Adsorption and valence electronic states of nitric oxide on metal surfaces

Among fundamental diatomic molecules, the adsorption of carbon monoxide (CO) and nitric oxide (NO) on metal surfaces has been a subject of intensive research in the surface science community, partly owing to its relevance to heterogeneous catalysis used for environmental control. Compared to the rather well-defined adsorption mechanism of CO, that of NO is less understood because the adsorption results in much more complex reactions. The complexity is ascribed to the open-shell structure of valence electrons, making the molecule readily interact with the metal surface itself as well as with co-adsorbed molecules. Furthermore, the interaction crucially depends on the local structure of the surface. Therefore, to elucidate the interaction at the molecular scale, it is essential to study the valence state as well as the bonding geometry for individual NO molecules placed in a well-defined environment on the surface. Scanning tunneling microscopy (STM) is suitable for this purpose. In this review, we summarize the knowledge about the interaction of NO with metal surfaces, mainly focused on the valence electronic states, followed by recent studies using STM and atomic force microscopy (AFM) at the level of individual molecules.     

金属原子修饰石墨烯体系催化性能的理论研究

采用基于密度泛函理论的第一性原理方法研究了单个CO和O2气体分子在金属原子修饰石墨烯表面的吸附和反应过程.结果表明:空位缺陷结构的石墨烯能够提高金属原子的稳定性,金属原子掺杂的石墨烯体系能够调控气体分子的吸附特性.通入混合的CO和O2作为反应气体,石墨烯表面容易被吸附性更强的O2分子占据,进而防止催化剂的CO中毒.此外,对比分析两种催化机理(Langmuir-Hinshelwood和Eley-Rideal)对CO氧化反应的影响.与其它金属原子相比,Al原子掺杂的石墨烯体系具有极低的反应势垒(0.4 e V),更有助于CO氧化反应的迅速进行.     

金属原子修饰石墨烯体系催化性能的理论研究

采用基于密度泛函理论的第一性原理方法研究了单个CO 和O2气体分子在金属原子修饰石墨烯表面的吸附和反应过程. 结果表明: 空位缺陷结构的石墨烯能够提高金属原子的稳定性, 金属原子掺杂的石墨烯体系能够调控气体分子的吸附特性. 通入混合的CO和O2作为反应气体, 石墨烯表面容易被吸附性更强的O2分子占据, 进而防止催化剂的CO 中毒. 此外, 对比分析两种催化机理(Langmuir-Hinshelwood和Eley-Rideal)对CO氧化反应的影响. 与其它金属原子相比, Al原子掺杂的石墨烯体系具有极低的反应势垒(< 0.4 eV), 更有助于CO氧化反应的迅速进行.     

Femtosecond dynamics of chemical reactions at surfaces

One of the major goals in physical chemistry is to obtain a microscopic understanding of chemical reactions. Recent developments in femtosecond laser techniques provide the opportunity to resolve the timescale of elementary steps of chemical reactions at surfaces. This is exemplified for the femtosecond laser-induced oxidation of CO on Ru(001). Among other adsorbate-specific probes vibrational sum-frequency generation spectroscopy offers the possibility to monitor adsorbates or reaction intermediates directly at the surface. Recently, we have employed this technique to investigate the dynamics of the CO-stretch vibration of CO adsorbed on Ru(001) after optical excitation leading to CO desorption. Received: 4 August 2000 / Accepted: 2 September 2000 / Published online: 12 October 2000     

Time-resolved two photon photoemission electron microscopy

Femtosecond, time-resolved two photon photoemission has been used to map the dynamics of photo-excited electrons at a structured metal/semiconductor surface. A photoemission microscope was employed as a spatially resolving electron detector. This novel setup has the potential to visualize variations of hot electron lifetimes in the femtosecond regime on heterogeneous sample surfaces and nanostructures. Received: 22 October 2001 / Revised version: 10 January 2002 / Published online: 7 February 2002     

Alkali-induced effects on metal substrates and coadsorbed molecules

We present results of ab initio electronic structure calculations based on density functional theory which show in detail several effects of alkali adsorption on metal substrates and on molecules coadsorbed on the substrate. First, calculations of the isoelectronic reactivity index demonstrate a dramatic enhancement of the electronic polarizability of the metal substrate extending it several angstroms into the vacuum. This phenomenon is traceable to an unusual feature induced in the surface potential on alkali adsorption. The effect appears to be general and helps explain the observed substantial decrease in the vibrational frequency of molecules such as CO and O₂ when co-adsorbed with alkalis on metal surfaces. Next, for the oxidation of CO on Pd(111), we illustrate the changes in the reaction pathway and activation energy barriers induced in the presence of coadsorbed K. PACS 73.20.-r; 71.15.-m     

