Efficient indium tin oxide/Cr-doped-TiO2 multilayer thin films for H2 production by photocatalytic water-splitting

Cr-doped-TiO₂ thin films, with three different Cr concentrations (2, 5.5, and 9 at.%), have been synthesized by radio-frequency magnetron sputtering in order to sensitize TiO₂ in visible light. UV–visible spectra showed that maximum narrowing (2.1 eV) of the TiO₂ band gap is obtained for the highest Cr concentration. However, negligible photocurrent was measured with Indium Tin Oxide (ITO)/Cr-doped-TiO₂ (9 at.%) single bilayer sample due to the increased recombination rate of the photo-generated charges on the defects associated to the Cr³⁺ ions. To lower the charge recombination rate in the Cr-doped-TiO₂, multilayer films with different numbers of ITO/Cr-doped-TiO₂ (9 at.%) bilayers (namely, 3-, 4-, 5-, 6- and 7-bilayers) were deposited by keeping the total thickness of TiO₂ constant in each multilayer film. When the multilayer films were exposed to visible light, we observed that the photocurrent increases as function of the number of bilayers by reaching the maximum with 6-bilayers of ITO/Cr-doped-TiO₂. The enhanced photocurrent is attributed to: 1) higher absorption of visible light by Cr-doped-TiO₂, 2) number of space charge layers in form of ITO/TiO₂ interfaces in multilayer films, and 3) generation of photoelectrons just in/or near to the space charge layer by decreasing the Cr-doped-TiO₂ layer thickness. The reduced charge recombination rate in multilayer films was also confirmed by studying the photocurrent kinetic curve. The superior photocatalytic efficiency of the 6-bilayers film implies higher hydrogen production rate through water-splitting: we obtained indeed 24.4 μmol/h of H₂ production rate, a value about two times higher than that of pure TiO₂ (12.5 μmol/h).     

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.     

Physically and chemically synthesized TiO2 composite thin films for hydrogen production by photocatalytic water splitting

TiO₂ thin films have been synthesized by radio-frequency magnetron sputtering and sol–gel method to study the hydrogen generation by photocatalytic water splitting under visible light irradiation. Photoelectrochemical cell with chemical bias, involving photo-anode in form of TiO₂ film deposited on conducting indium tin oxide (ITO) film and Pt as cathode, is developed. The effect of conducting ITO layer on photo-voltage is studied by varying the thickness of ITO films. Constant H₂ generation rate is obtained for long period of time by both the TiO₂ films because of the separated evolution of H₂ and O₂ gas, thus eliminating the back-reaction effect. Sputter-deposited film as compared to sol–gel-synthesized film showed better H₂ generation rate, mainly explained in terms of the higher visible light absorption achieved by oxygen vacancies created in the TiO₂ film by the energetic target ions during deposition in pure Ar gas pressure.     

Multi-electron storage of photoenergy using Cu2O–TiO2 thin film photocatalyst

UV–vis irradiation of thin films of TiO₂ (ITO/TiO₂) and Cu₂O/TiO₂ (ITO/Cu₂O/TiO₂) coated on conducting glasses generate H₂ from H₂O and once the illumination is ceased, the H₂ production was still noticeable under dark for ITO/Cu₂O/TiO₂ at a lesser production rate for up to 2 h. No such dark reactions were observed for ITO/TiO₂ or TiO₂-coated copper metal foil (Cu/TiO₂). It was noticed that the irradiation of ITO/Cu₂O/TiO₂ leads to formation of trapped electrons and this stored energy leads to generate H₂ from H₂O in the dark.     

Hydrogen generation from photocatalytic water splitting over TiO2 thin film prepared by electron beam-induced deposition

Photocatalytic TiO₂ thin films were prepared via an electron beam-induced deposition (EBID) method. The effects of post-calcination treatment on the properties of the prepared TiO₂ thin films were studied. X-ray diffraction (XRD), scanning electron microscope-energy dispersive spectrometry (SEM-EDS), and UV–V is absorption spectrometry were performed to reveal the crystallinity, surface morphology, chemical composition, and light absorbance of the prepared TiO₂ thin films. The photoelectrochemical characteristics of the TiO₂ thin films were investigated with a potentiostat. Under UV irradiation, a photocurrent of ˜2.1 mA was observed for the TiO₂ thin film with post-calcination at 500 °C. A water-splitting reaction was conducted over the TiO₂ thin film with the best photoelectrochemical performance. The yields of hydrogen and oxygen were 59.8 and 30.6 μmole, respectively, after 8 h of reaction under UV irradiation.     

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.     

