Hydrogen production from sulphide wastewater using Ce3+–TiO2 photocatalysis

Cerium (Ce³⁺) doped TiO₂ powder was synthesized by a sol-gel method and characterized by Transmission Electron Microscope (TEM), X-ray Diffraction (XRD), UV–Vis Diffuse Reflectance Spectroscopy (UV-DRS), Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The Ce³⁺ doping strongly reduced the band gap of the TiO₂ from 3.2 eV (UV) to 2.7 eV (visible region). The photocatalytic activity of Ce³⁺ doped TiO₂ catalysts was evaluated by hydrogen production from sulphide wastewater under visible light illumination. The photocatalytic production of H₂ was studied in a batch recycle tubular photocatalytic reactor. The results show that 0.4% Ce³⁺–TiO₂ suspended in 500 mL of simulated sulphide wastewater irradiated at 150 W visible lamp produced maximum H₂ of 6789 μmol h^?1. It was noticed that the Ce³⁺ doped TiO₂ performs well than Nano TiO₂ and P25 TiO₂ photocatalysts.     

Photocatalytic hydrogen production using bench-scale trapezoidal photocatalytic reactor

Hydrogen is the future fuel and energy carrier, which has numerous applications. During combustion, produces only water vapour instead of greenhouse gas emissions. Photocatalytic production of hydrogen as a clean fuel from sulphide wastewater arises as a necessary option that must be considered. Here we report the performance of CNT added CdZnS/Fe₂O₃ for hydrogen recovery from highly toxic sulphide containing wastewater. The prepared photocatalysts were characterised for XRD (structure), UV-DRS (band gap), HRTEM (particle size), XPS (binding energy), SEM (morphology) and ICP (elemental composition). The photocatalytic hydrogen recovery was performed using novel trapezoidal photocatalytic reactor. The synthesized novel CNT - CdZnS/Fe₂O₃ nano-photocatalyst has highest production of hydrogen (2679 μmol/h) than plain CdZnS/Fe₂O₃ (2009 μmol/h).The feasibility studies were conducted to optimize the operating variables viz., S^2- (sulphide ion) concentrations, SO₃^2- (sulphite ion) concentrations, catalyst amount, light irradiation and volume of wastewater. Reusability studies under natural solar irradiation were performed and the CNT deposited CdZnS/Fe₂O₃ photocatalyst was found to be stable upto seven runs.     

Performance of gas-phase photocatalytic reactors on hydrogen production

Three types of high-performance photocatalytic reactors were developed for gas-phase photocatalytic hydrogen (H₂) production from hydrogen sulphide (H₂S) and effective photocatalytic decomposition of gaseous H₂S at a very low concentration is investigated. In this paper, three lab-scale photocatalytic reactors viz., packed bed photocatalytic reactor, catalyst coated fixed bed photocatalytic reactor and catalyst dispersed photocatalytic reactors were developed to study the performance of reactors on hydrogen production. The novel photocatalyst (CdS + ZnS)/Fe₂O₃ and the optimized catalyst dosage, H₂S gas flow rate, pollutant concentration, light irradiations were used. The experimental result indicates that packed bed photocatalytic reactor can effectively splits the H₂S into hydrogen (i.e. 98%) and rapidly decompose H₂S toward zero concentration than the other two reactors. Hence the bench-scale photocatalytic reactor was fabricated in packed bed reactor and the maximum hydrogen conversion achieved from hydrogen sulphide was found to be 98%.     

Performance of nano photocatalysts for the recovery of hydrogen and sulphur from sulphide containing wastewater

Stability of photocatalyst plays an important role in efficient hydrogen recovery from sulphide waste streams. This research focuses on the stability and efficiency of visible light active photocatalysts viz., RuO₂/CuGa_1.6Fe_0.4O₄, ZnFe₂O₃, (CdS + ZnS)/Fe₂O₃ and Ce/TiO₂ for H₂ production. RuO₂/CuGa_1.6Fe_0.4O₄ photocatalyst was found to give maximum hydrogen production of 8370 μmol/h. The reusability of the photocatalysts was tested by multiple cycles of catalyst regeneration along with H₂ production. The result shows that (CdS + ZnS) coated iron oxide core shell particles were found to be stable than other prepared nano photocatalysts. It is also demonstrated that H₂S can be split into hydrogen and sulphur under visible light irradiation using sulphide and sulphite reaction media at room temperature. This research paper will help in search of stable photocatalysts in recovering hydrogen from sulphide wastewater along with sulphur separation.     

