Proton conduction via lattice water molecules in oxalato-bridged lanthanide porous coordination polymers

Dalton Trans. 2016 Oct 21;45(39):15399-15405. doi: 10.1039/c6dt02677j. Epub 2016 Sep 6.

Abstract

The proton conducting properties of two different structural types of porous coordination polymers [La2(ox)3(H2O)6]·4H2O (1) and [Er2(ox)3(H2O)6]·12H2O (2), where ox2- = oxalate, were investigated. 1 has a two-dimensional layered structure, whereas 2 has a three-dimensional structure. Both 1 and 2 have hydrophilic one-dimensional channels filled by lattice water molecules with hydrogen-bonding networks. The coordinated H2O molecules are Lewis acidic due to the lanthanoid ions donating protons to lattice-filling H2O molecules, thereby forming efficient proton conduction pathways. Alternating-current impedance analyses of 1 and 2 indicated significant proton conduction (σ = 3.35 × 10-7 S cm-1 at 368 K for 1, 1.79 × 10-6 S cm-1 at 363 K for 2 under RH = 100%, with Ea = 0.35 eV for 1 and 0.47 eV for 2), which was attributed to the Grotthuss mechanism via the lattice H2O molecules.