Depauw, Hannes

Nevjestic, Irena

Ghent University Academic Bibliography

Breathing of V-doped MIL-53(Al) monitored in situ by Electron Paramagnetic Resonance and X-ray diffraction Presenting authors: Hannes Depauwa and Irena Nevjestićb a) Dept. of Inorganic and Physical Chemistry (WE06), Ghent University, Krijgslaan 281-S3, B-9000 Gent (Belgium) b) Dept. of Solid State Sciences (WE04), Ghent University, Krijgslaan 281-S1, B-9000 Gent (Belgium)   Metal-Organic Frameworks (MOFs) are three-dimensional crystalline porous materials constructed of metal ions connected via organic bridges. Their large surface area and the possibility of tailoring their structure (e.g. pore size, shape, components) towards desired properties makes this class of materials promising for a wide range of applications, such as catalysis, gas storage, gas separation, sensing and fuel cell technology. Two characteristic types of MOFs with one-dimensional pores, originally synthesized by Férey’s group, are MIL-47 [VO(BDC); BDC = terephthalate or 1,4-benzenedicarboxylate, MIL = Materials of the Institute Lavoisier] 1 and MIL-53(Al) [Al(OH)(BDC)].2 It is reported that MIL-47(V) showed good catalytic performance but the framework exhibited a limited stability in the presence of water3. This problem may be solved by doping the highly stable MIL-53(Al) framework with catalytically active VIV-ions.  In collaboration between the Center for Ordered Materials, Organometallics and Catalysis (promoter P. Van Der Voort) and the research group Electron Magnetic Resonance (promoters F. Callens and H. Vrielinck), different loadings of V-ions were introduced in the MIL-53(Al) structure (see Fig.1).  From the resulting frameworks the gas sorption capacity (at T<300K) was studied. For samples with low V-loading, temperature-induced breathing (T>300K) was monitored by in situ X-ray Powder Diffraction and Electron Paramagnetic Resonance (EPR) in air and in vacuum.  In EPR, the VIV ions (3d1 configuration, S=1/2) were used as local probes to detect changes in the MIL-53(Al) framework.     References 1. K. Barthelet, J. Marrot, D. Riou and G. Ferey, Angew. Chem.-Int. Edit., 2002, 41, p. 281. 2. T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille and G. Ferey, Chem.-Eur. J., 2004, 10, p. 1373. 3. K. Leus, M. Vandichel, Y. Y. Liu, I. Muylaert, J. Musschoot, S. Pyl, H. Vrielinck, F. Callens, G. B. Marin, C. Detavernier, P. V. Wiper, Y. Z. Khimyak, M. Waroquier, V. Van Speybroeck and P. Van der Voort, Journal of Catalysis, 2012, 285, p. 196. Figure 1 Schematic structure of the bimetallic V/Al-MIL-53 framework. Aluminium: blue, vanadium: green, oxygen: red, carbon: grey 

Breathing of V-doped MIL-53(Al) monitored in situ by electron paramagnetic resonance and X-ray diffraction

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Breathing of V-doped MIL-53(Al) monitored in situ by electron paramagnetic resonance and X-ray diffraction

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Ghent University Academic Bibliography