Regulating the scaling relationship for high catalytic kinetics and selectivity of the oxygen reduction reaction

Wanlin Zhou; Hui Su; Weiren Cheng; Yuanli Li; Jingjing Jiang; Meihuan Liu; Feifan Yu; Wei Wang; Shiqiang Wei; Qinghua Liu

doi:10.1038/s41467-022-34169-w

Regulating the scaling relationship for high catalytic kinetics and selectivity of the oxygen reduction reaction

Nat Commun. 2022 Oct 27;13(1):6414. doi: 10.1038/s41467-022-34169-w.

Authors

Wanlin Zhou¹, Hui Su^{2

3}, Weiren Cheng^{1

4}, Yuanli Li⁵, Jingjing Jiang¹, Meihuan Liu¹, Feifan Yu⁶, Wei Wang⁶, Shiqiang Wei¹, Qinghua Liu⁷

Affiliations

¹ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, Anhui, P. R. China.
² National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, Anhui, P. R. China. suhui@ustc.edu.cn.
³ School of Materials Science and Engineering, Anhui University, Hefei, 230601, Anhui, P. R. China. suhui@ustc.edu.cn.
⁴ Institute for Catalysis, Hokkaido University, Sapporo, 001-0021, Japan.
⁵ Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Southwest University of Science and Technology, Mianyang, 621010, Sichuan, P. R. China.
⁶ School of Chemistry and Chemical Engineering, Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, Shihezi University, Shihezi, 832003, China.
⁷ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, Anhui, P. R. China. qhliu@ustc.edu.cn.

Abstract

The electrochemical oxygen reduction reaction (ORR) is at the heart of modern sustainable energy technologies. However, the linear scaling relationship of this multistep reaction now becomes the bottleneck for accelerating kinetics. Herein, we propose a strategy of using intermetallic-distance-regulated atomic-scale bimetal assembly (ABA) that can catalyse direct O‒O radical breakage without the formation of redundant *OOH intermediates, which could regulate the inherent linear scaling relationship and cause the ORR on ABA to follow a fast-kinetic dual-sites mechanism. Using in situ synchrotron spectroscopy, we directly observe that a self-adjustable N-bridged Pt = N₂ = Fe assembly promotes the generation of a key intermediate state (Pt‒O‒O‒Fe) during the ORR process, resulting in high reaction kinetics and selectivity. The well-designed Pt = N₂ = Fe ABA catalyst achieves a nearly two orders of magnitude enhanced kinetic current density at the half-wave potential of 0.95 V relative to commercial Pt/C and an almost 99% efficiency of 4-electron pathway selectivity, making it one of the potential ORR catalysts for application to the energy device of zinc‒air cells. This study provides a helpful design principle for developing and optimizing other efficient ORR electrocatalysts.

Abstract

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