Facile synthesis of Ti3+ doped Ag/AgITiO2 nanoparticles with efficient visible-light photocatalytic activity

We successfully synthesized novel Ti³⁺ doped TiO₂ and Ti³⁺ doped Ag/AgITiO₂ nanoparticles with efficient visible-light photocatalytic activity for hydrogen production by facile one-step solvothermal method. The as-prepared Ti³⁺ doped TiO₂ nanoparticles displayed excellent visible-light absorption and visible-light driven hydrogen production activity (115.3 μmol g^?1 h^?1), while the commercial TiO₂ had no visible-light response. Moreover, the as-prepared Ti³⁺ doped Ag/AgITiO₂ nanoparticles in this experiment showed highly enhanced visible-light absorption and efficient visible-light driven activity for hydrogen (571.0 μmol g^?1 h^?1), which was 4.95 times as high as that of the as-prepared TiO₂ nanoparticles. And the surface areas of the as-prepared TiO₂ and Ti³⁺ doped Ag/AgITiO₂ catalysts were up to 138.829 m² g^?1 and 102.988 m² g^?1, much higher than that of the commercial TiO₂ (55.516 m² g^?1). Finally, the visible-light photocatalytic mechanism of the Ti³⁺ doped Ag/AgITiO₂ nanoparticles for hydrogen generation was also proposed in detail.     

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.     

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.     

Hydrogen generation from photocatalytic hydrolysis of alkali‐metal borohydrides

The controllable photocatalytic hydrolysis of alkali‐metal borohydrides is studied for hydrogen generation in this work. The results indicate that the photocatalysis of P25 TiO₂ controllably promotes the hydrogen generation rates from alkali‐metal borohydride hydrolysis. Its apparent activation energy is calculated to be reduced from 57.20 to 53.86 kJ mol^?1. This is due to the mechanism of photocatalytic hydrolysis: holes (h⁺) react with BH₄‐ and OH^? to form H₂ and B(OH)₄‐, meanwhile electrons (e^?) react with H⁺ to from H₂. In addition, Ti³⁺‐doped TiO₂ with a crystalline‐disordered core‐shell structure can be generated during the photocatalytic hydrolysis process. The consumption of e^? is identified as the rate‐limiting step in photocatalytic hydrolysis process. Copyright © 2017 John Wiley & Sons, Ltd.     

LED light-induced enhanced photocatalytic hydrogen evolution on Au@TiO2 core–shell modified by nitrogen doping and reduced graphene oxide

This study focused on the large band gap of TiO₂ for its use as a photocatalyst under light emitting diode (LED) light irradiation. The photocatalytic activities of core–shell structured Au@TiO₂ nanoparticles (NPs), nitrogen doped Au@TiO₂ NPs, and Au@TiO₂/rGO nanocomposites (NCs) were investigated under various light intensities and sacrificial reagents. All the materials showed better photocatalytic activity under white LED light irradiation than under blue LED light. The N-doped core–shell structured Au@TiO₂ NPs (Au@N–TiO₂) and Au@TiO₂/rGO NCs showed enhanced photocatalytic activity with an average H₂ evolution rate of 9205 μmol h^?1g^?1 and 9815 μmol h^?1g^?1, respectively. All these materials showed an increasing rate of hydrogen evolution with increasing light intensity and catalyst loading. In addition, methanol was more suitable as a sacrificial reagent than lactic acid. The rate of hydrogen evolution increased with increasing methanol concentration up to 25% in DI water and decreased at higher concentrations. Overall, Au@TiO₂ core–shell-based nanocomposites can be used as an improved photocatalyst in photocatalytic hydrogen production.     

Photocatalytic hydrogen production from aqueous methanol solution using titanium dioxide with the aid of simultaneous metal deposition

The photocatalytic hydrogen generation from aqueous methanol solution using TiO₂ photocatalyst was investigated with the aid of simultaneous metal deposition. The photocatalytic hydrogen evolution with pure TiO₂ was very small. The simultaneous deposition for various metals was therefore evaluated. As a result, the additions of Au and Cu ions were effective for the improvement of photocatalytic hydrogen production. Methanol concentration and metal ion concentration were optimized for the system. The optimal methanol concentrations were 90 and 80 vol% in the case of addition of Au and Cu ions, respectively. Under the optimal conditions, the photocatalytic hydrogen production using TiO₂ photocatalyst with the aid of simultaneous Cu and Au deposition were approximately 25 and 120 times larger than those obtained with bare TiO₂.     

