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.     

Thermal decomposition of HSCH2CH2OH on Cu(111): identification and adsorption geometry of surface intermediates

X-ray photoelectron spectroscopy has been employed to study the surface intermediates from the thermal decomposition of HSCH2CH2OH on Cu(111) at elevated temperatures. On the basis of the changes of the core-level binding energies of C, O, and S as a function of temperature, it is found that HSCH2CH2OH decomposes sequentially to form -SCH2CH2OH and -SCH2CH2O-. Theoretical calculations based on density functional theory for an unreconstructed one-layer copper surface suggest that -SCH2CH2OH is preferentially bonded at a 3-fold hollow site, with an adsorption energy lower than the cases at bridging and atop sites by 15.6 and 47.5 kcal x mol(-1), respectively. Other structural characteristics for the energy-optimized geometry includes the tilted C-S bond (14.1 degrees with respect to the surface normal), the C-C bond titled toward a bridging site, and the C-O bond pointed toward the surface. In the case of -SCH2CH2O- on Cu(111), the calculations suggest that the most probable geometry of the adsorbate has its S and O bonded at hollow and bridging sites, respectively. With respect to the surface normal, the angles of the S-C and O-C are 27.9 and 34.0 degrees.     

Structure investigation of Ag(111)(radical7x radical7)R19 degrees -SCH3 by X-ray standing waves: a case of thiol-induced substrate reconstruction

The structure of the Ag(111)(radical7x radical7)R19 degrees-CH3S surface phase, formed by interaction of Ag(111) with gas-phase dimethyl disulfide, (CH3S)2, has been investigated by normal-incidence X-ray standing wave (NIXSW) analysis, using (111), (11), and (200) Bragg reflections. The resulting NIXSW structural parameter values clearly exclude any simple overlayer adsorption model on an Ag unreconstructed surface. A reconstructed surface model is proposed that is consistent with the NIXSW measurements and with previous scanning tunneling microscopy results. This comprises a near-hexagonal Ag surface layer with an Ag density of only 3/7 that of the underlying substrate layers; the methanethiolate molecules are adsorbed into 3-fold coordinated hollow sites on this open layer. The results are discussed in the context of the very limited published studies of longer alkyl chain thiolates on Ag(111).     

洁净和氧吸附的Cu(100)表面重构的理论研究

The interaction of atomic oxygen with the clean Cu(100) surface has been studied by means of cluster and periodic slab models density functional theory in the present paper. The Cu(4,9,4) cluster and a three-layer slab with c(2×2) structure are used to model the perfect Cu(100) surface. Three possible adsorption sites,top, bridge and hollow site, were considered in the calculations. The predicted results show that the hollow site is the prefer site for atomic oxygen adsorbed on Cu(100) surface energetically. This is in good agreement with the experiment. The calculated binding energies are respective 2.014, 3.154 and 3.942 eV for top, bridge and hollow sites at mPW1PW91/LanL2dz level for the cluster model. The geometry of Cu(100) surface has also been optimized theoretically with various density functional methods and the results show that the prediction from the B3PW91/LanL2dz and mPW1PW91/LanL2dz reproduce the experimental observation.The frontier molecular orbitals and partial density of states analysis show that the electron transfer from the d orbital of substrate to the p orbital of the surface oxygen atom.     

CO和H2分子在Cu(111)面的吸附和溶剂化效应

采用广义梯度近似(GGA)密度泛函理论(DFT)的PW91方法结合周期性模型, 在DNP基组下, 利用Dmol3模块研究了CO和H2在真空和液体石蜡环境下在Cu(111)表面上不同位置的吸附. 计算结果表明, 溶剂化效应对H2和CO的吸附结构参数和吸附能的影响非常显著. 在液体石蜡环境下, H2平行吸附在Cu(111)表面是解离吸附, 而CO 和H2在两种环境下的垂直吸附都是非解离吸附. 相比真空环境吸附, 在液体石蜡环境中, Cu(111)吸附CO时, 溶剂化效应能够提高CO吸附的稳定性, 同时有利于CO的活化. 在真空中, H2只能以垂直方式或接近垂直方式吸附在Cu(111)表面. 当Cu(111)顶位垂直吸附H2, 相比真空环境吸附, 溶剂化效应能够提高H2吸附的稳定性, 但对H2的活化没有明显影响. Cu(111)表面的桥位或三重穴位(hcp和fcc)垂直吸附H2时, 溶剂化效应能明显提高H2的活化程度, 但降低H2的吸附稳定性; 在液体石蜡中, 当H2平行Cu(111)表面吸附时, 溶剂化效应使H—H键断裂, 一个H原子吸附在fcc位, 另一个吸附在hcp位.     

