posted on 2016-06-21, 15:23authored byHala Assi, Laura
C. Pardo Pérez, Georges Mouchaham, Florence Ragon, Maxim Nasalevich, Nathalie Guillou, Charlotte Martineau, Hubert Chevreau, Freek Kapteijn, Jorge Gascon, Pierre Fertey, Erik Elkaim, Christian Serre, Thomas Devic
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.