Photocatalytic degradation of omethoate using NaY zeolite-supported TiO2

The degradation of omethoate was conducted using H₂O₂ as oxidant, TiO₂ supported on NaY zeolite as photocatalyst and a 300 W lamp as light source. The effect of the calcination temperature of the photocatalyst, the amount of TiO₂ loaded on NaY zeolite, the photocatalyst amount, the pH value and the radiation time on the degradation ratio of omethoate were investigated. The results show that TiO₂/NaY zeolite photocatalyst prepared by sol-gel method had good photocatalysis. The photocatalytic optimum oxidation conditions of omethoate are as follows: the calcination temperature of the photocatalyst is 550°C,the amount of TiO₂ loaded on NaY zeolite is 35.2 wt-%, the amount of photocatalyst is 5 g/L, pH=8 and the radiation time is 180 min. Under these conditions, the removal ratio of omethoate is up to 93%.     

TS-1分子筛光催化氧化降解氧化乐果

以TS-1分子筛为光催化剂,H2O2为氧化剂,紫外灯为光源,对农药氧化乐果进行光催化氧化降解研究。详细考察了催化剂添加质量浓度,H2O2添加体积分数和光照时间对氧化乐果降解率的影响。实验结果表明,TS-1分子筛催化剂对氧化乐果具有很好的催化降解活性。氧化乐果可以降解为CO2,NH3,SO42-,PO43-等。最佳反应条件:催化剂质量浓度5 g/L,H2O2体积分数30 mL/L,光照时间90 min,氧化乐果降解率高达96%。此反应为一级动力学反应。三次再生后,TS-1分子筛对氧化乐果的光催化活性没有明显降低。     

TiO2-V2O5纳米纤维光催化氧化烟气中的Hg0

对静电纺丝法制备的TiO₂和TiO₂-V₂O₅纳米纤维进行光催化脱除模拟烟气中Hg⁰的研究。对纳米纤维进行了SEM、TEM、XRD、BET和UV-Vis检测。结果表明TiO₂-V₂O₅纳米纤维为锐钛矿,V₂O₅高度分散在TiO₂中。纤维直径在200 nm左右,由粒径为10 nm左右的微粒组成。掺杂V₂O₅后,纤维的吸光范围扩大,在可见光范围内的吸光度比纯TiO₂时有了很大提高。实验研究了不同光照条件、V₂O₅的掺杂量和循环次数对脱汞的影响,分析了TiO₂-V₂O₅催化脱汞的机理。当V₂O₅的质量含量为3%时,TiO₂-V₂O₅在可见光下的脱汞率可达到66%,比纯TiO₂时的7%有了显著提高;纤维的脱汞性能稳定,多次循环后紫外光和可见光下的脱汞率仍分别保持在80%和65%左右。电子的跃迁和电子、空穴的快速分离是TiO₂-V₂O₅在可见光下脱汞率提高的主要原因。     

TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

Graphite-supported TiO2 for 4-nitrophenol degradation in a photoelectrocatalytic reactor

Amorphous TiO₂, prepared at room temperature through a sol–gel method implementing hydrolysis of TiCl₄, has been supported on graphite rods and then annealed at 673 K. In this way graphite was completely covered by a porous anatase TiO₂ layer, with an external thickness of about 1 μm, with graphite pores completely filled by the semiconductor particles. The obtained electrode was structurally characterized by SEM microscopy coupled to EDAX mapping and by Raman spectroscopy. A Pyrex annular reactor was designed in order to test the prepared electrodes for the photoelectrocatalytic degradation of 4-nitrophenol, a target pollutant dissolved in aqueous conductive solution. The continuous reactor worked in total recirculation mode and the degradation runs were carried out by applying near UV-light, bias or both energy sources. The influence of flow rate, initial 4-nitrophenol concentration and applied potential on the degradation rate was studied.     

