电极性矿物材料表面光催化功能膜研究
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摘要
本工作利用电气石矿物材料的天然电极性、辐射红外线性能和TiO_2的光催化性能，研制以电气石为载体，TiO_2薄膜和[TiO_2，SiO_2]复合薄膜为催化剂的新型复合催化材料。研究材料的制备技术、结构、性能及电气石表面TiO_2晶体生长机理、电气石增强TiO_2光催化效率机理。
用溶胶—凝胶技术在紫铜网表面成功生长电气石／TiO_2复合薄膜，该复合膜中电气石微粒表面形成了TiO_2空心球簇结构和TiO_2层状微粒簇结构。空心球平均粒径为2μm；TiO_2微粒簇平均直径为10μm，TiO_2微粒平均粒径为2μm，阶梯层厚度为10nm，表面凸起平均粒径15nm。研究表明，电气石／TiO_2复合薄膜的光催化效率比不含电气石的TiO_2薄膜提高15.6％。
电气石／[TiO_2，SiO_2]复合催化剂的最佳制备工艺参数为：[TiO_2，SiO_2]复合膜中SiO_2的质量分数为10％，热处理温度为600℃，热处理时间为3h。该复合催化剂对初始浓度为10mg／L的甲基澄溶液的光催化降解率(3h)达到97％以上，比电气石／TiO_2复合催化剂提高14.3％。
通过电气石促进TiO_2光催化反应机理的研究发现，在电气石／TiO_2光催化剂体系中，电气石天然电场不仅能够吸引并牢固的捕获由TiO_2在紫外线激发下产生的光生电子，避免光生电子和光生空穴发生再复合反应，而且能够电离水分子，促进羟基自由基的生成。同时，电气石辐射的红外线能够降低水分子团的直径，引起有机高分子强烈共振，加速光催化反应速度。
A kind of novel composite photocatalysts containing TiO2 and tourmaline particles, such as tourmaline/TiO2 composite photocatalysts and tourmaline/[TiO2, SiO2] composite photocalysts, were fabricated mainly by the sol-gel technique, whose microstructure, photocatalystic activities and spontaneous polarization were investigated by the scanning electron microscope(SEM), UV-visible spectro-photometer, etc.
The novel porous composite films of tourmaline/TiO2 were prepared from alkoxide solutions on the surface of copper by sol-gel method. Results show that the empty and porous balls of TiO2 were grown on the surface of fine tourmaline particles dispersing in the TiO2 film based on the copper net, under the effect of the nature electric field of fine tourmaline particles. The average diameter of the empty balls is 2 μm, and the photocatalystic degradation ratio of methyl orange increased by 15.6% with the composite film of TiO2 containing 0.5 wt % tourmaline than with the thin films of TiO2 under the irradiation of ultraviolet.
In this paper, not only a new method to testify the spontaneous polarization of tourmaline is provided, but also the influence of treatment temperature on the spontaneous polarization of tourmaline/[TiO2, SiO2] composite photocatalysts containing 10wt% SiO2 are observed. Results show that tourmaline/[TiO2, SiO2] composite photocatalysts granules, under the bombardment by electron beam in SEM, will turn to be brighter and attract each other, and the electrostatic gravitation among the tourmaline/[TiO2, SiO2] composite photocatalysts granules grow up evidently on their surfaces with the accumulations of electron from the electron probe, so as to be strong enough to force the tourmaline/[TiO2, SiO2] composite photocatalysts granules be shifted rapidly and accumulated into clusters ultimately.
Photocatalytic activities and mutual interactions mechanism between TiO2 and fine tourmaline particles were investigated, respectively. Photoelectrocalalytic reaction happens in the reaction system, in which electrons and cavities generated from nanometer TiO2 under irradiation of ultraviolet will be avoided compounding due to existence of permanent and strongly electric field of fine tourmaline powders.
