Photocatalytic ozonation of gallic acid in water

Aqueous solutions of gallic acid have been treated with five different oxidation‐radiation processes: visible and ultraviolet A radiation (VUVA), TiO₂ adsorption, ozonation, VUVA/TiO₂ photocatalysis and VUVA/O₃/TiO₂ photocatalytic ozonation. With the exception of VUVA radiation and TiO₂ adsorption, ozone and photolytic processes allow for the total removal of gallic acid in a period between 50 and 90 min. The time taken to achieve 100% gallic acid conversion depends on the oxidation process applied, photocatalytic ozonation being the most effective technique. Throughout the process, oxalic and formic acids were identified as byproducts. Some other unidentified compounds probably related to pyruvic, malonic and maleic acids were also detected. The appearance of these compounds can be justified from direct reactions of both hydroxyl radical and ozone in water. Only photocatalytic ozonation leads to total mineralisation of the organic matter in less than 90 min. The photocatalyst used, TiO₂, showed good activity and stability (no leaching was observed) after five consecutive photocatalytic ozonation runs with the same semiconductor‐catalyst mass. Copyright © 2006 Society of Chemical Industry     

钙镁离子对二氧化钛光催化氧化水中腐殖酸的影响

考察了间歇反应器中钙离子存在下腐殖酸分子在TiO2颗粒表面的吸附行为,进而以125 W (Emax=365 nm) 汞灯为中心光源,考察了钙镁离子对二氧化钛光催化氧化水中腐殖酸的影响. 结果表明,在腐殖酸初始浓度C0=20 mg/L, [Ca2+]=80 mg/L, pH=7和TiO2=1 mg/ml实验条件下,经2.5 h的光催化反应,腐殖酸的脱色率为100%,氧化分解率接近100%,矿化率大于95%.     

TiO2纳米管/UV/O3对腐殖酸的降解动力学

用自制的TiO₂纳米管（TNTs）作为催化剂,对腐殖酸进行TNTs/UV/O₃工艺降解研究.从动力学角度分析了光催化、臭氧化的协同作用及催化剂煅烧温度的影响,考察了反应温度、初始pH值、催化剂投加量和臭氧投加量对降解速率的影响,建立了新型动力学模型.结果表明,光催化和臭氧化有很强的协同作用,催化剂最佳煅烧温度为400℃,腐殖酸的TOC降解过程符合零级反应,模型显示当原水pH值为7.35,TNTs投加量0.806g·L^-1,O₃投加量0.49g·h^-1时TNTs/UV/O₃对腐殖酸TOC的降解取得最佳反应速率,当反应温度T为25℃时,最佳k为0.8095mg·L^-1·min^-1,当反应温度T为30℃时,最佳k为0.8231mg·L^-1·min^-1.试验结果和模型结果对比得出试验值基本符合动力学模型.     

Evaluation of humic acid photocatalytic degradation by UV–vis and fluorescence spectroscopy

Photodegradation of humic substances causes drastic changes in the UV–vis absorption and fluorescence properties of humic acids. In this study it is intended to fulfill the lack of knowledge about the spectral changes of humic acids during photocatalytic oxidation processes and elucidate the effects observed on the molecular size distribution of humic acid focusing on their analysis by UV–vis and fluorescence spectroscopy.

As confirmed by the spectroscopic evaluation of the molecular size distribution data, photocatalytic degradation of humic acid leads to the formation of lower molecular size (small fractions) and higher UV absorbing compounds. For fractions less than 10 kDa, UV₂₅₄ absorbing moieties in treated humic acid samples become higher than that of raw humic acid designating the generation of new species during photocatalysis. UV–vis spectroscopic changes were also evaluated by the parameters relating to the concomitant removal of the total organic carbon as well as by the ratios using absorption values at discrete wavelengths. Moreover, the fluorescence spectra of treated humic acid samples show decreasing intensity profiles with increasing photocatalytic irradiation time.     

Fe_2O_3可见光光催化降解水中腐殖酸的研究

采用均相沉淀法制备了Fe2O3光催化剂,并用XRD对其晶型进行了表征。研究了Fe2O3催化剂在可见光照射下对水中腐殖酸的降解行为,考察了催化剂用量、初始pH值、腐殖酸初始浓度等因素对光催化氧化过程的影响。结果表明,当Fe2O3用量为0.4 g/L,腐殖酸溶液的初始浓度为10 mg/L,pH为3.0,20 W黄色荧光灯(Em ax=548 nm)照射下反应150 m in,腐殖酸的降解率达到94.1%,说明所制备的Fe2O3光催化剂在可见光照射下对水中腐殖酸有较好的降解效果,并可多次重复使用。     

