Articles producció científica> Química Física i Inorgànica

On the formation of gold nanoparticles from [AuIIICl4]¿ and a non-classical reduced polyoxomolybdate as an electron source: a quantum mechanical modelling and experimental study

  • Dades identificatives

    Identificador: PC:3385
    Autors:
    Poblet, JMLopez, XClotet, AZhongling LangIsabel Maicas GabasJesús M. de la FuenteScott 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.
  • Altres:

    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
  • Paraules clau:

    Or
    Química
    Química
    Chemistry
    1144-0546
  • Documents:

  • Cerca a google

    Search to google scholar