High Electrocatalytic Activity of Pt–Pd Binary Spherocrystals Chemically Assembled in Vertically Aligned TiO2 Nanotubes

To obtain noble metal catalysts with high efficiency, long‐term stability, and poison resistance, Pt and Pd are assembled in highly ordered and vertically aligned TiO₂ nanotubes (NTs) by means of the pulsed‐current deposition (PCD) method with assistance of ultrasonication (UC). Here, Pd serves as a dispersant which prevents agglomeration of Pt. Thus Pt–Pd binary catalysts are embed into TiO₂ NTs array under UC in sunken patterns of composite spherocrystals (Sps). Owing to this synthesis method and restriction by the NTs, the these catalysts show improved dispersion, more catalytically active sites, and higher surface area. This nanotubular metallic support material with good physical and chemical stability prevents catalyst loss and poisoning. Compared with monometallic Pt and Pd, the sunken‐structured Pt–Pd spherocrystal catalyst exhibits better catalytic activity and poison resistance in electrocatalytic methanol oxidation because of its excellent dispersion. The catalytic current density is enhanced by about 15 and 310 times relative to monometallic Pt and Pd, respectively. The poison resistance of the Pt–Pd catalyst was 1.5 times higher than that of Pt and Pd, and they show high electrochemical stability with a stable current enduring for more than 2100 s. Thus, the TiO₂ NTs on a Ti substrate serve as an excellent support material for the loading and dispersion of noble metal catalysts.