用溶胶—凝胶技术在紫铜网表面成功生长电气石／TiO_2复合薄膜，该复合膜中电气石微粒表面形成了TiO_2空心球簇结构和TiO_2层状微粒簇结构。空心球平均粒径为2μm；TiO_2微粒簇平均直径为10μm，TiO_2微粒平均粒径为2μm，阶梯层厚度为10nm，表面凸起平均粒径15nm。研究表明，电气石／TiO_2复合薄膜的光催化效率比不含电气石的TiO_2薄膜提高15.6％。
电气石／[TiO_2，SiO_2]复合催化剂的最佳制备工艺参数为：[TiO_2，SiO_2]复合膜中SiO_2的质量分数为10％，热处理温度为600℃，热处理时间为3h。该复合催化剂对初始浓度为10mg／L的甲基澄溶液的光催化降解率(3h)达到97％以上，比电气石／TiO_2复合催化剂提高14.3％。
通过电气石促进TiO_2光催化反应机理的研究发现，在电气石／TiO_2光催化剂体系中，电气石天然电场不仅能够吸引并牢固的捕获由TiO_2在紫外线激发下产生的光生电子，避免光生电子和光生空穴发生再复合反应，而且能够电离水分子，促进羟基自由基的生成。同时，电气石辐射的红外线能够降低水分子团的直径，引起有机高分子强烈共振，加速光催化反应速度。
A kind of novel composite photocatalysts containing TiO2 and tourmaline particles, such as tourmaline/TiO2 composite photocatalysts and tourmaline/[TiO2, SiO2] composite photocalysts, were fabricated mainly by the sol-gel technique, whose microstructure, photocatalystic activities and spontaneous polarization were investigated by the scanning electron microscope(SEM), UV-visible spectro-photometer, etc.
The novel porous composite films of tourmaline/TiO2 were prepared from alkoxide solutions on the surface of copper by sol-gel method. Results show that the empty and porous balls of TiO2 were grown on the surface of fine tourmaline particles dispersing in the TiO2 film based on the copper net, under the effect of the nature electric field of fine tourmaline particles. The average diameter of the empty balls is 2 μm, and the photocatalystic degradation ratio of methyl orange increased by 15.6% with the composite film of TiO2 containing 0.5 wt % tourmaline than with the thin films of TiO2 under the irradiation of ultraviolet.
In this paper, not only a new method to testify the spontaneous polarization of tourmaline is provided, but also the influence of treatment temperature on the spontaneous polarization of tourmaline/[TiO2, SiO2] composite photocatalysts containing 10wt% SiO2 are observed. Results show that tourmaline/[TiO2, SiO2] composite photocatalysts granules, under the bombardment by electron beam in SEM, will turn to be brighter and attract each other, and the electrostatic gravitation among the tourmaline/[TiO2, SiO2] composite photocatalysts granules grow up evidently on their surfaces with the accumulations of electron from the electron probe, so as to be strong enough to force the tourmaline/[TiO2, SiO2] composite photocatalysts granules be shifted rapidly and accumulated into clusters ultimately.
Photocatalytic activities and mutual interactions mechanism between TiO2 and fine tourmaline particles were investigated, respectively. Photoelectrocalalytic reaction happens in the reaction system, in which electrons and cavities generated from nanometer TiO2 under irradiation of ultraviolet will be avoided compounding due to existence of permanent and strongly electric field of fine tourmaline powders.
引文
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5. Hoffman M R, Martin S T, Choi W, et al. Environmental applications of semiconductor photocatalysis[J]. Chem Rev, 1995, 95(1): 69～96.
6．梁金生，金宗哲，王静．环境净化功能M/TiO_2纳米材料光催化活性的研究．硅酸盐学报．1999，27(5)：601～604．
7. Jones A P, Watts R J. Dry phases titanium dioxide-mediated photocatalysis: basis for in situ surface destruction of hazardous chemicals[J]. Journal of Environmental Engineering, 1997, 10: 974～980.
8. Ikezawa S, Hamyara H, Kubota T, et al. Application of TiO_2 film for environmental purification deposite by controlled electron beam-excited plasma[J]. Thin Solid Films, 2001, 386: 173～176
9．王估中，符雁，汤鸿宵．甲基橙溶液多相光催化降解研究[J]．环境科学，1998，19(1)：1～4．
10．方世杰，徐明霞，黄卫友等．纳米TiO_2光催化降解甲基橙[J]．硅酸盐学报，2001，29(5)：435～442．
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13. Zongzhe Jin, Jinsheng Liang, Jing Wang, et al, Proc.3rd.Inte Conf.on Ecomaterials, Japan, P-12, 1997,201～205.
14. Jinsheng Liang, Zongzhe Jin, Jing Wang. Effects of TiO2 film photocatalyst tiles on growth of
experimental animals proc., Inte. Conf. on High-performance ceramics, Beijing, 1998.
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