路面材料负载纳米二氧化钛光催化降解氮氧化物

随着汽车工业的发展,汽车尾气排放的氮氧化物对环境造成了巨大污染。以路面材料为载体,研究了负载型纳米二氧化钛对氮氧化物的降解作用。研究表明：水泥混凝土负载的光催化剂具有优越的光催化功能,而沥青混合料的较差。从载体对气体的吸附能力、吸光性和透光性等方面进一步研究了这两类载体的差异,提出了负载型纳米二氧化钛光催化降解氮氧化物的机理模型。     

Photocatalytic degradation of humic acid in the presence of montmorillonite

Humic acids (HA) representing the major fraction of the naturally occurring humic substances (HS) are composed of highly functionalized carbon rich polydisperse organic fractions. Clay minerals which are responsible for the transport of inorganic and organic contaminants constitute the main component of the dispersed inorganic material in natural waters. The understanding of interactions between humic substances and clay minerals is an important task for the achievement of an effective water treatment performance. The aim of this research was to investigate the influence of montmorillonite as a representative clay mineral on the TiO₂ photocatalytic removal of humic acids as the model compound of natural organic matter. The interactions prevailing between humic acid, montmorillonite and TiO₂ surface were assessed prior to the application of photocatalysis in order to address the adsorptive and photolytic behavior of humic acids. The changes attained in humic acid were described by UV–vis spectroscopic i.e. color forming moieties (Color₄₃₆) and UV absorbing centers (UV₃₆₅ and UV₂₅₄), and dissolved organic carbon (DOC) contents. Application of the pseudo first order kinetic model revealed both an enhancement and retardation with respect to the applied montmorillonite dose. The overall effect of montmorillonite on the photocatalytic degradation of humic acid was also evaluated in terms of molecular size distribution profiles (0.45 μm filtered fraction, 100 kDa fraction, 30 kDa fraction and 3 kDa fraction) described by the specified and DOC normalized specific UV–vis parameters.     

TiO2-Based Heterogeneous Photocatalytic Water Treatment Combined with Ozonation

The degradations of aliphatic carboxylic acids (formic acid, acetic acid, and propionic acid) were investigated by a combination of TiO₂-based photocatalysis and ozonation at pH = 2. The carboxylic acids were analyzed by high-performance liquid chromatography (HPLC), while the mineralization process was characterized by measuring the dissolved organic carbon (DOC) content. The efficiency of heterogeneous photocatalysis combined with ozonation was compared with that of ozonation and that of heterogeneous photocatalysis alone. In all cases, the combined system proved most effective in the oxidation of carboxylic acids. The degradation of carboxylic acids was accompanied by a continuous decrease in the DOC content, and aldehydes and carboxylic acids containing one carbon atom less than the starting material were formed as intermediates.     

TiO2纳米管/UV/O3对腐殖酸的降解动力学

用自制的TiO₂纳米管（TNTs）作为催化剂,对腐殖酸进行TNTs/UV/O₃工艺降解研究.从动力学角度分析了光催化、臭氧化的协同作用及催化剂煅烧温度的影响,考察了反应温度、初始pH值、催化剂投加量和臭氧投加量对降解速率的影响,建立了新型动力学模型.结果表明,光催化和臭氧化有很强的协同作用,催化剂最佳煅烧温度为400℃,腐殖酸的TOC降解过程符合零级反应,模型显示当原水pH值为7.35,TNTs投加量0.806g·L^-1,O₃投加量0.49g·h^-1时TNTs/UV/O₃对腐殖酸TOC的降解取得最佳反应速率,当反应温度T为25℃时,最佳k为0.8095mg·L^-1·min^-1,当反应温度T为30℃时,最佳k为0.8231mg·L^-1·min^-1.试验结果和模型结果对比得出试验值基本符合动力学模型.     

Evaluation of adsorption and coagulation characteristics of humic acids preceded by alternative advanced oxidation techniques

Humic substances mainly humic acids constitute the major fraction of natural organic matter in water supplies. Humics express diverse actions primarily related to the formation of potentially harmful disinfection by products (DBPs). Therefore, the removal of DBP precursors through numerous treatment techniques gains high importance. Besides the conventional treatment processes, the applications of advanced oxidation techniques are considered as effective tools for the elimination of humic acids (HAs) from natural waters. In the present study, both the adsorption and coagulation characteristics of humic acid samples are evaluated subsequent to pretreatment by photocatalytic oxidation and ozonation. The changes in preoxidized humic acid solutions are assessed in relation to the alterations induced in the UV-vis and fluorescence spectroscopic properties. The removal efficiency of color in terms of Color₄₃₆ and aromaticity with respect to UV₂₅₄ are presented relevant to each treatment step. Major key parameters such as the selection of coagulant types (alum and ferric chloride), coagulant aids (ionic and non-ionic polyelectrolyte) and optimum coagulant dose were comparatively discussed. The adsorption characteristics of powdered activated carbon (PAC) and granular activated carbon (GAC) were investigated.     