甲硫醇在Cu(111)表面的解离吸附: 密度泛函理论研究

采用基于密度泛函理论的第一性原理方法和平板模型研究了CH₃SH分子在Cu(111)表面的吸附反应.系统地计算了S原子在不同位置以不同方式吸附的一系列构型, 第一次得到未解离的CH₃SH分子在Cu(111)表面顶位上的稳定吸附构型,该构型吸附属于弱的化学吸附, 吸附能为0.39 eV. 计算同时发现在热力学上解离结构比未解离结构更加稳定. 解离的CH₃S吸附在桥位和中空位之间, 吸附能为0.75-0.77 eV. 计算分析了未解离吸附到解离吸附的两条反应路径, 最小能量路径的能垒为0.57 eV. 计算结果还表明S―H键断裂后的H原子并不是以H₂分子的形式从表面解吸附而是以与表面成键的形式存在. 通过比较S原子在独立的CH₃SH分子和吸附状态下的局域态密度, 发现S―H键断裂后S原子和表面的键合强于未断裂时S原子和表面的键合.     

Chemisorption of (CHx and C2Hy) hydrocarbons on Pt(111) clusters and surfaces from DFT studies

We used the B3LYP flavor of density functional theory (DFT) to study the chemisorption of all CH(x) and C(2)H(y) intermediates on the Pt(111) surface. The surface was modeled with the 35 atom Pt(14.13.8) cluster, which was found to be reliable for describing all adsorption sites. We find that these hydrocarbons all bind covalently (sigma-bonds) to the surface, in agreement with the studies by Kua and Goddard on small Pt clusters. In nearly every case the structure of the adsorbed hydrocarbon achieves a saturated configuration in which each C is almost tetrahedral with the missing H atoms replaced by covalent bonds to the surface Pt atoms. Thus, (Pt(3))CH prefers a mu(3) hollow site (fcc), (Pt(2))CH(2) prefers a mu(2) bridge site, and PtCH(3) prefers mu(1) on-top sites. Vinyl leads to (Pt(2))CH-CH(2)(Pt), which prefers a mu(3) hollow site (fcc). The only exceptions to this model are ethynyl (CCH), which binds as (Pt(2))C=CH(Pt), retaining a CC pi-bond while binding at a mu(3) hollow site (fcc), and HCCH, which binds as (Pt)HC=CH(Pt), retaining a pi bond that coordinates to a third atom of a mu(3) hollow site (fcc) to form an off center structure. These structures are in good agreement with available experimental data. For all species we calculated heats of formation (DeltaH(f)) to be used for considering various reaction pathways on Pt(111). For conditions of low coverage, the most strongly bound CH(x) species is methylidyne (CH, BE = 146.61 kcal/mol), and ethylidyne (CCH(3), BE = 134.83 kcal/mol) among the C(2)H(y) molecules. We find that the net bond energy is nearly proportional to the number of C-Pt bonds (48.80 kcal/mol per bond) with the average bond energy decreasing slightly with the number of C ligands.     

CO adsorption and reaction on clean and oxygen-covered Au(211) surfaces

We have used primarily temperature-programmed desorption (TPD) and infrared reflection-absorption spectroscopy (IRAS) to investigate CO adsorption on a Au(211) stepped single-crystal surface. The Au(211) surface can be described as a step-terrace structure consisting of three-atom-wide terraces of (111) orientation and a monatomic step with a (100) orientation, or 3(111) x (100) in microfacet notation. CO was only weakly adsorbed but was more strongly bound at step sites (12 kcal mol(-1)) than at terrace sites (6.5-9 kcal mol(-1)). The sticking coefficient of CO on the Au(211) surface was also higher ( approximately 5x) during occupation of step sites compared to populating terrace sites at higher coverages. The nu(CO) stretching band energy in IRAS spectra indicated that CO was adsorbed at atop sites at all coverages and conditions. A small red shift of nu(CO) from 2126 to 2112 cm(-1) occurred with increasing CO coverage on the surface. We conclude that the presence of these particular step sites at the Au(211) surface imparts stronger CO bonding and a higher reactivity than on the flat Au(111) surface, but these changes are not remarkable compared to chemistry on other more reactive crystal planes or other stepped Au surfaces. Thus, it is unlikely that the presence or absence of this particular crystal plane alone at the surface of supported Au nanoparticles has much to do with the remarkable properties of highly active Au catalysts.     

