Photocatalytic hydrogen evolution under visible light irradiation by the polyoxometalate α-[AlSiW11(H2O)O39] -Eosin Y system

It is important to construct a stable and efficient dye sensitization system for visible-light photocatalytic hydrogen evolution. Eosin Y (EY)-sensitized α-[AlSiW₁₁(H₂O)O₃₉]⁵⁻ (AlSiW₁₁) (an Al³⁺ substituted Keggin polyoxometalate (POM)) for the hydrogen evolution under visible light irradiation (λ > 420 nm) has been carried out in the presence of triethanolamine as electron donor and Pt as co-catalyst. EY can coordinate with AlSiW₁₁. The coordination association between AlSiW₁₁ and EY is beneficial to the charge transfer from EY to AlSiW₁₁ and to stability of EY. The system displays efficient and stable photocatalytic hydrogen evolution. The average apparent quantum efficiency and turnover number of EY during 20 h irradiation (λ > 420 nm) are 10.3% and 473, respectively. The highest quantum efficiency amounts to 28.0% under 520 nm monochromatic light irradiation. The present study highlights linking between dye and POM molecule as a way to develop new visible-light stable photocatalyst or system.     

Significant improvement of photocatalytic hydrogen generation rate over TiO2 with deposited CuO

TiO₂ photocatalyst with deposited CuO (CuO-TiO₂) was synthesized by the impregnation method using P25 (Degussa) as support, and exhibited high photocatalytic hydrogen generation activity from methanol/water solution. A substantial hydrogen evolution rate of 10.2 ml min⁻¹ (18,500 μmol h⁻¹ g⁻¹_catalyst) was observed over this efficient CuO-TiO₂ with optimal Cu content of 9.1 mol% from an aqueous solution containing 10 vol% methanol; this improved hydrogen generation rate is significantly higher than the reported Cu-containing TiO₂, including some Pt and Pd loaded TiO₂. Optimal Cu content of 9.1 mol% provided maximum active sites and allowed good light penetration in TiO₂. Over this efficient CuO-TiO₂, the hydrogen generation rate was accelerated by increasing the methanol concentration according to Freundlich adsorption isotherm. However, the photocatalytic hydrogen generation rate was suppressed under long time irradiation mainly due to accumulation of by-products, reduction of CuO and copper leaching, which requires further investigation.     

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.     

CuCr2O4/TiO2 heterojunction for photocatalytic H2 evolution under simulated sunlight irradiation

CuCr₂O₄/TiO₂ heterojunction has been successfully synthesized via a facile citric acid (CA)-assisted sol-gel method. Techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectrum (UV-vis DRS) have been employed to characterize the as-synthesized nanocomposites. Furthermore, photocatalytic activities of the as-obtained nanocomposites have been evaluated based on the H₂ evolution from oxalic acid solution under simulated sunlight irradiation. Factors such as CuCr₂O₄ to TiO₂ molar ratio in the composites, calcination temperature, photocatalyst mass concentration, and initial oxalic acid concentration affecting the photocatalytic hydrogen producing have been studied in detail. The results showed that the nanocomposite of CuCr₂O₄/TiO₂ is more efficient than their single part of CuCr₂O₄ or TiO₂ in producing hydrogen. The optimized composition of the nanocomposites has been found to be CuCr₂O₄·0.7TiO₂. And the optimized calcination temperature and photocatalyst mass concentration are 500 °C and 0.8 g l⁻¹, respectively. The influence of initial oxalic acid concentration is consistent with the Langmuir model.     

