卟啉
选择性
电子转移
化学
氧气
键裂
水溶液
劈理(地质)
光化学
离子
有机化学
催化作用
材料科学
复合材料
断裂(地质)
作者
Jinxiu Han,Huang Tan,Kai Guo,Haoyuan Lv,Xinyang Peng,Wei Zhang,Haiping Lin,Ulf‐Peter Apfel,Rui Cao
标识
DOI:10.1002/anie.202409793
摘要
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.
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