Photocatalytic water splitting on protonated form of layered perovskites K0.5La0.5Bi2M2O9 (M = Ta; Nb) by ion-exchange

Protonated layered perovskite oxides H_1.9K_0.3La_0.5Bi_0.1Ta₂O₇ (HKLBT) and H_1.6K_0.2La_0.3Bi_0.1Nb₂O_6.5 (HKLBN), which were prepared from K_0.5La_0.5Bi₂M₂O₉(M = Ta; Nb)(KLBT(N)) by H ion-exchange in 3M HCl solution, were found as good photocatalysts for water splitting under UV light irradiation. The characterization by XRD, ICP and TG revealed that HKLBT(N) retained layered structure of their parent materials KLBT(N) after HCl treatment. An amount of exfoliation of Bi during the protonated process caused the decrease of contribution of Bi 6p in conduction band (CB) and thus resulted in more negative CB potential. HKLBT(N) showed considerable higher photocatalytic activity for H₂ and/or O₂ evolution than KLBT(N) in the absence of sacrificial reagents, which was attributed to the higher position of conduction band and the layered structure after acid treatment. It was concluded that the interlayer modification via ion-exchange for layered K_0.5La_0.5Bi₂M₂O₉ (M = Ta; Nb) is a potential way to construct novel photocatalysts with high activity for water splitting.     

Band structure and photocatalytic activities for H2 production of ABi2Nb2O9 (A = Ca,Sr, Ba)

A new series of layered perovskite photocatalysts, ABi₂Nb₂O₉ (A = Ca, Sr, Ba), were synthesized by the conventional solid-state reaction method and characterized by X-ray diffraction (XRD) and UV-visible spectrometer. The results showed that the structure of ABi₂Nb₂O₉ (A = Ca, Sr) is orthorhombic, while that of BaBi₂Nb₂O₉ is tetragonal. The band gaps of CaBi₂Nb₂O₉, SrBi₂Nb₂O₉, and BaBi₂Nb₂O₉ were estimated to be 3.46, 3.43, and 3.30 eV, respectively. It was found from the electronic band structure study, using the density functional theory (DFT) with planewave basis, that the conduction bands of these photocatalysts mainly consist of Nb 4d + Bi 6p + O 2p orbitals and the valence bands are composed of hybridization with O 2p + Nb 4d + Bi 6s orbitals. The photocatalytic activities for water splitting were investigated under UV-light irradiation and indicated that these photocatalysts showed photocatalytic activity for H₂ and O₂ evolution from aqueous solutions containing sacrificial reagents (methanol and Ag⁺).     

Photocatalytic property of partially substituted Pt-intercalated layered perovskite, ASr2TaxNb3−xO10 (A=K, H; x=0, 1, 1.5, 2 and 3)

A series of layered perovskite photocatalysts, ASr₂Ta_xNb_3−xO₁₀ (A=K, H; x=0, 1, 1.5, 2 and 3), were synthesized by conventional solid-state reaction followed by an ion-exchange reaction. Pt was incorporated in the interlayer of HSr₂Ta_xNb_3−xO₁₀ by the stepwise intercalation reaction. The HSr₂Ta_xNb_3−xO₁₀ showed hydrogen production activity and the activities were greatly enhanced by Pt co-incorporating. The x value in HSr₂Ta_xNb_3−xO₁₀ had an important effect on the photocatalytic activity of the catalyst. When the x=1, the HSr₂TaNb₂O₁₀/Pt photocatalyst showed a photocatalytic activity of 208 cm³ g⁻¹ h⁻¹ hydrogen evolution rate in 10 vol% methanol solution under irradiation with wavelength more than 290 nm from a 100-W mercury lamp at 333 K. The HSr₂TaNb₂O₁₀/Pt photocatalyst exhibited much higher photocatalytic activity than the well-known TiO₂/Pt photocatalyst under the same conditions.     

Photocatalytic hydrogen production with nickel oxide intercalated K4Nb6O17 under visible light irradiation

Nickel oxide nanoclusters were intercalated to layered niobate, K₄Nb₆O₁₇, to improve the photocatalytic hydrogen production for water splitting under visible light irradiation. A K₄Nb₆O₁₇–SSRx (Ni/Nb ratio range of 0.8–5%) series of nickel oxide intercalated layered niobates was prepared by a two-step solid-state reaction and characterized by Extended X-ray Absorption Fine Structure (EXAFS), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Energy Dispersive Spectrometer (EDS), X-ray Photoelectron Spectroscopy (XPS) and Ultraviolet–visible spectroscopy (UV–vis). The photocatalytic reaction was carried out in a quartz reactor irradiated under a 500-W halogen lamp. The K₄Nb₆O₁₇–SSR0.2 catalyst exhibited a much higher photocatalytic activity for water splitting than unloaded K₄Nb₆O₁₇ catalyst and NiO_y/K₄Nb₆O₁₇ catalyst prepared by the conventional impregnation method. The high catalytic performance was attributed to the well dispersed nickel oxide nanoclusters intercalated into the bulk structure of K₄Nb₆O₁₇ catalyst and the lack of NiO particles on the external particle surface.     

