Interaction of water with clean and oxygen precovered nickel surfaces

The adsorption of water on a Ni(111) single crystal surface, clean as well as precovered with oxygen, has been investigated with thermal desorption spectroscopy (TDS) and measurements of the adsorption-desorption equilibrium combined with XPS (X-ray photoelectron spectroscopy). The measurements have been carried out with water pressures up to 10^–5 mbar on surfaces, which have been either clean or precovered with oxygen. On the clean Ni(111) surface the first adsorbate layer with a maximum coverage of 0.42 ML (monolayers) has a desorption energy of 52 kJ/mol and a preexponential factor of desorption of 10¹⁶s^–1. A second water layer adsorbs with the desorption energy of the ice multilayer but with first order kinetics. On Ni(111) precovered with chemisorbed oxygen an additional state of molecular, more strongly bound water is found, but no dissociation. For higher oxygen precoverages where NiO islands are formed on the surface, also the water dissociation product OH is found adsorbed. On a sample covered with a closed NiO layer, adsorbed OH and molecular water in an energetically not well-defined state are found. High doses of water on oxygen-precovered Ni(111) induce a slow surface modification leading to water dissociation.     

A DFT study of H2O dissociation on metal‐precovered Fe (100) surface

The H₂O adsorption and dissociation on the Fe (100) surface with different precovered metals are studied by density functional theory. On both kinds of metal‐precovered surface, H₂O molecules prefer adsorb on hollow sites than bridge and top sites. The impurity energy difference is proportional to the adsorption energy, but the adsorbates are not sensitive to the adsorption orientation and height relative to the surface. The Hirshfeld charge analysis shows that water molecules act as an electron donor while the surface Fe atoms act as an electron acceptor. The rotation and dissociation of H₂O molecule occur on the Co‐ and Mn‐precovered surfaces. Some H₂O molecules are dissociated into OH and H groups. The energy barriers are about 0.5 to 1.0 eV, whose are consistence with the experimental data. H₂O molecules can be dissociated more easily at the top site on Co‐precovered surface 1 than that at bridge site on Mn‐precovered surface 2 because of the lower reaction barrier. The dispersion correction effects on the energies and adsorption configurations on Co‐precovered surface 1 were calculated by OBS + PW91. The dispersion contributions can improve a bit of the bond energy of adsorbates and weaken the hydrogen bond effect between adsorption molecules a little.     

甲醇在清洁和氧预吸咐Pd（100）面上的吸咐与分解

用高分辨电子能量损失谱（ＨＲＥＥＬＳ），热脱咐谱（ＴＤＳ）在１４０Ｋ—７００Ｋ温度范围内研究了清洁和氧改性Ｐｄ（１００）面上ＣＨ_３ＯＨ的吸咐与分解机理。ＨＲＥＥＬＳ结果表明：在１４０Ｋ吸咐甲醇能形成分子吸咐层；当加热甲醇分子层时，甲醇在１８５Ｋ先分解为ＣＨ_３Ｏ_（ａｄ）和Ｈ_（ａｄ），在２００Ｋ以上温度ＣＨ_３Ｏ_（ａｄ）逐步分解为ＣＯ_（ａｄ）和Ｈ_（ａｄ）；预吸咐氧后表面有甲酸物种生成。ＴＤＳ研究表明；除有少量甲醇在１８５Ｋ脱咐外，甲醇分解的主要脱咐产物为Ｈ_２（３２０Ｋ）和ＣＯ（４４０Ｋ）；次要脱附产物为甲烷（２００Ｋ—２１０Ｋ）。综合ＨＲＥＥＬＳ和ＴＤＳ研究指出，在清洁表面甲醇主要通过Ｏ—Ｈ键断裂，经甲氧基中间物种分解为ＣＯ和Ｈ_２，还有部分甲醇通过Ｃ—Ｏ键断裂分解为甲烷，预吸附氧后甲醇的分解除了存在以上两种方式外，氧的存在一方面能够转移ＣＨ_３Ｏ_（ａｄ）中的氢原子在表面形成一定量的甲酸中间物种，另一方面能够稍许提高少量ＣＨ_３Ｏ_（ａｄ）的热稳定性。     

