水在金属氧化物表面的吸附与解离

水(H2O)由H原子和O原子组成.地球上有大量的水,若能找到一种经济、实用的方法将H2O解离生成H2和O2,则在新能源的开发和应用方面,意义深远.水在固体表面的吸附现象极为普遍,在某些金属或金属氧化物表面,H2O被吸附并解离成OH-和H+.文章以有序氧化镁(MgO(100))薄膜和Pd/MgO(100)体系为例,在超高真空条件下,用光电子能谱和高分辨电子能量损失谱方法,研究了水在它们表面的吸附与解离.研究结果表明,H2O在MgO(100)表面可以被部分解离,而H2O在Pd/MgO(100)表面的解离与Pd的含量有关.了解水与固体表面的相互作用机理还需要做更多的基础研究工作.     

Photoelectron spectroscopy in the energy region 30 to 800 eV using synchrotron radiation

With the advent of synchrotron radiation, the photoemission techniques were extended to a continuous range of excitation energies in the far ultraviolet and soft x-ray regions, adding tremendously to the usefulness of photoemission as a probe of the electronic structure of materials. In this paper, we discuss the application of photoelectron spectroscopy using synchrotron radiation to the studies of oxygen chemisorption/oxidation of Si surfaces, metal overlayers on III-V semiconductor surfaces, chemisorption on transition metal surfaces, and the surface electronic structure of CuNi alloys.     

Surface morphology and surface chemical states of epitaxial Pb(Zr0.95Ti0.05)O3 thin films grown on SrTiO3(100) by sputter deposition

0.95 Ti_0.05)O₃ thin films of an orthorhombic perovskite structure were obtained on SrTiO₃(100) substrates by radio frequency sputter deposition. The surface morphology of the films was investigated with atomic force microscopy, scanning electron microscopy, and reflection electron microscopy. It is shown that the film surfaces are rather bumpy. There are undulations of about 400 nm in length in an in-plane direction. The mean roughness perpendicular to the surface is 39.6 nm, for the film thickness of 0.45 μm. The surface roughening was probably caused by island-shaped nucleation and growth during the film growth. It has also been found that some gorges and a number of small pits remain at the film surfaces. The surface chemical states of the films were characterized by using X-ray photoelectron spectroscopy. A Pb enrichment layer and a large amount of adsorbed oxygen have been found at the surfaces of the films. Near the film surface Pb and Zr exist mainly in the forms of, besides Pb(Zr,Ti)0₃, metal Pb, metal Zr, oxygen-chemisorbed Pb, and various lead oxides. In addition, a small amount of lead, whose binding energy of Pb 4f_7/2 is much lower than that of metal Pb, was observed at the film surfaces, but its chemical state is unknown up to now. Received: 2 June 1997/Accepted: 22 September 1997     

Chemisorption of nitric oxide by nickel

The adsorption of nitric oxide on clean and pre-oxidized nickel has been investigated by X-ray photoelectron spectroscopy. Three distinct states of chemisorption have been recognised at room temperature; one is dissociative while two involve molecularly adsorbed NO. Pre-exposing the nickel surface to oxygen enabled the activity of the surface to be controlled such that adsorption was confined to only one of the molecular states. The two molecular states are suggested to arise from “bent” and “linear” forms of NO.     

Highly active surfaces for CO oxidation on Rh, Pd, and Pt

Studies show that the rate of CO oxidation on Pt-group metals at temperatures between 450 and 600 K and pressures between 1 and 300 Torr increases markedly with an increase in the O₂/CO ratio above 0.5. The catalytic surfaces, formed at discrete O₂/CO ratios >0.5, exhibit rates 2-3 orders of magnitude greater than those rates observed for stoichiometric reaction conditions and similar reactant pressures or previously in ultrahigh vacuum studies at any reactant conditions and extrapolate to the collision limit of CO in the absence of mass transfer limitations. The O₂/CO ratios required to achieve these so-called “hyperactive” states (where the reaction probabilities of CO are thought to approach unity) for Rh, Pd, and Pt relate directly to the adsorption energies of oxygen, the heats of formation of the bulk oxides, and the metal particle sizes. Auger spectroscopy and X-ray photoemission spectroscopy reveal that the hyperactive surfaces consist of approximate 1 ML of surface oxygen. In situ polarization modulation reflectance absorption infrared spectroscopy measurements coupled with no detectable adsorbed CO. In contrast, under stoichiometric O₂/CO conditions and similar temperatures and pressures, Rh, Pd, and Pt are essentially saturated with chemisorbed CO and exhibit far less activity for CO oxidation.     

