Mechanisms of carbon dioxide reduction on strontium titanate perovskites

Umberto Terranova; Francesc Viñes; Nora H. De Leeuw; Francesc Illas

doi:10.1039/d0ta01502d

Mechanisms of carbon dioxide reduction on strontium titanate perovskites

Umberto Terranova^*, Francesc Viñes, Nora H. De Leeuw, Francesc Illas

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Strontium titanate (SrTiO₃) is a promising material for the light-driven conversion of carbon dioxide (CO₂) into renewable fuels. However, the mechanisms of the relevant reactions are not yet well understood. In this work, we have used density functional theory calculations to explore CO₂ reduction on the (001) surface of the SrTiO₃ photocatalyst. Our results indicate that, in contrast to COOH, the formation of a HCOO or CO₂^- intermediate is thermodynamically hindered, which is consistent with the fact that formic acid (HCOOH) is not a major product in the experiments reported in the literature. We show that a pathway to carbon monoxide (CO) is instead possible, and that the formation of COOH is the rate-limiting step. Finally, we suggest that substitutional doping of Sr ions represents a promising approach to lower the energy barrier of the COOH formation.

Original language	English
Pages (from-to)	9392-9398
Number of pages	7
Journal	Journal of Materials Chemistry A
Volume	8
Issue number	18
DOIs	https://doi.org/10.1039/d0ta01502d
Publication status	Published - 14 May 2020

Funding

This work has been performed under the HPC-EUROPA3 (INFRAIA-2016-1-730897) project, with the support of the EC Research Innovation Action under the H2020 Programme. UT gratefully acknowledges the support of the computer resources and the technical support provided by the Barcelona Supercomputing Center-Centro Nacional de Supercomputación. This work was supported by the Engineering and Physical Sciences Research Council (grant EP/K009567/2), and used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). FV and FI acknowledge nancial support from the Ministerio de Ciencia, Innovación y Universidades MICIUN RTI2018-095460-B-I00, and María de Maeztu MDM-2017-0767 grants and, in part, Generalitat de Catalunya 2017SGR13 and XRQTC grants. FV is thankful to the Ministerio de Economía y Competitividad (MEC) for his Ramón y Cajal (RYC-2012-10129) research contract, and FI acknowledges additional support from the 2015 ICREA Academia Award for Excellence in University Research. All data created during this research are openly available from the Cardiff University Research Portal at http://doi.org/10.17035/ d.2019.0086887209.

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abstract = "Strontium titanate (SrTiO3) is a promising material for the light-driven conversion of carbon dioxide (CO2) into renewable fuels. However, the mechanisms of the relevant reactions are not yet well understood. In this work, we have used density functional theory calculations to explore CO2 reduction on the (001) surface of the SrTiO3 photocatalyst. Our results indicate that, in contrast to COOH, the formation of a HCOO or CO2- intermediate is thermodynamically hindered, which is consistent with the fact that formic acid (HCOOH) is not a major product in the experiments reported in the literature. We show that a pathway to carbon monoxide (CO) is instead possible, and that the formation of COOH is the rate-limiting step. Finally, we suggest that substitutional doping of Sr ions represents a promising approach to lower the energy barrier of the COOH formation.",

author = "Umberto Terranova and Francesc Vi{\~n}es and {De Leeuw}, {Nora H.} and Francesc Illas",

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AU - Terranova, Umberto

AU - Viñes, Francesc

AU - De Leeuw, Nora H.

AU - Illas, Francesc

PY - 2020/5/14

Y1 - 2020/5/14

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Mechanisms of carbon dioxide reduction on strontium titanate perovskites

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