Rational Design of S-UiO-66@GO Hybrid Nanosheets for Proton Exchange Membranes with Significantly Enhanced Transport Performance.

Metal-organic frameworks (MOFs) are being intensively explored as filler materials for polymeric proton exchange membranes (PEMs) due to their potentials for the systematic design and modification of proton-conducting properties. S-UiO-66, a stable MOF with functional groups of -SO3H in its ligands, was selected here to prepare S-UiO-66@graphene oxide (GO) hybrid nanosheets via a facile in situ growth procedure, and then a series of composite PEMs were prepared by hybridizing S-UiO-66@GO and sulfonated poly(ether ether ketone) (SPEEK). The resultant hybrid nanosheets not only possessed abundant -SO3H groups derived from the ligands of S-UiO-66 but also yielded a uniform dispersion of S-UiO-66 onto GO nanosheets, thus effectively eliminating the agglomeration of S-UiO-66 in the membrane matrix. Thanks to the well-tailored chemical composition and nanostructure of S-UiO-66@GO, the as-prepared SPEEK/S-UiO-66@GO composite PEMs present a significant increase in their proton conductivity under various conditions. In particular, the proton conductivity of the SPEEK/S-UiO-66@GO-10 membrane was up to 0.268 S·cm-1 and 16.57 mS·cm-1 at 70 °C-95% RH and 100 °C-40% RH (2.6 and 6.0 times that of recast SPEEK under the same condition), respectively. Moreover, the mechanical property of composite membranes was substantially strengthened and the methanol penetration was well-suppressed. Our investigation indicates the great potential of S-UiO-66@GO in fabricating composite PEMs and also reveals that the high proton conductivity of MOFs can be fully utilized by means of MOF/polymer composite membranes.