Zhiping Zeng1,2, Li Yong Gan3, Hong Bin Yang4, Xiaozhi Su5, Jiajian Gao2, Wei Liu6, Hiroaki Matsumoto7, Jun Gong2, Junming Zhang2, Weizhen Cai2, Zheye Zhang2, Yibo Yan8, Bin Liu9, Peng Chen10. 1. State Key Laboratory of Optoelectronic Materials and Technologies, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou, China. 2. School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, Singapore. 3. Institute for Structure and Function, Department of Physics, Chongqing University, Chongqing, China. 4. Institute for Materials Science and Devices, Suzhou University of Science and Technology, Suzhou, China. yanghb@mail.usts.edu.cn. 5. Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, CAS, Shanghai, China. 6. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China. 7. Hitachi High-Technologies (Shanghai) Co. Ltd., Shanghai, People's Republic of China. 8. Shaanxi Institute of Flexible Electronics, Northwestern Polytechnical University, Xi'an, China. 9. School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, Singapore. liubin@ntu.edu.sg. 10. School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, Singapore. chenpeng@ntu.edu.sg.
Abstract
While inheriting the exceptional merits of single atom catalysts, diatomic site catalysts (DASCs) utilize two adjacent atomic metal species for their complementary functionalities and synergistic actions. Herein, a DASC consisting of nickel-iron hetero-diatomic pairs anchored on nitrogen-doped graphene is synthesized. It exhibits extraordinary electrocatalytic activities and stability for both CO2 reduction reaction (CO2RR) and oxygen evolution reaction (OER). Furthermore, the rechargeable Zn-CO2 battery equipped with such bifunctional catalyst shows high Faradaic efficiency and outstanding rechargeability. The in-depth experimental and theoretical analyses reveal the orbital coupling between the catalytic iron center and the adjacent nickel atom, which leads to alteration in orbital energy level, unique electronic states, higher oxidation state of iron, and weakened binding strength to the reaction intermediates, thus boosted CO2RR and OER performance. This work provides critical insights to rational design, working mechanism, and application of hetero-DASCs.
While inheriting the excen class="Chemical">ptional merits of single atom catalysts, diatomic site catalysts (DASCs) utilize two adjacent atomic metal species for their complementary functionalities and synergistic actions. Herein, a DASC consisting of nickel-iron hetero-diatomic pairs anchored on nitrogen-doped graphene is synthesized. It exhibits extraordinary electrocatalytic activities and stability for both CO2reduction reaction (CO2RR) and oxygen evolution reaction (OER). Furthermore, the rechargeable Zn-CO2 battery equipped with such bifunctional catalyst shows high Faradaic efficiency and outstanding rechargeability. The in-depth experimental and theoretical analyses reveal the orbitalcouplingbetween the catalytic iron center and the adjacent nickel atom, which leads to alteration in orbital energy level, unique electronic states, higher oxidation state of iron, and weakened binding strength to the reaction intermediates, thus boosted CO2RR and OER performance. This work provides critical insights to rational design, working mechanism, and application of hetero-DASCs.