Thermodynamics of xenon adsorption on Pd(s)[8(100) × (110)]: From steps to multilayers

The thermodynamic properties of the adsorption of xenon on the stepped Pd(s)[8(100)×(110)] surface have been studied over a wide range of pressure (5×10^?11 to 1×10^?4 Torr) and temperature (40–140 K). We have measured adsorption isobars using AES in order to evaluate the surface coverage. By choosing pressure and temperature we have studied under equilibrium conditions, the successive adsorption of xenon on the steps and on the terraces until the first layer is formed, the condensation of the second layer as well as the formation of xenon multilayers. For a small range of pressure and temperature, adsorption takes place only on the atomic steps. The LEED pattern shows that only every other site along the steps is occupied. The extrapolated initial heat of adsorption for steps is E_ad^S = 10.2 kcal/mol, decreasing monotonically by about 2 kcal/mol as the relative coverage of the step sites increases. The dipole moment of the Xe atoms adsorbed on steps is 1.12 D. During adsorption on the terraces the LEED observations suggest that the xenon adlayer is non-localized up to completion of the hexagonally close packed monolayer. The initial heat of adsorption on the terraces, E_ad^T is 8.2 kcal/mol and decreases continuously to a value of 6.9 kcal/mol for a complete monolayer due to lateral repulsive interactions between the adsorbed xenon atoms. The induced dipole moment of Xe on terraces is reduced to 0.49 D. The 5p_{$\text{1}\text{2}$} binding energy of Xe adsorbed on terrace sites is 0.3 eV smaller than that of Xe occuping step sites. The differential molar entropy of the adsorbed layer on the terraces as a function of coverage compares fairly well with the calculated value for an ideally mobile two-dimensional gas. No indication of the growth of two-dimensional xenon islands has been found under these conditions. The isosteric heat of adsorption for the second layer is E_ad^sec = 5.8 kcal/mol independently of the coverage. The condensation of the second layer is a first order two-dimensional gas ? two-dimensional solid phase transition in opposition to the continuous nature of the adsorption of the first layer (extending over a wide range of temperature for a given pressure). The induced dipole moment is further reduced for the Xe second layer to a value of 0.11 D. Finally, the condensation of multilayers proceeds with a latent heat of transformation of E_cond = 3.8 kcal/mol in excellent agreement with the known bulk value for the heat of sublimation of xenon. The line shape of the NVV low energy Auger transitions of xenon or the UPS binding energies of the Xe 5p_{$\text{3}\text{2}$,$\text{1}\text{2}$} spectra allow a clear distinction between first, second and higher layer Xe atoms. We have also established the temperature/pressure conditions for equilibrium between first, second and bulk xenon layers, i.e. a so-called “roughening point”.     

Modelling self-assembling of colloid particles in multilayered structures

Simulations of particle multilayer build-up in the layer by layer (LbL) self-assembling processes have been performed according to the generalized random sequential adsorption (RSA) scheme. The first (precursor) layer having an arbitrary coverage of adsorption centers was generated using the standard RSA scheme pertinent to homogeneous surface. Formation of the consecutive layers (up to 20) was simulated by assuming short-range interaction potentials for two kinds of particles of equal size. Interaction of two particles of different kind resulted in irreversible and localized adsorption upon their contact, whereas particles of the same kind were assumed to interact via the hard potential (no adsorption possible). Using this algorithm theoretical simulations were performed aimed at determining the particle volume fraction as a function of the distance from the interface, as well as the multilayer film roughness and thickness as a function of the number of layers. The simulations revealed that particle concentration distribution in the film was more uniform for low precursor layer density than for higher density, where well-defined layers of closely packed particles appeared. On the other hand, the roughness of the film was the lowest at the highest precursor layer density. It was also predicted theoretically that for low precursor layer density the film thickness increased with the number of layers in a non-linear way. However, for high precursor layer density, the film thickness increased linearly with the number of layers and the average layer thickness was equal to 1.58 of the particle radius, which is close to the closely packed hexagonal layer thickness equal to 1.73. It was concluded by analysing the existing data for colloid particles and polyelectrolytes that the theoretical results can be effectively exploited for interpretation of the LbL processes involving colloid particles and molecular species like polymers or proteins.     

