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

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 degrees 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 X 10(-3) S/cm at 120 degrees 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 X 10(-2) S/cm, which is 1.86, compared to that of the pure CS membrane at 100 degrees C and 98% relative humidity. The anhydrous proton conductivity of CS/A + B over 100 degrees 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.