Articles producció científica> Química Física i Inorgànica

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

  • Dades identificatives

    Identificador: imarina:3650722
    Autors:
    Jimenez-Lozano, PabloSole-Daura, AlbertWipff, GeorgesPoblet, Josep M.Chaumont, AlainCarbo, Jorge J.
    Resum:
    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.
  • Altres:

    Autor segons l'article: Jimenez-Lozano, Pablo; Sole-Daura, Albert; Wipff, Georges; Poblet, Josep M.; Chaumont, Alain; Carbo, Jorge J.;
    Departament: Química Física i Inorgànica
    Autor/s de la URV: Carbó Martin, Jorge Juan / Poblet Rius, Josep Maria / Solé Daura, Albert
    Paraules clau: Polyoxometalates Dft
    Resum: 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.
    Àrees temàtiques: 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
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    Adreça de correu electrònic de l'autor: josepmaria.poblet@urv.cat j.carbo@urv.cat
    Identificador de l'autor: 0000-0002-4533-0623 0000-0002-3945-6721
    Data d'alta del registre: 2024-09-07
    Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
    Enllaç font original: https://pubs.acs.org/doi/10.1021/acs.inorgchem.7b00096
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referència a l'article segons font original: Inorganic Chemistry. 56 (7): 4148-4156
    Referència 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 de l'article: 10.1021/acs.inorgchem.7b00096
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2017
    Tipus de publicació: Journal Publications
  • Paraules clau:

    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
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