Influence of the metal nanofilm-semiconductor interface on surface properties of the nanofilm: The CO-Yb-Si(111) system

The influence of the “ytterbium nanofilm-single-crystal silicon substrate” interface on properties of the films has been investigated. It has been shown that, if the film thickness is less than 10 monolayers, the Friedel oscillations (standing waves of electron density) generated by the interface affect the work function of the films and the rate of adsorption of CO molecules on their surface. In turn, the CO molecules modify the electronic structure of ytterbium during adsorption on the surface of nanofilms by transforming ytterbium from the divalent to trivalent state. The completely filled layer of adsorbed CO molecules consists of two phases. The first phase is a two-dimensional gas whose molecules weakly interact with each other, but their lone electron pairs form a donor-acceptor bond with the Yb 5d level; as a result, this level is located below the Fermi level and the metal transforms into the trivalent state. After filling the two-dimensional phase, the second (island) phase, in which the CO molecule are bound by horizontal π-bonds, begins to grow. The formation of these bonds becomes possible due to the filling of 2π states in the molecules upon compaction of the adsorbed layer. The considered the adsorbed two-phase layer is responsible for the complete transition of ytterbium into the trivalent state.     

Adsorption thermodynamics of a lattice–gas model with non-additive lateral interactions

In the present paper, we study the adsorption thermodynamics of a lattice–gas model with non-additive interactions between adsorbed particles. We have assumed that the energy which links a certain atom with any of its nearest neighbors strongly depends on the state of occupancy in the first coordination sphere of that adatom. By means of Monte Carlo simulations in the grand canonical ensemble the adsorption isotherms, isothermal susceptibility (or equivalently the mean square density fluctuations of adparticles), and isosteric heat of adsorption were calculated and their striking behavior was analyzed and discussed in terms of the low temperature phases formed in the system.     

Competitive adsorption of polymers on metal nanoparticles

We investigate the effect of system properties and adsorption sequence on competitive adsorption of poly(methyl methacrylate) (PMMA) and polystyrene (PS) on narrowly polydispersed cobalt (Co) nanoparticles (D ∼ 27 nm). The adsorbed layer composition is studied using thermo-gravimetric analysis (TGA). We find that adsorbed layers of PS are completely displaced by PMMA when the solvent is a common good solvent. An adsorbed layer of only PMMA is also obtained through competitive adsorption from a common good solvent. However, in a selective solvent that is poor for PS, sequential adsorption leads to the formation of mixed layers.     

New insights into the adsorption isotherm interpretation by a coupled molecular simulation—experimental procedure

We present here Grand Canonical Monte Carlo (GCMC) simulation results of nitrogen adsorption at 77 K on a crude model of activated carbon. The material is modeled as slit-like pores of different widths, with smooth surfaces. The individual adsorption isotherms serve as the basis to check the success and limitations of the assumptions made when using the BET model to characterize adsorbent materials, in particular to calculate the monolayer capacity and the C parameter. As done in our previous work with several experimental adsorption isotherms, different linearizations of the BET equation are used. The aim of this work is to quantify, using statistical mechanics tools, the changes in the C factor with surface coverage, showing that C is an intrinsically energetic meaningful quantity. The amount of molecules adsorbed at each pressure is calculated in the first and subsequent layers. We also keep track of the adsorbent-adsorbate and adsorbate-adsorbate energy along the simulations. The C factor is obtained following two different routes: as directly derived from the BET equation, once the monolayer capacity is known, and from the heat of adsorption obtained directly from the simulations. Results from simulations confirm the changes in the C values with surface coverage. In addition, molecular simulations provide independent and consistent ways of calculating the monolayer capacity.     

The interaction of oxygen and carbon monoxide with a carbided Ni(111) surface

The thermal decomposition of ethylene on Ni(111) at 250°C is shown to lead to carbon deposition on and - in a later stage - below the surface. Independent of the amount of carbon below the surface, CO is adsorbed with an isosteric heat of adsorption of 105 kJ/mol. The surface carbon reacts with oxygen at 250°C. The reaction rate is independent of the surface carbon coverage and first order in oxygen pressure. The subsurface carbon segregates to the surface after removal of the surface carbon layer.     

