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.     

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.     

Iron doped nanostructured TiO2 for photoelectrochemical generation of hydrogen

This paper describes the photoelectrochemical studies on nanostructured iron doped titanium dioxide (TiO₂) thin films prepared by sol-gel spin coating method. Thin films were characterized by X-ray diffraction, Raman spectroscopy, spectral absorbance, atomic force microscopy and photoelectrochemical (PEC) measurements. XRD study shows that the films were polycrystalline with the photoactive anatase phase of TiO₂. Doping of Fe in TiO₂ resulted in a shift of absorption edge towards the visible region of solar spectrum. The observed bandgap energy decreased from 3.3 to 2.89 eV on increasing the doping concentration upto 0.2 at.% Fe. 0.2 at.% Fe doped TiO₂ exhibited the highest photocurrent density, ∼0.92 mA/cm² at zero external bias. Flatband potential and donor density determined from the Mott–Schottky plots were found to vary with doping concentration from −0.54 to −0.92 V/SCE and 1.7 × 10¹⁹ to 4.3 × 10¹⁹ cm⁻³, respectively.     

Mesoporous nanocomposite Fe/Al2O3-MCM-41: An efficient photocatalyst for hydrogen production under visible light

The iron incorporated mesoporous Al₂O₃-MCM-41 nanocomposites, synthesized by sol-gel and followed by wetness impregnation method, were found to be active photocatalysts for evolution of hydrogen energy from water in the presence of sacrificial agent under visible light illumination (λ ≥ 400 nm). The key factors for water splitting are appropriate band gap energy, small particle size, high surface area and mesoporosity nature. The DRUV-vis spectra measured the band gap energy where as the particle sizes of the materials were evaluated by TEM. Beside these, the materials were characterized by small angle XRD, N₂ adsorption-desorption, FTIR and XPS. Moreover, among mesoporous support and mesoporous nanocomposites, 5Fe/Al₂O₃-MCM-41 exhibited highest water splitting ability and produced 146 μmol/h hydrogen gas with apparent quantum efficiency 6.1%. The textural properties (high surface area, narrow pore size, large pore volume and mesoporosity), visible light active band gap energy 1.90 eV and small particle size (47.95 nm) collectively contribute for high hydrogen production ability of 5Fe/Al₂O₃-MCM-41.     

High photocatalytic hydrogen production from methanol aqueous solution using the photocatalysts CuS/TiO2

Photocatalysts CuS/TiO₂ for hydrogen production were synthesized by hydrothermal method at high temperature and characterized by XRD, UV–visible DRS, XPS, EDX, SEM and TEM. When TiO₂ was loaded with CuS, it showed photocatalytic activities for water decomposition to hydrogen in methanol aqueous solution under 500 W Xe lamp. Among the photocatalysts with various compositions, the one with 1 wt% CuS-loaded TiO₂ showed the maximum photocatalytic activity for water splitting, which indicated CuS could improve the separation ratio of photoexcited electrons and holes. What's more, the amounts of the produced hydrogen was about 570 μmol h⁻¹, which had exceeded pure titania (P25) 32 times. In the present paper, it is proven that CuS can act as an effective co-catalyst to enhance the photocatalytic H₂ production activity of TiO₂.     

Hierarchical Gd–La codoped TiO2 microspheres as robust photocatalysts

Robust Gd–La codoped TiO₂ microspheres with diameter of 2∼3 μm were successfully synthesized via a hydrothermal method using poly(ethylene glycol)-block–poly(propylene glycol)-block–poly(ethylene glycol) as a template. The photocatalytic activity of the Gd–La codoped TiO₂ microspheres evaluated by photodegrading methyl orange (MO) has been significantly enhanced compared to that of undoped TiO₂ microspheres. Ti⁴⁺ may substitute for La³⁺ and Gd³⁺ in the lattices of rare earth oxides to create abundant oxygen vacancies and surface defects for electron trapping and dye adsorption, accelerating the separation of photogenerated electron–hole pairs and MO photodegradation. The formation of an exciton energy level below the conduction band of TiO₂ from the binding of electrons and oxygen vacancies decreases the excitation energy of Gd–La codoped TiO₂ microspheres, resulting in robust photocatalysts. The results suggest that Gd–La codoped TiO₂ microspheres calcined at 350 °C are very promising for enhancing the photocatalytic activity of photocatalysts.     

