Trends of Oxygen Reduction Reaction on Platinum Alloys: A Computational and Experimental Study
Trends of Oxygen Reduction Reaction on Platinum Alloys: A Computational and Experimental Study
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DOI：
10.1021/acs.jpcc.5b02849
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发表时间：
2015-06
影响因子：
3.7
通讯作者：
Syuan-Pei Lin;Kuan-Wen Wang;Chenwei Liu;Hong Chen;Jenghan Wang
中科院分区：
文献类型：
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作者：
Syuan-Pei Lin;Kuan-Wen Wang;Chenwei Liu;Hong Chen;Jenghan Wang
开发用于氧还原反应的铂基合金是提高聚合物电解质膜燃料电池（PEMFC）和金属空气电池性能的重要课题。在此，从计算和实验方法对Pt壳和芯合金中具有较小和较大掺杂剂的Pt合金上的ORR进行了广泛研究，以合理化详细机制。我们基于密度泛函理论（DFT）的计算发现，与较小掺杂剂（Co、Cu、Pd）合金化的Pt在Pt壳结构处是化学稳定的，并且它们的改善的ORR活性源于配体和几何效应。另一方面，Pt与较大且反应性较低的掺杂剂（如Au）合金化，在化学上有利于Pt核结构，并且通过表面掺杂剂的系综效应显示出最佳的ORR活性。此外，我们的研究结果表明，d-带中心的表面铂可以与ORR活性的铂壳合金，但没有铂核的。该com.
The development of Pt-based alloys for oxygen reduction reaction (ORR) is an important subject to enhance the performance of polymer electrolyte membrane fuel cells (PEMFCs) and metal–air batteries. Herein, ORR on Pt alloys with smaller and larger dopants in both Pt-shelled and cored alloys have been extensively investigated from both computational and experimental approaches to rationalize the detailed mechanism. Our density functional theory (DFT) based calculations found that Pt alloying with smaller dopants (Co, Cu, Pd) is thermodynamically stable at Pt-shelled structures and their improved ORR activity originates from ligand and geometric effects. On the other hand, Pt alloying with larger and less reactive dopants, such as Au, thermodynamically favors Pt-cored structure and shows the best ORR activity through ensemble effect of surface dopant. Additionally, our results revealed that d-band center of surface Pt can be correlated to ORR activity for Pt-shelled alloys, but not to Pt-cored ones. The com...