Energy Landscape for the Electrocatalytic Oxidation of Water by a Single-Site Oxomanganese(V) Porphyrin

Dong Wang; John T. Groves

doi:10.1021/acs.inorgchem.2c02284

Energy Landscape for the Electrocatalytic Oxidation of Water by a Single-Site Oxomanganese(V) Porphyrin

Dong Wang, John T. Groves

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Abstract

A cationic manganese porphyrin, MnIII-TDMImP, is an efficient, homogeneous, single-site water oxidation electrocatalyst at neutral pH. The measured turnover frequency for oxygen production is 32 s-1. Mechanistic analyses indicate that MnV(O)(OH2), the protonated form of the corresponding trans-MnV(O)2 species, is generated from the MnIII(OH2)2 precursor in a 2-e- two-proton process and is responsible for O-O bond formation with a H2O molecule. Chloride ion is a competitive substrate with H2O for the MnV(O)(OH2) oxidant, forming hypochlorous acid with a rate constant that is 3 orders of magnitude larger than that of water oxidation. The data allow the construction of an experimental energy landscape for this water oxidation catalysis process.

Original language	English (US)
Journal	Inorganic Chemistry
DOIs	https://doi.org/10.1021/acs.inorgchem.2c02284
State	Accepted/In press - 2022

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.2c02284

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@article{cac00b9209f0456d95319e6aaabd592e,

title = "Energy Landscape for the Electrocatalytic Oxidation of Water by a Single-Site Oxomanganese(V) Porphyrin",

abstract = "A cationic manganese porphyrin, MnIII-TDMImP, is an efficient, homogeneous, single-site water oxidation electrocatalyst at neutral pH. The measured turnover frequency for oxygen production is 32 s-1. Mechanistic analyses indicate that MnV(O)(OH2), the protonated form of the corresponding trans-MnV(O)2 species, is generated from the MnIII(OH2)2 precursor in a 2-e- two-proton process and is responsible for O-O bond formation with a H2O molecule. Chloride ion is a competitive substrate with H2O for the MnV(O)(OH2) oxidant, forming hypochlorous acid with a rate constant that is 3 orders of magnitude larger than that of water oxidation. The data allow the construction of an experimental energy landscape for this water oxidation catalysis process.",

author = "Dong Wang and Groves, {John T.}",

note = "Funding Information: Support of this research by the National Science Foundation (Grants CHE-1464578 and CHE-1900048) is gratefully acknowledged. Initial aspects were supported by the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center, U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0001298. Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",

year = "2022",

doi = "10.1021/acs.inorgchem.2c02284",

language = "English (US)",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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T1 - Energy Landscape for the Electrocatalytic Oxidation of Water by a Single-Site Oxomanganese(V) Porphyrin

AU - Wang, Dong

AU - Groves, John T.

N1 - Funding Information: Support of this research by the National Science Foundation (Grants CHE-1464578 and CHE-1900048) is gratefully acknowledged. Initial aspects were supported by the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center, U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0001298. Publisher Copyright: © 2022 American Chemical Society.

PY - 2022

Y1 - 2022

N2 - A cationic manganese porphyrin, MnIII-TDMImP, is an efficient, homogeneous, single-site water oxidation electrocatalyst at neutral pH. The measured turnover frequency for oxygen production is 32 s-1. Mechanistic analyses indicate that MnV(O)(OH2), the protonated form of the corresponding trans-MnV(O)2 species, is generated from the MnIII(OH2)2 precursor in a 2-e- two-proton process and is responsible for O-O bond formation with a H2O molecule. Chloride ion is a competitive substrate with H2O for the MnV(O)(OH2) oxidant, forming hypochlorous acid with a rate constant that is 3 orders of magnitude larger than that of water oxidation. The data allow the construction of an experimental energy landscape for this water oxidation catalysis process.

AB - A cationic manganese porphyrin, MnIII-TDMImP, is an efficient, homogeneous, single-site water oxidation electrocatalyst at neutral pH. The measured turnover frequency for oxygen production is 32 s-1. Mechanistic analyses indicate that MnV(O)(OH2), the protonated form of the corresponding trans-MnV(O)2 species, is generated from the MnIII(OH2)2 precursor in a 2-e- two-proton process and is responsible for O-O bond formation with a H2O molecule. Chloride ion is a competitive substrate with H2O for the MnV(O)(OH2) oxidant, forming hypochlorous acid with a rate constant that is 3 orders of magnitude larger than that of water oxidation. The data allow the construction of an experimental energy landscape for this water oxidation catalysis process.

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U2 - 10.1021/acs.inorgchem.2c02284

DO - 10.1021/acs.inorgchem.2c02284

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AN - SCOPUS:85137158584

SN - 0020-1669

JO - Inorganic Chemistry

JF - Inorganic Chemistry

ER -

Energy Landscape for the Electrocatalytic Oxidation of Water by a Single-Site Oxomanganese(V) Porphyrin

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