Metal–Organic‐Framework‐Supported Molecular Electrocatalysis for the Oxygen Reduction Reaction

Synthesizing molecule@support hybrids is appealing to improve molecular electrocatalysis. We report herein metal-organic framework (MOF)-supported Co porphyrins for the oxygen reduction reaction (ORR) with improved activity and selectivity. Co porphyrins can be grafted on MOF surfaces through ligand exchange. A variety of porphyrin@MOF hybrids were made using this method. Grafted Co porphyrins showed boosted ORR activity with large (>70 mV) anodic shift of the half-wave potential compared to ungrafted porphyrins. By using active MOFs for peroxide reduction, the number of electrons transferred per O₂ increased from 2.65 to 3.70, showing significantly improved selectivity for the 4e ORR. It is demonstrated that H₂ O₂ generated from O₂ reduction at Co porphyrins is further reduced at MOF surfaces, leading to improved 4e ORR. As a practical demonstration, these hybrids were used as air electrode catalysts in Zn-air batteries, which exhibited equal performance to that with Pt-based materials.