氢原子在Ni(111)次表面和Ni(211)、(533)台阶面上的吸附与振动

应用原子与表面簇合物相互作用的五参数Morse势(5-MP)方法对氢原子在Ni(111)表面和次表面以及Ni(211), (533)台阶面进行了系统研究, 得到了氢原子在上述各面的吸附位、吸附几何、结合能和本征振动频率. 计算结果表明, 在Ni(111)面上, 氢原子优先吸附在三重位, 随着覆盖度的增加会吸附在次表面八面体位和四面体位. Ni(211), (533)的最优先吸附位都是四重位, 当氢原子的覆盖度增大时占据(111)平台的三重吸附位. 靠近台阶面的吸附位受台阶和平台高度的影响很大. 此外, 我们计算了氢原子在各表面的不同吸附位的扩散势垒, 获得氢原子在各表面的最低能量扩散通道.     

Plasma-assisted oxidation of Cu(100) and Cu(111)

Oxidized copper surfaces have attracted significant attention in recent years due to their unique catalytic properties, including their enhanced hydrocarbon selectivity during the electrochemical reduction of CO₂. Although oxygen plasma has been used to create highly active copper oxide electrodes for CO₂RR, how such treatment alters the copper surface is still poorly understood. Here, we study the oxidation of Cu(100) and Cu(111) surfaces by sequential exposure to a low-pressure oxygen plasma at room temperature. We used scanning tunnelling microscopy (STM), low energy electron microscopy (LEEM), X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and low energy electron diffraction (LEED) for the comprehensive characterization of the resulting oxide films. O₂-plasma exposure initially induces the growth of 3-dimensional oxide islands surrounded by an O-covered Cu surface. With ongoing plasma exposure, the islands coalesce and form a closed oxide film. Utilizing spectroscopy, we traced the evolution of metallic Cu, Cu₂O and CuO species upon oxygen plasma exposure and found a dependence of the surface structure and chemical state on the substrate''s orientation. On Cu(100) the oxide islands grow with a lower rate than on the (111) surface. Furthermore, while on Cu(100) only Cu₂O is formed during the initial growth phase, both Cu₂O and CuO species are simultaneously generated on Cu(111). Finally, prolonged oxygen plasma exposure results in a sandwiched film structure with CuO at the surface and Cu₂O at the interface to the metallic support. A stable CuO(111) surface orientation is identified in both cases, aligned to the Cu(111) support, but with two coexisting rotational domains on Cu(100). These findings illustrate the possibility of tailoring the oxidation state, structure and morphology of metallic surfaces for a wide range of applications through oxygen plasma treatments.

A low-pressure oxygen plasma oxidized Cu(100) and Cu(111) surfaces at room temperature. The time-dependent evolution of surface structure and chemical composition is reported in detail for a range of exposure times up to 30 min.     

The reactive chemisorption of alkyl iodides at Cu(110) and Ag(111) surfaces: a combined STM and XPS study

The chemisorption of methyl and phenyl iodide has been studied at Cu(110) and Ag(111) surfaces at 290 K with STM and XPS. At both surfaces dissociative adsorption of both molecules leads to chemisorbed iodine, with the STM showing c(2 x 2) and (square root 3 x square root 3)R30 structures at the Cu(110) and Ag(111) surfaces, respectively. At the Cu(110) surface a comparison of coexisting c(2 x 2) I(a) and p(2 x 1) O(a) domains shows the iodine adatoms to be chemisorbed in hollow sites with evidence at low coverage for diffusion in the (110) direction. In the case of methyl iodide no carbon adsorption is observed at either the silver or the copper surfaces, but chemisorbed phenyl groups are imaged at the Cu(110) surface after exposure to phenyl iodide. The STM images show the phenyl groups as bright features approximately 0.7 nm in diameter and 0.11 nm above the iodine adlayer, reaching a maximum surface concentration after approximately 6 Langmuir exposure. However, the phenyl coverage decreases with subsequent exposures to PhI and is negligible by approximately 1000 L exposure, consistent with the formation and desorption of biphenyl. The adsorbed phenyls are located above hollow sites in the substrate, they are stabilized at the top and bottom of step edges and in paired chains (1.1 nm apart) on the terraces with a regular interphenyl spacing within the chains of 1.0 nm in the (110) direction. The interphenyl ring spacing and diffusion of individual phenyls from within the chains shows that the chains do not consist of biphenyl species but may be a precursor to their formation. Although the XPS data shows carbon present at the Ag(111) surface after exposure to PhI, no features attributable to phenyl groups were observed by STM.     

