Synthesis and photocatalytic activity for water-splitting reaction of nanocrystalline mesoporous titania prepared by hydrothermal method

Nanocrystalline mesoporous TiO₂ was synthesized by hydrothermal method using titanium butoxide as starting material. XRD, SEM, and TEM analyses revealed that the synthesized TiO₂ had anatase structure with crystalline size of about 8 nm. Moreover, the synthesized titania possessed a narrow pore size distribution with average pore diameter and high specific surface area of 215 m²/g. The photocatalytic activity of synthesized TiO₂ was evaluated with photocatalytic H₂ production from water-splitting reaction. The photocatalytic activity of synthesized TiO₂ treated with appropriate calcination temperature was considerably higher than that of commercial TiO₂ (Ishihara ST-01). The utilization of mesoporous TiO₂ photocatalyst with high crystallinity of anatase phase promoted great H₂ production. Furthermore, the reaction temperature significantly influences the water-splitting reaction.     

Solar hydrogen production. Significant effect of Na2CO3 addition on water splitting using simple oxide semiconductor photocatalysts

Recent progress in photocatalytic decomposition of water to H₂ and O₂ using simple oxide semiconductor catalysts has been reviewed. Addition of Na₂CO₃ to Pt/TiO₂ suspension in water enhanced the stoichiometric decomposition significantly. This Na₂CO₃ addition method has been proved to be very useful to accelerate water splitting over various kinds of oxide semiconductor photocatalysts. The role of CO₃ ^2– anion on the acceleration of water splitting was clarified. Finally, it was firstly demonstrated in the world that water was decomposed efficiently and stoichiometrically to H₂ and O₂ using a 3 wt% NiOx/TiO₂ photocatalyst under real solar light irradiation in Tsukuba, Japan by this Na₂CO₃ addition method.     

Study on mechanism of photocatalytic performance of La-doped TiO2/Ti photoelectrodes by theoretical and experimental methods

TiO₂ photoelectrodes with various nanostructures have been successfully prepared by the anodization method. The morphology, microstructure and optical properties of as-prepared photoelectrodes were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), ultraviolet/visible light diffuse reflectance spectra (UV/vis/DRS), surface photovoltage spectroscopy (SPS) and photocurrent. The electronic structure and optical properties of La doped/undoped TiO₂ photoelectrodes with different crystal structures were calculated by the density function theory. The photocatalytic and photoelectrocatalytic activities of as-prepared photoelectrodes were evaluated. The results showed that the anodization potentials played a crucial role in the surface morphology and microstructure. Both results of theoretical calculations and experimental tests demonstrated that La-doped photoelectrodes were more sensitive to light than undoped one. The difference of photoelectrodes performance was ascribed to the crystal configuration, impurity energy levels and long-range orientation moving of photogenerated carriers.     

Carbon modified (CM)-n-TiO2 thin films for efficient water splitting to H2 and O2 under xenon lamp light and natural sunlight illuminations

Visible light-active carbon modified n-type titanium oxide (CM-n-TiO₂) thin films were synthesized by both flame oxidation and a combination of spray pyrolysis and flame oxidation. An undoped reference sample was also synthesized in an electric oven for comparison. Photoresponse of CM-n-TiO₂ and n-TiO₂ was evaluated by measuring the rates of water splitting to hydrogen and oxygen, in terms of observed photocurrent densities. Under monochromatic illumination from a xenon lamp, the integrated photocurrent densities from 300 nm to wavelengths corresponding to band gaps were found to be 1.12, 7.7, and 12.7 mA cm⁻² for optimized oven-made n-TiO₂ (sample 1), flame-made (sample 2), and spray pyrolysis flame-made CM-n-TiO₂ (sample 3) thin films at 0.48, 0.24, and 0.215 V biases, respectively. The corresponding maximum photoconversion efficiencies for these thin films were 0.84%, 7.62%, and 12.89%, respectively. Under actual natural global AM 1.5 sunlight illumination of 1 sun, the photocurrent densities for water splitting were 0.85, 5.89, and 12.27 mA cm⁻² for samples 1, 2, and 3, respectively. These photocurrent densities generated the maximum photoconversion efficiencies of 0.67%, 5.63%, and 12.26% for samples 1, 2, and 3, respectively, under global sunlight illuminations. These values compared well with those found under monochromatic light illumination from the xenon lamp. The increasing efficiencies were found to be consistent with lowering of main band gap from 3.0 eV to 2.65 eV and the generation of mid-gap bands at 1.6 eV and 1.4 eV above the valence band for samples 2 and 3, respectively. Carbon contents were found to be 0.0, 17.60, and 23.23 atom% for samples 1, 2, and 3, respectively. Dedicated to the 85th birthday of John O’ M. Bockris.     

