Enhancing Solar‐Driven Water Splitting with Surface‐Engineered Nanostructures

摘要： Functional nanoscale interfaces that promote the transport of photoexcited charge carriers are fundamental to efficient hydrogen production during photoelectrochemical (PEC) splitting of water. Here, the realization of a functional one-dimensional nanostructure achieved through surface engineering of hematite (α-Fe2O3) nanorods with a TiO2 overlayer is reported. The surface-engineered hematite nanostructure exhibits significantly improved PEC performance as compared to untreated α-Fe2O3, with an increase in the maximum incident photon-to-current efficiency (IPCE) of nearly 400% at 350 nm. While addition of the TiO2 overlayer did not alter the lifetime of photoexcited charge carriers, as evidenced from transient absorption spectroscopy, it is found that the presence of TiO2 could enhance oxygen electrocatalysis by interfacial electron enrichment, largely attributed to enhanced O(2p)(cid:1)Fe(3d) hybridization. Moreover, the interfacial electronic structure revealed from XANES measurements of the α-Fe2O3/TiO2 nanorods suggests that photoexcited holes in α-Fe2O3 may efficiently transfer through the TiO2 overlayer to the electrolyte while electrons migrate to the external circuit along the one-dimensional nanorods, thereby promoting charge separation and enhancing PEC splitting of water.