Selective oxidation of styrene on an oxygen-adsorbed Au(111): A density functional theory study

The reaction mechanism for the styrene selective oxidation on the oxygen preadsorbed Au(111) surface has been studied by the density functional theory calculation with the periodic slab model. The calculated results showed that the process of reaction includes two steps: forming the oxametallacycle intermediate (OMME) and then producing the products. It was found that the second step, from OMME to product is the rate-controlling step, which is similar to ethylene selective oxidation on Ag. Importantly, the present density-functional-theory calculation results suggested that the mechanism via the OMME (2) (i.e. the preadsorbed atomic oxygen bound to the CH2 group involved in C6H5--CH=CH2) to produce styrene epoxide is kinetically favored than that of OMME (1).     

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.     

Selective oxidation of styrene on an oxygen-covered Au(111)

For the first time, we demonstrate olefin epoxidation promoted by an extended Au surface. The oxidation of styrene to styrene epoxide, benzoic acid, and benzeneacetic acid is promoted on Au(111) covered with 0.2 ML of oxygen atoms. The estimated selectivity for styrene epoxide formation is approximately 53%. Total combustion to CO2 accounts for approximately 20% of the styrene reaction. We propose that styrene epoxide, benzoic acid, and benzeneacetic acid are produced via two possible oxametallacycle intermediates. Our work demonstrates that extended Au is an effective material for olefin oxidation, which has implications for understanding the activity of nanoscale Au catalysts.     

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.     

Methanol oxidation on the PtPd(111) alloy surface: A density functional theory study

The mechanisms of methanol (CH₃OH) oxidation on the PtPd(111) alloy surface were systematically investigated by using density functional theory calculations. The energies of all the involved species were analyzed. The results indicated that with the removal of H atoms from adsorbates on PtPd(111) surface, the adsorption energies of (i) CH₃OH, CH₂OH, CHOH, and COH increased linearly, while those of (ii) CH₃OH, CH₃O, CH₂O, CHO, and CO exhibited odd‐even oscillation. On PtPd(111) surface, CH₃OH underwent the preferred initial C H bond scission followed by successive dehydrogenation and then CHO oxidation, that is, CH₃OH → CH₂OH → CHOH → CHO → CHOOH → COOH → CO₂. Importantly, the rate‐determining step of CH₃OH oxidation was found to switch from CO → CO₂ on Pt(111) to COOH → CO₂ + H on PtPd(111) with a lower energy barrier of 0.96 eV. Moreover, water also decomposed into OH more easily on PtPd(111) than on Pt(111). The calculated results indicate that alloying Pt with Pd could efficiently improve its catalytic performance for CH₃OH oxidation through altering the primary pathways from the CO path on pure Pt to the non‐CO path on PtPd(111).     

CO2 Reduction Mechanism on the Cu2O(110) Surface: A First-Principles Study

Cu₂O is an attractive catalyst for the selective reduction of CO₂ to methanol. However, the mechanism of the reaction and the role of the Cu species in different oxidation states are not well understood yet. In this work, by first-principles calculations, we investigate the mechanism of the reaction on the Cu₂O(110) surface, which is the most selective for methanol, in different degrees of reduction: ideal surface, slightly reduced surface (SRS), and partially reduced surface (PRS). The most favorable reaction pathways on the three surfaces were identified. We found that Cu(I) on the ideal surface is not capable of chemisorbing CO₂, but surface oxygen serves as the active site which selectively converts CO₂ to CH₃OH with a limiting potential of −0.77 V. The Cu(0) on the SRS and PRS promotes the adsorption and reduction of CO₂, while the removal of the residue O* becomes potential/rate limiting with a more negative limiting potential than the ideal surface. The SRS is selective to methanol while the PRS becomes selective to methane. The result suggests that the key to high methanol selectivity is to avoid the reduction of Cu(I), which provides a new strategy for the design of more efficient catalysts for selective CO₂ reduction to methanol.     

On the performance of Au(111) for ethylene epoxidation: a density functional study

This work presents a periodic density functional study of the epoxidation mechanism of ethylene on Au(111). It is found that, once atomic oxygen is adsorbed on the surface, partial oxidation to ethylene oxide becomes possible. Calculated transition state theory rate constants for the elementary steps involved in the reaction predict that the selectivity of Au(111) toward epoxide is of approximately 40% in good agreement with recent experimental findings for styrene epoxidation on Au(111).     

