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Identifying Intermediates in Electrocatalytic Water Oxidation with a Manganese Corrole Complex
- Title
- Identifying Intermediates in Electrocatalytic Water Oxidation with a Manganese Corrole Complex
- Authors
- Li, Xialiang; Zhang, Xue-Peng; Guo, Mian; Lv, Bin; Guo, Kai; Jin, Xiaotong; Zhang, Wei; Lee, Yong-Min; Fukuzumi, Shunichi; Nam, Wonwoo; Cao, Rui
- Ewha Authors
- 남원우; Shunichi Fukuzumi; 이용민; Mian Guo
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi; 이용민; Mian Guo
- Issue Date
- 2021
- Journal Title
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- ISSN
- 0002-7863
1520-5126
- Citation
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol. 143, no. 36, pp. 14613 - 14621
- Publisher
- AMER CHEMICAL SOC
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- Water nucleophilic attack (WNA) on high-valent terminal Mn-oxo species is proposed for O-O bond formation in natural and artificial water oxidation. Herein, we report an electrocatalytic water oxidation reaction with Mn-III tris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O-2 was generated at the Mn-V/IV potential with hydroxide, but a more anodic potential was required to evolve O-2 with only water. With a synthetic Mn-V(O) complex of 1, a second-order rate constant, k(2)(OH-), of 7.4 x 10(3) M-1 s(-1) was determined in the reaction of the Mn-V(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with a k(2)(H2O) value of 4.4 x 10(-3) M-1 s(-1). This large reactivity difference of Mn-V(O) with hydroxide and water is consistent with different electrocatalytic behaviors of 1 with these two substrates. Significantly, during the electrolysis of 1 with water, a MnIV-peroxo species was identified with various spectroscopic methods, including UV-vis, electron paramagnetic resonance, and infrared spectroscopy. Isotope-labeling experiments confirmed that both O atoms of this peroxo species are derived from water, suggesting the involvement of the WNA mechanism in water oxidation by a Mn complex. Density functional theory calculations suggested that the nucleophilic attack of hydroxide on Mn-V(O) and also WNA to 1e(-)oxidized Mn-V(O) are feasibly involved in the catalytic cycles but that direct WNA to Mn-V(O) is not likely to be the main O-O bond formation pathway in the electrocatalytic water oxidation by 1.
- DOI
- 10.1021/jacs.1c05204
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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