沸石类咪唑骨架材料吸附分离天然气的分子模拟

采用巨正则蒙特卡洛方法研究C₂H₆, CO₂和CH₄三种气体在两种沸石类咪唑骨架材料 (ZIF)-ZIF-2和ZIF-71中的吸附与分离性能. 考察了C₂H₆, CO₂和CH₄三种气体在ZIF-2和ZIF-71中的单组分吸附等温线、吸附热; C₂H₆-CH₄, CO₂-CH₄ 与C₂H₆-CO₂等摩尔二元混合物的分离; 以及C₂H₆-CO₂-CH₄三元体系的分离性能. 研究结果表明: 低压下不同气体的吸附量大小与其吸附热关系紧密; 而高压下因有限的孔空间, 尺寸较小的气体分子吸附量增长趋向更快; 多组分吸附分离中, 低压下能量效应通常占据主导, ZIF优先吸附作用力较强的组分; 高压下堆积效应影响显著, ZIF会优先吸附尺寸较小的组分. ZIF-2和ZIF-71对这3种二元体系的分离性能良好. 对于三元混合物吸附分离, 在常温下3000-4000kPa范围内, ZIF-2具有良好的天然气净化性能, 可有效地分离出天然气中的C₂H₆和CO₂. 关键词： 巨正则蒙特卡洛模拟 天然气分离 沸石类咪唑骨架     

The energetics of mercury adsorption on Cu(100)

We have investigated the adsorption of mercury overlayers on Cu(100) by atom beam scattering, low energy electron diffraction and angle resolved photoemission. From our data we have calculated the isosteric heats in the adsorbed Hg layer on Cu(100) and compared these with results obtained for mercury on Fe(100), W(100) and Ni(100). We observe changes in the isosteric heat of adsorption that can be associated with the ordering of a c(2 × 2) Hg overlayer phase and the transition from a c(2 × 2) overlayer to a c(4 × 4) overlayer. The isosteric heat of adsorption is 0.50 ± 0.07 eV/atom (48 ± 7 kJ/mol) at zero coverage and reaches a maximum of 0.73 ± 0.04 eV/atom (70 ± 4 kJ/mol). From a combination of ABS and LEED, the structures of the two equilibrium ordered phases of Hg on Cu(100) have been identified, as well as the structures of several non-equilibrium phases.     

石墨狭缝中甲烷吸附的分子动力学模拟

用分子动力学模拟研究石墨狭缝中甲烷的吸附,考察狭缝宽度和温度对甲烷吸附的影响.模拟发现甲烷在石墨狭缝中出现分层现象,吸附层中甲烷具有类液特征,第一吸附层内甲烷中总有两个氢原子的连线与另外两个氢原子的连线分别位于平行于狭缝壁的两个平面内,游离层中甲烷呈现气体的特征;碳原子间的平均作用势说明吸附层中甲烷分子间结合能力大于游离层,吸附态是甲烷在石墨狭缝中的主要赋存形式之一;伦敦力以及由吸附层净电荷产生的电场力是甲烷吸附和分层的主要原因;甲烷的吸附量随狭缝宽度增大或温度升高而减少,当狭缝宽度小于16.46Å时,甲烷仅以吸附形态存在.甲烷在第一吸附层中的扩散能力最弱、游离层中最强,甲烷扩散系数随狭缝宽度的增大或温度的升高而增大.     

The interaction of D2O with Zr(0001) at 80 K

The adsorption of D₂O on Zr(0001) at 80 K and its subsequent reactions at higher temperatures have been studied by thermal desorption spectroscopy (TDS), work-function measurements (Δф), nuclear reaction analysis (NRA), LEED, infrared reflection spectroscopy (FTIR-RAS), Auger electron spectroscopy (AES), and static secondary ion mass spectroscopy (SSIMS). D₂O adsorption on Zr(0001) at 80 K is accompanied by a Δф of −1.33 eV. The adsorbed D₂O can be characterized into three layers by TDS: a chemisorbed layer (up to 0.23 ML), a second adsorbed layer, and an ice layer. The chemisorbed D₂O dissociates into OD_ad and D_ad at 80 K (possibly also into O_ad) and no desorption products could be detected, implying that the reaction products dissolved into the zirconium at temperatures appropriate for each component. The ice layer and most of the second adsorbed layer desorb as molecular water during heating. The water adsorbed at 80 K did not form any long-range ordered structure, but a (2 × 2) LEED pattern that was formed by heating the sample to temperatures above 430 K is believed due to be an ordered oxygen superstructure.     

