle (WCA test. The surface microstructure was assessed with scanning electron microscopy (SEM and three-dimensional (3D optical microscopy. The elemental compositions of the surfaces were analyzed by X-ray photoelectron spectroscopy (XPS. The protein adsorption analysis was performed with fibronectin. Results showed that, after 1 M NaHCO3 treatment, the hydrophilicity of both SLA and machined surfaces was enhanced. No significant microstructural change presented on titanium surfaces after NaHCO3 treatment. The deprotonation and ion exchange activities might cause the enhanced hydrophilicity of titanium surfaces. The increased protein adsorption of NaHCO3-treated SLA surfaces might indicate their improved tissue-integration in clinical use.

Adsorption and diffusion of fluorine on Cr-doped Ni(111) surface: Fluorine-induced initial corrosion of non-passivated Ni-based alloy

Energy Technology Data Exchange (ETDEWEB)

Ren, Cui-Lan, E-mail: rencuilan@sinap.ac.cn [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Key Laboratory of Interfacial Physics and Technology, Chinese Academy of Sciences, Shanghai 201800 (China); Han, Han [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Gong, Wen-Bin [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Shanghai 215123 (China); Wang, Cheng-Bin; Zhang, Wei [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Key Laboratory of Interfacial Physics and Technology, Chinese Academy of Sciences, Shanghai 201800 (China); Cheng, Cheng [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Huai, Ping, E-mail: huaiping@sinap.ac.cn [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Zhu, Zhi-Yuan [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Key Laboratory of Interfacial Physics and Technology, Chinese Academy of Sciences, Shanghai 201800 (China)

2016-09-15

Adsorption and diffusion behaviors of fluorine on Cr-doped Ni(111) surface are investigated by using first-principles simulation. It shows that the Cr in the Cr-doped Ni(111) surface serve a trap site for fluorine with adsorption energy 3.52 eV, which is 1.04 eV higher than that on Ni(111) surface. Moreover, the Cr atom is pulled out the surface for 0.41 Å after the fluorine adsorption, much higher than that on Ni(111) surface. Further diffusion behaviors analysis confirms the conclusion because the fluorine diffusion from neighbored sites onto the Cr top site is an energy barrierless process. Detailed electronic structure analysis shows that a deeper hybrid state of F 2 p-Cr 3 d indicates a strong F−Cr interaction. The Ni−Cr bond is elongated and weakened due to the new formed F−Cr bonding. Our results help to understanding the basic fluorine-induced initial corrosion mechanism for Ni-based alloy in molten salt environment.

Sorption processes affecting arsenic solubility in oxidized surface sediments from Tulare Lake Bed, California

Science.gov (United States)

Gao, S.; Goldberg, S.; Herbel, M.J.; Chalmers, A.T.; Fujii, R.; Tanji, K.K.

2006-01-01

Elevated concentrations of arsenic (As) in shallow groundwater in Tulare Basin pose an environmental risk because of the carcinogenic properties of As and the potential for its migration to deep aquifers that could serve as a future drinking water source. Adsorption and desorption are hypothesized to be the major processes controlling As solubility in oxidized surface sediments where arsenate [As(V)] is dominant. This study examined the relationship between sorption processes and arsenic solubility in shallow sediments from the dry Tulare Lake bed by determining sorption isotherms, pH effect on solubility, and desorption-readsorption behavior (hysteresis), and by using a surface complexation model to describe sorption. The sediments showed a high capacity to adsorb As(V). Estimates of the maximum adsorption capacity were 92 mg As kg- 1 at pH 7.5 and 70 mg As kg- 1 at pH 8.5 obtained using the Langmuir adsorption isotherm. Soluble arsenic [> 97% As(V)] did not increase dramatically until above pH 10. In the native pH range (7.5-8.5), soluble As concentrations were close to the lowest, indicating that As was strongly retained on the sediment. A surface complexation model, the constant capacitance model, was able to provide a simultaneous fit to both adsorption isotherms (pH 7.5 and 8.5) and the adsorption envelope (pH effect on soluble As), although the data ranges are one order of magnitude different. A hysteresis phenomenon between As adsorbed on the sediment and As in solution phase was observed in the desorption-readsorption processes and differs from conventional hysteresis observed in adsorption-desorption processes. The cause is most likely due to modification of adsorbent surfaces in sediment samples upon extensive extractions (or desorption). The significance of the hysteresis phenomenon in affecting As solubility and mobility may be better understood by further microscopic studies of As interaction mechanisms with sediments subjected to extensive leaching

