Conductive Supramolecular Architecture Constructed from Polyoxovanadate Cluster and Heterocyclic Surfactant

Abstract

Proton-conductive solid electrolytes are significant for fuel-cell battery technology. Especially for use in motor vehicles, proton conductors which work at intermediate temperatures (373-673 K) under an anhydrous atmosphere are desired to improve the fuel cell stability and efficiency. Inorganic-organic hybrid supramolecular architectures are a promising option for the realization of highly conductive proton conductors. Here, a hybrid layered crystal was synthesized for the first time by using an proton-containing decavanadate (V 10 ) anion and a heterocyclic surfactant cation. A simple ion-exchange reaction led to the formation of an inorganic-organic hybrid of V 10 by using dodecylpyridazinium (C 12 pda) as the heterocyclic surfactant. Single crystal X-ray analyses revealed that four C 12 pda cations were associated with one V 10 anion, which was a diprotonated species forming a one-dimensional infinite chain structure through hydrogen bonds. Anhydrous proton conductivity was investigated by alternating current (AC) impedance spectroscopy in the range of 313-393 K, exhibiting a maximum value of 1.7 × 10 −5 S cm −1 at 373 K.

Porous Layered Inorganic–Organic Hybrid Frameworks Constructed from Polyoxovanadate and Bolaamphiphiles

“…The DMT hybrid crystal contained diprotonated H 2 V 10 species exhibiting water sorption properties. The structural anisotropy in these V 10 -bolaamphiphile hybrid crystals will be intrinsically beneficial to the emergence of anhydrous proton conductivity at the intermediate temperature range, − which is under investigation. The methodology hybridizing polyoxometalate with bolaamphiphiles presented here would be promising to prepare another series of functional materials with respect to crystal engineering.…”