Issue 17, 2015

On the mechanism of methanol photooxidation to methylformate and carbon dioxide on TiO2: an operando-FTIR study

Abstract

This work is a mechanistic study of total and partial methanol photooxidation using operando FTIR coupled to gas phase analysis techniques (gas-IR and MS). Methoxy and formate/formyl species play a key role in the reaction. Methoxy species are formed by thermal and photochemical dissociation of methanol. The formation of methylformate is favored by a high surface coverage by methoxy species. Surface and/or bridged oxygen atoms are also important actors. Steady State Isotopic Transient Kinetic Analysis (SSITKA) experiments showed that the limiting step is the conversion of chemisorbed formyl/formate and that methylformate is a secondary product from a reaction between methoxy and neighboring formyl species. Methanol concentration, among other reaction parameters, influences greatly the selectivity of photooxidation.

Graphical abstract: On the mechanism of methanol photooxidation to methylformate and carbon dioxide on TiO2: an operando-FTIR study

Supplementary files

Article information

Article type
Paper
Submitted
04 Feb 2015
Accepted
17 Mar 2015
First published
25 Mar 2015

Phys. Chem. Chem. Phys., 2015,17, 11277-11283

Author version available

On the mechanism of methanol photooxidation to methylformate and carbon dioxide on TiO2: an operando-FTIR study

M. El-Roz, P. Bazin, M. Daturi and F. Thibault-Starzyk, Phys. Chem. Chem. Phys., 2015, 17, 11277 DOI: 10.1039/C5CP00726G

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