Nanoparticulate TiN Loading to Promote Z-Scheme Water Splitting Using a Narrow-Bandgap Nonoxide-Based Photocatalyst Sheet.

Some oxide-based particulate photocatalyst sheets exhibit excellent activity during the water-splitting reaction. The replacement of oxide photocatalysts with narrow-bandgap photocatalysts based on nonoxides could provide the higher solar-to-hydrogen energy conversion efficiencies that are required for practical implementation. Unfortunately, the activity of nonoxide-based photocatalyst sheets is low in many cases, indicating the need for strategies to improve the quality of nonoxide photocatalysts and the charge transfer process. In this work, single-crystalline particulate SrTaO2N is studied as an oxygen evolution photocatalyst for photocatalyst sheets applied to Z-scheme water splitting, in combination with La5Ti2Cu0.9Ag0.1O7S5 and Au as the hydrogen evolution photocatalyst and conductive layer, respectively. The loading of SrTaO2N with CoOx provided increases activity during photocatalytic water oxidation, giving an apparent quantum yield of 15.7% at 420 nm. A photocatalyst sheet incorporating CoOx-loaded SrTaO2N is also found to promote Z-scheme water splitting under visible light. Notably, the additional loading of nanoparticulate TiN on the CoOx-loaded SrTaO2N improves the water splitting activity by six times because the TiN promotes electron transfer from the SrTaO2N particles to the Au layer. This work demonstrates key concepts related to the improvement of nonoxide-based photocatalyst sheets based on facilitating the charge transfer process through appropriate surface modifications.

Two-Dimensional Perovskite Oxynitride K2 LaTa2 O6 N with an H+ /K+ Exchangeability in Aqueous Solution Forming a Stable Photocatalyst for Visible-Light H2 Evolution.

Undoped layered oxynitrides have not been considered as promising H2 -evolution photocatalysts because of the low chemical stability of oxynitrides in aqueous solution. Here, we demonstrate the synthesis of a new layered perovskite oxynitride, K2 LaTa2 O6 N, as an exceptional example of a water-tolerant photocatalyst for H2 evolution under visible light. The material underwent in-situ H+ /K+ exchange in aqueous solution while keeping its visible-light-absorption capability. Protonated K2 LaTa2 O6 N, modified with an Ir cocatalyst, exhibited excellent catalytic activity toward H2 evolution in the presence of I- as an electron donor and under visible light; the activity was six times higher than Pt/ZrO2 /TaON, one of the best-performing oxynitride photocatalysts for H2 evolution. Overall water splitting was also achieved using the Ir-loaded, protonated K2 LaTa2 O6 N in combination with Cs-modified Pt/WO3 as an O2 evolution photocatalyst in the presence of an I3 - /I- shuttle redox couple.

A Stable, Narrow-Gap Oxyfluoride Photocatalyst for Visible-Light Hydrogen Evolution and Carbon Dioxide Reduction.

Mixed anion compounds such as oxynitrides and oxychalcogenides are recognized as potential candidates of visible-light-driven photocatalysts since, as compared with oxygen 2p orbitals, p orbitals of less electronegative anion (e.g., N3-, S2-) can form a valence band that has more negative potential. In this regard, oxyfluorides appear unsuitable because of the higher electronegativity of fluorine. Here we show an exceptional case, an anion-ordered pyrochlore oxyfluoride Pb2Ti2O5.4F1.2 that has a small band gap (ca. 2.4 eV). With suitable modification of Pb2Ti2O5.4F1.2 by promoters such as platinum nanoparticles and a binuclear ruthenium(II) complex, Pb2Ti2O5.4F1.2 worked as a stable photocatalyst for visible-light-driven H2 evolution and CO2 reduction. Density functional theory calculations have revealed that the unprecedented visible-light-response of Pb2Ti2O5.4F1.2 arises from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb-O bond in the pyrochlore lattice due to the fluorine substitution.

Undoped Layered Perovskite Oxynitride Li2 LaTa2 O6 N for Photocatalytic CO2 Reduction with Visible Light.

