具有可见光激发响应的纳米TiO_2光催化材料的研究
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摘要
本文采用溶胶-凝胶法,制备了Eu3+、Ce3+以及Ce-Eu共掺杂纳米TiO2。对Ce-Eu共掺杂样品采用正交试验方法研究了外部因素和内部因素对其光催化活性的影响。选取最佳配方对赤泥质陶瓷滤球进行涂覆试验并将其用于水处理。通过TG-DTA、XRD、FE-SEM、TEM、SEM、UV-Vis吸收谱等测试手段对样品进行了结构及性能表征,探讨了Eu3+、Ce3+以及Ce-Eu共掺杂纳米TiO2的光催化机理。
稀土元素Eu3+、Ce3+的掺杂量与样品的光催化性有一定的关系。在样品加入量为0.15g/50mL,亚甲基蓝溶液的初始浓度为10mg/L、pH=6.5、热处理温度为550℃的条件下,掺杂浓度(摩尔比)分别为n(Eu3+):n(TiO2)=0.5%, n(Ce3+):n(TiO2)=0.05%时,其对亚甲基蓝的降解率可以分别达到85.36%、85.15%,各比同等条件下制备的未掺杂YiO2提高了22.08%和21.78%。Ce3+掺杂TiO2可使出现金红石相的温度降低为650℃左右,金红石相的生成,对光催化活性有促进作用,掺杂浓度为n(Ce3+):n(TiO2)=0.05%的Ce3+掺杂TiO2样品的光催化降解率上升为85.52%。
正交试验结果表明,内部因素对掺杂TiO2光催化活性影响的主次顺序为：热处理温度>Ce的掺杂量＞Eu的掺杂量。样品制备的优化配方为：Ce的掺杂量为0.02mol%、Eu的掺杂量为0.2mol%、热处理温度为550℃。外部因素对TiO2光催化活性影响的主次顺序为：亚甲基蓝溶液的初始浓度>催化剂加入量>溶液的pH值。优化的外部光催化条件为：光催化剂加入量为0.15g/50mL、亚甲基蓝溶液的初始pH值及浓度分别为6.5和10 mg／L。
掺杂样品的光催化活性研究表明,Ce-Eu共掺杂TiO2＞Eu3+掺杂TiO2＞Ce3+掺杂TiO2>未掺杂TiO2。其中掺杂浓度(摩尔比)为n(Eu3+):n(Ce3+) : n(TiO2)=0.2：0.02：100的共掺杂样品的光催化效率可达到86.23%,比同等条件下制备的未掺杂TiO2提高了22.95%。晶粒尺寸为19.7nm,晶格畸变为0.5259,晶胞体积为136.26×10-3 nm3,光催化反应动力学常数为7.766×10-3。其吸收阈值为445nm,相应的禁带宽度为2.87 eV,比纯TiO2红移了53nm。本研究中,掺杂浓度为n(Ce3+):n(TiO2)=0.2%(摩尔百分数)的样品吸收边红移最多,吸收阈值达到446nm。
单掺杂和共掺杂纳米TiO2的光催化机理是：Eu3+的电子层结构[Xe]4f6和其较大的半径,造成Eu3+掺杂样品电荷不平衡,影响电子-空穴对的复合；产生的空位附加能级则会拓宽吸收光谱。Ce3+掺杂TiO2使Ce3+、Ce4+共存、产生晶格畸变,造成晶格中电荷不平衡,减小光生电子-空穴对的复合率；Ce3+掺杂形成光敏化结构,使激发电子注入TiO2的导带,扩大TiO2的光谱响应范围。Ce-Eu共掺杂纳米TiO2中,Ce3+作为敏化离子将能量传递给Eu3+,Eu3+捕获光生电子并传递给表面吸附的O2,增加有效的空穴电子数,另一方面可使样品吸收更低能量的波长而被激发。
在亚甲基蓝溶液浓度为15mg/L,pH值为6.5,滤球的加入量为5g/50mL的条件下,涂覆时间为10min、涂覆次数为2次的赤泥质陶瓷滤球光催化性能最佳可达到73.40%,优于未镀膜滤球的70.28%。涂覆时间为10min,热处理温度为550℃的赤泥质陶瓷滤球,其表面有一层厚度为2μm左右的均匀TiO2膜层。该滤球在As(v)离子的浓度为2mg／L,pH值为2,吸附时间为240min,样品加入量为2g的条件下,对As(v)离子去除率最高,可达95.96%。
Eu3+, Ce3+doped nano-TiO2 and Ce-Eu co-doped TiO2 were synthesized by sol-gel method. The effects of internal and external factors on photocatalystic activity of the Ce-Eu co-doped TiO2 were discussed by designing the orthogonal experiments. The red mud ceramic filter materials were coated with the optimal formula of TiO2, which was used for water treatment. The samples were characterized by the testing techniques such as TG-DTA, XRD, FE-SEM, TEM, SEM, UV-Vis absorption spectra and so on. The photocatalystic mechanism of Eu3+, Ce3+doped TiO2 and Ce-Eu co-doped TiO2 was discussed.
