原位高分辨率x射线光电子能谱-表面反应的基本见解

IF 8.2 1区 化学 Q1 CHEMISTRY, PHYSICAL Surface Science Reports Pub Date : 2013-11-01 DOI:10.1016/j.surfrep.2013.10.003
Christian Papp, Hans-Peter Steinrück
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引用次数: 79

摘要

自从第三代同步加速器光源的出现优化提供软x射线高达2 keV, x射线光电子能谱(XPS)已经发展成为一个杰出的工具,研究表面性质和表面反应在一个前所未有的水平。高分辨率可以识别各种表面物质,对于小分子甚至振动精细结构也可以在XP光谱中分辨出来。高光子通量将每个光谱所需的测量时间减少到几秒甚至更短,这使得能够在原位跟踪表面过程。此外,它还提供了非常小的覆盖范围,低至单层的0.1%以下,从而可以在缺陷位置调查少数物种或过程。光子能量可以根据特定实验的要求进行调节,即最大化或最小化衬底或吸附质的表面灵敏度或光电离截面。对于世界上的一些仪器来说,下一步是将原位高分辨率光谱仪与超音速分子束结合起来。这些光束允许控制和改变入射分子的动能和内能,并提供高达~10−5毫巴的局部压力,可以以可控的方式打开和关闭,从而为研究吸附或反应过程提供了明确的时间结构。在此,我们将回顾原位XPS可以解决的一些具体科学问题,以展示该方法的力量和潜力:特别是以下主题将讨论:(1)以CO在金属上的吸附为例,分析结合能对吸附位点的敏感性。通过在不同温度下的测量,可以推导出不同位点之间的结合能差,并可以跟踪台阶边缘不同吸附质之间的交换过程。(2)对金属表面吸附的烃类微粒的振动精细结构进行了详细的分析。我们将首先介绍线性耦合模型,然后讨论吸附甲基和其他一些小碳氢化合物的性质,并表明振动特征可以用作识别表面物种的指纹。(3)通过对底物的吸附,证明了分子中等效原子的结合能会发生差异变化;对于吸附的乙烯、苯和石墨烯,将讨论这种对局部环境的敏感性。(4)通过程序升温XPS,可以很详细地跟踪吸附物质的热演化过程,从而确定反应中间体及其稳定性。(5)讨论了等温XPS测量对反应动力学的研究;这里将给出硫和一氧化碳氧化的结果,并确定相应的限速步骤的活化能。
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In situ high-resolution X-ray photoelectron spectroscopy – Fundamental insights in surface reactions

Since the advent of third generation synchrotron light sources optimized for providing soft X-rays up to 2 keV, X-ray photoelectron spectroscopy (XPS) has been developed to be an outstanding tool to study surface properties and surface reactions at an unprecedented level. The high resolution allows identifying various surface species, and for small molecules even the vibrational fine structure can be resolved in the XP spectra. The high photon flux reduces the required measuring time per spectrum to the domain of a few seconds or even less, which enables to follow surface processes in situ. Moreover, it also provides access to very small coverages down to below 0.1% of a monolayer, enabling the investigation of minority species or processes at defect sites. The photon energy can be adjusted according to the requirement of a particular experiment, i.e., to maximize or minimize the surface sensitivity or the photoionization cross-section of the substrate or the adsorbate. For a few instruments worldwide, a next step forward was taken by combining in situ high-resolution spectrometers with supersonic molecular beams. These beams allow to control and vary the kinetic and internal energies of the incident molecules and provide a local pressure of up to ~10−5 mbar, which can be switched on and off in a controllable way, thus offering a well-defined time structure to study adsorption or reaction processes.

Herein, we will review some specific scientific aspects which can be addressed by in situ XPS in order to demonstrate the power and potential of the method: In particular, the following topics will be addressed: (1) The sensitivity of the binding energy to adsorption sites will be analyzed, using CO on metals as example. From measurements at different temperatures, the binding energy difference between different sites can be derived, and exchange processes between different adsorbate species at step edges can be followed. (2) The vibrational fine structure of adsorbed small hydrocarbon species on metal surfaces will be analyzed in detail. We will first introduce the linear coupling model, then discuss the properties of adsorbed methyl and of a number of other small hydrocarbons, and show that the vibrational signature can be used as fingerprint for identifying surface species. (3) It is demonstrated that the binding energy of equivalent atoms in a molecule can be differentially changed by adsorption to a substrate; this sensitivity to the local environment will be discussed for adsorbed ethylene, benzene and graphene. (4) By temperature programmed XPS, the thermal evolution of adsorbed species can be followed in great detail, allowing for the identification of reaction intermediates and the determination of their stabilities. (5) The investigation of reaction kinetics by isothermal XPS measurements will be discussed; here results for the oxidation of sulfur and of CO will be presented and the corresponding activation energies of the rate limiting steps will be determined.

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来源期刊
Surface Science Reports
Surface Science Reports 化学-物理:凝聚态物理
CiteScore
15.90
自引率
2.00%
发文量
9
审稿时长
178 days
期刊介绍: Surface Science Reports is a journal that specializes in invited review papers on experimental and theoretical studies in the physics, chemistry, and pioneering applications of surfaces, interfaces, and nanostructures. The topics covered in the journal aim to contribute to a better understanding of the fundamental phenomena that occur on surfaces and interfaces, as well as the application of this knowledge to the development of materials, processes, and devices. In this journal, the term "surfaces" encompasses all interfaces between solids, liquids, polymers, biomaterials, nanostructures, soft matter, gases, and vacuum. Additionally, the journal includes reviews of experimental techniques and methods used to characterize surfaces and surface processes, such as those based on the interactions of photons, electrons, and ions with surfaces.
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Editorial Board Hexagonal boron nitride on metal surfaces as a support and template X-ray photoelectron spectroscopy of epitaxial films and heterostructures Editorial Board Atomic wires on substrates: Physics between one and two dimensions
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