Anomalous self-optimization of sulfate ions for boosted oxygen evolution reaction

Dengfeng Cao; Oyawale Adetunji Moses; Beibei Sheng; Shuangming Chen; Haibin Pan; Lihui Wu; Hongwei Shou; Wenjie Xu; Dongdong Li; Lirong Zheng; Shengqi Chu; Chuansheng Hu; Daobin Liu; Shiqiang Wei; Xusheng Zheng; Zeming Qi; Xiaojun Wu; Jing Zhang; Li Song

doi:10.1016/j.scib.2020.09.037

Anomalous self-optimization of sulfate ions for boosted oxygen evolution reaction

Sci Bull (Beijing). 2021 Mar 30;66(6):553-561. doi: 10.1016/j.scib.2020.09.037. Epub 2020 Sep 30.

Authors

Dengfeng Cao¹, Oyawale Adetunji Moses¹, Beibei Sheng¹, Shuangming Chen², Haibin Pan¹, Lihui Wu¹, Hongwei Shou³, Wenjie Xu¹, Dongdong Li⁴, Lirong Zheng⁵, Shengqi Chu⁵, Chuansheng Hu¹, Daobin Liu⁶, Shiqiang Wei¹, Xusheng Zheng¹, Zeming Qi¹, Xiaojun Wu⁷, Jing Zhang⁵, Li Song⁸

Affiliations

¹ National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei 230026, China.
² National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei 230026, China. Electronic address: csmp@ustc.edu.cn.
³ National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei 230026, China; Hefei National Laboratory for Physical Sciences at the Microscales, Department of Materials Sciences and Engineering, University of Science and Technology of China, Hefei 230026, China.
⁴ Institute of Amorphous Matter Science, School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China.
⁵ Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.
⁶ National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei 230026, China; School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore.
⁷ Hefei National Laboratory for Physical Sciences at the Microscales, Department of Materials Sciences and Engineering, University of Science and Technology of China, Hefei 230026, China.
⁸ National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei 230026, China. Electronic address: song2012@ustc.edu.cn.

PMID: 36654425
DOI: 10.1016/j.scib.2020.09.037

Abstract

Broadly, the oxygen evolution reaction (OER) has been deeply understood as a significant part of energy conversion and storage. Nevertheless, the anions in the OER catalysts have been neglected for various reasons such as inactive sites, dissolution, and oxidation, amongst others. Herein, we applied a model catalyst s-Ni(OH)₂ to track the anionic behavior in the catalyst during the electrochemical process to fill this gap. The advanced operando synchrotron radiation Fourier transform infrared (SR-FTIR) spectroscopy, synchrotron radiation photoelectron spectroscopy (SRPES) depth detection and differential X-ray absorption fine structure (Δ-XAFS) spectrum jointly point out that some oxidized sulfur species (SO₄^2-) will self-optimize new Ni-S bonds during OER process. Such amazing anionic self-optimization (ASO) behavior has never been observed in the OER process. Subsequently, the optimization-derived component shows a significantly improved electrocatalytic performance (activity, stability, etc.) compared to reference catalyst Ni(OH)₂. Theoretical calculation further suggests that the ASO process indeed derives a thermodynamically stable structure of the OER catalyst, and then gives its superb catalytic performance by optimizing the thermodynamic and kinetic processes in the OER, respectively. This work demonstrates the vital role of anions in the electrochemical process, which will open up new perspectives for understanding OER and provide some new ideas in related fields (especially catalysis and chemistry).

Keywords: Anionic self-optimization (ASO); Differential X-ray absorption fine structure (Δ-XAFS) spectrum; Operando synchrotron radiation Fourier transform infrared (SR-FTIR) spectroscopy; Oxygen evolution reaction (OER); Synchrotron radiation photoelectron spectroscopy (SRPES) depth detection.