Covalently synthesized graphene oxide-aptamer nanosheets for efficient visible-light photocatalysis of nucleic acids and proteins of viruses

A novel photocatalyst, graphene oxide (GO) functioned aptamer, was covalently synthesized and characterized as being composed of photosensitive GO and target recognition aptamer. Aptamer enhanced photocatalytic activities of GO were studied under broad visible-light spectrum. The complex photocatalyst effectively inactivated viruses, and damaged the proteins capsid and nucleic acids of viruses in irradiation. Subsequently, the proteins posed carbonylation and the nucleic acid bases (especially for guanosine) received oxidized modification. GO was reduced by loss of oxygen elements. GO-aptamer and viruses constituted a redox system under visible-light irradiation. The photocatalysis paths involved energy transfer (generation of singlet oxygen), electron transfer (generation of anion radicals) and water dissociation (generation of the precursor to the hydrated electron). GO-aptamer is a smart photocatalyst to selectively photocatalyze of nucleic acids and proteins, which is attractive in environment protection, biochemical engineering and phototherapy.     

Effects of Ozonation on Molecular Weight Distribution of Humic Substances and Coagulation Processes – A Case Study: The Úzquiza Reservoir Water

In this article the influence of preozonation on the effectiveness of NOM removal via coagulation processes will be studied (focusing on the influence of the calcium hardness) as well as changes in MW (molecular weight) distribution of humic substances caused by ozonation. Additionally, THMFP removal in both ozonation and preozonation-coagulation processes is assessed. Three different types of water have been used in this study: a natural water from the Úzquiza Reservoir (Burgos, Spain), a synthetic water prepared using natural fulvic acids extracted from the Úzquiza Reservoir and a synthetic water prepared using a commercially supplied humic acid. Molecular weights of humic substances were determined using high-performance size exclusion chromatography (HPSEC); average molecular weights calculated for the unozonated humic substances are 4500 Da for the commercial humic acids and 1000 Da for the natural fulvic acids extracted from the Úzquiza Reservoir. Preozonation shifted the molecular weight distribution of humic substances (both humic and fulvic acids) towards lower average molecular weight values. For the natural water from the Úzquiza Reservoir (with low levels of calcium hardness and hydrophobic fraction (humic substances) being the main fraction of NOM), preozonation has a negative effect on the effectiveness of the coagulation process for NOM removal: the percentages of TOC removal via coagulation decrease with increasing ozone dosage; the maximum TOC removal (33%) is achieved for the unozonated water. Also for this water, ozonation reduced 5–25% of THMFP with ozone doses varying from 0.25 to 2.5 mg O₃/L. A preferential THMFP removal, that is to say, higher reduction in THMFP (43%) relative to TOC (28%) is achieved by the coagulation-flocculation process; this also occurs when preozonation is used, independently of ozone dosage.     

Kinetic Analysis of Heterogeneous Photocatalysis: Role of Hydroxyl Radicals

This article provides the current research activities that concentrate on the role of hydroxyl radicals in heterogeneous photocatalysis by transition metal oxides for different nanostructures. We devote most attention to Al-based Fe₂O₃ nanostructures that have been synthesized using chemical methods. The visible light photocatalytic activity of nanocrystalline pure and Al-based Fe₂O₃ photocatalysts for degradation of Salicylic acid, 4-Cholorphenol, and Acid orange 7 (Azo dye) is reported. The catalytic activity and selectivity for organic species are remarkably influenced by the size of the different photocatalyst. Utilization of various structures, advanced oxidation processes, heterojunction between Al-based Fe₂O₃ and TiO₂, and application of solar energy for heterogeneous photocatalysis of water impurities were discussed. Extent of complete mineralization of such compounds by measuring COD and TOC was discussed. We conclude this review with personal perspectives on the directions towards which future research on this new class of nanostructured materials for photocatalysis might be directed.     

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 300W 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%.     