Mechanistic Insights into Selectivity Control for Heterogeneous Olefin Oxidation: Styrene Oxidation on Au(111)

We demonstrate that intermolecular interactions, controlled by both oxygen and styrene coverage, alter reaction selectivity for styrene oxidation on oxygen‐covered Au(111). Several partial oxidation products are formed—styrene oxide, acetophenone, benzoic acid, benzeneacetic acid, and phenylketene—in competition with combustion. The maximum ratio of the yields of styrene oxide to the total CO₂ produced is obtained for the maximum styrene coverage for the first two layers (0.28 ML) adsorbed on Au(111) precovered with 0.2 ML of O. Furthermore, our reactivity and infrared studies support a mechanism whereby styrene oxidation proceeds via two oxametallacycle intermediates which, under oxygen‐lean conditions, lead to the formation of styrene oxide, acetophenone, and phenylketene. Benzoate, identified on the basis of infrared reflection absorption spectroscopy, is converted into benzoic acid during temperature‐programmed reaction. These results demonstrate the ability to tune the epoxidation selectivity using reactant coverages and provide important mechanistic insight into styrene oxidation reactions.     

Adsorption Behavior and Reaction Properties of NO and CO on Ir(111) and Rh(111)

Adsorption and reactions of NO over the clean and CO-preadsorbed Ir(111) and Rh(111) surfaces were investigated using infrared reflection absorption spectroscopy (IRAS) and temperature programmed desorption (TPD). Two NO adsorption states, indicative of hollow and atop sites, were present on Ir(111). Only NO adsorbed on hollow sites dissociated to N_a and O_a. The dissociated N_a desorbed as N₂ by recombination of N_a and by a disproportionation reaction between atop-NO and N_a. Preadsorbed CO inhibited atop-NO, whereas hollow-NO was not affected. Adsorbed CO reacted with O_a and desorbed as CO₂. NO adsorbed on the fcc-hollow, atop, and hcp-hollow sites in that order over Rh(111). The hcp-NO was inhibited by preadsorbed atop-CO, and fcc-NO and atop-NO were inhibited by CO preadsorbed on each type of the sites, indicating that NO and CO competitively adsorbed on Rh(111). From the Rh(111) surface-coadsorbed NO and CO, N₂ was produced by fcc-NO dissociation, and CO₂ was formed by reaction of adsorbed CO with O_a from dissociated fcc-NO.     

A DFT theoretical study of CH_4 dissociation on gold-alloyed Ni(111)surface

A density-functional theory(DFT)method has been conducted to systematically investigate the adsorption of CHx(x=0～4)as well as the dissociation of CHx(x=1～4)on(111)facets of gold-alloyed Ni surface.The results have been compared with those obtained on pure Ni(111)surface.It shows that the adsorption energies of CHx(x=1～3)are lower,and the reaction barriers of CH4 dissociation are higher in the first and the fourth steps on gold-alloyed Ni(111)compared with those on pure Ni(111).In particular,the rate-determining step for CH4 dissociation is considered as the first step of dehydrogenation on gold-alloyed Ni(111),while it is the fourth step of dehydrogenation on pure Ni(111).Furthermore,the activation barrier in rate-determining step is higher by 0.41 eV on gold-alloyed Ni(111)than that on pure Ni(111).From above results,it can be concluded that carbon is not easy to form on gold-alloyed Ni(111)compared with that on pure Ni(111).     

苯乙烯在Ag(111)和Ag(110)表面环氧化反应结构敏感性的理论研究

采用密度泛函理论(DFT)对苯乙烯在Ag(110)表面和Ag(111)表面的环氧化反应进行了计算研究. 经计算, 在Ag(110)表面预吸附氧原子更易吸附在3 重穴位(3h), 吸附能为-3.59 eV; 在Ag(111)表面预吸附氧原子的最稳定吸附位是fcc 位, 吸附能为-3.69 eV. 苯乙烯的环氧化反应过程首先经过一个金属中间体, 然后再进一步反应变为产物, 其中经过直链中间体较支链中间体更加有利. Ag(110)面的反应活化能一般大于Ag(111)面的, 并且微观动力学模拟结果表明, Ag(111)表面生成环氧苯乙烷的选择性要明显高于Ag(110)表面(0.38 与 0.003), 原因是Ag(111)面环氧化反应活化能小于苯乙醛及燃烧中间体的活化能, 而在Ag(110)上正相反.     

