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Confined Fe–Cu Clusters as Sub-Nanometer Reactors for Efficiently Regulating the Electrochemical Nitrogen Reduction Reaction |
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| Authors: | Xiaowei Wang Siyao Qiu Jianmin Feng Yueyu Tong Fengling Zhou Qinye Li Li Song Shuangming Chen Kuang-Hsu Wu Panpan Su Sheng Ye Feng Hou Shi Xue Dou Hua Kun Liu Gao Qing |
| Affiliation: | 1. Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, School of Materials Science and Engineering, Tianjin University, Tianjin, 300350 China
Applied Physics Department, College of Physics and Materials Science, Tianjin Normal University, No. 393 Binshui West Road, Xiqing District, Tianjin, 300387 China Institute for Superconducting and Electronic Materials, University of Wollongong, Wollongong, NSW, 2522 Australia;2. Science & Technology Innovation Institute, Dongguan University of Technology, Dongguan, 523000 China;3. Applied Physics Department, College of Physics and Materials Science, Tianjin Normal University, No. 393 Binshui West Road, Xiqing District, Tianjin, 300387 China;4. Institute for Superconducting and Electronic Materials, University of Wollongong, Wollongong, NSW, 2522 Australia;5. Department of Chemistry and Biotechnology, and Centre for Translational Atomaterials, FSET, Swinburne University of Technology, Hawthorn, Victoria, 3122 Australia;6. National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, Anhui, 230029 China;7. School of Chemical Engineering, The University of New South Wales, Kensington, Sydney, NSW, 2052 Australia;8. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023 China;9. Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, School of Materials Science and Engineering, Tianjin University, Tianjin, 300350 China;10. DICP-Surrey Joint Centre for Future Materials, Department of Chemical and Process Engineering, and Advanced Technology Institute, University of Surrey, Guilford, Surrey, GU2 7XH UK |
| Abstract: | Electrochemical nitrogen reduction reaction (NRR) over nonprecious-metal and single-atom catalysts has received increasing attention as a sustainable strategy to synthesize ammonia. However, the atomic-scale regulation of such active sites for NRR catalysis remains challenging because of the large distance between them, which significantly weakens their cooperation. Herein, the utilization of regular surface cavities with unique microenvironment on graphitic carbon nitride as “subnano reactors” to precisely confine multiple Fe and Cu atoms for NRR electrocatalysis is reported. The synergy of Fe and Cu atoms in such confined subnano space provides significantly enhanced NRR performance, with nearly doubles ammonia yield and 54%-increased Faradic efficiency up to 34%, comparing with the single-metal counterparts. First principle simulation reveals this synergistic effect originates from the unique Fe–Cu coordination, which effectively modifies the N2 absorption, improves electron transfer, and offers extra redox couples for NRR. This work thus provides new strategies of manipulating catalysts active centers at the sub-nanometer scale. |
| Keywords: | atomic clusters electrochemical nitrogen fixation graphitic carbon nitride sub-nanometer reactors synergistic effect |