Photocatalytic activity of N, S co-doped and N-doped commercial anatase TiO2 powders towards phenol oxidation and E. coli inactivation under simulated solar light irradiation

Nitrogen and sulfur co-doped and N-doped TiO₂ anatase TKP 102 (Tayca) were prepared by manual grinding with thiourea and urea, respectively, and annealing at 400 °C. Both materials showed visible-light absorption as measured by Diffuse Reflectance Spectroscopy (DRS). Interstitial N-doping, anionic and cationic S-doping was found when the TiO₂ was doped with thiourea while TiO₂ doped with urea showed only the presence of interstitial N-doping as measured by X-ray Photo-electron Spectroscopy (XPS). The N content on the surface of N-doped TKP 102 photocatalyst was 2.85 at.% and higher than the N content in the N, S co-doped TiO₂ photocatalyst (0.6 at.%).The photocatalytic activity of the doped catalysts was tested using phenol and Escherichia coli as chemical and biological targets, respectively, using N, S co-doped, N-doped TiO₂, undoped Degussa P-25 and undoped TKP 102 powders under simulated solar light. It was found that undoped Degussa P-25 was the photocatalyst with the highest photocatalytic activity towards phenol oxidation and E. coli inactivation. N, S co-doped powders showed almost the same photocatalytic activity as undoped TKP 102 while N-doped TKP 102 was the less active photocatalyst probably due the N impurities on the TiO₂ acting as recombination centers.     

Visible light induced hydrogen evolution on new hetero-system ZnFe2O4/SrTiO3

The physical properties and photoelectrochemical characterization of the spinel ZnFe₂O₄, elaborated by chemical route, have been investigated for the hydrogen production under visible light. The forbidden band is found to be 1.92 eV and the transition is indirectly allowed. The electrical conduction occurs by small polaron hopping with activation energy of 0.20 eV. p-type conductivity is evidenced from positive thermopower and cathodic photocurrent. The flat band potential (0.18 V_SCE) determined from the capacitance measurements is suitably positioned with respect to H₂O/H₂ level (−0.85 V_SCE). Hence, ZnFe₂O₄ is found to be an efficient photocatalyst for hydrogen generation under visible light. The photoactivity increases significantly when the spinel is combined with a wide band gap semiconductor. The best performance with a hydrogen rate evolution of 9.2 cm³ h⁻¹ (mg catalyst)⁻¹ occurs over the new hetero-system ZnFe₂O₄/SrTiO₃ in Na₂S₂O₃ (0.025 M) solution.     

Hydrothermally stabilized Fe(III) doped titania active under visible light for water splitting reaction

Fe³⁺ doped TiO₂ photocatalysts were prepared by hydrothermal treatment for the photocatalytic water splitting to produce stoichiometric hydrogen and oxygen under visible light irradiation. It was found that hydrothermal treatment at 110 °C for 10 h was essential for the synthesis of highly stabilized Fe³⁺ doped TiO₂ photocatalysts. The synthesized photocatalysts were characterized by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS) and BET surface area techniques. The doping of highly stabilized Fe³⁺ in the titania matrix leads to significant red shift of optical response towards visible light owing to the reduced band gap energy. Optimum amount of Fe³⁺ doped TiO₂, 1.0 wt% Fe/TiO₂, showed drastically improved hydrogen production performance of 12.5 μmol-H₂/h in aqueous methanol and 1.8 μmol-H₂/h in pure water, respectively. This Fe/TiO₂ photocatalyst was stable for 36 h without significant deactivation in the water splitting reaction.     

Visible-light-induced hydrogen production over Pt-Eosin Y catalysts with high surface area silica gel as matrix

A new system for the production of hydrogen, constructed using silica gel as a matrix, Eosin Y as a photosensitizer, and Pt as a cocatalyst, has been reported. It was found that the rate of photosensitized hydrogen evolution in the presence of silica gel is enhanced about 10-fold relative to the homogeneous phase, i.e. in the absence of silica gel. The pH value of the solution and the concentration of Eosin Y have remarkable effects on the rate of hydrogen evolution. The optimal pH and concentration of Eosin Y are 7 and 3.60 × 10⁻⁴ mol dm⁻³ (E/S = 1/3) to 7.24 × 10⁻⁴ mol dm⁻³ (E/S = 1/1), respectively. Triethanolamine (TEOA) as an electron donor, the rate of hydrogen evolution and the apparent quantum efficiency in the silica gel system under visible-light irradiation (λ ≥ 420 nm) can reach about 43 μmol h⁻¹ and 10.4%, respectively. In addition, the roles of silica gel, Pt and TEOA, respectively; and the probable mechanism of photosensitized hydrogen evolution have been discussed.     

