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11.
本文用化学吸附、原位IR、和XPS考察了钒助剂对Rh2/SiO2催化剂的H2和CO化学吸附的影响.结果表明,1)CO吸附在RhI、RhⅡ和RhⅢ中心上分别产生孪生、线式和桥式CO表面吸附物种.2)H2主要解离吸附在RhⅡ和RhⅢ中心上,但CO能优先吸附;RhI中心对H2的化学吸附能力弱,但H2和CO能共吸附在RhI中心上形成表面羰基氢化物.3)Rh2-V/SiO2催化剂在573K还原后,铑与钒助剂的强相互作用主要发生在RhⅡ和RhⅢ与钒助剂之间,H2吸附比CO吸附受到更强烈的抑制.用覆盖模型可以较好地解释钒助剂对Rh2/SiO2催化剂的H2和CO化学吸附的影响. 相似文献
12.
采用SCF-X_α-MS方法, 对于C(2×2)S/Fe(001)吸附体系, 选择Fe_5S和Fe_9S两种原子簇模型, 研究了该吸附体系的电子结构、吸附成键特征及其相互作用图象。结果表明, S吸附于Fe(001)单晶表面具有较强的定域性质, S原子与底物Fe原子之间的吸附相互作用主要表现为S(3p)-Fe(4s,3d)之间的轨道相互作用。通过对表面吸附键长的优化, 其结果与X.S.Zhang等的ARPEFS的实验结果一致。 相似文献
14.
The surface and materials science of tin oxide 总被引:3,自引:0,他引:3
The study of tin oxide is motivated by its applications as a solid state gas sensor material, oxidation catalyst, and transparent conductor. This review describes the physical and chemical properties that make tin oxide a suitable material for these purposes. The emphasis is on surface science studies of single crystal surfaces, but selected studies on powder and polycrystalline films are also incorporated in order to provide connecting points between surface science studies with the broader field of materials science of tin oxide. The key for understanding many aspects of SnO2 surface properties is the dual valency of Sn. The dual valency facilitates a reversible transformation of the surface composition from stoichiometric surfaces with Sn4+ surface cations into a reduced surface with Sn2+ surface cations depending on the oxygen chemical potential of the system. Reduction of the surface modifies the surface electronic structure by formation of Sn 5s derived surface states that lie deep within the band gap and also cause a lowering of the work function. The gas sensing mechanism appears, however, only to be indirectly influenced by the surface composition of SnO2. Critical for triggering a gas response are not the lattice oxygen concentration but chemisorbed (or ionosorbed) oxygen and other molecules with a net electric charge. Band bending induced by charged molecules cause the increase or decrease in surface conductivity responsible for the gas response signal. In most applications tin oxide is modified by additives to either increase the charge carrier concentration by donor atoms, or to increase the gas sensitivity or the catalytic activity by metal additives. Some of the basic concepts by which additives modify the gas sensing and catalytic properties of SnO2 are discussed and the few surface science studies of doped SnO2 are reviewed. Epitaxial SnO2 films may facilitate the surface science studies of doped films in the future. To this end film growth on titania, alumina, and Pt(1 1 1) is reviewed. Thin films on alumina also make promising test systems for probing gas sensing behavior. Molecular adsorption and reaction studies on SnO2 surfaces have been hampered by the challenges of preparing well-characterized surfaces. Nevertheless some experimental and theoretical studies have been performed and are reviewed. Of particular interest in these studies was the influence of the surface composition on its chemical properties. Finally, the variety of recently synthesized tin oxide nanoscopic materials is summarized. 相似文献
15.
