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

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 meth...

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Published inPhysical chemistry chemical physics : PCCP Vol. 17; no. 17; pp. 11277 - 11283
Main Authors El-Roz, Mohamad, Bazin, Philippe, Daturi, Marco, Thibault-Starzyk, Frederic
Format Journal Article
LanguageEnglish
Published England 07.05.2015
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Summary: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.
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ISSN:1463-9084
DOI:10.1039/c5cp00726g