Ni(100)表面吸附SO2的密度泛函研究

以原子簇Ni14为模拟表面,采用DFT/B3LYP方法研究了二氧化硫(SO2)分子在Ni(100)表面的吸附构型、能量、电荷及态密度。结果表明,SO2分子通过S原子平铺吸附在Ni(100)的桥位最有利,计算结果与实验相符。电荷密度及态密度分析表明,Ni原子的d轨道与SO2分子的空p轨道之间存在明显的s-p作用和电荷转移,这一作用可能导致SO2分子发生解离。     

Adsorption and reaction of methanol on clean and oxygen modified rhodium/vanadium surface alloys

The dehydrogenation of methanol on Rh(111), on a Rh(111)/V subsurface alloy and on Rh(111) with V islands has been studied with and without preadsorbed oxygen using a supersonic molecular beam and temperature programmed desorption. The reactivity is highest for the V islands surface without oxygen. But this surface is deactivated due to CO dissociation. The subsurface alloy is less reactive than the islands, but still more active than the Rh(111) surface. The reaction products are carbon monoxide and hydrogen only. With preadsorbed oxygen Rh(111) is the most active surface, but a strong dependence of the activity on the amount of preadsorbed oxygen is found for all three surfaces. The reaction products with preadsorbed oxygen are water, hydrogen, carbon dioxide and carbon monoxide. The reactions follow the same mechanism on all surfaces, but the activation energy of the individual reaction steps is different leading to significant changes in the thermal desorption spectra and in King and Wells-type experiments.     

Carbonate formation and decomposition on atomic oxygen precovered Au(111)

Experimental results supported by density functional theory calculations show carbonate formation and reaction on atomic oxygen precovered Au(111). Oxygen mixing is observed in temperature-programmed desorption measurements when a Au(111) precovered with 16O is exposed to isotopically labeled CO2 (C18O2). The presence of 16O18O is attributed to surface carbonate formation and decomposition at surface temperatures ranging from 77-400 K and initial oxygen coverages ranging from 0.18-2.1 ML. A reaction probability on the order of 10(-4) and an activation energy of -0.15+/- 0.08 eV are estimated for this reaction.     

Cryogenic CO oxidation on TiO(2)-supported gold nanoclusters precovered with atomic oxygen

Bulk gold has long been regarded as a noble metal, having very low chemical and catalytic activity. However, metal oxide-supported gold particles, particularly those that are less than 5 nm in diameter, have been found to have remarkable catalytic properties. In this study we show that impinging gas-phase CO molecules react readily with oxygen adatoms preadsorbed on Au/TiO(2)(110) to produce CO(2) even under conditions in which the sample is cryogenically cooled. Gold particle size seems to have little effect on the CO oxidation reaction when oxygen adatoms are preadsorbed. We also show that as the oxygen adatom coverage increases, the rate of CO oxidation decreases on Au/TiO(2) at cryogenic temperatures.     

Adsorption and reactions of ClCH2CH2OH on clean and oxygen-precovered Cu(100): experimental and computational studies

Temperature-programmed reaction/desorption, reflection-absorption infrared spectroscopy, and density functional theory calculations have been employed to investigate the adsorption and thermal reactions of ClCH2CH2OH on clean and oxygen-precovered Cu(100) surfaces. On Cu(100), ClCH2CH2OH is mainly adsorbed reversibly. The ClCH2CH2OH molecules at a submonolayer coverage can change their orientation with increasing temperature. However, on oxygen-precovered Cu(100), all of the adsorbed ClCH2CH2OH molecules below 0.5 langmuir exposures completely dissociate to generate ethylene and acetaldehyde via the intermediate of ClCH2CH2O-. The computational studies predict that the ClCH2CH2O- is most likely to be adsorbed at the 4-fold hollow sites of Cu(100), with its C-O bond only slightly titled away from the surface normal and with a gauche conformation with respect to the C-C bond. The hollow-site ClCH2CH2O- has an adsorption energy that is 4.4 and 19.2 kcal x mol(-1) lower than that of the ClCH2CH2O- bonded at the bridging and atop sites, respectively. No significant effect of precovered oxygen on the ClCH2CH2O- bonding geometry and infrared band frequencies has been observed, as compared with the case without oxygen.     

