无机离子对光催化水处理过程影响的研究进展

无机离子在自然水体和生产废水中广泛存在。在不同的反应体系，无机离子对光催化反应的影响不同。深入了解无机离子对光催化水处理过程的影响有助于研究光催化反应的机制，增强金属离子与有机污染物光催化反应的协同作用，提高光催化反应的效率。     

水体中常见无机阳离子对TiO2薄膜光催化还原Cr（Ⅵ）的影响

选择了6种水体中常见的阳离子（Na^＋、Mg^2＋、Ca^2＋、Al^3＋、Cu^2＋、Ni^2＋）,分别考查了其对TiO2薄膜光催化还原Cr（Ⅵ）的影响;从光吸收、无机离子本身的性质对光生电子的捕获及传递等讨论了上述离子影响TiO2薄膜光催化还原Cr（Ⅵ）的反应速率的原因。结果表明：由于其不能捕获光生电子,Na^＋、Mg^2＋、Ca^2＋本身对TiO2薄膜光催化还原Cr（Ⅵ）的反应速率影响不大;Al^3＋吸引电子能力较强,成为光生电子和Cr（Ⅵ）之间的桥梁,促进了Cr（Ⅵ）的还原;浓度为1 mmmol/L时,Cu^2＋显著地促进了Cr（Ⅵ）的光催化还原,其主要原因是Cu^2＋捕获光生电子的能力很强,起到了催化剂的作用,而浓度大于10 mmol/L时,Cu^2＋形成单质Cu以及对紫外光的吸收都使促进作用降低;Ni^2＋未充满的d轨道具有获得并传递光生电子的能力,也促进了Cr（Ⅵ）的还原;在浓度同为1mmol/L时,对Cr（Ⅵ）光催化还原的促进作用依次为：Cu^2＋〉Al^3＋〉Ni^2＋〉Na^＋、Ca^2＋、Mg^2＋。     

水体中常见无机阳离子对TiO_2薄膜光催化还原Cr(Ⅵ)的影响

选择了6种水体中常见的阳离子(Na+、Mg2+、Ca2+、Al3+、Cu2+、Ni2+),分别考查了其对TiO2薄膜光催化还原Cr(Ⅵ)的影响;从光吸收、无机离子本身的性质对光生电子的捕获及传递等讨论了上述离子影响TiO2薄膜光催化还原Cr(Ⅵ)的反应速率的原因。结果表明:由于其不能捕获光生电子,Na+、Mg2+、Ca2+本身对TiO2薄膜光催化还原Cr(Ⅵ)的反应速率影响不大;Al3+吸引电子能力较强,成为光生电子和Cr(Ⅵ)之间的桥梁,促进了Cr(Ⅵ)的还原;浓度为1 mmmol/L时,Cu2+显著地促进了Cr(Ⅵ)的光催化还原,其主要原因是Cu2+捕获光生电子的能力很强,起到了催化剂的作用,而浓度大于10 mmol/L时,Cu2+形成单质Cu以及对紫外光的吸收都使促进作用降低;Ni2+未充满的d轨道具有获得并传递光生电子的能力,也促进了Cr(Ⅵ)的还原;在浓度同为1mmol/L时,对Cr(Ⅵ)光催化还原的促进作用依次为:Cu2+Al3+Ni2+Na+、Ca2+、Mg2+。     

二氧化钛纳米管光催化降解水中百草枯

二氧化钛纳米管被用于光催化氧化水体中的百草枯,对光催化反应条件、常见Fe3+离子的干扰情况和百草枯光催化降解动力学规律进行了研究。结果表明,浓度为25 mg/L的百草枯溶液,在二氧化钛纳米管(TNT)1.0 g/L,H2O20.5 mL/50 mL,pH=5.0的最优光催化氧化条件下,经过30 min反应可以被100%从水体中去除,表现出非常高的光催化降解效率;动力学方程拟合表明,百草枯光催化氧化反应符合拟一级动力学规律,动力学方程为ln(C0/C)=1.0267t-0.1282,反应速率常数K为1.0267 h-1;双氧水存在时常见的Fe3+能够进一步提高百草枯光催化降解率;该光催化反应体系对低浓度百草枯废水有很好的处理效果,预示着光催化氧化技术适合地表或地下水体中百草枯的去除。     

