Synthesis and high photocatalytic hydrogen production of SrTiO3 nanoparticles from water splitting under UV irradiation

Cubic SrTiO₃ powders were synthesized by three methods: the polymerized complex (PC) method, the solid state reaction, and the milling assistant method. The samples obtained were characterized by X-ray diffraction (XRD), UV–vis spectroscopy (UV–vis), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The mean diameters of the as-synthesized SrTiO₃ particles were 30 nm by the polymerized complex method, 140 nm by the solid state reaction, and 30 nm by the milling assistant method. The photocatalytic activity of hydrogen evolution from water splitting over SrTiO₃ powders by the polymerized complex method is higher than that by the solid state reaction and the milling assistant method. Particle size, uniformity of components, and particle aggregation extent affect the photocatalytic activity of SrTiO₃ for hydrogen evolution. The best rate of photocatalytic hydrogen evolution over SrTiO₃ by the polymerized complex method under UV illumination is as high as 3.2 mmol h⁻¹ g⁻¹.     

Preparation of TiO2–SiO2 aperiodic mesoporous materials with controllable formation of tetrahedrally coordinated Ti ions and their performance for photocatalytic hydrogen production

The efficiency of photocatalytic water splitting for TiO₂ dispersed on four SiO₂ aperiodic porous supports is discussed in this work. The four TiO₂–SiO₂ composite materials were prepared via a sol–gel method and then subjected to supercritical drying, natural drying, rotatory vapor drying, or hydrothermal synthesis and the materials were subsequently calcined under identical conditions. These synthetic strategies result in differences in textural properties (specific surface area, pore diameter etc.) and in the amount of tetrahedrally coordinated Ti⁴⁺ ions. The TiO₂–SiO₂ materials were thoroughly characterized by powder X-ray diffraction (XRD), UV–Vis diffuse reflectance spectra (DRS), nitrogen adsorption studies, FT-IR spectroscopy, transmission electron microscopic (TEM) studies, and electron paramagnetic resonance (EPR) studies. The photocatalytic activity for hydrogen production is maximum when the amount of tetrahedrally coordinated Ti⁴⁺ ions is high. Thus, this work provides guidance towards the preparation of photoactive materials for generating hydrogen from water.     

Intermediate temperature single-chamber methane fed SOFC based on Gd doped ceria electrolyte and La0.5Sr0.5CoO3−δ as cathode

Single-chamber fuel cells with electrodes supported on an electrolyte of gadolinium doped ceria Ce_1−xGd_xO_2−y with x = 0.2 (CGO) 200 μm thickness has been successfully prepared and characterized. The cells were fed directly with a mixture of methane and air. Doped ceria electrolyte supports were prepared from powders obtained by the acetyl-acetonate sol–gel related method. Inks prepared from mixtures of precursor powders of NiO and CGO with different particle sizes and compositions were prepared, analysed and used to obtain optimal porous anodes thick films. Cathodes based on La_0.5Sr_0.5CoO₃ perovskites (LSCO) were also prepared and deposited on the other side of the electrolyte by inks prepared with a mixture of powders of LSCO, CGO and AgO obtained also by sol–gel related techniques. Both electrodes were deposited by dip coating at different thicknesses (20–30 μm) using a commercial resin where the electrode powders were dispersed. Finally, electrical properties were determined in a single-chamber reactor where methane, as fuel, was mixed with synthetic air below the direct combustion limit. Stable density currents were obtained in these experimental conditions. Temperature, composition and flux rate values of the carrier gas were determinants for the optimization of the electrical properties of the fuel cells.     

