TY - JOUR
T1 - DFT Study on the Mechanism of Water Oxidation Catalyzed by a Mononuclear Copper Complex
AU - Yang , Zhi-Bo
AU - Lu , Xin
AU - Li , Miao-Miao
AU - Guo , Han-Xiao
AU - Chen , Si-Xiang
JO - Communications in Computational Chemistry
VL - 2
SP - 145
EP - 151
PY - 2025
DA - 2025/06
SN - 7
DO - http://doi.org/10.4208/cicc.2025.49.01
UR - https://global-sci.org/intro/article_detail/cicc/24184.html
KW - water oxidation, density functional calculations
KW - reaction mechanism, copper complex.
AB - <p style="text-align: justify;">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.</p>