Pore-Space Design of Cobalt–Porphyrin Covalent Organic Frameworks Suppresses Inactive Bridged-CO Intermediates for Selective CO 2 Electroreduction

Metalated covalent organic frameworks (M-COFs) hold promise for CO2 capture and electrocatalytic conversion with their tunable cavities, well-defined metal centers, and extended charge delocalization. However, the systematic impact of the framework architecture on the CO2 electroreduction selectivity remains underexplored. Herein, we report a series of cobalt–porphyrin COFs, namely, Co-TBCOF, Co-TTCOF, and Co-TQCOF, with enlarged cavity apertures from 2.5 to 3.2 and 3.8 nm by extending linear dialdehyde linkers. Experiment and computation confirm increased interlayer spacing from 3.64 to 4.01 and 4.81 Å, enhancing the CO2 adsorption capacity. The structural expansion also promotes charge delocalization,…

• NN
  National Natural Science Foundation of China

  Award: 52273187
• BA
  Basic and Applied Basic Research Foundation of Guangdong Province

  Awards: 2023A1515240077, 2023A1515011306