The heat of adsorption of hydrogen on platinum

The heat of adsorption (q) of hydrogen on clean polycrystalline platinum filaments has been determined as a function of the coverage (θ), temperature and method of preadsorption using UHV adiabatic calorimetric techniques. Adsorption at 273 °K results in a stepped shape q-θ curve with q (θ=0)= 24.7 kcalmole^?1. At 77 °K, the form of the curve depends on the temperature of preadsorption. The relative roles of a priori and induced heterogeneity are discussed and while both must play a part, the temperature dependence of the form of the q-θ curves suggest that the latter is the more important of the two in these experiments.     

The adsorption of activated nitrogen on platinum single crystal faces

The adsorption of activated nitrogen on a stepped Pt(S)-[9(111) × (111)] face was investigated by LEED, AES and flash desorption. Nitrogen was supplied to the crystal from a high frequency discharge tube. For comparison some orienting measurements were also carried out on smooth (111) and (100) platinum faces. Activated nitrogen is adsorbed at room temperature on all three faces up to about half a monolayer coverage. No additional LEED patterns indicating long range order of the adsorbed layer were found. By flash heating a small desorption peak at 120°C and a large peak between 175 and 230°C depending on the initial coverage were observed on the (111) type faces. The desorption can be described approximately by a second order rate law with an energy of activation of 25± 3 kcal/mole. No influence of surface steps on the properties of the adsorbed layer was detected. On the (100) face two coverage independent desorption maxima at 120 and 170°C of about equal intensities were found.     

The adsorption of oxygen on a stepped platinum single crystal surface

The adsorption of oxygen on the Pt(S)-[12(111) × (111) surface has been studied by Auger electron spectroscopy, low energy electron diffraction and thermal desorption spectroscopy. Two types of adsorbed oxygen have been identified by thermal desorption spectroscopy and low energy electron diffraction: (a) atoms adsorbed on step sites; (b) atoms adsorbed on terrace sites. The kinetics of adsorption into these two states can be modeled by considering sequential filling of the two adsorbed atomic states from a mobile adsorbed molecular precursor state. Adsorption on the step sites occurs more rapidly than adsorption onto the terraces. The sticking coefficient for oxygen adsorption is initially 0.4 on the step sites and drops when the step sites are saturated. The heat of desorption from the step site (45 ± 4 kcal/mole) is about 15% larger than the heat of desorption from the terraces.     

The adsorption of sulfur on the platinum (100) surface

Clean platinum (100) surfaces of 1× 1 and 5 × 20 structure were exposed to H₂S. Surface coverage with Sulfur followed Langmuir kinetics, which, together with LEED data, points to a repulsive interaction between sulfur atoms. Sulfur adsorption causes a decrease in the work function of platinum by 0.7 eV at saturation coverage. This is attributed to polarization, rather than ionization, of the adsorbed sulfur. Photoemission measurements are difficult to interpret because of two-dimensional periodicity and the overlap of electronic structure of the adsorbate with the platinum d band. We observe peaks due to sulfur at 6.3, 4.5, and 2.5 eV below the Fermi level for the c(2 × 2) overlayer and at 6.8, 4.5, and 2.0 eV below E_F for the p(2 × 2) surface. A tentative interpretation in terms of sulfur orbitals is given. The decrease in work function and analogy with the properties of PtS₂ lead us to propose covalent bonding of sulfur to platinum, in which every sulfur atom is bonded to four Pt neighbors in both structures. The repulsive interaction between sulfur atoms is indirect through the platinum substrate.     

Molecular nitrogen adsorption on individual platinum and titanium nanoclusters

Molecular nitrogen adsorption on single platinum and titanium nanoclusters is investigated by scanning tunneling microscopy and spectroscopy, including the use of an inverse scheme of spectroscopic measurements. Some regularities of the occurring processes are found.     

Effect of platinum dispersion on photocatalytic performance of Pt-TiO2

Journal of Nanoparticle Research - The present work illustrates the effect of surface modification of silica nanoparticles (500 nm) with 3-(glycidoxypropyl)trimethoxy silane which was...     