Aging effect of diethanolamine stabilized sol on different properties of TiO2 films: Electrochromic applications

Diethanolamine derived clear precursor sol has been utilized for the deposition of TiO₂ films annealed at 470 °C for 5 min. Effect of the precursor sol's aging on different properties of the films has been examined in the present study. Films obtained from aged sol have exhibited superior electrochemical (diffusion coefficient—2.46×10⁻¹⁰ cm² s⁻¹) and electrochromic characteristics due to enhanced Li ion insertion upon application of electric field. The aged sol derived films have exhibited a higher optical modulation (40% at 550 nm) between the colored and bleached states. The ion storage capacities of the films derived from freshly prepared and aged sols are 4.1 and 8.1 mC cm⁻², respectively, upon applied voltage of ±1.5 V. X-ray diffraction studies have affirmed an increase in the TiO₂ crystallite size upon the use of aged sol for the deposition of films. FTIR investigations have confirmed the conversion of Ti–O–Ti to Ti–O network in the aged sol derived films. SEM studies have evidenced porosity changes in films obtained from the sol aged for different durations. The index of refraction as measured by the ellipsometry method corroborates the SEM results and shows reduced porosity (pore size—38 nm) in films derived from the sol just reaching the state of gelation. Thickness of the aged sol derived film is measured to be the highest i.e. 350 nm. Energy bandgaps of the films for both direct and indirect transitions tend to decrease as a function of sol's aging.     

Characterization and first principle study of ball milled Ti–Ni with Mg doping as hydrogen storage alloy

Microstructures, electrochemical properties of Ti–Ni and ternary Ti–Ni–Mg alloy were studied after they had been submitted to high-energy ball milling. Influence of milling time and Mg addition on the microstructures of the mechanically milled Ti–Ni alloys was investigated by XRD, SEM. Cycling performances of the electrodes prepared by the milled powders were measured under galvanostatic conditions. It is found that the binary Ti–Ni alloy undergoes a refinement, dynamical recrystallization and amorphization process. With doping of Mg to the starting Ti–Ni powders, an FCC Ti–Mg structure was detected along with the main TiNi BCC phase. First principle calculation was applied to compare the thermodynamic stabilities of several binary alloys involving Ti, Ni and Mg. It was decided that the final product of milling Mg doped Ti–Ni contains an FCC structured TiMg₃ phase, which damages electrochemical performance in general as a result of coating effect on the TiNi phase.     

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.     

Inflow performance relationships in geothermal and petroleum reservoir engineering: A review of the state of the art

The different inflow performance relationships (IPRs) that have been proposed in geothermal and petroleum reservoir engineering are reviewed. The applicability of these relationships to well production tests is analyzed, and the geothermal IPRs for pure water, for the binary H₂O–CO₂ and ternary H₂O–CO₂–NaCl mixtures (with different salinities) are presented. The method to determine the maximum flow rate for a well is described. Two representative IPRs for petroleum systems and two for geothermal systems that consider the fluid as a ternary mixture H₂O–CO₂–NaCl (for salinities less than 5%, and between 5% and 20%) are compared. It is concluded that IPRs may be used to determine the maximum flowrate of a well at any time during its productive life.     

Morphological, optical and photocatalytic properties of TiO2–Fe2O3 multilayers

Morphological, optical and photocatalytic properties of TiO₂, Fe₂O₃ and TiO₂–Fe₂O₃ samples (formed by 1, 3 and 5 coatings) were studied. The layers were deposited on glass substrate by the sol–gel method. The catalytic activity of the samples was studied by the photodecomposition of methylene blue (MB) under visible light illumination. The FTIR results indicate that all samples present surface OH radicals that are bound either to the Ti or Fe atoms. This effect is better visualized at larger number of coatings in the TiO₂–Fe₂O₃/glass systems. Also, two mechanisms are observed during the photodecomposition of the MB.     

Photocatalytic degradation of organic compounds in aqueous solution by a TiO2-coated rotating-drum reactor using solar light

This paper deals with the degradation of aqueous phenol by a newly proposed rotating-drum reactor coated with a TiO₂ photocatalyst, in which TiO₂ powders loaded with Pt are immobilized on the outer surface of a glass-drum. The reactor can receive solar light and oxygen from the atmosphere effectively. It was shown experimentally that phenol can be decomposed rapidly by this reactor under solar light: with our experimental conditions the phenol with an initial concentration of 22.0 mg/dm³ was decomposed within 60 min and was completely mineralized through intermediate products within 100 min. The photonic efficiency under solar light was shown to take the value 0.00742 mol-C/Einstein. The photocatalytic decomposition processes of phenol by this reactor were also discussed on the basis of the Langmuir–Hinshelwood kinetic model.     

