Modulation of a coordination structure in a europium(iii)-based metallo-supramolecular polymer for high proton conduction

Abstract

Developing high proton conducting solid materials is significant in the field of fuel cells. A europium(III)-based metallo-supramolecular polymer with uncoordinated carboxylic acids (PolyEu-H) was successfully synthesized by modifying the synthesis conditions. The proton conductivity was enhanced with increasing the relative humidity (RH) from 30 to 95% RH. PolyEu-H showed about 10⁴ times higher proton conductivity than the polymer with coordinated carboxylic acids (PolyEu) and about 400 times higher than the polymer without carboxylic acids (PolyEu-2). The proton conductivity of PolyEu-H reached 4.45 × 10⁻² S cm⁻¹ at 95% RH and 25 °C and 5.6 × 10⁻² S cm⁻¹ at 75 °C. The activation energy, E_a was ultralow (0.04 eV), which indicates proton conduction based on the Grotthuss mechanism. The results indicate that efficient proton conduction occurs through proton channels formed by moisture in PolyEu-H.