新型可见光响应纳米光催化剂的研制及其应用
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摘要
当今世界,环境污染和能源危机日趋严重,难降解、有毒、有害有机物目前引起的环境污染已经严重影响人类生存与发展,在工业和家用废水中常常发现有机污染物,但是用传统技术很难将其处理。随着公众对环境污染问题的关心与日俱增,污染物治理新方法不断被推动和发展,世界各国已经开始重视如何有效利用太阳能治理污染。光催化氧化技术氧化效率高,反应速度快,对多种有机污染物有良好的处理效果,并且可有效利用太阳能,绿色环保,是一种深度氧化技术。其中,二氧化钛改性和多元复合催化剂能达到大范围的光响应,高效率的电荷分离,充分吸收利用太阳光的要求,目前在光催化领域已经成为研究热点。
本论文继续沿着这个方向做积极的探索。简要地概述了光催化技术,探讨了影响光催化性能的重要因素,对光催化剂目前在国内外的改性情况和多元复合氧化物的最近进展以及可见光化研究开展了详细的综述,并对光催化技术处理染料废水和抗生素污染物的研究进展做了阐述。在总结前人工作经验研究,充分了解有机污染物和光催化剂的物性及其相互作用机制的基础上,本论文采用较为简单的制备方法成功合成了两个系列的新型纳米光催化剂,一类是稀土和非金属元素共掺杂改性TiO2系列；另一类是三元复合半导体(非TiO2基)系列。详细表征了其结构、形貌、光吸收特性和表面物理化学性质,研究了光催化剂催化活性所受制备工艺和反应条件的影响,并选取染料废水一活性艳蓝19和酸性蓝62,抗生素类药物—磺胺嘧啶和金霉素作为目标物,以含有目标物的实际水源水为研究对象,在模拟太阳光下,研究水环境中污染物的光催化反应的影响因素和动力学规律,探讨了光催化剂降解机理和过程。通过上述研究,本论文取得了一些有意义的成果和有用的结论,为有机污染物的光催化降解应用提供了依据。本论文研究主要内容和成果如下所述：
1.镧、碘共掺TiO2纳米复合光催化剂的制备和表征
采用沉淀-浸渍法合成了镧、碘共掺TiO2纳米复合光催化剂,并通过XRD、BET、TEM、XPS和TG-DSC等手段对其进行表征,XRD, TEM和BET的测试结果表明相对于单一镧或碘掺杂TiO2纳米光催化剂而言,在350℃下焙烧2h制得的La/I/TiO2纳米光催化剂粒径较小且比表面积较大。同时,测试表明元素离子掺杂TiO2在一定程度上能够抑制晶体的生长和团聚,本实验中稀土元素镧的最佳理论掺杂浓度为1.5%,通过镧、碘的共掺使得抑制作用变得更强。通过XPS光谱可以断定所制备的掺杂催化剂中Ti元素主要以Ti4+存在,一部分I5+进入晶格中取代了Ti4+,La3+主要以La2O3的形式富集在TiO2的表面,La2O3覆盖在TiO2的表面可使光生电子和空穴进一步分离。同时,研究发现在热处理过程中由于一部分稀土离子进入TiO2的晶格中取代部分Ti4+而导致局部的晶格畸变,并抑制了晶粒的增长。另外,根据紫外-可见光漫反射光谱可以得出,相比未掺杂改性的纯TiO2而言,光催化剂的最大吸收边在经掺杂改性后都向可见光区产生不同程度红移,但并没有削弱在紫外光区的吸收,此发现为光催化剂在模拟日光下有效进行光催化氧化反应提供了新的视野。
2. La/I/TiO2纳米复合光催化剂光催化活性研究
以氙灯为光源,以活性艳蓝19和磺胺嘧啶为模拟废水,对镧、碘掺杂TiO2纳米复合光催化剂的活性进行评价。光催化降解实验表明,于350。C下焙烧制备的La/I/TiO2纳米催化剂在模拟太阳光照下能够有效地降解活性艳蓝19染料废水和磺胺嘧啶类药物废水,并且两者的降解反应在一定浓度范围内,均符合表观一级反应动力学,可以证明La/I/TiO2纳米粒子具有优越的可见光催化能力。
在模拟太阳光照射下,当活性艳蓝19初始浓度为50 mg/L,溶液pH值范围在3-7,催化剂投加量为1.0 g/L时,光照80min, La/I/TiO2纳米光催化剂对活性艳蓝19的降解效率达到98.6%,TOC基本去除完全,显示了较好的催化活性。在不同光源下催化实验表明,在模拟太阳光体系中活性艳蓝19的降解能力要由于其他体系,可能的原因是反应中间产物被吸附在催化剂表面,大量累积会导致催化剂中毒,而模拟太阳光中的紫外光部分对其具有比较好的矿化作用,从而避免了反应中间产物的累积。光催化降解实际工业印染废水的试验表明：La/I/TiO2纳米光催化剂在一定的反应时间内,能够完全去除印染废水的色度,同时也会降低CODcr值,达到90%左右。
La/I/TiO2纳米光催化剂在模拟太阳光下也显示了较好的光催化降解磺胺嘧啶的能力,模拟太阳光照射90 min后,SD降解率可达到近90%,证明La/I/TiO2光催化氧化能够有效降解水中的低浓度磺胺类药物。La/I/TiO2纳米粒子对SD的降解机理是在羟基自由基的作用下进行的,活性-OH攻击SD的S-N键以及C-S键,脱去O=S=O,同时分子结构发生重组,生成4-(2-氨基吡啶-1(2H)-基)苯胺,然后再通过不同途径进一步矿化。经过多次使用后,La/I/TiO2纳米光催化剂仍有较好的催化活性,预示着La/I/TiO2纳米催化剂工业化前景广阔。
3.纳米La/CuO-SnO2三元复合光催化剂的制备、表征及光催化活性研究
