Adsorption and dissociation kinetics of alkanes on CaO(100)

The adsorption kinetics of ethane, butane, pentane, and hexane on CaO(100) have been studied by multi-mass thermal desorption (TDS) spectroscopy. The sample cleanliness was checked by Auger electron spectroscopy. A molecular and dissociative adsorption pathway was evident for the alkanes, except for ethane, which does not undergo bond activation. Two TDS peaks appeared when recording the parent mass, which are assigned to different adsorption sites/configurations of the molecularly adsorbed alkanes. Bond activation leads to desorption of hydrogen and several alkane fragments assigned to methane and ethylene formation. Only one TDS feature is seen in this case. Formation of carbon residuals was absent.     

Hydrogen-induced reconstruction on W(100) and Mo(100) by surface infrared spectroscopy

Infrared absorption and low-energy electron-diffraction measurements of H adsorbed on W(100) and Mo(100) show that on each surface, distinct wavenumbers characterize the H-substrate stretching modes associated with the different long-range structures of the complicated T-θ phase diagram. Hydrogen is bonded at a two-fold bridge site at all temperatures and coverages investigated and the wavenumber of the symmetric stretch mode, v₁, is determined by the local geometry, i.e. the substrate dimer length. Analysis of the coverage dependence of the v₁ wavenumber shows that, at low coverages (θ ≲0.3), the effective H-H interactions are very different for the two substrates, leading to a uniform H layer on W(100) and to island formation on Mo(100). In general, the phase transitions are continuous on W(100), with regions of intermediate structures, and first order on Mo(100), with regions of coexisting phases.     

Chemical reactions on metal oxide surfaces investigated by vibrational spectroscopy

The most successful method to unravel the microscopic mechanisms governing reactions in heterogeneous catalysis is the “surface science” approach which is based on well-controlled studies on model catalysts (usually single crystal surfaces) under ultrahigh vacuum (UHV) conditions [G. Ertl, Angew. Chem. 47 (2008) 3524]. In this review our recent vibrational spectroscopic studies on selected model reactions at various single-crystalline metal oxide surfaces are summarized. Two vibrational spectroscopic methods, high resolution electron energy loss spectroscopy (HREELS) and Fourier-transform infrared spectroscopy (FTIRS), were applied to characterize the adsorbed species and to elucidate the elementary processes of chemical reactions at oxide surfaces ranging from well-defined single crystals to modified surfaces with deliberately introduced defects. The combination of both methods allows us to extend the vibrational spectroscopic studies from ideal to complex systems.     

Adsorption of propylene carbonate on the Li Mn_2O_4 (100) surface investigated by DFT+U calculations

Understanding the mechanism of the interfacial reaction between the cathode material and the electrolyte is a significant work because the interfacial reaction is an important factor affecting the stability,capacity,and cycling performance of Li-ion batteries.In this work,spin-polarized density functional theory calculations with on-site Coulomb energy have been employed to study the adsorption of electrolyte components propylene carbonate(PC)on the LiMn2O4(100)surface.The findings show that the PC molecule prefers to interact with the Mn atom on the LiMn2O4(100)surface via the carbonyl oxygen(Oc),with the adsorption energy of?1.16 eV,which is an exothermic reaction.As the adsorption of organic molecule PC increases the Mn atoms coordination with O atoms on the(100)surface,the Mn3+ions on the surface lose charge and the reactivity is substantially decreased,which improves the stability of the surface and benefits the cycling performance.     

On surface states of the LaB6 (001) face

Simple qualitative reasoning is used to discuss the origin and the nature of surface states on the (001) face of LaB₆, found recently by Aono et al.     

A comment on surface states of the LaB6(001) face

An attempt is made to use the qualitative theory of surface states for the analysis of the nature of these states recently found by angle-resolved photoemission from the LaB₆ (001) surface. The character of chemical bonding in this compound is also discussed.     

