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Quantum chemical modelling of the rate determining step for oxygen reduction on quinones.

J R Tobias Johnsson Wass ; Elisabet Ahlberg ; Itai Panas (Institutionen för kemi- och bioteknik, Oorganisk miljökemi) ; David J Schiffrin
Physical chemistry chemical physics : PCCP (1463-9076). Vol. 8 (2006), 36, p. 4189-99.
[Artikel, refereegranskad vetenskaplig]

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.

Nyckelord: Computer Simulation, Hydrogen Peroxide, chemical synthesis, Kinetics, Models, Chemical, Models, Molecular, Oxidation-Reduction, Oxygen, chemistry, Quantum Theory, Quinones, chemistry

Denna post skapades 2007-10-16. Senast ändrad 2010-04-30.
CPL Pubid: 54281


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Institutionen för kemi (2001-2011)
Institutionen för kemi- och bioteknik, Oorganisk miljökemi (2005-2014)


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