纳米复合TiO_2-SnO_2介孔材料的制备、结构与性能研究
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摘要
介孔YiO2因其具有高比表面积,发达有序的孔道结构,孔径尺寸在一定范围内可调,表面易于改性等特点,可以有效地增强纳米YiO2光催化、光电转换等功能,使其在水处理、空气净化、太阳能电池、纳米材料微反应器、生物材料等方面表现出广阔的应用前景而备受瞩目。然而,YiO2是宽禁带材料,通常需要用紫外光源(λ≤388nm)来激发,而太阳光谱中紫外光部分仅占5%,这就导致太阳能利用效率低,在很大程度上限制了它的实际应用。为了提高二氧化钛的光谱响应和太阳光的利用率,人们做了大量的工作对二氧化钛进行改性,提出了染料敏化、贵金属掺杂以及利用溶胶-凝胶技术进行半导体-半导体复合等方法,但上述方法存在光化学稳定性差、原料成本高、操作工艺繁琐等弊端。为了弥补上述方法的不足,本文做了如下工作：
一、利用直接水解常压液相反应进行了半导体-半导体复合。本文以廉价无机盐为原料,采用直接水解常压液相反应对TiO2进行半导体-半导体掺杂耦合,制备出对紫外-可见光均有强吸收的纳米复合光催化材料。与目前报道的昂贵的贵金属掺杂和溶胶-凝胶法掺杂相比,具有工艺简单,成本低,易于工业化生产,实用化强等优点。
二、利用大分子链的空间位阻效应,高分子网络的阻隔作用以及固体模板剂的物理分散作用,有效地阻止了粒子间的粘连与团聚；低温富氧除碳之后,留下大量纳米孔穴,得到纳米介孔材料。此介孔材料不仅解决了长期以来纳米粉体材料过滤难、易团聚和不易回收等缺点,而且与传统粉体相比,可大大增强对所处理有机污染物的吸附能力、催化活性和降解能力,从而提高催化速率和效果。
三、纳米TiO2-SnO2复合介孔材料的应用。本文用此复合介孔材料对酸性红3R染料和三聚氯氰工业废水进行了光催化降解实验,结果表明,酸性红3R染料在太阳光下照射40min后,脱色率可达到100%；三聚氯氰工业废水在日光灯下照射3h后,废水中CN-的含量可完全达到污水综合排放标准(GB8978-1996)中的一级排放标准。
Mesoporous TiO2 has attracted much attention because of its high specific surface area, ordered drill way structure, adjustable aperture size and surface modification, which effectively enhance function of photocatalysis and photoelectric conversion. TiO2 has widely application prospect in water treatment, air purge, cell battery, nanomaterial mini-reactor and biological materials. But TiO2 is a wide band semiconductor, and it is excited only by ultraviolet light resource (wavelength lower than 388nm). Ultraviolet light possesses 5% in the whole sunlight, which leads to low utilization rate of photos and limited application. For the sake of widening spectral response range of TiO2 and enhancing the utilization rate of sun's rays, a lot of work has been done. People put forward to many modified methods, including the sensitization with organic dye, adulteration with notable metal, and complex of semiconductor with Sol-gel method. But above methods have some disadvantages of poor stability, high cost and complicated synthesizing technics. In order to offset these shortages, woke below is done in this paper:
Firstly, using cheap inorganic salt as raw material, semiconductor complex material is prepared by normal pressure liquid-phase method, which is sensitive to UV and visible light. This method has merits of simple craft, low cost, easy to commercial process and practical application, compare to costly adulteration with notable metal and complex of semiconductor with Sol-gel method.
Secondly, this method utilizes the positional hindrance effect of the long chain in space, obstruction effect of high polymer net and physics dispersion effect of solid template agent, which effectively inhibit adhesion and conglobation among particle. Mesoporous material can be get by oxygen-calcination. This material not only resolves filtering difficult, easy conglobation and non-reclaiming of nanometer powder, but also largely enhances adsorption, catalysis activity and degradation to organic pollutant.