Adsorption of ethylene on the Pt(100) surface

Clean Pt(100) surfaces with bulk-like 1×1 structure, or the stable, reconstructed 5×20 structure and held at 200 or 330 K were exposed to ethylene. Ultraviolet photoemission spectroscopy identified the nature of the adsorbed species which depends on the structure and temperature of the clean surface and the amount adsorbed. It is ethylene on the 5 × 20 structure at 200 K, a vinyl radical on the same surface at 300 K up to half a monolayer, the remainder being added as acetylene; it is acetylene on the 1 × 1 surface at 330 K and a mixture of acetylene, vinyl and ethylene on the 1 × 1 surface at 200 K. Whatever the nature of the adsorbate, the surface coverage θ increased with exposure ? as $\text{(1 ? θ = C?}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>3</mtext>}}\text{)}$. By contrast, on a surface covered with any C₂ hydrocarbon acetylene adsorbs with Langmuir kinetics. The kinetics are explained in terms of the relationship between the attraction an approaching molecule experiences from the bare surface and its Van der Waals repulsion from preadsorbed molecules.     

First-principles study of molecular NO dissociation on Ir(100) surface

The dissociation of NO on Ir(100) surface is investigated using density functional theory (DFT). The pathway and transition state (TS) of the dissociation of NO molecule are determined using climbing image nudge elastic band (CI-NEB). The prerequisite state of NO dissociation is determining the most stable sites of the reactant and products. We found that the most energetically stable sites are the hollow for N atom and the bridge for NO molecule as well as O atom. We found that the bending of NO is the first step of the dissociation reaction due to the increase of the back-donation from the d-band of Ir to 2π ^? orbital of NO, which causes the weakening of NO bond. The dissociation energy barrier of NO molecule on Ir(100) surface is 0.49 eV.     

Adsorption of carbon monoxide on the molybdenum (100) surface

The interaction of CO with Mo(100) has been studied by means of thermal desorption spectrometry, work function measurements and electron stimulated desorption, in conjunction with LEED and AES. Results have been obtained for adsorption at room temperature and at temperatures down to 200 K. The study confirms previous results, showing that the β-states formed at room temperature are atomic. The thermal desorption data for the β-states are analyzed to give directly the desorption activation energy as a function of coverage. This energy is found to vary smoothly from an initial value of 3.7 to a final value of 2.9 eV molecule, indicating an average repulsive interaction between a pair of adjacent adatoms of 0.2 eV. The data at low temperature indicate that a molecular state, virgin-CO, is produced in competition with β-CO and probably one other state, from a common precursor. The step leading to virgin-CO has both a low activation energy and a low pre-exponential factor, suggesting that a reorientation of the molecule is required.     

氢分子在Mg2Ni(010)面的吸附与分解

本文采用基于密度泛函理论(DFT)的第一原理赝势平面波(PW-PP)方法,对氢分子在Mg2Ni(010)面的吸附与分解进行了研究,发现氢分子以Horl的方式吸附在表面层Ni原子的顶位时吸附能最高,为0.6769 eV,这表明氢分子最可能以Horl的方式吸附在表面层Ni原子的顶位,此时氢分子跟表面的距离(rd)和氢分子的键长(rH)分别为1.6286 A和0.9174 (A).在分子吸附的基础上计算了氢分子沿着选取的反应路径分解时的反应势垒,发现要使氢分子分解需要0.2778 eV的活化能,而氢分子分解时的吸附能为0.8390 eV,分解后两个氢原子的距离为3.1712(A).在分子吸附和分解吸附时氢原子跟正下方的Ni原子都有较强的相互作用,氢原子所得到的电子主要来自氢分子正下方的Ni原子.     

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.     

A tilted precursor for CO dissociation on the Fe(100) surface

Near edge X-ray absorption fine structure (NEXAFS) has been used to study the molecular orientation of the α₃ state of CO on the Fe(100) surface. It is found that the molecule is tilted by 45° ± 10° with respect to the surface normal, allowing direct interaction of the oxygen end of the molecule with the iron surface. The C-O bond is found to be elongated by 0.07 ± 0.02 Å in the α₃ state, relative to the other molecularly adsorbed CO states on this surface.     

