Pinpointing the active species of the Cu(DAT) catalyzed oxygen reduction reaction

Physical Chemistry Chemical Physics : PCCP
Bas van DijkDennis G H Hetterscheid

Abstract

Dinuclear CuII complexes bearing two 3,5-diamino-1,2,4-triazole (DAT) ligands have gained considerable attention as a potential model system for laccase due to their low overpotential for the oxygen reduction reaction (ORR). In this study, the active species for the ORR was investigated. The water soluble dinuclear copper complex (Cu(DAT)) was obtained by mixing a 1 : 1 ratio of Cu(OTf)2 and DAT in water. The electron paramagnetic resonance (EPR) spectrum of Cu(DAT) showed a broad axial signal with a g factor of 2.16 as well as a low intensity Ms = ±2 absorption characteristic of the Cu2(μ-DAT)2 moiety. Monitoring the typical 380 nm peak with UV-Vis spectroscopy revealed that the Cu2(μ-DAT)2 core is extremely sensitive to changes in pH, copper to ligand ratios and the presence of anions. Electrochemical quartz crystal microbalance experiments displayed a large decrease in frequency below 0.5 V versus the reversible hydrogen electrode (RHE) in a Cu(DAT) solution implying the formation of deposition. Rotating ring disk electrode experiments showed that this deposition is an active ORR catalyst which reduces O2 all the way to water at pH 5. The activity increased significantly in the course of time. X-ray photoelectron spectroscop...Continue Reading

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Citations

Jul 25, 2019·Angewandte Chemie·Michiel Langerman, Dennis G H Hetterscheid
Apr 14, 2020·ACS Catalysis·Bas van DijkDennis G H Hetterscheid
Dec 25, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·N W G SmitsD G H Hetterscheid

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Methods Mentioned

BETA
quartz crystal microbalance
electron paramagnetic resonance
X-ray

Software Mentioned

NOVA

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