A1 Journal article (refereed)
Escaping scaling relationships for water dissociation at interfacial sites of zirconia-supported Rh and Pt clusters (2019)

Kauppinen, M. M., Korpelin, V., Verma, M. A., Melander, M. M., & Honkala, K. (2019). Escaping scaling relationships for water dissociation at interfacial sites of zirconia-supported Rh and Pt clusters. Journal of Chemical Physics, 151(16), Article 164302. https://doi.org/10.1063/1.5126261

JYU authors or editors

Kauppinen, Minttu
Korpelin, Ville
Verma, Anand
Melander, Marko
Honkala, Karoliina

Publication details

All authors or editors: Kauppinen, Minttu M.; Korpelin, Ville; Verma, Mohan Anand; Melander, Marko M.; Honkala, Karoliina

Journal or series: Journal of Chemical Physics

ISSN: 0021-9606

eISSN: 1089-7690

Publication year: 2019

Volume: 151

Issue number: 16

Article number: 164302

Publisher: American Institute of Physics

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1063/1.5126261

Publication open access: Not open

Publication channel open access:

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/68054

Web address of parallel published publication (pre-print): https://chemrxiv.org/articles/Escaping_Scaling_Relationships_for_Water_Dissociation_at_Interfacial_Sites_of_Zirconia-Supported_Rh_and_Pt_Clusters/9761477/1

Abstract

Water dissociation is an important reaction involved in many industrial processes. In this computational study, the dissociation of water is used as a model reaction for probing the activity of interfacial sites of globally optimized ZrO2 supported Pt and Rh clusters under the framework of density functional theory. Our findings demonstrate that the perimeter sites of these small clusters can activate water, but the dissociation behavior varies considerably between sites. It is shown that the studied clusters break scaling relationships for water dissociation, suggesting that these catalysts may achieve activities beyond the maximum imposed by such relations. Furthermore, we observed large differences in the thermodynamics of the water dissociation reaction between global minimum and near-global minimum isomers of the clusters. Overall, our results highlight the uniqueness of interfacial sites in catalytic reactions and the need for developing new concepts and tools to deal with the associated complexity.

Keywords: computational chemistry; disintegration; catalysts; nanoparticles; interfaces (surfaces); density functional theory