3种染料化合物在UV-TiO2/H2O2和UV-TiO2体系中的光催化降解研究

采用自制的TiO2膜和平板式固定床型光催化氧化反应装置,对甲基橙、茜素红和罗丹明B 3种含有不同生色基团的染料化合物进行了TiO2光催化氧化降解研究,通过对照测定降解过程中吸光度、电导率、pH的变化,分析了在加入和不加入H2O22种情况下降解过程的异同,比较了3种染料化合物脱色的难易程度,揭示了降解产物中无机离子的变化规律及某些可能的产物类型.     

3种染料化合物在UV-TiO2／H2O2和UV-TiO2体系中的光催化降解研究

采用自制的TiO2膜和平板式固定床型光催化氧化反应装置，对甲基橙、茜素红和罗丹明B3种含有不同生色基团的染料化合物进行了TiO2光催化氧化降解研究，通过对照测定降解过程中吸光度、电导率、pH的变化，分析了在加入和不加入H2O22种情况下降解过程的异同，比较了3种染料化合物脱色的难易程度，揭示了降解产物中无机离子的变化规律及某些可能的产物类型。     

臭氧-二氧化钛光催化技术脱除硫化氢

在连续性反应器内以臭氧-光催化技术氧化硫化氢,证实了臭氧对光催化脱除硫化氢有促进作用,探讨了可能存在的主要基元反应和二氧化钛失活的原因,考察了反应温度、臭氧含量、硫化氢初始体积分数等因素对臭氧-光催化技术脱除硫化氢的影响。结果表明,臭氧在光催化作用下快速分解为活性氧离子或自由基,硫化氢在臭氧和光催化联合作用下快速氧化为二氧化硫,最终转化为硫酸;硫酸在二氧化钛表面的沉积使其催化活性降低,导致硫化氢和二氧化硫的转化率逐渐下降。研究还发现,当硫化氢的初始体积分数为100×10-6时,臭氧和硫化氢的最佳摩尔比约为2∶1;臭氧-光催化脱除硫化氢的最佳温度为70℃左右;降低硫化氢的初始体积分数可大幅度降低二氧化硫的选择性。     

外负载Ce-TiO_2/活性炭复合体对亚甲基蓝光催化

用超临界流体沉积法处理过的活性炭（AC）为载体,钛酸丁酯为前驱物,硝酸铈为掺杂剂,乙醇为溶剂,制备了外负载TiO2-Ce/Csurf复合材料。在紫外灯照射下,以亚甲基蓝溶液为标准模拟降解物,研究了复合体不同热处理温度、不同浓度、不同亚甲基蓝浓度、不同铈掺杂量以及不同反应温度对光催化性能的影响。结果表明：外负载催化剂的催化性能要高于纯TiO2和体负载催化剂。铈离子掺杂能抑制TiO2晶粒生长,阻碍了TiO2由锐钛矿型向金红石型的转变。当铈离子掺杂量为1.5%,热处理温度为600℃,亚甲基蓝溶液初始浓度为5.5 mg/L,样品浓度为1.5 g/L时,光催化性能最好。     

