Surface Stress Induced By Adatoms Adsorption On Solid Surfaces

Based on the statistical thermodynamics theory, a theoretical model of adsorbate induced surface stress of adatoms adsorption on solid surface is presented. For the low coverage, the interaction between the adsorbed molecules is entirely negligible and the adsorption induced surface stress is found to be the function of the coverage and the adsorption energy change with strain. For the high coverage, the adsorbate-adsorbate interaction contributes to the adsorption-induced surface stress effectively. In the case of carbon adsorption on the Ni(100) surface, the value of 0.5 is obtained as a characteristic coverage to decide whether to take the interaction between the adsorabtes into consideration and the results also show that the adsorption induces a compressive surface stress.

Carbon monoxide adsorption on molybdenum phosphides: Fourier transform infrared spectroscopic and density functional theory studies

Molybdenum phosphide (MoP) and supported molybdenum phosphide (MoP/gamma-Al2O3) have been prepared by the temperature-programmed reduction method. The surface sites of the MoP/gamma-Al2O3 catalyst were characterized by carbon monoxide (CO) adsorption with in situ Fourier transform infrared (FT-IR) spectroscopy. A characteristic IR band at 2037 cm(-1) was observed on the MoP/gamma-Al2O3 that was reduced at 973 K. This band is attributed to linearly adsorbed CO on Mo atoms of the MoP surface and is similar to IR bands at 2040-2060 cm(-1), which correspond to CO that has been adsorbed on some noble metals, such as platinum, palladium, and rhodium. Density functional calculations of the structure of molybdenum phosphides, as well as CO chemisorption on the MoP(001) surface, have also been studied on periodic surface models, using the generalized gradient approximation (GGA) for the exchange-correlation functional. The results show that the chemisorption of CO on MoP occurred mainly on top of molybdenum, because the bonding of CO requires a localized mininum potential energy. The adsorption energy obtained is DeltaH(ads) approximate to -2.18 eV, and the vibrational frequency of CO is 2047 cm-1, which is in good agreement with the IR result of CO chernisorption on MoP/gamma-Al2O3.

Adsorption of His-tagged peptide to Ni, Cu and Au (100) surfaces: Molecular dynamics simulation

Molecular dynamics (MD) simulations are performed to study the interaction of His-tagged peptide with three different metal surfaces in explicit water. The equilibrium properties are analyzed by using pair correlation functions (PCF) to give an insight into the behavior of the peptide adsorption to metal surfaces in water solvent. The intermolecular interactions between peptide residues and the metal surfaces are evaluated. By pulling the peptide away from the peptide in the presence of solvent water, peeling forces are obtained and reveal the binding strength of peptide adsorption on nickel, copper and gold. From the analysis of the dynamics properties of the peptide interaction with the metal surfaces, it is shown that the affinity of peptide to Ni surface is the strongest, while on Cu and An the affinity is a little weaker. In MD simulations including metals, the His-tagged region interacts with the substrate to an extent greater than the other regions. The work presented here reveals various interactions between His-tagged peptide and Ni/Cu/Au surfaces. The interesting affinities and dynamical properties of the peptide are also derived. The results give predictions for the structure of His-tagged peptide adsorbing on three different metal surfaces and show the different affinities between them, which assist the understanding of how peptides behave on metal surfaces and of how designers select amino sequences in molecule devices design. (c) 2007 Elsevier Ltd. All rights reserved.

Adsorption of formaldehyde molecule on the intrinsic and Al-doped graphene: a first principle study

To search for a high sensitivity sensor for formaldehyde (H2CO), We investigated the adsorption of H2CO on the intrinsic and Al-doped graphene sheets using density functional theory (DFT) calculations. Compared with the intrinsic graphene, the Al-doped graphene system has high binding energy value and short connecting distance, which are caused by the chemisorption of H2CO molecule. Furthermore, the density of states (DOS) results show that orbital hybridization could be seen between H2CO and Al-doped graphene sheet, while there is no evidence for hybridization between the H2CO molecule and the intrinsic graphene sheet. Therefore, Al-doped graphene is expected to be a novel chemical sensor for H2CO gas. We hope our calculations are useful for the application of graphene in chemical sensor.

