Contracted Fe-N 5 -C 11 Sites in Single-Atom Catalysts Boosting Catalytic Performance for Oxygen Reduction Reaction.

Autor: Xu C; Key Laboratory for Advanced Materials, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China., Zhang YP; Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China., Zheng TL; College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang 310027, P. R. China., Wang ZQ; Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China., Zhao YM; Key Laboratory for Advanced Materials, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China., Guo PP; Key Laboratory for Advanced Materials, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China., Lu C; Key Laboratory for Advanced Materials, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China., Yang KZ; Key Laboratory for Advanced Materials, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China., Wei PJ; Key Laboratory for Advanced Materials, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China., He QG; College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang 310027, P. R. China., Gong XQ; Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China., Liu JG; Key Laboratory for Advanced Materials, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China.
Jazyk: angličtina
Zdroj: ACS applied materials & interfaces [ACS Appl Mater Interfaces] 2023 Jul 12; Vol. 15 (27), pp. 32341-32351. Date of Electronic Publication: 2023 Jun 28.
DOI: 10.1021/acsami.3c03982
Abstrakt: Promoting the catalyst performance for oxygen reduction reaction (ORR) in energy conversion devices through controlled manipulation of 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 the catalytic activity of the catalyst with shrinkable Fe-N 5 -C 11 sites for ORR was significantly improved compared with the catalyst bearing normal Fe-N 5 -C 12 sites. The catalyst C@PVI-(TPC)Fe-800, prepared by pyrolyzing an axial-imidazole-coordinated iron corrole precursor, exhibited positive shifted half-wave potential ( E 1/2 = 0.89 V vs RHE) and higher peak power density ( P max = 129 mW/cm 2 ) than the iron porphyrin-derived counterpart C@PVI-(TPP)Fe-800 ( E 1/2 = 0.81 V, P max = 110 mW/cm 2 ) in 0.1 M KOH electrolyte and 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 oxidation state than the porphyrin-derived Fe-N 5 -C 12 counterpart. Density functional theory (DFT) calculations demonstrated that C@PVI-(TPC)Fe-800 possesses a higher HOMO energy level than C@PVI-(TPP)Fe-800, which can increase its electron-donating ability and thus help achieve enhanced O 2 adsorption as well as O-O bond activation. This work provides a new approach to tune the active site structure of SACs with unique contracted Fe-N 5 -C 11 sites that remarkably promote the catalyst performance, suggesting significant implications for catalyst design in energy conversion devices.
Databáze: MEDLINE
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