Visible light photocatalytic water splitting for hydrogen production from N-TiO2 rice grain shaped electrospun nanostructures

We report on the visible light-driven hydrogen production from splitting of water molecules by nitrogen-doped TiO₂ (N-TiO₂) with a rice grain-like nanostructure morphology. The N-TiO₂ nanostructures are prepared using sol-gel and electrospinning methods followed by post-annealing of the composite nanofibers. The nanostructures are characterized by microscopy and spectroscopy. First order rate constants for the visible light-assisted photocatalysis in the degradation of methylene blue (MB) dye are found to be 0.2 × 10⁻³ and 1.8 × 10⁻³ min⁻¹ for TiO₂ and N-TiO₂ (5 wt% of nitrogen), respectively. The N-TiO₂ utilized in water splitting experiments and evaluated hydrogen (H₂) of 28 and 2 μmol/h for N-TiO₂ and TiO₂, respectively. The improvement may be attributed due to the N-doping and higher surface area as ∼70 m²/g.     

Efficient photocatalytic hydrogen generation by Pt modified TiO2 nanotubes fabricated by rapid breakdown anodization

Photo-assisted hydrogen generation studies of platinum loaded titanium (IV) oxide nanotubes suspended in ethanol–water mixture were carried out at room temperature. The TiO₂ nanotubes synthesized by rapid breakdown anodization technique were loaded with Pt nanoparticles by chemical reduction of aqueous chloroplatinic acid solution using sodium borohydride. The chemisorption (active) surface area of the synthesized nanocomposites for hydrogen was measured by pulse chemisorption method using temperature programmed desorption reduction oxidation equipment and found to decrease with increase in platinum loading in the range 1–10 wt%. The platinum supported nanotube composites were characterized for phase and morphology by XRD, TEM and SEM. The hydrogen generated by the photocatalytic reduction of water from water–ethanol mixture at different wavelengths of incident light, using the Pt-TiO₂ nanocomposite photocatalyst, was determined by using a proton exchange membrane based hydrogen meter. The highest hydrogen generation efficiency was observed at 1–2.5 wt% of Pt loading. The maximum photocatalytic hydrogen generation of 0.03 mol/h/g of Pt-TiO₂ was observed with a 64 W UV light source (λ = 254 nm). The photoluminescence property of the Pt loaded TiO₂ has been correlated with the hydrogen generation efficiency and the reaction mechanism briefly discussed.     

Fabrication and comparison of highly efficient Cu incorporated TiO2 photocatalyst for hydrogen generation from water

Efficient Cu incorporated TiO₂ (Cu–TiO₂) photocatalysts for hydrogen generation were fabricated by four methods: in situ sol–gel, wet impregnation, chemical reduction of Cu salt, and in situ photo-deposition. All prepared samples are characterized by good dispersion of Cu components, and excellent light absorption ability. Depending on the preparation process, hydrogen generation rates of the as-prepared Cu–TiO₂ were recorded in the range of 9–20 mmol h⁻¹ g_catalyst⁻¹, which were even more superior to some noble metal (Pt/Au) loaded TiO₂. The various fabrication methods led to different chemical states of Cu, as well as different distribution ratio of Cu between surface and bulk phases of the photocatalyst. Both factors have been proven to influence photocatalytic hydrogen generation. In addition, the Cu content in the photocatalyst played a significant role in hydrogen generation. Among the four photocatalysts, the sample that was synthesized by in situ sol–gel method exhibited the highest stability. High efficiency, low cost, good stability are some of the merits that underline the promising potential of Cu–TiO₂ in photocatalytic hydrogen generation.     

