摘要
纳米TiO_2是一种新型半导体材料,其化学性质稳定、无毒、难溶、价格低廉,是一种较为理想的半导体光催化剂,在太阳能的储存与利用、光电转换、光致变色及光催化降解大气和水中的污染物等诸多方面具有广阔的应用前景。但其禁带宽约3.2eV,激发产生电子-空穴对需用(近)紫外线光照射,其电荷载流子复合速率很快,一般发生在皮秒和纳秒的时间尺度范围内,导致光催化活性不高,制约了其广泛的实际应用,提高其光催化性能是目前研究的主要方向之一。目前该方向的研究主要集中在对TiO_2纳米粉体和薄膜的改性上,但改性的TiO_2纳米粉体和薄膜光催化性能仍较低。TiO_2纳米管具有比纳米粉体和薄膜更大的比表面积,将TiO_2制备成纳米管是一种提高其光催化性能的新途径,但目前国内外对其研究报道极少,对掺杂稀土元素的TiO_2纳米管制备及其光催化性能研究鲜见报道。
本文利用溶胶-凝胶法,以多孔有序阳极氧化铝膜为模板制备掺杂稀土元素镧和铈的TiO_2纳米管,以甲基橙为目标降解物,对比未掺杂的TiO_2纳米管以及未掺杂和掺杂稀土元素的纳米粉进行光催化降解试验,研究其光催化性能,并对降解机理及稀土元素掺杂对TiO_2纳米管光催化性能影响机理进行分析。本文的主要工作包括模板和纳米管的制备及研究:
以高纯铝片为原料,分别以草酸和硫酸为电解液,采用二步阳极氧化法制备多孔有序阳极氧化铝膜,制得的膜厚为1～4μm,孔径在100nm左右,孔径均匀,排列有序的阳极氧化铝膜可作为制备TiO_2纳米管的模板。利用场发射扫描电子显微镜、透射电子显微镜和X射线衍射仪等对其进行表征,并对阳极氧化铝膜及其阵列孔的形成机理进行分析。根据试验结果并结合目前几种常见机理,可较圆满解释阳极氧化铝膜及其阵列孔的形成。
以钛酸丁脂为前驱物,采用溶胶-凝胶法,以多孔阳极氧化铝膜为模板,经后续热处理制得分别掺杂稀土镧、铈和稀土镧、铈混合掺杂的锐钛矿晶型TiO_2纳米管及纳米粉,利用场发射扫描电子显微镜、透射电子显微镜、比表面仪、荧光光谱仪和X射线衍射仪等对其进行表征,并对其形成的影响因素及机理进行分析。
本试验条件下制得的TiO_2纳米管外径80～130nm,内径50～70nm,较均匀;同样以溶胶-凝胶法并经后续热处理制得的TiO_2纳米粉粒径在20～30nm,较均匀。
在15W紫外光源照射下,经150min光催化降解试验表明:TiO_2纳米管比纳米粉具有更高的光催化性能;掺杂稀土元素的TiO_2纳米管光催化性能优于未掺杂的TiO_2纳米管;掺杂稀土镧0.5%的锐钛矿晶型TiO_2纳米管降解率达89.11%;掺杂稀土铈2.0%的锐钛矿晶型TiO_2纳米管降解率达76.87%;稀土镧、铈混合掺杂的锐钛矿晶型TiO_2纳米管在掺杂镧0.3%和掺杂铈1.5%时降解率可达95.24%,正交试验表明该混合掺杂量下,光催化性能最优。
稀土元素掺杂降低了TiO_2电子-空穴对的复合几率,使其光催化性能提高;TiO_2制备成纳米管大大增加了比表面积,增大催化活性,从而进一步提高其光催化性能。
本研究为进一步提高TiO_2光催化性能,使其在诸多领域得到广泛的实质性应用提供了一种新的途径。
Nanometer TiO_2 is a new type of semiconductor material. It is a kind of ideal semiconductor photocatalyst becase of its properties such as stable, poisonless, difficultly soluble and cheap. It has wide application prospects in solar energy storage and utilization, photoelectric conversion, photochromism, photocatalysis in degradation of pollutants in atmosphere and water and so on. But the electron-hole pairs can only be excited by ultraviolet light or near ultraviolet rays because of its 3.2eV forbidden band, The recombination rate of charge carriers is rapid and this mostly occur within picosecond and nanosecond, so lead to its low photocatalysis activity and can not be applied widely and actually. At present, it is one of main directions to improve the photocatalysis property of nanometer TiO_2, the research mainly focus on the modification of nanometer powders and nanometer films, but the photocatalysis property is still low. TiO_2 nanotubes have more specific surface area than nanometer powders and nanometer films, it is a kind of new approach to improve the photocatalysis property of nanometer TiO_2 by prepare nanometer TiO_2 to nanotube, but there are seldom researches about this at home and abroad. The researches on the preparation and photocatalysis property of rare earth ions doped TiO_2 nanotubes is scarcely reported.
In this thesis, the rare earth ions doped titanium dioxide nanotubes are prepared by sol-gel method using Anodic Aluminum Oxide (AAO) film as template. The photocatalytic properties of doped and undoped nanotubes and nanopowders were researched by degrading the methyl orange solution. The degradation mechanism and the influence mechanism of photocatalytic properties by rare earth ions doped are researched. The main researches of this thesis include the preparations and studies of templates and nanotubes:
AAO films were prepared by two-step anodizing in sulfuric and oxalic acid solutions. The AAO films can be used as template of TiO_2 nanotube, which thickness is about 1～4μm and the apertures on it are about 100nm and uniform. The samples are observed by field emission scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction(XRD).The formation mechanism of film and array holes is researched. The formation of the AAO film and array holes could be explained based on the present experiment and some former models.
The La-doped, Ce-doped and La-Ce co-doped anatase TiO_2 nanotubes and nanopowders are prepared by sol-gel method using porous anodic alumina as template with C_(16)H_(36)O_4Ti as precursors. The samples are observed by field emission scanning electron microscope (SEM), transmission electron microscope (TEM), specific surface area measurement (BET), fluorescence spectrometer(FS) and X-ray diffraction(XRD).The formation mechanism and influencing factors are researched.
The external diameters of TiO_2 nanotubes are 80～130nm and the internal diameters are 50～70nm, the diameters are uniform in this experiment condition. The TiO_2 nanopowders are made by sol-gel method at the same conditions, their particle sizes are 20～30nm and the diameters are uniform.
At the irradiation of 15W ultraviolet light source, after 150min, the results of photodegradation show that the photocatalytic properties of TiO_2 nanotubes are better than those of nanopowders, the doped nanotubes are better than those of undoped nanotube. The degradation rate of La-doped anatase TiO_2 nanotubes is 89.11%, the degradation rate of Ce-doped anatase TiO_2 nanotubes is 76.87%, the degradation rate of 0.3%La-1.5%Ce doped anatase TiO_2 nanotubes is 95.24%. The orthogonal test shows that the photocatalytic property is optimal at the 0.3%La-1.5%Ce doped content.
The photocatalytic properties of TiO_2 are improved because that the TiO_2 electron-hole pairs of recombination probability is reduced with the rare earth ions doped in. The specific surface areas of TiO_2 are greatly increased when it become to nanotube, this made the catalytic activities increasing and the photocatalytic properties improved further.
This research provides a kind of new approach to improve the photocatalysis property of TiO_2 and made the application of nano TiO_2 to become extensive and substantive in many fields.
引文
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