Isolated Electron-Rich Ruthenium Atoms in Intermetallic Compounds for Boosting Electrochemical Nitric Oxide Reduction to Ammonia

Huaifang Zhang; Yanbo Li; Chuanqi Cheng; Jin Zhou; Pengfei Yin; Haoming Wu; Zhiqin Liang; Jiangwei Zhang; Qinbai Yun; An-Liang Wang; Lijie Zhu; Bin Zhang; Wenbin Cao; Xiangmin Meng; Jing Xia; Yifu Yu; Qipeng Lu

doi:10.1002/anie.202213351

Isolated Electron-Rich Ruthenium Atoms in Intermetallic Compounds for Boosting Electrochemical Nitric Oxide Reduction to Ammonia

Angew Chem Int Ed Engl. 2023 Jan 23;62(4):e202213351. doi: 10.1002/anie.202213351. Epub 2022 Dec 14.

Authors

Huaifang Zhang^{1

2}, Yanbo Li³, Chuanqi Cheng⁴, Jin Zhou³, Pengfei Yin⁴, Haoming Wu^{1

2}, Zhiqin Liang⁵, Jiangwei Zhang⁶, Qinbai Yun⁷, An-Liang Wang⁸, Lijie Zhu⁹, Bin Zhang³, Wenbin Cao^{1

2}, Xiangmin Meng¹⁰, Jing Xia¹⁰, Yifu Yu³, Qipeng Lu^{1

2}

Affiliations

¹ School of Materials Science and Engineering, University of Science and Technology, Beijing, Beijing, 100083, China.
² Shunde Innovation School, University of Science and Technology, Beijing Foshan, Beijing, 528399, China.
³ Institute of Molecular Plus, School of Science, Tianjin University, Tianjin, 300072, China.
⁴ Institute of New Energy Materials, School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China.
⁵ Institute of Optoelectronics Technology, Key Laboratory of Luminescence and Optical Information, Ministry of Education, Beijing Jiaotong University, Beijing, 100044, China.
⁶ College of Energy Material and Chemistry, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, China.
⁷ Department of Chemistry, City University of Hong Kong, Hong Kong, China.
⁸ School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China.
⁹ School of Instrument Science and Opto-Electronics Engineering, Beijing Information Science and Technology University, Beijing, 100192, China.
¹⁰ Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.

PMID: 36357325
DOI: 10.1002/anie.202213351

Abstract

The direct electrochemical nitric oxide reduction reaction (NORR) is an attractive technique for converting NO into NH₃ with low power consumption under ambient conditions. Optimizing the electronic structure of the active sites can greatly improve the performance of electrocatalysts. Herein, we prepare body-centered cubic RuGa intermetallic compounds (i.e., bcc RuGa IMCs) via a substrate-anchored thermal annealing method. The electrocatalyst exhibits a remarkable NH₄ ⁺ yield rate of 320.6 μmol h^-1 mg^-1 _Ru with the corresponding Faradaic efficiency of 72.3 % at very low potential of -0.2 V vs. reversible hydrogen electrode (RHE) in neutral media. Theoretical calculations reveal that the electron-rich Ru atoms in bcc RuGa IMCs facilitate the adsorption and activation of *HNO intermediate. Hence, the energy barrier of the potential-determining step in NORR could be greatly reduced.

Keywords: Body-Centered Cubic; Electron-Rich Environments; Intermetallic Compounds; NO Reduction Reaction; Ruthenium.