A DNA‐Threaded ZIF‐8 Membrane with High Proton Conductivity and Low Methanol Permeability

Natural biomolecules have potential as proton-conducting materials, in which the hydrogen-bond networks can facilitate proton transportation. Herein, a biomolecule/metal-organic framework (MOF) approach to develop hybrid proton-conductive membranes is reported. Single-strand DNA molecules are introduced into DNA@ZIF-8 membranes through a solid-confined conversion process. The DNA-threaded ZIF-8 membrane exhibits high proton conductivity of 3.40 × 10-4 S cm-1 at 25 °C and the highest one ever reported of 0.17 S cm-1 at 75 °C, under 97% relatively humidity, attributed to the formed hydrogen-bond networks between the DNA molecules and the water molecules inside the cavities of the ZIF-8, but very low methanol permeability of 1.25 × 10-8 cm2 s-1 due to the small pore entrance of the DNA@ZIF-8 membranes. The selectivity of the DNA@ZIF-8 membrane is thus significantly higher than that of developed proton-exchange membranes for fuel cells. After assembling the DNA@ZIF-8 hybrid membrane into direct methanol fuel cells, it exhibits a power density of 9.87 mW cm-2 . This is the first MOF-based proton-conductivity membrane used for direct methanol fuel cells, providing bright promise for such hybrid membranes in this application.