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

  • Identification data

    Identifier: PC:3385
    Authors:
    Poblet, JMLopez, XClotet, AZhongling LangIsabel Maicas GabasJesús M. de la FuenteScott G. Mitchell
    Abstract:
    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.
  • Others:

    Author, as appears in the article.: Poblet, JM; Lopez, X; Clotet, A; Zhongling Lang; Isabel Maicas Gabas; Jesús M. de la Fuente; Scott G. Mitchell
    Department: Química Física i Inorgànica
    URV's Author/s: POBLET RIUS, JOSEP MARIA; LÓPEZ FERNÁNDEZ, JAVIER; CLOTET ROMEU, ANNA MARIA; Zhongling Lang; Isabel Maicas Gabas; Jesús M. de la Fuente; Scott G. Mitchell
    Abstract: 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.
    Research group: Química Quàntica
    Thematic Areas: Química Química Chemistry
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 1144-0546
    Author identifier: 0000-0002-4533-0623; 0000-0003-0322-6796; 0000-0003-0543-6607; ; ; ;
    Record's date: 2019-01-14
    Last page: 1038
    Journal volume: 40
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2016/NJ/C5NJ02773J#!divAbstract
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: 10.1039/c5nj02773j
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2016
    First page: 1029
    Publication Type: Article Artículo Article
  • Keywords:

    Or
    Química
    Química
    Chemistry
    1144-0546
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