Interaction of CO with Cu(111)-Fe

The interaction of CO with a Cu(111) crystal alloyed with different amounts of iron is studied with ellipsometry and AES. Both molecular and dissociative adsorption are observed. The final coverages of oxygen and carbon are equal and such that the sum is the same or larger than the mole fraction of iron in the surface layer. The amount of molecularly adsorbed CO does not increase when a quantity of more than about four monolayers of iron is deposited. This is most probably due to the fact that the iron enrichment of the outer surface layer ceases as well. The isosteric heat of adsorption of CO on the Cu(111)-Fe crystal is 70±15 kJ/mol, independent of coverage and iron content of the surface within experimental error.     

Absolute coverage and isostemc heat of adsorption of deuterium on Pt(111) studied by nuclear microanalysis

The absolute coverage (θ) of deuterium adsorbed on Pt(111) in the ranges 180< T<440 K and 5 × 10^?6 < P < 5 × 10^?2 Pa D₂ has been determined by nuclear microanalysis using the D(³He, p)⁴He reaction. From these data, the isosteric heat of adsorption (E_a) has been determined to be 67 ± 7 kJ mol^?1 at θ ? 0.3. This heat of adsorption yields values of the pre-exponential for desorption (10^?5 to 10^?2 cm² atom^?1 s^?1) that lie much closer to the normal range for a second order process than those determined from previous isosteric heat measurements. The E_a versus θ relationship indicates that the adsorbed D atoms are mobile and that there is a repulsive interaction of 6–8 kJ mol^?1 at nearest neighbour distances. At 300 K the coverage decreases to ? 0.05 monolayer (? 8 × 10¹³ D atoms cm^?2) as P→ 0, apparently invalidating a recent model of site exchange in the adsorbed layer.     

The adsorption of Xe and CO on a Cu (311) single crystal surface

LEED, electron energy loss spectroscopy and surface potential measurements have been used to study the adsorption of Xe and CO on Cu (311). Xe is adsorbed with a heat of 19 ± 2 kJ mol^/t-1. The complete monolayer has a surface potential of 0.58 V and a hexagonal close-packed structure with an interatomic distance of 4.45 ± 0.05 Å. CO gives a positive surface potential increasing with coverage to a maximum of 0.34 V and then falling to 0.22 V at saturation. The heat of adsorption is initially 61 ± 2 kJ mol^?1, falling as the surface potential maximum is approached to about 45 kJ mol^?1. At this coverage streaks appear in the LEED pattern corresponding to an overlayer which is one-dimensionally ordered in the [011&#x0304;] direction. Additional CO adsorption causes the heat of adsorption to decrease further and the overlayer structure to be compressed in the [011&#x0304;] direction. At saturation the LEED pattern shows extra spots which are tentatively attributed to domains of a new overlayer structure coexisting with the first. Electron energy loss spectra (EELS) of adsorbed CO show two characteristic peaks at 4.5 and 13.5 eV probably arising from transitions between the electronic levels of chemisorbed CO.     

Heat of adsorption and density distribution in slit pores with defective walls: GCMC simulation studies and comparison with experimental data

The adsorption behavior (capacity, density distribution and packing density) and the isosteric heat versus loading in a slit pore whose walls contain defective graphene layers are investigated in this paper. The defective wall is characterized by the extent and size of the defect. Simulation results obtained with the Grand Canonical Monte Carlo method reveal complex patterns of isosteric heat, and this complex behavior is a result of the interplay between three factors: (i) the surface heterogeneity (solid-fluid interaction, sites with varying degree of affinity), (ii) fluid-fluid interaction and (iii) the overlapping of potentials exerted by the two defective walls. We illustrate this with argon adsorption in pores of various sizes, and results obtained from the simulation agree qualitatively with the experimental data at 77 K on Saran microporous S600H and micro-mesoporous S84 charcoals of Beebe et al. [R.A. Beebe, B. Millard, J. Cynarski, J. Am. Chem. Soc. 75 (1953) 839]. The S600H was found to contain pores predominantly in the neighborhood of 7 Å with 30% of defect and a defective size of 2.84 Å. This is consistent with the argument made by Beebe et al. that this sample is a microporous solid and most pores can accommodate only one layer. The other sample, S84, has larger pores than S600H, and it is found that it has a wider pore size distribution and the pore width is centered at about 12 Å.     

