Articles producció científica> Química Física i Inorgànica

Assembly Mechanism of Zr-Containing and Other TM-Containing Polyoxometalates

  • Datos identificativos

    Identificador: imarina:3650722
    Autores:
    Jimenez-Lozano, PabloSole-Daura, AlbertWipff, GeorgesPoblet, Josep M.Chaumont, AlainCarbo, Jorge J.
    Resumen:
    The mechanism by which Zr-substituted and other transition metal-substituted polyoxometalates (POMs) form covalently linked dimers has been analyzed by means of static density functional theory (DFT) calculations with a continuous solvent model as well as Car-Parrinello molecular dynamics (CPMD) simulations with explicit solvent molecules. The study includes different stages of the process: the formation of the active species by alkalination of the solution and formation of intercluster linkages. CPMD simulations show that the Zr-triaqua precursor, [W5O18Zr(H2O)3]2-, under basic conditions, reacts with hydroxide anions to form Zr-aqua-hydroxo active species, [W5O18Zr(OH)(H2O)]3-. We computed the DFT potential energy profile for dimerization of [W5O18TM(OH)]n¿ [TM = ZrIV(H2O), ZrIV, TiIV, and WVI] anions. The resulting overall energy barrier is low for ZrIV, moderate for TiIV, and high for WVI. The computed thermodynamic balance favors the dibridged (¿OH)2 linkages for ZrIV, the monobridged (¿OH) linkage for TiIV, and the monomeric forms for WVI, in agreement with experimentally observed trends. The lowest energy barrier and largest coordination number of Zr-substituted POMs are both a consequence of the flexible coordination environment and larger radius of Zr.
  • Otros:

    Autor según el artículo: Jimenez-Lozano, Pablo; Sole-Daura, Albert; Wipff, Georges; Poblet, Josep M.; Chaumont, Alain; Carbo, Jorge J.;
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Carbó Martin, Jorge Juan / Poblet Rius, Josep Maria / Solé Daura, Albert
    Palabras clave: Polyoxometalates Dft
    Resumen: The mechanism by which Zr-substituted and other transition metal-substituted polyoxometalates (POMs) form covalently linked dimers has been analyzed by means of static density functional theory (DFT) calculations with a continuous solvent model as well as Car-Parrinello molecular dynamics (CPMD) simulations with explicit solvent molecules. The study includes different stages of the process: the formation of the active species by alkalination of the solution and formation of intercluster linkages. CPMD simulations show that the Zr-triaqua precursor, [W5O18Zr(H2O)3]2-, under basic conditions, reacts with hydroxide anions to form Zr-aqua-hydroxo active species, [W5O18Zr(OH)(H2O)]3-. We computed the DFT potential energy profile for dimerization of [W5O18TM(OH)]n¿ [TM = ZrIV(H2O), ZrIV, TiIV, and WVI] anions. The resulting overall energy barrier is low for ZrIV, moderate for TiIV, and high for WVI. The computed thermodynamic balance favors the dibridged (¿OH)2 linkages for ZrIV, the monobridged (¿OH) linkage for TiIV, and the monomeric forms for WVI, in agreement with experimentally observed trends. The lowest energy barrier and largest coordination number of Zr-substituted POMs are both a consequence of the flexible coordination environment and larger radius of Zr.
    Áreas temáticas: Química Physical and theoretical chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Engenharias iii Engenharias ii Engenharias i Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, inorganic & nuclear Chemistry (miscellaneous) Biotecnología Astronomia / física
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    Direcció de correo del autor: josepmaria.poblet@urv.cat j.carbo@urv.cat
    Identificador del autor: 0000-0002-4533-0623 0000-0002-3945-6721
    Fecha de alta del registro: 2024-09-07
    Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion
    Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/acs.inorgchem.7b00096
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Inorganic Chemistry. 56 (7): 4148-4156
    Referencia de l'ítem segons les normes APA: Jimenez-Lozano, Pablo; Sole-Daura, Albert; Wipff, Georges; Poblet, Josep M.; Chaumont, Alain; Carbo, Jorge J.; (2017). Assembly Mechanism of Zr-Containing and Other TM-Containing Polyoxometalates. Inorganic Chemistry, 56(7), 4148-4156. DOI: 10.1021/acs.inorgchem.7b00096
    DOI del artículo: 10.1021/acs.inorgchem.7b00096
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2017
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Chemistry (Miscellaneous),Chemistry, Inorganic & Nuclear,Inorganic Chemistry,Physical and Theoretical Chemistry
    Polyoxometalates
    Dft
    Química
    Physical and theoretical chemistry
    Medicina i
    Materiais
    Interdisciplinar
    Inorganic chemistry
    General medicine
    Farmacia
    Engenharias iii
    Engenharias ii
    Engenharias i
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Chemistry, inorganic & nuclear
    Chemistry (miscellaneous)
    Biotecnología
    Astronomia / física
  • Documentos:

  • Cerca a google

    Search to google scholar