Year: 2025
Author: Zhi-Bo Yang, Xin Lu, Miao-Miao Li, Han-Xiao Guo, Si-Xiang Chen
Communications in Computational Chemistry, Vol. 7 (2025), Iss. 2 : pp. 145–151
Abstract
This work employed DFT calculations to elucidate the mechanism of water oxidation reaction catalyzed by a mononuclear pyridine-based copper complex, which was reported to be a homogeneous water oxidation catalyst in a pH=11.84 buffer solution. The coordination of one water molecule with the ${\rm Cu}^{{\rm II}}$ center leads to the generation of the ${\rm Cu}^{{\rm II}}-{\rm OH}_2 (1-{\rm H}_2{\rm O}).$ The active species $({\rm Cu}^{{\rm IV}}={\rm O, 3})$ is generated after two subsequent proton-coupled electron transfer processes from $1-{\rm H}_2{\rm O}.$ $3$ triggers the O-O bond formation via water nucleophilic attack mechanism. The triplet ${\rm O}_2$ can be released after following two oxidation processes. The formation of the O-O bond is the rate-determining step for the catalytic cycle associated with a total barrier of 19.3 kcal/mol.
Journal Article Details
Publisher Name: Global Science Press
Language: English
DOI: https://doi.org/10.4208/cicc.2025.49.01
Communications in Computational Chemistry, Vol. 7 (2025), Iss. 2 : pp. 145–151
Published online: 2025-01
AMS Subject Headings: Global Science Press
Copyright: COPYRIGHT: © Global Science Press
Pages: 7
Keywords: water oxidation density functional calculations