The Role of an Inert Electrode Support in Plasmonic Electrocatalysis

Plasmonic nanostructures loaded onto catalytically inert conductive support materials are believed to be advantageous for maximizing photocatalytic effects in photoelectrochemical systems due to the increased efficiency of Schottky barrier-free architectures in collecting hot charge carriers. However, the systematic mechanistic investigation and description of the inert electrode support contribution to plasmonic electrocatalysis is missing. Herein, we systematically investigated the effect of the supporting electrode material on the observed photocatalytic enhancement by comparing photoelectrocatalytic properties of AuNPs supported on highly oriented pyrolytic graphite (HOPG) and on indium tin oxide (ITO) electrodes using electrocatalytic benzyl alcohol (BnOH) oxidation as a model system. Upon illumination, only ~(3 ± 1)% enhancement in catalytic current was recorded on the AuNP/ITO electrodes in contrast to ~(42 ± 6)% enhancement on AuNP/HOPG electrodes. Our results showed that the local heating due to light absorption by the electrode material itself independent of localized surface plasmon effects is the primary source of the observed significant photo-induced enhancement on the HOPG electrodes in comparison to the ITO electrodes. Moreover, we demonstrated that an increased interfacial charge transfer at elevated temperatures, and not faster substrate diffusion is the main source of the enhancement. This work highlights the importance of systematic evaluation of contributions of all parts, even if they are catalytically inert, to the light-induced facilitation of catalytic reactions in plasmonic systems.