Modulating Metal-Nitrogen Coupling in Anti-Perovskite Nitride via Cation Doping for Efficient Reduction of Nitrate to Ammonia
Zhiheng Gong
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
These authors contributed equally to this work.
Contribution: Conceptualization (equal), Data curation (lead), Investigation (lead), Methodology (lead), Visualization (lead), Writing - original draft (lead), Writing - review & editing (equal)
Search for more papers by this authorXuepeng Xiang
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Department of Mechanical Engineering, City University of Hong Kong, Hong Kong, 999077 P. R. China
These authors contributed equally to this work.
Contribution: Data curation (equal), Formal analysis (equal), Software (lead), Visualization (equal), Writing - review & editing (equal)
Search for more papers by this authorWenye Zhong
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Formal analysis (supporting), Investigation (supporting)
Search for more papers by this authorChenghao Jia
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Formal analysis (supporting), Investigation (supporting)
Search for more papers by this authorPeiyan Chen
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Formal analysis (supporting), Investigation (supporting)
Search for more papers by this authorProf. Nian Zhang
Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204 P. R. China
Contribution: Resources (equal), Supervision (equal)
Search for more papers by this authorProf. Shijun Zhao
Department of Mechanical Engineering, City University of Hong Kong, Hong Kong, 999077 P. R. China
Contribution: Resources (equal), Software (equal)
Search for more papers by this authorCorresponding Author
Prof. Weizhen Liu
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Supervision (equal), Validation (equal), Visualization (equal), Writing - review & editing (supporting)
Search for more papers by this authorCorresponding Author
Prof. Yan Chen
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Conceptualization (lead), Funding acquisition (lead), Resources (lead), Supervision (lead), Validation (lead), Writing - review & editing (lead)
Search for more papers by this authorProf. Zhang Lin
Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, School of Metallurgy and Environment, Central South University, Changsha, 410083 P. R. China
Contribution: Conceptualization (equal), Resources (equal), Supervision (equal)
Search for more papers by this authorZhiheng Gong
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
These authors contributed equally to this work.
Contribution: Conceptualization (equal), Data curation (lead), Investigation (lead), Methodology (lead), Visualization (lead), Writing - original draft (lead), Writing - review & editing (equal)
Search for more papers by this authorXuepeng Xiang
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Department of Mechanical Engineering, City University of Hong Kong, Hong Kong, 999077 P. R. China
These authors contributed equally to this work.
Contribution: Data curation (equal), Formal analysis (equal), Software (lead), Visualization (equal), Writing - review & editing (equal)
Search for more papers by this authorWenye Zhong
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Formal analysis (supporting), Investigation (supporting)
Search for more papers by this authorChenghao Jia
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Formal analysis (supporting), Investigation (supporting)
Search for more papers by this authorPeiyan Chen
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Formal analysis (supporting), Investigation (supporting)
Search for more papers by this authorProf. Nian Zhang
Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204 P. R. China
Contribution: Resources (equal), Supervision (equal)
Search for more papers by this authorProf. Shijun Zhao
Department of Mechanical Engineering, City University of Hong Kong, Hong Kong, 999077 P. R. China
Contribution: Resources (equal), Software (equal)
Search for more papers by this authorCorresponding Author
Prof. Weizhen Liu
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Supervision (equal), Validation (equal), Visualization (equal), Writing - review & editing (supporting)
Search for more papers by this authorCorresponding Author
Prof. Yan Chen
Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, School of Environment and Energy, South China University of Technology, Guangzhou, 510006 P. R. China
Contribution: Conceptualization (lead), Funding acquisition (lead), Resources (lead), Supervision (lead), Validation (lead), Writing - review & editing (lead)
Search for more papers by this authorProf. Zhang Lin
Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, School of Metallurgy and Environment, Central South University, Changsha, 410083 P. R. China
Contribution: Conceptualization (equal), Resources (equal), Supervision (equal)
Search for more papers by this authorGraphical Abstract
This work demonstrates that the metal-nitrogen coupling in anti-perovskite Co4N can be effective modulated by Cu doping, leading to strongly promoted hydrogenation process during electrochemical reduction of nitrate (NO3−RR) to ammonia.
Abstract
The complexes of metal center and nitrogen ligands are the most representative systems for catalyzing hydrogenation reactions in small molecule conversion. Developing heterogeneous catalysts with similar active metal-nitrogen functional centers, nevertheless, still remains challenging. In this work, we demonstrate that the metal-nitrogen coupling in anti-perovskite Co4N can be effective modulated by Cu doping to form Co3CuN, leading to strongly promoted hydrogenation process during electrochemical reduction of nitrate (NO3−RR) to ammonia. The combination of advanced spectroscopic techniques and density functional theory calculations reveal that Cu dopants strengthen the Co−N bond and upshifted the metal d-band towards the Fermi level, promoting the adsorption of NO3− and *H and facilitating the transition from *NO2/*NO to *NO2H/*NOH. Consequently, the Co3CuN delivers noticeably better NO3−RR activity than the pristine Co4N, with optimal Faradaic efficiency of 97 % and ammonia yield of 455.3 mmol h−1 cm−2 at −0.3 V vs. RHE. This work provides an effective strategy for developing high-performance heterogeneous catalyst for electrochemical synthesis.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Supporting Information
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