外负载Ce-TiO2/活性炭复合体对亚甲基蓝光催化

用超临界流体沉积法处理过的活性炭(AC)为载体,钛酸丁酯为前驱物,硝酸铈为掺杂剂,乙醇为溶剂,制备了外负载TiO2-Ce/Csurf复合材料。在紫外灯照射下,以亚甲基蓝溶液为标准模拟降解物,研究了复合体不同热处理温度、不同浓度、不同亚甲基蓝浓度、不同铈掺杂量以及不同反应温度对光催化性能的影响。结果表明:外负载催化剂的催化性能要高于纯TiO2和体负载催化剂。铈离子掺杂能抑制TiO2晶粒生长,阻碍了TiO2由锐钛矿型向金红石型的转变。当铈离子掺杂量为1.5%,热处理温度为600℃,亚甲基蓝溶液初始浓度为5.5 mg/L,样品浓度为1.5 g/L时,光催化性能最好。     

光催化氧化处理有机废水

介绍了光催化氧化法的原理,对光催化氧化法处理有机废水的可行性进行了试验,探讨了ＣＯＤ随反应时间的变化规律及催化剂用量,温度、浓度的影响。试验表明,光催化氧化可降解象洗涤剂这样难降解的有机物,反应１２０ｍｉｎＣＯＤ去除率可达５０％以上。     

Graphene-based photocatalytic nanocomposites used to treat pharmaceutical and personal care product wastewater: A review

Photocatalytic technology has been widely studied by researchers in the field of environmental purification. This technology can not only completely convert organic pollutants into small molecules of CO₂ and H₂O through redox reactions but also remove metal ions and other inorganic substances from water. This article reviews the research progress of graphene-based photocatalytic nanocomposites in the treatment of wastewater. First, we elucidate the basic principles of photocatalysis, the types of graphene-based nanocomposites, and the role of graphene in photocatalysis (e.g., graphene can accelerate the separation of photon-hole pairs and increase the intensity and range of light absorption). Second, the preparation, characterization, and application of composites in wastewater are introduced. We also discuss the kinetic model of the photocatalytic degradation of pollutants. Finally, the enhancement mechanism of graphene in terms of photocatalysis is not completely clear, and graphene-based photocatalysts with high catalytic efficiency, low cost, and large-scale production have not yet appeared, so there is an urgent need for more extensive and in-depth research.

     

多相光催化在水污染治理中的应用

多相光催化过程是近年来日益引起重视的污染治理新技术，具有适用范围广、可使污染物彻底破坏、适用于低浓污染物治理等优点，本文对国外近年有关多相光催化在水污染治理中应用的研究结果进行了总结，包括各种有机污染物的氧化及各种无机离子的治理，并讨论了多相光催化过程的优点及实用性。     

Photocatalytic degradation of pesticides in pure water and a commercial agricultural solution on TiO2 coated media

Heterogeneous photocatalysis of pesticides is an effective process for removing pesticides from pure water. With a view to treating real agricultural effluents, this paper deals with the degradation of the chlortoluron and cyproconazole pesticides in pure water and the treatment of commercial solutions by photocatalysis on TiO2 coated media. The process was effective in degrading and mineralizing the pesticides. The changes of the fate of heteroatoms showed that during irradiation of the chlortoluron and cyproconazole, NH4+ and NO3(-) ions were produced. A release of chloride ions was observed from the beginning of the irradiation and stoichiometry was achieved. The photodegradation of chlortoluton and cyproconazole in commercial solutions was studied. For the degradation of chlortoluton in a commercial solution, the mineralization was completely achieved whereas in the case of the commercial cyproconazole solution, the degradation kinetic was lower. These results highlight the fact that the chemical nature of the additives in the commercial pesticide solutions does significantly affect the degradation yield of the target compound by photocatalysis.     

Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation

This work aimed to investigate the effectiveness of ultraviolet (UV) radiation on the degradation of the antimicrobial triclocarban (TCC). We investigated the effects of several operational parameters, including solution pH, initial TCC concentration, photocatalyst TiO₂ loading, presence of natural organic matter, and most common anions in surface waters (e.g., bicarbonate, nitrate, and sulfate). The results showed that UV radiation was very effective for TCC photodegradation and that the photolysis followed pseudo-first-order kinetics. The TCC photolysis rate was pH dependent and favored at high pH. A higher TCC photolysis rate was observed by direct photolysis than TiO₂ photocatalysis. The presence of the inorganic ions bicarbonate, nitrate, and sulfate hindered TCC photolysis. Negative effects on TCC photolysis were also observed by the addition of humic acid due to competitive UV absorbance. The main degradation products of TCC were tentatively identified by gas chromatograph with mass spectrometer, and a possible degradation pathway of TCC was also proposed.     