Efficient epoxidation of a terminal alkene containing allylic hydrogen atoms: trans-methylstyrene on Cu{111}

The selective oxidation of trans-methylstyrene, a phenyl-substituted propene that contains labile allylic hydrogen atoms, has been studied on Cu{111}. Mass spectrometry and synchrotron fast XPS were used to detect, respectively, desorbing gaseous products and the evolution of surface species as a function of temperature and time. Efficient partial oxidation occurs yielding principally the epoxide, and the behavior of the system is sensitive to the order in which reactants are adsorbed. The latter is understandable in terms of differences in the spatial distribution of oxygen adatoms; isolated adatoms lead to epoxidation, while islands of "oxidic" oxygen do not. NEXAFS data taken over a range of coverages and in the presence and absence of coadsorbed oxygen indicate that the adsorbed alkene lies essentially flat with the allylic hydrogen atoms close to the surface. The photoemission results and comparison with the corresponding behavior of styrene on Cu{111} strongly suggest that allylic hydrogen abstraction is indeed a critical factor that limits epoxidation selectivity. An overall mechanism consistent with the structural and reactive properties is proposed.     

Ambient Pressure X-ray Photoelectron Spectroscopy Study of Oxidation Phase Transitions on Cu(111) and Cu(110)

The surface structure effect on the oxidation of Cu has been investigated by performing ambient-pressure X-ray photoelectron spectroscopy (APXPS) on Cu(111) and Cu(110) surfaces under oxygen pressures ranging from 10⁻⁸ to 1 mbar and temperatures from 300 to 750 K. The APXPS results show a subsequential phase transition from chemisorbed O/Cu overlayer to Cu₂O and then to CuO on both surfaces. For a given temperature, the oxygen pressure needed to induce initial formation of Cu₂O on Cu(110) is about two orders of magnitude greater than that on Cu(111), which is in contrast with the facile formation of O/Cu overlayer on clean Cu(110). The depth profile measurements during the initial stage of Cu₂O formation indicate the distinct growth modes of Cu₂O on the two surface orientations. We attribute these prominent effects of surface structure to the disparities in the kinetic processes, such as the dissociation and surface/bulk diffusion over O/Cu overlayers. Our findings provide new insights into the kinetics-controlled process of Cu oxidation by oxygen.     

Pd/Cu(111)双金属表面催化糠醛脱碳及加氢的反应机理

采用密度泛函理论(DFT)研究糠醛在最稳定Pd/Cu(111)双金属表面上的吸附构型和糠醛脱碳及加氢的反应机理。结果表明,当糠醛初始吸附于O_3-Pd-top、O_7-Cu-hcp位时,吸附构型最稳定,其吸附能为73.4 kJ/mol。糠醛在Pd/Cu(111)双金属表面上更易发生脱碳反应。对于糠醛脱碳反应,所需活化能较低,各个基元反应均为放热反应,糠醛更易先失去支链上的H形成(C_4H_3O)CO,然后中间体脱碳加氢得到呋喃,其中,C_4H_3O加氢生成呋喃所需活化能(72.6 kJ/mol)最高,是反应的控速步骤。对于加氢反应,糠醛与首个氢原子的反应需要最大的活化能(290.4 kJ/mol),是反应的限速步骤。     

单原子Ge助剂修饰Cu(111)晶面上CO2加氢制甲醇的机理研究

针对CO₂热催化转化制甲醇过程中CO₂吸附、活化较困难及副产物较多的问题,提出采用单原子Ge助剂修饰Cu (111)晶面的解决思路,通过密度泛函理论(DFT)计算研究了CO₂在Ge-Cu(111)晶面上加氢合成甲醇的反应机理。结果表明,单原子Ge助剂的电子调控增加了与其相邻的Cu原子的电子云密度,使CO₂分子在含Ge活性界面上的吸附能力显著增强：CO₂在Ge-Cu(111)晶面上的吸附能约为Cu (111)晶面的1.5倍,约为Pd改性Cu(111)晶面的2.4倍,进而使逆水煤气变换(RWGS)反应路径速控步骤的活化能降低了近20 kJ·mol^-1,同时衍生出3条生成甲醇的RWGS新路径;此外,Ge-Cu(111)晶面上甲酸盐路径由于速控步骤活化能大幅上升而被禁阻,进而CO及烃类等副产物选择性大幅降低,Ge-Cu(111)晶面上CO₂加氢制甲醇选择性升高。     

Water Formation for the Metalation of Porphyrin Molecules on Oxidized Cu(111)

Herein the formation of water molecules in the intermediate step of the redox reaction of porphyrins self‐metalation on O/Cu(111) is demonstrated. Photoemission measurements show that the temperature on which porphyrins pick‐up a substrate metal atom on O/Cu(111) is reduced by about 185±15 K with respect to the pure Cu(111). DFT calculations clearly indicate that the formation of a water molecule is less expensive than the formation of H₂ on the O/Cu(111) substrate and, in some cases, it can be also exothermic.     