Methane generated during photocatalytic redox reaction of alcohols on TiO2 suspension in aqueous solutions

Studies on the photo-catalytic redox reaction of C1–C3 alcohols such as methanol, ethanol and 2-propanol were carried out in aqueous solution containing TiO₂ photocatalyst (0.1% w/v) as suspension using 350 nm light. Other hydrocarbons such as ethane and ethene in the case of ethanol, and propene in the case of 2-propanol with low yields were produced along with the major photolytic products methane and carbon dioxide. The yields of methane and CO₂ were found to be dependent on the light exposure time and ambient conditions. Methane yields were higher in 2-propanol and ethanol systems than in methanol system, showing their better hole-scavenging properties. In the aerated condition, methane was produced during photolysis of all alcohols in the presence of TiO₂ and the yield was comparable to those observed in the corresponding CO₂-saturated systems. The overall results reveal that the surface adsorbed, as well as in-situ-generated CO₂ from photo-oxidation of alcohols are equally responsible for methane formation through photo-reduction in presence of TiO₂. In the O₂-saturated system, the methane yield was lower as compared to that in aerated system, in contrast to the CO₂ yield. In N₂O-and N₂-purged systems, the yield of methane was observed to be low, inferring that the methane generation has not taken place through photodecomposition/photodissociation of alcohols. Again, photolysis of alcohols without TiO₂ did not generate any methane.     

Photoelectrochemical water splitting and simultaneous photoelectrocatalytic degradation of organic pollutant on highly smooth and ordered TiO2 nanotube arrays

The photoelectrochemical water splitting and simultaneous photoelectrocatalytic degradation of organic pollutant were achieved on TiO₂ nanotube electrodes with double purposes of environmental protection and renewable energy production under illumination of simulated solar light. The TiO₂ nanotube arrays (TiO₂ NTs) were fabricated by a two-step anodization method. The TiO₂ NTs prepared in two-step anodization process (2-step TiO₂ NTs) showed much better surface smoothness and tube orderliness than TiO₂ NTs prepared in one-step anodization process (1-step TiO₂ NTs). In the photoelectrochemical water splitting and simultaneous photoelectrocatalytic decomposition process, the 2-step TiO₂ NTs electrode showed both highest photo-conversion efficiency of 1.25% and effective photodecomposition efficiency with existing of methylene blue (MB) as sacrificial agent and as pollutant target. Those results implied that the highly ordered nanostructures provided direct pathway and uniform electric field distribution for effective charges transfer, as well as superior capabilities of light harvesting.     

Effect of electrolysis conditions on photocatalytic activities of the anodized TiO2 films

Photocatalytic activities of anodized TiO₂ films for decomposition of gaseous acetaldehyde were investigated. The anodized TiO₂ films were fabricated by galvanostatic anodization in a mixed electrolyte composed of H₂SO₄, H₃PO₄, and H₂O₂. Pre-nitridation treatment effectively enhanced the photocatalytic activity of the anodized TiO₂ films. The electrolysis parameters such as anodization time, current density, electrolyte temperature, and electrolyte composition significantly affected the photocatalytic activity of the anodized TiO₂ films. The improvement of photocatalytic activity of the anodized films is attributed to increase in surface areas of the anodized specimens.     