The chemisorption of hydrogen on Cu(111): A dynamical study

Ab initio band-structure calculations within a density functional formalism were performed to compute the binding energy curves of atomic hydrogen with the high-symmetry adsorption sites of the (111) surface of copper. For a two-layer slab of Cu atoms and H coverage equal to 0.25, the binding energies are 2.25, 3.12, and 3.24 eV, for on-top, bridge, and threefold sites, so that the chemisorption of H₂ on Cu(111) is exothermic for threefold and bridge sites, but endothermic for on-top sites. Starting from these results, an LEPS potential for the interaction of H₂ with the Cu(111) surface was built. In this model potential, the most favored approaches correspond to a H₂ molecule parallel to the Cu surface, and for them, the activation barrier is located at the corner between the entrance and the exit channels of the reaction, and its lowest value is 0.6 eV. The LEPS potential was used in quasi-classical trajectories calculations to simulate the adsorption of a beam of H₂ molecules on Cu(111). The results show that (a) when H₂ is in the ground vibrational state the dissociative adsorption probability P_a increases from 0 to .90 along a roughly sigmoidal curve by increasing the collision kinetic energy from 0.4 to 1.3 eV, and (b) the vibrational energy can be as effective as the translational one in promoting dissociative chemisorption, in agreement with the experimental results. © 1994 John Wiley & Sons, Inc.     

NO在Rh(100),Rh(111)面上吸附与直接分解的密度泛函理论研究

本文应用第一性原理的密度泛函(DFT)方法,使用DMol³计算程序,对NO在Rh(100)和Rh(111)面上的吸附与分解进行量化计算,力图解决NO在Rh(100)和Rh(111)面上的优选吸附位、直接分解的过渡态和活化能等重要问题.     

丙烯腈在Cu(111)面上化学吸附的密度泛函研究及NBO分析

利用密度泛函方法对丙烯腈在Cu(111)面上不同吸附位的吸附状态进行了理论研究. 计算结果表明, 丙烯腈分子通过端位N原子立式吸附在金属铜表面为弱化学吸附, 其中桥位为较佳吸附位, 结合能为-40.16 kJ/mol; 丙烯腈分子和金属铜之间发生了电荷转移, N原子的孤对电子与金属形成σ共价键; 对丙烯腈分子结构变化进行了NBO分析, 解释了丙烯腈分子吸附后被活化的原因.     

氢原子在Pt及Pt系双金属催化表面吸附的密度泛函理论研究

采用密度泛函理论(dFT)考察了Pt(100)、(110)、(111)三种表面氢原子的吸附行为, 计算了覆盖度为0.25 ML时氢原子在Pt 三种表面和M-Pt(111)双金属(M=Al, Fe, Co, Ni, Cu, Pd)上的最稳定吸附位、表面能以及吸附前后金属表面原子层间弛豫情况. 分析了氢原子在不同双金属表面吸附前后的局域态密度变化以及双金属表面d 带中心偏离费米能级的程度并与氢吸附能进行了关联. 计算结果表明, 在Pt(100), Pt(110)和Pt(111)表面, 氢原子的稳定吸附位分别为桥位、短桥位和fcc 穴位. 三种表面中以Pt(111)的表面能最低, 结构最稳定. 氢原子在不同M-Pt(111)双金属表面上的最稳定吸附位均为fcc 穴位, 其中在Ni-Pt 双金属表面的吸附能最低, Co-Pt 次之. 表明氢原子在Ni-Pt 和Co-Pt 双金属表面的吸附最稳定. 通过对氢原子在M-Pt(111)双金属表面吸附前后的局域态密度变化的分析, 验证了氢原子吸附能计算结果的准确性. 掺杂金属Ni、Co、Fe 的3d-Pt(111)双金属表面在吸附氢原子后发生弛豫, 第一层和第二层金属原子均不同程度地向外膨胀. 此外, 3d金属的掺入使得其对应的M-Pt(111)双金属表面d带中心与Pt 相比更靠近费米能级, 吸附氢原子能力增强, 表明3d-Pt系双金属表面有可能比Pt具有更好的脱氢活性.     