Photocatalytic water splitting on Au/HTiNbO5 nanosheets

The layered potassium titanium niobate, KTiNbO₅, is known as a photocatalyst for hydrogen production from water splitting under UV light. Here we show that titanium niobate nanosheets with a slit like framework can be obtained by exfoliation of KTiNbO₅ followed by proton exchange. Gold nanoparticles were deposited on the titanium niobate nanosheets using deposition-precipitation (DP), photo-deposition (PD) and impregnation (IMP) method in order to improve photocatalytic hydrogen production from water splitting.     

Photocatalytic water splitting for hydrogen production on Au/KTiNbO5

Gold nanoparticles were deposited on potassium titanoniobate, KTiNbO₅ using deposition-precipitation (DP), conventional impregnation (IMP) and photodeposition method in order to improve photocatalytic hydrogen production from water splitting. The effect of synthesis pH value of a HAuCl₄ aqueous solution used in the DP process on the morphology of gold nanoparticles, optical property and photocatalytic activity of water splitting under UV light irradiation was investigated. These catalysts were characterized by powder X-ray diffraction patterns (XRD), inductively coupled plasma mass spectrometry (ICP-MS), UV–visible spectroscopy (UV–vis), and Transmission Electron Microscopy (TEM). The Au/KTiNbO₅ catalysts prepared by the DP method consisted of a good metal–semiconductor interface which allowed for a much higher efficient electron-hole separation. The 0.63 wt% Au/KTiNbO₅ catalyst prepared by the DP method at pH = 10 showed a uniform dispersion of gold nanoparticles with an average gold particle size of 4.2 nm and exhibited an ultra-high photocatalytic water splitting activity (3522 μmol g⁻¹ h⁻¹), about 47 times higher than that exhibited by the KTiNbO₅ photocatalyst.     

Synthesis and performance of layered perovskite-type H-ABi2Ta2O9 (A = Ca,Sr, Ba,K0.5La0.5) for photocatalytic water splitting

Novel photocatalysts, protonated layered perovskite oxides H-ABi₂Ta₂O₉ (A = Ca, Sr, Ba, K_0.5La_0.5) for overall water splitting were synthesized by ion exchange with acid treating. The characterization by XRD, HRTEM indicated that all of ABi₂Ta₂O₉ (A = Ca, Sr, Ba, K_0.5La_0.5) were able to form new single-phase protonated layered oxides. The measurement of photocatalytic activity showed every protonated layered oxide could overall split water into H₂ and O₂, although the ratios of H₂ and O₂ are unstoichiometric. The sequence of photocatalytic H₂ production is HCBT(107.0 μmol/h) < HBBT(119.5 μmol/h) < HSBT(162.7 μmol/h) < HKLBT(189.3 μmol/h). The difference of ionic radius of cations in interlayer influenced the band gaps, and resulted in the distinction of photocatalytic activity. Pt loading enhanced apparently the photocatalytic activity. Among all of photocatalysts in this study, 0.1 wt%Pt/HSBT showed the highest photocatalytic activity for H₂ evolution, reaching 491 μmol/h.     

Photocatalytic activities of HLaNb2O7 prepared by polymerized complex method

HLaNb₂O₇ photocatalyst was prepared by the proton exchange reaction of KLaNb₂O₇ with diluted acid. The layered perovskite KLaNb₂O₇ has been successfully synthesized by the polymerized complex method. The product was characterized by X-ray diffraction, ultraviolet–visible spectra, scan electron microscope, TG–DSC, specific surface area, and FTIR. The layered perovskite KLaNb₂O₇ was formed at a lower calcination temperature (1000 °C, 6 h) by the polymerized complex method than a solid-state reaction method (1150 °C, 24 h). Photocatalytic decomposition of water to produce hydrogen under UV irradiation with methanol as electron donor was studied over layered perovskite HLaNb₂O₇ photocatalysts. The HLaNb₂O₇ photocatalyst prepared by the polymerized complex method showed much higher activity than that prepared by conventional solid-state reaction method.     