A Surface Femtosecond Two-Photon Photoemission Spectrometer for Excited Electron Dynamics and Time-Dependent Photochemical Kinetics

搭建了一套研究金属和金属氧化物表面的超快激发态电子动力学和光化学动力学的飞秒双光子光电子能谱仪. 该装置将半球形电子能量分析仪和成像技术相结合,同时测量光电子的能量和角度分布.通过Mach-Zehnder干涉仪测量时间分辨的双光子光电子能谱获得超快激发电子态的动力学信息. 这一功能在Cu(111)上得到了证实. 另外还发展了一个通过实时测量双光子光电子能谱来研究表面光化学的方法,并成功应用到CH₃CH₂OH/TiO₂(110)体系. 研究表明,只有将两种方法结合起来才能正确地研究光诱导的表面激发共振的动力学.     

The steady state of heterogeneous catalysis, studied by first-principles statistical mechanics

The turnover frequency of the catalytic oxidation of CO at RuO2(110) was calculated as a function of temperature and partial pressures using ab initio statistical mechanics. The underlying energetics of the gas-phase molecules, dissociation, adsorption, surface diffusion, surface chemical reactions, and desorption were obtained by all-electron density-functional theory. The resulting CO2 formation rate [in the full (T,p(CO),p(O2)) space], the movies displaying the atomic motion and reactions over times scales from picoseconds to seconds, and the statistical analyses provide insight into the concerted actions ruling heterogeneous catalysis and open thermodynamic systems in general.     

Interferometric two-photon photoemission correlation technique and femtosecond wet-electron dynamics at the TiO (110) surface

The femtosecond time-resolved two-photon photoemission (TR-2PP) and the ultra high vacuum (UHV) surface science techniques are integrated to investigate the elec- tronic structures and the interfacial electron transfer dynamics at the atomically ordered adsorbate overlayers on TiO₂ single- crystalline surfaces. Our research into the CH₃OH/TiO₂ system exhibits complex dynamics, providing abundant informa- tion with regard to electron transport and solvation processes in the interfacial solvent structures. These represent the fundamentally physical, photochemical, and photocatalytic reactions of protic chemicals covered with metal-oxides.     

Enhanced optical sensitivity to adsorption due to depolarization of anisotropic surface states

Reflectance difference spectroscopy is used to probe the optical transitions between surface states on the Cu(110) surface. Upon deposition of smallest amounts of carbon monoxide (CO) the signal is strongly quenched, which translates into a huge cross section of the order of 1000 A(2) for a single adsorbed CO molecule. This strongly enhanced surface sensitivity is interpreted as the loss in anisotropy (depolarization) of the surface states due to scattering from the adsorbed CO molecules. This feature renders RDS an extremely sensitive tool to probe the adsorption kinetics on anisotropic metal surfaces.     

Interferometric two-photon photoemission correlation technique and femtosecond wet-electron dynamics at the TiO2(110) surface

The femtosecond time-resolved two-photon photoemission (TR-2PP) and the ultra high vacuum (UHV) surface science techniques are integrated to investigate the electronic structures and the interfacial electron transfer dynamics at the atomically ordered adsorbate overlayers on TiO₂ singlecrystalline surfaces. Our research into the CH₃OH/TiO₂ system exhibits complex dynamics, providing abundant information with regard to electron transport and solvation processes in the interfacial solvent structures. These represent the fundamentally physical, photochemical, and photocatalytic reactions of protic chemicals covered with metal-oxides.     

Femtosecond relaxation dynamics of surface plasmon-polaritons in the vicinity of fano-type resonance

Temporal modification of femtosecond laser pulses reflected from planar periodic metal nanostructures with resonant excitation of surface plasmon-polaritons is experimentally studied. Spectral time-resolved measurements of the second-order cross-correlation function performed with the pulse duration comparable with the surface plasmon-polariton relaxation time (about 100 fs) show the strong spectral dependence of the envelope of the reflected femtosecond pulse described by Fano-resonance parameters.     

第一性原理研究气体小分子吸附的石墨烯负载金属原子体系

石墨烯负载的单个金属原子体系(M-gra)具有高的结构稳定性,显正电性的金属原子可作为活性位用在气敏器件和催化材料.本文采用基于密度泛函理论的第一性原理方法研究单个有毒气体小分子(NO和CO)在M-gra表面的吸附特性.研究结果表明:单个NO分子吸附的稳定性高于CO分子,由于其能够从反应衬底获得更多的转移电荷,因此,M-gra衬底对NO分子表现出高的灵敏度.此外,不同小分子吸附能够改变M-gra体系的电荷密度和自旋电荷分布,进而使得气体分子吸附体系表现出不同大小的磁矩.通过对比气体分子吸附前后M-gra体系的磁矩变化,能够有效判断吸附分子和反应衬底的类型.     