Oxynitrides are promising visible-light-responsive photocatalysts, but their structures are almost confined with three-dimensional (3D) structures such as perovskites. A phase-pure Li2 LaTa2 O6 N with a layered perovskite structure was successfully prepared by thermal ammonolysis of a lithium-rich oxide precursor. Li2 LaTa2 O6 N exhibited high crystallinity and visible-light absorption up to 500 nm. As opposed to well-known 3D oxynitride perovskites, Li2 LaTa2 O6 N supported by a binuclear RuII complex was capable of stably and selectively converting CO2 into formate under visible light (λ>400 nm). Transient absorption spectroscopy indicated that, as compared to 3D oxynitrides, Li2 LaTa2 O6 N possesses a lower density of mid-gap states that work as recombination centers of photogenerated electron/hole pairs, but a higher density of reactive electrons, which is responsible for the higher photocatalytic performance of this layered oxynitride.

Graphitic carbon nitride prepared from urea as a photocatalyst for visible-light carbon dioxide reduction with the aid of a mononuclear ruthenium(II) complex.

Graphitic carbon nitride (g-C3N4) was synthesized by heating urea at different temperatures (773-923 K) in air, and was examined as a photocatalyst for CO2 reduction. With increasing synthesis temperature, the conversion of urea into g-C3N4 was facilitated, as confirmed by X-ray diffraction, FTIR spectroscopy and elemental analysis. The as-synthesized g-C3N4 samples, further modified with Ag nanoparticles, were capable of reducing CO2 into formate under visible light (λ > 400 nm) in the presence of triethanolamine as an electron donor, with the aid of a molecular Ru(II) cocatalyst (RuP). The CO2 reduction activity was improved by increasing the synthesis temperature of g-C3N4, with the maximum activity obtained at 873-923 K. This trend was also consistent with that observed in photocatalytic H2 evolution using Pt-loaded g-C3N4. The photocatalytic activities of RuP/g-C3N4 for CO2 reduction and H2 evolution were thus shown to be strongly associated with the generation of the crystallized g-C3N4 phase.

Robust Binding between Carbon Nitride Nanosheets and a Binuclear Ruthenium(II) Complex Enabling Durable, Selective CO2 Reduction under Visible Light in Aqueous Solution.

Carbon nitride nanosheets (NS-C3 N4 ) were found to undergo robust binding with a binuclear ruthenium(II) complex (RuRu') even in basic aqueous solution. A hybrid material consisting of NS-C3 N4 (further modified with nanoparticulate Ag) and RuRu' promoted the photocatalytic reduction of CO2 to formate in aqueous media, in conjunction with high selectivity (approximately 98 %) and a good turnover number (>2000 with respect to the loaded Ru complex). These represent the highest values yet reported for a powder-based photocatalytic system during CO2 reduction under visible light in an aqueous environment. We also assessed the desorption of RuRu' from the Ag/C3 N4 surface, a factor that can contribute to a loss of activity. It was determined that desorption is not induced by salt additives, pH changes, or photoirradiation, which partly explains the high photocatalytic performance of this material.

Modification of Wide-Band-Gap Oxide Semiconductors with Cobalt Hydroxide Nanoclusters for Visible-Light Water Oxidation.

Cobalt-based compounds, such as cobalt(II) hydroxide, are known to be good catalysts for water oxidation. Herein, we report that such cobalt species can also activate wide-band-gap semiconductors towards visible-light water oxidation. Rutile TiO2 powder, a well-known wide-band-gap semiconductor, was capable of harvesting visible light with wavelengths of up to 850 nm, and thus catalyzed water oxidation to produce molecular oxygen, when decorated with cobalt(II) hydroxide nanoclusters. To the best of our knowledge, this system constitutes the first example that a particulate photocatalytic material that is capable of water oxidation upon excitation by visible light can also operate at such long wavelengths, even when it is based on earth-abundant elements only.

Intercalation of highly dispersed metal nanoclusters into a layered metal oxide for photocatalytic overall water splitting.

