The development of water-mediated proton-conducting materials operating above 100 degrees C remains challenging because the extended structures of existing materials usually deteriorate at high temperatures. A new triazolyl phosphonate metal-organic framework (MOF) [La3L4(H2O)(6)]Cl center dot xH(2)O (1, L2- = 4-(4H-1,2,4-triazol-4-yl)phenyl phosphonate) with highly hydrophilic 1D channels was synthesized hydrothermally. Compound 1 is an example of a phosphonate MOF with large regular pores with 1.9 nm in diameter. It forms a water-stable, porous structure that can be reversibly hydrated and dehydrated. The proton-conducting properties of 1 were investigated by impedance spectroscopy. Magic-angle spinning (MAS) and pulse field gradient (PFG) NMR spectroscopies confirm the dynamic nature of the incorporated water molecules. The diffusivities, determined by PFG NMR and IR microscopy, were found to be close to that of liquid water. This porous framework accomplishes the challenges of water stability and proton conduction even at 110 degrees C. The conductivity in 1 is proposed to occur by the vehicle mechanism.

Water-Mediated Proton Conduction in a Robust Triazolyl Phosphonate Metal-Organic Framework with Hydrophilic Nanochannels

DONNADIO, Anna;COSTANTINO, FERDINANDO;CASCIOLA, Mario;
2014

Abstract

The development of water-mediated proton-conducting materials operating above 100 degrees C remains challenging because the extended structures of existing materials usually deteriorate at high temperatures. A new triazolyl phosphonate metal-organic framework (MOF) [La3L4(H2O)(6)]Cl center dot xH(2)O (1, L2- = 4-(4H-1,2,4-triazol-4-yl)phenyl phosphonate) with highly hydrophilic 1D channels was synthesized hydrothermally. Compound 1 is an example of a phosphonate MOF with large regular pores with 1.9 nm in diameter. It forms a water-stable, porous structure that can be reversibly hydrated and dehydrated. The proton-conducting properties of 1 were investigated by impedance spectroscopy. Magic-angle spinning (MAS) and pulse field gradient (PFG) NMR spectroscopies confirm the dynamic nature of the incorporated water molecules. The diffusivities, determined by PFG NMR and IR microscopy, were found to be close to that of liquid water. This porous framework accomplishes the challenges of water stability and proton conduction even at 110 degrees C. The conductivity in 1 is proposed to occur by the vehicle mechanism.
2014
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11391/1259899
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