Hydrogen evolution by photocatalytic decomposition of water under ultraviolet–visible irradiation over K2La2Ti3−xMxO10+δ perovskite

New layered transition metal substituted perovskite-type oxides K₂La₂Ti_3−xM_xO_10+δ (M = Fe, Ni, W; δ varies with different M) were synthesized with high-temperature solid state reaction, and characterized with X-ray diffraction (XRD) and ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS). The photocatalytic activity of these catalysts was studied under ultraviolet and visible light irradiation. The results indicated that substitution of a part of Ti⁴⁺ with Fe³⁺ and W⁶⁺ resulted in a marked increase in water splitting activity. The activity of these catalysts for water splitting decreased in the order: Fe³⁺ > W⁶⁺ > Ni²⁺ ≥ no substitution. The effect of different amounts of Ti⁴⁺ with Fe³⁺ substitution on water splitting was also evaluated. The highest hydrogen evolution was observed for perovskite composition having a Fe:Ti molar ratio of 1:14 (1:12 weight ratio) and this hydrogen evolution was over 4 times higher than the Fe-free K₂La₂Ti₃O₁₀ composition. Fe was also found to be a promising component for photo activity under visible light irradiation. Finally, the effect of Na₂S/Na₂SO₃ system as the sacrificial agent on the photocatalytic activity was also studied.     

Cobalt doped TiO2: A stable and efficient photocatalyst for continuous hydrogen production from glycerol: Water mixtures under solar light irradiation

Glycerol is the main by-product during the trans-esterification of vegetable oils to biodiesel. In this study, we investigate the process of photocatalytic hydrogen production from glycerol aqueous solution, with the use of cobalt doped TiO₂ photocatalyst under solar light irradiation. Cobalt doped TiO₂ photocatalysts are prepared by impregnation method and these catalysts are characterized by XRD, EDAX, DRS, TEM, EPR and XPS techniques. DRS studies clearly show the expanded photo response of TiO₂ into visible region on impregnation of Co²⁺ ions on surface of TiO₂. XPS studies also show change in the binding energy values of O1s, Ti 2p and Co 2p, indicating that Co²⁺ ions are in interaction with TiO₂. Maximum hydrogen production of 220 μ mol h⁻¹ g⁻¹ is observed on 2 wt% cobalt doped TiO₂ catalysts in pure water under solar irradiation. A significant improvement in hydrogen production is observed in glycerol: water mixtures; and maximum hydrogen production of 11,021 μ mol h⁻¹ g⁻¹ is obtained over 1 wt% cobalt doped TiO₂ in 5% glycerol aqueous solutions. Furthermore, to evaluate some reaction parameters such as cobalt wt% on TiO₂, glycerol concentration, substrate effect (alcohols) and pH of the solution on the hydrogen production activity are systematically investigated. When the catalysts are examined under UV irradiation, a 3–4 fold increase in activity is observed where this activity seems to decrease with time; however, a continuous activity is observed under solar irradiation on these catalysts. The decreased activity could be ascribed the loss of cobalt ions under UV irradiation, as evidenced by EDAX and TEM analysis. A possible explanation for the stable and continuous activity of cobalt doped TiO₂ photocatalysts under solar irradiation is proposed.     

