Three-Dimensional Pinecone-like Binder-Free Pt-TiO Nanorods on Ti Mesh Structures: Synthesis, Characterization and Electroactivity towards Ethanol Oxidation.

We report here the synthesis of binderless and template-less three-dimensional (3D) pinecone-shaped Pt/TiO/Ti mesh structure. The TiO hydrothermally synthesized onto Ti mesh is composed of a mixture of flower-like nanorods and vertically aligned bar-shaped structures, whereas Pt film grown by pulsed laser deposition displays a smooth surface. XRD analyses reveal an average crystallite size of 41.4 nm and 68.5 nm of the TiO nanorods and Pt, respectively. In HSO solution, the platinum oxide formation at the Pt/TiO/Ti mesh electrode is 180 mV more negative than that at the Pt/Ti mesh electrode, indicating that TiO provides oxygeneous species at lower potentials, which will facilitate the removal of CO-like intermediates and accelerate an ethanol oxidation reaction (EOR). Indeed, the Pt/TiO/Ti mesh catalyst exhibits current activity of 1.19 mA towards an EOR at a remarkably superior rate of 4.4 times that of the Pt/Ti mesh electrode (0.27 mA). Moreover, the presence of TiO as a support to Pt delivers a steady-state current of 2.1 mA, with an increment in durability of 6.6 times compared to Pt/Ti mesh (0.32 mA). Pt is chosen here as a benchmark catalyst and we believe that with catalysts that perform better than Pt, such 3D pinecone structures can be useful for a variety of catalytic or photoelectrochemical reactions.