作为一种n型半导体,纳米SnO2光学、电学及催化性能独特,且晶体结构与金红石TiO2相似。实验选用SnO2与CuO和La2O3复合,采用条件温和、操作简便的共沉淀法合成了La/CuO-SnO2三元复合纳米光催化剂。XRD、BET、TEM和UV-Vis漫反射等手段测试表明所制备催化剂的晶型、晶粒、对光的吸收性以及比表面积能都会受到焙烧温度显著的影响。实验结果表明,催化剂的最佳热处理温度为450℃,当在该温度下焙烧2.5 h, CuO与SnO2摩尔比为1：1,La的掺杂量为2.0%时,制得的La/CuO-SnO2纳米复合光催化剂颗粒粒径较小、分布相对比较均匀,平均晶粒大小为15.4 nm,比表面为110.35 m2/g,对可见光有一定的吸收,具有最高的光催化活性。以氙灯为光源,以酸性蓝62为模拟废水,对La/CuO-SnO2三元复合光催化剂的活性进行评价。在模拟太阳光照射下,酸性蓝62溶液废水的降解反应速率常数随着溶液初始浓度的增加反而逐渐减小,并且在一定浓度范围内,此反应符合表观一级反应动力学。反应当溶液pH值大小在5.35左右,酸性蓝62初始浓度为50 mg/L,La/CuO-SnO2纳米复合光催化剂投加量为1.0 g/L,光照反应120 min后对酸性蓝62溶液的降解率达到了97.7%,明显高于在同等条件下P25的催化活性。
4.纳米La/CuO-SnO2复合光催化剂降解盐酸金霉素废水的光催化研究
选取盐酸金霉素作为La/CuO-SnO2复合光催化剂光催化氧化的对象,分析其光催化降解的可行性,采用实际水源水代替蒸馏水配置一定浓度的盐酸金霉素溶液,进行光催化降解反应。考察了溶液初始浓度、催化剂用量、溶液初始pH值、不同光源等因素的最佳条件,并且研究了添加氧化剂后对光催化降解效果的影响,并对盐酸金霉素废水的反应动力学进行分析。结果显示,在光催化剂催化降解盐酸金霉素的过程中,纳米La/CuO-Sn02复合光催化剂表现出较高地催化活性。对于初始浓度为50 mg/L的金霉素溶液废水而言,其最佳实验条件为La/CuO-SnO2的用量为1.5 g/L、溶液的初始pH值为3,在模拟太阳光下反应120 min,CTC降解率达到88.7%,COD、TOC降解较为完全,显示了较为显著的可见光催化活性。并且,光照反应40 min后BOD5/COD>0.3,明显改善了水质地可生化性能。添加氧化剂可以提高盐酸四环素光催化降解的效果。当加入浓度为300 mg/L的H2O2时,反应时间可大大缩短。盐酸金霉素的光催化反应符合Langmuir-Hinshelwood一级动力学数学模型。在光催化氧化过程中,金霉素发生了一系列反应,反应中间产物包括多种多环化合物,这些多环化合物继续被光催化氧化会进一步开环促使分子从大分子向小分子变化,进而被氧化分解,最后氧化成无机物。结果表明La/CuO-SnO2光催化剂对盐酸金霉素废水具有显著的可见光降解能力,有望进行实际应用。
Worldwide energy resource crisis and environment pollution are becoming more severe with each passing day. In the 21st century, environmental problems caused by noxious and nonbiodegradable organic pollutions such as dyes and PPCPs have deeply affected the survival and development of human beings. Such pollution is difficult to solve with traditional environment technology. How effective use of sunlight to solve environment pollution problems has become the focus to the world. With the public concern for environmental problems increased, novel treatment methods being promoted and developed. Photocatalysis has gained a great deal of attention in the field of pollutant degradation. Photocatalytic technology, an advanced oxidation technology, is a green utilization of solar energy. Studies have proven that photocatalysis oxidation technology is able to treat many kinds of organic pollutants. In recent years, many researchers have focused on modified nano titanium dioxide and binary or ternary compound photocatalysts, because of extending the photoresponse rangea and increasing the efficiency of charge separation.
