Cation-doping strategies for tuning of zirconia acid?base properties

Delarmelina, Maicon ORCID: https://orcid.org/0000-0002-6414-552X and Catlow, C. Richard A. 2022. Cation-doping strategies for tuning of zirconia acid?base properties. Royal Society Open Science 9 (2) , 211423. 10.1098/rsos.211423

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Abstract

The role of Y-, Ca- and Ce-doping of cubic zirconia (c-ZrO2) (111) surface on its acidity, basicity and the interplay between surface acid–base pairs is investigated by computational methods. The most stable surface structures for this investigation were initially determined based on previous studies of Y-doped c-ZrO2 (111) and by a detailed exploration of the most stable configuration for Ca-doped c-ZrO2 (111) and Ce-doped c-ZrO2 (111). Next, surface mapping by basic probe molecules (NH3 and pyridine) revealed a general reduction of the acidity of the surface sites, although a few exceptions were observed for zirconium ions at next nearest neighbour (NNN) positions to the oxygen vacancy and at the nearest neighbour (NN) position to the dopants. Adsorption of CO2 over basic sites revealed a cooperative interplay between acid–base groups. In this case, the overall effect observed was the decrease of the calculated adsorption energies when compared with the pristine surface. Moreover, spontaneous formation of η3-CO2 systems from initial η2-CO2 configurations indicates a decrease in the required energy for forming oxygen vacancies in the doped ZrO2 systems at NNN positions or further away from the existing vacancy site.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI) Advanced Research Computing @ Cardiff (ARCCA)
Additional Information:	Published by the Royal Society under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/4.0/
Publisher:	The Royal Society
ISSN:	2054-5703
Funders:	EPSRC
Date of First Compliant Deposit:	22 March 2022
Date of Acceptance:	14 January 2022
Last Modified:	07 Jun 2023 17:10
URI:	https://orca.cardiff.ac.uk/id/eprint/148589

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