Autor segons l'article: Poblet, JM; Lopez, X; Clotet, A; Zhongling Lang; Isabel Maicas Gabas; Jesús M. de la Fuente; Scott G. Mitchell
Departament: Química Física i Inorgànica
Autor/s 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
Resum: 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.
Grup de recerca: Química Quàntica
Àrees temàtiques: Química Química Chemistry
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 1144-0546
Identificador de l'autor: 0000-0002-4533-0623; 0000-0003-0322-6796; 0000-0003-0543-6607; ; ; ;
Data d'alta del registre: 2019-01-14
Pàgina final: 1038
Volum de revista: 40
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://pubs.rsc.org/en/content/articlelanding/2016/NJ/C5NJ02773J#!divAbstract
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
DOI de l'article: 10.1039/c5nj02773j
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2016
Pàgina inicial: 1029
Tipus de publicació: Article Artículo Article