Pd loading,Mn+ (n=1, 2, 3) metal ions doped TiO2 nanosheets for enhanced photocatalytic H2 production and reaction mechanism

Pd nanoparticles (NPs) loading, main group metal ions doped TiO₂ nanosheets were prepared by a hydrothermal method, followed by photo-deposition of Pd. The samples were characterized, and their photocatalytic hydrogen production activities were tested in a methanol aqueous solution. The effects of cationic charge, radius and concentration of the doping ions (Na⁺, K⁺, Mg²⁺, Al³⁺) on the photocatalytic activities were investigated systematically. The photocatalytic reaction mechanism was discussed by considering the three aspects: specific surface area, light absorption and charge transfer/separation. The results show that the cation dopings significantly increased the photocatalytic activities of the TiO₂ nanosheets, which may be attributed to the enhanced UV-vis light absorption and accelerated charge transfer/separation of the catalysts. Particularly, the Pd/0.2%K⁺-TiO₂ possesses the highest photocatalytic H₂ production activity (76.6 μmol h^?1), which is more than twofold higher than that of the undoped Pd/TiO₂. The apparent quantum efficiency of hydrogen evolution system reaches 3.0% at 365 nm. The high activity of the Pd/K⁺-TiO₂ may be attributed to the lower electronegativity of K⁺, caused by the lower cationic charge or the larger cationic radius, compared to Na⁺, Mg²⁺ and Al³⁺. The doping metal cations with higher electronegativity may compete electrons with H⁺, which eventually partly depressed the reduction of H⁺ to H₂.     

Co-application of liquid phase plasma process for hydrogen production and degradation of acetaldehyde over NiTiO2 supported on porous materials

Photocatalytic decomposition of acetaldehyde-contained wastewater was assessed for the degradation of pollutants and the production of hydrogen. Liquid phase plasma was applied in the photoreaction as a light source. The evolution of hydrogen and acetaldehyde degradation were characterized by the photocatalytic decomposition system. Ni-loaded TiO₂ photocatalysts and various porous materials were introduced to the photocatalytic reaction. The photochemical decomposition by irradiation of the liquid phase plasma without photocatalysts produced some hydrogen evolution with the degradation of acetaldehyde, which was attributed to the decomposition of the reactant by active species generated by the irradiation of liquid phase plasma. The Ni loading on TiO₂ brought out an enhancement of acetaldehyde degradation and hydrogen evolution. In the photocatalysis of acetaldehyde-contained wastewater using the liquid phase plasma, hydrogen evolution was accelerated due to the additional hydrogen production by the photocatalytic decomposition of acetaldehyde. The porous materials could be used as an effective photocatalytic support. MCM-41 mesoporous material has acted as a highly efficient photocatalytic support to the TiO₂ photocatalyst.     

Effect of impurities in TiO2 thin films on trichloroethylene conversion

In this study, we investigate the physical properties and photocatalytic activities of TiO₂ thin films doped with low valence (Fe³⁺, Co²⁺, and Ni²⁺) and high valence (Mo⁵⁺, Nb⁵⁺, and W⁶⁺) cations. Clear difference in results from various analytical tools between groups was identified. The presence of different oxidation states and a higher degree of crystallinity in the high valence cation doped-TiO₂ thin films seemed beneficial in terms of the transfer and separation of photo-generated electrons and holes in the TiO₂ medium and on the surface, resulting in higher photocatalytic conversion of trichloroetylene.     

Effect of Pt loading on the hydrogen production of CNT/Pt composites functionalized with carboxylic groups

This work reports the morphological and photocatalytic hydrogen generation properties of CNT/Pt composites with and without functionalization by carboxylic/oxygen groups. The composites with and without functionalization were named f-CNT/Pt and CNT/Pt, respectively. Several f-CNT/Pt and CNT/Pt composites with different content of Pt NPs (from 0 to 30 wt%) were synthesized and analyzed by scanning electron microscopy (SEM). Those images revealed that the composites without functionalization presented higher agglomerations of Pt nanoparticles (NPs). Furthermore, the average sizes of the Pt NPs in the named f-CNT/Pt composites (2.3–2.9 nm) were lower than these in the CNT/Pt composites (2.5–3.1 nm). The hydrogen generation rates were also calculated from the decomposition of pure water under UV irradiation (365 nm) and found maximum values of 45.4 and 193.9 μmol·h⁻¹ g⁻¹ for the CNT/Pt and f-CNT/Pt composites (they contained 20 wt% of Pt NPs), respectively. Additional experiments for hydrogen generation were achieved using sodium sulfite as sacrificial agent; in this case, a maximum value of 13850 μmol·h⁻¹ g⁻¹ was obtained for the f-CNT/Pt composite. The f-CNT/Pt composites produced more hydrogen than the CNT/Pt composites because they presented higher content of defects; this was confirmed by the Raman spectra. We also showed that the Pt NPs acted as electron trap centers, which delayed the recombination of the photogenerated electrons and holes, this in turn, enhanced the hydrogen generation rates of the composites (the hydrogen generation was maximized by varying the content of Pt NPs deposited on the CNTs). The CNT/Pt composites presented here were simpler and easier to synthesize than the previous published ternary systems based on TiO₂, CNTs and Pt NPs.     