TiO2 and TiO2–SiO2 thin films and powders by one-step soft-solution method: Synthesis and characterizations

Simple soft-solution method has been developed to synthesize films and powders of TiO₂ and mixed TiO₂–SiO₂ at relatively low temperatures. This method is simple and inexpensive. Furthermore, reactor can be designed for large-scale applications as well as to produce large quantities of composite powders in a single step. For the preparation of TiO₂, we used aqueous acidic medium containing TiOSO₄ and H₂O₂, which results in a peroxo-titanium precursor while colloidal SiO₂ has been added to the precursor for the formation of TiO₂–SiO₂. Post annealing at 500 °C is necessary to have anatase structure. Resulting films and powders were characterized by different techniques. TiO₂ (anatase) phase with (1 0 1) preferred orientation has been obtained. Also in TiO₂–SiO₂ mixed films and powders, TiO₂ (anatase) phase was found. Fourier transform infrared spectroscopy (FTIR) results for TiO₂ and mixed TiO₂–SiO₂ films have been presented and discussed. The method developed in this paper allowed obtaining compact and homogeneous TiO₂ films. These compact films are highly photoactive when TiO₂ is used as photo anode in an photoelectrochemical cell. Nanoporous morphology is obtained when SiO₂ colloids are added into the solution.     

Development of copper-doped TiO2 photocatalyst for hydrogen production under visible light

The advantage of copper doping onto TiO₂ semiconductor photocatalyst for enhanced hydrogen generation under irradiation at the visible range of the electromagnetic spectrum has been investigated. Two methods of preparation for the copper-doped catalyst were selected – complex precipitation and wet impregnation methods – using copper nitrate trihydrate as the starting material. The dopant loading varied from 2 to 15%. Characterization of the photocatalysts was done by thermogravimetric analysis (TGA), temperature programmed reduction (TPR), diffuse reflectance UV-Vis (DR-UV-Vis), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD). Photocatalytic activity towards hydrogen generation from water was investigated using a multiport photocatalytic reactor under visible light illumination with methanol added as a hole scavenger. Three calcination temperatures were selected – 300, 400 and 500 °C. It was found that 10 wt.% Cu/TiO₂ calcined at 300 °C for 30 min yielded the maximum quantity of hydrogen. The reduction of band gap as a result of doping was estimated and the influence of the process parameters on catalytic activity is explained.     

Hydrogen production using Pt-loaded TiO2 photocatalysts

A series of synthesised TiO₂-based and commercial photocatalysts were modified by Pt photodeposition and a study made of their photocatalytic activity in hydrogen production. The modified commercial photocatalysts were Evonik P25, Kronos vlp7000 and Hombikat UV-100, and the other modified photocatalysts were synthesised by our group using sol–gel and sol–gel hydrothermal processes (SG400, SG750 and HT). Pt weight percentages used in the study were 0.5, 1.0 and 2.1 wt.% (Pt/TiO₂). The photocatalysts were extensively characterised by X-ray diffraction (XRD), UV–vis diffuse reflectance, Brunauer–Emmett–Teller (BET) surface area measurement, transmission electron microscopy (TEM), scanning electron microscopy (SEM–EDX), Fourier transform infrared spectroscopy (FTIR) and laser light dispersion. Methanol (25% vol.) was used as sacrificial agent over the 8 h of the hydrogen production tests and measurements were taken of the final concentrations of formaldehyde and formic acid as well as initial and final TOC. Photoactivity of all photocatalysts increased in the presence of Pt. The most efficient of the synthesised photocatalysts was SG750 and of the commercial photocatalysts P25. Maximum production of SG750 was 1846 μmol h⁻¹ at 1.0 wt.% Pt and its production per surface unit was notably higher than that of P25.     

Electrospun TiO2/SnO2 nanofibers with innovative structure and chemical properties for highly efficient photocatalytic H2 generation

Innovative TiO₂/SnO₂ nanofibers were fabricated via electrospinning an innovated precursor solution and used for photocatalytic H₂ generation. The nanofibers exhibited greatly enhanced H₂ evolution rate compared to bare TiO₂ nanofiber and P25. The enhanced efficiency of the TiO₂/SnO₂ nanofibers was attributed to its excellent synergistic properties: (1) its good mesoporosity; (2) the red-shift of absorbance spectra to enhance light absorbance capability; (3) its long nanofibrous structure and (4) anatase TiO₂ – rutile TiO₂ – rutile SnO₂ ternary junctions favorable for the separation of electrons and holes. Based on our experimental results, the optimum ratio of TiO₂/SnO₂ nanofibers with 3% Sn demonstrated the highest efficiency in H₂ generation.     

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.     

