Boosting plasmon-enhanced electrochemistry by in situ surface cleaning of plasmonic nanocatalysts

Abstract

The application of surface plasmons in heterogeneous catalysis has attracted widespread attention due to their promising potential for harvesting solar energy. The effect of surface adsorbates on catalysts has been well documented in many traditional reactions; nonetheless, their role in plasmonic catalysis has been rarely studied. In this study, an in situ electrochemical surface cleaning strategy is developed and the influence of surface adsorbates on plasmon-enhanced electrochemistry is investigated. Taking Au nanocubes as an example, plasmonic catalysts with clean surfaces are obtained by Cu₂O coating and in situ electrochemical etching. During this process, the surface adsorbates of Au nanocubes are removed together with the Cu₂O shells. The Au nanocubes with clean surfaces exhibit remarkable performance in plasmon-enhanced electrooxidation of glucose and an enhancement of 445% is demonstrated. The Au NCs with clean surfaces can not only provide more active sites but also avoid halides as hole scavengers, and therefore, the efficient utilization of hot holes by plasmonic excitation is achieved. This process is also generalized to other molecules and applied in electrochemical sensing with high sensitivity. These results highlight the critical role of surface adsorbates in plasmonic catalysis and may forward the design of efficient plasmonic catalysts for plasmon-enhanced electrochemistry.