原子H在Cu(100)(111)(110)上的吸附扩散研究

采用5-MP势方法,对原子氢在金属Cu的3个低指数面上的吸附特性,如吸附几何、吸附能、振动频率等以及吸附扩散势能面结构进行了比较系统的研究,计算结果显示低温低覆盖条件下,氢原子在Cu(110)表面上只存在赝式三重位和长桥位吸附态,没有短桥位吸附态,并且获得了实验和理论的支持.     

A theoretical study of atomic oxygen chemisorption on the Ni(100) and Ni(111) surfaces

Atomic oxygen chemisorption has been studied for the fourfold hollow site of the Ni(100) surface and for the threefold hollow site of the Ni(111) surface. To model the Ni(100) surface, 10 different clusters in the range Ni₅ to Ni₄₁ were used, and for the Ni(111) surface, 11 different clusters in the range Ni₁₃ to Ni₄₃ were used. A detailed analysis of the orbital occupations of the cluster with and without oxygen for the different clusters shows that there are three different possible bonding mechanisms. In two of these, the basic feature is that a₁ electrons of the cluster are kicked out by the oxygen 2p_z orbital and moved to holes in the 2p_{x, y} orbitals. A picture where the oxygen electrons fit into the electronic structure of the cluster is emphasized. The third mechanism, which is applicable for only one cluster, can be described as the formation of two covalent bonds of E symmetry. The final best estimate of the oxygen chemisorption energy for the Ni(100) surface is about 130 kcal/mol, and for the Ni(111) surface, about 115 kcal/mol. In particular for the Ni(111) surface, an excited oxygen state with radical character is identified, which might be a catalytically important species. The excitation energy to reach this state should be on the order of 10 kcal/mol for the Ni(111) surface.     

Theoretical study of NO adsorption/dissociation on Pd (100) and (111) surfaces

Both adsorption and dissociation of the diatomic molecular NO on Pd (100) and (111) surfaces are studied using the extended London‐Eyring‐Polyani‐Sato (LEPS) method constructed by means of 5‐MP (the 5‐parameter Morse potential). All critical characteristics of the system that we obtain, such as adsorption geometry, binding energy, eigenvalues for vibration, are in good agreement with the experimental results. On Pd (100) surface, NO prefers to adsorb in fourfold hollow site (H) uprightly at low coverage. With increase in the coverage NO gradually tilts in fourfold hollow and bridge sites. For NO? Pd (111) system, two adsorption states are found at low coverage, of which one adsorption state is the B(tilt) state that the centroid of NO projects at bridge site, another (H? B? H state) that NO almost parallels to the (111) surface with the vibration frequency of 610 cm^?1, but the frequency is near to that of the atoms, which is easy to be ignored in experiments. At high coverage, two transitional states (BH and HT) are found. NO is difficult to dissociate on Pd (100) and (111) surfaces. Especially for NO? Pd (111) system, the three‐well‐potential dissociation mode is initially put forward to show the remarkable dissociation process with two dissociation transitional states of NO on Pd (111). Copyright © 2008 John Wiley & Sons, Ltd.     

Adsorption of O, H, OH, and H2O on Ag(100)

The adsorption of H(2)O and its dissociation products, O, H, and OH, on Ag(100) has been studied using an ab initio embedding method. Results at different sites (atop, bridge, and hollow) are presented. The four-fold hollow site is found to be the most stable adsorption site for O, H, and OH, and the calculated adsorption energies are 87.1, 42.7, and 76.2 kcal mol(-1), respectively. The adsorption energy of water at the atop and bridge sites is almost identical with values of 11.1 and 12.0 kcal mol(-1), respectively. The formation of adsorbed OH species by adsorption of water on oxygen-precovered Ag(100) is predicted to be exothermic by 36 kcal mol(-1).     

The reaction kinetics of Cu with the CdTe(111)-B surface: formation of metastable Cu(x)Te (x approximately 2)

In the present study, elemental Cu is deposited on the clean CdTe(111)-B surface and annealed in vacuum. Surface-composition maps generated by scanning Auger microcopy provide evidence that a reaction occurs between Cu and the CdTe(111)-B substrate that results in the formation of a metastable copper telluride phase Cu(x)Te (x approximately 2) at the surface. In situ thermal-desorption mass spectrometry measurements show that elemental Cd is released during the reaction and desorbs from the surface. Desorption of Te from the substrate is suppressed during the reaction. Analysis of Cd desorption traces demonstrates that the Cu + CdTe(111)-B reaction proceeds via zero-order kinetics, with an activation energy of 180 +/- 5 kJ mol(-1).