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

Dong Wang, John T. Groves

Research output: Contribution to journalArticlepeer-review

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 languageEnglish (US)
JournalInorganic Chemistry
DOIs
StateAccepted/In press - 2022

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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