Enhanced photocatalytic hydrogen production by improving the Pt dispersion over mesostructured TiO2

Among other potential applications, mesoporous titania with high surface area and crystalline framework is attractive in photocatalytic hydrogen production. The mesoporous structure with pore walls formed by nanocrystals of anatase would provide a shorter distance of the electron–hole pairs to reach the photocatalyst surface and a higher surface area to deposit modifiers of its photocatalytic activity. In this work, we have successfully applied a hard-templating pathway to obtain ordered mesoporous titania (m-TiO₂) with high surface area and anatase as main crystalline phase. Subsequently, various amounts of metallic Pt have been deposited using different impregnation methods. All reactions performed exhibit, at short times, a rapid increase in the hydrogen production rate until a point in which a nearly constant value is achieved. The material prepared by the “citrate method”, based on reduction and encapsulation with sodium citrate of Pt nanoparticles before the photocatalytic reaction, leads to the highest hydrogen production rates with the shortest time to reach the change on the trend of the activity curve. The reason of this result is that citrate method provides very good dispersion and, specially, because the Pt nanoparticles are deposited and reduced preferentially within the pores of m-TiO₂, leading to stronger interactions than the other two explored dispersion routes (wetness impregnation and photodeposition). Thus, despite introducing less than half of the theoretical amount of Pt, citrate method produces close to twice the amount of hydrogen obtained by the other dispersion routes. This production capacity is even higher when the amount of Pt loaded is increased, with the optimal concentration being determined as 2% (w/w).     

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.     

Electrospun Pt/TiO2 hybrid nanofibers for visible-light-driven H2 evolution

One-dimensional (1D) Pt/TiO₂ hybrid nanofibers (HNFs) with different concentrations of Pt were fabricated by a facile two-step synthesis route combining an electrospinning technique and calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) results showed that the Pt nanoparticles (NPs) with the size of 5–10 nm were well dispersed in the TiO₂ nanofibers (NFs). Further investigations from the UV–Vis diffuse reflectance (DR) and X-ray photoelectron spectroscopy (XPS) analysis revealed that some Pt ions were incorporated into the TiO₂ lattice as Pt⁴⁺ state, which contributed to the visible light absorption of TiO₂ NFs. Meanwhile, the Pt²⁺ ions existing on the surface of Pt NPs resulted in the formation of Pt–O–Ti bond at Pt NPs/TiO₂ NFs interfaces that might serve as an effective channel for improving the charge transfer. The as-electrospun Pt/TiO₂ HNFs exhibited remarkable activities for photocatalytic H₂ evolution under visible light irradiation in the presence of l-ascorbic acid as the sacrificial agent. In particular, the optimal HNFs containing 1.0 at% Pt showed the H₂ evolution rate of 2.91 μmol h⁻¹ and apparent quantum efficiency of 0.04% at 420 nm by using only 5 mg of photocatalysts. The higher photocatalytic activity could be ascribed to the appropriate amount of Pt ions doping and excellent electron-sink effect of Pt NPs co-catalysts.     

Preferential oxidation of CO in H2 stream on Au/CeO2–TiO2 catalysts

A series of Au catalysts supported on CeO₂–TiO₂ with various CeO₂ contents were prepared. CeO₂–TiO₂ was prepared by incipient-wetness impregnation with aqueous solution of Ce(NO₃)₃ on TiO₂. Gold catalysts were prepared by deposition–precipitation method at pH 7 and 65 °C. The catalysts were characterized by XRD, TEM and XPS. The preferential oxidation of CO in hydrogen stream was carried out in a fixed bed reactor. The catalyst mainly had metallic gold species and small amount of oxidic Au species. The average gold particle size was 2.5 nm. Adding suitable amount of CeO₂ on Au/TiO₂ catalyst could enhance CO oxidation and suppress H₂ oxidation at high reaction temperature (>50 °C). Additives such as La₂O₃, Co₃O₄ and CuO were added to Au/CeO₂–TiO₂ catalyst and tested for the preferential oxidation of CO in hydrogen stream. The addition of CuO on Au/CeO₂–TiO₂ catalyst increased the CO conversion and CO selectivity effectively. Au/CuO–CeO₂–TiO₂ with molar ratio of Cu:Ce:Ti = 0.5:1:9 demonstrated very high CO conversion when the temperature was higher than 65 °C and the CO selectivity also improved substantially. Thus the additive CuO along with the promoter and amorphous oxide ceria and titania not only enhances the electronic interaction, but also stabilizes the nanosize gold particles and thereby enhancing the catalytic activity for PROX reaction to a greater extent.     

