S-TiO_2光催化剂的制备改性与负载的研究
摘要
本研究用溶胶凝胶法制备了TiO_2、S掺杂改性的S-TiO_2、La掺杂改性的La-TiO_2和La/S共掺杂改性的La/S-TiO_2,对制备的掺杂改性的样品进行XRD、UV-vis、FTIR表征分析。以活性碳纤维(ACF)为载体,采用溶胶-凝胶法和偶联法两种方法制备了载有S掺杂TiO_2薄膜的负载型复合光催化剂S-TiO_2/ACF。实验中以甲基橙为模拟污染物,测试了样品的光催化活性。
S的加入抑制了催化剂粒子的增长,起到细化粒子的作用,并且S的加入会引起晶格畸变;UV-vis分析表明,S掺杂使TiO_2的吸收边带红移,帯隙减小，提高了其光催化活性。IR分析表明,S掺杂后TiO_2的结构发生了变化。在紫外光下,S的最佳掺杂摩尔百分比为10%,最佳煅烧温度为500℃;在可见光下,S的最佳掺杂摩尔百分比为5%,最佳煅烧温度为600℃。
La/S共掺杂TiO_2的掺杂型催化剂中,最佳煅烧温度为600℃,最佳掺杂量为n(La)∶n(S)∶n(TiO_2)=0.1%∶10%∶1。共掺杂制备的光催化剂的光催化活性高于纯TiO_2和S、La单掺杂TiO_2。La掺杂后使得S-TiO_2光吸收增强且明显红移。
负载体系中,偶联法制备的催化剂由于环氧树脂的粘结作用,催化剂的重复使用性好。在紫外光照射下,负载型催化剂能在较短时间内将甲基橙降解,是由ACF的吸附和TiO_2的光催化协同降解。在循环使用中,形成污染物分子吸附、光催化降解、降解矿化的小分子脱附这种动态平衡。
In this study,Pure titania, S-doped TiO_2,La-doped TiO_2 and co-doped with La and S were prepared by sol-gel method. The catalysts obtained were characterized by XRD, DRS and FTIR. And activated carbon fibers (ACFs) as the support for S-doped TiO_2 loading, S-doped TiO_2 were loaded ACF (S-TiO_2/ACF)samples were prepared by sol-gel method and coupling method. The methyl orange in water were chosen as the model to evaluate the photocatalytic activity of all samples.
The S single-doping could restrain the increase of catalyst particle and refine particle. Besides, adding S could led to distortion, it could also broad light absorption range of TiO_2 and decrease band gap, which could improve the photocatalytic ability. It was found that the samples calcined at 500℃and S doped with 10% (in mole) possessed the highest photocatalytic activity among of all the prepared samples under UV-light irradiation, and calcined at 600℃, S doped with 5% (in mole) under Visible-light irradiation.
The optimal doping amount (in molar ratio) was La:N:TiO_2 =0.1%:10%:1 in La/S co-dopedTiO_2. The optimal temperature of heat treatment for La-N co-doped TiO_2 was 600℃. The photocatalysis properties of co-doped TiO_2 prepared under this condition can be enhanced largely than N-doped TiO_2、La-doped TiO_2 and pure TiO_2 . The result of DRS showed that La/S co-doped enhanced light absorption in ultraviolet light region and visible light region.
In immobilization system, catalysts which were prepared by coupling method could recycled many times,because of epoxy resin’s bonding effection. Methyl orange in water could be degraded fleetly because of the dual function of adsorption and photocatalysis. In recycling, it was gradually formed dynamic balance of pollutants molecular adsorption, potocatalytic degradation and small molecules desorption.
S的加入抑制了催化剂粒子的增长,起到细化粒子的作用,并且S的加入会引起晶格畸变;UV-vis分析表明,S掺杂使TiO_2的吸收边带红移,帯隙减小，提高了其光催化活性。IR分析表明,S掺杂后TiO_2的结构发生了变化。在紫外光下,S的最佳掺杂摩尔百分比为10%,最佳煅烧温度为500℃;在可见光下,S的最佳掺杂摩尔百分比为5%,最佳煅烧温度为600℃。
La/S共掺杂TiO_2的掺杂型催化剂中,最佳煅烧温度为600℃,最佳掺杂量为n(La)∶n(S)∶n(TiO_2)=0.1%∶10%∶1。共掺杂制备的光催化剂的光催化活性高于纯TiO_2和S、La单掺杂TiO_2。La掺杂后使得S-TiO_2光吸收增强且明显红移。
负载体系中,偶联法制备的催化剂由于环氧树脂的粘结作用,催化剂的重复使用性好。在紫外光照射下,负载型催化剂能在较短时间内将甲基橙降解,是由ACF的吸附和TiO_2的光催化协同降解。在循环使用中,形成污染物分子吸附、光催化降解、降解矿化的小分子脱附这种动态平衡。
In this study,Pure titania, S-doped TiO_2,La-doped TiO_2 and co-doped with La and S were prepared by sol-gel method. The catalysts obtained were characterized by XRD, DRS and FTIR. And activated carbon fibers (ACFs) as the support for S-doped TiO_2 loading, S-doped TiO_2 were loaded ACF (S-TiO_2/ACF)samples were prepared by sol-gel method and coupling method. The methyl orange in water were chosen as the model to evaluate the photocatalytic activity of all samples.
The S single-doping could restrain the increase of catalyst particle and refine particle. Besides, adding S could led to distortion, it could also broad light absorption range of TiO_2 and decrease band gap, which could improve the photocatalytic ability. It was found that the samples calcined at 500℃and S doped with 10% (in mole) possessed the highest photocatalytic activity among of all the prepared samples under UV-light irradiation, and calcined at 600℃, S doped with 5% (in mole) under Visible-light irradiation.
The optimal doping amount (in molar ratio) was La:N:TiO_2 =0.1%:10%:1 in La/S co-dopedTiO_2. The optimal temperature of heat treatment for La-N co-doped TiO_2 was 600℃. The photocatalysis properties of co-doped TiO_2 prepared under this condition can be enhanced largely than N-doped TiO_2、La-doped TiO_2 and pure TiO_2 . The result of DRS showed that La/S co-doped enhanced light absorption in ultraviolet light region and visible light region.
In immobilization system, catalysts which were prepared by coupling method could recycled many times,because of epoxy resin’s bonding effection. Methyl orange in water could be degraded fleetly because of the dual function of adsorption and photocatalysis. In recycling, it was gradually formed dynamic balance of pollutants molecular adsorption, potocatalytic degradation and small molecules desorption.
引文
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