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1.
The adsorption and reaction of water on clean and oxygen covered Ag(110) surfaces has been studied with high resolution electron energy loss (EELS), temperature programmed desorption (TPD), and X-ray photoelectron (XPS) spectroscopy. Non-dissociative adsorption of water was observed on both surfaces at 100 K. The vibrational spectra of these adsorbates at 100 K compared favorably to infrared absorption spectra of ice Ih. Both surfaces exhibited a desorption state at 170 K representative of multilayer H 2O desorption. Desorption states due to hydrogen-bonded and non-hydrogen-bonded water molecules at 200 and 240 K, respectively, were observed from the surface predosed with oxygen. EEL spectra of the 240 K state showed features at 550 and 840 cm ?1 which were assigned to restricted rotations of the adsorbed molecule. The reaction of adsorbed H 2O with pre-adsorbed oxygen to produce adsorbed hydroxyl groups was observed by EELS in the temperature range 205 to 255 K. The adsorbed hydroxyl groups recombined at 320 K to yield both a TPD water peak at 320 K and adsorbed atomic oxygen. XPS results indicated that water reacted completely with adsorbed oxygen to form OH with no residual atomic oxygen. Solvation between hydrogen-bonded H 2O molecules and hydroxyl groups is proposed to account for the results of this work and earlier work showing complete isotopic exchange between H 216O (a) and 18O (a). 相似文献
2.
The reactions of H 2S with predosed surface oxygen on Ni(110) surfaces were studied for a variety of coverage conditions. The primary reaction product is H 2O, but the details of the water formation and desorption depends on the coverage of both O and H 2S. For high coverages of oxygen (p(2 × 1)−O; 0.5 ML), the reaction to form water is quantitative. The loss of oxygen from the surface (as measured by AES) is equal to the increase in sulfur coverage. XPS and HREELS measurements indicate the presence of chemisorbed H2O immediately following large exposures of H2S on the oxygen predosed surface at 110 K. Deuterium incorporation results suggest that the primary mechanism for these coverage conditions involves direct transfer of hydrogen from SH or H2S moieties to the oxygen. A second mechanism involving reaction of surface hydroxyl groups with surface hydrogen was also identified. This mechanism is particularly important for high coverages of oxygen (0.5 ML) and low coverages of H2S (0.15 ML), where water desorption was observed at 235 K, but was not observed spectroscopically at 110 K. The sequential addition of two surface hydrogen atoms to surface oxygen is not an important mechanism in this system. These reactions were modeled using a bond-order conservation method, and the model successfully reproduced the important mechanistic conclusions. 相似文献
3.
The water adsorption on clean and oxygen precovered Cu(110) surfaces is studied by means of UPS, LEED, work function measurements and ELS. At 90 K on the clean surface molecular water adsorption is indicated by UPS. The H 2O molecules are bonded at the oxygen end and the H-O-H angle is increased as compared with the free molecule. In the temperature range between 90 and 300 K distorted H 2O molecules and adsorbed hydroxyl species (OH) are detected, which are desorbed at room temperature. On an oxygen covered surface hydroxyl groups are formed by dissociation of adsorbed water molecules at a lower temperature than on the clean surface. Multilayers of condensed water are found below 140 K in both cases. 相似文献
4.
