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The ethanol–metal interaction in bimetallic clusters of Pt and Rh

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Abstract

The comprehension of the reaction mechanism for ethanol steam reforming over metal particles requires the knowledge of the forces governing the ethanol–metal interaction. In this work, we used a combination of wave function analysis techniques (NCI, QTAIM, CMOEDA and NBO) to unveil the chemical origin of the ethanol–metal interaction in bimetallic clusters of Pt and Rh of varied proportions (Pt\(_5\)Rh, Pt\(_4\)Rh\(_2\), Pt\(_3\)Rh\(_3\), Pt\(_2\)Rh\(_4\) and PtRh\(_5\)). These clusters are highly polarized with the Pt atoms bearing the negative charge. This polarization guides the interaction with ethanol which complexes by orienting an oxygen lone pair over the most positive cluster site. In this way, a O–Rh contact is observed in most of the bimetallic clusters, although in the pure clusters the O–Pt interaction is stronger. QTAIM shows that the O–Metal interaction in the bimetallic clusters weakens as more Rh atoms are present, but the final complexation energy is a balance between several factors. NBO analysis describes the complexation as a compromise between donation of charge from oxygen to the cluster, back donation from the cluster to oxygen and, in some cases, the formation of a hydrogen bond involving the O–H bond and a partially negative Pt atom in the cluster.

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Acknowledgements

We would like to acknowledge the scholarship from CNPq to G. N. Radael.

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  1. Departamento de Química, Universidade Estadual de Maringá, Av. Colombo 5790, Maringá, Paraná, 87020-900, Brazil

    Graziela N. Radael, Vinicius Martinelli & Rodrigo M. Pontes

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Correspondence to Rodrigo M. Pontes.

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Radael, G.N., Martinelli, V. & Pontes, R.M. The ethanol–metal interaction in bimetallic clusters of Pt and Rh. Theor Chem Acc 141, 13 (2022). https://doi.org/10.1007/s00214-022-02877-7

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