Polyoxometalate Complexes of Anatase-Titanium Dioxide Cores in Water†
Dr. Manoj Raula
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Search for more papers by this authorGal Gan Or
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Search for more papers by this authorMarina Saganovich
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Search for more papers by this authorDr. Offer Zeiri
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Search for more papers by this authorProf. Yifeng Wang
School of Chemistry and Chemical Engineering, Shandong University, Ji'nan 250100 (China)
Search for more papers by this authorDr. Michele R. Chierotti
Department of Chemistry and NIS Centre, University of Turin, Via P. Giuria n° 7, Torino, 10125 (Italy)
Search for more papers by this authorProf. Roberto Gobetto
Department of Chemistry and NIS Centre, University of Turin, Via P. Giuria n° 7, Torino, 10125 (Italy)
Search for more papers by this authorCorresponding Author
Prof. Ira A. Weinstock
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼irawSearch for more papers by this authorDr. Manoj Raula
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Search for more papers by this authorGal Gan Or
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Search for more papers by this authorMarina Saganovich
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Search for more papers by this authorDr. Offer Zeiri
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Search for more papers by this authorProf. Yifeng Wang
School of Chemistry and Chemical Engineering, Shandong University, Ji'nan 250100 (China)
Search for more papers by this authorDr. Michele R. Chierotti
Department of Chemistry and NIS Centre, University of Turin, Via P. Giuria n° 7, Torino, 10125 (Italy)
Search for more papers by this authorProf. Roberto Gobetto
Department of Chemistry and NIS Centre, University of Turin, Via P. Giuria n° 7, Torino, 10125 (Italy)
Search for more papers by this authorCorresponding Author
Prof. Ira A. Weinstock
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼iraw
Department of Chemistry, Ben Gurion University of the Negev and the Ilse Katz Institute for Nanoscale Science & Technology, Beer Sheva, 84105 (Israel) http://www.bgu.ac.il/∼irawSearch for more papers by this authorI.A.W. thanks the Israel Science Foundation (ISF; 190/13), the ISF & Planning and Budgeting Committee (I-CORE Program 152/11), and the Adelis Foundation, and M.R. thanks the PBC for a Fellowship.
Abstract
Polyoxometalate (POM) cluster anions are shown to serve as covalently coordinated ligands for anatase-TiO2 nanocrystals, giving isolable assemblies uniquely positioned between molecular macroanions and traditional colloidal nanoparticles. Na+ salts of the water-soluble polyanionic structures are obtained by reacting amorphous TiO2 with the 1 nm lacunary ion, Na7[α-XW11O39] (X=P5+), at 170 °C, after which an average of 55 α-PW11O397− clusters are found as pentadentate ligands for TiIV ions covalently linked to 6 nm single-crystal anatase cores. The attached POMs are reversible electron acceptors, the reduction potentials of which shift in a predictable fashion by changing the central heteroatom, X, directly influencing a model catalytic reaction. Just as POM cluster anions control the reactivities of metal centers in molecular complexes, directly coordinated POM ligands with tunable redox potentials now provide new options for rationally controlling the reactions of semiconductor nanocrystals.
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