The photocatalystic properties of samples had some relation with the doping amount of rare earth Eu3+and Ce3+. The photocatalystic degradation on methyl blue of samples can reach 85.36% and 85.15% respectively, when the addition amount is 0.15g/50mL, the initial concentration of MB solution is 10mg/L, the pH value is 6.5, the heating temperature is 550℃and doping amount (molar ratio) was n(Eu3+): n(TiO2)=0.5% or n(Ce3+):n(TiO2)=0.05%. They showed better photocatalystic properties than the undoped TiO2, the degradation rate was increased by 22.08% and 21.78% accordingly. The temperature when the Rutil appeared was decreased to 650℃because of the addition of Ce3+. The Rutil was beneficial to the photocatalystic properties of the sample. The degradation rate of the sample whose doping amount was n(Ce3+):n(TiO2)=0.05% increased to 85.52%.
The results of the orthogonal experiments showed that the important order of the internal factors that affect the photocatalystic properties of doped TiO2 were heating temperature, the amount of Ce3+, the amount of Eu3+in turn. The optimal formula of the sample is that the amount of Ce3+ and Eu3+ is 0.02mol% and 0.02mol% respectively, heating temperature is 550℃. The important order of the external factors that affect the photocatalystic properties were the initial concentration of MB, the addition amount of samples, the pH value in turn. The photocatalystic activity was the best when the addition amount is 0.15g/50mL, the initial concentration is 10mg/L and the pH value is 6.5.
The study on the photocatalystic properties of the rare earth doped TiO2 showed that the photocatalytic activity were Co-doped TiO2> Eu3+doped> Ce3+doped> undoped samples. When the doping amount (molar ratio) was n(Eu3+):n(Ce3+): n(TiO2)=0.2:0.02:100, the photocatalystic degradation can reach 86.23%, which increased by 22.95% compared to the un-doped TiO2 samples.The grain size was 19.7nm, lattice distortion was 0.5259, unit cell volume was 136.26×10-3nm3, the kinetic constant of the photocatalytic reaction was 7.766×10-3. The absorption threshold was 445nm, and the band gap was 2.87 eV, which had 53nm red shifted than that of pure TiO2. The sample with the doping amount (molar percent) n(Ce3+): n(TiO2)=0.2%, had the maximum red shift, and the absorption threshold reached 446nm.
The photocatalystic mechanism of Eu3+, Ce3+doped TiO2 and Ce-Eu co-doped TiO2 was as follows:A charge imbalance was caused because of the electron structure ([Xe]4f6)and radius of Eu3+, which had an effect on the recombination of e- and h+, the additional energy band of h+ broaden the absorption spectra. Ce3+ doped TiO2 brought out a series of poor results, like Ce3+, Ce4+co-exist, lattice distortion, the charge imbalance, low recombination of e-and h+; It made up of photosensitive structure formation, leading to excited electrons entered into the conduction band and enlarged the spectral response range of TiO2. When Ce-Eu co-doped nano-TiO2, Ce3+as a sensitizer ion transfer the energy to Eu3+, it captured and passed electrons to the O2 be absorbed on the surface, which resulted in the increase of effective electron and hole, also made the sample be excited by wavelength with lower energy.