纳米TiO2-UV光催化降解乙酰甲胺磷影响因素的研究

考察了UV-纳米TiO2光催化降解乙酰甲胺磷的可行性,就高压汞灯照射时间及照射方式、催化剂种类及用量、pH值、反应温度、乙酰甲胺磷初始浓度等对光催化降解效率的影响进行了研究,并探索了催化剂的重复利用。结果表明,当添加0.1 g/L的纳米TiO2(德国P25),乙酰甲胺磷的起始浓度为20 mg/L,温度控制在25℃,反应体系的pH为11时,以高压汞灯持续照射80 min,即可实现对乙酰甲胺磷99.9%的光催化降解。     

Photocatalytic degradation of methylene blue with TiO2 nanoparticles prepared by a thermal decomposition process

The generation of TiO₂ nanoparticles by the thermal decomposition of titanium tetraisopropoxide (TTIP) was carried out experimentally using a tubular electric furnace at various synthesis temperatures (700-1300 °C) and TTIP heating temperatures (80-110 °C). The photocatalytic activity of the resulting TiO₂ nanoparticles was examined by measuring the rate of methylene blue decomposition. The TiO₂ nanoparticles were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) measurements and transmission electron microscopy (TEM). The crystallite size and crystallinity increased with increasing synthesis temperature and TTIP heating temperature. A TTIP heating temperature and synthesis temperature of 95 °C and 900 °C, respectively, were found to be the optimal synthesis conditions. The primary particle diameter obtained under optimum synthesis conditions was considerably smaller than the commercial photocatalyst (Degussa, P25). The specific surface areas were more than 134.4 m² g^− 1. Under the optimal conditions, the photocatalytic activity for methylene blue was higher than that of the commercial photocatalyst.     

Photoelectrocatalytic degradation of rhodamine B using Ti/TiO2 electrode prepared by laser calcination method

The method of Ti/TiO₂ photoelectrode prepared by using laser calcination method instead of oven calcination process was introduced. The prepared TiO₂ film was observed with AFM and XRD. Photoelectrocatalytic degradation of rhodamine B (RB) using this electrode was investigated, and anodic potential and pH were optimized. The laser power applied in this electrode preparation was also discussed, and it indicated that TiO₂ particle prepared with high laser power was crystallized adequately and the photoelectrocatalytic ability was satisfactory. RB degradation was investigated under different conditions, and it showed that photoelectrocatalytic degradation could achieve efficient and complete mineralization of organic pollutant. The photoelectrocatalytic oxidation using the Ti/TiO₂ electrode calcinated by laser was compared with that of the electrode calcinated by furnace, and it showed that the reaction rate of RB degradation using the electrode by laser was faster than that by furnace. Additionally, electrochemical impedance spectroscopy (EIS) was performed at the two different photoelectrodes, which verified the higher photocatalytic activity of the laser-treated electrode further.     

Photocatalytic conversion of benzene to phenol using modified TiO2 and polyoxometalates

The application of photocatalytic reactions to organic synthesis has attracted interests in view of the development of environmentally benign synthetic processes. This study investigated the effects of various parameters (electron acceptor, surface modification, and the combination of photocatalysts) on the direct synthesis of phenol from benzene using photocatalytic oxidation processes. The OH radicals generated on UV-illuminated TiO₂ photocatalyst directly hydroxylate benzene to produce phenol, hydroquinone, and catechol. The addition of Fe³⁺, H₂O₂, or Fe³⁺ + H₂O₂ highly enhanced the phenol production yield and selectivity in TiO₂ suspension. Surface modifications of TiO₂ had significant influence on the phenol synthetic reaction. Depositing Pt nanoparticles on TiO₂ (Pt/TiO₂) markedly enhanced the yield and selectivity. Surface fluorination of TiO₂ (F-TiO₂) increased the phenol yield two-fold because of the enhanced production of mobile (free) OH radicals on F-TiO₂. Polyoxometalate (POM) in phenol synthesis played the dual role both as a homogeneous photocatalyst and as a reversible electron acceptor in TiO₂ suspension. POM alone was as efficient as TiO₂ alone in the phenol production. In particular, the addition of POM to the TiO₂ suspension increased the phenol yield from 2.6% to 11% (the highest yield obtained in this study). Reaction mechanisms for each photocatalytic system were discussed in relation to the phenol synthesis.     