A study of nitric oxide adsorbed on nickel oxide,cobalt oxide,and graphite by X-ray photoelectron spectroscopy

The nitrogen 1s binding energy of nitric oxide adsorbed on nickel oxide, cobalt oxide and graphite was measured at several temperatures by X-ray photoelectron spectroscopy. For the oxides, a temperature dependent range of binding energies was observed, but for graphite the nitrogen 1s binding energy was independent of temperature. The values obtained suggest that significant back donation of electrons occurs from the oxides to the adsorbed nitric oxides, but no back donation occurs from graphite to adsorbed nitric oxide. However, adsorption did not cause changes in the binding energy of substrate core electrons. It is believed that unless the mean free path of electrons is short, the total photoelectron signal will not reveal changes in binding energy of electrons from substrate atoms at the surface.     

金属Sn薄膜的高温氧化与表面特征

侧重研究了高温氧化（300－550℃）引起金属Sn薄膜的表面显微形貌和表面氧化状态的变化．利用原子力显微镜（AFM）的测量，观察到金属Sn薄膜表面的金属晶粒呈现近似方形的显微形貌，但是金属Sn氧化薄膜表面的金属氧化物颗粒却具有近似圆形的显微形貌，因此，金属晶粒的高温氧化是一个各向异性的过程．在X射线光电子能谱（XPS）测量的基础上，不仅发现在金属Sn薄膜和金属Sn氧化薄膜的表面都存在大量的吸附氧粒子，而且发现吸附氧粒子的吸附形式与表面的氧化程度有关 关键词：     

ESCA study of carbon monoxide and oxygen adsorption on tungsten

The chemisorption of both CO and O₂ on a clean tungsten ribbon has been studied using an ultrahigh vacuum X-ray photoelectron spectrometer. For CO, the energy and intensity of photoemission from O(1s) and C(1s) core levels have been studied for various adsorption temperatures.At adsorption temperatures of ～100 K., the “virgin”-CO state was the dominant adsorbed species. Conversion of this state to more strongly-bound β-CO is observed upon heating the adsorbed layer to ～320K. Thermal desorption of CO at 300?T?640 K causes sequential loss of α₁-CO and α₂-CO as judged by the disappearance of O(1s) and C(1s) photoelectron peaks characteristic of these states.Oxygen adsorption at 300K gives a single main O(ls) peak at all coverages, although at high oxygen coverages there exist small auxiliary peaks at ～2eV lower kinetic energy. The photoelectron C(1s) and O(1s) binding energies observed for these adsorbed species are all lower than for gaseous molecules containing C and O atoms. For CO adsorption states there is a systematic decrease in photoelectron binding energy as the strength of adsorption increases. These observations are in general accord with expectations based on electronic relaxation effects in condensed materials.     

Sulfur dioxide adsorption and reaction with atomic oxygen on the Ag(110) surface

The adsorption of SO₂ on Ag(110) and the reaction of SO₂ with oxygen adatoms have been studied under ultrahigh vacuum conditions using low energy electron diffraction, temperature programmed reaction spectroscopy and photoelectron spectroscopy. Below 300 K, SO₂ adsorbs molecularly giving p(1×2) and c(4×2) LEED patterns at coverages of one half and three quarter monolayers. respectively. At intermediate coverages, streaked diffraction patterns, similar to those reported for noble gas and alkali metal adsorption on the (110) face of face-centered cubic metals were observed, indicating adsorption out of registry with the surface. A feature at low binding energy in the ultraviolet photoemission spectrum appeared which was assigned to a weak chemisorption bond to the surface via the sulfur, analogous to bonding observed in SO₂-amine charge transfer complexes and in transition metal complexes. SO₂ exhibited three binding states on Ag(110) with binding energies of 41, 53 and 64 kJ mol^?1; no decomposition on clean Ag(110) was observed. On oxygen pretreated Ag(110), SO₂ reacted with oxygen adatoms to form SO_3(a), as determined by X-ray photoelectron spectroscopy. Reacting preadsorbed atomic oxygen in a p(2 × 1) structure with SO₂ resulted in a c(6 × 2) pattern for SO_3(a). The adsorbed SO_3(a) decomposed and disproportionated upon heating to 500 K to yield SO_2(g), SO_4(a) and subsurface oxygen.     

