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激光蒸发制备的负载型金催化剂上一氧化碳的氧化:载体作用的直接证据

Oxidation of CO on gold supported catalysts prepared by laser vaporization: direct evidence of support contribution.

作者信息

Arrii S, Morfin F, Renouprez A J, Rousset J L

机构信息

Institut de Recherches sur la Catalyse, 2 Av. A. Einstein, 69626 Villeurbanne.

出版信息

J Am Chem Soc. 2004 Feb 4;126(4):1199-205. doi: 10.1021/ja036352y.

Abstract

Gamma-Al2O3, ZrO2, and TiO2 gold supported model catalysts have been synthesized by laser vaporization. Structural characterization using Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy experiments have shown that the gold clusters deposited on the different supports have similar distribution of size centered around 3 nm and are in the metallic state. However, X-ray photoemission measurements also indicate lower binding energies than the usual Au 4f(7/2) at 84.0 eV for both alumina and titania supported catalysts, indicating a modification of the electronic structure of the metal. One has taken benefit of these features to study the influence of the nature of the support toward CO oxidation activities without being hindered by particle size or gold oxidic species effects. By comparing the activities of the different catalysts, it is concluded that the nature of the support directly affects the activity of gold. The following tendency is observed: titania and zirconia are superior to alumina as supports, titania being slightly better than zirconia. From XPS and activity results we can conclude that the existence of negatively charged clusters is not the key point to explain the high activity observed for Au/ZrO2 and Au/TiO2 catalysts and also that metallic Au is the major catalytically active phase. Hence, due to their very nature, titania and to a less extent zirconia should participate to the catalytic process.

摘要

通过激光蒸发合成了负载金的γ - Al₂O₃、ZrO₂和TiO₂模型催化剂。利用透射电子显微镜和X射线光电子能谱实验进行的结构表征表明,沉积在不同载体上的金簇具有相似的尺寸分布,中心尺寸约为3 nm,且处于金属态。然而,X射线光电子能谱测量还表明,对于氧化铝和二氧化钛负载的催化剂,其结合能低于通常的84.0 eV的Au 4f(7/2),这表明金属的电子结构发生了改变。利用这些特性研究了载体性质对CO氧化活性的影响,而不受粒径或金的氧化态物种效应的干扰。通过比较不同催化剂的活性,得出载体性质直接影响金的活性的结论。观察到以下趋势:二氧化钛和氧化锆作为载体优于氧化铝,二氧化钛略优于氧化锆。从XPS和活性结果可以得出结论,带负电荷的簇的存在不是解释Au/ZrO₂和Au/TiO₂催化剂所观察到的高活性的关键因素,金属Au是主要的催化活性相。因此,由于其本质特性,二氧化钛以及在较小程度上氧化锆应该参与了催化过程。

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