Removal of fluoride from aqueous solution by adsorption on hydroxyapatite (HAp using response surface methodology

Directory of Open Access Journals (Sweden)

M. Mourabet

2015-11-01

Full Text Available A study on the adsorption of fluoride onto hydroxyapatite was conducted and the process parameters were optimized using Response Surface Methodology (RSM. Hydroxyapatite has been characterized by using different physicochemical methods. In order to determine the effects of process parameters namely temperature (20–40 °C, initial solution pH (4–11, adsorbent dose (0.1–0.3 g and initial fluoride concentration (10–20 mg L−1 on fluoride uptake from aqueous solution, a three-level, four-factor, Box–Behnken design has been employed. The second order mathematical model was developed by regression analysis of the experimental data obtained from 29 batch runs. The optimum pH, temperature, adsorbent dose and initial concentration were found by desirability function to be 4.16, 39.02 °C, 0.28 g and 20 mg L−1, respectively. Fluoride removal was 86.34% at the optimum combination of process parameters. Dynamic adsorption data were applied to pseudo-first-order and pseudo-second-order rate equations. The time data fitted well to pseudo second order kinetic model. According to the correlation coefficients, the adsorption of fluoride on the hydroxyapatite was correlated well with the Langmuir and Freundlich models.

Adsorption of small NaCl clusters on surfaces of silicon nanostructures

International Nuclear Information System (INIS)

Amsler, Maximilian; Alireza Ghasemi, S; Goedecker, Stefan; Neelov, Alexey; Genovese, Luigi

2009-01-01

We have studied possible adsorption geometries of neutral NaCl clusters on the disordered surface of a large silicon model tip used in non-contact atomic force microscopy. The minima hopping method was used to determine low energy model tip configurations as well as ground state geometries of isolated NaCl clusters. The combined system was treated with density functional theory. Alkali halides have proven to be strong structure seekers and tend to form highly stable ground state configurations whenever possible. The favored adsorption geometry for four Na and four Cl atoms was found to be an adsorption of four NaCl dimers due to the formation of Cl-Si bonds. However, for larger NaCl clusters, the increasing energy required to dissociate the cluster into NaCl dimers suggests that adsorption of whole clusters in their isolated ground state configuration is preferred.

Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

International Nuclear Information System (INIS)

Yuan, Huihui; Qian, Bin; Zhang, Wei; Lan, Minbo

2016-01-01

Highlights: • Antifouling PVP brushes were successfully grafted on PU films by SI-ATRP. • The effect of polymerization time on surface property and topography was studied. • Hydrophilicity and protein fouling resistance of PVP–PU films were greatly promoted. • Competitive adsorption of three proteins on PVP–PU films was evaluated. - Abstract: An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU–PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU–PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU–PVP (6.0 h) film reduced greatly to 0.08 μg/cm"2, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Yuan, Huihui; Qian, Bin; Zhang, Wei [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); Lan, Minbo, E-mail: minbolan@ecust.edu.cn [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai 200237 (China)

2016-02-15

Highlights: • Antifouling PVP brushes were successfully grafted on PU films by SI-ATRP. • The effect of polymerization time on surface property and topography was studied. • Hydrophilicity and protein fouling resistance of PVP–PU films were greatly promoted. • Competitive adsorption of three proteins on PVP–PU films was evaluated. - Abstract: An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU–PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU–PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU–PVP (6.0 h) film reduced greatly to 0.08 μg/cm{sup 2}, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