太赫兹波段金属线栅的紫外光控特性研究

基于氧化铟纳米薄膜及金属线栅的特性,利用紫外激光诱导以金属线栅为衬底的氧化铟纳米结构,研究其对于太赫兹偏振透射的调制特性。实验中在金属线栅上滴入溶于乙醇的氧化铟溶液,并使溶液恰好浸润在金属线栅缝隙中,同时将加热台的温度调至340 ℃,对金属线栅中的氧化铟进行热退火。结果表明,氧化铟-金属线栅线长方向与太赫兹电场偏振方向垂直时,在低强度紫外光的照射下,该样品对太赫兹的透射强度有较为明显的衰减,当紫外光功率密度为7 mW·cm-2时,样品对太赫兹的调制深度可达71%;当氧化铟-金属线栅线长方向与太赫兹电场偏振方向平行时,紫外光激发下的样品对太赫兹的调制效果明显减弱,当紫外光功率密度为7 mW·cm-2时,调制深度约为20%。氧化铟纳米薄膜中存在的氧空位,使该材料对紫外光具有特殊响应。在无紫外光照射下,样品环境中的氧气分子被吸附到氧化铟表面,由于化学反应生成O2-离子态。当用光子能量大于氧化铟禁带宽度的紫外光激发样品时,在氧化铟表面激发出电子空穴对,空穴会被氧化铟表面的O2-离子态和缺陷态束缚,从而释放电子到导带,增强了样品的电导率。在太赫兹波频段内,透过氧化铟样品的太赫兹强度与氧化铟电导率有很好的相关性。金属线栅利用金属表面可存在的自由电子的振荡, 使电场方向与线栅方向平行的太赫兹偏振光激发电子沿线栅方向振荡,当电子与金属晶格中的原子碰撞时,此偏振光发生衰减并伴随辐射;而电场方向与线栅方向垂直的太赫兹偏振光,由于周期性结构的限制,无法激发自由电子振荡, 主要表现出透射特性。结合氧化铟的表面缺陷特性,紫外光可实现作为氧化铟-金属线栅结构的光控偏振开关作用,氧化铟-金属线栅结构偏振器能很好地应用于太赫兹波频段的光控偏振调制。     

Semiempirical model calculations for chemisorption on transition metals: III. CO,N2 and NO on Ni,Cu, Pd and Ag

An effective one electron Hamiltonian is used to calculate the qualitative behaviour of various physical quantities (adsorption energy, shifts of ionization energies, energy profiles, etc.) over a series of different adsorption systems. The numerical calculations allow for several orbitals on the adsorbed particle as well as for the s- and the d-and in the metal. The experimentally found trends concerning the general features of photoelectron spectra and the variation of the adsorption energy with adsorbate and substrate as well as with the surface orientation and the location of the adsorbed species are reproduced reasonably well. A simple theory of photoemission (the final state is a plane wave) has been combined with the semiempirical calculations. The generally observed decrease of emission from the d-band region can be understood as an interference effect in the initial state.     

Valence band studies of clean and oxygen exposed GaAs(100) surfaces

We found, by correlating band bending, ultraviolet photoemission spectroscopy, and partial yield spectroscopy measurements, that Fermi level pinning at midgap of n-type GaAs(110) is caused by extrinsic states. The exact nature of these states is not yet clear, but the surfaces with Fermi level pinning were strained as evidence by a smeared valence band emission. This smearing was removed by as little as one oxygen per 10⁴ to 10⁵ surface atoms. This implies that the oxygen has very long range effects in causing spontanesous but small rearrangement of the surface lattice and removing surface strains. When about 5% of a monolayer of oxygen is adsorbed, a major change in the electronic structure takes place. Again, the oxygen coverage is very small, which suggests long range effects now leading to a fairly large rearrrangement of the surface lattice. Finally, from comparing the oxygen induced emission for exposures greater than 10⁷ L O₂, with the spectra from gas photoemission measurements on molecular oxygen, we suggest that the oxygen is chemisorbed as a molecule on the (110) surface of GaAs.     

Spin-polarized metastable deexcitation spectroscopy study of iron films

A spin-polarized metastable deexcitation spectroscopy apparatus using a nozzle-skimmer pulsed discharge metastable atom source was developed. The oxygen adsorption dependence of the surface magnetism of thin iron films deposited on MgO(100) was investigated using this apparatus. The surface local density of states spilling towards the vacuum (SDOS) at around the Fermi energy, E_F, for the clean surface shows a negative polarization to the bulk. The oxygen derived SDOS for the lightly oxygen adsorbed surfaces (2–10 L) also shows a negative polarization while the SDOS at E_F changes its polarity to positive. The polarization of SDOS is not detected for the heavily oxidized surfaces (20–100 L).     