单原子Ge助剂修饰Cu(111)晶面上CO2加氢制甲醇的机理研究

针对CO₂热催化转化制甲醇过程中CO₂吸附、活化较困难及副产物较多的问题,提出采用单原子Ge助剂修饰Cu(111)晶面的解决思路,通过密度泛函理论(DFT)计算研究了CO₂在Ge-Cu(111)晶面上加氢合成甲醇的反应机理。结果表明,单原子Ge助剂的电子调控增加了与其相邻的 Cu 原子的电子云密度,使 CO₂分子在含 Ge 活性界面上的吸附能力显著增强:CO₂在 Ge-Cu(111)晶面上的吸附能约为Cu(111)晶面的1.5倍,约为Pd改性Cu(111)晶面的2.4倍,进而使逆水煤气变换(RWGS)反应路径速控步骤的活化能降低了近 20 kJ·mol^-1,同时衍生出 3条生成甲醇的 RWGS新路径;此外,Ge-Cu(111)晶面上甲酸盐路径由于速控步骤活化能大幅上升而被禁阻,进而CO及烃类等副产物选择性大幅降低,Ge-Cu(111)晶面上CO₂加氢制甲醇选择性升高。     

The electrochemical interface between copper(111) and aqueous electrolytes

The electrochemical double layer between Cu(111) electrodes and aqueous electrolytes (F⁻ and SO²⁻₄ at various pH values) was studied by means of linear scan voltammetry and ac impedance measurements. It is found that electrochemisorption of oxygen species proceeds on the Cu(111) surface in the potential regions more negative than the electrodissolution potential of copper. The adsorption-desorption kinetics are analysed; the anodic and cathodic symmetry coefficients are found to be equal (α = β = 0.3), and the standard rate constant is k° = 4 × 10⁻¹⁰cm s⁻¹.     

Softening of C-H Symmetric Stretching Vibrational Modes for CH2 and CH3 Radicals Adsorbed on Cun (n=1-6) Clusters

The properties of C-H vibration softening for CH₂ and CH₃ radicals absorbed on Cu_n(n=1-6) clusters have been investigated, using the density functional theory with hybrid functional. The results indicate that the absorption of CH₂ on Cu clusters is stronger than the case of CH₃. The vibrational frequencies of C-H bonding agree with the experimental results obtained for CH₂ and CH₃ absorbed on Cu(111). With the increase of cluster size, the softening (Einstein shift) of C-H vibrational modes become stronger.     

氧化锌有序结构在Au(111)和Cu(111)上的生长

利用NO₂或O₂作为氧化剂,研究了氧化锌在Au(111)和Cu(111)上的生长和结构。NO₂表现了更好的氧化性能,有利于有序氧化锌纳米结构或薄膜的生长。在Au(111)和Cu(111)这两个表面上,化学计量比氧化锌都形成非极性的平面化ZnO(0001)的表面结构。在Au(111)上,NO₂气氛下室温沉积锌倾向于形成双层氧化锌纳米结构;而在更高的沉积温度下,在NO₂气氛中沉积锌则可同时观测到单层和双层氧化锌纳米结构。O₂作为氧化剂时可导致形成亚化学计量比的ZnO_x结构。由于铜和锌之间的强相互作用会促进锌的体相扩散,并且铜表面可以被氧化形成表面氧化物,整层氧化锌在Cu(111)上的生长相当困难。我们通过使用NO₂作为氧化剂解决了这个问题,生长出了覆盖Cu(111)表面的满层有序氧化锌薄膜。这些有序氧化锌薄膜表面显示出莫尔条纹,表明存在一个ZnO和Cu(111)之间的莫尔超晶格。实验上观察到的超晶格结构与最近理论计算提出的Cu(111)上的氧化锌薄膜结构相符,具有最小应力。我们的研究表明,氧化锌薄膜的表界面结构可能会随氧化程度或氧化剂的不同而变化,而Cu(111)的表面氧化也可能影响氧化锌的生长。当Cu(111)表面被预氧化成铜表面氧化物时,ZnO_x的生长模式会发生变化,锌原子会受到铜氧化物晶格的限域形成单位点锌。我们的研究表明了氧化锌的生长需要抑制锌向金属基底的扩散,并阻止亚化学计量比ZnO_x的形成。因此,使用原子氧源有利于在Au(111)和Cu(111)表面上生长有序氧化锌薄膜。