Abstract

Semiconductor electrodes integrated with cocatalysts are key components of photoelectrochemistry (PEC)-based solar-energy conversion. However, efforts to optimize the PEC device have been limited by an inadequate understanding of the interface interactions between the semiconductor-cocatalyst (sem|cat) and cocatalyst-electrolyte (cat|ele) interface. In our work, we used ferrihydrite (Fh)-modified Ti-Fe2 O3 as a model to explore the transfer process of photogenerated charge carriers between the Ti-Fe2 O3 -Fh (Ti-Fe2 O3 |Fh) interface and Fh-electrolyte (Fh|ele) interface. The results demonstrate that the biphasic structure (Fh/Ti-Fe2 O3 ) possesses the advantage that the minority hole transfer from Ti-Fe2 O3 to Fh is driven by the interfacial electric field at the Ti-Fe2 O3 |Fh interface; meanwhile, the holes reached at the surface of Fh can rapidly inject into the electrolyte across the Fh|ele interface. As a benefit from the improved charge transfer at the Ti-Fe2 O3 |Fh and Fh|ele interface, the photocurrent density obtained by Fh/Ti-Fe2 O3 can reach 2.32 mA cm-2 at 1.23 V versus RHE, which is three times higher than that of Ti-Fe2 O3 .

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