Effect of metal deposition on the photocatalytic activity of titania-silica for the removal of 2-propanol diluted in water

The influence of transition metals, such as Ag, Cr, and Co, on the photocatalytic properties of titania-silica (TiO₂-SiO₂) prepared via both impregnation (imp) and photo-assisted deposition (PAD) methods has been investigated. The decomposition of 2-propanol under UV-light irradiation was used to probe the effect of transition metals deposition on the activity of titania-silica. PAD-Ag/TiO₂-SiO₂ prepared by the PAD method was highly active compared to the original TiO₂-SiO₂, while imp-Cr/TiO₂-SiO₂ prepared by conventional impregnation method showed a weak tendency toward the decomposition of 2-propanol.     

Composition dependence of the photophysical and photocatalytic properties of (AgNbO3)1−x(NaNbO3)x solid solutions

A series of orthorhombic photocatalysts (AgNbO₃)_1−x(NaNbO₃)_x solid solutions have been synthesized by a solid-state reaction method. The composition dependence of the photophysical and photocatalytic properties of synthesized solid solutions has been investigated systematically. With an increase in the content of NaNbO₃, we found that (1) the lattice parameters decreased; (2) the Nb-O bond length in NbO₆ octahedron reduced; (3) the band gap increased; and (4) the mean particle size decreased while the Brunauer-Emmett-Teller (BET) surface area increased. Photocatalytic activities of the (AgNbO₃)_1−x(NaNbO₃)_x (0?x?0.5) samples were evaluated from gaseous 2-propanol (IPA) decomposition into acetone and CO₂ under visible-light irradiation emitted from blue-light-emitting diodes (BLEDs; light intensity: 0.01 mW cm⁻²). Among all the samples, the (AgNbO₃)_0.6(NaNbO₃)_0.4 sample showed the highest photocatalytic activity.     

Parameters controlling the photocatalytic performance of ZnO/Hombikat TiO2 composites

Commercial TiO₂ (Hombikat, UV-100) was impregnated with different loadings of zinc nitrate solution and subsequently calcined at different temperatures in order to obtain a stable homogeneous solid composite of ZnO/TiO₂. The prepared samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM), UV-vis and Raman spectroscopy, inductively coupled plasma mass spectroscopy (ICP), X-ray photoelectron spectroscopy (XPS) as well as N₂ adsorption and desorption measurements. Results show that ZnO was incorporated within the TiO₂ crystals and did not form a separate bulky phase or metallic zinc. Moreover, the calcination temperature dramatically modifies the texture properties of the prepared samples compared with original Hombikat TiO₂. The photocatalytic performance of the prepared samples was evaluated by monitoring the degradation of methyl orange dye under black light illumination. Three main parameters were studied; ZnO loading, surface area and initial pH of the methyl orange solution. The variation in ZnO loading appears to have less influence on the catalytic activity than either the surface area or the pH.     

Influence of thermal treatment on the ion-storage capacity of Ce oxide and Ce-V mixed oxide films

Thin films and the corresponding xerogels of CeO₂ and Ce-V mixed oxides with a molar ratio equal to 2 (Ce/V=2) were prepared from CeCl₃·7H₂O and NH₄VO₃ precursors using the sol-gel route and the dip-coating technique. The thermal decomposition of both forms of samples (thin films and xerogels) were studied by dynamic TG and DSC in two different atmospheres (air and argon). For the thermal studies the thin films were deposited on aluminium foil to reduce the unfavourable substrate to film mass ratio S/F, which is a consequence of using a glass substrate. The mode of heat treatment in a tube furnace of films deposited on conductive glass was defined from the TG curves of the films. The influence of annealing conditions (temperature, atmosphere and time) on the charge capacity of the films during application of the cycling process is reported.     

