文献类型：期刊文献

英文题名：Creating Asymmetric Fe-N3C-N Sites in Single-Atom Catalysts Boosts Catalytic Performance for Oxygen Reduction Reaction

作者：Xu, Chao[1];Li, Xuewen[2];Guo, Peng-Peng[1];Yang, Kun-Zu[1];Zhao, Ye-Min[1];Chi, Hua-Min[1];Xu, Ying[1];Wei, Ping-Jie[1];Wang, Zhi-Qiang[3,4];Xu, Qing[2];Liu, Jin-Gang[1]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]Chinese Acad Sci, Shanghai Adv Res Inst SARI, CAS Key Lab Low Carbon Convers Sci & Engn, Shanghai 201210, Peoples R China;[3]East China Univ Sci & Technol, Ctr Computat Chem, Sch Chem & Mol Engn, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2024

卷号：16

期号：29

起止页码：37927

外文期刊名：ACS APPLIED MATERIALS & INTERFACES

收录：;EI(收录号：20242916704786);WOS:【SCI-EXPANDED(收录号:WOS:001265798200001)】；

基金：This study was financially supported by the National Natural Science Foundation of China (Nos. 21571062, 22203030, 52303288), the National Key R&D Program of China (2023YFA1508500), the Program for Professor of Special Appointment (Eastern Scholar) at the Shanghai Institutions of Higher Learning to J.-G.L., and the Fundamental Research Funds for the Central Universities (No. 222201717003).

语种：英文

外文关键词：Oxygen Reduction Reaction; Electrocatalyst; Asymmetric catalysis; Single-atom Catalyst; Zn-AirBattery

摘要：Fine tuning of the metal site coordination environment of a single-atom catalyst (SAC) to boost its catalytic activity for oxygen reduction reaction (ORR) is of significance but challenging. Herein, we report a new SAC bearing Fe-N3C-N sites with asymmetric in-plane coordinated Fe-N3C and axial coordinated N atom for ORR, which was obtained by pyrolysis of an iron isoporphyrin on polyvinylimidazole (PVI) coated carbon black. The C@PVI-(NCTPP)Fe-800 catalyst exhibited significantly improved ORR activity (E-1/2 = 0.89 V vs RHE) than the counterpart SAC with Fe-N-4-N sites in 0.1 M KOH. Significantly, the Zn-air batteries equipped with the C@PVI-(NCTPP)Fe-800 catalyst demonstrated an open-circuit voltage (OCV) of 1.45 V and a peak power density (P-max) of 130 mW/cm(2), outperforming the commercial Pt/C catalyst (OCV = 1.42 V; P-max = 119 mW/cm(2)). The density functional theory (DFT) calculations revealed that the d-band center of the asymmetric Fe-N3C-N structure shifted upward, which enhances its electron-donating ability, favors O-2 adsorption, and supports O-O bond activation, thus leading to significantly promoted catalytic activity. This research presents an intriguing strategy for the designing of the active site architecture in metal SACs with a structure-function controlled approach, significantly enhancing their catalytic efficiency for the ORR and offering promising prospects in energy-conversion technologies.