Using micro-solvation and generalized coordination numbers to estimate the solvation energies of adsorbed hydroxyl on metal nanoparticles

Physical Chemistry Chemical Physics, vol. 25, pp. 3211–3219

Abstract

Solvent-adsorbate interactions have a great impact on catalytic processes in aqueous systems. Implicit solvent calculations are inexpensive but inaccurate toward hydrogen bonds, while a full incorporation of explicit solvation is computationally demanding. Micro-solvation attempts to break this dilemma by including only those solvent molecules directly interacting with the solute and any nearby interfaces, thereby providing a compromise between accuracy and computational expenses. Here, we show that micro-solvation of *OH and its relation to adsorption sites is largely transferable across late transition metal nanoparticles. Solvation energies for *OH on nanoparticles of Ir, Pd, and Pt range from -0.63 ± 0.04 eV to -0.67 ± 0.12 eV, while those on Au and Ag are -0.75 ± 0.07 eV and -1.01 ± 0.05 eV, respectively. These results enable the use of average solvation corrections for *OH on late transition metal nanostructures.

Authors 3

1. Selwyn Hanselman Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands

2. Marc T. M. Koper corresponding Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands

3. Federico Calle‐Vallejo corresponding

   Universitat de Barcelona · University of the Basque Country · Ikerbasque · European Theoretical Spectroscopy Facility

   Affiliation as printed

   Department of Materials Science and Chemical Physics & Institute of Theoretical and Computational Chemistry (IQTC), University de Barcelona, Martí i Franquès 1, 08028 Barcelona, Spain

   IKERBASQUE, Basque Foundation for Science, Plaza de Euskadi 5, 48009 Bilbao, Spain

   Nano–Bio Spectroscopy Group and European Theoretical Spectroscopy Facility (ETSF), Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, University of the Basque Country UPV/EHU, Av. Tolosa 72, 20018 San Sebastián, Spain