Cation ordering in the layered Li1+x(Ni0.425Mn0.425Co0.15)1 − xO2 materials (x = 0 and 0.12)

The layered Li_1+x(Ni_0.425Mn_0.425Co_0.15)_1 − xO₂ (x = 0 and 0.12) materials were prepared by a coprecipitation method. Their structure was investigated using the combination of X-ray and electron diffraction experiments. For both materials (x = 0 and 0.12), the electron diffraction patterns revealed an in-plane √3a_hex. × √3a_hex. superstructure in agreement with the ordering of the Li⁺, Ni²⁺, Ni³⁺, Mn⁴⁺ and Co³⁺ ions in the transition metal layers. The stoichiometry of these materials was not in agreement with an ideal ordering: the possible presence of point defects or of a domain microstructure was thus discussed. Electron diffraction also revealed that these ordered layers were slightly correlated along the c_hex. axis for both materials.     

Photocatalytic water splitting with In-doped H2LaNb2O7 composite oxide semiconductors

The In-doped HLaNb₂O₇ oxide semiconductors synthesized by solid-state reaction followed by an ion-exchange reaction were found to be a novel composite photocatalyst system with enhanced activity for water splitting. Pt was incorporated in the interlayer of In-doped HLaNb₂O₇ by the stepwise intercalation reaction. The In-doped HLaNb₂O₇ powder samples were characterized with X-ray diffraction (XRD) and UV-vis diffuse reflectance spectrometry. The photocatalytic activities of Pt-loaded In-doped HLaNb₂O₇ and individual precursor materials were evaluated by H₂ evolution from aqueous CH₃OH solution under UV light irradiation. It was found that the composite In-doped HLaNb₂O₇ showed a higher H₂ evolution rate in comparison with individual materials. The hydrogen production activity of In-doped HLaNb₂O₇ was greatly enhanced by Pt co-incorporation. The In content in the In-doped HLaNb₂O₇ system was discussed in relation to the photophysical and photocatalytic properties. As In content equal 5 mol%, the HLaNb₂O₇:In/Pt showed a photocatalytic activity of 354 cm³ g⁻¹ hydrogen evolution in 10 vol% methanol solution under irradiation from a 100 W mercury lamp at 333 K for 3 h.     

Photocatalytic activities of Sr2Ta2O7 nanosheets synthesized by a hydrothermal method

Sr₂Ta₂O₇ nanosheets have been synthesized by a hydrothermal method without using any template. The thickness, widths, and lengths of Sr₂Ta₂O₇ nanosheets are about 10–50 nm, 50–150 nm, and 500 nm, respectively. The optimum conditions for the formation of the nanosheets are maintaining the reactants at 260 °C for 7 days. On basis of the experimental data, a possible formation mechanism of the nanosheets under the hydrothermal conditions was proposed. The photocatalytic activity for water splitting was investigated under ultraviolet irradiation. It has been found that Sr₂Ta₂O₇ nanosheets, compared to the bulk Sr₂Ta₂O₇ sample, showed a higher photocatalytic activity even in the absence of a cocatalyst. The higher activity of the hydrothermally synthesized sample is attributed to its larger surface areas and nanoscale structure.     

Photocatalytic hydrogen production by water splitting over Au/Al-SrTiO3

Visible light water splitting activity of Au-Al/SrTiO₃ was tested in this work. Al/SrTiO₃ was synthesized via solid state reaction while Au loading was done with homogenous deposition precipitation method. The effects of Au loading and Al doping were investigated in 10, 20 and 30% aqueous solutions of methanol, ethanol, and isopropyl alcohol. The methanol was performed better over 0.25%Au-1.0%Al/SrTiO₃ at 20% alcohol concentration while the isopropyl alcohol resulted in better performance over the same catalyst at 30% concentration; the latter was also the best result obtained in this work with the hydrogen evolution rate of 347 μmol/h.gcat. Ethanol showed lower performance than other two alcohols. It was found from UV–vis analysis that Al doping increased the band energy of SrTiO₃. XRD and XPS analyses clearly showed that the dominant structure was SrTiO₃ in all samples. Au was found to be generally loaded as 30–40 nm particles by SEM.     

