一氧化碳在原子簇Zn_4O_4上吸附的从头算研究

以原子簇Zn_4O_4模型,用量子化学的从头算方法与补偿方法（counterpoise ）相结合研究了一氧化碳在氧化锌极化表面Zn-ZnO(0001)和O-ZnO(000-1)及在非极 化（10-10）表面的吸附态和吸附键能。研究表明,无论锌离子以何种方式出现在 晶体表面,锌离子都是较强的活化吸附中心,CO的碳原子向内的吸附键最强。这一 结论与宏观实验测试的结果相一致,尽管宏观实验测试的结果在上述不同晶体表在 相近的CO脱附热。这种不同氧化锌晶体表面有相近的CO脱附热的现象是由于晶体表 面存在固有的晶体缺陷-表面层阶梯造成的。补偿方法,主要用于计算不同活化吸 附点的吸附质与吸附剂的弱作用。以Zn_4O_4为模型,以氧离子为活化吸附位,对 CO在氧化锌表面的计算结果表明,当CO分子垂直于晶体表面显排斥作用,当CO分子 平行于晶体表面仅有弱的吸附键。     

The nature of the oxidation states of gold on ZnO

The interaction between gold in the 0, i, ii and iii oxidation states and the zinc-terminated ZnO(0001) surface is studied via the QM/MM electronic embedding method using density functional theory. The surface sites considered are the vacant zinc interstitial surface site (VZISS) and the bulk-terminated island site (BTIS). We find that on the VZISS, only Au(0) and Au(i) are stable oxidation states. However, all clusters of i to iii oxidation states are stable as substitutionals for Zn2+ in the bulk terminated island site. Au(OH)(x) complexes (x= 1-3) can adsorb exothermically onto the VZISS, indicating that higher oxidation states of gold can be stabilised at this site in the presence of hydroxyl groups. CO is used as a probe molecule to study the reactivity of Au in different oxidation states in VZISS and BTIS. In all cases, we find that the strongest binding of CO is to surface Au(i). Furthermore, CO binding onto Au(0) is stronger when the gold atom is adsorbed onto the VZISS compared to CO binding onto a gas phase neutral gold atom. These results indicate that the nature of the oxidation states of Au on ZnO(0001) will depend on the type of adsorption site. The role of ZnO in Au/ZnO catalysts is not, therefore, merely to disperse gold atoms/particles, but to also modify their electronic properties.     

Adsorption of single Cu atoms at differently stabilized polar ZnO surfaces: An ab initio study

In this study, the adsorption of a single Cu atom on the polar ZnO(0001) and ZnO(0001) surfaces was investigated by means of highly accurate wave function based ab initio methods. Different modifications of the polar surfaces were investigated: unstabilized surfaces, surfaces with hydrogen and OH overlayers, and defectious surfaces. Cu is strongly bound at the unstabilized surfaces by a charge transfer mechanism which induces a stabilization of the surface. At regular adsorption sites of stabilized surfaces the binding energies are much smaller. At oxygen defects, the Cu electron is transferred to the defect and a Cu(+) ion sits on top of the defect. At the Zn terminated surface the Cu moves into the Zn defects.     

Structure and dynamics of CO overlayers on a hydroxylated metal oxide: the polar ZnO(0001) surface

The adsorption and desorption of CO on the hydroxylated, O-terminated polar ZnO(0001) surface has been studied using He-atom scattering. The experimental results reveal the formation of a physisorbed ordered CO overlayer. In addition to recording angular distributions of elastically scattered He atoms, also the dynamical properties of the CO overlayer have been investigated using inelastic He-atom scattering. With the aid of electronic structure calculations a loss peak with an energy transfer of 7.2 meV is assigned to the frustrated translation of the CO molecule normal to the surface.     

Interaction between poly(styrene-acrylic acid) latex nanoparticles and zinc oxide surfaces

Latex particles with an average diameter of 70 nm, functionalized at the surface with carboxylic groups, are chemically coated by layer-by-layer deposition onto a spherical probe attached on an atomic force microscope cantilever. The forces between poly(styrene-acrylic acid) latex nanoparticles and differently terminated zinc oxide surfaces are studied by a homemade atomic force microscope based apparatus. The results confirmed a preferred adhesion of the latex particles to zinc-terminated ZnO faces, 0001, compared to oxygen-terminated and apolar faces. The method proposed allows the measurement of the interaction between nanometric particles and planar surfaces, which may be of interest for different applications in surface and colloid sciences.     

