Kordatos, A., Mohammed, K., Vakili, R., Goguet, A., Manyar, H., Gibson, E. , Carravetta, M., Wells, P. and Skylaris, C. - K. (2023) Atomistic simulations on the carbidisation processes in Pd nanoparticles. RSC Advances, 13(9), pp. 5619-5626. (doi: 10.1039/D2RA07462A) (PMID:36798744) (PMCID:PMC9926891)
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Abstract
The formation of interstitial PdCx nanoparticles (NPs) is investigated through DFT calculations. Insights on the mechanisms of carbidisation are obtained whilst the material's behaviour under conditions of increasing C-concentration is examined. Incorporation of C atoms in the Pd octahedral interstitial sites is occurring through the [111] facet with an activation energy barrier of 19.3–35.7 kJ mol−1 whilst migration through the [100] facet corresponds to higher activation energy barriers of 124.5–127.4 kJ mol−1. Furthermore, interstitial-type diffusion shows that C will preferentially migrate and reside at the octahedral interstitial sites in the subsurface region with limited mobility towards the core of the NP. For low C-concentrations, migration from the surface into the interstitial sites of the NPs is thermodynamically favored, resulting in the formation of interstitial carbide. Carbidisation reaction energies are exothermic up to 11–14% of C-concentration and slightly vary depending on the shape of the structure. The reaction mechanisms turn to endothermic for higher concentration levels showing that C will preferentially reside on the surface making the interstitial carbide formation unfavorable. As experimentally observed, our simulations confirm that there is a maximum concentration of C in Pd carbide NPs opening the way for further computational investigations on the activity of Pd carbides in directed catalysis.
Item Type: | Articles |
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Additional Information: | AK, KM and RV are grateful to EPSRC (grant number EP/ V000691/1) for postdoctoral funding. We are grateful to The Materials and Molecular Modelling MMM Hub (EPSRC grant number EP/T022213/1) for access to the Young supercomputer, the UKCP consortium (EPSRC grant number EP/P022030/1) for access to the ARCHER2 supercomputer and the University of Southampton for access to the Iridis5 supercomputer. |
Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Gibson, Dr Emma |
Authors: | Kordatos, A., Mohammed, K., Vakili, R., Goguet, A., Manyar, H., Gibson, E., Carravetta, M., Wells, P., and Skylaris, C. - K. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | RSC Advances |
Publisher: | Royal Society of Chemistry |
ISSN: | 2046-2069 |
ISSN (Online): | 2046-2069 |
Published Online: | 14 February 2023 |
Copyright Holders: | Copyright © 2023 The Authors |
First Published: | First published in RSC Advances 13(9): 5619-5626 |
Publisher Policy: | Reproduced under a Creative Commons License |
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