The photocatalystic properties of the filter coated with TiO2 for 10min twice was 73.40%, when the amount of filter is 0.15g/50mL, the concentration of MB is 15mg/L and the pH value is 6.5, and this value was higher than that of uncoated filter, which was 70.28%.There was a 2μm TiO2 film on the surface of the red mud ceramic filter which was heated at 550℃. The removal rate of As(v) by TiO2 modified filter was 95.96%, when 2g TiO2 modified filter absorbing in a solution of 2mg/L As (v)at pH=2 for 240min.
稀土元素Eu3+、Ce3+的掺杂量与样品的光催化性有一定的关系。在样品加入量为0.15g/50mL,亚甲基蓝溶液的初始浓度为10mg/L、pH=6.5、热处理温度为550℃的条件下,掺杂浓度(摩尔比)分别为n(Eu3+):n(TiO2)=0.5%, n(Ce3+):n(TiO2)=0.05%时,其对亚甲基蓝的降解率可以分别达到85.36%、85.15%,各比同等条件下制备的未掺杂YiO2提高了22.08%和21.78%。Ce3+掺杂TiO2可使出现金红石相的温度降低为650℃左右,金红石相的生成,对光催化活性有促进作用,掺杂浓度为n(Ce3+):n(TiO2)=0.05%的Ce3+掺杂TiO2样品的光催化降解率上升为85.52%。
正交试验结果表明,内部因素对掺杂TiO2光催化活性影响的主次顺序为：热处理温度>Ce的掺杂量＞Eu的掺杂量。样品制备的优化配方为：Ce的掺杂量为0.02mol%、Eu的掺杂量为0.2mol%、热处理温度为550℃。外部因素对TiO2光催化活性影响的主次顺序为：亚甲基蓝溶液的初始浓度>催化剂加入量>溶液的pH值。优化的外部光催化条件为：光催化剂加入量为0.15g/50mL、亚甲基蓝溶液的初始pH值及浓度分别为6.5和10 mg／L。
掺杂样品的光催化活性研究表明,Ce-Eu共掺杂TiO2＞Eu3+掺杂TiO2＞Ce3+掺杂TiO2>未掺杂TiO2。其中掺杂浓度(摩尔比)为n(Eu3+):n(Ce3+) : n(TiO2)=0.2：0.02：100的共掺杂样品的光催化效率可达到86.23%,比同等条件下制备的未掺杂TiO2提高了22.95%。晶粒尺寸为19.7nm,晶格畸变为0.5259,晶胞体积为136.26×10-3 nm3,光催化反应动力学常数为7.766×10-3。其吸收阈值为445nm,相应的禁带宽度为2.87 eV,比纯TiO2红移了53nm。本研究中,掺杂浓度为n(Ce3+):n(TiO2)=0.2%(摩尔百分数)的样品吸收边红移最多,吸收阈值达到446nm。
单掺杂和共掺杂纳米TiO2的光催化机理是：Eu3+的电子层结构[Xe]4f6和其较大的半径,造成Eu3+掺杂样品电荷不平衡,影响电子-空穴对的复合；产生的空位附加能级则会拓宽吸收光谱。Ce3+掺杂TiO2使Ce3+、Ce4+共存、产生晶格畸变,造成晶格中电荷不平衡,减小光生电子-空穴对的复合率；Ce3+掺杂形成光敏化结构,使激发电子注入TiO2的导带,扩大TiO2的光谱响应范围。Ce-Eu共掺杂纳米TiO2中,Ce3+作为敏化离子将能量传递给Eu3+,Eu3+捕获光生电子并传递给表面吸附的O2,增加有效的空穴电子数,另一方面可使样品吸收更低能量的波长而被激发。
在亚甲基蓝溶液浓度为15mg/L,pH值为6.5,滤球的加入量为5g/50mL的条件下,涂覆时间为10min、涂覆次数为2次的赤泥质陶瓷滤球光催化性能最佳可达到73.40%,优于未镀膜滤球的70.28%。涂覆时间为10min,热处理温度为550℃的赤泥质陶瓷滤球,其表面有一层厚度为2μm左右的均匀TiO2膜层。该滤球在As(v)离子的浓度为2mg／L,pH值为2,吸附时间为240min,样品加入量为2g的条件下,对As(v)离子去除率最高,可达95.96%。
Eu3+, Ce3+doped nano-TiO2 and Ce-Eu co-doped TiO2 were synthesized by sol-gel method. The effects of internal and external factors on photocatalystic activity of the Ce-Eu co-doped TiO2 were discussed by designing the orthogonal experiments. The red mud ceramic filter materials were coated with the optimal formula of TiO2, which was used for water treatment. The samples were characterized by the testing techniques such as TG-DTA, XRD, FE-SEM, TEM, SEM, UV-Vis absorption spectra and so on. The photocatalystic mechanism of Eu3+, Ce3+doped TiO2 and Ce-Eu co-doped TiO2 was discussed.
