Theory-Guided Design of N-Confused Porphyrinic Covalent Organic Frameworks for Oxygen Reduction Reaction

Covalent organic frameworks (COFs) enable the precise and controlled synthesis of single-atom catalysts with uniformly distributed active metal centers, offering opportunities to elucidate the impact of subtle coordination environment changes on the catalytic performance. Inspired by N-confused porphyrins, we designed 20 metalloporphyrin-based COFs with either M–N3C1 or M–N4 centers, where M refers to 3d transition metals from Sc to Zn, for the electrocatalysis of oxygen reduction reaction (ORR). Density functional theory calculations predicted Co-based COFs to be the best ORR catalysts among the screened catalysts. Hence, Co–N3C1–COF and Co–N4–COF with a high crystallinity were synthesized. The Co–N3C1–COF…

• NN
  National Natural Science Foundation of China

  Awards: 22301014, 21922502, 21971017, 22171022
• CP
  China Postdoctoral Science Foundation

  Award: 2023M740241
• BI
  Beijing Institute of Technology
• NK
  National Key Research and Development Program of China

  Award: 2023YFC3310600