Synergy between Isomorphous Acid and Basic Metal–Organic Frameworks for Anhydrous Proton Conduction of Low-Cost Hybrid Membranes at High Temperatures

Abstract

Metal-organic frameworks (MOFs) embedded in polymer have showed efficiency in improving proton conduction of hybrid membranes under hydrated conditions. However, anhydrous proton conduction of such hybrid membranes over 100 °C remains great challenge. Here, proton conductive hybrid membranes combined acid group (-SO₃H)- and basic group (-NH₂)-modified isomorphous MOFs, namely UiO-66(SO₃H) (abbreviated as A, the initial of acid) and UiO-66(NH₂) (abbreviated as B, the initial of basic) and a low-cost polymer (chitosan, CS) were prepared. The proton conductivity of the optimum dual MOF-cofilled hybrid membranes (CS/A + B) reached 3.78 × 10^-3 S/cm at 120 °C and under anhydrous conditions, under which each component, that is MOF A, MOF B and CS, and single MOF-filled hybrid membranes (CS/A and CS/B) nearly lost proton conduction without exception, producing unprecedented results of one plus one more greater than two. The synergistic effects among UiO-66(SO₃H), UiO-66(NH₂), and CS on improving conductivity are also observed under hydrated conditions, the highest proton conductivity of CS/A + B reached 5.2 × 10^-2 S/cm, which is 1.86, compared to that of the pure CS membrane at 100 °C and 98% relative humidity. The anhydrous proton conductivity of CS/A + B over 100 °C is one of the highest for MOF-based hybrid membranes. MOFs and hybrid membranes were extensively characterized and the proton conductive mechanism was revealed. The achievements open a new avenue for MOF-based anhydrous proton-conducting membranes and would advance the exploration of future application of these MOFs in fuel cells.