The photoinduced evolution of O2 and H2 from a WO3 aqueous suspension in the presence of Ce/Ce

This is a report on the production of O₂ and H₂ from photocatalytic and photochemical processes in the WO₃–H₂O–Ce⁴⁺_aq–hν system. The photoproduction of O₂ and H₂ was studied over the range of WO₃ concentrations from 2 to 8 g dm⁻³, and conduction band electron scavenger concentrations 1–20 mM Ce_aq⁴⁺. Medium and high concentrations of the electron scavenger gave mainly O₂ as the main product. Dilute solutions of [Ce_aq⁴⁺]< 2 mM initially produced dioxygen, and then hydrogen after an induction period of 3–4 h. Yields of 140–250 μmol O₂  h⁻¹ and 1–7 μmol H₂ h⁻¹ were obtained and were found to depend on the physical properties and content of WO₃, the concentration of the electron scavenger, illumination period and wavelength, and the radiation geometry. The photoactivity of the suspension was correlated to the level of crystallinity of WO₃ powders. The studied system utilizes WO₃ to accomplish the initial light absorption, charge separation, and production of O₂ and H⁺ from the interaction of water molecules with photogenerated WO₃ valence band holes, in the presence of Ce⁴⁺_aq species as a scavenger of conduction band electrons. This is followed by the evolution of H₂ from a homogeneous photochemical reduction of H⁺ and/or H₂O by photoexcited Ce³⁺_aq, formed from the earlier reduction of Ce⁴⁺_aq. The obtained results show that, with an appropriate design, tungsten trioxide is a promising material that can be used as a photoactive component in energy conversion systems or in environmental photocatalysis, using artificial or solar light.     

Ternary compounds in the magnesium–titanium hydrogen storage system

Mg–Ti–H samples were mechano-chemically synthesized by ball milling in argon atmosphere or under elevated hydrogen pressure. The detailed reaction mechanism during hydrogen release and uptake during continuous cycling was investigated by in-situ synchrotron radiation powder X-ray diffraction (SR-PXD) experiments. The thermal behaviour of the samples and hydrogen desorption properties were examined by simultaneous thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and mass spectrometry (MS) measurements. A ternary Ti–Mg–H compound with a fcc lattice form during mechano-chemical sample preparation in hydrogen atmosphere using metal powders, but not using metal hydrides as reactants. The amount of β-MgH₂ increases during the first hydrogen absorption cycle at 300 °C at the expense of the high-pressure polymorph, γ-MgH₂ and the amount of β-MgH₂ remain constant during the following hydrogenations. This study reveals that the ternary compound tends to absorb increasing amounts of magnesium in the dehydrogenated state during cycling. A strong coupling between the amounts of magnesium in the ternary Ti–Mg–H phase and the formation of magnesium and magnesium hydride during hydrogen release and uptake at 300 °C is observed. The composition and the amount of the Ti–Mg–H phase appear to be similar in the hydrogenated state. Fast absorption–desorption kinetics at 300 °C and lower onset temperatures for hydrogen release is observed for all investigated samples (lowest onset temperature of desorption T_on = 217 °C).     

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.     

Solar photocatalytic mineralization of isoproturon over TiO2/HY composite systems

The present investigation covers immobilization of titanium dioxide over HY support for the treatment of isoproturon pesticide. Catalysts are characterized by XRD, SEM–EDAX, TEM, BET surface area and UV–vis DRS. A detailed photocatalytic degradation study under solar light in aqueous suspensions with parameters like loading of TiO₂ over HY, amount of the catalyst, concentration of substrate, pH effect, durability of the catalyst and comparison between suspended TiO₂ and supported systems are reported. Mineralization of isoproturon is monitored by total organic carbon, chemical oxygen demand and a plausible mechanism is proposed for photocatalytic degradation based on degradation products.     

