Highly dispersed Cu atoms in MOF-derived N-doped porous carbon inducing Pt loads for superior oxygen reduction and hydrogen evolution

化学工程 材料科学 还原(数学) 兴奋剂 碳纤维 氢 氧还原反应 多孔性 化学 无机化学 电化学 氧气 氧还原 有机化学 复合材料 物理化学 复合数 电极 光电子学 工程类 几何学 数学
作者
Chao Wang,Long Kuai,Wei Cao,Harishchandra Singh,Alexei A. Zakharov,Yuran Niu,Hongxia Sun,Baoyou Geng
出处
期刊:Chemical Engineering Journal [Elsevier BV]
卷期号:426: 130749-130749 被引量:88
标识
DOI:10.1016/j.cej.2021.130749
摘要

• Monoatomic copper induces platinum atoms to be loaded on N-doped porous carbon. • The Pt mass activity of C-ZIF-CuPt is 4.4 times (ORR) and 6.7 times (HER) of the commercial Pt/C. • The carbon carrier and CuPt clusters have a strong orbital interaction. • Cu doping reduces the ORR overpotential of Pt and the activation energy barrier to water molecules. The preparation of oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) catalysts with high activity, stability and low platinum loading has always been the focus of research. The single-atom platinum supported catalyst greatly improves the utilization of platinum, but the catalytic activity and selectivity are greatly affected by the platinum coordination environment, and the preparation of the material is difficult. Doping base metals to adjust the electronic structure of platinum is an effective strategy to improve catalyst performance. In this work, copper-platinum alloy nanoparticles were loaded on N-doped porous carbon via a targeted route guided by highly dispersed Cu atoms derived from MOF. The product C-ZIF-CuPt has high activity and high stability ORR, HER bifunctional catalytic performance, which is better than commercial Pt/C (20 wt%). The Pt activity in C-ZIF-CuPt is 4.4 times (ORR) and 6.7 times (HER) than Pt/C. Spectromicroscopic determinations unveiled that strong interactions between carbon carrier and the CuPt alloys contribute to the overall stabilities. DFT calculations show that Cu doping can increase the d-band center of Pt, reduce the ORR overpotential, and the activation energy barrier to water molecules, which is beneficial to ORR and HER catalysis. Under the same carrier conditions, the performance of sub-nano (single atoms, clusters) platinum-supported catalysts (C-ZIF-Cu-Pt) is inferior to C-ZIF-CuPt. This further shows that platinum alloying can effectively improve the performance of the catalyst.
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