水在金属氧化物表面的吸附与解离

（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.     

Electronic surface states investigated by means of photoemission spectroscopy

Ultraviolet photoemission spectroscopy (UPS) as an investigative method for surface states is presented. The measured energy distribution curve (EDC) furnishes information on the electronic density of states distribution in the valence band, nearest to the core levels and surface states. The measured angle resolved EDC's provide the possibility to determine the energy-momentum E(k) dependence of electrons in the bulk of the crystal and on the surface. Application of the synchrotron-storage ring system as a source of ultraviolet radiation in the energy range from 10 to 300 eV opens new avenues to investigate structure of electronic states. It features the following possibilities: (1) To distinguish the contribution of the surface and bulk states to the obtained EDC by measuring the change of the EDC when varying the exciting energy hv around the minimum of the escape depth (E = 80 eV) and outside of this region. (2) To discriminate in the valence band the contribution of the d-electrons from that of the s-p electrons due to a different change of the photoemission cross section of the d and s-p electrons with a change of hv. (3) To recognize the localized and delocalized contribution to the density of states in the valence band and to determine E(k) for these electrons by measurements of the angle resolved EDC. (4) To obtain information on the initial and final state distribution using the constant initial states (CIS) and/or constant final states (CFS) techniques. The potential of the photoemission technique will be illustrated by the results of the electronic structure investigation of some metals and semiconductors.     

Femtosecond surface vibrational spectroscopy of CO adsorbed on Ru(001) during desorption

Using time-resolved sum-frequency generation spectroscopy, the C- O stretch vibration of carbon monoxide adsorbed on a single-crystal Ru(001) surface is investigated during femtosecond near-IR laser excitation leading to desorption. A large transient redshift, a broadening of the resonance, and a strong decrease in intensity are observed. These originate from coupling of the C- O stretch to low-frequency modes, especially the frustrated rotation, that are highly excited in the desorption process.     

Hydrogen-induced reconstruction of the W(100) surface,studied by surface core level spectroscopy

We report W(4?) surface core level shifts which yield new information on the energetics of the W(100) (1 × 1) → C(2 × 2)H phase transition. At small hydrogen coverages we find two co-existing surface core levels from atoms on normal lattice sites and from atoms in reconstructed domains. These surface levels are shifted to smaller binding energy (toward E_F) by 0.35 eV and 0.13 eV relative to the bulk level, respectively. The most stable configuration is obtained at a fractional coverage θ_H ? 0.2, at which all surface atoms are shown to be paired with neighboring atoms in the surface plane.     

Photoemission spectroscopy at MOVPE-prepared InGaAs(100) surface reconstructions

Angular resolved ultraviolet photoemission spectroscopy at BESSY was employed to study the electronic structure of the three different, (4 × 3)-, (2 × 4)-, and (4 × 2)-surface reconstructions of In_0.53 Ga_0.47As, which was grown lattice-matched to InP(100). The surfaces have been prepared using metal organic vapor phase epitaxy (MOVPE). For spectroscopy, a dedicated transfer system was employed and samples were transferred contamination-free from the MOVPE reactor to UHV-based analysis tools. For the different surface reconstructions, the Γ ? Δ ? X direction was scanned while varying the photon energy between 10 eV and 28 eV. We observed two surface states in the photoelectron spectra on all of these surface reconstructions in addition to the bulk derived valence band emissions. Different binding energies of the surface states originating from different surface band bending were detected and described.     

CO adsorbed on a Xe covered Cu(100) surface studied by infrared spectroscopy

When a Cu(100) surface covered by a full Xe monolayer is exposed to CO at 60 K no infrared absorption associated with the CO vibration is observed. If the temperature is increased to 90 K, when the Xe atoms are desorbed, the ordinary CO spectrum develops. This observation can be explained, if the CO molecules on the Xe covered surface are oriented on the average with their molecular axes parallel to the surface.