金属纳米椭球结构表面的局域电场和吸附分子分布

过渡金属纳米结构表面吸附CO分子时会出现异常红外效应,这一现象可以用纳米结构表面吸附分子在外电场作用下产生局部凝聚从而相互作用能增加来解释.在前期研究的基础上,给出金属基底表面生长出的纳米颗粒为椭球状颗粒的理论计算结果.基于均匀外电场中金属纳米椭球颗粒按一定对称性排列的表面结构模型,用经典电磁学理论计算了纳米椭球颗粒表面附近的局域电场.在此基础上,将吸附的CO分子等效为偶极子,在考虑了偶极子与局域电场、偶极子之间以及偶极子与金属基底三种相互作用的情况下,用Monte-Carlo方法进行数值模拟,最后给出纳 关键词： 金属纳米结构表面 纳米椭球 吸附分子 局域电场     

Infrared emission spectroscopy of CO on Ni

We report the first observation of thermally emitted infrared radiation from vibrational modes of molecules adsorbed on clean, single crystal metal surfaces. The observation of emission from CO adsorbed on Ni demonstrates the surface sensitivity of a novel apparatus for infrared vibrational spectroscopy, with a resolution of 1 to 15 cm^?1 over the frequency range from 330 to 3000 cm^?1. A liquid helium cooled grating spectrometer measures the thermal radiation from a room temperature, single crystal sample, which is mounted in an ultrahigh vacuum system. Measurements of frequencies and linewidths of CO on a single crystal Ni sample, as a function of coverage, are discussed.     

Study of reactive film heterostructures with several interfaces using the thermal desorption spectroscopy

The thermal desorption spectroscopy is used to study the interaction of the chemisorbed oxygen and carbon monoxide molecules with the nanometer-thick ytterbium films that are formed on the surfaces of silicon substrates at room temperature. In accordance with the results at a temperature of 300 K, the O₂ and CO molecules are chemisorbed on the surface of a metal film and do not exhibit dissociation to atoms under such conditions. The molecular dissociation is observed at higher temperatures. The liberated oxygen is involved in reactions with ytterbium and silicon that lead to the formation of complicated silicates, which dissociate at even higher temperatures.     

Interferometric two-photon photoemission correlation technique and femtosecond wet-electron dynamics at the TiO2 (110) surface

The femtosecond time-resolved two-photon photoemission (TR-2PP) and the ultra high vacuum (UHV) surface science techniques are integrated to investigate the electronic structures and the interfacial electron transfer dynamics at the atomically ordered adsorbate overlayers on TiO₂ singlecrystalline surfaces. Our research into the CH₃OH/TiO₂ system exhibits complex dynamics, providing abundant information with regard to electron transport and solvation processes in the interfacial solvent structures. These represent the fundamentally physical, photochemical, and photocatalytic reactions of protic chemicals covered with metal-oxides.      

Low temperature surface chemistry and nanostructures

The new scientific field of low temperature surface chemistry, which combines the low temperature chemistry (cryochemistry) and surface chemistry approaches, is reviewed in this paper. One of the most exciting achievements in this field of science is the development of methods to create highly ordered hybrid nanosized structures on different organic and inorganic surfaces and to encapsulate nanosized metal particles in organic and polymer matrices. We consider physical and chemical behaviour for the systems obtained by co-condensation of the components vapours on the surfaces cooled down to 4–10 and 70–100 K. In particular the size effect of both types, the number of atoms in the reactive species structure and the thickness of growing co-condensate film, on the chemical activity of the system is analysed in detail. The effect of the internal mechanical stresses on the growing interfacial co-condensate film formation and on the generation of fast (explosive) spontaneous reactions at low temperatures is discussed. The examples of unusual chemical interactions of metal atoms, clusters and nanosized particles, obtained in co-condensate films on the cooled surfaces under different conditions, are presented. The examples of highly ordered surface and volume hybrid nanostructures formation are analysed.     

Time-Resolved Crystallography at X-ray Free Electron Lasers and Synchrotron Light Sources

Serial femtosecond crystallography with biological macromolecules is a rapidly developing method tailored to the immense brilliance of the emerging free electron lasers for hard X-rays (X-ray FELs). Recently, the first successful time-resolved serial femtosecond crystallographic experiment at near atomic resolution was conducted at the Linac Coherent Light Source. The X-ray FEL-based experiments will trigger new developments not only at the X-ray FELs, but also at existing synchrotron light sources. This review will attempt to summarize some of the most important experiments to date and give a brief outlook on what to expect.