Combined Effect of Hydrophilic Pore and the Type of Protons on Proton Conductivity in Porous Metal–Organic Frameworks: A Feasible Approach to Achieve a Super Proton Conductor under Hydrated Conditions

There has been a steady growth of interest in proton-conductive metal-organic frameworks (MOFs) due to their potential utility in proton-exchange membrane fuel cells. To attain a super proton conductivity (>1 × 10^-2 S cm^-1) in a MOF-based proton conductor is a key step toward practical application. Currently, most studies are focused on enhancing the proton conductivity of porous MOFs by controlling a single factor, such as the type of protons or hydrophilic pore or hydrogen bond. However, a limited contribution from a single factor cannot afford to remarkably increase the proton conductivity of the MOF and form a super proton conductor. Herein, we constructed two distinct porous MOFs, {(H₃O⁺)₄[Cu₁₂(ci)₁₂(OH)₄(H₂O)₁₂]·3H₂O·9DMF} (Cu-ci-3D, H₂ci = 1<i>H</i>-indazole-5-carboxylic acid, DMF = <i>N</i>,<i>N</i>'-dimethylformamide) and {[Co(Hppca)₂]·2HN(CH₃)₂·CH₃OH·2H₂O} (Co-ppca-2D, H₂ppca = 5-(pyridin-3-yl)-1<i>H</i>-pyrazole-3-carboxylic acid), to tune their proton conductivities at high relative humidity (RH) using the combined effect of hydrophilic pore and the type of protons, ultimately achieving super proton conduction. Excitingly, Cu-ci-3D indeed harvests a super proton conductivity of 1.37 × 10^-2 S cm^-1 at 353 K and ∼97% RH, superior to some previously reported MOF-based proton conductors. The results present a unique perspective for developing high-performance MOF-based proton conductors and understanding their structure-performance relationships.