Assessment of solar driven TiO2-assisted photocatalysis efficiency on amoxicillin degradation

The objective of this work was to evaluate the efficiency of a solar TiO₂-assisted photocatalytic process on amoxicillin (AMX) degradation, an antibiotic widely used in human and veterinary medicine. Firstly, solar photolysis of AMX was compared with solar photocatalysis in a compound parabolic collectors pilot scale photoreactor to assess the amount of accumulated UV energy in the system (Q _UV) necessary to remove 20 mg L^?1 AMX from aqueous solution and mineralize the intermediary by-products. Another experiment was also carried out to accurately follow the antibacterial activity against Escherichia coli DSM 1103 and Staphylococcus aureus DSM 1104 and mineralization of AMX by tracing the contents of dissolved organic carbon (DOC), low molecular weight carboxylate anions, and inorganic anions. Finally, the influence of individual inorganic ions on AMX photocatalytic degradation efficiency and the involvement of some reactive oxygen species were also assessed. Photolysis was shown to be completely ineffective, while only 3.1 kJ_UV?L^?1 was sufficient to fully degrade 20 mg L^?1 AMX and remove 61 % of initial DOC content in the presence of the photocatalyst and sunlight. In the experiment with an initial AMX concentration of 40 mg L^?1, antibacterial activity of the solution was considerably reduced after elimination of AMX to levels below the respective detection limit. After 11.7 kJ_UV?L^?1, DOC decreased by 71 %; 30 % of the AMX nitrogen was converted into ammonium and all sulfur compounds were converted into sulfate. A large percentage of the remaining DOC was in the form of low molecular weight carboxylic acids. Presence of phosphate ions promoted the removal of AMX from solution, while no sizeable effects on the kinetics were found for other inorganic ions. Although the AMX degradation was mainly attributed to hydroxyl radicals, singlet oxygen also plays an important role in AMX self-photosensitization under UV/visible solar light.     

Photocatalytic degradation of molinate in aqueous solutions

In this study, the degradation of molinate through heterogeneous photocatalysis, using two different types of the semiconductor TiO₂ as photocatalyst, as well as through homogeneous treatment, applying the photo-Fenton reaction, has been investigated. As far as heterogeneous photocatalysis is concerned, the degradation of the pesticide follows apparent first-order kinetics, while the type of the catalyst and the pH value of the solution affect the degradation rate. The effect of the addition of electron scavengers (H₂O₂ and K₂S₂O₈) was also studied. In the case of photo-Fenton-assisted system, the degradation also follows pseudo-first-order kinetics. Parameters such as iron’s and electron scavenger’s concentration and inorganic ions strongly affect the degradation rate. The extent of pesticide mineralization was investigated using dissolved organic carbon (DOC) measurements. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fischeri. The detoxification and mineralization efficiency was found to be dependent on the system studied, and although it did not follow the rate of pesticide disappearance, it took place in considerable extent. The study of the photodegradation treatment was completed by the determination of the intermediate by-products formed during the process, which was carried out using LC-MS/MS technique and led to similar compounds with both processes.     

Effect of chlorides and sulfates on the performance of a Fe3+/H2O2 Fenton-like system in the degradation of methyl tert-butyl ether and its byproducts.