Microfabries of lacustrine sediments to pollutant adsorption from a polluted Eutrophic lake, the Yangtze delta region

Two types of microfabrics relating to pollutant adsorption were studied in the scanning electronic microscope (SEM) in a polluted, eutrophic lake, the Yangtze delta region. Agglutinational texture or the aggregates of small particles are composed of clay minerals and fine organic fragments among the silty grains and the coatings with a thickness about 1 mu m were on the surfaces of the silty grains in the sediments. The chemical constituents of the aggregates and the coatings are K, Na, Ca, Mg, Si, Al, O, Fe, Ti, C, N and P determined in X-ray energy spectrometry connected with the SEM. In some cases, Pb was detected in the aggregates in the top sediment. It is suggested that nutrients and metals are adsorbed to the aggregates, which were formed by electrostatic attraction of physicochemical floes. The coatings on the surface of quartz grains were formed by the interaction of dissociated Al, Si, Fe, etc from silicates with dissolved N, P and C nutrients in interstitial water, which was aroused by human pollution to the lake in recent two decades.

Kinetics of dissociative water adsorption on stepped Si(001), on Si(115), Si(113), Si(5,5,12) and Si(112)

We present photoelectron spectroscopic and low energy electron diffraction measurements of water adsorption on flat Si samples of the orientations (001), (115), (113), (5,5,12) and (112) as well as on curved samples covering continuously the ranges (001)-(117) and (113)-(5,5,12)-(112). On all orientations, water adsorption is dissociative (OH and H) and non-destructive. On Si(001) the sticking coefficient S and the saturation coverage Theta(sat) are largest. On Si(001) and for small miscuts in the [110]-azimuth, S is constant nearly up to saturation which proves that the kinetics involves a weakly bound mobile precursor state. For (001)-vicinals with high miscut angles (9-13 degrees), the step structure breaks down, the precursor mobility is affected and the adsorption kinetics changed. On (115), (113), (5,5,12) and (112), the values of S and Theta(sat) are smaller which indicates that not all sites are able to dissociate and bind water. For (113) the shape of the adsorption curves Theta versus exposure shows the existence of two adsorption processes, one with mobile precursor kinetics and one with Langmuir-like kinetics. On (5,5,12), two processes with mobile precursor kinetics are observed which are ascribed to adsorption on different surface regions within the large surface unit cell. From the corresponding values of S and Theta(sat), data for structure models are deduced. (C) 1997 Elsevier Science B.V.

Hydrogen adsorption induced surface reconstructions on Si(113) studied by LEED

Surface reconstructions on Si(113) induced by dissociated hydrogen adsorption have been studied using low energy electron diffraction (LEED). It has been found that: (1) at 300 K and 80 K temperatures, with the increase of hydrogen coverage on the surface, the (3 x 1) phase transferred continuously into a hydrogen saturated (1 x 1)-2H phase; (2) flashing of the (1 x 1)-2H surface at about 1100 degrees C resulted in a complete new phase of(1 x 3) and further annealing of the sample at 1250 degrees C gave back the starting surface of (3 x 1); (3) saturated hydrogen adsorption at a sample temperature of 700 degrees C resulted in a stable new phase of(1 x 2)-H and further saturation doses of hydrogen at other temperatures below 700 degrees C did not change the (1 x 2) LEED pattern; (4) annealing of the (I x 2)-H surface in the same manner as (2) gave similar results.

Investigations on the adsorption behavior of Neutral Red on mercaptoethane sulfonate protected gold nanoparticles

A detailed investigation on the adsorption behavior of Neutral Red (NR) molecules on mercaptoethane sulfonate-monolayer protected gold clusters (MES-MPCs) has been conducted by the spectroscopic method. It is found that cationic NR molecules are adsorbed on the negatively charged MPCs surfaces via electrostatic attractive forces. The absorption study shows that the optical properties of NR molecules are significantly influenced upon the adsorption. Based on the electrostatic adsorption nature and the excellent stability of MES-MPCs against the electrolytes, this association can be released by the addition of electrolyte salts, which can be monitored by both absorption and fluorescence spectroscopy. In addition, dication Ca2+ is found to be more effective in the release of NR than univalent Na+. Moreover, the MES-MPCs exert energy transfer quenching of NR fluorescence by both static and dynamic quenching. However, static quenching seems to be the dominating quenching mechanism. Furthermore, this energy transfer quenching exhibits strong dependence of Au core size, and 5.0 nm MPCs show stronger ability in quenching the NR fluorescence than that of 2.7 nm MPCs.