Dye-sensitized cobalt catalysts for high efficient visible light hydrogen evolution

In this work, high efficient non-noble metal cobalt cocatalysts implanted on the surface of graphene (G) by one-step photoreduction and in-situ chemical deposition methods for hydrogen evolution were reported. XRD and TEM characterizations showed that the Co and CoS_x nanoparticles were deposited on the graphene surface as Co/G and CoS_x/G composites. CoS_x/G and Co/G nanohybrids exhibited high photocatalytic activities for hydrogen evolution sensitized by Eosin Y (EY). The amounts of H₂ evolution reached 708.5 and 675.5 μmol over the EY-sensitized CoS_x/G and Co/G nanohybrids irradiated under visible light with wavelength longer than 420 nm in 3 h respectively. The apparent quantum efficiency (AQE) of 8.71% over EY-Co/G was accomplished under 520 nm illumination. The fluorescence results indicated that the lifetime of excited electron was remarkably increased. Graphene might promote the photogenerated electrons transfer from excited dye to the hydrogen evolution active sites such as Co or CoS_x, and consequently enhance photocatalytic hydrogen evolution efficiency.     

Visible light induced dye-sensitized photocatalytic hydrogen production over platinized TiO2 derived from decomposition of platinum complex precursor

Pt/TiO₂ derived from complete decomposition of the surface-anchored Pt(dcbpy)Cl₂ (dcbpy = 4,4′-dicarboxy-2,2′-bipyridine) precursor (denoted as C-Pt/TiO₂) was prepared to serve as photocatalyst in visible light region. For dye-sensitized hydrogen production experiments, the photocatalyst was sensitized by Ru(2,2′-bipyridine-4,4′-dicarboxylic)₂(NCS)₂ (the N3 dye) and Ru(2,2′bipyridyl-4,4′-dicarboxylic) (4,4′- dinonyl-2,2′bipyridine) (NCS)₂ (the Z907 dye) to induce hydrogen evolution in the presence of sacrificial electron donor, triethanolamine (TEA). The hydrogen generation results showed that C-Pt/TiO₂ was found to be a much more active photocatalyst when compared to P-Pt/TiO₂, prepared by conventional method of photochemical deposition of H₂PtCl₆ (denoted as P-Pt/TiO₂). For further investigation, the photodegradation experiments in visible region were also confirmed the better photocatalytic activity of C-Pt/TiO₂. The enhanced catalytic activity is due to efficient interparticle electron transfer with the small-size and high-disperse platinum particles generated from photodeposition of Pt(dcbpy)Cl₂, which was verified by the transmission electron microscopy (TEM) measurement.     

Sonochemistry synthesis of Bi2S3/CdS heterostructure with enhanced performance for photocatalytic hydrogen evolution

Photocatalytic hydrogen evolution from water splitting is an efficient, eco-friendly method for the conversion of solar energy to chemical energy. A great number of photocatalysts have been reported but only a few of them can respond to visible-light. Metal sulfides, a class of visible-light response semiconductor photocatalysts for hydrogen evolution and organic pollutant degradation, receive a lot of attention due to their narrow band gaps. Herein, we report the sonochemical synthesis of Bi₂S₃/CdS nanocrystal composites with microsphere structure at mild temperature. The phases of Bi₂S₃ and CdS can be observed obviously in HRTEM image. The heterostructure consisting of the two species of nanocrystals plays a key role in separating photo-generated charge carriers. Photocatalytic activities for water splitting are investigated under visible-light irradiation (λ > 400 nm) and an enhanced photocatalytic activity is achieved. The initial rate of H₂ evolution is up to 5.5 mmol h⁻¹ g⁻¹ without resorting to any cocatalysts.     