CuS,NiS as co-catalyst for enhanced photocatalytic hydrogen evolution over TiO2

TiO₂ photocatalysts loaded CuS and NiS as co-catalyst were prepared by hydrothermal approach and characterized by XRD, UV–visible DRS, BET, XPS, SEM and TEM. When TiO₂ was loaded MS as co-catalyst, it showed higher photocatalytic activities for splitting water into hydrogen in methanol aqueous solution under 500 W Xe lamp. Among the photocatalysts with various compositions, the maximum evolution of H₂ obtained from 5 wt% CuS–5 wt% NiS–TiO₂ sample was about 800 μmol h⁻¹, which was increased up to about twenty-eight times than that of TiO₂ alone. It was proven that CuS, NiS can act as effective dual co-catalysts to enhance the photocatalytic H₂ production activity of TiO₂.     

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.     

Hydrogen production by photocatalytic water-splitting using Cr- or Fe-doped TiO2 composite thin films photocatalyst

Cr- or Fe-ion-doped TiO₂ thin films have been synthesized by radio-frequency magnetron sputtering and a sol–gel method to study hydrogen generation by photocatalytic water-splitting under visible light irradiation. The doping method, dopant concentration, charge transfer from metal dopants to TiO₂, and type of dopants used for modification of TiO₂ were investigated for their ability to enhance photocatalytic activity. UV–Visible spectra show that the metal-doped-TiO₂ obtained by sputtering is much more efficient than that obtained by the sol–gel technique at inducing a red shift of the absorption edge in the visible light range. Low concentration metal ion doping must be done near the conducting indium tin oxide (ITO) – TiO₂ interface to avoid the formation of recombination centers for photo-generated electron–hole pairs. H₂ production rate (μmol/h) is higher for Fe-doped TiO₂ (15.5 μmol/h) than for Cr-doped TiO₂ (5.3 μmol/h) due to the ability of Fe ions to trap both electrons and holes, thus avoiding recombination, while Cr can only trap one type of charge carrier. A constant H₂ generation rate is obtained for long periods of time by all the investigated TiO₂ films because of the separate evolution of H₂ and O₂ gases, thus eliminating the back-reaction effect.     

Photocatalytic splitting of seawater and degradation of methylene blue on CuO/nano TiO2

The main objective of this study was to prepare effective photocatalysts for splitting of seawater for solar fuel – H₂ and degradation of seawater organic pollutants such as dyes. To enhance photocatalytic activities, CuO is supported on nano TiO₂ (CuO/nano TiO₂). By X-ray absorption near edge structure (XANES) spectroscopy, CuO clusters are found on nano TiO₂. The 2.5% CuO/nano TiO₂ has greater activities in photocatalytic splitting of water and seawater than nano TiO₂ by 9.9 and 7.8 times, respectively. Interestingly, the 2.5% CuO/nano TiO₂ is also very active for photocatalytic splitting of water and seawater contaminated with dyes such as methylene blue (MB) (10 ppm). Under a 5-h irradiation of the UV–Vis light, about 99% of MB is degraded while 3.1 μmol/h g cat of H₂ are generated from seawater in the photocatalysis process.     

Modification of the photocatalytic properties of self doped TiO2 nanoparticles for hydrogen generation using sunlight type radiation

Synthetic approaches/methodologies can change the properties of nanoparticles significantly. In this study, the photocatalytic property of self (Ti³⁺) doped TiO₂ nanoparticles was modified by synthesizing through different routes. Solvothermal (T-Sol), sonochemical (T-Son) and polyol (T-Pol) methods were employed to prepare TiO₂ nanoparticles and the photocatalytic activities of these samples were compared with that of the sample prepared by precipitation using ammonia solution (T-Ppt). All samples had particle size below 30 nm except T-Son, where small nanoparticles existed as large spherical agglomerates with size around 500 nm. Surface area and porosity measurements of these different TiO₂ samples showed a significant dependency on the synthesis method. UV–Visible absorption spectra showed the onset of absorption at ∼440 nm for all samples due to the presence of defect levels originating from anion vacancies. Photocatalytic activity for hydrogen generation decreased in the order T-Sol > T-Son > T-Pol > T-Ppt and the observed activity is correlated with their physical properties such as surface area and crystallinity. The hydrogen yield was highly enhanced by the addition of Pd metal as co-catalyst on the surface of TiO₂ photocatalysts. Present experiments clearly demonstrate the importance of synthesis route to improve the photocatalytic activity of TiO₂.     

