Plasmon-Driven Electrochemical Methanol Oxidation on Gold Nanohole Electrodes.

Direct methanol oxidation is expected to play a central role in low-polluting future power sources. However, the sluggish and complex electro-oxidation of methanol is one of the limiting factors for any practical application. To solve this issue, the use of plasmonic is considered as a promising way to accelerate the methanol oxidation reaction. In this study, we report on a novel approach for achieving enhanced methanol oxidation currents. Perforated gold thin film anodes were decorated with Pt/Ru via electrochemical deposition and investigated for their ability for plasmon-enhanced electrocatalytic methanol oxidation in alkaline media. The novel methanol oxidation anode (AuNHs/PtRu), combining the strong light absorption properties of a gold nanoholes array-based electrode (AuNHs) with surface-anchored bimetallic Pt/Ru nanostructures, known for their high activity toward methanol oxidation, proved to be highly efficient in converting methanol via the hot holes generated in the plasmonic electrode. Without light illumination, AuNHs/PtRu displayed a maximal current density of 13.7 mA/cm at -0.11 V vs Ag/AgCl. Enhancement to 17.2 mA/cm was achieved under 980 nm laser light illumination at a power density of 2 W/cm. The thermal effect was negligible in this system, underlining a dominant plasmon process. Fast generation and injection of charge carriers were also evidenced by the abrupt change in the current density upon laser irradiation. The good stability of the interface over several cycles makes this system interesting for methanol electro-oxidation.