Insulator-to-Proton-Conductor Transition in a Dense Metal-Organic Framework

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[1] [1,Tominaka, Satoshi

[2] Coudert, François-Xavier

[3] Dao, Thang D.

[4] Nagao, Tadaaki

[5] Cheetham, Anthony K.

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Tominaka, Satoshi | 1600年 / American Chemical Society卷 / 137期

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Metal-organic frameworks (MOFs) are prone to exhibit phase transitions under stimuli such as changes in pressure; temperature; or gas sorption because of their flexible and responsive structures. Here we report that a dense MOF; ((CH3)2NH2)2[Li2Zr(C2O4)4; exhibits an abrupt increase in proton conductivity from -9 to 3.9 × 10-5 S/cm at 17°C (activation energy; 0.64 eV) upon exposure to humidity. The conductivities were determined using single crystals; and the structures were analyzed by X-ray diffraction and X-ray pair distribution function analysis. The initial anhydrous structure transforms to another dense structure via topotactic hydration (H2O/Zr = 0.5); wherein one-fourth of the Li ions are irreversibly rearranged and coordinated by water molecules. This structure further transforms into a third crystalline structure by water uptake (H2O/Zr = 4.0). The abrupt increase in conductivity is reversible and is associated with the latter reversible structure transformation. The H2O molecules coordinated to Li ions; which are formed in the first step of the transformation; are considered to be the proton source; and the absorbed water molecules; which are formed in the second step; are considered to be proton carriers. © 2015 American Chemical Society;

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