We are motivated to work in this direction in the present dissertation, and summarized the mechanism and influencing factors of photocatalysis techniques, and reviewed the study on development and application of modified nano-titanium dioxide and coupled oxide semiconductors visible light-activated photocatalysts. As well as treatment effect of photocatalysis of dye and antibiotic wastewater are illustrated in details.
Based on a sufficient understanding of the relationship between the organic pollution and photocatalyst specialty, two series of novel nanocomposite photocatalysts are successfully prepared using simple methods. One type comprises rare earth and nonmetal elements co-doped TiO2 photocatalyst. whereas the other comprises ternary nano-composite photocatalysts. Subsequently, the effects of photocatalysts synthesis and reaction conditions on photocatalytic activity are systematically analyzed. Dye wastewater (Reactive Blue 19 and Acid Blue 62) and antibiotic wastewater [sulfadiazine (SD) and chlortetracycline (CTC)]. the target compounds in source water and the most widely used antibiotics, respectively, have been chosen as the study samples. The effects of main factors of photochemical degradation, degradation mechanisms, kinetics, and reaction pathways of the processes under simulated sunlight irradiation are amply studied. Some important valuable achievements and conclusions have been obtained in the current thesis, offering theoretical and experimental guidelines with practical applications for the degradation of organic pollutants. The current dissertation contains the following major parts:
1. Preparation and characterization of lanthanum and iodine co-doped TiO2 photocatalyst
The novel visible-light-activated La/I/TiO2 nano-composition photocatalyst was successfully synthesized using precipitation-dipping method, and characterized by XRD, BET, TEM, XPS, TG-DSC, and UV-Vis DRS. The characterization results of XRD, TEM, and BET indicate that the La/I/TiO2 photocatalyst calcined at 350℃for 2 h resulted in bigger BET surface area and smaller crystal size, in comparison with La/TiO2 or I/TiO2 photocatalysts. Characterization results also reveal that the lanthanum and iodine co-doped can hinder the aggregation and growth of TiO2 particles, which cause the decrease in particle sizes and the increase internal surface areas. The La optimal doping concentration is 1.5% in the present dissertation. In addition, the XPS spectra indicate that Ti atoms exist in the form of Ti4+ state and that part of I5+ replaced Ti4+ of the prepared photocatalysts. La2O3 was converted on the surface of nano TiO2 particles, resulting in the separation of electrons and holes and structural deformation of TiO2 The crystal size of the TiO2 particles was restrained after the La3+ elements were doped onto the crystal lattice. The UV-Vis-DRS of the as-prepared La/I/TiO2 photocatalysts shows that the absorption edge of the lanthanum and iodine co-doped TiO2 shifting significantly to the visible-light region in comparison with the TiO2, and this work may provide new insights into the development of novel sunlight photocatalysts.
2. Photocatalytic activity of visible-light-driven TiO2 photocatalyst co-doped with lanthanum and iodine under simulated sunlight
The photocatalytic activity of lanthanum and iodine co-doped TiO2 photocatalyst was evaluated by studying the photodegradation of Reactive Blue 19 and SD as a probe reaction under Xe light irradiation. Studies have indicated that the La/I/TiO2 photocatalyst calcined at 350℃could effectively mineralize Reactive Blue 19 and SD under simulated sunlight irradiation. In addition, the degradation kinetics of reactive blue 19 and SD in aqueous La/I/TiO2 suspensions follow pseudo-first-order kinetics under simulated sunlight irradiation, when both of the concentration is in the range of investigation, demonstrating that La/I/TiO2 photocatalyst has remarkable photocatalytic activity.
