Thermodynamic Evolution of Cerium Oxide Nanoparticle Morphology Using Carbon Dioxide

Adam R. Symington, Robert M. Harker, Mark T. Storr, Marco Molinari, Stephen C. Parker

Research output: Contribution to journalArticlepeer-review

18 Citations (SciVal)

Abstract

Surface morphology is known to affect catalytic activity, as some surfaces show greater activity than others. One of the key challenges is to identify strategies to enhance the expression of such surfaces and also to prevent their disappearance over time. Here, we apply density functional theory to the catalytic material CeO2 to predict the effect of adsorbed CO2 on the morphology of the material as a function of temperature and pressure. We predict that CO2 adsorbs as surface carbonates and that the magnitude of the adsorption energy is surface dependent, following the order {100} > {110} > {111}. We show that this difference leads to selective thermodynamic enhancement of {100} surfaces as a function of CO2 partial pressure and temperature. Finally, we show how the calculated surface free energies as a function of external conditions can be deployed to predict changes in the equilibrium particle morphology. These include the prediction that ceria nanoparticles prepared in the presence of supercritical CO2 will favor enhanced cubelike morphologies.

Original languageEnglish
Pages (from-to)23210-23220
Number of pages11
JournalJournal of Physical Chemistry C
Volume124
Issue number42
Early online date25 Sept 2020
DOIs
Publication statusPublished - 22 Oct 2020

Bibliographical note

Funding Information:
We would like to acknowledge AWE and EPSRC (EP/P007821/1, EP/R010366/1, EP/R023603/1) for funding. Computations were run on the Balena HPC facility at the University of Bath and the ARCHER UK National Supercomputing Service ( http://www.archer.ac.uk ) via our membership in the U.K.’s HEC Materials Chemistry Consortium (HEC MCC) funded by EPSRC (EP/L000202, EP/R029431).

Publisher Copyright:
© 2020 American Chemical Society.

Copyright:
Copyright 2020 Elsevier B.V., All rights reserved.

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • General Energy
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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