Solar photocatalytic degradation of methylene blue in carbon-doped TiO2 nanoparticles suspension

Carbon-doped TiO₂ nanoparticles were prepared by sol–gel auto-combustion method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Brunauer–Emmett–Teller method (BET), UV–vis diffuses reflectance spectroscopy (DRS). UV–vis diffuse reflectance spectra showed that carbon-doped TiO₂ exhibited obvious absorption in the visible light range. The visible light photocatalytic activity of carbon-doped TiO₂ was ascribed to the presence of oxygen vacancy state between the valence and the conduction bands because of the formation of Ti³⁺ species in the as-synthesized carbon-doped TiO₂. The sample calcined at 873 K showed the highest photocatalytic activity under solar irradiation. The effects of photocatalyst concentration, initial concentration of methylene blue, and pH value in aqueous solution were also presented.     

Photocatalytic reduction of CO2 using TiO2 powders in supercritical fluid CO2

The photocatalytic reduction of CO₂ was investigated using TiO₂ powders in supercritical fluid CO₂. These were irradiated in a stainless steel vessel at 9.0 MPa and 35°C. After reducing the CO₂ pressure to the ordinary state, pure water was added to the vessel while avoiding air contamination. No gaseous reduction products were observed. Formic acid was obtained only in aqueous solution. The optimal irradiation time for the production of formic acid was 5 h. Addition of acidic solutions rather than pure water was preferable for formic acid formation. Formic acid seems to be produced through the protonation of reaction intermediates on TiO₂ powders in solutions. The CO₂-reduction system described here may be of practical value for efficient CO₂-conversion and fixation, storage of solar energy, and production of raw materials for the photochemical industry.     

Parallel-plate solar photocatalytic reactor for air purification: Semi-empirical correlation, modeling, and optimization

This study focused on modeling and optimization of a photoreactor packed with parallel glass plates coated with sol–gel TiO₂ thin films on both sides. The photoreactor design has great potential for solar photocatalytic air purification. Borosilicate glass substrate was selected because its high transmissivity facilitated the transmission and distribution of exterior solar radiation onto interior immobilized photocatalyst. Flat-plate configuration was adopted because a TiO₂-coated plate could be easily set up for effective ion implantation treatment to extend the activating spectral range from UV to visible light for a higher solar photonic efficiency. In the analytical study of this research, a semi-empirical correlation model was formulated for prediction of the photoreactor performance. The correlation coefficients were obtained based on the results of photocatalytic air purification experiments conducted. Additional experimental tests were carried out for validation of the model. In the photoreactor design optimization analysis, the semi-empirical correlation model was used as an optimizer to determine the number of parallel TiO₂-coated plates needed for efficient photocatalytic air purification. It was found that the optimal number of plates was dependent of the incident irradiance. The modeling and optimization methods developed for solar photocatalytic air purification are equally applicable for solar photocatalytic water purification.     

Preparation and performance of novel Li–Ti–Si–P–O–N thin-film electrolyte for thin-film lithium batteries

Novel Li–Ti–Si–P–O–N thin-film electrolyte was successfully fabricated by RF magnetron sputtering from a Li–Ti–Si–P–O target in N₂ atmosphere at various temperatures. XRD, SEM, EDX, XPS, and EIS were employed to characterize their structure, morphology, composition and electrochemical performances. The films were smooth, dense, uniform, without cracks or voids, and possessed an amorphous structure. Their room temperature lithium-ion conductivities were measured to be from 3.6 × 10⁻⁷ S cm⁻¹ to 9.2 × 10⁻⁶ S cm⁻¹, and the temperature dependence of the ionic conductivities fits the Arrhenius relation. This kind of electrolyte possessed good properties is a promising candidate material for solid-state thin-film lithium batteries.     