Study of the influential factors in the simultaneous photocatalytic degradation process of three textile dyes

The influence of several factors in the simultaneous photocatalytic degradation of three textile dyes - Acid Red 97, Acid Orange 61 and Acid Brown 425 - has been studied using a fractional factorial design 2^5-1. The considered factors were: the initial concentration of each dye, the catalyst concentration (TiO₂) and pH.First, we developed a rapid analytical methodology based on recording UV-visible spectra during the degradation process and a data treatment using multivariate curve resolution with alternating least squares (MCR-ALS), which enabled the three dyes to be quantified simultaneously despite the overlap of their spectra.The kinetic constant of degradation for each dye in all the experiments was evaluated. In all cases the degradation followed a first order kinetics. For a significance level of 5%, the most important factor in the photodegradation of each dye is the concentration of Acid Red 97, the degradation is more effective at higher pHs and, in the studied range, the concentration of the catalyst is not important.     

Characterization of TiO2 thin film immobilized on glass tube and its application to PCE photocatalytic destruction

TiO₂ was immobilized on to the surface of a pyrex glass tube through a dip coating process, and a pyrex glass tube with TiO₂ thin film was used as a batch reactor and continuous flow reactor for the photocatalytic destruction of PCE in water. TiO₂ could be successfully immobilized with a thickness of 0.3 μm in the pyrex glass tube. The TiO₂-immobilized pyrex glass tube itself showed high photocatalytic activity for the destruction of PCE in water.     

ESR study on the visible photocatalytic mechanism of nitrogen-doped novel TiO2: Synergistic effect of two kinds of oxygen vacancies

The visible photocatalytic mechanism of nitrogen-doped novel TiO₂ was studied by means of electron spin resonance spectroscopy (ESR). It was found that, under visible light irradiation, the concentration of single-electron-trapped oxygen vacancy (SETOV, V_o^•) of novel TiO₂ remained unchanged, but that of nitrogen-doped novel TiO₂ increased and returned to original state when the light was turned off. This implies that, aside from V_o^• in bulk of nitrogen-doped novel TiO₂, oxygen vacancy without trapped electron (V_o^••) was formed on its surface. V_o^•• as a surface electron trap captured photogenerated electron from the bulk to generate extra V_o^•, carrying out photocatalytic reaction on the surface. At the same time, nitrogen doping product NO was chemically adsorbed on the vicinity of V_o^•• and inhibited the attack of oxygen, allowing V_o^•• to remain stable in air. The synergistic action of the two kinds of active structures, i.e., bulk V_o^•–NO–Ti and surface V_o^••–NO–Ti, accounted for the visible photocatalytic activity of N-doped novel TiO₂.     

Hydrothermal synthesis of mesostructured nanocrystalline TiO2 in an ionic liquid–water mixture and its photocatalytic performance

Anatase mesostructured TiO₂ nanocrystalline was prepared in a mixture of 1-butyl-3-methyl-imidazolium tetrafluoroborate (BMIM⁺BF₄⁻) ionic liquid and water by a low temperature hydrothermal method. The obtained materials were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and N₂ adsorption–desorption. The existence of BMIM⁺BF₄⁻ enhanced the polycondensation and crystallization rate, which encouraged the formation of anatase crystal. The TiO₂ particles were thermally very stable and thus resistant to anatase-rutile phase transformation during calcination at high temperatures. The anatase TiO₂ showed high photocatalytic activity in the degradation of p-chlorophenol than that of the commercially available TiO₂, Degussa P25. After 2 h reaction under the UV-irradiation of 250 W, the removing rate of p-chlorophenol was up to 96.3%.     

