Synthesis, characterization and photocatalytic reactivity of Ti-containing micro- and mesoporous materials

Ti-oxides incorporated within the framework of microporous zeolites and mesoporous molecular sieves were found to exhibit high and unique photocatalytic activity for the decomposition of NO into N₂ and O₂ as well as the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH. Spectroscopic investigations of these catalytic systems using photoluminescence, UV-vis, XAFS (XANES and FT-EXAFS) and IR analyses revealed that the charge transfer excited state of the isolated tetra-coordinated Ti-oxides plays a vital role in these photocatalytic reactions. The reactivity of such Ti-oxides was found to depend strongly on their local structures which were controlled by the unique framework structures of the micro- and mesoporous material supports.     

The effect of platinum and silver deposits in the photocatalytic oxidation of resorcinol

The effects of platinum (Pt) and silver (Ag) metallisation in the photocatalytic oxidation of resorcinol at pH 3 ± 0.5 have been investigated. The photocatalytic degradation of resorcinol was significantly improved by Pt/TiO₂, while the presence of Ag/TiO₂ enhanced the initial photocatalytic degradation rate of resorcinol slightly. Likewise, the photocatalytic mineralisation of resorcinol continued to be enhanced by Pt/TiO₂, but it was retarded when Ag/TiO₂ was used.

The function of Pt and Ag deposits on the surface of TiO₂ has been found to be markedly influenced by the interaction of resorcinol and its degradation products with the metal deposits. The presence of Pt or Ag on the surface of TiO₂ altered the distribution of degradation products of resorcinol as well as the production of photoactive species for the photocatalytic oxidation of resorcinol. The X-ray photoelectron spectroscopy (XPS), zeta potential and transmission electron microscopy (TEM) analyses have indicated that the contrasting effect of Pt and Ag deposits were governed by the oxidation states and the catalytic property of metal deposits. In addition to that, it has been found that the roles of metal deposits are specific and should not be generalised.     

Decolorization of organic dyes on Pilkington Activ™ photocatalytic glass

The air–solid photocatalytic degradation of organic dye films Acid Blue 9 (AB9) and Reactive Black 5 (RBk5) is studied on Pilkington Activ™ glass. The Activ™ glass comprises of a colorless TiO₂ layer deposited on clear glass. The Activ™ glass is characterized using atomic force microscopy (AFM) and X-ray diffraction (XRD). Using AFM, the TiO₂ average agglomerate particle size is 95 nm, with an apparent TiO₂ thickness of 12 nm. The XRD results indicate the anatase phase of TiO₂, with a calculated crystallite size of 18 nm.

Dyes AB9 and RBk5 are deposited in a liquid film and dried on the Activ™ glass to test for photodecolorization in air, using eight UVA blacklight-blue fluorescent lamps with an average UVA irradiance of 1.4 mW/cm². A novel horizontal coat method is used for dye deposition, minimizing the amount of solution used while forming a fairly uniform dye layer. About 35–75 monolayers of dye are placed on the Activ™ glass, with a covered area of 7–10 cm². Dye degradation is observed visually and via UV–vis spectroscopy.

The kinetics of photodecolorization satisfactorily fit a two-step series reaction model, indicating that the dye degrades to a single colored intermediate compound before reaching its final colorless product(s). Each reaction step follows a simple irreversible first-order reaction rate form. The average k₁ is 0.017 and 0.021 min⁻¹ for AB9 and RBk5, respectively, and the corresponding average k₂ is 2.0 × 10⁻³ and 1.5 × 10⁻³ min⁻¹. Variable light intensity experiments reveal a p = 0.44 ± 0.02 exponent dependency of initial decolorization rate on the UV irradiance. Solar experiments are conducted outdoors with an average temperature, water vapor density, and UVA irradiance of 30.8 °C, 6.4 g water/m³ dry air, and 1.5 mW/cm², respectively. For AB9, the average solar k₁ is 0.041 min⁻¹ and k₂ is 5.7 × 10⁻³ min⁻¹.     

