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Vol. 17 (2025)

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

https://doi.org/10.1007/s40820-024-01562-7
Li An
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
Jianyi Li
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
Yuanmiao Sun
School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore
Jiamin Zhu
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
Justin Zhu Yeow Seow
School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore
Hong Zhang
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
Nan Zhang
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
Pinxian Xi
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
Zhichuan J. Xu
School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore
Chun‑Hua Yan
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

Corresponding Author: Zhichuan J. Xu

xuzc@ntu.edu.sg

Nano-Micro Letters, Vol. 17 (2025), Article Number: 70

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. LaNi0.9Fe0.1O3 is found exhibiting a volcano-peak intrinsic activity in both pristine and reconstructed among all substituted perovskites in the LaNi1-xFexO3 (x = 0.00, 0.10, 0.25, 0.50, 0.75, 1.00) series. The reconstructed LaNi0.9Fe0.1O3 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 LaNi0.9Fe0.1O3 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.


Highlights:
1 Demonstrate that the key factor to determine the activity of reconstructed surfaces is the surface chemistry, instead of reconstruction degree using the popular perovskite LaNi1-xFexO3 oxides as model materials.
2 Fe content can influence both the surface reconstruction degree, the activation degree, and the activity of reconstructed surfaces.
3 The oxygen evolution reaction activity of reconstructed catalysts is primarily governed by the chemistry of the reconstructed surface species.

Keywords

Oxygen evolution reaction Perovskite oxides Doping Activation and reconstruction
An, Li, Jianyi Li, Yuanmiao Sun, Jiamin Zhu, Justin Zhu Yeow Seow, Hong Zhang, Nan Zhang, Pinxian Xi, Zhichuan J. Xu, and Chun‑Hua Yan. 2024. “Deciphering Water Oxidation Catalysts: The Dominant Role of Surface Chemistry over Reconstruction Degree in Activity Promotion”. Nano-Micro Letters 17 (November):70. https://doi.org/10.1007/s40820-024-01562-7.
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