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

Chemistry and Biochemistry

Princeton University

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

10 Scopus citations

Abstract

A cationic manganese porphyrin, Mn^III-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 Mn^V(O)(OH₂), the protonated form of the corresponding trans-Mn^V(O)₂species, is generated from the Mn^III(OH₂)₂precursor 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 Mn^V(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
Pages (from-to)	13667-13672
Number of pages	6
Journal	Inorganic Chemistry
Volume	61
Issue number	35
DOIs	https://doi.org/10.1021/acs.inorgchem.2c02284
State	Published - Sep 5 2022

Funding

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.

Funder number
CHE-1464578, CHE-1900048
DE-SC0001298

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10.1021/acs.inorgchem.2c02284

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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)2species, is generated from the MnIII(OH2)2precursor 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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T1 - Energy Landscape for the Electrocatalytic Oxidation of Water by a Single-Site Oxomanganese(V) Porphyrin

AU - Wang, Dong

AU - Groves, John T.

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Y1 - 2022/9/5

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)2species, is generated from the MnIII(OH2)2precursor 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)2species, is generated from the MnIII(OH2)2precursor 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.

UR - https://www.scopus.com/pages/publications/85137158584

U2 - 10.1021/acs.inorgchem.2c02284

DO - 10.1021/acs.inorgchem.2c02284

M3 - Article

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AN - SCOPUS:85137158584

SN - 0020-1669

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 35

ER -

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

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