Factors Influencing NO2 Adsorption/Reduction on Microporous Activated Carbon: Porosity vs. Surface Chemistry

Directory of Open Access Journals (Sweden)

Imen Ghouma

2018-04-01

Full Text Available The textural properties and surface chemistry of different activated carbons, prepared by the chemical activation of olive stones, have been investigated in order to gain insight on the NO2 adsorption mechanism. The parent chemical activated carbon was prepared by the impregnation of olive stones in phosphoric acid followed by thermal carbonization. Then, the textural properties and surface chemistry were modified by chemical treatments including nitric acid, sodium hydroxide and/or a thermal treatment at 900 °C. The main properties of the parent and modified activated carbons were analyzed by N2-adsorption, scanning electron microscopy (SEM, and Fourier transform infrared spectroscopy (FTIR techniques, in order to enlighten the modifications issued from the chemical and thermal treatments. The NO2 adsorption capacities of the different activated carbons were measured in fixed bed experiments under 500 ppmv NO2 concentrations at room temperature. Temperature programmed desorption (TPD was applied after adsorption tests in order to quantify the amount of the physisorbed and chemisorbed NO2. The obtained results showed that the development of microporosity, the presence of oxygen-free sites, and the presence of basic surface groups are key factors for the efficient adsorption of NO2.

Water Adsorption on Clean and Defective Anatase TiO2 (001) Nanotube Surfaces: A Surface Science Approach.

Science.gov (United States)

Kenmoe, Stephane; Lisovski, Oleg; Piskunov, Sergei; Bocharov, Dmitry; Zhukovskii, Yuri F; Spohr, Eckhard

2018-04-11

We use ab initio molecular dynamics simulations to study the adsorption of thin water films with 1 and 2 ML coverage on anatase TiO 2 (001) nanotubes. The nanotubes are modeled as 2D slabs, which consist of partially constrained and partially relaxed structural motifs from nanotubes. The effect of anion doping on the adsorption is investigated by substituting O atoms with N and S impurities on the nanotube slab surface. Due to strain-induced curvature effects, water adsorbs molecularly on defect-free surfaces via weak bonds on Ti sites and H bonds to surface oxygens. While the introduction of an S atom weakens the interaction of the surface with water, which adsorbs molecularly, the presence of an N impurity renders the surface more reactive to water, with a proton transfer from the water film and the formation of an NH group at the N site. At 2 ML coverage, a further surface-assisted proton transfer takes place in the water film, resulting in the formation of an OH - group and an NH 2 + cationic site on the surface.

What is the time scale of random sequential adsorption?

OpenAIRE

Erban, Radek; Chapman, S. Jonathan

2006-01-01

A simple multiscale approach to the diffusion-driven adsorption from a solution to a solid surface is presented. The model combines two important features of the adsorption process: (i) the kinetics of the chemical reaction between adsorbing molecules and the surface; and (ii) geometrical constraints on the surface made by molecules which are already adsorbed. The process (i) is modelled in a diffusion-driven context, i.e. the conditional probability of adsorbing a molecule provided that the ...

Theoretical study of ZnO adsorption and bonding on Al2O3 (0001) surface

Institute of Scientific and Technical Information of China (English)

LI Yanrong; YANG Chun; XUE Weidong; LI Jinshan; LIU Yonghua

2004-01-01

ZnO adsorption on sapphire (0001) surface is theoretically calculated by using a plane wave ultrasoft pseudo-potential method based on ab initio molecular dynamics. The results reveal that the surface relaxation in the first layer Al-O is reduced, even eliminated after the surface adsorption of ZnO, and the chemical bonding energy is 434.3(±38.6) kJ·mol-1. The chemical bond of ZnO (0.185 ± 0.01 nm) has a 30° angle away from the adjacent Al-O bond, and the stable chemical adsorption position of the Zn is deflected from the surface O-hexagonal symmetry with an angle of about 30°. The analysis of the atomic populations, density of state and bonding electronic density before and after the adsorption indicates that the chemical bond formed by the O2- of the ZnO and the surface Al3+ has a strong ionic bonding characteristic, while the chemical bond formed by the Zn2+ and the surface O2- has an obvious covalent characteristic, which comes mainly from the hybridization of the Zn 4s and the O 2p and partially from that of the Zn 3d and the O 2p.