The interaction of water vapour with clean as well as with oxygen precovered Ni(110) surfaces was studied at 150 and 273 K, using UPS, ΔΦ, TDS, and ELS. The He(I) (He(II)) excited UPS indicate a molecular adsorption of H 2O on Ni(110) at 150 K, showing three water-induced peaks at 6.5, 9.5 and 12.2 eV below EF (6.8, 9.4 and 12.7 eV below EF). The dramatic decrease of the Ni d-band intensity at higher exposures, as well as the course of the work function change, demonstrates the formation of H 2O multilayers (ice). The observed energy shift of all water-induced UPS peaks relative to the Fermi level ( ΔEmax = 1.5 eVat 200 L) with increasing coverage is related to extra-atomic relaxation effects. The activation energies of desorption were estimated as 14.9 and 17.3 kcal/mole. From the ELS measurements we conclude a great sensitivity of H 2O for electron beam induced dissociation. At 273 K water adsorbs on Ni(110) only in the presence of oxygen, with two peaks at 5.7 and 9.3 eV below EF (He(II)), being interpreted as due to hydroxyl species (OH) δ? on the surface. A kinetic model for the H 2O adsorption on oxygen precovered Ni(110) surfaces is proposed, and verified by a simple Monte Carlo calculation leading to the same dependence of the maximum amount of adsorbed H 2O on the oxygen precoverage as revealed by work function measurements. On heating, some of the (OH) δ? recombines and desorbs as H 2O at ? 320 K, leaving behind an oxygen covered Ni surface. 相似文献
5.
Adsorbed H 2S decomposes on Ni(110) to form primarily surface S and H for coverages of less than 0.5 ML. The hydrogen evolves in two separate TPD peaks, characteristic of hydrogen recombination and desorption from the clean surface and from regions perturbed by chemisorbed sulfur. XPS and HREELS indicate the presence of SH and possibly H 2S groups on the surface at 110 K. The XPS data indicates that for coverages less than about 0.5 ML, the concentration of molecular H 2S is small, but it is difficult to asess the coverage of SH groups. However, all of the molecular species decompose prior to hydrogen desorption (for high coverage, 180 K). Physisorbed H 2S is observed on the surface for coverages greater than about 0.5 ML. The sulfur Auger lineshape was observed to be a function of both coverage and temperature. The changes in the lineshape were attributed to perturbations in local bonding interactions between the S and the Ni surface, perhaps involving some change in either bonding sites or distances but not involving SH bond scission. The decomposition reaction was modeled using a bond order conservation method which successfully reproduced the experimental results. 相似文献
6.
Adsorption of water at 100 K. on clean and oxygen-covered Cu(110) has been studied using UPS, TDS, Δφ and LEED measurements. The results indicate that two-dimensional hydrogenbonded islands are formed on the clean surface. The long-range order in these islands is in registry with the substrate lattice and gives rise to a c(2×2) LEED pattern. Upon the formation of multilayer ice, the ordering disappears. The presence of oxygen on the surface disrupts the hydrogen bonding, and composite oxygen-water layers are formed. A model of the arrangement of oxygen atoms and water molecules is presented, based upon the LEED observations for these layers and an estimate of the relative oxygen and water coverages. The intensity variation of a thermal desorption peak at 290 K, attributed to adsorbed OH species, with oxygen coverage is in accordance with this model. For low oxygen coverages, the TDS and Δφ results indicate that small oxygen-water clusters with an enhanced ratio of water molecules per adsorbed oxygen atom are present. 相似文献
7.
The oxidation of H 2C 16O by adsorbed 18O was studied on an Cu(110) sample by temperature programmed reaction spectroscopy. Formaldehyde exchanged its oxygen with surface 18O upon adsorption to yield H 2C 18O (a) and 16O (a). Formaldehyde was also oxidized by surface 16O and 18O atoms to H 2COO which subsequently released one of the hydrogen atoms to form HCOO. The evolution of H 2 from the Cu(110) surface was desorption limited, and the low pre-exponential factor for the recombination of the surface hydrogen atoms suggested stringent requirement on the trajectories of the colliding partners. The formate was very stable and dissociated at elevated temperatures to simultaneously yield H 2 and CO 2. The surface concentration of 18O exerted a pronounced affect on the activity of the oxidation of formaldehyde on Cu(110). 相似文献
8.