非金属掺杂的第二代二氧化钛光催化剂研究进展

寻求廉价、环境友好并具有可见光光催化活性的第二代光催化剂将是光催化发展进一步走向实用化的关键。氮掺杂的TIO2是新发现的具有可见光光催化活性的复合光催化剂,非金属掺杂可以使复合物的复合禁带宽度小于TIO2的禁带宽度,从而使TIO2的吸收边向可见光移动。对TIO2的氮、碳、硫、卤素掺杂国内外研究现状进行了系统评述,分析了提高TIO2可见光活性的原因,指出非金属元素特别是氮元素的阴离子掺杂是在不降低紫外光催化活性的基础上实现可见光响应的较好方法。     

g-C3N4-triggered super synergy between photocatalysis and ozonation attributed to promoted OH generation

We coupled g-C₃N₄ or chlorine modified g-C₃N₄ (Cl/g-C₃N₄) photocatalysis with ozonation for mineralization of oxalic acid (OA) under visible light. g-C₃N₄ and Cl/g-C₃N₄ could trigger a super synergy between photocatalysis and ozonation, with a coupling coefficient at 17.8 and 9.9, respectively. The great gap of redox potential between the conduction band of g-C₃N₄ and ozone greatly benefitted electrons captured by ozone molecules, and thus promoted charge separation and ozone self-decomposition into a growing number of hydroxyl radicals in a photocatalytic ozonation process. Besides, the influence of chlorine modification on g-C₃N₄ to photocatalysis and photocatalytic ozonation was also clearly stated.     

Mechanistic aspects of oxalic acid oxidation by photocatalysis and ozonation

Oxalic acid has been oxidised in acidic aqueous solutions (pH 3) using photocatalysis and ozonation alone or coupled. The simultaneous presence of ozone, titanium dioxide and near UV irradiation increases the oxidation rate of oxalic acid to values greater than those deriving from the single contributions of photocatalysis and ozonation. In particular in the present paper ozonation alone, heterogeneous photocatalysis and also combined ozonation with heterogeneous photocatalysis have been used for the oxidation of oxalic acid at acidic pH in the presence of TiO₂ Degussa P25. A likely mechanism, able to explain both the homogeneous and heterogeneous processes, is discussed.     

Photocatalytic membrane reactor for degradation of acid red B wastewater

Nano-titanium dioxide (TiO₂) photocatalyst was prepared by acid–sol method using tetrabutyl titanate and ethanol, which appeared to be anatase by XRD analysis. The wastewater containing azo dye acid red B was then subjected to photocatalytic degradation with photocatalyst TiO₂ and UV as light source in a slurry photocatalytic membrane reactor, which included a double layer cylindrical photocatalytic reaction zone and a plate frame membrane separation part. Two kinds of ultrafiltration (UF) membranes PVDF700 and PAN700 were applied and the combined process with photocatalysis was operated by a continuous re-circulating mode during treatment. At first, the adsorption characteristic of the titanium dioxide catalyst under different pH values was analyzed and the optimal operation condition of the photocatalytic process was achieved by changing TiO₂ dose and initial concentration of the dye. Then the performance of photocatalyst separation process by ultrafiltration (UF) was investigated. It was found that the degradation of acid red B was followed by first-order kinetics and the efficiency of photocatalysis can be evaluated by the initial reaction rate. Finally, the conglomeration and hydrophilizion phenomena by TiO₂ in the coupling system and its effect to different ultrafiltration membranes were analyzed.     

光催化降解活性染料K-GL的动力学及其盐效应

以分散态纳米TiO2为光催化剂,在鼓泡流化床光催化反应器中对活性翠兰K-GL染料溶液进行光催化降解实验研究。通过改变光催化剂投入量、染料溶液的初始浓度和Na2SO4与NaCl的掺加,探讨了影响光催化降解K-GL的因素,运用Langrmuir-Hinshelwood动力学方程对染料降解动力学规律进行了研究。结果表明,TiO2光催化降解活性翠兰K-GL的反应遵循准一级反应动力学方程,且表观反应速率表常数随活性翠兰溶液初始浓度的升高而降低;反应的催化剂最佳投入量为0.122g/L;光催化体系中的Na2SO4对于染料K-GL的降解表现出明显的促进作用,在较低浓度下,Na2SO4的最佳添加量为0.104mol/g,且随着其浓度的升高,表观反应速率常数随之增大;而掺加不同浓度的NaCl对光催化降解K-GL有抑止作用。     

光催化自洁涂料的制备及其光活性研究

以钛酸四丁酯、正硅酸乙酯作为前驱体,通过溶胶—凝胶二步水解法制备了TiO2/SiO2复合物,并以此为光催化剂,创新性地将其应用于丙烯酸清漆,制成光催化自洁涂料。以亚甲基蓝为降解对象,考察了自洁涂料的光催化性能。光催化研究表明：与单一的锐钛型TiO2相比,添加TiO2/SiO2复合物的涂料具有更强的光催化性能,添加量为3%（质量分数,下同）时对亚甲基蓝的降解性能最好。