Investigating the Case of Titanium(IV) Carboxyphenolate Photoactive Coordination Polymers.
The reactivity of 2,5-dihydroxyterephthalic acid (H4DOBDC) with titanium(IV) precursors was thoroughly investigated for the synthesis of metal-organic frameworks under solvothermal conditions. Four crystalline phases were isolated whose structures were studied by a combination of single-crystal or powder X-ray diffraction and solid-state NMR. The strong coordination ability of the phenolate moieties was found to favor the formation of isolated TiO6 octahedra bearing solely organic ligands in the resulting structures, unless hydrothermal conditions and precondensed inorganic precursors are used. It is worth noting that these solids strongly absorb visible light, as a consequence of the ligand-to-metal charge transfer (LMCT) arising from Ti-phenolate bonds. Preliminary photocatalytic tests suggest that one compound, namely, MIL-167, presents a higher activity for hydrogen evolution than the titanium carboxylate MIL-125-NH2 but that such an effect cannot be directly correlated with its improved light absorption feature.
Institut Lavoisier, UMR 8180 CNRS, Université de Versailles St. Quentin, Université Paris-Saclay , 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
Hala
H
Assi
Institut Lavoisier, UMR 8180 CNRS, Université de Versailles St. Quentin, Université Paris-Saclay , 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
Laura C
LC
Pardo Pérez
Institut Lavoisier, UMR 8180 CNRS, Université de Versailles St. Quentin, Université Paris-Saclay , 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
Georges
G
Mouchaham
Institut Lavoisier, UMR 8180 CNRS, Université de Versailles St. Quentin, Université Paris-Saclay , 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
Florence
F
Ragon
Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology (TUDelft) , Julianalaan 136, Delft 2628, The Netherlands.
Maxim
M
Nasalevich
Institut Lavoisier, UMR 8180 CNRS, Université de Versailles St. Quentin, Université Paris-Saclay , 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
Nathalie
N
Guillou
Institut Lavoisier, UMR 8180 CNRS, Université de Versailles St. Quentin, Université Paris-Saclay , 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.|CEMHTI, UPR 3079 CNRS, Université d'Orléans , 45071 Orléans, France.
Charlotte
C
Martineau
Institut Lavoisier, UMR 8180 CNRS, Université de Versailles St. Quentin, Université Paris-Saclay , 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
Hubert
H
Chevreau
Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology (TUDelft) , Julianalaan 136, Delft 2628, The Netherlands.
Freek
F
Kapteijn
Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology (TUDelft) , Julianalaan 136, Delft 2628, The Netherlands.
Jorge
J
Gascon
Synchrotron Soleil, beamline Crystal, L'Orme les Merisiers Saint-Aubin , 91192 Gif-sur-Yvette Cedex, France.
Pierre
P
Fertey
Synchrotron Soleil, beamline Crystal, L'Orme les Merisiers Saint-Aubin , 91192 Gif-sur-Yvette Cedex, France.
Erik
E
Elkaim
Institut Lavoisier, UMR 8180 CNRS, Université de Versailles St. Quentin, Université Paris-Saclay , 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
Christian
C
Serre
Institut Lavoisier, UMR 8180 CNRS, Université de Versailles St. Quentin, Université Paris-Saclay , 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
Thomas
T
Devic