Landfill leachate treatment by solar-driven AOPs

Sanitary landfill leachate resulting from the rainwater percolation through the landfill layers and waste material decomposition is a complex mixture of high-strength organic and inorganic compounds which constitutes serious environmental problems. In this study, different heterogeneous (TiO₂/UV, TiO₂/H₂O₂/UV) and homogenous (H₂O₂/UV, Fe²⁺/H₂O₂/UV) photocatalytic processes were investigated as an alternative for the treatment of a mature landfill leachate. The addition of H₂O₂ to TiO₂/UV system increased the reduction of the aromatic compounds from 15% to 61%, although mineralization was almost the same. The DOC and aromatic content abatement is similar for the H₂O₂/UV and TiO₂/H₂O₂/UV processes, although the H₂O₂ consumption is three times higher in the H₂O₂/UV system. The low efficiency of TiO₂/H₂O₂/UV system is presumably due to the alkaline leachate solution, for which the H₂O₂ becomes highly unstable and self-decomposition of H₂O₂ occurs. The efficiency of the TiO₂/H₂O₂/UV system increased 10 times after a preliminary pH correction to 4. The photo-Fenton process is much more efficient than heterogeneous (TiO₂, TiO₂/H₂O₂/UV) or homogeneous (H₂O₂/UV) photocatalysis, showing an initial reaction rate more than 20 times higher, and leading to almost complete mineralization of the wastewater. However, when compared with TiO₂/H₂O₂/UV with acidification, the photo-Fenton reaction is only two times faster.The optimal initial iron dose for the photo-Fenton treatment of the leachate is 60 mg Fe²⁺ L⁻¹, which is in agreement with path length of 5 cm in the photoreactor. The kinetic behaviour of the process (60 mg Fe²⁺ L⁻¹) comprises a slow initial reaction, followed by a first-order kinetics (k = 0.020 , r₀ = 12.5 mg ), with H₂O₂ consumption rate of k_H2O2 = 3.0 mmol H₂O₂, and finally, the third reaction period, characterized by a lower DOC degradation and H₂O₂ consumption until the end of the experiment, presumably due to the formation of low-molecular-weight carboxylic groups. A total of 306 mM of H₂O₂ was consumed for achieving 86% mineralization (DOC_final = 134 mg L⁻¹) and 94% aromatic content reduction after 110 kJ_UV L⁻¹, using an initial iron concentration of 60 mg Fe²⁺ L⁻¹.     

Photocatalytic overall water splitting with dual-bed system under visible light irradiation

Photocatalytic overall water splitting has been demonstrated with WO₃ for oxygen producing photocatalyst (OPC), and Rh-doped SrTiO₃ for hydrogen producing photocatalyst (HPC) in a simulated dual-bed system under visible light irradiation (λ ≥ 400 nm). The Fe³⁺/Fe²⁺ redox couple was chosen as the most effective electron mediator between OPC and HPC. The overall performance of the dual-bed system was limited by the low activity of HPC, and thus the activity of HPC should be increased to improve the overall performance. For overall water splitting reaction in a dual-bed system, the conduction band of OPC must be more negative than the redox potential of the electron acceptors and the valence band of HPC must be more positive than the redox potential of the electron donors.     

Factorial design analysis for dye-sensitized hydrogen generation from water

A factorial design at two levels and four factors has been carried out in order to investigate the potential for hydrogen generation using Eosin Y-sensitized TiO₂/Pt catalyst under visible solar light in presence of triethanolamine (TEOA) as electron donor. The solution pH was found to be a significant parameter, and was maintained at pH 7.0 throughout the investigation. Visible light irradiation time (I-time) showed highest positive effect on hydrogen generation followed by initial Eosin Y concentration (for dye-sensitization) and the TEOA concentration while Pt content (wt %) in TiO₂ showed negative effect toward hydrogen generation. Experimental data were analyzed using both “Pareto analysis” as well as conventional regression analysis techniques. A regression function is proposed that satisfactorily predicts hydrogen generation.     

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.     

Ab initio study of electronic structures and absorption properties of pure and Fedoped anatase TiO2

Using the first-principles calculations, the band structure, total and partial density of states (DOS) and absorption properties of anatase TiO₂, Fe³⁺ doped TiO₂ and FeTiO₃ were calculated by a plane-wave pseudopotential method based on density functional theory (DFT). From the calculated results, the band gaps of anatase TiO₂, Fe³⁺ doped TiO₂ and FeTiO₃ are about 2.4, 0.32 and 0.28 eV, respectively. The states of the valence bands and conduction bands of undoped and Fe³⁺ doped TiO₂ with anatase structure were calculated. As shown in the absorption spectra, the FeTiO₃ has the strongest absorption and the Fe-TiO₂ has the weakest absorption. Effect of Fe³⁺ dopant on the absorption property of the anatase TiO₂ is explained in detail based on the calculations using the first-principles. The Fe³⁺ doped anatase TiO₂ could be a potential candidate for photocatalyst because of the absorption ability of visible light.