Bimetallic PtSn catalyst for selective CO oxidation in H2-rich gases at low temperatures

双金属片 催化作用 双功能 吸附 解吸 化学 近程 选择性 一氧化碳 X射线光电子能谱 无机化学 热脱附光谱法 化学工程 物理化学 有机化学 工程类
作者
Markus M. Schubert,M.J. Kahlich,G.J. Feldmeyer,M. Hüttner,Stefan Hackenberg,Hubert A. Gasteiger,Luis A Mancera
出处
期刊:Physical Chemistry Chemical Physics [The Royal Society of Chemistry]
卷期号:3 (6): 1123-1131 被引量:157
标识
DOI:10.1039/b008062o
摘要

Kinetic measurements on preferential CO oxidation in a H2-rich atmosphere (PROX) over a bimetallic, carbon supported PtSn catalyst reveal a high activity and selectivity already at low temperatures (0–80°C), superior to a commercial Pt/Al2O3 system. The selectivity, though steadily decreasing with temperature, is remarkably high, 85% at low temperatures around 0–20°C, and even at 120°C it is, at 45%, still higher than that of standard Pt catalysts. The observation that CO desorption is not rate limiting and that the selectivity decreases with increasing temperature, can be explained in a mechanistic model involving separation of the reactant adsorption sites (bifunctional surface), with competing CO and hydrogen adsorption on Pt sites/areas and oxygen adsorption predominantly on Sn sites and SnOx islands on/adjacent to the active PtSn particles. The reaction takes place in a bifunctional way at the perimeter of these islands or by invoking a spill-over process. This model is supported by CO temperature-programmed desorption (TPD), in situ diffuse reflectance IR Fourier transform spectroscopy (DRIFTS), and x-ray photon spectroscopy (XPS) measurements, which indicate that under reaction conditions the surface CO coverage on the metallic particles is high, but decreases with temperature, and that only part of the Sn is reduced, included in PtSn alloy particles, while another part is in an oxidic state, forming SnOx islands on and presumably also beside the active particles. Its excellent performance makes PtSn an interesting catalyst for fuel gas purification in low temperature polymer electrolyte membrane fuel cell technology (PEM-FC).
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