Improvement of gas-adsorption performances of Ag-functionalized monolayer MoS2 surfaces: A first-principles study

Science.gov (United States)

Song, Jian; Lou, Huan

2018-05-01

Investigations of the adsorptions of representative gases (NO2, NH3, H2S, SO2, CO, and HCHO) on different Ag-functionalized monolayer MoS2 surfaces were performed by first principles methods. The adsorption configurations, adsorption energies, electronic structure properties, and charge transfer were calculated, and the results show that the adsorption activities to gases of monolayer MoS2 are dramatically enhanced by the Ag-modification. The Ag-modified perfect MoS2 (Ag-P) and MoS2 with S-vacancy (Ag-Vs) substrates exhibit a more superior adsorption activity to NO2 than other gases, which is consistent with the experimental reports. The charge transfer processes of different molecules adsorbed on different surfaces exhibit various characteristics, with potential benefits to gas selectivity. For instance, the NO2 and SO2 obtain more electrons from both Ag-P and Ag-Vs substrates but the NH3 and H2S donate more electrons to materials than others. In addition, the CO and HCHO possess totally opposite charge transfer directs on both substrates, respectively. The BS and PDOS calculations show that semiconductor types of gas/Ag-MoS2 systems are more determined by the metal-functionalization of material, and the directs and numbers of charge transfer process between gases and adsorbents can cause the increase or decline of material resistance theoretically, which is helpful to gas detection and distinction. The further analysis indicates suitable co-operation between the gain-lost electron ability of gas and metallicity of featuring metal might adjust the resistivity of complex and contribute to new thought for metal-functionalization. Our works provide new valuable ideas and theoretical foundation for the potential improvement of MoS2-based gas sensor performances, such as sensitivity and selectivity.

Adsorption of fluids on solid surfaces: A route toward very dense layers

Energy Technology Data Exchange (ETDEWEB)

Sartarelli, S.A. [Instituto de Desarrollo Humano, Universidad Nacional de General Sarmiento, San Miguel (Argentina); Szybisz, L., E-mail: szybisz@tandar.cnea.gov.ar [Laboratorio TANDAR, Departamento de Fisica, Comision Nacional de Energia Atomica, RA-1429 Buenos Aires (Argentina); Departamento de Fiica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas, RA-1033 Buenos Aires (Argentina)

2012-08-15

Adsorption of Xe on single planar walls is investigated in the frame of a density functional theory. The strength of the adsorbate-substrate attraction is changed by considering surfaces of Cs, Na, Li, and Mg. The behavior is analyzed by varying the temperature T (between the triple point T{sub t} and the critical T{sub c}) and the coverage {Gamma}{sub Script-Small-L }. The obtained adsorption isotherms exhibit a variety of wetting situations. Density profiles are reported. It is shown that for strongly attractive surfaces the adsorbed liquid becomes very dense reaching densities characteristic of solids.

Multilayer Choline Phosphate Molecule Modified Surface with Enhanced Cell Adhesion but Resistance to Protein Adsorption.