Adsorption dynamics of double-stranded DNA on a graphene oxide surface with both large unoxidized and oxidized regions

The adsorption dynamics of double-stranded DNA (dsDNA) molecules on a graphene oxide (GO) surface are important for applications of DNA/GO functional structures in biosensors, biomedicine and materials science. In this work, molecular dynamics simulations were used to examine the adsorption of different length dsDNA molecules (from 4 bp to 24 bp) on the GO surface. The dsDNA molecules could be adsorbed on the GO surface through the terminal bases and stand on the GO surface. For short dsDNA (4 bp) molecules, the double-helix structure was partially or totally broken and the adsorption dynamics was affected by the structural fluctuation of short dsDNA and the distribution of the oxidized groups on the GO surface. For long dsDNA molecules (from 8 bp to 24 bp) adsorption is stable. By nonlinear fitting of the contact angle between the axis of the dsDNA molecule and the GO surface, we found that a dsDNA molecule adsorbed on a GO surface has the chance of orienting parallel to the GO surface if the length of the dsDNA molecule is longer than 54 bp. We attributed this behavior to the flexibility of dsDNA molecules. With increasing length, the flexibility of dsDNA molecules also increases, and this increasing flexibility gives an adsorbed dsDNA molecule more chance of reaching the GO surface with the free terminal. This work provides a whole picture of adsorption of dsDNA molecules on the GO surface and should be of benefit for the design of DNA/GO based biosensors.     

Adsorption et condensation en couches mixtes: II. Sur l`interpre´tation des mesures des chaleurs d'adsorption

The significance of the results for the isosteric heat of adsorption obtained by measurements of the temperature dependence of the adsorption isothermes is discussed. In addition to the well-known cases of adsorption on active spots and adsorption of well-condensing adsorbates, the formation of mixed adsorption layers could increase the varieties of relationship between heat of adsorption and coverage. In fact, the information about the character of adsorption, available from such kind of measurements may be doubtfull.     

甲烷在不同分子筛中吸附的理论对比研究

使用巨正则蒙特卡罗方法研究了CH₄分子在MOR和MFI分子筛中的物理吸附行为, 主要对比研究了这两种分子筛对CH₄分子在不同温度和压强下的物理吸附量、等量吸附热、 分子筛和CH₄以及CH₄和CH₄分子之间的相互作用能等物理量. 研究结果表明:在所有的温度和压力下, MOR分子筛对CH₄分子的吸附性能均优于相应的MFI分子筛, 这表明它是一种比MFI吸附性能更优异的吸附剂材料.从CH₄在这两种分子筛中的等量吸附热随吸附量的变化关系,分子筛和CH₄以及CH₄和CH₄之间的相互作用能分布曲线等角度出发分析了二者有不同吸附行为的原因.     

A molecular dynamics simulation of tje uniaxial phase of N2 adsorbed on graphite

A computer simulation study of a nitrogen monolayer adsorbed on a graphite substrate at low temperatures is reported. The adsorbed phase was slightly compressed relative to the commensurate √3 × √3 phase. The compression was taken to be uniaxial; i.e. a 5% change in the large intermolecular spacing along a glide line of the oriented herringbone structure (UXI phase). Thermodynamic properties were evaluated together with orientational and translational ordering parameters at two temperatures, one above (≈ 40 K) and one below (≈ 15 K) the in-plane disordering transition. For purposes of comparison, simulations of the commensurate phase at these temperatures are reported, together with a 15 K simulation of a phase that has been uniaxially compressed in the direction perpendicular to that of the UXI phase (UYI phase). The simulations indicate that the UXI phase is stable but the UYI phase tends to transform into domains of UXI; it is also concluded that the compression necessary to form the UXI phase from the commensurate does not produce a significant change in the out-of-plane ordering, at least at the lower temperature, but does bring about changes in the in-plane ordering of these molecules.