Atomic chemisorption of hydrogen and oxygen on the Ni(100) surface has been studied using an Effective Core Potential (ECP) approach described in a previous paper. Clusters of up to 50 nickel atoms have been used to model the surface. The computed chemisorption energies are 62 kcal/mol (exp. 63 kcal/mol) for hydrogen and 106 kcal/mol (exp. 115–130 kcal/mol) for oxygen. Correlating the adsorbate and the cluster-adsorbate bonds is extremely important for obtaining accceptable results, particularly for oxygen. Reasonable convergence of chemisorption energies is obtained with 40–50 cluster atoms for both hydrogen and oxygen. For hydrogen the addition of a third cluster layer stabilizes the results considerably. Both hydrogen and oxygen are adsorbed at (or close to) the four-fold hollow site. The calculated barriers for surface migration are also in good agreement with the experimental estimates. The calculated equilibrium heights above the surface are on the other hand too high compared with experiments. This disagreement is believed to be due to core-valence correlation effects, which are not incorporated in the present ECP. The cluster convergence for the height above the surface is much slower than for the chemisorption energy. 相似文献
16.
New polymeric adsorbents (ZH-02, ZH-03) containing benzoyl group for adsorbing and removing 4-methylaniline from its aqueous solutions were prepared. Studies on the isotherms and the comparison of desorption conditions evidenced through the adsorption of 4-methylaniline in water onto ZH-02 and ZH-03, namely that there are chemisorption‘s transitions at a proper higher temperature. Mini-colunm adsorption studies of 4-methylaniline on XAD-4, ZH-02 and ZH-03 at 288 K show that the breakthrough capacities are 2.39, 2.99 and 3.19 mmol/g and the total capacities are 3.45, 3.92 and 4.35 mmol/g, respectively. 相似文献
17.
Teng-Yuan Dong Chienlin Huang Chiao-Pei Chen Ming-Cheng Lin 《Journal of organometallic chemistry》2007,692(23):5147-5155
We describe the formation of stable dithiol-bifunctionalized Ru(II)-terpyridine monolayer onto gold electrode. The coverage-dependent behavior onto gold electrode has been studied by electrochemical technique. The stability, surface charge coverage, and electron-transfer kinetics were assessed by cyclic voltammetry. Functionalized monolayer-protected Au clusters (MPCs) were also prepared. The spectroscopic characterization data of MPCs using UV-Vis and TEM techniques are discussed. TEM images showed that functionalized spherical nanoclusters of 4.7 ± 0.3 and 4.3 ± 0.2 nm were produced. The particle sizes are uniform with a narrow size distribution. The morphology of Au(1 1 1) metal surface modified with MPCs was imaged using atomic force microscopy (AFM). The nanoparticle layer exhibits a distinct surface morphology, irregularly shaped domains with dimensions from 20 to 60 nm and root mean square heights of 2.401 nm. 相似文献
18.
19.
由RhCl_3·xH_2O制备了不同Rh含量的Rh/SiO_2和Rh-V/SiO_2催化剂,采用化学吸附和原位TPD-IR方法考察钒助剂对Rh/SiO_2催化剂在常温和高温的H_2和CO化学吸附的影响。结果再次表明:1)不同Rh中心对H_2和CO的化学吸附性能不同,钒助剂对不同Rh中心的H_2和CO吸附的影响也不同。H_2主要吸附在Rh~Ⅱ和Rh~Ⅲ中心上,而在Rh~Ⅰ中心上的吸附弱。2)Rh-钒助剂的强相互作用主要是Rh~Ⅱ和Rh~Ⅲ与钒助剂之间的相互作用,H_2吸附受到比CO吸附更强烈的抑制。钒助剂对Rh/SiO_2的H_2和CO吸附性能的影响可用覆盖模型解释。 相似文献
20.
用从头算研究了d空穴位置不同对Ni—CO成键机制的影响。结果表明,Ni—CO键中σ/π接受作用的相对强弱,取决于Ni—CO簇所处的能态。σ空间电子云较π空间电子云弥散,因而Ni—CO簇的稳定性与σ空间电子云的排斥密切相关。随着Ni4pσ轨道上电子占据数的增加,Ni—CO稳定性减弱。比较了分子簇Ni—CO与NiCO分子及CO/Ni化学吸附体系之间的性质。 相似文献