Metal nanoclusters (involving metals such as platinum) with a diameter smaller than 1 nm were deposited on the interlayer nanospace of KCa2 Nb3 O10 using the electrostatic attraction between a cationic metal complex (e.g., [Pt(NH3 )4 ]Cl2 ) and a negatively charged two-dimensional Ca2 Nb3 O10 (-) sheet, without the aid of any additional reagent. The material obtained possessed eight-fold greater photocatalytic activity for water splitting into H2 and O2 under band-gap irradiation than the previously reported analog using a RuO2 promoter. This study highlighted the superior functionality of Pt nanoclusters with diameters smaller than 1 nm for photocatalytic overall water splitting. This material shows the greatest efficiency among nanosheet-based photocatalysts reported to date.

PdPt/SrTiO3:Al-catalysed redox-selective photoreduction of unsaturated carboxylic acids using minimal electron-donor and water.

We developed a semiconductor photocatalyst, Pd-Pt alloy nanoparticle-loaded, Al-doped SrTiO3 (PdPt/STO:Al), for photoreduction of unsaturated carboxylic acids. Due to the cooperative STO:Al surface and Pd-Pt alloy nanoparticles, the catalyst dispersed in water provided highly redox-selective photoreduction against oxidative degradation of starting materials/products and against reductive evolution of H2, where minimal glycolic acid worked as an efficient electron-donating fuel.

Photocatalyst releasing hydrogen from water.

Direct splitting of water using a particulate photocatalyst would be a good way to produce clean and recyclable hydrogen on a large scale, and in the past 30 years various photocatalysts have been found that function under visible light. Here we describe an advance in the catalysis of the overall splitting of water under visible light: the new catalyst is a solid solution of gallium and zinc nitrogen oxide, (Ga(1-x)Zn(x))(N(1-x)O(x)), modified with nanoparticles of a mixed oxide of rhodium and chromium. The mixture functions as a promising and efficient photocatalyst in promoting the evolution of hydrogen gas.

Efficient nonsacrificial water splitting through two-step photoexcitation by visible light using a modified oxynitride as a hydrogen evolution photocatalyst.

A two-step photocatalytic water splitting (Z-scheme) system consisting of a modified ZrO(2)/TaON species (H(2) evolution photocatalyst), an O(2) evolution photocatalyst, and a reversible donor/acceptor pair (i.e., redox mediator) was investigated. Among the O(2) evolution photocatalysts and redox mediators examined, Pt-loaded WO(3) (Pt/WO(3)) and the IO(3)(-)/I(-) pair were respectively found to be the most active components. Combining these two components with Pt-loaded ZrO(2)/TaON achieved stoichiometric water splitting into H(2) and O(2) under visible light, achieving an apparent quantum yield of 6.3% under irradiation by 420.5 nm monochromatic light under optimal conditions, 6 times greater than the yield achieved using a TaON analogue. To the best of our knowledge, this is the highest reported value to date for a nonsacrificial visible-light-driven water splitting system. The high activity of this system is due to the efficient reaction of electron donors (I(-) ions) and acceptors (IO(3)(-) ions) on the Pt/ZrO(2)/TaON and Pt/WO(3) photocatalysts, respectively, which suppresses undesirable reverse reactions involving the redox couple that would otherwise occur on the photocatalysts. Photoluminescence and photoelectrochemical measurements indicated that the high activity of this Z-scheme system results from the moderated n-type semiconducting character of ZrO(2)/TaON, which results in a lower probability of undesirable electron-hole recombination in ZrO(2)/TaON than in TaON.

Preparation of core-shell-structured nanoparticles (with a noble-metal or metal oxide core and a chromia shell) and their application in water splitting by means of visible light.

