Fine‐Tuning the Electrochemical Methanol Oxidation Activity of Pt@TiO 2 Nanocomposites by Hydrophobic Nanoreactor Templating

In this work, Pt@TiO 2 nanocomposite nanoarray electrocatalysts for methanol oxidation were synthesized by a one‐pot hydrophobic nanoreactor templating (HNT) approach using PS‐ b ‐P4VP inverse micelles as the template and H 2 PtCl 6 ·6H 2 O and TiCl 4 as the Pt and Ti precursors, respectively. The resulting Pt@TiO 2 nanoarray electrocatalysts consist of a monolayer of spherical nanocomposite superstructures composed of finely dispersed Pt nanoparticles firmly anchored on/in a polycrystalline TiO 2 matrix. Their electrocatalytic activity toward methanol oxidation was evaluated by cyclic voltammetry and CO stripping measurements. By varying the Pt and Ti precursor loadings within the precursor micelles as well as the calcination temperature, the catalytic performance could be tuned from moderate to high and surpass that of the benchmark Pt/C catalyst. The optimized catalyst reached a peak specific activity of 4.63 mA cm −2 Pt , corresponding to a ∼3.2 times higher activity than that of a reference Pt/C catalyst. The enhanced performance is attributed to the precise nanostructure control attainable via HNT and the optimized related balance between Pt nanoparticle size, Pt surface accessibility, and Pt/TiO 2 interfacial contact, which facilitates CO oxidation as a key step in methanol electrooxidation.