Potential energy calculations for argon and methane adsorbed on MgO(001) substrate

A semi-empirical potential model is used to calculate the interaction energy of a rare gas atom or a methane molecule adsorbed on a MgO substrate with square symmetry. The potential surfaces are drawn and compared with the results obtained on the hexagonal (0001) face of graphite. MgO appears as a corrugated surface for both argon and methane whereas graphite is a nearly perfect planar surface. The calculated holding and corrugation energies are in agreement with experimental data.     

Self-localization of polyacrylic acid molecules on polar ZnO(0001)-Zn surfaces

The adsorption of single polyacrylic acid (PAAc) molecules was investigated on stepped hydroxide-stabilized polar ZnO(0001)-Zn surfaces using atomic force microscope (AFM) topography and force distance spectroscopy. Stepped surfaces of ZnO(0001)-Zn were prepared by a wet chemical etching procedure and PAAc molecules were adsorbed from aqueous NaClO(4) solutions. AFM single molecule topography studies could be utilized to show that polyacrylic acid molecules specifically adsorb on the non-polar (10-10) step edge faces at low ionic strengths. The radius of gyration of the dissolved PAAc in aqueous solution was measured by means of static light scattering experiments yielding a radius of gyration of R(g)=136 nm at pH 7.4 in 50 mM NaClO(4)/NaOH solution, which is in good agreement with the size of the adsorbed PAAc molecules as measured using AFM. The obtained results could be rationalized in terms of binding-site configurations at step edges and the effect of the chemical environment on both local electric double layer charge and molecular conformation of the PAAc molecules. The point of zero charge of the ZnO(10-10) surface was measured with chemical force microscopy to be pH(PZC)=10.2 ± 0.2. The specific adsorption of polyacrylic acid at non-polar ZnO step-edges can be explained by coordinative bonds formed between the carboxylic acid group and the Zn-surface atoms. On the hydroxide stabilized polar surface only weak hydrogen bonds can be formed in addition to van-der-Waals forces. Thus a "diffusion and trapping" mechanism keeps the adsorbed PAAc molecules mobile on the ZnO(0001)-Zn surface terraces due to small interaction forces until they are trapped at the (10-10) step faces by stronger coordinative bonds from the carboxylic groups to zinc atoms located in the first atomic layer of the crystal structure.     

Stabilization and acidic dissolution mechanism of single-crystalline ZnO(0001) surfaces in electrolytes studied by in-situ AFM imaging and ex-situ LEED

A combined approach of pH-dependent in-situ AFM topography and ex-situ LEED studies of the stability and dissolution of single-crystalline ZnO(0001)-Zn surfaces in aqueous media is presented. Hydroxide-stabilized and single-crystalline ZnO(0001)-Zn surfaces turned out to be stable within a wide pH range between 11 and 4 around the point of zero charge of pH PZC = 8.7 +/- 0.2. Hydroxide stabilization turned out to be a very effective stabilization mechanism for polar oxide surfaces in electrolyte solutions. The dissolution of the oxide surface started at an acidic pH level of 5.5 and occurred selectively at the pre-existing step edges, which consist of nonpolar surfaces. In comparison, the oxide dissolution along the ZnO(0001) direction proved to be effectively inhibited above a pH value of 3.8. On the basis of these microscopic observations, the mechanistic understanding of the acidic dissolution process of ZnO could be supported. Moreover, both the in-situ AFM and the ex-situ LEED studies showed that the stabilization mechanism of the ZnO(0001) surfaces changes in acidic electrolytes. At pH values below 3.8, the hydroxide-stabilized surface is destabilized by dissolution of the well-ordered radical3. radical3. R30 hydroxide ad-layer as proven by LEED. Restabilization occurs and leads to the formation of triangular nanoterraces with a specific edge termination. However, below pH 4 the surface structure of the crystal itself is ill-defined on the macroscopic scale because preferable etching along crystal defects as dislocations into the bulk oxide results in very deep hexagonal etching pits.     

Ab initio cluster calculations on the electronic structure of oxygen vacancies at the polar ZnO(0001) surface and on the adsorption of H2, CO, and CO2 at these sites

Oxygen vacancies at the polar O terminated (0001) surface of ZnO are of particular interest, because they are discussed as active sites in the methanol synthesis. In general, the polar ZnO surfaces are stabilized by OH groups, therefore O vacancies can be generated by removing either O atoms or OH or H2O groups from the surface. These defects differ in the number of electrons in the vacancy and the number of OH groups in the neighborhood. In the present study, the electronic structure and the adsorption properties of four different types of oxygen vacancies have been investigated by means of embedded cluster calculations. We performed ab initio calculations on F+ like surface excitations for the different defect types and found that the transition energies are above the optical band-gap, while F+ centers in bulk ZnO show a characteristic optical excitation at 3.19 eV. Furthermore, we studied the adsorption of CO2 and CO at the different defect sites by DFT calculations. We found that CO2 dissociates at electron rich vacancies into CO and an O atom which remains in the vacancy. At the OH vacancy which contains an unpaired electron CO2 adsorbed in the form of CO2-, while it adsorbed as a linear neutral molecule at the H2O defect. CO adsorbed preferentially at the H2O defect and the OH defect, both with a binding energy of 0.3 eV.     