关于解决g-C3N4在光催化制氢领域的两个局限的研究进展

随着工业的发展，化石燃料消耗巨大，环境问题也日益突出，寻找一种绿色新型能源已成为一个被广泛讨论的问题。氢气是一种清洁、可再生燃料，利用光催化剂分解水制氢气是一种制取氢气的有效途径。石墨碳氮化物（g-C3N4）作为光催化剂不仅成本低、反应稳定，而且其尺寸、厚度、结构、形貌等可控，在众多光催化剂中脱颖而出。但g-C3N4目前在光催化领域主要存在两个局限：g-C3N4不能有效地吸收光来产生足够多的光生电子-空穴对；g-C3N4不能有效的运输及分离光生电子-空穴对，以至于电子与空穴的复合率较高。文章综述了g-C3N4在光催化制氢领域的进展成果，分析了g-C3N4存在的问题并总结了其改进方法，最后对g-C3N4进行了展望，以期为设计高效、稳定的光催化制氢材料提供参考。     

In-situ synthesis of TiO2 nanostructures on Ti foil for enhanced and stable photocatalytic performance

TiO_2 nanostructures with strong interfacial adhesion and diverse morphologies have been in-situ grown on Ti foil substrate through a multiple-step method based on conventional plasma electrolytic oxidation(PEO) technology, hydrothermal reaction and ion exchange process. The PEO process is critical to the formation of TiO_2 seeding layer for the nucleation of Na_2Ti_3O_7 and H_2Ti_3O_7 mediates that are strongly attached to the Ti foil. An ion exchange reaction can finally lead to the formation of H_2Ti_3O_7 nanostructures with diverse morphologies and the calcination process can turn the H_2Ti_3O_7 nanostructures into TiO_2 nanostructures with enhanced crystallinity. The morphology of the TiO_2 nanostructures including nanoparticles(NP), nanowhiskers(NWK), nanowires(NW) and nanosheets(NS) can be easily tailored by controlling the NaOH concentration and reaction time during hydrothermal process. The morphology, composition and optical properties of TiO_2 photocatalysts were analyzed using scanning electron microscope(SEM), X-ray diffraction(XRD), photoluminescence(PL) spectroscopy and UV–vis absorption spectrum. Photocatalytic tests indicate that the TiO_2 nanosheets calcined at 500?C show good crystallization and the best capability of decomposing organic pollutants. The decoration of Ag cocatalyst can further improve the photocatalytic performance of the TiO_2 nanosheets as a result of the enhanced charger separation efficiency. Cyclic photocatalytic test using TiO_2 nanostructures grown on Ti foil substrate demonstrates the superior stability in the photodegradation of organic pollutant, suggesting the promising potential of in-situ growth technology for industrial application.     

Relationship of structure and enhanced photocatalytic activity of S-scheme BiOCl/g-C3N4 heterojunction for xanthate removal under visible light

Constructing heterojunctions is an excellent way to enhance the photocatalytic property of semiconductors. Herein, a range of S-scheme BiOCl/g-C₃N₄ heterojunctions with varying mass ratios were designed using a facile hydrothermal route, and their photocatalytic ability was assessed by degrading the ethyl xanthate (EX) under visible light (λ > 400 nm). The results showed that the degradation efficiency of BiOCl/g-C₃N₄-0.1 heterojunction for EX was up to 91.2 % within 180 min, and its apparent rate constants (K_app) were 4.3 and 11 times greater than those of BiOCl and g-C₃N₄, respectively. The experimental and characterization results revealed that the excellent photocatalytic property was ascribed to the construction of S-scheme heterojunctions. Such structure not only enhanced the visible light response but also facilitated the efficient separation of photoinduced carriers with the S-scheme transfer route, retaining strong redox-capable holes and electrons to participate in surface reactions. Furthermore, the cycling experiments indicated that the fabricated photocatalysts have great recyclability and stability. Based on the results of active substance capture, the S-scheme charge transfer model was proposed and the photodegradation mechanism of EX was reasonably elucidated. Overall, this work offers some theoretical direction for the design and construction of S-scheme heterojunctions with superior visible-light-driven photocatalytic performance.     

