In this study, we successfully synthesized a Pd/ZnO/Ni hierarchical porous array-film catalyst by electrodeposition and magnetron sputtering with the assistance of the monodisperse colloidal sphere template. Structural characterisation indicated that a layer of Pd nanoparticles was uniformly grown on the ZnO/Ni ordered bowl-like micro/nano array film. Electrochemical measurements in alkaline solution demonstrated that the as-grown array film had outstanding electrocatalytic activity for methanol oxidation. The specific activity of the Pd/ZnO/Ni porous array film was up to 130.1 mA cm−2. The corresponding mass activity (812.7 mA mg−1) was 6 times higher than that of commercial Pd/C catalyst (134.8 mA mg−1), and the stability was also much better than the commercial one. These excellent electrochemical properties can be attributed to the unique hierarchical porous structure, which offers a high specific surface area for the methanol reaction, and ZnO intermediate layer, which effectively removes the poisoning species from the Pd sites through the strong oxidative hydroxyl radicals.
