In this work, the morphology of TiO2 nanotubes with little nanowires directly formed on top (designed as TTW) was treated by the method of wet-chemical reaction (designed as WCR) with alkaline solution. It was designed to change the surface morphology and chemical activity, thus improving the UV-visible (UV-vis) light absorption and photoelectrochemistry (PEC) performance. We explored different alkaline reagents and different processing time to deal with TTW. After the WCR method with ammonia water (NH3·H2O), it was found that a hybrid nanostructure, thinner wall TiO2 nanotubes array at bottom and nanowires porous film on top (designed as TTWPF), was obtained. The wires are formed by chemical dissolution of oxide on the top, and there is no grain boundary between the tubes and wires in TTWPF. So, it can make full use of the advantages of nanotubes and nanowires. For one thing, the nanowires porous film on top can fully utilize both the characteristic of large specific surface and the high activeness to gengerate electronhole pairs, and the thinner wall nanotubes array at bottom can provide more direct pathways for photogenerated electron transfer. For another, nanowires porous film can recycle the light scattered by the three-dimensional topography of the highly ordered nanotubes array. Meanwhile, the TTWPF exposes more {001} facets of high energy, which have substantial effects on the surface separation and the transportation of photogenerated electron-hole pairs. The data of the PEC performance indicate that the photocurrent density of the bare TTW treated by the method of WCR with NH3·H2O can be increased by up to 238%.
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