A New Photoactive Crystalline Highly Porous Titanium(IV) Dicarboxylate

Titanium is a very attractive candidate for MOFs due to its low toxicity, redox activity, and photocatalytic properties. We present here MIL-125, the first example of a highly porous and crystalline titanium(IV) dicarboxylate (MIL stands for Materials of Institut Lavoisier) with a high thermal stabi...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2009-08, Vol.131 (31), p.10857-10859
Main Authors: Dan-Hardi, Meenakshi, Serre, Christian, Frot, Théo, Rozes, Laurence, Maurin, Guillaume, Sanchez, Clément, Férey, Gérard
Format: Article
Language:English
Subjects:
Adsorption
Alcohols
Chemical Physics
Crystallization
Dicarboxylic Acids - chemistry
Electrons
Nitrogen
Photochemical Processes
Physics
Porosity
Titanium - chemistry
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Summary:Titanium is a very attractive candidate for MOFs due to its low toxicity, redox activity, and photocatalytic properties. We present here MIL-125, the first example of a highly porous and crystalline titanium(IV) dicarboxylate (MIL stands for Materials of Institut Lavoisier) with a high thermal stability and photochemical properties. Its structure is built up from a pseudo cubic arrangement of octameric wheels, built up from edge- or corner-sharing titanium octahedra, and terephthalate dianions leading to a three-dimensional periodic array of two types of hybrid cages with accessible pore diameters of 6.13 and 12.55 Å. X-ray thermodiffractometry and thermal analysis show that MIL-125 is stable up to 360 °C under air atmosphere while nitrogen sorption analysis indicates a surface area (BET) of 1550 m2·g−1. Moreover, under nitrogen and alcohol adsorption, MIL-125 exhibits a photochromic behavior associated with the formation of stable mixed valence titanium-oxo compounds. The titanium oxo cluster are back oxidized in the presence of oxygen. This photochemical phenomenon is analyzed through the combined use of Electron Spin Resonance (ESR) and UV−visible absorption spectroscopies. The photogenerated electrons are trapped as Ti(III) centers, while a concomitant oxidation of the adsorbed alcohol molecules occurs. This new microporous hybrid is a very promising candidate for applications in smart photonic devices, sensors, and catalysis
ISSN:0002-7863
1520-5126
DOI:10.1021/ja903726m