簇模型选取的配位数原则——CO/ZnO吸附体系的ab initio研究

提出并以ZnO为例初步考察了用于金属氧化物的簇模型选取的配位数原则,即尽可能选取边界悬空键总数最少的簇模型,使簇模型"边界效应"尽可能低.在此基础上研究了CO在一系列按配位数原则选取的(ZnO)n表面簇模型上的吸附行为.结果表明,配位数原则有效地缩小了簇模型的选取范围;依配位数原则确立的ZnO表面簇模型,能够对CO/ZnO吸附体系给出合理的定性解释.计算还表明,考虑相关效应有助于进一步改善计算结果.     

H2O and H2 interaction with ZnO surfaces: A MNDO,AM1, and PM3 theoretical study with large cluster models

We investigated the adsorption and heterolytic dissociation of H₂O and H₂ molecules on a (ZnO)₂₂ cluster corresponding to ZnO (0001), (000(OVERBAR)1), and (10(OVERBAR)10) surfaces using MNDO , AM 1 and PM 3 semiempirical procedures. The geometry of the adsorbed molecule has been optimized in order to analyze binding energies, charge transfer, and preferential sites of interaction. The adsorbed species interact most strongly when it is bonded to the twofold coordinated zinc atom of the cluster surface. The interaction of the H₂O molecule with the surface of ZnO has a charge transfer from H₂O to the surface ranging between 0.17 and 0.27 au. The neighboring atoms of the surface are the main receptors during the process of charge transfer. Our results indicate that there is a weak bonding of the hydrogen atom from OH with the oxygen surface atom that could produce the O(SINGLE BOND)H·O band. The interaction of the H₂ molecule with the surface is generally weak and only the PM 3 method yields a strong binding energy for this interaction. There is a charge transfer from the H₂ molecule to the surface. The chemisorption of H on oxygen atom of the surface transfer charge from the surface to the H. We also calculated the vibrational analyses for these interactions on ZnO surface and compared our results with available experimental data. © 1996 John Wiley & Sons, Inc.     

Reaction pathways for ethanol on model Co/ZnO(0001) catalysts

The pathways for the reaction of ethanol on model catalysts consisting of Co and CoO films and particles supported on single crystal ZnO(0001) surfaces were studied using X-ray Photoelectron Spectroscopy (XPS) and Temperature Programmed Desorption (TPD). On supported metallic Co films and particles ethanol was found to primarily undergo decarbonylation forming CO, H(2), and adsorbed methyl groups. In contrast, supported CoO particles were found to be largely unreactive toward ethanol. High selectivity to the dehydrogenation product, acetaldehyde, was only observed when the supported Co was partially oxidized and contained both Co(0) and Co(2+). Since acetaldehyde is thought to be a critical intermediate during steam reforming of ethanol (SRE) to produce H(2) and CO(2), the results of this study suggest that partially oxidized Co species provide the active sites for this reaction. This result is consistent with studies of high surface area Co/ZnO catalysts which also suggest that both Co(0) and Co(2+) species are present under typical SRE reaction conditions.     

Pd(Cu)在MgO(100)表面吸附CO和O2的理论研究

采用固体镶嵌势能模型和DFT/B3LYP方法研究了在Pd/MgO和Cu/MgO表面吸附CO和O₂分子的电子性质. 计算结果表明, 在完美MgO(100)表面Pd原子对CO和O₂的吸附能分别为206.5和84.8 kJ/mol, 因此可知Pd原子更容易吸附CO分子; 而当Pd原子附着于有氧缺陷的MgO表面时, 它对两种分子的吸附都非常弱. 相反, 附着于MgO表面的Cu原子对O₂分子的吸附更为有利, 其吸附能在140～155 kJ/mol之间. 研究结果还表明, 对于双分子吸附体系, 即CO＋CO, CO＋O₂, O₂＋O₂体系, 双分子之间的结合力可减小完美MgO表面上Pd原子与被吸附分子的相互作用, 使吸附能减少了46～96 kJ/mol. 而对于在MgO表面上的Cu原子, 只有O₂＋O₂ 体系使吸附能减少了大约50～71 kJ/mol.     

