TiO_2/累托石复合材料制备及光降解酸性红B染料废水研究
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摘要
1972年，藤岛昭和本多健一在n-型半导体TiO_2电极上发现了水的光电催化分解作用，以此为契机，开始了多相光催化研究的新纪元。半导体光催化氧化技术是一种新型的现代水处理技术，由于它能广泛地利用天然能源——太阳能，且对多种有机物有明显的降解效果，具有广阔的应用前景。
但是以TiO_2为典型代表的光催化剂在传统方法上的应用存在着量子效率低以及回收困难等缺点而限制其工业化的推广应用，因此国内外学者积极展开了对这方面的系统研究，其中包括ZiO_2催化剂的表面修饰、固载、重金属沉积、复合半导体、掺杂稀土元素等技术。
本课题旨在开展对二氧化钛与累托石的复合条件以及光催化降解酸性红B的研究，探索其最佳制备工艺条件及降解有机物的一般规律，以期进一步充实光催化剂的负载技术以及有机污水治理方面的研究，为光催化剂的工业化推广运用补充血液。
本课题主要用累托石矿物和四氯化钛等作为原料，制备了二氧化钛／累托石复合材料，并研究了复合反应温度、灼烧温度、灼烧时间等不同因素对产物的光催化活性的影响，初步探讨了各种影响因素的机理所在，总结了最佳的复合工艺条件。
实验用光催化降解酸性红B作为模拟反应，结合X射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)等表征手段，研究了复合材料的制备条件与其光催化活性的关系。XRD和TEM等测试表明，一定热处理温度范围内温度越高，产物晶化越明显。在500℃温度下处理的复合材料明显含有锐钛矿型和金红石型TiO_2；实验发现不同复合条件产物对酸性红3B的光催化降解效果不同，最佳制备工艺条件可以概括为：灼烧温度：500℃；复合反应温度：60℃；HCI／Ti=10～2.0(mol／mol)；TiCl_4／累托石=15～25(g／mmol)；灼烧时间：1～2h；老化时间：24h；较缓慢的柱撑液滴加速度、较稀的累托石悬浮液浓度以及较适宜的反应产物洗涤程度。
本课题还以自制的材料作为光催化剂，紫外杀菌灯作光源，进一步探讨了模拟污染物酸性红3B的光催化反应中影响反应速度的相关因素，实验结果表明污染物初始浓度、催化剂添加量、光源种类、pH值等是影响反应的重要因素。实验初步探讨了各种影响因素的机理以及光催化降解动力学模型。
作为对比，本课题还以钛酸正丁酯为前驱物、无水乙醇为溶剂，在不同反应条件下研究了溶胶．凝胶法制备的TiO_2／累托石复合光催化剂的光催化活性。
A lot of research works have focused on understanding the fundamental processes and on enhancing the photocatalytic efficiency of semiconductor catalysts since A. Fujishima and K. Honda reported the photoelectrochemical water-splitting by TiO2 electrodes in 1972. The technique of photocatalytic oxidation which utilizes a semiconductor as catalyst is a new kind of water treatment process with great potential application in water treatment for its good ability to utilize natural resource, solar energy, and its outstanding effect on degradation of organic substances.
However, the use of conventional photocatalyst that is typically delegated by titanium dioxide results in disadvantages of low quanta efficiency and of separation after the reaction, which confined the industrial application. And different methods including surface of TiO2, support, deposition of heavy metals, the compounded semiconductors, the rare elements mixed into TiO2 were studied abroad and at home.
The aim of this dissertation is to initiate the research of the synthesis conditions of photocatalysts based on titania pillared clays rectorite (TiO2/R) and the decolorization of Acid Red 3B (ARB) aqueous solution and seek after optimal condition and general degradation rules, by which we look forward to building up the base for further research.
In this study, photocatalysts based on TiO2/R have been synthesized by using a commercial rectorite and a reaction mixture containing titanium tetrachloride. Different factors, including temperature of reaction, heat treatment, etc that influence the photocatalytic activity of samples were discussed in detail and the mechanism was explained primarily, also the optimal synthesis condition was concluded.
The resultant TiO2/R were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM)
and the photocatalytic activity of the photocatalysts was evaluated by the decolorization of ARB aqueous solution. It can be seen from XRD, TEM, etc. that titanium dioxide were incorporated, and the higher the calcining temperature, the more clearly crystalline structure of the samples presented, and rutile and anatase TiO2 have been present when the samples were cacined at the temperature 500 C. Different methods have been found to have different effects on the photocatalytic efficiency of the resultant catalysts for the decolorization of ARB in water. It can be concluded that a 500 C calcining temperature, a 60 C synthesis temperature, a HCl/Ti molar ratio in the range of 1.0-2.0, a proper Ti/rectorite (mmol/g) ratio in the range of 15-25, a slower speed of addition of the pillaring solution to the rectorite suspension, and a sparse clay suspension concentration would be the optimal conditions for the preparation of TiOa-CLR sample.
Using the samples synthesized as photocatalysts, the effects of ARB initial concentration, catalyst quantity, light source, solution pH on decolorization ratio were further discussed. The kinetics of photocatalytic oxidation of ARB was also studied.