Photocatalytic hydrogen generation through water splitting on nano-crystalline LaFeO3 perovskite

Visible light active ABO₃ type photocatalyst with LaFeO₃ composition was synthesized by sol-gel method. The photocatalyst was characterized by different techniques such as X-ray diffraction, BET surface area analysis, particle size analysis, scanning electron microscopy, UV–visible diffuse reflectance spectroscopy (UV–Visible DRS), and photoluminescence spectroscopy. LaFeO₃ photocatalyst exhibited an optical band gap of 2.07 eV with the absorption spectrum predominantly in visible region of the spectrum. The BET surface area of photocatalyst LaFeO₃ was observed as 9.5 m²/g, with the crystallite size of 38.8 nm as calculated by the Debye-Scherer equation. The photocatalytic activity of LaFeO₃ was investigated for hydrogen generation through sacrificial donor assisted photocatalytic water splitting reaction by varying conditions in feasible parametric changes using visible light source, ethanol as a sacrificial donor and Pt solution of H₂PtCl₆ as a co-catalyst. The rate of photocatalytic hydrogen evolution was observed to be 3315 μmol g⁻¹ h⁻¹ under optimized conditions and using 1 mg dose of photocatalyst with reaction time of 4 h and illumination of 400 W.     

Crystalline phase-dependent photocatalytic water splitting for hydrogen generation on KNbO3 submicro-crystals

Potassium niobate (KNbO₃) submicro-crystals with cubic and orthorhombic phases were hydrothermally prepared and characterized by powder X-ray diffraction, micro-Raman spectroscopy, Fourier transform infrared spectroscopy, nitrogen adsorption–desorption, diffuse reflectance UV–visible spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The photocatalytic performance of the as-prepared KNbO₃ samples was evaluated toward H₂ generation from an aqueous methanol solution under UV. The surface area-normalized rate of H₂ production over submicro-cubes with cubic phase is two times larger than that of submicro-rods with orthorhombic phase. In addition, both cubic and orthorhombic KNbO₃ submicro-crystals showed much higher reactivity than commercial KNbO₃ bulk-like powders. The underlying mechanism was discussed in terms of crystal structure and electronic structure. The results from this study are potentially applicable to a range of perovskites useful in water splitting as well as other areas of heterogeneous photocatalysis.     

Photophysical and photocatalytic water splitting performance of stibiotantalite type-structure compounds,SbMO4 (M = Nb,Ta)

Metal oxides with ferroelectric properties are considered to be a new family of efficient photocatalysts. Here, we investigate stibiotantalite type-structure compounds, SbMO₄ (M = Nb, Ta), with layered crystal structures, and ferroelectric properties as photocatalysts for hydrogen generation from the splitting of pure water. Both compounds were prepared by a conventional solid-state reaction method, and their optical properties, electronic band structure, and photocatalytic water splitting performance were characterized and evaluated. Diffuse reflectance analysis showed that both compounds have moderate band gaps of 3.7 eV for SbTaO₄ and 3.1 eV for SbNbO₄ (cf. 3.0 eV for TiO₂). Mott–Schottky analysis reveals that their conduction-band edge potentials are higher than the water reduction (hydrogen evolution) potential (0 V vs. RHE), indicating both compounds can generate hydrogen from water splitting. The photocatalytic water splitting performance was conducted by using pure water and UV-light irradiation, and photocatalytic H₂ production was confirmed for both compounds. After loading RuO₂ cocatalyst, the rates of hydrogen evolution of SbNbO₄ and SbTaO₄ were 24 μmol/g h and 58 μmol/g h, respectively. It was concluded that both compounds can be used as photocatalysts for water splitting under UV irradiation. The photocatalytic activity difference in both compounds was discussed with regard to electronic band structure and dipole moment difference, resulting from their crystal structures.     

Photocatalytic H2 production from water splitting under visible light irradiation using Eosin Y-sensitized mesoporous-assembled Pt/TiO2 nanocrystal photocatalyst

Sensitized photocatalytic production of hydrogen from water splitting is investigated under visible light irradiation over mesoporous-assembled titanium dioxide (TiO₂) nanocrystal photocatalysts, without and with Pt loading. The photocatalysts are synthesized by a sol–gel process with the aid of a structure-directing surfactant and are characterized by N₂ adsorption–desorption analysis, X-ray diffraction, UV–vis spectroscopy, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray analysis. The dependence of hydrogen production on the type of TiO₂ photocatalyst (synthesized mesoporous-assembled and commercial non-mesoporous-assembled TiO₂ without and with Pt loading), the calcination temperature of the synthesized photocatalyst, the sensitizer (Eosin Y) concentration, the electron donor (diethanolamine) concentration, the photocatalyst dosage and the initial solution pH is systematically studied. The results show that in the presence of the Eosin Y sensitizer, the Pt-loaded mesoporous-assembled TiO₂ synthesized by a single-step sol–gel process and calcined at 500 °C exhibits the highest photocatalytic activity for hydrogen production from a 30 vol.% diethanolamine aqueous solution with dissolved 2 mM Eosin Y. Moreover, the optimum photocatalyst dosage and initial solution pH for the maximum photocatalytic activity for hydrogen production are 3.33 g dm⁻³ and 11.5, respectively.     

