Novel catalytic membranes and methods of synthesizing the membranes are disclosed herein. The technology involves the synthesis of a new type of permselective membrane that combines a hollow porous support with strategically positioned catalytic and selective transport functions to overcome thermodynamic, kinetic, and thermal obstacles, such as in the production of hydrogen. Sub-micron, dense metallic catalysts and films may be deposited within porous hollow substrates to create the membranes using the techniques of sol slip casting, film coating and electroless plating.