Thirdly, the practical application of nanometric TiO2-SnO2 compound mesoporous material. This article studies photocatalysis degradation experiment to acid red 3R dye and cyanuric chloride, using the compound mesoporous material. The experiment results indicat that the decolorizing rate of acid red 3R dye could be to 100% after 40min under sunlight, the CN content of cyanuric chloride could reach primary emission standard after 3h under sunlight lamp.
一、利用直接水解常压液相反应进行了半导体-半导体复合。本文以廉价无机盐为原料,采用直接水解常压液相反应对TiO2进行半导体-半导体掺杂耦合,制备出对紫外-可见光均有强吸收的纳米复合光催化材料。与目前报道的昂贵的贵金属掺杂和溶胶-凝胶法掺杂相比,具有工艺简单,成本低,易于工业化生产,实用化强等优点。
二、利用大分子链的空间位阻效应,高分子网络的阻隔作用以及固体模板剂的物理分散作用,有效地阻止了粒子间的粘连与团聚；低温富氧除碳之后,留下大量纳米孔穴,得到纳米介孔材料。此介孔材料不仅解决了长期以来纳米粉体材料过滤难、易团聚和不易回收等缺点,而且与传统粉体相比,可大大增强对所处理有机污染物的吸附能力、催化活性和降解能力,从而提高催化速率和效果。
三、纳米TiO2-SnO2复合介孔材料的应用。本文用此复合介孔材料对酸性红3R染料和三聚氯氰工业废水进行了光催化降解实验,结果表明,酸性红3R染料在太阳光下照射40min后,脱色率可达到100%；三聚氯氰工业废水在日光灯下照射3h后,废水中CN-的含量可完全达到污水综合排放标准(GB8978-1996)中的一级排放标准。
Mesoporous TiO2 has attracted much attention because of its high specific surface area, ordered drill way structure, adjustable aperture size and surface modification, which effectively enhance function of photocatalysis and photoelectric conversion. TiO2 has widely application prospect in water treatment, air purge, cell battery, nanomaterial mini-reactor and biological materials. But TiO2 is a wide band semiconductor, and it is excited only by ultraviolet light resource (wavelength lower than 388nm). Ultraviolet light possesses 5% in the whole sunlight, which leads to low utilization rate of photos and limited application. For the sake of widening spectral response range of TiO2 and enhancing the utilization rate of sun's rays, a lot of work has been done. People put forward to many modified methods, including the sensitization with organic dye, adulteration with notable metal, and complex of semiconductor with Sol-gel method. But above methods have some disadvantages of poor stability, high cost and complicated synthesizing technics. In order to offset these shortages, woke below is done in this paper:
Firstly, using cheap inorganic salt as raw material, semiconductor complex material is prepared by normal pressure liquid-phase method, which is sensitive to UV and visible light. This method has merits of simple craft, low cost, easy to commercial process and practical application, compare to costly adulteration with notable metal and complex of semiconductor with Sol-gel method.
Secondly, this method utilizes the positional hindrance effect of the long chain in space, obstruction effect of high polymer net and physics dispersion effect of solid template agent, which effectively inhibit adhesion and conglobation among particle. Mesoporous material can be get by oxygen-calcination. This material not only resolves filtering difficult, easy conglobation and non-reclaiming of nanometer powder, but also largely enhances adsorption, catalysis activity and degradation to organic pollutant.
Thirdly, the practical application of nanometric TiO2-SnO2 compound mesoporous material. This article studies photocatalysis degradation experiment to acid red 3R dye and cyanuric chloride, using the compound mesoporous material. The experiment results indicat that the decolorizing rate of acid red 3R dye could be to 100% after 40min under sunlight, the CN content of cyanuric chloride could reach primary emission standard after 3h under sunlight lamp.
引文
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