Ip, Chung Man and Troisi, Alessandro (2016) A computational study of the competing reaction mechanisms of the photo-catalytic reduction of CO2 on anatase(101). Physical Chemistry Chemical Physics, 18 (36). pp. 25010-25021. doi:10.1039/C6CP02642G ISSN 1463-9076.

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Abstract

We perform a computational study of three different reaction mechanisms for the photo-catalytic reduction of CO2 on the TiO2 anatase(101) surface known as (i) the carbene, (ii) the formaldehyde and (iii) the glyoxal pathways. We define a set of approximations that allows testing a number of mechanistic hypotheses and design experiments to validate them. We find that the energetically most favourable reaction mechanism among those proposed in the literature is the formaldehyde path, and the rate-limiting step is likely to be the formation of CH3 radicals from dissociation of CH3OH. We show that an intermediate that supports this mechanism is OCH2OH. We also find that formaldehyde would be an energetically favorable intermediate forming from CO and HCO, intermediates that are proposed in the early stage of the carbene and glyoxal pathways respectively. Some possible variants of mechanisms and methods to ease the formation of CH3 radicals are also discussed.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry T Technology > TJ Mechanical engineering and machinery
Divisions:	Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH):	Photocatalysis, Solar energy, Carbon dioxide, Methane
Journal or Publication Title:	Physical Chemistry Chemical Physics
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Official Date:	28 September 2016
Dates:	Date Event 28 September 2016 Published 12 August 2016 Available 8 August 2016 Accepted 20 April 2016 Submitted
Volume:	18
Number:	36
Page Range:	pp. 25010-25021
DOI:	10.1039/C6CP02642G
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Date of first compliant deposit:	16 November 2016
Date of first compliant Open Access:	12 August 2017
Funder:	Engineering and Physical Sciences Research Council (EPSRC), European Research Council (ERC)

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