Surface reaction kinetics and bulk charge separation are both critical to the efficiency of solar water splitting. In addition to the well-documented surface catalytic effect, the promotion of bulk charge separation upon loading of cocatalysts has rarely been reported. This paper describes the synergetic enhancement of surface reaction kinetics and bulk charge separation by introducing discrete nanoisland p-type Co3O4 cocatalysts onto n-type BiVO4, forming a p-n Co3O4/BiVO4 heterojunction with an internal electric field to facilitate charge transport. Being highly dispersed on the surface of photoanodes, the nanoisland cocatalysts could suppress the formation of recombination centers at the photoanode/cocatalyst interface. This cocatalyst-loading method achieved a charge separation efficiency of up to 77% in the bulk and 47% on the surface of catalysts. An AM 1.5G photocurrent of 2.71 mA/cm(2) at 1.23 V versus the reversible hydrogen electrode for water oxidation was obtained, which is the highest photocurrent yet reported for Co-catalyzed undoped BiVO4 photoanodes, with a photoconversion efficiency of 0.659%.

Solar energy utilization is one of the most promising solutions for the energy crises. Among all the possible means to make use of solar energy, solar water splitting is remarkable since it can accomplish the conversion of solar energy into chemical energy. The produced hydrogen is clean and sustainable which could be used in various areas. For the past decades, numerous efforts have been put into this research area with many important achievements. Improving the overall efficiency and stability of semiconductor photocatalysts are the research focuses for the solar water splitting. Tantalum-based semiconductors, including tantalum oxide, tantalate and tantalum (oxy)nitride, are among the most important photocatalysts. Tantalum oxide has the band gap energy that is suitable for the overall solar water splitting. The more negative conduction band minimum of tantalum oxide provides photogenerated electrons with higher potential for the hydrogen generation reaction. Tantalates, with tunable compositions, show high activities owning to their layered perovskite structure. (Oxy)nitrides, especially TaON and Ta3N5, have small band gaps to respond to visible-light, whereas they can still realize overall solar water splitting with the proper positions of conduction band minimum and valence band maximum. This review describes recent progress regarding the improvement of photocatalytic activities of tantalum-based semiconductors. Basic concepts and principles of solar water splitting will be discussed in the introduction section, followed by the three main categories regarding to the different types of tantalum-based semiconductors. In each category, synthetic methodologies, influencing factors on the photocatalytic activities, strategies to enhance the efficiencies of photocatalysts and morphology control of tantalum-based materials will be discussed in detail. Future directions to further explore the research area of tantalum-based semiconductors for solar water splitting are also discussed.

This paper describes the synthesis of TiO₂ branched nanorod arrays (TiO₂ BNRs) with plasmonic Au nanoparticles attached on the surface. Such Au/TiO₂ BNR composites exhibit high photocatalytic activity in photoelectrochemical (PEC) water splitting. The unique structure of Au/TiO₂ BNRs shows enhanced activity with a photocurrent of 0.125 mA cm(-2) under visible light (≥420 nm) and 2.32 ± 0.1 mA cm(-2) under AM 1.5 G illumination (100 mW cm(-2)). The obtained photocurrent is comparable to the highest value ever reported. Furthermore, the Au/TiO₂ BNRs achieve the highest efficiency of ∼1.27% at a low bias of 0.50 V vs. RHE, indicating elevated charge separation and transportation efficiencies. The high PEC performance is mainly due to the plasmonic effect of Au nanoparticles, which enhances the visible light absorption, together with the large surface area, efficient charge separation and high carrier mobility of the TiO₂ BNRs. The carrier density of Au/TiO₂ BNRs is nearly 6 times higher than the pristine TiO₂ BNRs as calculated by the Mott-Schottky plot. Based on the analysis by UV-Vis spectroscopy, electrochemical impedance spectroscopy, and photoluminescence, a mechanism was proposed to explain the high activity of Au/TiO₂ BNRs in PEC water splitting. The capability of synthesizing highly visible light active Au/TiO₂ BNR based photocatalysts is useful for solar conversion applications, such as PEC water splitting, dye-sensitized solar cells and photovoltaic devices.