Contracted Fe–N₅–C₁₁ Sites in Single-Atom Catalysts Boosting Catalytic Performance for Oxygen Reduction Reaction

Abstract

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-N₅ active sites and found that the catalytic activity of the catalyst with shrinkable Fe-N₅-C₁₁ sites for ORR was significantly improved compared with the catalyst bearing normal Fe-N₅-C₁₂ sites. The catalyst C@PVI-(TPC)Fe-800, prepared by pyrolyzing an axial-imidazole-coordinated iron corrole precursor, exhibited positive shifted half-wave potential (<i>E</i>_1/2 = 0.89 V vs RHE) and higher peak power density (<i>P</i>_max = 129 mW/cm²) than the iron porphyrin-derived counterpart C@PVI-(TPP)Fe-800 (<i>E</i>_1/2 = 0.81 V, <i>P</i>_max = 110 mW/cm²) 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-N₅-C₁₁ structure with iron in a higher oxidation state than the porphyrin-derived Fe-N₅-C₁₂ 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 O₂ 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-N₅-C₁₁ sites that remarkably promote the catalyst performance, suggesting significant implications for catalyst design in energy conversion devices.