CO oxidation on Pd(100) and Pd(111): a comparative study of reaction pathways and reactivity at low and medium coverages.

We have performed density functional theory calculations with the generalized gradient approximation to investigate CO oxidation on a close-packed transition metal surface, Pd(111), and a more open surface, Pd(100), aiming to shed light on surface structure effects on reaction pathways and reactivity, an important issue in catalysis. Reaction pathways on both surfaces at two different coverages have been studied. It is found that the reaction pathways on both surfaces possess crucial common features despite the fact that they have different surface symmetries. Having determined reaction barriers in these systems, we find that the reaction on Pd(111) is strongly coverage dependent. Surface coverages, however, have little effect on the reaction on Pd(100). Calculations also reveal that the low coverage reactions are structure sensitive while the medium coverage reactions are not. Detailed discussions on these results are given.     

Structure and reactivity of intermediates. N-overlayer on Pd(100), Rh(100) and Pt-Rh(110) and its reaction with H2

Rh(100), Pt(100), and Pt-Rh(100) surfaces are inert for the dissociative adsorption of N₂, but they are active for the catalytic reaction of NO with H₂ During the reaction on Rh(100) and Pt-Rh(100) surfaces, N atoms are accumulated by making a c(2x2)-N overlayer, but no accumulation of N atoms occurs on Pt(100) surface. The fact that N atoms on the Pt-Rh(100) surface gives the c(2x2) structure indicates that the N atoms have equal affinity to Pt and Rh on the alloy surface. When the c(2x2)-N surface was exposed to H₂ of 10^-7 to 10^-8 Torr, a prominent loss peak being assignable to NH_x appeared at 3200 – 3240 cm^-1 at around 400 K. The in-situ HREELS study proved that NH are prominent species which are formed during the hydrogenation of the c(2x2)-N, that is, a quasi-equilibrium of N + 1/2 H₂ - NH is established. When a clean Pt-Rh(100) (Pt/Rh = 1/3) alloy surface is exposed to NO at about 440 K, the LEED pattern changes sequentially as (1x1) → c(2x2) → c(2x2) + p(3x1) → p(3x1), where the c(2x2) pattern appears instantaneously on the alloy surface of any Pt/Rh ratio but the p(3x1) pattern accompanies a certain characteristic interval times being responsible to the segregation of Rh. The p(3x1) surface reflects the formation of an intermediate of Rh-O complex overlayer and it reacts rapidly with H₂.     

Density functional theory study of CHx (x=1-3) adsorption on clean and CO precovered Rh(111) surfaces

CH(x) (x=1-3) adsorptions on clean and CO precovered Rh(111) surfaces were studied by density functional theory calculations. It is found that CH(x) (x=1-3) radicals prefer threefold hollow sites on Rh(111) surfaces, and the bond strength between CH(x) and Rh(111) follows the order of CH(3)相似文献   

Adsorption and thermal evolution of SO2 on Ru(0001)

Using high resolution S 2p and O 1s x-ray photoelectron spectroscopies, the adsorption of SO2 and its surface bound reaction products on Ru(0001) have been investigated simultaneously while dosing SO2 and while heating the adsorbed species. SO2 is found to adsorb on Ru(0001) at 100 K molecularly in two variants as well as dissociatively and to react to SO3, SO4, SO, and S with increasing coverage. After the monolayer has been saturated, SO2 adsorbs molecularly in multilayers. When heating adsorbed SO2 from 100 K, SO, SO2, and SO4 decompose in a wide temperature range up to 305 K. In contrast SO3 is found to be stable bound to Ru(0001) up to 300 K and to disappear from the surface to below 325 K. At 550 K the surface remains with a saturated atomic sulfur and oxygen layer and some sulfur species in a second layer. Our quantitative analysis of the sulfur amount bound to the surface supports a simple desorption process only for SO4. All other species mainly or partly decompose on the surface.     

