过渡金属掺杂TiO_2薄膜亲水性及光催化性能研究
摘要
本研究从提高TiO_2光催化活性和亲水性的角度对TiO_2进行掺杂改性，用溶胶-凝胶法在玻璃基底上制备出了高活性的过渡金属离子掺杂的TiO_2光催化剂，通过X射线衍射、原子力显微镜(AFM)、热重(TG)、红外光谱(FT-IR)、紫外-可见光谱(UV-vis)、表面接触角测量仪等多种检测手段对薄膜的形成、形貌、结构等进行了表征。探讨了光催化改性的微观机理，寻找制约光催化效率的本质原因，为高效光催化剂的设计和制备提供理论依据。本论文有创新和有意义的研究结果如下：
系统研究了Ni~(2+)、Cu~(2+)、Fe~(3+)掺杂对TiO_2亲水性能的影响。实验结果表明，当Ni~(2+)离子的掺杂摩尔浓度为3％、催化剂热处理温度为500℃，锻烧时间为2h时，在黑暗的条件下能保持一周的超亲水性。XRD和AFM分析表明，Ni~(2+)离子TiO_2抑制晶粒生长，使得粒径变小，增强TiO_2薄膜的亲水性能。薄膜在经紫外光照2h后，Ni~(2+)离子掺杂TiO_2薄膜可恢复超亲水性能，一定程度上解决了催化剂中毒问题。而Cu~(2+)、Fe(3+)掺杂对TiO_2薄膜亲水性能影响不大。
系统研究了Ni~(2+)、Cu~(2+)、Fe~(3+)掺杂对TiO_2光催化降解有机物性能的影响。研究结果表明，Cu~(2+)掺杂TiO_2的光催化性能最好，掺杂Cu~(2+)能大幅度提高纳米TiO_2的光催化特性；Fe~(3+)掺杂效果略差；Ni~(2+)掺杂反而使光催化性能降低。当Cu~(2+)的掺杂摩尔浓度为3％、催化剂热处理温度为500℃，退火时间为2h时，薄膜降解甲基橙的能力增加了14％。Ni~(2+)、Fe~(3+)和Cu~(2+)离子掺杂后使TiO_2的晶格发生畸变，产生晶格缺陷，从而使TiO_2晶体中电子浓度发生变化，进而影响TiO_2薄膜光催化性能和亲水性能。我们通过对过渡金属离子掺杂改性的微观机理进行了探讨，认为掺杂TiO_2光催化剂的光催化活性与掺杂离子的大小和掺杂离子在TiO_2晶格中所处的位置有关。当掺杂离子的半径小于或接近Ti~(4+)离子半径时，杂质离子的掺入将大大提高TiO_2光催化剂的活性；当杂质离子的半径远远大于Ti~(4+)离子半径时，掺杂效果较低，ZiO_2光催化活性变化不大。于我们的研究而言，过渡金属离子掺杂TiO_2光催化剂的活性大小次序为Cu~(2+)＞Fe~(3+)＞未掺杂＞Ni~(2+)。
In this paper, TiO_2 was doped to enhance photocatalytic activity and hydrophilicity. TiO_2 films and Ni~(2+), Fe~(3+) and Cu~(2+) doped TiO_2 multilayers were grown by sol-gel on glass substrates were characterized with X-ray diffraction (XRD), atomic force microscopy (AFM) and water contact angle measurement. By means of many advanced experiments, the microcosmic mechanism of photocatalytic process was studied in order to find basic factors that affect photocatalytic efficiency and provide theoretical basis of designing and preparing high efficient photocatalys.
