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Achieving Remarkable Activity and Durability toward Oxygen Reduction Reaction Based on Ultrathin Rh-Doped Pt Nanowires

Huang, Hongwen, Li, Kan, Chen, Zhao, Luo, Laihao, Gu, Yuqian, Zhang, Dongyan, Ma, Chao, Si, Rui, Yang, Jinlong, Peng, Zhenmeng, Zeng, Jie
Journal of the American Chemical Society 2017 v.139 no.24 pp. 8152-8159
adsorption, anisotropy, catalysts, compression strength, density functional theory, durability, electrochemistry, energy, fuel cells, industrial applications, ligands, nanowires, oxygen, platinum, rhodium
The research of active and sustainable electrocatalysts toward oxygen reduction reaction (ORR) is of great importance for industrial application of fuel cells. Here, we report a remarkable ORR catalyst with both excellent mass activity and durability based on sub 2 nm thick Rh-doped Pt nanowires, which combine the merits of high utilization efficiency of Pt atoms, anisotropic one-dimensional nanostructure, and doping of Rh atoms. Compared with commercial Pt/C catalyst, the Rh-doped Pt nanowires/C catalyst shows a 7.8 and 5.4-fold enhancement in mass activity and specific activity, respectively. The combination of extended X-ray absorption fine structure analysis and density functional theory calculations reveals that the compressive strain and ligand effect in Rh-doped Pt nanowires optimize the adsorption energy of hydroxyl and in turn enhance the specific activity. Moreover, even after 10000 cycles of accelerated durability test in O₂ condition, the Rh-doped Pt nanowires/C catalyst exhibits a drop of 9.2% in mass activity, against a big decrease of 72.3% for commercial Pt/C. The improved durability can be rationalized by the increased vacancy formation energy of Pt atoms for Rh-doped Pt nanowires.