Science.gov (United States)

Chen, Xingyu; Yang, Ming; Liu, Botao; Li, Zhiqiang; Tan, Hong; Li, Jianshu

2017-08-22

Choline phosphate (CP), which is a new zwitterionic molecule, and has the reverse order of phosphate choline (PC) and could bind to the cell membrane though the unique CP-PC interaction. Here we modified a glass surface with multilayer CP molecules using surface-initiated atom-transfer radical polymerization (SI-ATRP) and the ring-opening method. Polymeric brushes of (dimethylamino)ethyl methacrylate (DMAEMA) were synthesized by SI-ATRP from the glass surface. Then the grafted PDMAEMA brushes were used to introduce CP groups to fabricate the multilayer CP molecule modified surface. The protein adsorption experiment and cell culture test were used to evaluate the biocompatibility of the modified surfaces by using human umbilical veinendothelial cells (HUVECs). The protein adsorption results demonstrated that the multilayer CP molecule decorated surface could prevent the adsorption of fibrinogen and serum protein. The adhesion and proliferation of cells were improved significantly on the multilayer CP molecule modified surface. Therefore, the biocompatibility of the material surface could be improved by the modified multilayer CP molecule, which exhibits great potential for biomedical applications, e.g., scaffolds in tissue engineering.

A computational study on the adsorption configurations and reactions of SiHx(x = 1-4) on clean and H-covered Si(100) surfaces

Science.gov (United States)

Le, Thong N.-M.; Raghunath, P.; Huynh, Lam K.; Lin, M. C.

2016-11-01

Possible adsorption configurations of H and SiHx (x = 1 - 4) on clean and H-covered Si(100) surfaces are determined by using spin-polarized DFT calculations. The results show that, on the clean surface, the gas-phase hydrogen atom and SiH3 radicals effectively adsorb on the top sites, while SiH and SiH2 prefer the bridge sites of the first layer. Another possibility for SiH is to reside on the hollow sites with a triple-bond configuration. For a partially H-coverd Si(100) surface, the mechanism is similar but with higher adsorption energies in most cases. This suggests that the surface species become more stable in the presence of surface hydrogens. The minimum energy paths for the adsorption/migration and reactions of H/SiHx species on the surfaces are explored using the climbing image-nudged elastic band method. The competitive surface processes for Si thin-film formation from SiHx precursors are also predicted. The study reveals that the migration of hydrogen adatom is unimportant with respect to leaving open surface sites because of its high barriers (>29.0 kcal/mol). Alternatively, the abstraction of hydrogen adatoms by H/SiHx radicals is more favorable. Moreover, the removal of hydrogen atoms from adsorbed SiHx, an essential step for forming Si layers, is dominated by abstraction rather than the decomposition processes.

Investigation of fluorine adsorption on nitrogen doped MgAl_2O_4 surface by first-principles

International Nuclear Information System (INIS)

Lv, Xiaojun; Xu, Zhenming; Li, Jie; Chen, Jiangan; Liu, Qingsheng

2016-01-01

Graphical abstract: First-principles calculations indicate that MgAl_2O_4 surface is fluorine-loving, but hydrophobic. N doped MgAl_2O_4 (100) surface structure shows the highest fluorine adsorption performance and fluorine atom is more preferentially adsorbed on the Mg-Al bridge site. The fluorine adsorption intensity follow this order: N doped MgAl_2O_4 (100) > Al_2O_3 (0001) > MgAl_2O_4 (100) > MgO (100). N doped MgAl_2O_4 is a promising candidate for fluorine removal. - Highlights: • MgAl_2O_4 surface is fluorine-loving, not hydrophilic. • Fluorine preferentially adsorbs on the Mg-Al bridge site. • Adsorption intensity follow this order: N doped MgAl_2O_4 > Al_2O_3 > MgAl_2O_4 > MgO. • Excellent adsorption performance attributes to electron compensation of N atom. • Nitrogen doped MgAl_2O_4 is a promising candidate for fluorine removal. - Abstract: The nature of fluorine adsorption on pure and N doped MgAl_2O_4 surface has been investigated by first-principles calculations based on the density functional theory. Calculated results indicate that MgAl_2O_4 surface is fluorine-loving, not hydrophilic. Nitrogen doped MgAl_2O_4 (100) surface shows the highest fluorine adsorption performance and fluorine atom preferentially adsorbs on the Mg-Al bridge site. The fluorine adsorption intensity follow this order: Nitrogen doped MgAl_2O_4 (100) > Al_2O_3 (0001) > MgAl_2O_4 (100) > MgO (100). In-depth PDOS analysis suggested that 2p orbitals of F atom strongly hybridized with 3s- and 3p-orbitals of Al atom contribute to its high adsorption intensity. According to the analysis of Hirshfeld charge, the excellent fluorine adsorption performance of nitrogen doped MgAl_2O_4 attributes to the electron compensation effect of nitrogen atom and strong electrostatic interactions. All these evidences demonstrate a fact nitrogen doped MgAl_2O_4 is a promising candidate for fluorine removal.

