An (hk0)-oriented p-type CaFe2O4 (E(g): 1.9 eV) photocathode was prepared, and hydrogen and oxygen gases were produced from a photocell short-circuited by connecting the CaFe2O4 and n-type TiO2 electrodes under illumination without applying an external voltage. The open-circuited voltage was 0.97 V and the short-circuit current was about 200 μA/cm(2), and the amount of evaluated hydrogen and oxygen gases after 2 days of reaction were about 70 and 4 μmol, respectively.
Supporting Information. Raman spectra, UVÀvis spectra, reaction equations, photoelectrochemical data, XPS spectra, and UPS spectra. This material is available free of charge via the Internet at http://pubs.acs.org.
One-nanometer-thick nickel hydroxide nanosheets were prepared by exfoliation of layered nickel hydroxides intercalated with dodecyl sulfate (DS) ions. The shape of the nanosheets was hexagonal, as was that of the layered nickel hydroxides intercalated with DS ions. The nickel hydroxide nanosheets exhibited charge-discharge properties in strong alkaline electrolyte. The morphology of the nanosheet changed during the electrochemical reaction.
Luminescent perovskite nanosheets were prepared by exfoliation of single- or double-layered perovskite oxides, K2Ln2Ti3O10, KLnNb2O7, and RbLnTa2O7 (Ln: lanthanide ion). The thickness of the individual nanosheets corresponded to those of the perovskite block in the parent layered compounds. Intense red and green emissions were observed in aqueous solutions with Gd1.4Eu0.6Ti3O10- and La0.7Tb0.3Ta2O7-nanosheets, respectively, under UV illumination with energies greater than the corresponding host oxide band gap. The coincidence of the excitation spectrum and the band gap absorbance indicates that the visible emission results from energy transfer within the nanosheet. The red emission intensity of the Gd1.4Eu0.6Ti3O10-nanosheets was much stronger than that of the La0.90Eu0.05Nb2O7-nanosheets reported previously. The strong emission intensity is a result of a two-step energy transfer cascade within the nanosheet from the Ti-O network to Gd(3+) and then to Eu(3+). The emission intensities of the Gd1.4Eu0.6Ti3O10- and La0.7Tb0.3Ta2O7-nanosheets can be modulated by applying a magnetic field (1.3-1.4 T), which brings about a change in orientation of the nanosheets in solution. The emission intensities increased when the excitation light and the magnetic field directions were perpendicular to each other, and they decreased when the excitation and magnetic field were collinear and mutually perpendicular to the direction of detection of the emitted light.
Graphene oxide (GO) nanosheets were reduced by UV irradiation in H2 or N2 under mild conditions (at room temperature) without a photocatalyst. Photoreduction proceeded even in an aqueous suspension of nanosheets. The GO nanosheets reduced by this method were analyzed by X-ray photoelectron spectroscopy and Raman spectroscopy. It was found that epoxy groups attached to the interiors of aromatic domains of the GO nanosheet were destroyed during UV irradiation to form relatively large sp2 islands resulting in a high conductivity. I-V curves were measured by conductive atomic force microscopy (AFM; perpendicular to a single nanosheet) and a two-electrode system (parallel to the nanosheet). They revealed that photoreduced GO nanosheets have high conductivities, whereas nonreduced GO nanosheets are nearly insulating. Ag+ adsorbed on GO nanosheets promoted the photoreduction. This photoreduction method was very useful for photopatterning a conducting section of micrometer size on insulating GO. The developed photoreduction process based on a photoreaction will extend the applications of GO to many fields because it can be performed in mild conditions without a photocatalyst.
Rhodium-doped calcium niobate nanosheets were synthesized by exfoliating layered KCa(2)Nb(3-x)Rh(x)O(10-δ) and exhibited high photocatalytic activity for H(2) production from a water/methanol system without cocatalyst loading. The maximum H(2) production rate of the nanosheets was 165 times larger than that of the parent Rh-doped layered oxide. The quantum efficiency at 300 nm was 65%. In this system, the methanol was oxidized to formaldehyde (main product), formic acid, and carbon dioxide by holes, whereas electrons cause the reduction of water to H(2). The conductivity of the parent layered oxide was decreased by doping, which indicates the octahedral RhO(6) unit in the lattice of the nanosheet functions as an electron trap site. The RhO(6) units in the nanosheet probably also act as reaction sites for H(2) evolution.
This Perspective focuses on the photocatalytic activity of two-dimensional (2D) oxide and nitrogen-doped oxide crystals and the effective use of 2D photocatalysts for understanding the mechanism of the water splitting reaction. Strategies for improving the activities of 2D photocatalysts are slightly different from those of bulk photocatalysts. Although it is well-known that a photocatalyst without co-catalyst loading has low activity for hydrogen production from water, a certain type of 2D oxide nanosheet shows high activity without co-catalyst loading. It is difficult to determine what factors contribute to this separation of oxidation and reduction sites of water because there are many factors on the reaction surface. A nanosheet p-n junction surface is an ideal surface for understanding the carrier transfer during the photocatalytic reaction. In this system, the driving force of the carrier transfer to the reaction sites was found to be the potential gradient generated by the nanosheet junction.
Co-catalysts play an important role in photocatalytic water splitting. The co-catalyst is generally deposited in the form of nanoparticles on the catalyst surface, and is believed to provide water oxidation and reduction sites. However, the minimum size of a co-catalyst that can function as a reaction site and the detailed local environment of the photocatalytic reaction centers are not yet fully understood. Here, we show that even isolated single-atom Rh dopants in two-dimensional titanium oxide crystals can effectively act as co-catalysts for the water-splitting reaction. At an optimal doping concentration, the hydrogen production rate is increased substantially in comparison to that found with the undoped crystals. We also present first-principles simulations based on density functional theory to provide insights into the atomic-scale mechanism by which the isolated Rh dopants induce changes to the dissociation reaction energy landscape. These results provide new insights for better understanding the role of the co-catalyst in the photocatalytic reaction.
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