Isomer-Effects of Aminophenol Decorated Gold Nanoclusters for H2O2 Photoproduction via Two-Step One-Electron Oxygen Reduction Reaction

Small. 2025 Jan 9:e2410843. doi: 10.1002/smll.202410843. Online ahead of print.

Abstract

Gold (Au) nanoclustersare promising photocatalysts for biomedicine, sensing, and environmental remediation. However, the short carrier lifetime, inherent instability, and unclear charge transfer mechanism hinder their application. Herein, the Au nanoclusters decorated with three different isomers of o-Aminophenol, m-Aminophenol, and p-Aminophenol are synthesized, namely o-Au, m-Au, and p-Au, which achieve efficient hydrogen peroxide (H2O2) photoproduction through two-step one-electron oxygen reduction reaction (ORR). The interfacial kinetics for the photocatalytic process in this system are investigated in detail, in which, the isomer-effects of aminophenol decorated in Au nanoclusters are definitely elucidated by combining transient photovoltage (TPV), transient potential scanning (TPS), and photo-induced current (TPC) tests. The reaction pathway of o-Au, m-Au, and p-Au is confirmed to be the same through TPC. Although the conduction band values of o-Au, m-Au, and p-Au are essentially the same under working conditions, the values of surface effective charges (ne) for both m-Au and p-Au are higher than that of o-Au. In addition, m-Au has a stronger adsorption capacity for O2 and a faster ORR rate. Thus, the m-Au manifests the highest photocatalytic activity for the H2O2 photoproduction. This work shows a new way for the in-situ study on charge distribution and transfer on photocatalysts.

Keywords: Au nanoclusters; H2O2 photoproduction; isomer‐effects; oxygen reduction reaction.