Identifying Intermediates in Electrocatalytic Water Oxidation with a Manganese Corrole Complex

Xialiang Li; Xue Peng Zhang; Mian Guo; Bin Lv; Kai Guo; Xiaotong Jin; Wei Zhang; Yong Min Lee; Shunichi Fukuzumi; Wonwoo Nam; Rui Cao

doi:10.1021/jacs.1c05204

Identifying Intermediates in Electrocatalytic Water Oxidation with a Manganese Corrole Complex

Xialiang Li, Xue Peng Zhang, Mian Guo, Bin Lv, Kai Guo, Xiaotong Jin, Wei Zhang, Yong Min Lee, Shunichi Fukuzumi, Wonwoo Nam, Rui Cao

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

98 Scopus citations

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^IIItris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O₂was generated at the Mn^V/IVpotential with hydroxide, but a more anodic potential was required to evolve O₂with only water. With a synthetic Mn^V(O) complex of 1 , a second-order rate constant,k₂(OH^-), of 7.4 × 10³M^-1s^-1was determined in the reaction of the Mn^V(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with ak₂(H₂O) value of 4.4 × 10^-3M^-1s^-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 Mn^IV-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.

Original language	English
Pages (from-to)	14613-14621
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	143
Issue number	36
DOIs	https://doi.org/10.1021/jacs.1c05204
State	Published - 15 Sep 2021

Bibliographical note

Funding Information:
We are grateful for support from the Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University, the National Natural Science Foundation of China (21573139 and 21773146), the Fundamental Research Funds for the Central Universities (GK202103045 and GK202003037), the Research Funds of Shaanxi Normal University, China Postdoctoral Science Foundation (2019M663614), the NRF of Korea (NRF-2021R1A3B1076539 to W.N. and NRF-2020R1I1A1A01074630 to Y.-M.L.), and the MEXT (Japan, 16H02268 to S.F.).

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© 2021 American Chemical Society

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@article{112b4fb0afc848ca8a39c14e858a5538,

title = "Identifying Intermediates in Electrocatalytic Water Oxidation with a Manganese Corrole Complex",

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 MnIIItris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O2was generated at the MnV/IVpotential with hydroxide, but a more anodic potential was required to evolve O2with only water. With a synthetic MnV(O) complex of 1 , a second-order rate constant,k2(OH-), of 7.4 × 103M-1s-1was determined in the reaction of the MnV(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with ak2(H2O) value of 4.4 × 10-3M-1s-1. This large reactivity difference of MnV(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.",

author = "Xialiang Li and Zhang, {Xue Peng} and Mian Guo and Bin Lv and Kai Guo and Xiaotong Jin and Wei Zhang and Lee, {Yong Min} and Shunichi Fukuzumi and Wonwoo Nam and Rui Cao",

note = "Funding Information: We are grateful for support from the Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University, the National Natural Science Foundation of China (21573139 and 21773146), the Fundamental Research Funds for the Central Universities (GK202103045 and GK202003037), the Research Funds of Shaanxi Normal University, China Postdoctoral Science Foundation (2019M663614), the NRF of Korea (NRF-2021R1A3B1076539 to W.N. and NRF-2020R1I1A1A01074630 to Y.-M.L.), and the MEXT (Japan, 16H02268 to S.F.). Publisher Copyright: {\textcopyright} 2021 American Chemical Society",

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doi = "10.1021/jacs.1c05204",

language = "English",

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AU - Li, Xialiang

AU - Zhang, Xue Peng

AU - Guo, Mian

AU - Lv, Bin

AU - Guo, Kai

AU - Jin, Xiaotong

AU - Zhang, Wei

AU - Lee, Yong Min

AU - Fukuzumi, Shunichi

AU - Nam, Wonwoo

AU - Cao, Rui

N1 - Funding Information: We are grateful for support from the Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University, the National Natural Science Foundation of China (21573139 and 21773146), the Fundamental Research Funds for the Central Universities (GK202103045 and GK202003037), the Research Funds of Shaanxi Normal University, China Postdoctoral Science Foundation (2019M663614), the NRF of Korea (NRF-2021R1A3B1076539 to W.N. and NRF-2020R1I1A1A01074630 to Y.-M.L.), and the MEXT (Japan, 16H02268 to S.F.). Publisher Copyright: © 2021 American Chemical Society

PY - 2021/9/15

Y1 - 2021/9/15

N2 - 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 MnIIItris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O2was generated at the MnV/IVpotential with hydroxide, but a more anodic potential was required to evolve O2with only water. With a synthetic MnV(O) complex of 1 , a second-order rate constant,k2(OH-), of 7.4 × 103M-1s-1was determined in the reaction of the MnV(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with ak2(H2O) value of 4.4 × 10-3M-1s-1. This large reactivity difference of MnV(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.

AB - 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 MnIIItris(pentafluorophenyl)corrole (1) in propylene carbonate (PC). O2was generated at the MnV/IVpotential with hydroxide, but a more anodic potential was required to evolve O2with only water. With a synthetic MnV(O) complex of 1 , a second-order rate constant,k2(OH-), of 7.4 × 103M-1s-1was determined in the reaction of the MnV(O) complex of 1 with hydroxide, whereas its reaction with water occurred much more slowly with ak2(H2O) value of 4.4 × 10-3M-1s-1. This large reactivity difference of MnV(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.

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DO - 10.1021/jacs.1c05204

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AN - SCOPUS:85114871152

SN - 0002-7863

VL - 143

SP - 14613

EP - 14621

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 36

ER -

Identifying Intermediates in Electrocatalytic Water Oxidation with a Manganese Corrole Complex

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