Adsorption and reaction of CO and CO2 on oxidized and reduced SrTiO3(100) surfaces

The adsorption and reaction of CO and CO(2) on oxidized and reduced SrTiO(3)(100) surfaces have been studied with temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). XPS results indicate that the oxidized SrTiO(3)(100) surfaces are nearly defect-free with predominantly Ti(4+) ions whereas the sputter-reduced surfaces contain substantial amounts of defects. Both CO and CO(2) are found to adsorb weakly on the oxidized SrTiO(3)(100) surfaces. On sputter-reduced surfaces, enhanced reactivity of CO and CO(2) is observed due to the presence of oxygen vacancy sites, which are responsible for dissociative adsorption of these molecules. Our studies indicate that the CO and CO(2) molecules exhibit relatively weaker interactions with SrTiO(3)(100) compared to those with TiO(2)(110) and TiO(2)(100) surfaces. This is most likely an influence of the Sr cations on the electronic structure of the Ti cations in the mixed oxide of SrTiO(3).     

Vibrational spectroscopy study of H2O on Pd/MgO(100) films

A study of water on Pd/MgO(100) films prepared in situ upon Mo(100) single crystals has been performed by using low-energy electron diffraction, high-resolution electron energy-loss spectroscopy, and ultraviolet photoelectron spectroscopy in an ultrahigh vacuum system. The results show that the adsorption of water on MgO(100) film surfaces is enhanced significantly owing to the presence of Pd particles. The formation of a hydroxyl group suggests a dissociation of the water. The size and density of Pd particles on the substrate of MgO(100) films play an important part in the adsorption of water.     

Adsorption of N2O on Cu(100): a combined scanning tunneling microscopy and density functional theory study

The adsorption of N(2)O on Cu(100) has been studied by using scanning tunneling microscopy (STM). In the first molecular layer N(2)O forms a densely packed c(3 x 2) structure, in which the molecules occupy two different adsorption sites. The bonding strength of this layer is found to be very weak as revealed by a low desorption temperature and the formation of misalignments and defects. Density functional theory (DFT) finds a stable c(3 x 2) structure in which the molecules are considerably bent due to charge transfer. In model calculations for a 2 x 2 hollow phase we show that in order to reach the chemisorbed, bent configuration, the molecules have to pass an activation barrier. In the experimentally accessible range, this is apparently not possible and the molecules remain in a stable physisorbed state.     

Infrared chemiluminescence study of CO2 formation in CO + NO reaction on Pd(110) and Pd(111) surfaces

Infrared (IR) chemiluminescence studies of CO2 formed during steady-state CO + NO reaction over Pd(110) and Pd(111) surfaces were carried out. Kinetics of the CO + NO reaction were studied over Pd(110) using a molecular-beam reaction system in the pressure range of 10-2-10-1 Torr. The activity of the CO + NO reaction on Pd(110) was much higher than that of Pd(111), which was quite different from the result of other experiments under a higher pressure range. On the basis of the experimental data on the dependence of the reaction rate on CO and NO pressures and the reaction rate constants obtained by using a reaction model, the coverage of NO, CO, N, and O was calculated under various flux conditions. From the analysis of IR emission spectra in the CO + O2 reaction on Pd(110) and Pd(111), the antisymmetric vibrational temperature (TVAS) was seen to be higher than the bending vibrational temperature (TVB) on Pd(110). In contrast, TVB was higher than TVAS on Pd(111). These behaviors suggest that the activated complex for CO2 formation is more bent on Pd(111) than that on Pd(110), which is reflected by the surface structure. Both TVB and TVAS for the CO + O2 reaction on Pd(110) and Pd(111) increased gradually with increasing surface temperature (TS). On the other hand, in the case of the CO + NO reaction on Pd(110) and Pd(111), TVAS decreased and TVB increased significantly with increasing TS. TVB was lower than TVAS at lower TS, while TVB was higher than TVAS at higher TS. Comparison of the data obtained for the two reactions indicates that TVB in the CO + NO reaction on Pd(110) at TS = 800 and 850 K is much higher than that in the CO + O2 reaction on Pd(110).     

