NiO Matrix Decorated by Ru Single Atoms: Electron-Rich Ru-Induced High Activity and Selectivity toward Electrochemical N2 Reduction

Xiang Huang; Jiong Wang; Changming Zhao; Li-Yong Gan; Hu Xu

doi:10.1021/acs.jpclett.3c00372

NiO Matrix Decorated by Ru Single Atoms: Electron-Rich Ru-Induced High Activity and Selectivity toward Electrochemical N₂ Reduction

J Phys Chem Lett. 2023 Apr 27;14(16):3785-3793. doi: 10.1021/acs.jpclett.3c00372. Epub 2023 Apr 13.

Authors

Xiang Huang¹, Jiong Wang², Changming Zhao¹, Li-Yong Gan³, Hu Xu^{1

4}

Affiliations

¹ Department of Physics, Southern University of Science and Technology, Shenzhen 518055, China.
² Innovation Center for Chemical Sciences, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
³ Institute for Structure and Function and Department of Physics, Chongqing University, Chongqing 400030, China.
⁴ Guangdong Provincial Key Laboratory of Computational Science and Material Design, Southern University of Science and Technology, Shenzhen 518055, China.

PMID: 37052489
DOI: 10.1021/acs.jpclett.3c00372

Abstract

Developing a single-atom catalyst with electron-rich active sites is a promising strategy for catalyzing the electrochemical N₂ reduction reaction (NRR). Herein, we choose NiO(001) as a model template and deposit a series of single transition metal (TM) atoms with higher formal charges to create the electron-rich active centers. Our first-principles calculations show that low-valent Ru (+2) on NiO(001) can significantly activate N₂, with its oxidation states varying from +2 to +4 throughout the catalytic cycle. The Ru/NiO(001) catalyst exhibits the best activity with a relatively low limiting potential of -0.49 V. Furthermore, under NRR operating conditions, the Ru site is primarily occupied by *N₂ rather than *H, indicating that NRR overwhelms the hydrogen evolution reaction and thus exhibits excellent selectivity. Our work highlights the potential of designing catalysts with electron-rich active sites for NRR.