In Situ Aliovalent Nickle Substitution and Acidic Modification of Nanowalls Promoted Proton Conductivity in InOF with 1D Helical Channel

Proton-conductive materials have attracted increasing attention because of their broad explorations in chemical sensors, water electrolysis, fuel cells, and biological systems. Especially, metal–organic frameworks (MOFs) have been demonstrated to be extremely promising candidates as proton-exchange membrane (PEM) fuel cells. Compared with other configurations, MOFs with one-dimensional (1D) channels have the characteristics of enhancing the host–guest interaction and promoting the anisotropic motion of proton carriers in restricted volume, which are beneficial for acquiring rich proton sources and forming successive hydrogen bonds to improve proton conductivity. We are endeavored to screen and find a helical three-dimensional (3D) framework InOF-1, namely, [In2(OH)2(BPTC)]·6H2O (BPTC4– = 3,3′,5,5′-biphenyl tetracarboxylate), as a typical 1D-channel MOF, which is pristinely grafted with spirally distributed −OH groups on the channel surface. Accompanied by an aliovalent substitution Ni(II) for In(III), isostructural NiOF-1 ([Ni2(BPTC)(HCOOH)2]·3H2O) is successfully prepared and massive formic acids are anchored at interior walls, which are interacted with adsorbed water molecules via the formation of stronger O–H···O bonds. This interaction between host–guest molecules and dynamics of lattice water has already led to a remarkable conductivity of InOF-1 (σ = 7.86 × 10–3 S/cm at 328 K under 95% RH). The synergistic effect of the acidic-modified nanowall, contracted volume, and enhanced adsorption of water molecules in the NiOF-1 channel contributes to a high conductivity value of 3.41 × 10–2 S/cm (at 328 K under 95% RH). Moreover, the proton conduction mechanism is further visually presented by molecular dynamic (MD) simulation. In contrast to InOF-1, aliovalent-substituted and acidic-modified NiOF-1 has a stronger host–guest interaction and more abundant hydrogen-bond networks, resulting in shorter proton migration distances and more frequent proton hopping, in agreement with the experimental results.