Oxidation of methanol by FeO2+ in water: DFT calculations in the gas phase and ab initio MD simulations in water solution

The Journal of Physical Chemistry. a
Manuel J LouwerseEvert Jan Baerends

Abstract

We investigate the mechanism of methanol oxidation to formaldehyde by ironoxido ([Fe(IV)O]2+), the alleged active intermediate in the Fenton reaction. The most likely reaction mechanisms are explored with density functional theory (DFT) calculations on microsolvated clusters in the gas phase and, for a selected set of mechanisms, with constrained Car-Parrinello molecular dynamics (CPMD) simulations in water solution. Helmholtz free energy differences are calculated using thermodynamic integration in a simulation box with 31 water molecules at 300 K. The mechanism of the reaction is investigated with an emphasis on whether FeO2+ attacks methanol at a C-H bond or at the O-H bond. We conclude that the most likely mechanism is attack by the oxido oxygen at the C-H bond ("direct CH mechanism"). We calculate an upper bound for the reaction Helmholtz free energy barrier in solution of 50 kJ/mol for the C-H hydrogen transfer, after which transfer of the O-H hydrogen proceeds spontaneously. An alternative mechanism, starting with coordination of methanol directly to Fe ("coordination OH mechanism"), cannot be ruled out, as it involves a reaction Helmholtz free energy barrier in solution of 44 +/- 10 kJ/mol. However, this coordination me...Continue Reading

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Dec 14, 2006·Physical Chemistry Chemical Physics : PCCP·Manuel J Louwerse, Evert Jan Baerends

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Citations

Mar 26, 2009·The Journal of Chemical Physics·Yan XieElliot R Bernstein
Feb 12, 2014·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Ali A HassanaliMichele Parrinello
Jan 1, 2014·Proceedings of the National Academy of Sciences of the United States of America·Shinichi EnamiAgustín J Colussi
Jun 10, 2011·Angewandte Chemie·Helmut Schwarz
Feb 3, 2015·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Anawat ThivasasithJumras Limtrakul
Nov 10, 2011·Physical Chemistry Chemical Physics : PCCP·Ji-Lai LiXu-Ri Huang
Nov 15, 2012·The Journal of Physical Chemistry. B·Norifumi YamamotoMasataka Nagaoka
Dec 14, 2011·The Journal of Physical Chemistry. B·Todd F MarkleJames M Mayer
Sep 29, 2018·Physical Chemistry Chemical Physics : PCCP·Anis GannouniPhilippe Sautet
Jul 16, 2013·Physical Chemistry Chemical Physics : PCCP·Mehmet Ferdi Fellah, Isik Onal
Jan 14, 2010·Chemical Reviews·David BalcellsOdile Eisenstein

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