ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
Kauppinen_et_al_manuscript.pdf (4.46 MB)
0/0

Escaping Scaling Relationships for Water Dissociation at Interfacial Sites of Zirconia-Supported Rh and Pt Clusters

preprint
submitted on 03.09.2019 and posted on 05.09.2019 by Minttu M. Kauppinen, Ville Korpelin, Anand Mohan Verma, Marko Melander, Karoliina Honkala

Water dissociation is an important reaction involved in many industrial processes and a good model reaction for probing the activity of catalytic sites. In this computational study, the dissociation of water at interfacial sites of globally optimized ZrO2 sup- ported Pt and Rh clusters is investigated 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 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.

Funding

Academy of Finland projects 307853, 317739, and University of Jyväskylä.

History

Email Address of Submitting Author

marko.m.melander@jyu.fi

Institution

University of Jyväskylä

Country

Finland

ORCID For Submitting Author

0000-0001-7111-1603

Declaration of Conflict of Interest

None

Version Notes

First version

Exports