title: 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.
authors.affiliation: Laboratoire Catalyse et Spectrochimie, ENSICAEN, Université de Caen, CNRS, 6, boulevard du Maréchal juin, 14050 Caen, France. mohamad.el-roz@ensicaen.fr.
authors.forename: Mohamad
authors.initials: M
authors.lastname: El-Roz
authors.forename: Philippe
authors.initials: P
authors.lastname: Bazin
authors.forename: Marco
authors.initials: M
authors.lastname: Daturi
authors.forename: Frederic
authors.initials: F
authors.lastname: Thibault-Starzyk