For comparing, the preparation of TiO2-CLR samples and their photocatalytic activity were also studied under different conditions using Ti(OC4H9)4 as precursor and C2H5OH as solvent.
但是以TiO_2为典型代表的光催化剂在传统方法上的应用存在着量子效率低以及回收困难等缺点而限制其工业化的推广应用，因此国内外学者积极展开了对这方面的系统研究，其中包括ZiO_2催化剂的表面修饰、固载、重金属沉积、复合半导体、掺杂稀土元素等技术。
本课题旨在开展对二氧化钛与累托石的复合条件以及光催化降解酸性红B的研究，探索其最佳制备工艺条件及降解有机物的一般规律，以期进一步充实光催化剂的负载技术以及有机污水治理方面的研究，为光催化剂的工业化推广运用补充血液。
本课题主要用累托石矿物和四氯化钛等作为原料，制备了二氧化钛／累托石复合材料，并研究了复合反应温度、灼烧温度、灼烧时间等不同因素对产物的光催化活性的影响，初步探讨了各种影响因素的机理所在，总结了最佳的复合工艺条件。
实验用光催化降解酸性红B作为模拟反应，结合X射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)等表征手段，研究了复合材料的制备条件与其光催化活性的关系。XRD和TEM等测试表明，一定热处理温度范围内温度越高，产物晶化越明显。在500℃温度下处理的复合材料明显含有锐钛矿型和金红石型TiO_2；实验发现不同复合条件产物对酸性红3B的光催化降解效果不同，最佳制备工艺条件可以概括为：灼烧温度：500℃；复合反应温度：60℃；HCI／Ti=10～2.0(mol／mol)；TiCl_4／累托石=15～25(g／mmol)；灼烧时间：1～2h；老化时间：24h；较缓慢的柱撑液滴加速度、较稀的累托石悬浮液浓度以及较适宜的反应产物洗涤程度。
本课题还以自制的材料作为光催化剂，紫外杀菌灯作光源，进一步探讨了模拟污染物酸性红3B的光催化反应中影响反应速度的相关因素，实验结果表明污染物初始浓度、催化剂添加量、光源种类、pH值等是影响反应的重要因素。实验初步探讨了各种影响因素的机理以及光催化降解动力学模型。
作为对比，本课题还以钛酸正丁酯为前驱物、无水乙醇为溶剂，在不同反应条件下研究了溶胶．凝胶法制备的TiO_2／累托石复合光催化剂的光催化活性。
A lot of research works have focused on understanding the fundamental processes and on enhancing the photocatalytic efficiency of semiconductor catalysts since A. Fujishima and K. Honda reported the photoelectrochemical water-splitting by TiO2 electrodes in 1972. The technique of photocatalytic oxidation which utilizes a semiconductor as catalyst is a new kind of water treatment process with great potential application in water treatment for its good ability to utilize natural resource, solar energy, and its outstanding effect on degradation of organic substances.
However, the use of conventional photocatalyst that is typically delegated by titanium dioxide results in disadvantages of low quanta efficiency and of separation after the reaction, which confined the industrial application. And different methods including surface of TiO2, support, deposition of heavy metals, the compounded semiconductors, the rare elements mixed into TiO2 were studied abroad and at home.
The aim of this dissertation is to initiate the research of the synthesis conditions of photocatalysts based on titania pillared clays rectorite (TiO2/R) and the decolorization of Acid Red 3B (ARB) aqueous solution and seek after optimal condition and general degradation rules, by which we look forward to building up the base for further research.
In this study, photocatalysts based on TiO2/R have been synthesized by using a commercial rectorite and a reaction mixture containing titanium tetrachloride. Different factors, including temperature of reaction, heat treatment, etc that influence the photocatalytic activity of samples were discussed in detail and the mechanism was explained primarily, also the optimal synthesis condition was concluded.
The resultant TiO2/R were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM)
and the photocatalytic activity of the photocatalysts was evaluated by the decolorization of ARB aqueous solution. It can be seen from XRD, TEM, etc. that titanium dioxide were incorporated, and the higher the calcining temperature, the more clearly crystalline structure of the samples presented, and rutile and anatase TiO2 have been present when the samples were cacined at the temperature 500 C. Different methods have been found to have different effects on the photocatalytic efficiency of the resultant catalysts for the decolorization of ARB in water. It can be concluded that a 500 C calcining temperature, a 60 C synthesis temperature, a HCl/Ti molar ratio in the range of 1.0-2.0, a proper Ti/rectorite (mmol/g) ratio in the range of 15-25, a slower speed of addition of the pillaring solution to the rectorite suspension, and a sparse clay suspension concentration would be the optimal conditions for the preparation of TiOa-CLR sample.
Using the samples synthesized as photocatalysts, the effects of ARB initial concentration, catalyst quantity, light source, solution pH on decolorization ratio were further discussed. The kinetics of photocatalytic oxidation of ARB was also studied.
For comparing, the preparation of TiO2-CLR samples and their photocatalytic activity were also studied under different conditions using Ti(OC4H9)4 as precursor and C2H5OH as solvent.
引文
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