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  4. The "Pull Effect" of a Hanging ZnII on Improving the Four-Electron Oxygen Reduction Selectivity with Co Porphyrin
 
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2024
Journal Article
Title

The "Pull Effect" of a Hanging ZnII on Improving the Four-Electron Oxygen Reduction Selectivity with Co Porphyrin

Abstract
Due to the challenge of cleaving O-O bonds at single Co sites, mononuclear Co complexes typically show poor selectivity for the four-electron (4e-) oxygen reduction reaction (ORR). Herein, we report on selective 4e- ORR catalyzed by a Co porphyrin with a hanged ZnII ion. Inspired by Cu/Zn-superoxide dismutase, we designed and synthesized 1-CoZn with a hanging ZnII at the second sphere of a Co porphyrin. Complex 1-CoZn is much more effective than its Zn-lacking analogues to catalyze the 4e- ORR in neutral aqueous solutions, giving an electron number of 3.91 per O2 reduction. With spectroscopic studies, the hanging ZnII was demonstrated to be able to facilitate the electron transfer from CoII to O2, through an electronic "pull effect", to give CoIII-superoxo. Theoretical studies further suggested that this "pull effect" plays crucial roles in assisting O−O bond cleavage. This work is significant to present a new strategy of hanging a ZnII to improve O2 activation and O-O bond cleavage.
Author(s)
Han, Jinxiu
Shaanxi Normal University
Tan, Huang
Shaanxi Normal University
Guo, Kai
Shaanxi Normal University
Lv, Haoyuan
Shaanxi Normal University
Peng, Xinyang
Shaanxi Normal University
Zhang, Wei
Shaanxi Normal University
Lin, Haiping
Shaanxi Normal University
Apfel, Ulf-Peter  
Ruhr-Universität Bochum  
Cao, Rui
Shaanxi Normal University
Journal
Angewandte Chemie. International edition  
DOI
10.1002/anie.202409793
Language
English
Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik UMSICHT  
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