Adsorption of atomic oxygen and nitrogen at beta-cristobalite (100): a density functional theory study

The adsorption of atomic oxygen and nitrogen on the beta-cristobalite (100) surface is investigated from first principles density functional calculations within the generalized gradient approximation. A periodic SiO2 slab model (6 layers relaxing 4 or 6) ended with a layer of Si or O atoms is employed throughout the study. Several adsorption minima and diffusion transition states have been characterized for the two lowest spin states of both systems. A strong chemisorption is found for either O or N in several sites with both slab endings (e.g., it is found an average adsorption energy of 5.89 eV for O (singlet state) and 4.12 eV for N (doublet state) over the Si face). The approach of O or N on top O gives place to the O2 and NO abstraction reactions without energy barriers. Atomic sticking coefficients and desorption rate constants have been estimated (300-1900 K) by using the standard transition state theory. The high adsorption energies found for O and N over silica point out that the atomic recombination processes (i.e., Eley-Rideal and Langmuir-Hinshelwood mechanisms) will play a more important role in the atomic detachment processes than the thermal desorption processes. Furthermore, the different behavior observed for the O and N thermal desorption processes suggests that the published kinetic models for atomic O and N recombination reactions on SiO2 surfaces, based on low adsorption energies (e.g., 3.5 eV for both O and N), should probably be revised.     

Adsorption and reaction of CO2 and SO2 at a water surface

The orientation and hydrogen bonding of water molecules in the vapor/water interfacial region in the presence of SO2 and CO2 gas are examined using vibrational sum-frequency spectroscopy (VSFS) to gain insight into the adsorption and reactions of these gases in atmospheric aerosols. The results show that an SO2 surface complex forms when the water surface is exposed to an atmosphere of SO2 gas. Reaction of SO2 with interfacial water leads to other spectral changes that are examined by studying the VSF spectra and surface tension isotherms of several salts added to the aqueous phase, specifically NaHSO3, NaHCO3, Na2SO3, Na2CO3, Na2SO4, and NaHSO4. The results are compared with similar studies of CO2 adsorption and reaction at the surface. A weakly bound surface complex is not observed with CO2.     

Adsorption and reaction of methanol on stoichiometric and defective SrTiO3(100) surfaces

The adsorption and reaction of methanol (CH(3)OH) on stoichiometric (TiO(2)-terminated) and reduced SrTiO(3)(100) surfaces have been investigated using temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and first-principles density-functional calculations. Methanol adsorbs mostly nondissociatively on the stoichiometric SrTiO(3)(100) surface that contains predominately Ti(4+) cations. Desorption of a monolayer methanol from the stoichiometric surface is observed at approximately 250 K, whereas desorption of a multilayer methanol is found to occur at approximately 140 K. Theoretical calculations predict weak adsorption of methanol on TiO(2)-terminated SrTiO(3)(100) surfaces, in agreement with the experimental results. However, the reduced SrTiO(3)(100) surface containing Ti(3+) cations exhibits higher reactivity toward adsorbed methanol, and H(2), CH(4), and CO are the major decomposition products. The surface defects on the reduced SrTiO(3)(100) surface are partially reoxidized upon saturation exposure of CH(3)OH onto this surface at 300 K.