Photocatalytic treatment of water-soluble pesticides by photo-Fenton and TiO2 using solar energy

The technical feasibility and performance of photocatalytic degradation of four water-soluble pesticides (diuron, imidacloprid, formetanate and methomyl) have been studied at pilot scale in two well-defined systems of special interest because natural-solar UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. The pilot plant is made up of compound parabolic collectors (CPCs) specially designed for solar photocatalytic applications. Experimental conditions allowed disappearance of pesticide and degree of mineralisation achieved in the two photocatalytic systems to be compared. In order to assure that the photocatalytic results are consistent, hydrolysis and photolysis tests have been performed with the four pesticides. The initial concentration tested with imidacloprid, formetanate and methomyl was 50 and 30 mg/l with diuron, and the catalyst concentrations were 200 mg/l and 0.05 mM with TiO₂ and iron, respectively. Total disappearance of the parent compounds and 90% mineralisation have been attained with all pesticides tested, methomyl being the most difficult to be degraded with both treatments. First-order rate constants, initial rate, time necessary for mineralising 90% of the initial TOC and hydrogen peroxide consumption were calculated in all cases, enabling comparison both of treatments and of the selected pesticide reactivity.     

Photocatalytic property of SiO2/TiO2 nanoparticles prepared by sol-hydrothermal process

Silica-embedded nanocrystalline TiO₂ powders were synthesized by sol-hydrothermal process. The influence of the composition of the solvent and the embedded silica content on the phase transition, grain growth and subsequently, on the photoactivity of TiO₂ were investigated. The volume ratio of ethanol to water for the solvent composition was varied from 0.125 to 8 and the mole fraction of silica content was changed from 0 to 0.4, while the condition for hydrothermal reaction was fixed at 250^∘C for 2 hour. With an increase in ethanol content in solvent composition, the crystallite sizes of pure TiO₂ particles decreased from 15 nm to 6 nm and crystal phase changed from rutile/anatase mixed phase to pure anatase phase. Addition of silica to TiO₂ brought about an increase in the photocatalytic activity by suppressing the phase transition from anatase to rutile. Judging from the result of the decomposition of 1, 4-dichlorobenzene, the most efficient catalyst was found to be 0.2 mole fraction SiO₂ embedded TiO₂ prepared with ethanol-rich solvent (the volume ratio of ethanol to water is 4).     

Preparation and characterisation of titanium dioxide films for catalytic applications generated by anodic spark deposition

The advanced plasma electrochemical process of anodic spark deposition (ASD) was used to generate photoactive titanium dioxide films on titanium metal substrates. A shift to easier-to-machine substrates was demonstrated by the deposition of a titanium film with physical vapour deposition onto different materials such as glass, silicon, and stainless steel prior to ASD. Obtained films were characterised by scanning electron microscopy, surface area measurement (Brunnauer-Emmett-Teller method, BET), X-ray diffraction, electron-probe microanalysis, and glow discharge spectroscopy. Additionally, film thickness was determined by eddy current measurements. Standard ASD conditions were defined as 180 V applied voltage over a 180 s hold time, a voltage ramp of 20 V/s, a duty cycle of 0.5 and a frequency of 1500 Hz. Most prominent characteristics of the titanium films produced under these standard conditions are a film thickness of ≤80 μm, a surface area of approximately 51 m²/g (BET) and an anatase content of approximately 30% and rutile content of approximately 70%. Furthermore, the film formation process is elucidated and the dependence of film thickness on deposition time and the dependence of the anatase and rutile content on the deposited mass are shown for varying ASD conditions.     

水滑石类光催化剂在污水处理中的应用

双金属复合氢氧化物（LDHs,又叫水滑石）因具有层状结构、稳定的物化性质和电子特性等优点,可以大范围地应用在污水处理中。目前,水滑石作为光催化剂及其复合材料在污水处理上的应用受到越来越多的关注。综述了水滑石光催化剂的制备及其改性,着重介绍了不同类型水滑石对水中不同污染物的去除效果,并简要阐述了水滑石光催化剂的作用机理和研究现状。最后,展望了水滑石光催化剂的发展趋势,以期为后续水滑石在污水处理上的应用提供借鉴。