Under simulated sunlight irradiation, the degradation of Reactive Blue 19 aqueous solution reached 98.6% in 80 min, and the removal rate of TOC was about 90% when the initial concentration of Reactive Blue 19 solution was 50 mg/L, the pH value was approximately 3 to 7, whereas the concentration of La/I/TiO2 photocatalyst was 1.0 g/L. These results show that La/I/TiO2 photocatalyst maximal photocatalytic activity. Furthermore, the degradation of Reactive Blue 19 on La/I/TiO2 photocatalyst under irradiation of different light sources shown in the simulated sunlight system was the best. The possible reason is that the gathering of intermediates adsorbed on the photocatalysts surface will cause the catalysts poisoning, however, the ultraviolet rays in the simulated sunlight can effectively mineralize the intermediates and prevents photocatalysts from poisoning. Experimental results indicate that the La/I/TiO2 photocatalysts can degrade and mineralize the industry dye wastewater when the reaction time is in the range of investigation, and can reach a removal rate of COD was approximately 90%.
The La/I/TiO2 photocatalyst also exhibited strong photocatalytic activity in photodegradation of SD wastewater, the degradation of SD aqueous solution reached 90% in 90 min under simulated sunlight irradiation.·OH radicals are the most important oxidizing species which can attack and transform the organic molecules to inorganic micro molecule. The mechanism of La/I/TiO2 degradation SD may involved in high oxidation ability of active hydroxyl radicals(·OH) which are strongly enough to break the S-N and C-S bond of SD.-SO2 functional group was removed from SD molecule, generated the intermediate product 4-(2-iminopyrimidine-1(2H)-vl) aniline under the condition of simulated sunlight irradiation. And then·OH again attacks, SD is broken into inorganic micro molecule through different Pathway. After many times of recycle use, La/I/TiO2 photocatalysts still keep high photocatalytic activity, which shows that La/I/TiO2 photocatalysts are promising catalysts in the industrialization field.
3. Preparation, characterization and photocatalytic activity of La/CuO-SnO2 in simulated sunlight irradiation
SnO2 is an n-type semiconductor and it has the similar to rutile TiO2 crystal structure. In view of these properties, La/CuO-SnO2 ternary nano-composite photocatalysts were prepared under different calcination temperatures using a simple co-precipitation method in the current dissertation. With different calcining temperatures, the characterization results of XRD, BET, TEM. and UV-Vis display that the samples particle size, crystalline structures, photo absorption and surface area varied significantly. The photocatalytic experimental results show that the maximum specific photocatalytic activity of the La/CuO-SnO2 nano-composite photocatalysts appears after calcination at 450℃for 2.5 h, the molar ratio of CuO to SnO2 of 1:1, and doping concentration of La at 2.0% because of the good crystallization, high BET surface areas (110.35 m2/g), small crystal size (15.4 nm) and strong optical absorption of the sample. The photocatalytic activity of La/CuO-SnO2 nanocomposite oxide was evaluated using the photodegradation efficiency of acid blue 62 as a probe under Xe light.irradiation. Under simulated sunlight irradiation, the degradation kinetics of Acid Blue 62 in aqueous La/CuO-SnO2 suspensions followed pseudo-first-order kinetics, and when the concentration of Acid Blue 62 in the range of investigation, as the initial Acid Blue 62 concentration increased, the degradation rates decreased. The degradation of Acid Blue 62 aqueous solution can reach a removal rate of TOC was approximately 68%, and the degradation rate of 97.71% in 2 h when the initial concentration of Acid Blue 62 solution of 50 mg/L, the concentration of La/CuO-SnO2 photocatalyst was 1.0 g/L, and the pH value was approximately 5.35, showing that the La/CuO-SnO2 nanocomposite photocatalyst has a much higher photocatalytic activity than the standard Degussa P25 photocatalyst.
4. Photocatalytic degradation of chlortetracycline over La/CuO-SnO2 photocatalysts under simulated sunlight
The paper chose CTC as the object, and analyzed the feasibility of CTC treatment by La/CuO-SnO2 photocatalysis. The experiment result shows that the La/CuO-SnO2 ternary nano-composite photocatalysts exhibits excellent photocatalytic activity. The paper reviewed the optimal condition of CTC initial concentration, La/CuO-SnO2 photocatalyst concentration, different pH values, and different lights for CTC treatment by La/CuO-SnO2 photocatalysis. In addition, the effect of various oxidant supplies and the dynamics of CTC treatment by photocatalysis were studied. The maximum degradation ratio of CTC by photocatalysis was 88.7% under the following conditions:CTC initial concentration 50 mg/L, La/CuO-SnO2 photocatalyst concentration 1.5 g/L, and pH 3, and COD removal efficiency could reach up to 93% in 120 min. Meanwhile, the value of BOD5/COD> 0.3 of wastewater after 40 min irradiation, it showed chemical and biologic properties were improved. The addition of oxidant also improved the photocatalysis result. When the concentration exceeded 300 mg/L of H2O2 added into the reaction system, the time was cut down. The rate of degradation of CTC can be described by the Langmuir-Hinshelwood equation. A series of photo-oxidation and subsequent chemical reactions were involved on degradation of CTC chemical mechanisms during the photo-catalytic processes. A variety of bicyclic and tricyclic compounds were included in intermediate products of CTC. Polycyclic compounds were opened up, and then small molecular compounds were produced. Ultimately, some inorganic products were investigated. The results indicated that La/CuO-SnO2 photocatalysts have high photocatalytic activity, and have important value in practical application.
