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Mixed matrix membranes (MMM) based on chitosan (CS) and poly (vinyl) alcohol (PVA) with a 50:50 w/w ratio doped with graphene oxide (GO) are prepared by solution casting and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), water uptake, alcohol permeability, ion exchange capacity (IEC) and OH−conductivity measurements. The SEM analysis revealed a dense MMM where the GO nanosheets were well dispersed over the entire polymer matrix. The incorporation of GO increased considerably the thermal stability of the CS:PVA membrane. The GO-based MMM exhibited a low conductivity of 0.19 mS·cm−1 in part because the GO sheets did not change the crystallinity of the CS:PVA matrix. The reinforced structure created by the hydrogen bonds between the GO filler and the CS:PVA matrix resulted to be a good physical barrier for alcohol permeability, achieving a coefficient of diffusion of 3.38 × 10−7 and 2.43 × 10−7 cm2·s−1 after 60 and 120 min, respectively, thus avoiding additional alcohol crossover. Finally, the electrochemical performance of the GO-based MMM in the electrooxidation of propargyl alcohol was investigated in a Polymer Electrolyte Membrane Electrochemical Reactor (PEMER) under alkaline conditions, through the polarization curve and the electrolysis reactions, showing a performance comparable to anion-exchange commercial membranes.This work has been funded by the Spanish MINECO through projects CTQ2012-31229 and the “Ramón y Cajal” grant RYC2011-08550 (C.C.C.), at the University of Cantabria, and the PhD fellowship BES-2011-045147 and EEBB-14-09094 mobility grant for L.G.C’s research stay at the University of Cantabria

High Performance of Alkaline Anion-Exchange Membranes Based on Chitosan/Poly (vinyl) Alcohol Doped with Graphene Oxide for the Electrooxidation of Primary Alcohols