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Updated: Aug 31, 2025

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
Energy Landscape for the Electrocatalytic Oxidation of Water by a Single-Site Oxomanganese(V) Porphyrin
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
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.
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