文献类型：期刊文献

英文题名：Boosting Oxygen Reduction Reaction through Substrate Fluorination-Mediated d-Band Center Tuning and Microenvironment Optimization of Molecular Catalysts

作者：Yang, Kun-Zu[1];Su, Yong-Zhi[1];Xu, Chao[2];Guo, Peng-Peng[1];Zhao, Ye-Min[1];Liu, Xin[1];Jia, Ling[1];Yang, Yong[1];Zhu, Hao-Ning[1];Wei, Ping-Jie[1];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, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2025

卷号：15

期号：10

起止页码：8114

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20251818354073);WOS:【SCI-EXPANDED(收录号:WOS:001480010900001)】；

基金：This study was financially supported by the National Natural Science Foundation of China (Nos. 21571062 and 22178307), the Program for Professor of Special Appointment (Eastern Scholar) at the Shanghai Institutions of Higher Learning, and the Fundamental Research Funds for the Central Universities (No. 222201717003).

语种：英文

外文关键词：substrate fluorination engineering; poly(iron phthalocyanine); oxygen reduction reaction; d-band center tuning; microenvironment regulation

摘要：Metal macrocyclic compounds as an electrocatalyst for catalyzing the cathodic oxygen reduction reaction (ORR) in energy conversion devices have been intensively investigated. Promoting the intrinsic ORR activity of catalysts has always been focused on molecular structure design; however, the impact of their loading carbon matrix has been much less explored. In this work, we developed an efficient carbon reconstruction approach to obtain a high level (6.29 at. %) of fluorine-doped carbon substrate (FC), on which poly(iron phthalocyanine) (PFePc) was assembled. The optimized PFePc/FC catalyst composite exhibited efficient activity for ORR in both acidic and alkaline media, achieving a half-wave potential of 0.93 V vs RHE in 0.1 M KOH and 0.74 V in 0.1 M HClO4, respectively. Experimental results and theoretical studies demonstrated that carbon matrix fluorination engineering not only optimized the interfacial hydrophilic/hydrophobic microenvironment but also modulated the d-band center of Fe-N4 sites of the loaded PFePc, thereby reducing the adsorption of oxygen-containing intermediates and promoting its intrinsic ORR activity accordingly. In situ electrochemical impedance spectroscopy (EIS) analysis indicated efficient charge transfer and faster ORR kinetics facilitated by matrix fluorination. This work highlights the advantages of facile substrate fluorination engineering on boosting intrinsic catalytic activity of molecular catalysts for energy conversion applications.