本论文继续沿着这个方向做积极的探索。简要地概述了光催化技术,探讨了影响光催化性能的重要因素,对光催化剂目前在国内外的改性情况和多元复合氧化物的最近进展以及可见光化研究开展了详细的综述,并对光催化技术处理染料废水和抗生素污染物的研究进展做了阐述。在总结前人工作经验研究,充分了解有机污染物和光催化剂的物性及其相互作用机制的基础上,本论文采用较为简单的制备方法成功合成了两个系列的新型纳米光催化剂,一类是稀土和非金属元素共掺杂改性TiO2系列；另一类是三元复合半导体(非TiO2基)系列。详细表征了其结构、形貌、光吸收特性和表面物理化学性质,研究了光催化剂催化活性所受制备工艺和反应条件的影响,并选取染料废水一活性艳蓝19和酸性蓝62,抗生素类药物—磺胺嘧啶和金霉素作为目标物,以含有目标物的实际水源水为研究对象,在模拟太阳光下,研究水环境中污染物的光催化反应的影响因素和动力学规律,探讨了光催化剂降解机理和过程。通过上述研究,本论文取得了一些有意义的成果和有用的结论,为有机污染物的光催化降解应用提供了依据。本论文研究主要内容和成果如下所述：
1.镧、碘共掺TiO2纳米复合光催化剂的制备和表征
采用沉淀-浸渍法合成了镧、碘共掺TiO2纳米复合光催化剂,并通过XRD、BET、TEM、XPS和TG-DSC等手段对其进行表征,XRD, TEM和BET的测试结果表明相对于单一镧或碘掺杂TiO2纳米光催化剂而言,在350℃下焙烧2h制得的La/I/TiO2纳米光催化剂粒径较小且比表面积较大。同时,测试表明元素离子掺杂TiO2在一定程度上能够抑制晶体的生长和团聚,本实验中稀土元素镧的最佳理论掺杂浓度为1.5%,通过镧、碘的共掺使得抑制作用变得更强。通过XPS光谱可以断定所制备的掺杂催化剂中Ti元素主要以Ti4+存在,一部分I5+进入晶格中取代了Ti4+,La3+主要以La2O3的形式富集在TiO2的表面,La2O3覆盖在TiO2的表面可使光生电子和空穴进一步分离。同时,研究发现在热处理过程中由于一部分稀土离子进入TiO2的晶格中取代部分Ti4+而导致局部的晶格畸变,并抑制了晶粒的增长。另外,根据紫外-可见光漫反射光谱可以得出,相比未掺杂改性的纯TiO2而言,光催化剂的最大吸收边在经掺杂改性后都向可见光区产生不同程度红移,但并没有削弱在紫外光区的吸收,此发现为光催化剂在模拟日光下有效进行光催化氧化反应提供了新的视野。
2. La/I/TiO2纳米复合光催化剂光催化活性研究
以氙灯为光源,以活性艳蓝19和磺胺嘧啶为模拟废水,对镧、碘掺杂TiO2纳米复合光催化剂的活性进行评价。光催化降解实验表明,于350。C下焙烧制备的La/I/TiO2纳米催化剂在模拟太阳光照下能够有效地降解活性艳蓝19染料废水和磺胺嘧啶类药物废水,并且两者的降解反应在一定浓度范围内,均符合表观一级反应动力学,可以证明La/I/TiO2纳米粒子具有优越的可见光催化能力。
在模拟太阳光照射下,当活性艳蓝19初始浓度为50 mg/L,溶液pH值范围在3-7,催化剂投加量为1.0 g/L时,光照80min, La/I/TiO2纳米光催化剂对活性艳蓝19的降解效率达到98.6%,TOC基本去除完全,显示了较好的催化活性。在不同光源下催化实验表明,在模拟太阳光体系中活性艳蓝19的降解能力要由于其他体系,可能的原因是反应中间产物被吸附在催化剂表面,大量累积会导致催化剂中毒,而模拟太阳光中的紫外光部分对其具有比较好的矿化作用,从而避免了反应中间产物的累积。光催化降解实际工业印染废水的试验表明：La/I/TiO2纳米光催化剂在一定的反应时间内,能够完全去除印染废水的色度,同时也会降低CODcr值,达到90%左右。
La/I/TiO2纳米光催化剂在模拟太阳光下也显示了较好的光催化降解磺胺嘧啶的能力,模拟太阳光照射90 min后,SD降解率可达到近90%,证明La/I/TiO2光催化氧化能够有效降解水中的低浓度磺胺类药物。La/I/TiO2纳米粒子对SD的降解机理是在羟基自由基的作用下进行的,活性-OH攻击SD的S-N键以及C-S键,脱去O=S=O,同时分子结构发生重组,生成4-(2-氨基吡啶-1(2H)-基)苯胺,然后再通过不同途径进一步矿化。经过多次使用后,La/I/TiO2纳米光催化剂仍有较好的催化活性,预示着La/I/TiO2纳米催化剂工业化前景广阔。
3.纳米La/CuO-SnO2三元复合光催化剂的制备、表征及光催化活性研究
