Tuning the transition barrier of H2 dissociation in the hydrogenation of CO2 to formic acid on Ti-doped Sn2O4 cluster

Sarma, Plaban Jyoti, Dowerah, Dikshita, Gour, Nand Kishor, Logsdail, Andrew J. ORCID: https://orcid.org/0000-0002-2277-415X, Catlow, C. Richard A. ORCID: https://orcid.org/0000-0002-1341-1541 and Deka, Ramesh 2021. Tuning the transition barrier of H2 dissociation in the hydrogenation of CO2 to formic acid on Ti-doped Sn2O4 cluster. Physical Chemistry Chemical Physics 23 (1) , pp. 204-210. 10.1039/D0CP04472E

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Abstract

Titanium doped Sn2O4 cluster shows robust catalytic activity for selective CO2 reduction from density functional theory study. Our study focuses on the importance of small sized clusters in catalytic reduction of CO2 at lower overpotential. We investigate the influence of dopants on the height of the H2 dissociation barrier on the doped systems, and then the subsequent mechanism for the conversion of CO2 into formic acid (FA) via a hydride pinning pathway. The lowest barrier height for H2 dissociation is observed across the ‘Ti-O’ bond of the Ti-doped Sn2O4 cluster, with a negatively charged hydride (Ti-H) formed during the heterolytic H2 dissociation, bringing selectivity towards the desired FA product. The formation of a formate intermediate is identified as the rate determining step (RDS) for the whole pathway, but the barrier height is substantially reduced for the Ti-doped system when compared to the same steps on the undoped Sn2O4 cluster. The free energy of formate formation in the RDS is calculated to be negative, which reveals that the hydride transfer would occur spontaneously. Overall, our results show that small sized Ti-doped Sn2O4 clusters exhibit better catalytic activity than undoped clusters in the important process of reducing CO2 to FA when proceeding via the hydride pinning pathway.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Advanced Research Computing @ Cardiff (ARCCA) Cardiff Catalysis Institute (CCI) Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Date of First Compliant Deposit:	10 December 2020
Date of Acceptance:	26 November 2020
Last Modified:	08 Nov 2024 23:00
URI:	https://orca.cardiff.ac.uk/id/eprint/136936

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