Incorporating metal nanocrystals with semiconductor photoanodes significantly enhances the efficiency of the energy conversion in the visible range during water splitting due to the excitation of hot electrons. While extensively studied on ensemble samples, hot electron response of metal nanocrystals in a photoelectrochemical cell remains unexploited at the single-particle level. Herein, we systematically investigate hot electron response of individual single-crystalline gold nanocrystals (AuNCs) on a TiO2 photoanode during water splitting. We directly correlate the morphology of the AuNC and its plasmonic property to the efficiencies involving hot electrons with the help of single-particle dark-field microscopy and photocurrent mapping. Our results show that the efficiencies of individual AuNCs are dependent on a variety of factors including interface condition, applied bias, excitation power, incident angle, and AuNC size. Our research may shed light on optimizing the light-harvesting capability of metal/semiconductor photoanodes by providing insights into the photocatalytic processes.
Keywords: Gold nanocrystals; Hot electrons; Photoelectrochemical reaction; Single-particle characterization; Surface plasmon resonance; Water splitting.