My Research History on the Chemical Standpoint—From Molecular Structure to Surface Science

The structure of molecules using gas electron diffraction (GED) was my graduate study. However, I was making a new apparatus for precise measurements by GED and formulated a scheme for the least‐squares analysis for a smooth continuous curve of scattering intensity. My research was completely shifted to the solid surface after moving to Gakushuin University, where I briefly studied the liquid structure of CCl₄ molecules, and I then moved to the Institute for Solid State Physics, the University of Tokyo. My studies of surface science were focused on the electronic properties and related phenomena, and various experimental methods were developed. The plasmon dispersions elucidated the initial oxidation of aluminum and one‐dimensional metal on Si(001)2 × 1–K. Irreversible phase transition was discovered on MgO(001) using the LEED Kikuchi pattern. The electronic structure of the dislocation was observed on MgO(001) by the electron time‐of‐flight method. The phase transition on Si(001) and the rotational epitaxy in a K monoatomic layer on Cu(001) were found. Next, I changed to studies of the dynamical phenomena on the surface, where very low energy reactive ion scattering on metal surfaces and laser‐induced desorption caused by electronic transition of NO and CO molecules from metal surfaces were observed, and the hydrogen atom location at the surface and interface was measured with a high depth resolution using a resonance nuclear reaction of ¹H + ¹⁵N²⁺ at 6.385 MeV. Finally, I moved to the University of Electro‐Communications and studied thin single‐crystal oxide layers on transition metals, in which the band‐gap narrowing was found, and then a Pt monoatomic layer was prepared on the α‐Al₂O₃ film.     

Atom-surface potentials by inversion of diffraction data:application to He/MgO(100)

A direct inversion method is used to transform measured intensities of He diffraction from MgO(100) over a wide energy range into the part of the interaction potential that depends on surface structure. This provides the first inversion of atom/surface scattering data. Intensities computed from the inverted potential reproduce the input data to great accuracy. The uniqueness problem of potentials obtained from diffraction experiments is discussed.     

Collisional line shapes for low frequency vibrations of adsorbates on a metal surface

The dynamics of atoms or molecules adsorbed on a metal surface, and excited by collisions with an atomic beam, are treated within a theory that includes energy dissipation into lattice vibrations by means of a frequency and temperature dependent friction function. The theory provides dynamic structure factors for energy transfer derived from collisional time correlation functions. It describes the relaxation of a vibrationally excited atom or molecule within a model of a damped quantum harmonic oscillator bilinearly coupled to a bath of lattice oscillators. The collisional time correlation function is generalized to include friction effects and is applied to the vibrational relaxation of the frustrated translation mode of Na adsorbed on a Cu(001) surface, CO on Cu(001), and CO on Pt(111), following excitation by collisions with He atoms. Results for the frequency shift and width of line shapes versus surface temperature are in very good agreement with experimental measurements of inelastic He atom scattering. Our interpretation of the experimental results provides insight on the relative role of phonon versus electron-hole relaxation.     

First-principle study of adsorption of hydrogen on Ti-doped Mg(0001) surface

Ab initio density functional theory (DFT) calculations are performed to study the adsorption of H2 molecules on a Ti-doped Mg(0001) surface. We find that two hydrogen molecules are able to dissociate on top of the Ti atom with very small activation barriers (0.103 and 0.145 eV for the first and second H2 molecules, respectively). Additionally, a molecular adsorption state of H2 above the Ti atom is observed for the first time and is attributed to the polarization of the H2 molecule by the Ti cation. Our results parallel recent findings for H2 adsorption on Ti-doped carbon nanotubes or fullerenes. They provide new insight into the preliminary stages of hydrogen adsorption onto Ti-incorporated Mg surfaces.     

Mg-ZnO复合物的紫外光催化效率及协同作用研究

采用化学沉淀法合成了一系列Mg-ZnO光催化剂. 研究了在Mg ²⁺和MgO绝缘介质共同作用下Mg-ZnO光催化剂的活性. 结果表明, 紫外光照射5 min后, 10%Mg-ZnO复合物对10 mg/L RhB的降解率达到81.3%, 光降解速率常数为0.3271 min ^-1, 是纯ZnO的3.42倍. 瞬态光电压(TPV)、 接触电势差、 表面光电流(SPC)和Cr(Ⅵ)还原等实验结果表明, MgO绝缘颗粒的形成抑制了ZnO中光生电子的“逆向”传输, 使电子和空穴的复合时间延长, 从而间接提高了光生空穴的利用率.     

Rh和Pt超薄层电极上的CO吸附行为(英文)

利用沉积在粗糙金电极上的过渡金属超薄层电极技术 ,我们获得了氢及一氧化碳在Rh和Pt表面上吸附的拉曼信号 ,并对两者之间的相互作用进行了分析 ..我们还进行了二氧化碳在这两种金属表面的还原行为的初步研究 ,以及对不同方式获得的一氧化碳吸附拉曼信号的特点进行了分析 .