N掺杂对TiO2形态结构及光催化活性的影响

以TiCl₄为钛源,采用酸催化水解法合成TiO₂前驱体,在NH₃/N₂气氛下经不同温度处理制得浅黄色的N掺杂TiO₂(TON)光催化剂。以苯酚为模型物,考察了催化剂在紫外光区、可见光区及太阳下催化活性;采用DRS、XPS、XRD、FTIR、SEM及低温氮物理吸附对光催化剂的晶相结构、光谱特征和表面结构等进行表征。系统研究了N掺杂对TiO₂形态结构及光催化活性的影响。结果表明,掺杂N以阴离子形式进入TiO₂体相中置换晶格中的O,适宜温度下制得适量N掺杂的TON在紫外光区、可见光区及太阳光下均表现出较高的活性。N掺杂在TiO₂表面生成Ti-O-N键,形成新的能级结构,使催化剂的吸收红移至450～550 nm,诱发TiO₂可见光催化活性。同时高温下煅烧,N掺杂可抑制TiO₂晶粒生长,减缓TiO₂粒子间团聚,提高锐钛矿相向金红石相转变温度,减缓相转化速度。     

Influence of High-energy electron-beam on photocatalytic activity of TiO2 films on carbon-fiber deposited by atomic layer deposition

High-energy electron-beam with energy of 1 MeV was used for modifying surface structure of TiO₂ thin films on carbon fiber prepared by using atomic layer deposition under atmospheric pressure. TiO₂ nanoparticles (∼20 nm) on carbon fiber underwent structural modification of the surface upon electron-beam treatment, resulting in enhanced photocatalytic activity. In contrast, a thicker film of TiO₂ did not show such changes in surface structure and photocatalytic activity by electron-beam treatment. We demonstrate that electron-beam can be used for modifying surface structure of photocatalysts consisting of nanoparticles for improvement of their activity.     

MoS2核壳球上氧掺杂的动力学调制及其电化学分解水效应

在氩气气氛中900℃煅烧前驱物MoS₂核壳超级球得到MoS₂核壳球。在升温速率为20、10、5、2℃·min^-1时,MoS₂核壳球上氧掺杂量分别从前驱物的23.1%降低到17.6%、10.8%、5.5%、6.2%。结果表明较低的升温速率可以导致更低的氧掺杂量。基于前驱物特殊的准分子超晶格结构,提出了原位阴离子交换反应机理,以深入理解MoS₂核壳球上氧掺杂的动力学调制机理。电化学性能研究表明通过调制氧掺杂量可以有效改善MoS₂核壳球电化学分解水的性能。     

Preparation and characterization of Zr doped TiO2 nanotube arrays on the titanium sheet and their enhanced photocatalytic activity

This paper described a new method for the preparation of Zr doped TiO₂ nanotube arrays by electrochemical method. TiO₂ nanotube arrays were prepared by anodization with titanium anode and platinum cathode. Afterwards, the formed TiO₂ nanotube arrays and Pt were used as cathode and anode, respectively, for preparation of Zr/TiO₂ nanotube arrays in the electrolyte of 0.1 M Zr(NO₃)₄ with different voltage and post-calcination process. The nanotube arrays were characterized by field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS) and UV-Vis diffusion reflection spectra (DRS). The photocatalytic activities of these nanotubes were investigated with Rhodamine B as the model pollutant and the results demonstrated that the photocatalytic efficiency of Zr doped TiO₂ nanotubes was much better than that of TiO₂ nanotubes under UV irradiation. Zr/TiO₂ nanotube arrays doped at 7 V and calcined at 600 °C (denoted as TiO₂-7 V-600) achieved the best photocatalytic efficiency and the most optimal doping ratio was 0.047 (Zr/Ti). TiO₂-7 V-600 could be reused for more than 20 times and maintained good photocatalytic activities.     

掺杂钒和硅对TiO2薄膜超亲水性的影响

0引言 TiO2薄膜是众多氧化物半导体薄膜中研究最为广泛的一种材料．其表面的超亲水性和表面自清洁效应开辟了光催化薄膜功能材料的新的研究领域，已成为众多研究者研究的对象。但是如果薄膜仅由TiO2组成，当光照停止，水在TiO2薄膜表面的润湿角逐渐升高．并恢复原始状态。TiO2的禁带较宽，普通光线如太阳光等都不能将其激发．限制了其实际应用。因此如何使TiO2材料的光谱响应范围由紫外光反扩展到可见．光区一日如何更长时间地保持薄膜良好的亲水性是目前研究的重点。