First-principles considerations in the design of Pd-alloy catalysts for oxygen reduction
First-principles considerations in the design of Pd-alloy catalysts for oxygen reduction
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氧还原钯合金催化剂设计的第一性原理考虑
DOI：
10.1002/anie.200604332
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发表时间：
2007-01-01
影响因子：
16.6
通讯作者：
Lu, Juntao
中科院分区：
文献类型：
--
作者：
Suo, Yange;Zhuang, Lin;Lu, Juntao
我们报告的第一性原理的考虑，提高催化活性的Pd合金催化剂在氧还原反应（ORR）和“火山”的活性和合金化程度之间的关系，并阐明相反的影响，从晶格应变和表面配体效应。在过去的两年中，人们一直致力于使用Pd合金作为ORR的催化剂。[1-3]发现与例如Co、Fe和Ni合金化强烈地提高Pd的催化活性，这代表了质子交换膜燃料电池（PEMFC）的非Pt催化剂的研究的重大进展。虽然合金化的性能已经得到了初步的证实，但是还需要系统的研究，特别是合金化的增强效应。[2a]以解释合金化后增强的活性。他们认为，掺入更活泼的金属，如Co，将促进O2的解离吸附[反应（1）]，由此产生的Oads可以从Co位点迁移到Pd位点，在那里可以发生电还原[反应（2）]，极化较小。
We report first-principles considerations of the enhanced catalytic activity of Pd-alloy catalysts in the oxygen reduction reaction (ORR) and the “volcano” relationship between the activity and the degree of alloying, and elucidate contrary influences from the lattice-strain and surface-ligand effects. In the past two years, much effort has been devoted to employing Pd alloys as catalysts for ORR.[1–3] Alloying with, for example, Co, Fe, and Ni was found to increase strongly the catalytic activity of Pd, and this represented significant progress in research on non-Pt catalysts for proton-exchange membrane fuel cells (PEMFC). Although promising performances have been preliminarily demonstrated, systematic work is required, especially for comprehending the enhancing effect of alloying.A simple thermodynamic model based on the data of bulk metal oxides was proposed by Fernĩndez et al.[2a] to interpret the enhanced activity upon alloying. They suggested that the incorporation of more active metals, such as Co, would facilitate the dissociative adsorption of O2 [Reaction (1)], and the thus-produced Oads could migrate from the Co site to the Pd site, where electroreduction [Reaction (2)] could occur with less polarization.