Efficient photoelectrochemical water splitting of CaBi6O10 decorated with Cu2O and NiOOH for improved photogenerated carriers

Broadening the light absorption and accelerating the separation of photogenerated electron-hole pairs is of crucial importance for strongly enhancing the photoelectrochemical (PEC) water splitting performances of photoelectrode. In this paper, a novel CaBi₆O₁₀/Cu₂O/NiOOH photoanode for photoelectrochemical water splitting is prepared, where, the NiOOH acts as water oxidation catalyst to accelerate water oxidation taking place in the interfaces between electrode and electrolyte, Cu₂O is chosen to extend the absorption range of the light absorber, enhancing an efficient separation and transfer of the electron-hole pairs. This triple CaBi₆O₁₀/Cu₂O/NiOOH photoanode negatively shifts the onset potential and exhibits an improved photocurrent density 1.89 mA·cm^?2 at 1.23 V vs RHE, which is 1.4 and 4.8 times higher compared to CaBi₆O₁₀/Cu₂O and CaBi₆O₁₀, respectively. More importantly, the CaBi₆O₁₀/Cu₂O/NiOOH electrode shows excellent photoelectrochemical stability in comparison with CaBi₆O₁₀/Cu₂O after 2 h irradiation. The amazing photoelectrochemical performance is due to the broader light absorption spectrum, the improved photogenerated carriers separation, transfer and consumption. The research results demonstrate a promising ternary semiconductor structure, which can improve photoelectrochemical performance effectively. Moreover, these results also imply that the CaBi₆O₁₀/Cu₂O/NiOOH heterojunction structure has a great potential application for photoelectrochemical water splitting systems.     

Photocatalytic water splitting of surfactant-free fabricated high surface area NaTaO3 nanocrystals

Uniform NaTaO₃ ca. 15 nm and ca. 70 nm nanocrystals were synthesized via a novel surfactant-free solvothermal reaction. The acidic alkoxide hydrolyzation leads to small size and high surface area particles. The different size of the nanocrystals was controlled by altering concentration. The alkoxide-based synthetic route leads to small particle size and high surface area, which improved the charge separation and migration of photogenerated carriers and benefited the surface chemical reaction of catalysts. As a result, the high total yield of photocatalytic water splitting hydrogen generation was obtained, which was as high as 3.106 mmol h⁻¹ g⁻¹.     

Thermochemical two-step water splitting cycles by monoclinic ZrO2-supported NiFe2O4 and Fe3O4 powders and ceramic foam devices

A thermochemical two-step water splitting cycle is examined for NiFe₂O₄ and Fe₃O₄ supported on monoclinic ZrO₂ (NiFe₂O₄/m-ZrO₂ and Fe₃O₄/m-ZrO₂) in order to produce hydrogen from water at a high-temperature. The evolution of oxygen and hydrogen by m-ZrO₂-supported ferrite powders was studied, and reproducible and stoichiometric oxygen/hydrogen productions were demonstrated through a repeatable two-step reaction. Subsequently, a ceramic foam device coated with NiFe₂O₄/m-ZrO₂ powder was made and examined as a water splitting device by the direct irradiation of concentrated Xe-light in order to simulate solar radiation. The reaction mechanism of the two-step water splitting cycle is associated with the redox transition of ferrite/wustite on the surface of m-ZrO₂. A hydrogen/oxygen ratio for these redox powder systems exhibited good reproducibility of approximately two throughout the repeated cycles. The foam device loaded NiFe₂O₄/m-ZrO₂ powder was also successful with respect to hydrogen production through 10 repeated cycles. A ferrite conversion of 24-76% was obtained over an irradiation period of 30 min.     

GdBaCo2O5+x layered perovskite as an intermediate temperature solid oxide fuel cell cathode

GdBaCo₂O_5+x (GBCO) was evaluated as a cathode for intermediate-temperature solid oxide fuel cells. A porous layer of GBCO was deposited on an anode-supported fuel cell consisting of a 15 μm thick electrolyte of yttria-stabilized zirconia (YSZ) prepared by dense screen-printing and a Ni–YSZ cermet as an anode (Ni–YSZ/YSZ/GBCO). Values of power density of 150 mW cm⁻² at 700 °C and ca. 250 mW cm⁻² at 800 °C are reported for this standard configuration using 5% of H₂ in nitrogen as fuel. An intermediate porous layer of YSZ was introduced between the electrolyte and the cathode improving the performance of the cell. Values for power density of 300 mW cm⁻² at 700 °C and ca. 500 mW cm⁻² at 800 °C in this configuration were achieved.