The photocatalystic properties of samples had some relation with the doping amount of rare earth Eu3+and Ce3+. The photocatalystic degradation on methyl blue of samples can reach 85.36% and 85.15% respectively, when the addition amount is 0.15g/50mL, the initial concentration of MB solution is 10mg/L, the pH value is 6.5, the heating temperature is 550℃and doping amount (molar ratio) was n(Eu3+): n(TiO2)=0.5% or n(Ce3+):n(TiO2)=0.05%. They showed better photocatalystic properties than the undoped TiO2, the degradation rate was increased by 22.08% and 21.78% accordingly. The temperature when the Rutil appeared was decreased to 650℃because of the addition of Ce3+. The Rutil was beneficial to the photocatalystic properties of the sample. The degradation rate of the sample whose doping amount was n(Ce3+):n(TiO2)=0.05% increased to 85.52%.
The results of the orthogonal experiments showed that the important order of the internal factors that affect the photocatalystic properties of doped TiO2 were heating temperature, the amount of Ce3+, the amount of Eu3+in turn. The optimal formula of the sample is that the amount of Ce3+ and Eu3+ is 0.02mol% and 0.02mol% respectively, heating temperature is 550℃. The important order of the external factors that affect the photocatalystic properties were the initial concentration of MB, the addition amount of samples, the pH value in turn. The photocatalystic activity was the best when the addition amount is 0.15g/50mL, the initial concentration is 10mg/L and the pH value is 6.5.
The study on the photocatalystic properties of the rare earth doped TiO2 showed that the photocatalytic activity were Co-doped TiO2> Eu3+doped> Ce3+doped> undoped samples. When the doping amount (molar ratio) was n(Eu3+):n(Ce3+): n(TiO2)=0.2:0.02:100, the photocatalystic degradation can reach 86.23%, which increased by 22.95% compared to the un-doped TiO2 samples.The grain size was 19.7nm, lattice distortion was 0.5259, unit cell volume was 136.26×10-3nm3, the kinetic constant of the photocatalytic reaction was 7.766×10-3. The absorption threshold was 445nm, and the band gap was 2.87 eV, which had 53nm red shifted than that of pure TiO2. The sample with the doping amount (molar percent) n(Ce3+): n(TiO2)=0.2%, had the maximum red shift, and the absorption threshold reached 446nm.
The photocatalystic mechanism of Eu3+, Ce3+doped TiO2 and Ce-Eu co-doped TiO2 was as follows:A charge imbalance was caused because of the electron structure ([Xe]4f6)and radius of Eu3+, which had an effect on the recombination of e- and h+, the additional energy band of h+ broaden the absorption spectra. Ce3+ doped TiO2 brought out a series of poor results, like Ce3+, Ce4+co-exist, lattice distortion, the charge imbalance, low recombination of e-and h+; It made up of photosensitive structure formation, leading to excited electrons entered into the conduction band and enlarged the spectral response range of TiO2. When Ce-Eu co-doped nano-TiO2, Ce3+as a sensitizer ion transfer the energy to Eu3+, it captured and passed electrons to the O2 be absorbed on the surface, which resulted in the increase of effective electron and hole, also made the sample be excited by wavelength with lower energy.
The photocatalystic properties of the filter coated with TiO2 for 10min twice was 73.40%, when the amount of filter is 0.15g/50mL, the concentration of MB is 15mg/L and the pH value is 6.5, and this value was higher than that of uncoated filter, which was 70.28%.There was a 2μm TiO2 film on the surface of the red mud ceramic filter which was heated at 550℃. The removal rate of As(v) by TiO2 modified filter was 95.96%, when 2g TiO2 modified filter absorbing in a solution of 2mg/L As (v)at pH=2 for 240min.
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