CdS is a promising visible light response photoanode of photoelectrochemical (PEC) water splitting, but it remains a great challenge for practical application, due to the photohole‐induced self‐corrosion, and sulfide/sulfite ions as hole scavengers are always necessary for stable solar hydrogen generation. Herein, a CdS/SnSx nanorods/nanosheets hierarchical heterostructure with novel phase‐engineered band alignment is rationally designed via a two‐step solution reaction route for PEC water splitting. In the Na2SO4 aqueous electrolyte without any hole scavengers, compared with the pristine CdS, the CdS/SnSx photoanode achieves a remarkably enhanced photocurrent density of 1.59 mA cm−2 and a considerable stability at bias potential 1.23 V versus reversible hydrogen electrode (RHE) under simulated sunlight. It is proposed that the deposited SnSx nanosheets not only act as protective layers to restrain the photocorrosion of CdS, but also facilitate the charge separation in CdS by the virtue of the Type II heterojunction formed between CdS and SnSx.
In this study, Nb-doped a-Fe 2 O 3 nanorod photoanodes were prepared via a facile solution-based process by directly adding NbCl 5 in the aqueous solution. The morphology and electronic structure of Nb-doped a-Fe 2 O 3 films depended strongly on the dopant concentrations. Compared with the undoped sample, the optimal Nb-doped a-Fe 2 O 3 film showed an approximately 4-fold photocurrent increase under solar light at 1.0 V versus Ag/AgCl, and the incident photon-to-current conversion efficiency was increased by 2.5 times, reaching 13.7 % at 350 nm and 1.23 V versus RHE. The enhancement in PEC activity, as induced by moderate Nb doping, was attributed to the increased charge carrier density for promoted charge transfer ability as well as the smaller nanorod diameter for shortened charge transfer distance. However, superfluous Nb dopants would destroy the nanorod structure and greatly reduce the thickness of a-Fe 2 O 3 films, leading to poor optical absorption and thus decreased photoelectrochemical performance.
Ta-doped hematite (α-Fe2O3) nanorod array films were successfully prepared on fluorine-doped tin dioxide (FTO) coated glass substrates via a facile solution growth process with TaCl5 as a Ta doping precursor. Under 1 sun illumination and at an applied potential of 1.0 V vs. Ag/AgCl, the Ta-doped α-Fe2O3 photoanode with optimized dopant concentration showed a photocurrent density as high as 0.53 mA cm(-2), which was about 3.5 times higher than that of the undoped sample. As demonstrated by Mott-Schottky and X-ray absorption spectroscopy measurements, considerable increase in photoelectrochemical (PEC) performance achieved for Ta-doped α-Fe2O3 nanorod films should be mainly attributed to the increased electron donor density induced by Ta doping. However, with superfluous Ta doping, the [110]-oriented nanorod structure was destroyed, which caused greatly restrained photoinduced holes transferring to the surface and retarded surface water oxidation reaction, leading to decreased PEC water splitting activity. This study clearly demonstrated that doping could be effective to enhance the PEC activity of α-Fe2O3 nanorods as photoanodes, while it is of great necessity to balance the trade-off between the electronic structure and nanostructure evolution by optimizing the dopant concentration, for increased donor density and meanwhile with the nanorod nanostructure well preserved for directed charge transfer.
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