TiO2 photocatalyst loaded on hydrophobic Si3N4 support for efficient degradation of organics diluted in water

TiO₂ photocatalyst loaded on Si₃N₄ (TiO₂/Si₃N₄) was prepared by a conventional impregnation method and its photocatalytic performance for the degradation of organics (2-propanol) diluted in water was compared with that of TiO₂ photocatalysts (TiO₂/SiO₂, TiO₂/Al₂O₃, and TiO₂/SiC) loaded on various types of supports (SiO₂, Al₂O₃, and SiC). The formation of the well-crystallized anatase phase of TiO₂ was observed on the calcined TiO₂/Si₃N₄ photocatalyst, while a small anatase phase of TiO₂ was observed on the TiO₂/SiC photocatalyst and amorphous TiO₂ species was the main component on the TiO₂/SiO₂ and TiO₂/Al₂O₃ photocatalysts. The measurements of the water adsorption ability of photocatalysts indicated that the TiO₂/Si₃N₄ photocatalyst exhibited more hydrophobic surface properties in comparison to other support photocatalysts. Under UV-light irradiation, the TiO₂/Si₃N₄ photocatalyst decomposed 2-propanol diluted in water into acetone, CO₂, and H₂O, and finally, acetone was also decomposed into CO₂ and H₂O. The TiO₂/Si₃N₄ photocatalyst showed higher photocatalytic activity than TiO₂ photocatalyst loaded on other supports. The well-crystallized TiO₂ phase deposited on Si₃N₄ and the hydrophobic surface of Si₃N₄ support are important factors for the enhancement of photocatalytic activity for the degradation of organic compounds in liquid-phase reactions.     

Synthesis and electrochemiluminescence of the CeO2/TiO2 composite

CeO₂/TiO₂ composite with kernel–shell structure was synthesized by a sol–gel process. The characterization results show that the composite is made up of anatase phase TiO₂ and cubic system CeO₂. The electrochemiluminescence (ECL) behavior of the CeO₂/TiO₂ composite was studied by a cyclic voltammetry in the presence of persulfate, and the effect factors on ECL emission were discussed. Based on a series of experiments, it is proposed that the strong dual ECL emission produced by the CeO₂/TiO₂ composite resulted from the benefit ECL effect of interface heterojunction in composite.     

Combined TiO2/SiO2 mesoporous photocatalysts with location and phase controllable TiO2 nanoparticles

Combined TiO₂/SiO₂ mesoporous materials were prepared by deposition of TiO₂ nanoparticles synthesised via the acid-catalysed sol–gel method. In the first synthesis step a titania solution is prepared, by dissolving titaniumtetraisopropoxide in nitric acid. The influences of the initial titaniumtetraisopropoxide concentration and the temperature of dissolving on the final structural properties were investigated. In the second step of the synthesis, the titania nanoparticles were deposited on a silica support. Here, the influence of the temperature during deposition was studied. The depositions were carried out on two different mesoporous silica supports, SBA-15 and MCF, leading to substantial differences in the catalytic and structural properties. The samples were analysed with N₂-sorption, X-ray diffraction (XRD), electron probe microanalysis (EPMA) and transmission electron microscopy (TEM) to obtain structural information, determining the amount of titania, the crystal phase and the location of the titania particles on the mesoporous material (inside or outside the mesoporous channels). The structural differences of the support strongly determine the location of the nanoparticles and the subsequent photocatalytic activity towards the degradation of rhodamine 6G in aqueous solution under UV irradiation.     

Photocatalytic properties of TiO2 sol-gel modified nanocomposite films

TiO₂ nanocomposite films with different concentrations of TiO₂ MT-150A nanoparticles were immobilized on glass substrates using a dip coating process. The crystalline structure and surface chemical state of nanocomposite film properties were examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The specific surface area and morphology of TiO₂ MT-150A nanoparticles were evaluated by the BET method and Field Emission Scanning Electron Microscopy (FE-SEM). The photocatalytic activities of films were evaluated by the methyl orange decoloring rate. XPS measurements showed that the oxygen amount (%) was related to the film composition. The composite film with 10 g/L MT-150A loading yielded the highest amount of surface oxygen (26.82%) and TiO₂ rutile showed the lowest amount of surface oxygen (13.67%) in the form of surface hydroxyl groups. The remaining oxygen was identified as lattice oxygen. In addition, the nanocomposite film with 10 g/L MT-150A loading yielded the highest photocatalytic activity.     

