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Issue 17, 2015
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On the mechanism of methanol photooxidation to methylformate and carbon dioxide on TiO2: an operando-FTIR study

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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

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Publication details

The article was received on 04 Feb 2015, accepted on 17 Mar 2015 and first published on 25 Mar 2015


Article type: Paper
DOI: 10.1039/C5CP00726G
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2015,17, 11277-11283
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    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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