作为一种n型半导体,纳米SnO2光学、电学及催化性能独特,且晶体结构与金红石TiO2相似。实验选用SnO2与CuO和La2O3复合,采用条件温和、操作简便的共沉淀法合成了La/CuO-SnO2三元复合纳米光催化剂。XRD、BET、TEM和UV-Vis漫反射等手段测试表明所制备催化剂的晶型、晶粒、对光的吸收性以及比表面积能都会受到焙烧温度显著的影响。实验结果表明,催化剂的最佳热处理温度为450℃,当在该温度下焙烧2.5 h, CuO与SnO2摩尔比为1：1,La的掺杂量为2.0%时,制得的La/CuO-SnO2纳米复合光催化剂颗粒粒径较小、分布相对比较均匀,平均晶粒大小为15.4 nm,比表面为110.35 m2/g,对可见光有一定的吸收,具有最高的光催化活性。以氙灯为光源,以酸性蓝62为模拟废水,对La/CuO-SnO2三元复合光催化剂的活性进行评价。在模拟太阳光照射下,酸性蓝62溶液废水的降解反应速率常数随着溶液初始浓度的增加反而逐渐减小,并且在一定浓度范围内,此反应符合表观一级反应动力学。反应当溶液pH值大小在5.35左右,酸性蓝62初始浓度为50 mg/L,La/CuO-SnO2纳米复合光催化剂投加量为1.0 g/L,光照反应120 min后对酸性蓝62溶液的降解率达到了97.7%,明显高于在同等条件下P25的催化活性。
4.纳米La/CuO-SnO2复合光催化剂降解盐酸金霉素废水的光催化研究
选取盐酸金霉素作为La/CuO-SnO2复合光催化剂光催化氧化的对象,分析其光催化降解的可行性,采用实际水源水代替蒸馏水配置一定浓度的盐酸金霉素溶液,进行光催化降解反应。考察了溶液初始浓度、催化剂用量、溶液初始pH值、不同光源等因素的最佳条件,并且研究了添加氧化剂后对光催化降解效果的影响,并对盐酸金霉素废水的反应动力学进行分析。结果显示,在光催化剂催化降解盐酸金霉素的过程中,纳米La/CuO-Sn02复合光催化剂表现出较高地催化活性。对于初始浓度为50 mg/L的金霉素溶液废水而言,其最佳实验条件为La/CuO-SnO2的用量为1.5 g/L、溶液的初始pH值为3,在模拟太阳光下反应120 min,CTC降解率达到88.7%,COD、TOC降解较为完全,显示了较为显著的可见光催化活性。并且,光照反应40 min后BOD5/COD>0.3,明显改善了水质地可生化性能。添加氧化剂可以提高盐酸四环素光催化降解的效果。当加入浓度为300 mg/L的H2O2时,反应时间可大大缩短。盐酸金霉素的光催化反应符合Langmuir-Hinshelwood一级动力学数学模型。在光催化氧化过程中,金霉素发生了一系列反应,反应中间产物包括多种多环化合物,这些多环化合物继续被光催化氧化会进一步开环促使分子从大分子向小分子变化,进而被氧化分解,最后氧化成无机物。结果表明La/CuO-SnO2光催化剂对盐酸金霉素废水具有显著的可见光降解能力,有望进行实际应用。
Worldwide energy resource crisis and environment pollution are becoming more severe with each passing day. In the 21st century, environmental problems caused by noxious and nonbiodegradable organic pollutions such as dyes and PPCPs have deeply affected the survival and development of human beings. Such pollution is difficult to solve with traditional environment technology. How effective use of sunlight to solve environment pollution problems has become the focus to the world. With the public concern for environmental problems increased, novel treatment methods being promoted and developed. Photocatalysis has gained a great deal of attention in the field of pollutant degradation. Photocatalytic technology, an advanced oxidation technology, is a green utilization of solar energy. Studies have proven that photocatalysis oxidation technology is able to treat many kinds of organic pollutants. In recent years, many researchers have focused on modified nano titanium dioxide and binary or ternary compound photocatalysts, because of extending the photoresponse rangea and increasing the efficiency of charge separation.