Adsorption of small palladium clusters on the relaxed α-Al2O3(0001) surface

DEFF Research Database (Denmark)

Gomes, J.R.B.; Lodziana, Zbiegniew; Illas, F.

2003-01-01

of supported Pd-3 is largely distorted from the gas-phase equilibrium geometry whereas the structure of supported Pd-4 is less distorted and reminiscent of the most stable gas-phase isomer. Consequently, the adhesion energy of Pd-3 on the relaxed alpha-Al2O3(0001) surface is smaller than that of Pd-4...... adsorption on other oxide surfaces, there are no preferred adsorption sites for Pd deposited on the corundum surface....

Co adsorption in kaolinite

International Nuclear Information System (INIS)

Souza, Eliel S.; Silva, Paulo S.C.

2017-01-01

Adsorption of metal ions in clay minerals has been used as an alternative to water and effluents treatment. Kaolinite is a clay mineral that presents low specific surface area and exchange ion capacity. Nevertheless, structural modifications can be achieved by means of acid or thermal activation. In this paper, it was studied the surface area of kaolinite/bentonite, kaolinite/activated carbon mixtures, thermal activated kaolinite and thermal activated kaolinite/activated carbon mixture. The mixture of kaolinite/activated carbon was tested for pH, contact time, interfering ions and initial concentration effects in the cobalt adsorption. Results showed that the optimized parameters are pH 6 and contact time of 30 min. Chromium acted as a competitive ion, zinc does not appear to have affected adsorption while iron seems to have favored it. Langmuir and Freundlich isotherms indicated that the adsorption of Co in the mixture of kaolinite/activated carbon is a spontaneous process. (author)

Co adsorption in kaolinite

Energy Technology Data Exchange (ETDEWEB)

Souza, Eliel S.; Silva, Paulo S.C., E-mail: eliel201019@hotmail.com, E-mail: pscsilva@ipen.br [Instituto de Pesquisas Energética s e Nucleares (IPEN/CNEN-SP), São Paulo, SP (Brazil)

2017-07-01

Adsorption of metal ions in clay minerals has been used as an alternative to water and effluents treatment. Kaolinite is a clay mineral that presents low specific surface area and exchange ion capacity. Nevertheless, structural modifications can be achieved by means of acid or thermal activation. In this paper, it was studied the surface area of kaolinite/bentonite, kaolinite/activated carbon mixtures, thermal activated kaolinite and thermal activated kaolinite/activated carbon mixture. The mixture of kaolinite/activated carbon was tested for pH, contact time, interfering ions and initial concentration effects in the cobalt adsorption. Results showed that the optimized parameters are pH 6 and contact time of 30 min. Chromium acted as a competitive ion, zinc does not appear to have affected adsorption while iron seems to have favored it. Langmuir and Freundlich isotherms indicated that the adsorption of Co in the mixture of kaolinite/activated carbon is a spontaneous process. (author)

The toxicity of plastic nanoparticles to green algae as influenced by surface modification, medium hardness and cellular adsorption

Energy Technology Data Exchange (ETDEWEB)

