Adapting Synthetic Models of Heme/Cu Sites to Energy-Efficient Electrocatalytic Oxygen Reduction Reaction |
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| Authors: | Jia Meng Haonan Qin Dr. Haitao Lei Dr. Xialiang Li Juan Fan Prof. Dr. Wei Zhang Prof. Dr. Ulf-Peter Apfel Prof. Dr. Rui Cao |
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| Affiliation: | 1. Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119 China;2. Ruhr-Universität Bochum, Fakultät für Chemie und Biochemie, Anorganische Chemie I, Universitätsstrasse 150, 44801 Bochum, Germany Fraunhofer UMSICHT, Osterfelder Strasse 3, 46047 Oberhausen, Germany |
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| Abstract: | In nature, cytochrome c oxidases catalyze the 4e− oxygen reduction reaction (ORR) at the heme/Cu site, in which CuI is used to assist O2 activation. Because of the thermodynamic barrier to generate CuI, synthetic Fe-porphyrin/Cu complexes usually show moderate electrocatalytic ORR activity. We herein report on a Co-corrole/Co complex 1-Co for energy-efficient electrocatalytic ORR. By hanging a CoII ion over Co corrole, 1-Co realizes electrocatalytic 4e− ORR with a half-wave potential of 0.89 V versus RHE, which is outstanding among corrole-based electrocatalysts. Notably, 1-Co outperforms Co corrole hanged with CuII or ZnII. We revealed that the hanging CoII ion can provide an electron to improve O2 binding thermodynamically and dynamically, a function represented by the biological CuI ion of the heme/Cu site. This work is significant to present a remarkable ORR electrocatalyst and to show the vital role of a second-sphere redox-active metal ion in promoting O2 binding and activation. |
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| Keywords: | Bioinspired Catalyst Cobalt Corrole Molecular Electrocatalysis Oxygen Reduction Second Sphere |
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