ZnmIn2S3+m (m = 1–5, integer): A new series of visible-light-driven photocatalysts for splitting water to hydrogen

A new series of Zn_mIn₂S_3+m (m = 1–5, integer) photocatalysts was synthesized via a simple hydrothermal method. X-ray diffraction (XRD), Raman spectra, UV–vis–near-IR diffuse reflectance spectra (UV–vis), X-ray fluorescence (XRF) and scanning electron microscope (FESEM) were used to characterize these photocatalysts. These Zn_mIn₂S_3+m photocatalysts had a similar layered crystal structure. The absorption edge of Zn_mIn₂S_3+m shifted to shorter wavelength as the atomic ratio of Zn/In in the synthetic solution was increased (i.e. m increased from 1 to 5). Additionally, the morphology of Zn_mIn₂S_3+m greatly depended on the atomic ratio of Zn/In. The photocatalytic activity of Zn_mIn₂S_3+m was evaluated by photocatalytic hydrogen production from water under visible light. The Zn₂In₂S₅ product, with quantum yield at 420 nm determined to be 11.1%, had the highest photocatalytic activity among these Zn_mIn₂S_3+m (m = 1–5, integer) photocatalysts.     

Novel twin reactor for separate evolution of hydrogen and oxygen in photocatalytic water splitting

Photocatalytic water splitting with separate H₂ and O₂ evolution is crucial because it eliminates the explosion potential and hydrogen-purification cost. A novel twin reactor was designed to separate the evolution of hydrogen and oxygen in photocatalytic water splitting under visible light. A modified Nafion membrane was employed to segregate the two photocatalysts in the twin reactor so that hydrogen and oxygen can be evolved separately. Conventional Z-scheme catalysts, Pt/SrTiO₃:Rh and WO₃, were used as hydrogen-photocatalyst and oxygen-photocatalyst, respectively. Fe²⁺ and Fe³⁺ were added in the reaction solution as electron-transfer mediator. The ratio of evolved H₂ and O₂ was in agreement with the stoichiometric ratio (2:1) of hydrogen and oxygen of water. An average hydrogen generation rate of 1.59 μmol/g-h was achieved in the twin-reactor system, which was twice as much as that in the conventional Z-scheme system. The improved H₂ yield was due to the prevention of the water-splitting backward reaction in the twin reactor.     

Synthesis of (CuIn)xCd2(1−x)S2 photocatalysts for H2 evolution under visible light by using a low-temperature hydrothermal method

A new series visible-light driven photocatalysts (CuIn)_xCd_2(1−x)S₂ was successfully synthesized by a simple and facile, low-temperature hydrothermal method. The synthesized materials were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area measurement, X-ray photoelectron spectroscopy (XPS) and ultraviolet-visible spectroscopy (UV–Vis DRS). The results show that the morphology of the photocatalysts changes with the increase of x from 0.01 to 0.3 and their band gap can be correspondingly tuned from 2.37 eV to 2.30 eV. The (CuIn)_xCd_2(1−x)S₂ nanocomposite show highly photocatalytic activities for H₂ evolution from aqueous solutions containing sacrificial reagents, SO₃²⁻ and S²⁻ under visible light. Substantially, (CuIn)_0.05Cd_1.9S₂ with the band gap of 2.36 eV exhibits the highest photocatalytic activity even without a Pt cocatalyst (649.9 μmol/(g h)). Theoretical calculations about electronic property of the (CuIn)_xCd_2(1−x)S₂ indicate that Cu 3d and In 5s5p states should be responsible for the photocatalytic activity. Moreover, the deposition of Pt on the doping sample results in a substantial improvement in H₂ evolution than the Pt-loaded pure CdS and the amount of H₂ produced (2456 μmol/(g h)) in the Pt-loaded doping system is much higher than that of the latter (40.2 μmol/(g h)). The (CuIn)_0.05Cd_1.9S₂ nanocomposite can keep the activity for a long time due to its stability in the photocatalytic process. Therefore, the doping of CuInS₂ not only facilitates the photocatalytic activity of CdS for H₂ evolution, but also improves its stability in photocatalytic process.     

