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Metal–Organic‐Framework‐Supported Molecular Electrocatalysis for the Oxygen Reduction Reaction
Author(s) -
Liang Zuozhong,
Guo Hongbo,
Zhou Guojun,
Guo Kai,
Wang Bin,
Lei Haitao,
Zhang Wei,
Zheng Haoquan,
Apfel UlfPeter,
Cao Rui
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202016024
Subject(s) - electrocatalyst , porphyrin , chemistry , selectivity , metal organic framework , catalysis , metal , inorganic chemistry , molecule , ligand (biochemistry) , oxygen , peroxide , photochemistry , combinatorial chemistry , electrode , electrochemistry , organic chemistry , adsorption , biochemistry , receptor
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 O 2 increased from 2.65 to 3.70, showing significantly improved selectivity for the 4e ORR. It is demonstrated that H 2 O 2 generated from O 2 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.