Author, as appears in the article.: Poblet, J. M: ; Lang, Z. ; Aparicio-Anglès, X.;  Weinstock, I.;  Clotet, A.

Department: Química Física i Inorgànica

URV's Author/s: POBLET RIUS, JOSEP MARIA; Lang, Z. ; Aparicio-Anglès, X.;  Weinstock, I.;  Clotet, A.

Keywords: polyoxometalates DFT

Abstract: Understanding the interaction between charged species and surfaces is one of the most challenging topics in chemistry, given its wide involvement in several fields such as electrocatalysis, stabilization of metal nanoparticles, preparation of devices, etc. In general, these systems are particularly complex to model because of the elevated number of factors that must be taken into account. Here, we report a robust strategy based on density functional theory for studying these interactions, which has been applied to the highly charged lacunary [PW11O39]7– (PW11) adsorbed on gold and silver surfaces. In this context, we find that, unlike the modeling of polyoxoanions in solution, the incorporation of counterions in the computational models is crucial for accurately reproducing the properties of the system, even if an implicit solvent is used. Most interestingly, we find that the PW11 cluster does not preferentially adsorb to the gold surface via its more nucleophilic monodefect face but, rather, through less negatively charged terminal oxygen ligands, with an orientation similar to that found for the nondefective Keggin anion [SiW12O40]4–, induced by the strong anion–cation interactions from the same and neighboring units. This counterintuitive result is important for ongoing efforts to understand and utilize the properties of polyoxometalate monolayers on gold and other reactive metal surfaces.

Research group: Química Quàntica

Thematic Areas: Química Química Chemistry

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 0020-1669

Author identifier: 0000-0002-4533-0623; ; ; ;

Record's date: 2018-03-05

Last page: 3969

Journal volume: 56

Papper version: info:eu-repo/semantics/submittedVersion

Link to the original source: https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b03035

Funding program: plan; Excelencia; CTQ2014-52774-P altres; Grupos Consolidados; 2014SGR199 altres; ICREA Academia

Article's DOI: 10.1021/acs.inorgchem.6b03035

Entity: Universitat Rovira i Virgili

Journal publication year: 2017

First page: 3961

Publication Type: Article Artículo Article