Nolte, Tom M., E-mail: T.Nolte@science.ru.nl [Department of Environmental Engineering, Technical University of Denmark, Miljøvej, B113, 2800 Kgs. Lyngby (Denmark); Radboud University Nijmegen, Institute for Water and Wetland Research, Department of Environmental Science, P.O. Box 9010, NL-6500 GL, Nijmegen (Netherlands); Hartmann, Nanna B. [Department of Environmental Engineering, Technical University of Denmark, Miljøvej, B113, 2800 Kgs. Lyngby (Denmark); Kleijn, J. Mieke [Physical Chemistry Soft Matter, Wageningen University, Stippeneng 4, NL-6708WE Wageningen (Netherlands); Garnæs, Jørgen [Danish Fundamental Metrology, Matematiktorvet 307, 2800 Kgs. Lyngby (Denmark); Meent, Dik van de [Radboud University Nijmegen, Institute for Water and Wetland Research, Department of Environmental Science, P.O. Box 9010, NL-6500 GL, Nijmegen (Netherlands); National Institute of Public Health and the Environment RIVM, P.O. Box 1, 3720 BA, Bilthoven (Netherlands); Jan Hendriks, A. [Radboud University Nijmegen, Institute for Water and Wetland Research, Department of Environmental Science, P.O. Box 9010, NL-6500 GL, Nijmegen (Netherlands); Baun, Anders [Department of Environmental Engineering, Technical University of Denmark, Miljøvej, B113, 2800 Kgs. Lyngby (Denmark)

2017-02-15

Highlights: • P. subcapitata cultures were exposed to plastic nanoparticles in adsorption assays. • UV/Vis and AFM showed ionic strength and surface chemistry influence adsorption of anionic and neutral nanoplastics. • Growth inhibition of algae is antagonistically influenced by carboxylate-modified polystyrene and calcium. • Physico-chemical characterization and proper dose metrics can be used to predict ecotoxicity. - Abstract: To investigate processes possibly underlying accumulation and ecological effects of plastic nano-particles we have characterized their interaction with the cell wall of green algae. More specifically, we have investigated the influence of particle surface functionality and water hardness (Ca{sup 2+} concentration) on particle adsorption to algae cell walls. Polystyrene nanoparticles with different functional groups (non-functionalized, −COOH and −NH{sub 2}) as well as coated (starch and PEG) gold nanoparticles were applied in these studies. Depletion measurements and atomic force microscopy (AFM) showed that adsorption of neutral and positively charged plastic nanoparticles onto the cell wall of P. subcapitata was stronger than that of negatively charged plastic particles. Results indicated that binding affinity is a function of both inter-particle and particle-cell wall interactions which are in turn influenced by the medium hardness and particle concentration. Physicochemical modelling using DLVO theory was used to interpret the experimental data, using also values for interfacial surface free energies. Our study shows that material properties and medium conditions play a crucial role in the rate and state of nanoparticle bio-adsorption for green algae. The results show that the toxicity of nanoparticles can be better described and assessed by using appropriate dose metrics including material properties, complexation/agglomeration behavior and cellular attachment and adsorption. The applied methodology provides an efficient

The toxicity of plastic nanoparticles to green algae as influenced by surface modification, medium hardness and cellular adsorption

International Nuclear Information System (INIS)

Nolte, Tom M.; Hartmann, Nanna B.; Kleijn, J. Mieke; Garnæs, Jørgen; Meent, Dik van de; Jan Hendriks, A.; Baun, Anders