Novel, low cost CaCl2 based desiccants for solar crop drying applications

Drying with solar-heated air is satisfactory so long as the sun is shining. To continue this process through the night-time and periods of cloud cover, it is necessary to either store some of this energy in a thermal mass or incorporate desiccants within the drying system. This paper reports the results from studies undertaken to develop three low cost, solar regenerative clay–CaCl₂ based solid desiccant materials; establish their moisture sorption and regeneration characteristics; assess their performance when compared with commercial desiccants; and integrate these within a low cost solar drying system for small-scale village-based crop drying. The moisture sorption and desorption performance of the desiccants were characterised in a Fison Environmental Cabinet at conditions of 85% (RH) and 25°C for 120 h for moisture sorption and 50°C and 20% (RH) for 8 h for regeneration. These conditions were representative of the environmental conditions monitored in the solar drying system. The bentonite–CaCl₂ (type 1) desiccant gave a maximum moisture sorption of 45% dry weight basis (dwb) while bentonite–CaCl₂ (type 2) and kaolinite–CaCl₂ (type 3) solid desiccants each gave moisture sorption values of 30% (dwb). It was concluded from the moisture sorption and regeneration characteristics that their application in solar crop drying and air dehumidification is highly useful due to their low regeneration temperatures, sub 100°C.     

Visible-light-assisted photocatalytic degradation of gaseous formaldehyde by parallel-plate reactor coated with Cr ion-implanted TiO2 thin film

Sol–gel nano titanium dioxide (TiO₂) thin film can be activated by the ultraviolet (UV) radiation available in sunlight to perform solar photocatalysis. The useful spectral range can be extended from UV to visible light by implantation of metal ion into the TiO₂ lattice. As a result, the solar visible light can be utilized more efficiently to enhance the solar photocatalysis. In this study, visible-light-assisted photocatalytic glass reactors were built by parallel borosilicate glass plates coated on the upper surfaces with sol–gel TiO₂ thin films implanted with chromium (Cr) ion. The properties of the Cr/TiO₂ thin films were fully characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermal gravity (TG) analysis, scanning-electron microscopy (SEM), and energy dispersive X-ray (EDX) analysis. In the performance tests, a metal halide lamp was used as an external light source to resemble the solar visible spectral radiation. The performance of a Cr/TiO₂ photoreactor was measured in terms of its photocatalytic degradation of gaseous formaldehyde in a single pass of contaminated air flowing through the photoreactor. The experimental results demonstrated the promise of using light-transmitting glass substrate to allow transmission and distribution of light from an external source to achieve solar photocatalysis. In the design of a parallel-plate photoreactor, it is important to properly control the Cr ion loading so that each Cr/TiO₂-coated glass plate absorbs a portion of the incident light for its photocatalytic activation and allows light transmission available for the remaining coated plates.     

Preparation of a TiMEMO nanocomposite by the sol–gel method and its application in coloured thickness insensitive spectrally selective (TISS) coatings

An organic–inorganic nanocomposite was prepared via sol–gel processing from 3-(trimethoxysilyl)propyl methacrylate (MAPTMS) and titanium(IV) isopropoxide (TIP) precursors (TiMEMO) in the form of a viscous resin, and used as a binder for the preparation of coloured thickness insensitive spectrally selective (TISS) paints and corresponding solar absorber coatings. The spectral selectivity of TiMEMO-based TISS paints was optimized by varying the concentrations of binder and different pigments: black, coloured (red, green and blue) and aluminium flakes, the latter imparting low thermal emittance, which was correlated to the presence of titanium in the TiMEMO sol–gel host. The formation and the ensuing structure of the sol–gel TiMEMO hybrid was studied in detail and the nanocomposite structure of the TiMEMO binder formed was assessed from infrared and ²⁹Si NMR measurements, which confirmed the formation of Ti–O–Si linkages established after the hydrolysed precursors condensed into a compliant resinous material. XRD measurements provided additional information about the existence of small coherent domains of silsesquioxane units in the sol–gel host. The abrasion resistance of the non-pigmented TiMEMO binder deposited in thin film form on a PMMA substrate was assessed by the Taber test, and its hardness compared with other resin binders which have been used for making TISS paint coatings. The surface properties of the non-pigmented TiMEMO binder and the ensuing TISS paint coatings were determined from contact angle measurements. The results showed that the water contact angles of non-pigmented TiMEMO binder increased from 70° to 125–135° for the corresponding pigmented TISS paint coatings, inferring the influence of surface roughness on surface energy in the presence of pigments. SEM measurements revealed a striking similarity in the surface morphology of the TISS paint coatings with some other surfaces exhibiting the Lotus effect.