Photocatalytic conversion of NO using TiO2–NH3 catalysts in ambient air environment

Photocatalytic conversion of nitric oxide (NO) in ambient air was studied in a continuous-flow photoreactor system at room temperature using different TiO₂ catalysts prepared with different titanium precursors of Ti(SO₄)₂, TiOSO₄, and Ti(O-Bu)₄ by either a moderate-temperature hydrothermal process or a hydrothermal reflux process. The physicochemical properties of the prepared catalysts were characterized by XRD, BET, FTIR, and SEM. Analytical results showed that the crystallinity, morphology, nitrogen adsorption–desorption isotherms, specific surface area, and pore size distribution of catalysts were significantly affected by the precursors and hydrothermal processes, but the crystal structure and crystal size of catalysts were not significantly influenced. The NO conversion experiments demonstrated that the TiO₂ catalysts prepared by the moderate-temperature hydrothermal process without ammonia pretreatment could effectively reduce NO to different low levels, in which the catalysts with longer aging time of more than 12 h performed better than the catalysts with shorter aging time. However, it was found that the NO₂ concentration in outlet gas was gradually increased with extension of an experimental period. Two TiO₂ catalysts (TOSO-NH₃ and TOB-NH₃) prepared by the hydrothermal reflux process with ammonia pretreatment demonstrated a very good performance in NO conversion and also maintained a low level of NO₂ concentration in outlet gas. This study indicated that using the TiO₂ catalysts modified with ammonia pretreatment in photocatalytic reaction could provide a good approach to effectively eliminate the accumulation of NO₂ product from NO oxidation in the system and to achieve a sustainable process, which may be applicable for NO elimination in ambient air environment.     

ML-WO3/TiO2异质结的制备及其对罗丹明B的光催化降解

采用空间限域法制备了单层三氧化钨纳米片(ML-WO₃),然后将其与TiO₂复合得到ML-WO₃/TiO₂纳米材料,被用来在模拟太阳光下对罗丹明B进行光催化降解。ML-WO₃/TiO₂的组成和光学特性通过扫描电镜、透射电镜、高分辨透射电镜、X射线衍射、紫外-可见吸收光谱和光致发光光谱手段进行表征。结果证实,纳米ML-WO₃/TiO₂克服了纯TiO₂带隙较大的缺陷,在全波段太阳光表现出比ML-WO₃和TiO₂更强的吸收性能,ML-WO₃与TiO₂之间具有明显的协同效应。活性物种捕获实验表明.OH和.O_2^-自由基是RhB降解的主要活性物种。ML-WO₃和TiO₂之间构建的Z型异质结电荷转移路径能够保证光生载流子的高效分离和重组。在5次循环实验后ML-WO₃/TiO₂的光催化活性仍能接近80%,具有良好的光化学稳定性。通过高效液相色谱-质谱检测RhB的中间产物,推测了RhB可能的降解路径。     

Solid-phase photocatalytic degradation of polystyrene with modified nano-TiO2 catalyst

A novel photodegradable polystyrene-grafted-TiO₂ (PS-g-TiO₂) nanocomposite was prepared by embedding the grafted-TiO₂ into the commercial polystyrene. Solid-phase photocatalytic degradation of the PS-g-TiO₂ nanocomposite was carried out in ambient air at room temperature under ultraviolet lamp and/or sunlight irradiation. The properties of composite film were compared with those of the pure PS film by methods such as weight loss measurement, scanning electron microscope (SEM), gel permeation chromatogram (GPC), X-ray photoelectron spectroscopy (XPS), FT-IR spectroscopy, and UV-vis spectroscopy. The results show that the photo-induced degradation of PS-g-TiO₂ composite film is significantly higher than that of pure PS film. The weight loss of composite film reached 31.9%, average molecular weight (M_w) of composite film decreased by 53.1%, and the number average molecular weight (M_n) decreased by 73.2% after 396 h of UV-light irradiation. FT-IR analysis and weight loss indicated that the benzene rings in PS-matrix of composite film were cleaved during UV-light irradiation. The photocatalytic degradation mechanism of the films is briefly discussed.