基于密度泛函理论第一性原理, 在广义梯度近似下, 研究了表面覆盖度为0.25 ML (monolayer)时硫化氢分子在Fe(100)面吸附的结构和电子性质, 并与单个硫原子吸附结果进行了对比. 结果表明: 硫化氢分子吸附在B2位吸附能最小为-1.23 eV, 最稳定, B1位吸附能最大为-0.01 eV, 最不稳定; 并对硫化氢分子在B1位和B2位吸附后的电子态密度进行了分析, 也表明了吸附在B2位稳定, 且吸附在B2位后硫化氢分子几何结构变化不大; 将硫化氢中硫原子吸附与单个硫原子吸附的电子性质进行了比较, 发现前者吸附作用非常微弱; 同时对吸附后的Fe(100)面进行了对比, 单个硫原子吸附的Fe(100)面电子态密度出现了一系列峰值且离散分布, 生成了硫化亚铁, 表明在硫化氢环境下, 主要是硫化氢析出的硫原子发生了吸附.
关键词:
第一性原理
Fe(100)表面
吸附能
硫化氢 相似文献
9.
Pure single crystals of MoO 3 were carefully grown by physical vapor transport. The initial stages of the interaction of H 2S with a MoO 3 (010) surface were studied by RHEED and AES at low pressure p <133 Pa and at T < 700 K. Three main stages were found: (a) The formation of either a completely disordered sulphur adiayer (with pure H 2S) or a superstructure MoO 3(010)-[2 × 1]S (with H 2S/H 2). (b) A reduction of MoO 3 producing oriented three-dimensional MoO 2 islands, (c) An epitaxial overgrowth of MoS 2 from the MoO 2 three-dimensional crystallites. 相似文献
10.
The adsorption and reaction of H 2O on clean and oxygen precovered Ni(110) surfaces was studied by XPS from 100 to 520 K. At low temperature ( T<150 K), a multilayer adsorption of H 2O on the clean surface with nearly constant sticking coefficient was observed. The O 1s binding energy shifted with coverage from 533.5 to 534.4 eV. H 2O adsorption on an oxygen precovered Ni(110) surface in the temperature range from 150 to 300 K leads to an O 1s double peak with maxima at 531.0 and 532.6 eV for T=150 K (530.8 and 532.8 eV at 300 K), proposed to be due to hydrogen bonded O ads… HOH species on the surface. For T>350 K, only one sharp peak at 530.0 eV binding energy was detected, due to a dissociation of H 2O into O ads and H 2. The s-shaped O 1s intensity-exposure curves are discussed on the basis of an autocatalytic process with a temperature dependent precursor state. 相似文献
11.
The adsorption and reaction of acetonitrile (CH 3CN) on clean and oxygen covered Ag(110) surfaces has been studied using temperature programmed reaction spectroscopy (TPRS), isotope exchange, chemical displacement reactions and high resolution electron energy loss spectroscopy (EELS). On the clean Ag(110) surface, CH 3CN was reversibly adsorbed, desorbing with an activation energy of 10 kcal mol -1 at 166 K from a monolayer state and at 158 K from a multilayer state. Vibrational spectra of multilayer, monolayer and sub-monolayer CH 3CN were in excellent agreement with that of gas phase CH 3CN indicating that CH 3CN is only weakly bonded to the clean Ag(110) surface. On the partially oxidized surface CH 3CN reacts with atomic oxygen to form adsorbed CH 2CN, OH and H 2O in addition to forming another molecular adsorption state with a desorption peak at 240 K. This molecular state shows a CN stretching frequency of 1840 cm -1, which is indicative of substantial rehybridization of the CN bond and is associated with side-on coordination via the π system. The CH 2CN species is stable up to 430 K, where C-H bond breaking and reformation begins, leading to the formation of CH 3CN at 480 K and HCN at 510 K and leaving only carbon on the surface. In the presence of excess oxygen atoms C-H bond breaking and reformation is more facile leading to additional desorption peaks for CH 3CN and H 2O at 420 K. This destabilizing effect of O (a) on Ch 2CN (a) is explained in terms of an anionic (CH 2CN -1) species. Comparison of the vibrational spectra from CH 2CN (a) and CD 2CN (a) supports the following assignment for the modes of adsorbed CH 2CN: ν(Ag-C) 215: δ(CCN) 545; ϱ t(CH 2) 695; ϱ w(CH 2) 850; ν(C-C) 960; ϱ r(CH 2) 1060; δ(CH 2) 1375; ν(CN) 2075; and ν(CH 2) 2940 cm -1. These results serve to further indicate the wide applicability of the acid-base reaction concept for reactions between gas phase Brönsted acids and adsorbed oxygen atoms on solver surfaces. 相似文献
13.