XPS study of vanadium surface oxidation by oxygen ion bombardment

Oxidation of vanadium metal surfaces at room temperature by low-energy oxygen ion beams is investigated by X-ray photoelectron spectroscopy (XPS). It is observed that ion-beam irradiation of clean V results in formation of thin oxide layer containing vanadium in oxidation states corresponding to VO, V₂O₃, VO₂ and V₂O₅ oxides. The composition of the products of ion-beam oxidation depends markedly on oxygen ion fluence. The results of angle-resolved XPS measurements are consistent with a structure of oxide film with the outermost part enriched in V₂O₅ and VO₂ oxides and with V₂O₃ and VO oxides located in the inner region of the oxide layer.     

DFT calculations of the electronic structure of SnOx layers on Pd(110)

The electronic structures of Sn and SnO _x layers adsorbed on the Pd(110) surface have been calculated by DFT. In agreement with available results of photoemission studies, it is found that the formation of the oxides induces pronounced changes in the related peak in the DOS. In particular, it is shown that the formation of SnO₂ adsorbed layers leads to a transformation of the Sn 4d spin-orbit doublet into a quadruple peak, while for SnO the peak retains its shape. Due to this feature, the shape of the Sn 4d peak in photoemission spectra can serve as an unambiguous indicator of the degree of oxidation of Sn layers on transition metal surfaces.     

Substrate mediated stabilization of methylphosphonic acid on ZnO non-polar surfaces'

The adsorption of methylphosphonic acid (MPA, formula CH₃–PO₃H₂) on ZnO(10-10) surfaces has been investigated by first-principles density-functional total energy calculations. We show that substrate mediated interactions between co-adsorbates can significantly affect the binding energy of MPA on the ZnO surface, which leads to a preferential molecular dimer assembly along the polar [0001] direction (i.e. along the Zn–O dimer direction). We propose that this is caused by a local charge compensation mechanism due to the relaxation of the ZnO surface and suggest that this concept can be applied to other adsorbates on metal oxide surfaces with metal–oxygen dimers.     

Formation of interface and surface oxides on supported Pd nanoparticles

We have quantitatively studied the interaction between oxygen and an Fe₃O₄-supported Pd model catalyst by molecular beam (MB) methods, time resolved IR reflection absorption spectroscopy (TR-IRAS) and photoelectron spectroscopy (PES) using synchrotron radiation. The well-shaped Pd particles were prepared in situ by metal evaporation and growth under ultrahigh vacuum (UHV) conditions on a well-ordered Fe₃O₄ film on Pt(1 1 1).It is found that for oxidation temperatures up to 450 K oxygen predominantly chemisorbs on metallic Pd whereas at 500 K and above (∼10⁻⁶ mbar effective oxygen pressure) large amounts of Pd oxide are formed. These Pd oxide species preferentially form a thin layer at the particle/support interface, stabilized by the iron-oxide support. Their formation and reduction is fully reversible. Upon decomposition, oxygen is released which migrates back onto the metallic part of the Pd surface. In consequence, the Pd interface oxide layer acts as an oxygen reservoir, the capacity of which by far exceeds the amount of chemisorbed oxygen on the metallic surface.Additionally, Pd surface oxides can also be formed at temperatures above 500 K. The extent of surface oxide formation critically depends on the oxidation temperature. This effect is addressed to different onset temperatures for oxidation of the particle facets and sites. It is shown that the presence of Pd surface oxides sensitively modifies the adsorption and reaction properties of the model catalyst, i.e. by lowering the CO adsorption energy and CO oxidation probability. Still, a complete reduction of the Pd surface oxides can be obtained by extended CO exposure, fully reestablishing the metallic Pd surface.     

On surface states at superconductor oxide interfaces

Localized electron states in oxides on metal surfaces hybridize with conduction electrons leaking into the oxide and form so a metallic layer and a new type of surface state. For a superconductor such surface states weaken the superconductivity. Because these surface states extend into the oxide, they cause an enhanced tunnel conductivity, which is finite below the gap voltage due to resonance tunneling via the surface states below the gap.     

Generation of singlet oxygen on the surface of metal oxides

Generation of singlet oxygen on the surface of metal oxides is studied. It is shown that, under conditions of heterogeneous photo-catalysis, along with the conventional mechanism of singlet oxygen formation due to the formation of electron–hole pairs in the oxide structure, there is an additional and more efficient mechanism involving direct optical excitation of molecular oxygen adsorbed on the oxide surface. The excited adsorbate molecule then interacts with the surface or with other adsorbate molecules. It is shown that, with respect to singlet oxygen generation, yttrium oxide is more than an order of magnitude more efficient than other oxides, including titanium dioxide.