Core-shell-structured nanoparticles, consisting of a noble metal or metal oxide core and a chromia (Cr(2)O(3)) shell, were studied as promoters for photocatalytic water splitting under visible light. Core nanoparticles were loaded by impregnation, adsorption or photodeposition onto a solid solution of gallium nitride and zinc oxide (abbreviated GaN:ZnO), which is a particulate semiconductor photocatalyst with a band gap of approximately 2.7 eV, and a Cr(2)O(3) shell was formed by photodeposition using a K(2)CrO(4) precursor. Photodeposition of Cr(2)O(3) on GaN:ZnO modified with a noble metal (Rh, Pd and Pt) or metal oxide (NiO(x), RuO(2) and Rh(2)O(3)) co-catalyst resulted in enhanced photocatalytic activity for overall water splitting under visible light (lambda>400 nm). This enhancement in activity was primarily due to the suppression of undesirable reverse reactions (H(2)-O(2) recombination and/or O(2) photoreduction) and/or protection of the core component from chemical corrosion, depending on the core type. Among the core materials examined, Rh species exhibited relatively high performance for this application. The activity for visible-light water splitting on GaN:ZnO modified with an Rh/Cr(2)O(3) core-shell configuration was dependent on both the dispersion of Rh nanoparticles and the valence state. In addition, the morphology of the Cr(2)O(3) photodeposits was significantly affected by the valence state of Rh and the pH at which the photoreduction of K(2)CrO(4) was conducted. When a sufficient amount of K(2)CrO(4) was used as the precursor and the solution pH ranged from 3 to 7.5, Cr(2)O(3) was successfully formed with a constant shell thickness (approximately 2 nm) on metallic Rh nanoparticles, which resulted in an effective promoter for overall water splitting.

Modified Ta3N5 powder as a photocatalyst for O2 evolution in a two-step water splitting system with an iodate/iodide shuttle redox mediator under visible light.

Modification of tantalum nitride (Ta(3)N(5)), which has a band gap of 2.1 eV, with nanoparticulate iridium (Ir) and rutile titania (R-TiO(2)) achieved functionality as an O(2) evolution photocatalyst in a two-step water-splitting system with an IO(3)(-)/I(-) shuttle redox mediator under visible light (lambda > 420 nm) in combination with a Pt/ZrO(2)/TaON H(2) evolution photocatalyst. The loaded Ir nanoparticles acted as active sites to reduce IO(3)(-) to I(-), while the R-TiO(2) modifier suppressed the adsorption of I(-) on Ta(3)N(5), allowing Ta(3)N(5) to evolve O(2) in the two-step water-splitting system.

Photocatalytic overall water splitting on Pt nanocluster-intercalated, restacked KCa2Nb3O10 nanosheets: the promotional effect of co-existing ions.

Promotional effects of co-existing ions on overall water splitting into H2 and O2 have been studied in bulk-type semiconductor photocatalysts (e.g., TiO2), but such an effect remains unexplored in two-dimensional nanosheet photocatalysts. Here we examined the effect of co-existing ions on the photocatalytic water splitting activity of Pt nanocluster-intercalated KCa2Nb3O10 nanosheets. Interestingly, not only anions, as usually observed in bulk-type photocatalysts, but also cations had a significant influence on the photocatalytic performance. The rates of H2 and O2 evolution over Pt/KCa2Nb3O10 as well as the product stoichiometry were improved in the presence of NaI. I- ions were found to effectively suppress undesirable backward reactions, consistent with the previous work by Abe et al. (Chem. Phys. Lett., 2003, 371, 360-364). On the other hand, Na+ ions in the reaction solution were exchanged for K+ in the interlayer space of KCa2Nb3O10 during the water splitting reaction, which promoted interlayer hydration and consequently improved photocatalytic performance.

Synergistic Effect of Hydrochloric Acid and Phytic Acid Doping on Polyaniline-Coupled g-C3N4 Nanosheets for Photocatalytic Cr(VI) Reduction and Dye Degradation.

In this study, graphitic carbon nitride (g-C3N4) nanosheets (CNns) were modified using polyaniline (PANI) codoped with an inorganic (hydrochloric acid, HCl) and an organic (phytic acid, PA) acid. Our results revealed that these samples exhibited extended visible-light absorption and a three-dimensional (3D) hierarchical structure with a large specific surface area. They also inhibited photoluminescence emission, reduced electrical resistance, and provided abundant free radicals, resulting in high photocatalytic performance. The PANI/g-C3N4 sample demonstrated outstanding photocatalytic activity of a Cr(VI) removal capacity of 4.76 mg·min-1·gc-1, which is the best record for the reduction of a 100 ppm K2Cr2O7 solution. Moreover, g-C3N4 coupled with PANI monotonically doped with HCl or PA did not demonstrate increased activity, suggesting that the codoping of HCl and PA plays a significant role in enhancing the performance. The improved photocatalytic activity of PANI/g-C3N4 can be attributed to the interchain and intrachain doping of PA and HCl over PANI, respectively, to create a 3D connected network and synergistically increase the electrical conductivity. Therefore, new insights into g-C3N4 coupled with PANI and codoped by HCl and PA may have excellent potential for the design of g-C3N4-based compounds for efficient photocatalytic reactions.