2017-01-01

Highlights: • P. subcapitata cultures were exposed to plastic nanoparticles in adsorption assays. • UV/Vis and AFM showed ionic strength and surface chemistry influence adsorption of anionic and neutral nanoplastics. • Growth inhibition of algae is antagonistically influenced by carboxylate-modified polystyrene and calcium. • Physico-chemical characterization and proper dose metrics can be used to predict ecotoxicity. - Abstract: To investigate processes possibly underlying accumulation and ecological effects of plastic nano-particles we have characterized their interaction with the cell wall of green algae. More specifically, we have investigated the influence of particle surface functionality and water hardness (Ca"2"+ concentration) on particle adsorption to algae cell walls. Polystyrene nanoparticles with different functional groups (non-functionalized, −COOH and −NH_2) as well as coated (starch and PEG) gold nanoparticles were applied in these studies. Depletion measurements and atomic force microscopy (AFM) showed that adsorption of neutral and positively charged plastic nanoparticles onto the cell wall of P. subcapitata was stronger than that of negatively charged plastic particles. Results indicated that binding affinity is a function of both inter-particle and particle-cell wall interactions which are in turn influenced by the medium hardness and particle concentration. Physicochemical modelling using DLVO theory was used to interpret the experimental data, using also values for interfacial surface free energies. Our study shows that material properties and medium conditions play a crucial role in the rate and state of nanoparticle bio-adsorption for green algae. The results show that the toxicity of nanoparticles can be better described and assessed by using appropriate dose metrics including material properties, complexation/agglomeration behavior and cellular attachment and adsorption. The applied methodology provides an efficient and

CO adsorption and dissociation on Pt(111) and Ni(111) surfaces

DEFF Research Database (Denmark)

Morikawa, Y.; Mortensen, Jens Jørgen; Hammer, Bjørk

1997-01-01

CO adsorption and dissociation processes have been studied using first-principles total energy and force calculations. The adsorption energies, atomic structures and vibrational modes of molecularly chemisorbed states are well reproduced in the present calculations. We have examined several...

Modification process optimization, characterization and adsorption property of granular fir-based activated carbon

Energy Technology Data Exchange (ETDEWEB)

Chen, Congjin, E-mail: gxdxccj@163.com [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University, Nanning 530004 (China); Li, Xin [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Tong, Zhangfa [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University, Nanning 530004 (China); Li, Yue [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Li, Mingfei [Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083 (China)

2014-10-01

Highlights: • Granular fir-based activated carbon (GFAC) was modified with H{sub 2}O{sub 2}. • Orthogonal array design method was used to optimize the modification process. • Optimized parameters were: aqueous H{sub 2}O{sub 2} concentration 1.0 mol l{sup −1}, modification temperature and time 30.0 °C and 4.0 h. • Adsorption capacity of the modified GFAC increased by 500.0% (caramel), 59.7% (methylene blue), 32.5% (phenol), and 15.1% (I{sub 2}). • The pore structure parameters and surface oxygen groups changed in the modified GFAC. - Abstract: Granular fir-based activated carbon (GFAC) was modified with H{sub 2}O{sub 2}, and orthogonal array experimental design method was used to optimize the process. The properties of the original and modified GFAC were characterized by N{sub 2} adsorption–desorption isotherms, Brunauer–Emmett–Teller (BET) equation, Barett–Joyner–Halenda (BJH) equation, field emission scanning electron microscopy (FESEM), and Fourier transform infrared spectroscopy (FT-IR) analysis, etc. When 10.00 g of GFAC with particle size of 0.25–0.85 mm was modified by 150.0 ml of aqueous H{sub 2}O{sub 2} solution, the optimized conditions were found to be as follows: aqueous H{sub 2}O{sub 2} solution concentration 1.0 mol·l{sup −1}, modification temperature 30.0 °C, modification time 4.0 h. Modified under the optimized conditions, decolonization of caramel, methylene blue adsorption, phenol adsorption and iodine number of the modified GFAC increased by 500.0%, 59.7%, 32.5%, and 15.1%, respectively. The original and optimally modified GFAC exhibited adsorption isotherms of hybrid Type I–IV isotherms with H4 hysteresis. BET surface area, micropore area, total pore volume, micropore volume, and microporosity of the modified GFAC increased by 7.33%, 11.25%, 3.89%, 14.23%, 9.91%, respectively. Whereas the average pore width decreased by 3.16%. In addition, the amount of surface oxygen groups (such as carbonyl or carboxyl) increased