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Titanium dioxide (TiO2) has attracted increasing attention as a candidate for the photocatalytic reduction of carbon dioxide (CO2) to convert anthropogenic CO2 gas into fuels combined with storage of intermittent and renewable solar energy in forms of chemical bonds for closing the carbon cycle. However, pristine TiO2 possesses a large band gap (3.2 eV), fast recombination of electrons and holes, and low selectivity for the photoreduction of CO2. Recently, considerable progress has been made in the improvement of the performance of TiO2 photocatalysts for CO2 reduction. In this review, we first discuss the fundamentals of and challenges in CO2 photoreduction on TiO2-based catalysts. Next, the recently emerging progress and advances in TiO2 nanostructured and hybrid materials for overcoming the mentioned obstacles to achieve high light-harvesting capability, improved adsorption and activation of CO2, excellent photocatalytic activity, the ability to impede the recombination of electrons-holes pairs, and efficient suppression of hydrogen evolution are discussed. In addition, approaches and strategies for improvements in TiO2-based photocatalysts and their working mechanisms are thoroughly summarized and analyzed. Lastly, the current challenges and prospects of CO2 photocatalytic reactions on TiO2-based catalysts are also presented.

Recently, the WO/BiVO heterojunction has shown promising photoelectrochemical (PEC) water splitting activity based on its charge transfer and light absorption capability, and notable enhancement of the photocurrent has been achieved via morphological modification of WO. We developed a graft copolymer-assisted protocol for the synthesis of WO mesoporous thin films on a transparent conducting electrode, wherein the particle size, particle shape, and thickness of the WO layer were controlled by tuning the interactions in the polymer/sol-gel hybrid. The PEC performance of the WO mesoporous photoanodes with various morphologies and the individual heterojunctions with BiVO (WO/BiVO) were characterized by measuring the photocurrents in the absence/presence of hole scavengers using light absorption spectroscopy and intensity-modulated photocurrent spectroscopy. The morphology of the WO photoanode directly influenced the charge separation efficiency within the WO layer and concomitant charge collection efficiency in the WO/BiVO heterojunction, showing the smaller sized nanosphere WO layer showed higher values than did the plate-like or rod-like one. Notably, we observed that photocurrent density of WO/BiVO was not dependent on the thickness of WO film or its charge collection time, implying slow charge flow from BiVO to WO can be a crucial issue in determining the photocurrent, rather than the charge separation within the nanosphere WO layer.

Chalcopyrite Cu(In,Ga)(Se,S) (CIGS) semiconductors are potential candidates for use in photoelectrochemical (PEC) hydrogen generation due to their excellent optical absorption properties and high conduction band edge position. In the present research, CIGS thin film was successfully prepared on a transparent substrate (F:SnO glass) using a solution-based process and applied for a photocathode in solar water splitting, which shows control of the surface state associated with sulfurization/selenization process significantly influences on the PEC activity. A ZnS passivation surface layer was introduced, which effectively suppresses charge recombination by surface states of CIGS. The CIGS/ZnS/Pt photocathode exhibited highly enhanced PEC activity (∼24 mA·cm at -0.3 V vs RHE). The performances of our CIGS photocathode on the transparent substrate were also characterized under front/back light illumination, and the incident photon to current conversion efficiency (IPCE) drastically changed depending on the illumination directions showing decreased IPCE especially under UV region with back illumination. The slow minority carrier (electron) transportation is suggested as a limiting factor for the PEC activity of the CIGS photocathode.

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We prepared TiO2 nanorod (NR) arrays on a fluorine-doped tin oxide substrate and decorated with graphene oxide (GO) to study their photoelectrochemical (PEC) water oxidation activities in two different electrolytes. The PEC performances of GO-decorated TiO2 NR photoanodes were characterized by optical and electrochemical impedance spectroscopy measurements. In 1 M KOH, the photocurrent density of the TiO2 NR film decreased after deposition of GO, while in the neutral pH electrolyte (phosphate buffered 0.5 M Na2SO4), the TiO2 NR photoanode showed enhanced performance after deposition with the 2 wt% GO solution. This was a consequence of the decrease in charge transfer resistance between the electrode surface and the electrolyte. The improvement of photocurrents by GO decoration was obvious near the onset potential of the photocurrents in the neutral pH electrolyte. These opposite contributions of GO on the TiO2 NR photoanodes suggest that GO can promote water oxidation effectively in a neutral electrolyte because depending on the pH of the electrolyte, different chemical species interact with the surface of the photoanode in the water oxidation reaction.

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BiVO4 has been formed into heterojunctions with other metal oxide semiconductors to increase the efficiency for solar water oxidation. Here, we suggest that heterojunction photoanodes of Si and BiVO4 can also increase the efficiency of charge separation and reduce the onset potential of the photocurrent by utilizing the high conduction band edge potential of Si in a dual-absorber system. We found that a thin TiO2 interlayer is required in this structure to realize the suggested photocurrent density enhancement and shifts in onset potential. Si/TiO2/BiVO4 photoanodes showed 1.0 mA/cm(2) at 1.23 V versus the reversible hydrogen electrode (RHE) with 0.11 V (vs RHE) of onset potential, which were a 3.3-fold photocurrent density enhancement and a negative shift in onset potential of 300 mV compared to the performance of FTO/BiVO4 photoanodes.