External differential reflection measurements were carried out on clean Si(100) and (110) surfaces in the photon energy range of 1.0 to 3.0 eV at 300 and 80 K. The results for Si(100) at 300 K showed two peaks in the joint density of states curve, which sharpened at 80 K. One peak at 3.0 ± 0.2 eV can be attributed to optical transitions from a filled surface states band near the top of the valence band to empty bulk conduction band levels. The other peak at 1.60 ± 0.05 eV may be attributed to transitions to an empty surface states band in the energy gap. This result favours the asymmetric dimer model for the Si(100) surface. For the (110) surface at 300 K only one peak was found at 3.0 ± 0.2 eV. At 80 K the peak height diminished by a factor of two. Oxygen adsorption in the submonolayer region on the clean Si(100) surface appeared to proceed in a similar way as on the Si(111) 7 × 7 surface. For the Si(110) surface the kinetics of the adsorption process at 80 K deviated clearly. The binding state of oxygen on this surface at 80 K appeared to be different from that on the same surface at 300 K. 相似文献
14.
The adsorption and decomposition of H 2S on the Ge(100) surface is investigated. H 2S is a simple sulfur containing molecule that eventually decomposes to yield hydrogen gas and deposits sulfur on the germanium surface. The surface reactions of H 2S are investigated by ultraviolet photoelectron spectroscopy, Auger electron spectroscopy, and temperature programmed desorption. Room temperature exposure of H 2S to Ge(100) results in dissociative adsorption which can be followed easily by ultraviolet photoelectron spectroscopy. Warming the H 2S exposed surface results in some molecular desorption and further decomposition of the adsorbed species. At saturation, 0.25 ML of H 2S decomposes generating 0.5 ML of atomic hydrogen. Above the hydrogen desorption temperature some etching of the germanium surface is observed by sulfur. The etch product, GeS, is subsequently observed in temperature programmed desorption experiments. Exposure of H 2S to the Ge surface at elevated temperatures leads to higher sulfur coverages. A sulfur coverage approaching 0.5 ML can be deposited at the higher exposure temperatures. 相似文献
15.
The kinetics of H 2 desorption from H/W(110) and H/Fe 1/W(110) were studied by measuring work function changes Δø vs time at a number of temperatures. Combination with previously determined Δø vs coverage data and differentiation at various fixed coverages gave rate vs T data from which activation energies of desorption could be obtained. E vs coverage results agree well with previously determine Δ Hdes results. In the case of H/Fe 1/W(110) this includes a rise from 20 to 30 kcal mol −1 of H 2 at H/Fe = H/W > 0.3. Plots of rate −dθ/d t vs θ (θ being coverage in units of H/W) vary much more steeply than θ 2 at most coverages for both systems. The θ dependence can be explained almost quantitatively in terms of the variations of Δ Hdes and surface entropy Ss with coverage, by assuming that rates of desorption are equal to the equilibrium rates of adsorption. The latter can be formulated thermodynamically, except for a sticking coefficient, s. Values for s(θ, T) can also be obtained and show relatively little temperature dependence. 相似文献
16.