Cobalt Oxide Nanoclusters on Rutile Titania as Bifunctional Units for Water Oxidation Catalysis and Visible Light Absorption: Understanding the Structure-Activity Relationship.

The structure of cobalt oxide (CoOx) nanoparticles dispersed on rutile TiO2 (R-TiO2) was characterized by X-ray diffraction, UV-vis-NIR diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray absorption fine-structure spectroscopy, and X-ray photoelectron spectroscopy. The CoOx nanoparticles were loaded onto R-TiO2 by an impregnation method from an aqueous solution containing Co(NO3)2·6H2O followed by heating in air. Modification of the R-TiO2 with 2.0 wt % Co followed by heating at 423 K for 1 h resulted in the highest photocatalytic activity with good reproducibility. Structural analyses revealed that the activity of this photocatalyst depended strongly on the generation of Co3O4 nanoclusters with an optimal distribution. These nanoclusters are thought to interact with the R-TiO2 surface, resulting in visible light absorption and active sites for water oxidation.

Effects of the SrTiO3 support on visible-light water oxidation with Co3O4 nanoparticles.

The photocatalytic activity of SrTiO3 modified with Co3O4 nanoparticles for water oxidation under visible light (λ > 480 nm) was investigated with respect to the physicochemical properties of the SrTiO3 support. SrTiO3 was synthesized by a polymerized complex method or a hydrothermal method, followed by calcination in air at different temperatures in order to obtain SrTiO3 particles having different sizes. Co3O4 nanoparticles, which provide both visible light absorption and water oxidation centers, were loaded on the as-prepared SrTiO3 by an impregnation method using Co(NO3)2 as the precursor, followed by heating at 423 K in air. Decreasing the SrTiO3 particle size (that is, improving the crystallinity) enhanced the photocatalytic activity by promoting the formation of Co3O4 nanoparticles that provided optimal light absorption and catalytic sites. However, Co3O4 aggregation occurred on overly large SrTiO3 particles, leading to a decrease in activity. This study demonstrates the possibility of tuning the photocatalytic activity of a Co3O4-loaded wide-gap semiconductor for visible light water oxidation through the appropriate selection of the support material.

Characterization of Rh-Cr mixed-oxide nanoparticles dispersed on (Ga(1-x)Zn(x))(N(1-x)Ox) as a cocatalyst for visible-light-driven overall water splitting.

The structure of Rh-Cr mixed-oxide (Rh(2)(-)(y)Cr(y)O(3)) nanoparticles dispersed on (Ga(1)(-)(x)Zn(x))(N(1)(-)(x)O(x)) is characterized by electron microscopy and X-ray spectroscopy. The Rh(2)(-)(y)Cr(y)O(3) nanoparticle is an efficient cocatalyst for photocatalytic overall water splitting on the (Ga(1)(-)(x)Zn(x))(N(1)(-)(x)O(x)) solid solution and is loaded onto the catalyst by impregnation from an aqueous solution containing Na(3)RhCl(6).2H(2)O and Cr(NO(3))(3).9H(2)O followed by calcination in air. Impregnation of the (Ga(1)(-)(x)Zn(x))(N(1)(-)(x)O(x)) with 1 wt % Rh and 1.5 wt % Cr followed by calcination at 623 K for 1 h provides the highest photocatalytic activity. Structural analyses reveal that the activity of this photocatalyst is strongly dependent on the generation of trivalent Rh-Cr mixed-oxide nanoparticles with optimal composition and distribution.