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Vol. 15 (2023)

Tuning Active Metal Atomic Spacing by Filling of Light Atoms and Resulting Reversed Hydrogen Adsorption-Distance Relationship for Efficient Catalysis

https://doi.org/10.1007/s40820-023-01142-1
Ding Chen
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Ruihu Lu
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Ruohan Yu
NRC (Nanostructure Research Centre), Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Hongyu Zhao
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Dulan Wu
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Youtao Yao
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Kesong Yu
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Jiawei Zhu
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Pengxia Ji
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Zonghua Pu
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Zongkui Kou
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Jun Yu
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Jinsong Wu
NRC (Nanostructure Research Centre), Wuhan University of Technology, Wuhan 430070, People’s Republic of China
Shichun Mu
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, People’s Republic of China

Corresponding Author: Shichun Mu

msc@whut.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 168

Abstract

Precisely tuning the spacing of the active centers on the atomic scale is of great significance to improve the catalytic activity and deepen the understanding of the catalytic mechanism, but still remains a challenge. Here, we develop a strategy to dilute catalytically active metal interatomic spacing (dM-M) with light atoms and discover the unusual adsorption patterns. For example, by elevating the content of boron as interstitial atoms, the atomic spacing of osmium (dOs-Os) gradually increases from 2.73 to 2.96 Å. More importantly, we find that, with the increase in dOs-Os, the hydrogen adsorption-distance relationship is reversed via downshifting d-band states, which breaks the traditional cognition, thereby optimizing the H adsorption and H2O dissociation on the electrode surface during the catalytic process; this finally leads to a nearly linear increase in hydrogen evolution reaction activity. Namely, the maximum dOs-Os of 2.96 Å presents the optimal HER activity (8 mV @ 10 mA cm−2) in alkaline media as well as suppressed O adsorption and thus promoted stability. It is believed that this novel atomic-level distance modulation strategy of catalytic sites and the reversed hydrogen adsorption-distance relationship can shew new insights for optimal design of highly efficient catalysts.


Highlights:


1 Density functional theory calculations indicates that interstitial B atoms can tune the atomic spacing of host metal Os and achieve a reversal hydrogen adsorption-distance relationship.
2 The structure–activity relationship between the spacing of active Os atoms and catalytic activity is established.
3 Prepared OsB2 with increasing dOs-Os of 2.96 Å presents the optimal hydrogen evolution reaction activity (8 mV @ 10 mA cm−2) and robust stability in alkaline media.

Keywords

Electrocatalysis DFT calculation Interstitial filling Hydrogen evolution Structure–activity relationships
Chen, Ding, Ruihu Lu, Ruohan Yu, Hongyu Zhao, Dulan Wu, Youtao Yao, Kesong Yu, Jiawei Zhu, Pengxia Ji, Zonghua Pu, Zongkui Kou, Jun Yu, Jinsong Wu, and Shichun Mu. 2023. “Tuning Active Metal Atomic Spacing by Filling of Light Atoms and Resulting Reversed Hydrogen Adsorption-Distance Relationship for Efficient Catalysis”. Nano-Micro Letters 15 (July):168. https://doi.org/10.1007/s40820-023-01142-1.
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