We are motivated to work in this direction in the present dissertation, and summarized the mechanism and influencing factors of photocatalysis techniques, and reviewed the study on development and application of modified nano-titanium dioxide and coupled oxide semiconductors visible light-activated photocatalysts. As well as treatment effect of photocatalysis of dye and antibiotic wastewater are illustrated in details.
Based on a sufficient understanding of the relationship between the organic pollution and photocatalyst specialty, two series of novel nanocomposite photocatalysts are successfully prepared using simple methods. One type comprises rare earth and nonmetal elements co-doped TiO2 photocatalyst. whereas the other comprises ternary nano-composite photocatalysts. Subsequently, the effects of photocatalysts synthesis and reaction conditions on photocatalytic activity are systematically analyzed. Dye wastewater (Reactive Blue 19 and Acid Blue 62) and antibiotic wastewater [sulfadiazine (SD) and chlortetracycline (CTC)]. the target compounds in source water and the most widely used antibiotics, respectively, have been chosen as the study samples. The effects of main factors of photochemical degradation, degradation mechanisms, kinetics, and reaction pathways of the processes under simulated sunlight irradiation are amply studied. Some important valuable achievements and conclusions have been obtained in the current thesis, offering theoretical and experimental guidelines with practical applications for the degradation of organic pollutants. The current dissertation contains the following major parts:
1. Preparation and characterization of lanthanum and iodine co-doped TiO2 photocatalyst
The novel visible-light-activated La/I/TiO2 nano-composition photocatalyst was successfully synthesized using precipitation-dipping method, and characterized by XRD, BET, TEM, XPS, TG-DSC, and UV-Vis DRS. The characterization results of XRD, TEM, and BET indicate that the La/I/TiO2 photocatalyst calcined at 350℃for 2 h resulted in bigger BET surface area and smaller crystal size, in comparison with La/TiO2 or I/TiO2 photocatalysts. Characterization results also reveal that the lanthanum and iodine co-doped can hinder the aggregation and growth of TiO2 particles, which cause the decrease in particle sizes and the increase internal surface areas. The La optimal doping concentration is 1.5% in the present dissertation. In addition, the XPS spectra indicate that Ti atoms exist in the form of Ti4+ state and that part of I5+ replaced Ti4+ of the prepared photocatalysts. La2O3 was converted on the surface of nano TiO2 particles, resulting in the separation of electrons and holes and structural deformation of TiO2 The crystal size of the TiO2 particles was restrained after the La3+ elements were doped onto the crystal lattice. The UV-Vis-DRS of the as-prepared La/I/TiO2 photocatalysts shows that the absorption edge of the lanthanum and iodine co-doped TiO2 shifting significantly to the visible-light region in comparison with the TiO2, and this work may provide new insights into the development of novel sunlight photocatalysts.
2. Photocatalytic activity of visible-light-driven TiO2 photocatalyst co-doped with lanthanum and iodine under simulated sunlight
The photocatalytic activity of lanthanum and iodine co-doped TiO2 photocatalyst was evaluated by studying the photodegradation of Reactive Blue 19 and SD as a probe reaction under Xe light irradiation. Studies have indicated that the La/I/TiO2 photocatalyst calcined at 350℃could effectively mineralize Reactive Blue 19 and SD under simulated sunlight irradiation. In addition, the degradation kinetics of reactive blue 19 and SD in aqueous La/I/TiO2 suspensions follow pseudo-first-order kinetics under simulated sunlight irradiation, when both of the concentration is in the range of investigation, demonstrating that La/I/TiO2 photocatalyst has remarkable photocatalytic activity.
Under simulated sunlight irradiation, the degradation of Reactive Blue 19 aqueous solution reached 98.6% in 80 min, and the removal rate of TOC was about 90% when the initial concentration of Reactive Blue 19 solution was 50 mg/L, the pH value was approximately 3 to 7, whereas the concentration of La/I/TiO2 photocatalyst was 1.0 g/L. These results show that La/I/TiO2 photocatalyst maximal photocatalytic activity. Furthermore, the degradation of Reactive Blue 19 on La/I/TiO2 photocatalyst under irradiation of different light sources shown in the simulated sunlight system was the best. The possible reason is that the gathering of intermediates adsorbed on the photocatalysts surface will cause the catalysts poisoning, however, the ultraviolet rays in the simulated sunlight can effectively mineralize the intermediates and prevents photocatalysts from poisoning. Experimental results indicate that the La/I/TiO2 photocatalysts can degrade and mineralize the industry dye wastewater when the reaction time is in the range of investigation, and can reach a removal rate of COD was approximately 90%.
