Autor según el artículo: Poblet, JM; Lopez, X; Clotet, A; Zhongling Lang; Isabel Maicas Gabas; Jesús M. de la Fuente; Scott G. Mitchell

Departamento: Química Física i Inorgànica

Autor/es de la URV: POBLET RIUS, JOSEP MARIA; LÓPEZ FERNÁNDEZ, JAVIER; CLOTET ROMEU, ANNA MARIA; Zhongling Lang; Isabel Maicas Gabas; Jesús M. de la Fuente; Scott G. Mitchell

Resumen: Polyoxometalate (POM)-mediated reduction and nucleation mechanisms in nanoparticle (NP) syntheses are still largely unknown. We carried out comprehensive theoretical analysis using density functional theory (DFT) to gain insight into the molecular and electronic changes that occur during the reduction of HAuIIICl4 with the Kabanos-type polyoxomolybdate, [Na{(MoV2 O4)3(m2-O)3(m2-SO3)3(m6-SO3)}2]15. In the system presented herein the electrons are supplied by the POM, making the computational thermodynamic analysis more feasible. Our results reveal that this particular POM is a multi-electron source and the proton-coupled electron transfer (PCET) greatly promotes the reduction process. Based on the energy and molecular orbital studies of the intermediate species the reduction of AuIII to AuI is shown to be thermodynamically favourable, and a low HOMO–LUMO gap of the POM–Au superstructure is advantageous for electron transfer. By modelling the reduction of three couples of AuIII - AuI by the same POM unit, it is proposed that the reduced polyoxomolybdate is finally fully oxidised. The subjacent idea of using the Kabanos POM was confirmed by comprehensive experimental characterisation of POMstabilised gold nanoparticles (AuNPs@POM). Present theoretical analysis suggests that protons have a significant influence on the final AuI to Au0 reduction step that ultimately leads to colloidal AuNPs@POM.

Grupo de investigación: Química Quàntica

Áreas temáticas: Química Química Chemistry

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 1144-0546

Identificador del autor: 0000-0002-4533-0623; 0000-0003-0322-6796; 0000-0003-0543-6607; ; ; ;

Fecha de alta del registro: 2019-01-14

Página final: 1038

Volumen de revista: 40

Versión del articulo depositado: info:eu-repo/semantics/publishedVersion

Enlace a la fuente original: https://pubs.rsc.org/en/content/articlelanding/2016/NJ/C5NJ02773J#!divAbstract

DOI del artículo: 10.1039/c5nj02773j

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2016

Página inicial: 1029

Tipo de publicación: Article Artículo Article