We investigated systematically the effect of transition metal ions doping TiO_2 on its activity of hydrophilicity production. The high active hydrophilic of transition metal ions doping TiO_2 had been prepared by sol-gel method.Among all the doped samples, TiO_2 doped with Ni~(2+)photocatalyst has the best hydrophilicity activity. When the doped molar content of Ni~(2+) was 2m01%, the calcinated temperature was 500℃and the calcinated time was 2h, the contact angles of Ni~(2+) doping TiO_2 can keep hydropilicity after storage in dark for 7 days. The sample of Ni~(2+) doping TiO_2 also had excellent photo-induced superhydrophilicity. After under UV irradiation for 2h, the contact angles were reduced to 0°, the hydropilicity activity of Ni~(2+) doped TiO_2 was well repaired, the TiO_2 photocatalyst poisoning problem has been well solved. The analysis of structure indicated that transition metal ions doping in TiO_2 didn't influence the crystal paterns of TiO_2 particle, the crystal transformation of TiO_2 from anatase to rutile was prevented, the particle diameter decreased and the hydroplicity of TiO_2 was increased. The hydrophilicity of TiO_2 films was little affected by Cu~(2+) doping and Fe~(3+) doping.
We investigated systematically the effect of transition metal ions doping TiO_2 on its activity of photocatalytic production. The high active photocatalyst of transition metal ions doping TiO_2 had been prepared by sol-gel method. Among all the doped samples, TiO_2 doped with Cu~(2+) photocatalyst has the highest activity, Fe~(3+) doping caused little affect on photocatalytic activity and Ni~(2+) doping even caused a decrease in the photocatalytic activity. When the doped molar content of Cu~(2+) was 3mol%, the calcinated temperature was 500℃and the calcinated time was 2h, the photocatalytic activity of Cu~(2+) doping TiO_2 after UV light irradiating for lh had increased from pure TiO_2 40% to 54%. The analysis of structure indicated that transition metal ions doping in TiO_2 didn't influence the crystal paterns of TiO_2 particle, but Ni~(2+), Cu~(2+)or Fe~(3+) doping produced latice deformation which caused the change of the electron density in TiO_2, and then influcenced the hydroplicity and photocatalytic of TiO_2. We researched the doping mechanism of TiO_2. It was found that the photocatalytic activities depend on the size and location of the doping ions in TiO_2. When the radii of doping ions were smaller than that of Ti~(4+) or closer to the Ti~(4+), the doping effect was obvious; while the radii of doping ions were much larger than that of Ti~(4+), the doping effect was lower. The doped TiO_2 photocatalytica ctivities were in the order: Cu~(2+)＞Fe~(3+)＞Ni~(2+). This result is very important to realize the essence of photocatalysis.
系统研究了Ni~(2+)、Cu~(2+)、Fe~(3+)掺杂对TiO_2亲水性能的影响。实验结果表明，当Ni~(2+)离子的掺杂摩尔浓度为3％、催化剂热处理温度为500℃，锻烧时间为2h时，在黑暗的条件下能保持一周的超亲水性。XRD和AFM分析表明，Ni~(2+)离子TiO_2抑制晶粒生长，使得粒径变小，增强TiO_2薄膜的亲水性能。薄膜在经紫外光照2h后，Ni~(2+)离子掺杂TiO_2薄膜可恢复超亲水性能，一定程度上解决了催化剂中毒问题。而Cu~(2+)、Fe(3+)掺杂对TiO_2薄膜亲水性能影响不大。
系统研究了Ni~(2+)、Cu~(2+)、Fe~(3+)掺杂对TiO_2光催化降解有机物性能的影响。研究结果表明，Cu~(2+)掺杂TiO_2的光催化性能最好，掺杂Cu~(2+)能大幅度提高纳米TiO_2的光催化特性；Fe~(3+)掺杂效果略差；Ni~(2+)掺杂反而使光催化性能降低。当Cu~(2+)的掺杂摩尔浓度为3％、催化剂热处理温度为500℃，退火时间为2h时，薄膜降解甲基橙的能力增加了14％。Ni~(2+)、Fe~(3+)和Cu~(2+)离子掺杂后使TiO_2的晶格发生畸变，产生晶格缺陷，从而使TiO_2晶体中电子浓度发生变化，进而影响TiO_2薄膜光催化性能和亲水性能。我们通过对过渡金属离子掺杂改性的微观机理进行了探讨，认为掺杂TiO_2光催化剂的光催化活性与掺杂离子的大小和掺杂离子在TiO_2晶格中所处的位置有关。当掺杂离子的半径小于或接近Ti~(4+)离子半径时，杂质离子的掺入将大大提高TiO_2光催化剂的活性；当杂质离子的半径远远大于Ti~(4+)离子半径时，掺杂效果较低，ZiO_2光催化活性变化不大。于我们的研究而言，过渡金属离子掺杂TiO_2光催化剂的活性大小次序为Cu~(2+)＞Fe~(3+)＞未掺杂＞Ni~(2+)。