The adsorption of water vapour on the (110)Cu face has been studied by AES and Δφ measurements in the 5 × 10 ?9 to 3 × 10 ?7 Torr range between 75 and 500°C. At lower temperatures, an initial physisorption of oriented water dipoles produces a fast initial Δφ decrease. Further adsorption causes no important changes of the Cu surface potential. At higher temperatures (above 100°C) a partial dissociation of the water molecules leads to a dissociative chemisorption producing a Δφ increase after the initial Δφ decrease due to water physisorption. 相似文献
17.
The UHV cleaved (110) face has been exposed to water in the range from 10 L to 2 × 10 4 L. The main TDS peak in H 2O desorption appears at 350 K, independent of coverage. The low desorption energy of 0.7 eV (16 kcal/mol) is reasonable for oxygen atoms bound via the lone pair orbital to As as was earlier derived from UPS measurements. A broad spur between 450 and 600 K may be related to O-Ga bonds. The sticking probability shows values below 10 -4; only near 4.8 × 10 3 L (6 × 10 15 cm -2 s -1 H 2O molecules for 300 s) corresponding to a coverage of about 0.4 monolayes a steep maximum appears. At about one monolayer saturation is observed. Exposures to more than 10 4 L of water quench the intensity of the (10) LEED spot considerably stronger than the intensity of the (11) spot. A comparison of the I( E) curves with existing model calculations suggests that the observed behaviour of the LEED spots is caused by a change in surface structure towards the unrelaxed configuration. The higher sticking coefficient observed near 0.4 monolayers may be connected with this rearrangement of surface atoms. 相似文献
18.
An all-electron scalar relativistic calculation on Au nH 2S ( n = 1-13) clusters has been performed by using density functional theory with the generalized gradient approximation at PW91 level. The small gold cluster would like to bond with sulfur in the same plane and the H 2S molecule prefers to occupy the on-top and single fold coordination site in the cluster. The Au n structures and H 2S molecule in all Au nH 2S clusters are only slightly perturbed and still maintain their structural integrity. After adsorption, the S-H, H-H bond-lengths and most Au-Au bond-lengths are elongated, only a few Au-Au bond-lengths far from H 2S molecule are shortened. The reactivity enhancement of H 2S molecule is obvious and the strong gold-sulfur bond is observed expectedly. The most favorable adsorption takes place in the case that the H 2S molecule is adsorbed by an even-numbered Au n cluster and becomes Au nH 2S cluster with even number of valence electrons. It is believed that the strong scalar relativistic effect is favorable to H 2S molecule adsorption onto small gold clusters and is also one of the important reasons for the strong gold-sulfur bond. 相似文献
19.
Electron energy loss spectra of clean and oxygen covered GaAs(110) surfaces have been measured with a four grid retarding field analyser. Loss spectra of clean cleaved p- and n-type surfaces are slightly different and different states of adsorption for the oxygen on the two surfaces are found. The loss peaks which are common in the spectra obtained from clean surfaces of both types of material have been interpreted in terms of bulk and surface excitations. The data associated with the bulk excitations are in good agreement with previous optical and electron transmission data while loss peaks at 11.5 and 18.5 eV are interpreted as the surface plasma loss and a surface state transition respectively. For n-type material extra loss peaks were observed. In the case of oxygen adsorption on these surfaces new loss peaks were found at 13.5, 17.2 and 28.1 eV in both spectra and are assumed to be characteristic of the oxygen. Further, for n-type material an extra peak occurs at 8.2 eV. 相似文献
20.
采用第一性原理方法研究了H 2分子在Li 3N(110)晶面的表面吸附. 通过研究H 2/Li 3N(110)体系的吸附位置、吸附能和电子结构发现: H 2分子吸附在N桥位要比吸附在其他位置稳定,此时在Li 3N(110)面形成两个-NH基,其吸附能为1.909 eV,属于强化学吸附;H 2与Li 3N(110)面的相互作用主要是H 1s轨道与N
关键词:
第一性原理
3N(110)')" href="#">Li 3N(110)
2')" href="#">H 2
吸附和解离 相似文献
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