As renewable electricity becomes less and less expensive and it's use becomes more widespread, there is a need for electrical energy-to-chemical energy conversion for both storage and for the use of electrons as reagents. Current electrolysis applications focus on large-scale alkaline water electrolysis (\ or proton exchange membrane water electrolyzers, featuring well-developed technology and industrial equivalent current densities. However, significant drawbacks, such as high overpotential, poor design, inherent environmental risks, reliance on hard-to-access chemicals, and poor understanding of membrane and electrode properties, have constrained opportunities for improvement. We have been working on anion exchange membranes for a number of years and we are now addressing the cationic ionomers and electrocatlysts needed for device fabrication. To address this we are investigating the interaction of ionomers on metal substrates and the use of structured ionomers as templates to produce nano-structured metal particles as heterogeneous electrocatlayt/ionomer compose materials . We use a series of random and structured block co-polymers with unsaturated hydrophobic components that can be hydrogenated to rubbery polymethylbutylene or semi-crystalline polyethylene. Co-polymerized with these components we use vinyl benzyl chloride which once polymerized can be quaternized with a large variety of amines to systematically vary the size and nature of the organic cation in the polymer. Initial studies using commercial Ag nano-particles or flat Ag substrates indicated that we could vary the interaction of the ionomer with the metal surfaced by changing the polymer chemistry. Unsaturated unquaternized polymers showed very strong orthogonal alignment on flat Ag surfaces. When quaternized the material became less ordered but still maintained vertical transport channels to the catalysts surface. Ag nano-particle effected the crystal city of the polyethylene component of the block co-polymers via interaction with the cations. We have recently been extending these studies to Nickel foam electrodes and studying the effect if ionomer and ionomer/Ag composites on electrochemical processes important to electrolysis.