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采用EDE/DRIFTS/MS联用技术研究Rh及RhPd合金负载型催化剂的结构-性能关系

Structure-performance relationships of Rh and RhPd alloy supported catalysts using combined EDE/DRIFTS/MS.

作者信息

Dent Andy J, Evans John, Fiddy Steven G, Jyoti Bhrat, Newton Mark A, Tromp Moniek

机构信息

University of Southampton, School of Chemistry, Southampton, UK SO17 1BJ.

出版信息

Faraday Discuss. 2008;138:287-300; discussion 317-35, 433-4. doi: 10.1039/b706294j.

Abstract

Energy dispersive extended X-ray absorption fine structure spectroscopy (ED-XAFS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and mass spectrometry (MS), have been combined for the structure-function study of Rh and RhPd supported catalysts for the reduction of NO by CO. The combined results show that although alloying of Rh with Pd prevents the dissociative oxidation of the Rh by NO, it does not prevent the extensive disruptive oxidation of Rh by CO. The influence of oxidative disruption by molecular CO in such systems may therefore be far more pervasive and catalytically important than has been previously observed. The overall metal particle size observed in the RhPd alloy system during the CO/NO reaction is significantly larger than for the Rh-only system for the entire temperature range employed. The catalytically active sites, however, are likely to be similar, with the overall activity of the alloy system to be reduced due to inactive RhPd alloy nanoparticles.

摘要

能量色散扩展X射线吸收精细结构光谱(ED-XAFS)、漫反射红外傅里叶变换光谱(DRIFTS)和质谱(MS)已被结合起来用于研究负载型Rh和RhPd催化剂上CO还原NO的结构与功能关系。综合结果表明,虽然Rh与Pd合金化可防止Rh被NO进行解离氧化,但并不能阻止Rh被CO进行广泛的破坏性氧化。因此,在这类体系中,分子CO的氧化破坏作用可能比之前观察到的更为普遍且在催化方面更为重要。在整个使用温度范围内,RhPd合金体系在CO/NO反应过程中观察到的整体金属颗粒尺寸明显大于仅含Rh的体系。然而,催化活性位点可能相似,合金体系的整体活性因无活性的RhPd合金纳米颗粒而降低。

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