Deciphering Water Oxidation Catalysts: The Dominant Role of Surface Chemistry over Reconstruction Degree in Activity Promotion

Li An; Jianyi Li; Yuanmiao Sun; Jiamin Zhu; Justin Zhu Yeow Seow; Hong Zhang; Nan Zhang; Pinxian Xi; Zhichuan J Xu; Chun-Hua Yan

doi:10.1007/s40820-024-01562-7

Deciphering Water Oxidation Catalysts: The Dominant Role of Surface Chemistry over Reconstruction Degree in Activity Promotion

Nanomicro Lett. 2024 Nov 26;17(1):70. doi: 10.1007/s40820-024-01562-7.

Authors

Li An^#¹, Jianyi Li^#¹, Yuanmiao Sun^#^{2

3}, Jiamin Zhu^#¹, Justin Zhu Yeow Seow², Hong Zhang⁴, Nan Zhang¹, Pinxian Xi^{5

6}, Zhichuan J Xu⁷, Chun-Hua Yan^{1

8}

Affiliations

¹ State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, People's Republic of China.
² School of Materials Science and Engineering, Nanyang Technological University, Singapore, 639798, Singapore.
³ Faculty of Materials Science and Energy Engineering, Institute of Technology for Carbon Neutrality, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055, People's Republic of China.
⁴ Key Laboratory of Electromagnetic Materials and Devices, National Center for International Research On Photoelectric and Energy Materials, School of Materials and Energy, Electron Microscopy Center, Yunnan University, Kunming, 650091, People's Republic of China.
⁵ State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, People's Republic of China. [email protected].
⁶ State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization, Baotou Research Institute of Rare Earths, Baotou, 014030, People's Republic of China. [email protected].
⁷ School of Materials Science and Engineering, Nanyang Technological University, Singapore, 639798, Singapore. [email protected].
⁸ Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, Peking University, Beijing, 100871, People's Republic of China.

^# Contributed equally.

Abstract

Water splitting hinges crucially on the availability of electrocatalysts for the oxygen evolution reaction. The surface reconstruction has been widely observed in perovskite catalysts, and the reconstruction degree has been often correlated with the activity enhancement. Here, a systematic study on the roles of Fe substitution in activation of perovskite LaNiO₃ is reported. The substituting Fe content influences both current change tendency and surface reconstruction degree. LaNi_0.9Fe_0.1O₃ is found exhibiting a volcano-peak intrinsic activity in both pristine and reconstructed among all substituted perovskites in the LaNi_1-xFe_xO₃ (x = 0.00, 0.10, 0.25, 0.50, 0.75, 1.00) series. The reconstructed LaNi_0.9Fe_0.1O₃ shows a higher intrinsic activity than most reported NiFe-based catalysts. Besides, density functional theory calculations reveal that Fe substitution can lower the O 2p level, which thus stabilize lattice oxygen in LaNi_0.9Fe_0.1O₃ and ensure its long-term stability. Furthermore, it is vital interesting that activity of the reconstructed catalysts relied more on the surface chemistry rather than the reconstruction degree. The effect of Fe on the degree of surface reconstruction of the perovskite is decoupled from that on its activity enhancement after surface reconstruction. This finding showcases the importance to customize the surface chemistry of reconstructed catalysts for water oxidation.

Keywords: Activation and reconstruction; Doping; Oxygen evolution reaction; Perovskite oxides.