The La/I/TiO2 photocatalyst also exhibited strong photocatalytic activity in photodegradation of SD wastewater, the degradation of SD aqueous solution reached 90% in 90 min under simulated sunlight irradiation.·OH radicals are the most important oxidizing species which can attack and transform the organic molecules to inorganic micro molecule. The mechanism of La/I/TiO2 degradation SD may involved in high oxidation ability of active hydroxyl radicals(·OH) which are strongly enough to break the S-N and C-S bond of SD.-SO2 functional group was removed from SD molecule, generated the intermediate product 4-(2-iminopyrimidine-1(2H)-vl) aniline under the condition of simulated sunlight irradiation. And then·OH again attacks, SD is broken into inorganic micro molecule through different Pathway. After many times of recycle use, La/I/TiO2 photocatalysts still keep high photocatalytic activity, which shows that La/I/TiO2 photocatalysts are promising catalysts in the industrialization field.
3. Preparation, characterization and photocatalytic activity of La/CuO-SnO2 in simulated sunlight irradiation
SnO2 is an n-type semiconductor and it has the similar to rutile TiO2 crystal structure. In view of these properties, La/CuO-SnO2 ternary nano-composite photocatalysts were prepared under different calcination temperatures using a simple co-precipitation method in the current dissertation. With different calcining temperatures, the characterization results of XRD, BET, TEM. and UV-Vis display that the samples particle size, crystalline structures, photo absorption and surface area varied significantly. The photocatalytic experimental results show that the maximum specific photocatalytic activity of the La/CuO-SnO2 nano-composite photocatalysts appears after calcination at 450℃for 2.5 h, the molar ratio of CuO to SnO2 of 1:1, and doping concentration of La at 2.0% because of the good crystallization, high BET surface areas (110.35 m2/g), small crystal size (15.4 nm) and strong optical absorption of the sample. The photocatalytic activity of La/CuO-SnO2 nanocomposite oxide was evaluated using the photodegradation efficiency of acid blue 62 as a probe under Xe light.irradiation. Under simulated sunlight irradiation, the degradation kinetics of Acid Blue 62 in aqueous La/CuO-SnO2 suspensions followed pseudo-first-order kinetics, and when the concentration of Acid Blue 62 in the range of investigation, as the initial Acid Blue 62 concentration increased, the degradation rates decreased. The degradation of Acid Blue 62 aqueous solution can reach a removal rate of TOC was approximately 68%, and the degradation rate of 97.71% in 2 h when the initial concentration of Acid Blue 62 solution of 50 mg/L, the concentration of La/CuO-SnO2 photocatalyst was 1.0 g/L, and the pH value was approximately 5.35, showing that the La/CuO-SnO2 nanocomposite photocatalyst has a much higher photocatalytic activity than the standard Degussa P25 photocatalyst.
4. Photocatalytic degradation of chlortetracycline over La/CuO-SnO2 photocatalysts under simulated sunlight
The paper chose CTC as the object, and analyzed the feasibility of CTC treatment by La/CuO-SnO2 photocatalysis. The experiment result shows that the La/CuO-SnO2 ternary nano-composite photocatalysts exhibits excellent photocatalytic activity. The paper reviewed the optimal condition of CTC initial concentration, La/CuO-SnO2 photocatalyst concentration, different pH values, and different lights for CTC treatment by La/CuO-SnO2 photocatalysis. In addition, the effect of various oxidant supplies and the dynamics of CTC treatment by photocatalysis were studied. The maximum degradation ratio of CTC by photocatalysis was 88.7% under the following conditions:CTC initial concentration 50 mg/L, La/CuO-SnO2 photocatalyst concentration 1.5 g/L, and pH 3, and COD removal efficiency could reach up to 93% in 120 min. Meanwhile, the value of BOD5/COD> 0.3 of wastewater after 40 min irradiation, it showed chemical and biologic properties were improved. The addition of oxidant also improved the photocatalysis result. When the concentration exceeded 300 mg/L of H2O2 added into the reaction system, the time was cut down. The rate of degradation of CTC can be described by the Langmuir-Hinshelwood equation. A series of photo-oxidation and subsequent chemical reactions were involved on degradation of CTC chemical mechanisms during the photo-catalytic processes. A variety of bicyclic and tricyclic compounds were included in intermediate products of CTC. Polycyclic compounds were opened up, and then small molecular compounds were produced. Ultimately, some inorganic products were investigated. The results indicated that La/CuO-SnO2 photocatalysts have high photocatalytic activity, and have important value in practical application.
引文
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