| Abstract: | Surface plasmon resonance (SPR) enhancement in photocatalyst and photovoltaics has been widely studied and different enhancement mechanisms have been established based on different heterostructure interface configurations. This work is intended to unveil the mechanisms behind charge or energy transfer in different plasmonic configurations of metal particle–semiconductor interfaces, especially with a dielectric layer. For this purpose, a series of composite photoelectrodes based on anodic TiO2 nanotube (TONT) backbones coated with Au, Al2O3, or both are designed and characterized systematically. In conjunction with both experimental measurements and numerical simulations, it is revealed that in the TONT‐Al2O3‐Au electrode system (i.e., a thin nonconductive spacer between semiconductor and metal), the enhancement is dominantly governed by SPR‐mediated hot‐electron injection rather than conventional‐thought near‐field electromagnetic enhancement. Among all configurations, the TONT‐Au‐Al2O3 electrode shows the best photoresponse in both UV and visible regions. The superior visible light response of the TONT‐Au‐Al2O3 electrode is ascribed to the Al2O3 intensified local electromagnetic field that enhances the hot‐electron injection through the TiO2‐Au interface, and an effective surface passivation by the Al2O3 coating. |