Synthesis of mesoporous-assembled TiO2 nanocrystals by a modified urea-aided sol-gel process and their outstanding photocatalytic H2 production activity

Mesoporous-assembled TiO₂ nanocrystals with very high photocatalytic H₂ production activity were synthesized through a modified sol-gel process with the aid of urea as mesopore-directing agent, heat-treated under various calcination temperatures, and assessed for their photocatalytic H₂ production activity via water splitting reaction. The resulting mesoporous-assembled TiO₂ nanocrystals were systematically characterized by N₂ adsorption-desorption analysis, surface area and pore size distribution analyses, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The experimental results showed that the photocatalytic H₂ production activity of the synthesized mesoporous-assembled TiO₂ nanocrystal calcined at 500 °C, which possessed very narrow pore size distribution, was extraordinarily higher than that of the commercially available P-25 TiO₂ and ST-01 TiO₂ powders.     

Synergistic effect of Cu2O/TiO2 heterostructure nanoparticle and its high H2 evolution activity

Cu₂O/TiO₂ nanoparticles were prepared by solvothermal method, which formed the heterostructure of Cu₂O/TiO₂. Due to the heterostructure, the H₂ evolution rate under simulated solar irradiation was increasingly promoted. Meanwhile a certain amount of Cu particles which were confirmed by Transmission Electro Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS), formed on the surface of Cu₂O/TiO₂, and the photoactivity was accordingly further enhanced. The stabilized activity was maintained after many times irradiation. It is interesting that after a few hours irradiation the amount of Cu particles on the surface kept unchanged in the presence of Cu₂O and TiO₂. The Cu particles that formed during hydrogen generation reaction play a key role in the further enhancement of the hydrogen production activity. In this study, it is the first time to study the details on the formation of the stable ternary structure under simulated solar irradiation and their synergistic effect on the photoactivity of the water splitting.     

Efficient visible-light-driven photocatalytic H2 production over Cr/N-codoped SrTiO3

Visible-light-response Cr/N-codoped SrTiO₃ was prepared by a sol–gel hydrothermal method. The comparison studies indicate that Cr-doped and Cr/N-codoped SrTiO₃ can be synthesized by this means, but not the N-doped SrTiO₃. The theoretical calculations exhibit the defect formation energy of the Cr/N codoping into SrTiO₃ is much smaller than that of the N doping into SrTiO₃, illuminating that the incorporation of Cr can promote the N doping into the O sites in the SrTiO₃. Compared to the Cr-doped SrTiO₃, the Cr/N-codoped SrTiO₃ photocatalyst shows the high photocatalytic activities for hydrogen production with the quantum efficiency of 3.1% at 420 nm, due to the smaller band gap and much less vacancy defects.     

Visible-light-driven TiO2 catalysts doped with low-concentration nitrogen species

Visible-light-driven nitrogen-doped TiO₂ was synthesized using a novel nitrogen-ion donor of hydrazine hydrate. Low-concentration (0.2 at%) nitrogen species and Ti³⁺ were detected in the TiO₂-based photocatalyst by X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) spectroscopy. The trace amount of Ti–N would contribute to the minor band-gap narrowing of about 0.02 eV. Those nitrogen-containing species, especially the NO₂²⁻ species, form surface states, which make the catalysts possible to degrade 4-chlorophenol (4-CP) under visible irradiation (λ>400 nm). Moreover, Ti³⁺ species induce oxygen vacancy states between the valence and the conduction bands, which would also contribute to the visible response. The photocatalytic activity of the nitrogen-doped TiO₂ catalyst was thought to be the synergistic effect of nitrogen and Ti³⁺ species. The catalysts showed higher photocatalytic activity for degradation of 4-CP than pure TiO₂ under not only visible but also UV irradiation. The visible response and the higher UV activity of the nitrogen-doped TiO₂ make it possible to utilize solar energy efficiently to execute photocatalysis processes.     

Highly efficient CuO incorporated TiO2 nanotube photocatalyst for hydrogen production from water

Highly dispersed CuO was introduced into TiO₂ nanotube (TNT) made by hydrothermal method via adsorption-calcination process or wet impregnation process, to fabricate CuO incorporated TNT photocatalysts (CuO-TNT) for hydrogen production. It was found that CuO-TNT possessed excellent hydrogen generation activity, which was constantly vigorous throughout 5 h reaction. Depending on the preparation method, hydrogen evolution rates over CuO-TNT were founded in the range of 64.2-71.6 mmol h⁻¹ g⁻¹_catalyst, which was much higher than the benchmark P25 based photocatalysts, and even superior to some Pt/Ni incorporated TNT. This high photocatalytic activity of CuO-TNT was mainly attributed to the unique 1-D tubular structure, large BET surface area and high dispersion of copper component. Compared to wet impregnation, adsorption-calcination process was superior to produce active photocatalyst, since it was prone to produce photocatalyst with more highly dispersed CuO.