In this paper, TiO_2 was doped to enhance photocatalytic activity and hydrophilicity. TiO_2 films and Ni~(2+), Fe~(3+) and Cu~(2+) doped TiO_2 multilayers were grown by sol-gel on glass substrates were characterized with X-ray diffraction (XRD), atomic force microscopy (AFM) and water contact angle measurement. By means of many advanced experiments, the microcosmic mechanism of photocatalytic process was studied in order to find basic factors that affect photocatalytic efficiency and provide theoretical basis of designing and preparing high efficient photocatalys.
We investigated systematically the effect of transition metal ions doping TiO_2 on its activity of hydrophilicity production. The high active hydrophilic of transition metal ions doping TiO_2 had been prepared by sol-gel method.Among all the doped samples, TiO_2 doped with Ni~(2+)photocatalyst has the best hydrophilicity activity. When the doped molar content of Ni~(2+) was 2m01%, the calcinated temperature was 500℃and the calcinated time was 2h, the contact angles of Ni~(2+) doping TiO_2 can keep hydropilicity after storage in dark for 7 days. The sample of Ni~(2+) doping TiO_2 also had excellent photo-induced superhydrophilicity. After under UV irradiation for 2h, the contact angles were reduced to 0°, the hydropilicity activity of Ni~(2+) doped TiO_2 was well repaired, the TiO_2 photocatalyst poisoning problem has been well solved. The analysis of structure indicated that transition metal ions doping in TiO_2 didn't influence the crystal paterns of TiO_2 particle, the crystal transformation of TiO_2 from anatase to rutile was prevented, the particle diameter decreased and the hydroplicity of TiO_2 was increased. The hydrophilicity of TiO_2 films was little affected by Cu~(2+) doping and Fe~(3+) doping.
We investigated systematically the effect of transition metal ions doping TiO_2 on its activity of photocatalytic production. The high active photocatalyst of transition metal ions doping TiO_2 had been prepared by sol-gel method. Among all the doped samples, TiO_2 doped with Cu~(2+) photocatalyst has the highest activity, Fe~(3+) doping caused little affect on photocatalytic activity and Ni~(2+) doping even caused a decrease in the photocatalytic activity. When the doped molar content of Cu~(2+) was 3mol%, the calcinated temperature was 500℃and the calcinated time was 2h, the photocatalytic activity of Cu~(2+) doping TiO_2 after UV light irradiating for lh had increased from pure TiO_2 40% to 54%. The analysis of structure indicated that transition metal ions doping in TiO_2 didn't influence the crystal paterns of TiO_2 particle, but Ni~(2+), Cu~(2+)or Fe~(3+) doping produced latice deformation which caused the change of the electron density in TiO_2, and then influcenced the hydroplicity and photocatalytic of TiO_2. We researched the doping mechanism of TiO_2. It was found that the photocatalytic activities depend on the size and location of the doping ions in TiO_2. When the radii of doping ions were smaller than that of Ti~(4+) or closer to the Ti~(4+), the doping effect was obvious; while the radii of doping ions were much larger than that of Ti~(4+), the doping effect was lower. The doped TiO_2 photocatalytica ctivities were in the order: Cu~(2+)＞Fe~(3+)＞Ni~(2+). This result is very important to realize the essence of photocatalysis.
引文
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