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.     

TiO2 nanotubes incorporated with CdS for photocatalytic hydrogen production from splitting water under visible light irradiation

The CdS/TiO₂ composites were synthesized using titanate nanotubes (TiO₂NTs) with different pore diameters as the precursor by simple ion change and followed by sulfurization process at a moderate temperature. Some of results obtained from XRD, TEM, BET, UV–vis and PL analysis confirmed that cadmium sulfide nanoparticles (CdSNPs) incorporated into the titanium dioxide nanotubes. The photocatalytic production of H₂ was remarkably enhanced when CdS nanoparticles was incorporated into TiO₂NTs. The apparent quantum yield for hydrogen production reached about 43.4% under visible light around λ = 420 nm. The high activity might be attributed to the following reasons: (1) the quantum size effect and homogeneous distribution of CdSNPs; (2) the synergetic effects between CdS particles and TiO₂NTs, viz., the potential gradient at the interface between CdSNPs and TiO₂NTs.     

Photocatalytic hydrogen production using TiO2 coated iron-oxide core shell particles

Photocatalytic water splitting plays a challenging role as it is one of the most important reactions for solving energy, environmental problems and sustainability. Photocatalytic water splitting was improved by using a novel kind of magnetically separable core shell nano photocatalyst TiO₂/Fe₂O₃, prepared by co-precipitation method. It was characterised for particle size (XRD), band gap (UV-DRS), morphology (SEM), particle size (HRTEM), elemental composition (EDS) and electrochemical studies. Photocatalytic splitting of water was examined in tubular reactor of 500 mL capacity with various sacrificial agents viz., methanol, ethanol, acetic acid, lactic acid, EDTA and triethanolamine. To enhance the hydrogen production, various operating parameters viz., effect of sacrificial agents, catalytic dosage, light irradiation and recycle flow rate were optimized. With the optimized operating parameters (0.2 g catalyst dosage, 60 mL/min recycle flow rate, 96 W/m² light irradiation and EDTA as sacrificial agent) the maximum hydrogen achieved was 2700 μmol/h for the quantum yield of 3.86% at 550 nm. The reusability studies were conducted and the TiO₂ coated Fe₂O₃ core shell particles were found to be stable than the plain TiO₂ nano particles. Effective charge transfer from TiO₂ to Fe₂O₃ and the suppression of e^?/h⁺ pair recombination attributed significant enhancement in photoactivity, thereby increasing the hydrogen production.     

Heterogeneous photocatalytic hydrogen generation in a solar pilot plant

Few studies have been published about large scale heterogeneous photocatalysis hydrogen generation with simultaneous removal of organic pollutants. The purpose of the present work was to study the simultaneous photocatalytic hydrogen production and organic pollutant removal under direct solar irradiation at pilot-plant scale. The experiments were performed in a Compound Parabolic Collector (CPC) at the Plataforma Solar de Almería (PSA). The efficiencies of two different photocatalytic systems, one based on a nitrogen doped and platinized TiO₂, and the other using a platinized CdS–ZnS composite were evaluated. Formic acid and glycerol were used as sacrificial electron donors. Also, experiments using real municipal wastewaters were carried out showing simultaneous hydrogen generation and partial water pollutant removal. The largest amounts of hydrogen were obtained with aqueous solutions of formic acid, although the experiments with real wastewater gave moderate amounts of hydrogen, pointing towards the possible future use of such waters for photocatalytic hydrogen generation.     

Recent progress in metal-doped TiO2, non-metal doped/codoped TiO2 and TiO2 nanostructured hybrids for enhanced photocatalysis

Titanium dioxide remains a benchmark photocatalyst with high stability, low cost, and less toxicity, but it is active only under UV light; thus, in practical applications using visible light, its catalytic reactions are stalled. To enhance its catalytic activity under visible light, non-metal/codoped TiO₂ structures are being studied. These structures improve the photocatalytic activity of TiO₂ in visible light by reducing its energy bandgap. This might be useful in wastewater treatment for the photocatalytic degradation of organic contaminants under visible and UV light irradiation. In this intensive review, we describe recent developments in TiO₂ nanostructured materials for visible-light driven photocatalysis, such as (i) mechanistic studies on photo-induced charge separation to understand the photocatalytic activity and (ii) synthesis of non-metal doped/codoped TiO₂ and TiO₂ nanostructured hybrid photocatalysts. Furthermore, the effects of various parameters on their photocatalytic efficiency, photodegradation of various organic contaminants present in wastewater, and photocatalytic disinfection are delineated.     

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.