Design and Characterization of Hybrid Multilayer Structures: Layer-by-Layer Growth of Polymer and Graphene Oxide Assemblies and Their Utility in Fuel Cell Applications

We report the layer-by-layer growth of poly-(ethylenimine) (PEI) that has been modified with sulfamate functionalities (S-PEI) using Zr⁴⁺-complexation interlayer linking chemistry. We have also deposited adlayers of graphene oxide (GO) that have been modified to possess sulfate functionalities (S-GO), onto the S-PEI layers. The multilayer assemblies are formed with sulfamate/sulfate and sulfate/sulfate (S-PEI + S-GO) interlayer linking chemistry. In all cases the adlayer thickness is consistent with predictions based on van der Waals volume and/or molecular mechanics calculations. X-ray photoelectron spectroscopy (XPS) is used to characterize the Zr/S stoichiometry in the multilayer assembly. The utility of these hybrid multilayer structures is demonstrated in a Proton Exchange Membrane (PEM) fuel cell, where they are shown to reduce H₂ gas crossover by 15% with only a 12 nm thick layer.