INVESTIGATION OF CETYLPYRIDINIUM BROMIDE ADSORPTION AT A GLASSY-CARBON ELECTRODE SURFACE BY SPECTROELECTROCHEMISTRY WITH A LONG OPTICAL-PATH LENGTH THIN-LAYER CELL

The adsorption of cationic surfactant cetylpyridinium bromide (CPB) on a glassy carbon (GC) electrode surface has been studied by spectroelectrochemistry with a long optical path length thin-layer cell (LOPTLC) for the first time. A fine adsorption isotherm of CPB molecules from an aqueous solution containing 0.10 M KBr has been obtained over the range of (1.00-8.00) x 10(-5) M. From theoretical calculation and experimental data, adsorption of CPB on the GC electrode surface shows four distinct orientations and three large orientation transitions. Compared with the ordinary isotherm, the differential isotherm is more characteristic and would be suitable for the study of orientation transitions of organic compounds. With a theoretical treatment of the adsorption isotherm, four orientations of adsorbed CPB on a GC electrode surface coincide with the Frumkin-Langmuir type. From adsorption parameters the Frumkin-Langmuir equations, the adsorption free energy and, therefore, the equilibrium constants of orientation transitions of the CPB molecule can be obtained.

Experimental and theoretical investigation of the adsorption behaviour of new triazole derivatives as inhibitors for mild steel corrosion in acid media

Three triazole derivatives (4-chloro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (CATM), 4-methoxyl-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (MATM) and 4-fluoro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (FATM)) have been synthesized as new inhibitors for the corrosion of mild steel in acid media. The inhibition efficiencies of these inhibitors were evaluated by means of weight loss and electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and polarization curves. Then the surface morphology was studied by scanning electron microscopy (SEM). The adsorption of triazole derivatives is found to obey Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The relationship between molecular structure of these compounds and their inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were computed. (c) 2007 Elsevier Ltd. All rights reserved.

Theoretical study on adsorption of Na+ and Na+(H2O)(n) (n=1-6) on a clean Si(111) surface

To model the adsorption of Na+ in aqueous solution on the semiconductor surface, the interactions of Na+ and Na+(H2O)(n) (n = 1-6) with a clean Si(111) surface were investigated by using hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The Si(111) surface was described with Si8H12, Si16H20, and Si22H21 Cluster models. The effect of the basis set superposition error (BSSE) was taken into account by applying the counterpoise (CP) correction. The calculated results indicated that the interactions between the Na+ cation and the dangling bonds of the Si(111) surface are primarily electrostatic with partial orbital interactions. The magnitude of the binding energies depends weakly on the adsorption sites and the size of the clusters. When water molecules are present, the interaction between the Nal and Si(I 11) surfaces weakens and the binding energy has the tendency to saturate. On a Si22H21 cluster described surface, the optimized Na+-surface distance for Na+(H2O)(5) adsorbed at on-top site is 4.16 angstrom and the CP-corrected binding energy (MP2) is -35.4 kJ/mol, implying a weakly adsorption of hydrated Na+ cation on clean Si(111) surface.

Comparative study by infrared spectroscopy and microcalorimetry of the CO adsorption over supported palladium catalysts

The adsorption of CO on Al(2)O(3), ZrO(2), ZrO(2)-SiO(2), and ZrO(2)-La(2)O(3) supported Pd catalysts was studied by adsorption microcalorimetry and infrared (TR) spectroscopy. Some interesting and new correlations between the results of microcalorimetry and IR spectroscopy have been found. The CO is adsorbed on palladium catalysts in three different modes: multibonded (3-fold), bridged (2-fold), both on Pd(lll) and (100) planes, and linear (1-fold) adsorbed species. The corresponding differential adsorption heats lie in the field of high (210-170 kJ/mol), medium (140-120 kJ/mol), and low (95-60 kJ/mol) values, respectively. The nature of the support, the reduction temperature, and the pretreatment conditions affect the surface structure of the Pd catalysts, resulting in variations in the site energy distribution, i.e., changes in the fraction of sites adsorbing CO with specific heats of adsorption. Moreover, the CeO(2); promoter addition weakens the adsorption strength of CO on palladium. Based on the exposed results, a correctness factor, which considers the percentages of various CO adsorption states, must be introduced when one calculates the Pd dispersion using CO adsorption data.

Prediction of soil adsorption coefficients from retention parameters on three reversed-phase liquid chromatographic columns

Reversed-phase high-performance liquid chromatographic (RP-HPLC) retention parameters, which are determined by the intermolecular interactions in retention process, can be considered as the chemical molecular descriptors in linear free energy relationships (LFERs). On the basis of the characterization and comparison of octadecyl-bonded silica gel (ODS), cyano-bonded silica gel (CN), and phenyl-bonded silica gel (Ph) columns with linear solvation energy relationships (LSERs), a new multiple linear regression model using RP-HPLC retention parameters on ODS and CN columns as variables for estimation of soil adsorption coefficients was developed. It was tested on a set of reference substances from various chemical classes. The results showed that the multicolumn method was more promising than a single-column method was for the estimation of soil adsorption coefficients. The accuracy of the suggested model is identical with that of LSERs.