Carbon monoxide and hydrogen adsorption on a calcium-covered polycrystalline platinum foil

The effect of Ca on the adsorption of CO and H₂ is investigated. Ca influences the desorption of both species.     

Theoretical studies of hydrogen molecule adsorption on flat and stepped platinum surfaces

Theoretical calculations have been applied to the adsorption of hydrogen molecule on flat and stepped platinum surfaces. The method of large unit cell is modified to deal with the stepped surface as well as the flat one. This method is free from the boundary effect which is inevitable in the cluster method. The results calculated for the d-band width and the highest occupied level are in good agreement with the experiments. For the dissociative adsorption, the bottom of the step site is the most favorable, and the result is attributed to the extra orbital interactions at this site.     

页岩矿物不同润湿性表征与吸附微观机理

无机矿物作为页岩气吸附的重要载体,其表面性质对甲烷吸附能力有着重要影响,而润湿性作为固体重要表面性质之一,对矿物气体吸附能力的影响不可忽视.文章以蒙脱石和石英作为研究对象,通过对矿物表面甲基化(-CH₃)和羟基化(-OH)处理来改变其润湿性,以探究无机矿物表面润湿性对甲烷吸附能力的影响.采用分子动力学方法研究矿物体系的润湿性,用接触角对润湿性进行定量表征,并构建纳米狭缝,结合巨正则蒙特卡罗方法模拟润湿性改变前后,CH₄在矿物中的吸附变化.研究结果表明,水滴在羟基化矿物表面迅速破裂并铺展在矿物表面,而在甲基化表面铺展程度较小,普遍呈半球形.羟基化蒙脱石和石英表面的润湿接触角分别为12.7°和26.5°,均小于其甲基化表面接触角62.5°和85.7°.甲基化矿物甲烷吸附量均高于其羟基化,气体几乎大都以吸附状态位于孔隙壁面,随着矿物亲水性的减弱,其对甲烷吸附能力增强.     

The dispersion force of physical adsorption: II. Nonlocal theory

We present a nonlocal theory of the dispersion force of physisorption for non-polar atoms or molecules. The calculation uses linear response theory and the surface impedance method. The results generalize those presented previously, which relied on a local theory of the dielectric response. Also included in the treatment is the role of diffuseness of the interface between substrate and vacuum. Adatom dipole and quadrupole fluctuations are treated. Several diverse contributions to the potential are thus calculated, giving rise to a substantial modification of the conventional expression V ? -C₃(z-z₀)^?3, especially at small separation z.     

The permittivity of a monatomic gas with spatial dispersion

The longitudinal, ε^l(ω, k), and transverse, ε^tr(ω, k), permittivities of a monatomic gas were calculated. The frequency ranges in which the permittivity ε(ω) and permeability μ(ω) of a gas without spatial dispersion have a physical meaning were determined. The limiting magnetic susceptibility χ(ω) at ω=0 and the static magnetic susceptibility were found. The question of whether an electromagnetic wave with antiparallel group and phase velocities can propagate through a monatomic gas is discussed.     

Adsorption of hydrogen on rhodium; Comparison with hydrogen adsorption on platinum and iridium

The adsorption of hydrogen on Rh has been studied (i) on a single crystal tip using field electron microscopy, and (ii) on a filament carrying this tip, using thermal desorption spectroscopy. The results are compared to those of other Group VIII metals. An isosteric heat of adsorption of 19 kcal/mole was found at low coverage, decreasing slightly with increasing coverage. This heat is substantially lower than that on Ru and Ir, determined by the same method. The work function increases by 0.4 eV, a value comparable to data reported for Ni and Ru, but significantly larger than those of Ir and Pt. An electropositive state of hydrogen as observed for Pt and Ir was not found for Rh. A small fraction of the adsorbed hydrogen is not desorbed at temperatures where other transition metal surfaces are completely denuded. This β₂-hydrogen which is desorbed only at 600–800 K, is tentatively assigned to a subsurface species.     