In situ tuning of band gap of Sn doped composite for sustained photocatalytic hydrogen generation under visible light irradiation

The significance of Sn dopant on the photocatalytic performance of Iron/Titanium nanocomposite towards photocatalytic hydrogen generation by water splitting reaction is investigated. Iron/Titanium nanocomposite modified by Sn⁴⁺ dopant acts as a suitable photocatalyst for induced visible light absorption facilitating pronounced charge separation efficiency. Various characterization techniques reveal the heterojunction formation of hematite Fe₂O₃ with anatase - rutile mixed phase of TiO₂ employing Sn doping, where Sn⁴⁺ dopant accomplishes the phase transformation of anatase to rutile, entering into the TiO₂ lattice. This extended the lifetime of photogenerated charge carriers and enhanced the quantum efficiency of the photocatalyst. The band gap of the nanocomposite is tuned to ~2.4 eV, favoring visible light absorption. A hydrogen generation activity of 1102.8 μmol, approximately five times higher than the lone system (216.5 μmol) is achieved for the 5% Sn doped system for an average of 5 h. Heterojunctions of hematite with anatase-rutile mixed phase, generated as a consequence of tin doping facilitated the enhanced hydrogen generation activity of photocatalyst.     

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.     

Formation of multilayer-Eosin Y-sensitized TiO2 via Fe coupling for efficient visible-light photocatalytic hydrogen evolution

An efficient visible-light active photocatalyst of multilayer-Eosin Y-sensitized TiO₂ is prepared through linkage of Fe³⁺ between not only TiO₂ and Eosin Y but also different Eosin Y molecules to form three-dimensional polymeric dye structure. The multilayer-dye-sensitized photocatalyst is found to have high light harvesting efficiency and photocatalytic activity for hydrogen evolution under visible light irradiation (λ > 420 nm). On the optimum conditions (1:1 initial molar ratio of Eosin Y to Fe(NO₃)₃, initial 10 × 10⁻³ M Eosin Y, and 1.0 wt% Pt deposited by in situ photoreduction), its maximal apparent quantum yield for hydrogen evolution is 19.1% from aqueous triethanolamine solution (TEOA aq). The present study highlights linking between dye molecules via metal ions as a general way to develop efficient visible-light photocatalyst.     

Cetyltrimethylammoniumbromide (CTAB)-assisted hydrothermal synthesis of ZnIn2S4 as an efficient visible-light-driven photocatalyst for hydrogen production

A series of ZnIn₂S₄ photocatalysts was synthesized via a cetyltrimethylammoniumbromide (CTAB)-assisted hydrothermal method. These ZnIn₂S₄ products were characterized by X-ray diffraction (XRD), UV–visible absorption spectra (UV–vis) and scanning electron microscopy (FESEM). The effects of hydrothermal time and CTAB on the crystal structures, morphologies and optical properties of ZnIn₂S₄ products were discussed in detail. The photocatalytic activities of the as-prepared samples were evaluated by photocatalytic hydrogen production from water under visible-light irradiation. It was found that the photocatalytic activities of these ZnIn₂S₄ products decreased with the hydrothermal time prolonging while increased with the amount of CTAB increasing. The highest quantum yield at 420 nm of ZnIn₂S₄ photocatalyst, which was prepared through the CTAB (9.6 mmol)-assisted hydrothermal procedure for 1 h, was determined to be 18.4%. The optimum amount of Pt loaded for the ZnIn₂S₄ photocatalyst was about 1.0 wt%, under the present photocatalytic system.