The effect of chloride and sulfate ions on the oxidation of methyl tert-butyl ether (MTBE) and its degradation products in a Fenton-like system was studied. Although both chloride and sulfate ions inhibited the decomposition of H202, chlorides were found to be the more effective inhibitor of MTBE degradation. In the presence of sulfates, MTBE decomposition can be attributed to oxidation not only by hydroxyl radicals, but also likely by SO4*- species. In the presence of chloride ions, it is possible that the dichloride radical is formed, which is less reactive than OH*. In the system under investigation, t-butyl alcohol was found to be the major byproduct, followed by t-butyl formate and acetone. The degradation rates of all intermediates and their inhibition in the presence of inorganic ions are similar to those obtained for MTBE, although their distributions are related to the concentrations of inorganic salts added.     

壳聚糖-TiO2吸附剂对银的吸附及纳米银的生成

将生物选择性吸附和光催化技术耦合合成一种新型的多功能壳聚糖-二氧化钛吸附剂（CTA）,这种新型的多功能壳聚糖-二氧化钛吸附剂能够同时吸附重金属和降解有机污染物。实验发现,CTA对银离子有较好的吸附容量,在初始浓度为1 000 mg/L时吸附容量为100.3 mg/g,且吸附了银离子的吸附剂对甲基橙有更好的降解效果。扫描电镜表明,CTA紫外条件下吸附银以后表面会有纳米银的生成,能谱显示纳米银颗粒在一定条件下可以由CTA表面自行脱落。     

Inorganic and carbonaceous components in indoor/outdoor particulate matter in two residential houses in Oslo, Norway

A detailed analysis of indoor/outdoor physicochemical aerosol properties has been performed. Aerosol measurements were taken at two dwellings, one in the city center and the other in the suburbs of the Oslo metropolitan area, during summer/fall and winter/spring periods of 2002-2003. In this paper, emphasis is placed on the chemical characteristics (water-soluble ions and carbonaceous components) of fine (PM2.5) and coarse (PM2.5-10) particles and their indoor/outdoor relationship. Results demonstrate that the carbonaceous species were dominant in all fractions of the PM10 particles (cut off size: 0.09-11.31 microm) during all measurement periods, except winter 2003, when increased concentrations of water-soluble inorganic ions were predominant because of sea salt transport. The concentration of organic carbon was higher in the fine and coarse PM10 fractions indoors, whereas elemental carbon was higher indoors only in the coarse fraction. In regards to the carbonaceous species, local traffic and secondary organic aerosol formation were, probably, the main sources outdoors, whereas indoors combustion activities such as preparation of food, burning of candles, and cigarette smoking were the main sources. In contrast, the concentrations of water-soluble inorganic ions were higher outdoors than indoors. The variability of water-soluble inorganic ion concentrations outdoors was related to changes in emissions from local anthropogenic sources, long-range transport of particles, sea salt emissions, and resuspension of roadside and soil dusts. In the indoor environment the infiltration of the outdoor air indoors was the major source of inorganic ions.     

Are photocatalytic processes effective for removal of airborne viruses from indoor air? A narrative review

A wide variety of methods have been applied in indoor air to reduce the microbial load and reduce the transmission rate of acute respiratory diseases to personnel in healthcare sittings. In recent months, with the occurrence of COVID-19 pandemic, the role of portable ventilation systems in reducing the load of virus in indoor air has received much attention. The present study delineates a comprehensive up-to-date overview of the available photocatalysis technologies that have been applied for inactivating and removing airborne viruses. The detection methods for identifying viral particles in air and the main mechanisms involving in virus inactivation during photocatalysis are described and discussed. The photocatalytic processes could effectively decrease the load of viruses in indoor air. However, a constant viral model may not be generalizable to other airborne viruses. In photocatalytic processes, temperature and humidity play a distinct role in the inactivation of viruses through changing photocatalytic rate. The main mechanisms for inactivation of airborne viruses in the photocatalytic processes included chemical oxidation by the reactive oxygen species (ROS), the toxicity of metal ions released from metal-containing photocatalysts, and morphological damage of viruses.