Annealing and refinement of platinum in gas atmospheres

The influence of surrounding gas atmosphere on the purity of thin platinum wires annealed at medium and high temperatures is experimentally studied. The residual resistance ratio serves as a measure of the “purity” of the specimens, and is supplemented by the determination of the changes of geometrical factor of the specimen during annealing. Empirical rules are deduced and partly explained.     

Methane adsorption on graphene from first principles including dispersion interaction

The methane–graphene interaction is studied using density functional theory complemented with a semiempirical dispersion correction scheme (DFT-D), an ab initio van der Waals density functional (vdW-DF) ansatz as well as using Møller Plesset perturbation theory (MP2). The adsorption energy of 0.17 eV and the molecular distance of 3.28 Å obtained from the MP2 calculations are close to the experimental data, while the vdW-DF scheme results either in a realistic adsorption energy or a realistic adsorption geometry, depending on the underlying exchange-correlation functional. The present implementation of DFT-D overbinds about as much as bare DFT calculations underbind, but yields a meaningful adsorption height.     

Effect of strong magnetic fields on gas adsorption

The effect of strong pulsed magnetic fields on gas adsorption at dielectric surfaces is demonstrated. We describe the experimental technique and the results indicating a considerable increase in the surface concentration of the adsorbed substance under the action of pulsed magnetic fields with an induction amplitude up to 50 T. The increase in the lifetime and stability of the adsorbed layer is observed. It is shown that the effect of magnetically induced sorption is also manifested in the interaction of iodine vapor with the surface of dielectrics.     

Sensitivity of surface plasmon dispersion and damping to alkali adsorption

I have studied the sensitivity to alkali adsorption of the linear coefficients of surface plasmon dispersion and damping, through the use of self-consistent surface potential barriers which have been shown by Lang to give a good account of the work function changes due to such adsorption. The coefficient of dispersion increases strongly with alkali adsorption on an r_S = 2 substrate, while the coefficient of damping changes less.     

NMR studies of hydrocarbon gas flow and dispersion

It is demonstrated that nuclear magnetic resonance (NMR) flow imaging on the basis of phase encoding of flow velocities as well as NMR flow tagging can be successfully employed to visualize laminar but not necessarily fully developed flow of thermally polarized hydrocarbon gases at atmospheric pressure. Gas flow in the nonconsolidated bed composed of solid glass beads was characterized by the displacement NMR spectroscopy on the basis of pulsed-field-gradient-stimulatedecho NMR technique. The effective diffusivity values and aerodynamic dispersion coefficients on the time scale from milliseconds to hundreds of milliseconds were extracted from the experimental data. In a similar experiment with the beds composed of porous silica gel grains, strong adsorption of hydrocarbon gases was observed.     

The effect of gas adsorption on the electrical resistivity of thin silver films

Silver films in the thickness range 20–60 nm deposited on glass substrates in UHV conditions were covered stepwise with oxygen, carbon monoxide and ethylene at 77 K. Resistivity was measured in situ. The evaluation of the thickness dependence of resistivity on the basis of a scattering hypothesis leads to scattering cross sections decreasing from O₂ to CO and C₂H₄. The results are explained by considering the energetic structure of the broadened molecular orbitals of the adsorbates near the Fermi level.     

Phase diagram of molecular oxygen adsorption on the (111) platinum surface

Molecular oxygen adsorption on the Pt(111) surface is studied based on ab initio computations and thermodynamics. An O2 adsorption phase diagram is determined. There are two possible chemisorbed molecular states: one at a bridge site and another one at an fcc hollow site. While some population in the bridge sites persists at all coverages, the states coexist through the intermediate coverage phases. The relative coverage of the two species on the surface is determined by the competition between the Pt lattice distortion energy (that results from O2 adsorption) and the O2 repulsion energy. Our results give a reasonable explanation for the seemingly contradictory findings in previous experimental and theoretical work.