文献类型：期刊文献

英文题名：Contracted Fe-N5-C11 Sites in Single-Atom Catalysts Boosting Catalytic Performance for Oxygen Reduction Reaction

作者：Xu, Chao[1];Zhang, Yan-Ping[2,3];Zheng, Tian-Long[4];Wang, Zhi-Qiang[2,3];Zhao, Ye-Min[1];Guo, Peng-Peng[1];Lu, Chen[1];Yang, Kun-Zu[1];Wei, Ping-Jie[1];He, Qing-Gang[4];Gong, Xue-Qing[2,3];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]East China Univ Sci & Technol, Sch Chem & Mol Engn, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[4]Zhejiang Univ, Coll Chem & Biol Engn, Hangzhou 310027, Zhejiang, Peoples R China

年份：2023

卷号：15

期号：27

起止页码：32341

外文期刊名：ACS APPLIED MATERIALS & INTERFACES

收录：;EI(收录号：20232914412544);WOS:【SCI-EXPANDED(收录号:WOS:001016549900001)】；

基金：This study was financially supported by the National Natural Science Foundation of China (No. 21571062, 21978260, 22178307), 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; single-atom catalyst; active site engineering; metal macrocycles; Zn-air battery

摘要：Promoting the catalyst performance for oxygen reductionreaction(ORR) in energy conversion devices through controlled manipulationof the structure of catalytic active sites has been a major challenge.In this work, we prepared Fe-N-C single-atom catalysts(SACs) with Fe-N-5 active sites and found that thecatalytic activity of the catalyst with shrinkable Fe-N-5-C-11 sites for ORR was significantly improvedcompared with the catalyst bearing normal Fe-N-5-C-12 sites. The catalyst C@PVI-(TPC)Fe-800, prepared by pyrolyzingan axial-imidazole-coordinated iron corrole precursor, exhibited positiveshifted half-wave potential (E (1/2) = 0.89V vs RHE) and higher peak power density (P (max) = 129 mW/cm(2)) than the iron porphyrin-derived counterpartC@PVI-(TPP)Fe-800 (E (1/2) = 0.81 V, P (max) = 110 mW/cm(2)) in 0.1 M KOH electrolyteand Zn-air batteries, respectively. X-ray absorption spectroscopy(XAS) analysis of C@PVI-(TPC)Fe-800 revealed a contracted Fe-N-5-C-11 structure with iron in a higher oxidationstate than the porphyrin-derived Fe-N-5-C-12 counterpart. Density functional theory (DFT) calculationsdemonstrated that C@PVI-(TPC)Fe-800 possesses a higher HOMO energylevel than C@PVI-(TPP)Fe-800, which can increase its electron-donatingability and thus help achieve enhanced O-2 adsorption aswell as O-O bond activation. This work provides a new approachto tune the active site structure of SACs with unique contracted Fe-N-5-C-11 sites that remarkably promote the catalystperformance, suggesting significant implications for catalyst designin energy conversion devices.