Quantum chemical modelling of the rate determining step for oxygen reduction on quinones
文献情報
Elisabet Ahlberg, Itai Panas, David J. Schiffrin
Two inner-sphere electrocatalytic channels for quinone-mediated reduction of molecular oxygen to form hydrogen peroxide have been addressed by means of density functional theory. Each of the channels comprises an initial rate determining chemical step and a subsequent electrochemical reduction step by which peroxide is produced. The reduction mechanism was determined for 9,10-anthraquinone and 9,10-phenanthrenequinone and the quantum chemical results are compared with experimental results. Two distinctly different structures were determined for the critical chemical step depending on whether the catalytic site is present as HQ˙ or Q˙−. While a superoxo species is formed on HQ˙, a van der Waals (vdW) type compound is formed on Q˙−. It is shown that the Gibbs energy of activation for the semiquinone/oxygen reaction is largely determined by the entropy term. The results explain the experimentally observed pH dependence of the O2 reduction rate on quinone functionalised electrodes.
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Journal of the Indian Institute of Science

NDT & E International

Bioorganic & Medicinal Chemistry

Medicinal Chemistry Research

Electroanalysis

Biocatalysis and Biotransformation

Critical Reviews in Solid State and Materials Sciences

Main Group Chemistry

Atomization and Sprays

Herald of the Russian Academy of Sciences
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