Direct Plasmon-Accelerated Electrochemical Reaction on Gold Nanoparticles.

Direct photocatalysis making use of plasmonic metals has attracted significant attention due to the light-harnessing capabilities of these materials associated with localized surface plasmon resonance (LSPR) features. Thus far, most reported work has been limited to plasmon-induced chemical transformations. Herein, we demonstrate that electrochemical reactions can also be accelerated by plasmonic nanoparticles upon LSPR excitation. Using glucose electrocatalysis as a model reaction system, the direct plasmon-accelerated electrochemical reaction (PAER) on gold nanoparticles is observed. The wavelength- and solution-pH-dependent electrochemical oxidation rate and the dark-field scattering spectroscopy results confirm that the hot charge carriers generated during plasmon decay are responsible for the enhanced electrocatalysis performance. Based on the proposed PAER mechanism, a plasmon-improved glucose electrochemical sensor is constructed, demonstrating the enhanced performance of the non-enzyme sensor upon LSPR excitation. This plasmon-accelerated electrochemistry promises potential applications in (bio)electrochemical energy conversion, electroanalysis, and electrochemical devices.