Preparation and photocatalytic properties of nano TiO2/carbonized plant fiber composites
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摘要: 以碳化植物纤维(CPF)为载体，将纳米TiO2附着于纤维表面，通过浸渍煅烧法和溶剂热法合成纳米TiO2/CPF复合光催化剂，并对其光催化性能进行了研究。通过SEM、HRTEM、XRD、EDS分析了纳米TiO2/CPF复合光催化剂的微观结构和化学组成；以光催化降解亚甲基蓝为模型反应，考察复合材料中不同纤维种类和TiO2负载量对光催化活性的影响。结果表明，在一定范围内随TiO2负载量的增加，纳米TiO2/CPF复合材料光催化性能先增强后减弱。纳米TiO2/CPF复合材料的光催化性能明显提高是由于在TiO2和碳纤维界面的良好电荷分离能力。降解染料的活性物种有超氧负离子和羟基自由基，但羟基自由基是主要物种。此外，浸渍煅烧法和溶剂热法生成的纳米TiO2在纤维表面的存在形式不同，浸渍煅烧法生成纳米TiO2薄膜，包裹纤维；而溶剂热法生成的TiO2结晶成纳米颗粒，附着于纤维表面。Abstract: The nano TiO2/carbonized plant fiber (CPF) composite photocatalysts were synthesized by impregnation-calcination and solvothermal methods, anchored with the nano TiO2 photocatalyst on the surface of carbon fiber, and the photocatalytic properties of the nano TiO2/CPF composite photocatalysts were studied by photocatalytic degradation of methylene blue. The microstructure and chemical compositions of the nano TiO2/CPF composite photocatalysts were characterized by SEM, HRTEM, XRD and EDS, and the effects of fiber and loading of TiO2 on the photocatalytic activity were studied via degradation of methylene blue. The results show that photocatalytic performance of nano TiO2/CPF composite photocatalysts enhances first and then decreases with the increase of the loading of TiO2 in a certain range. The improved photocatalytic activity of nano TiO2/CPF composite photocatalysts can be attributed to the synergistic effect of CPF and TiO2, and the excellent separation efficiency of charged carriers at the interface of TiO2 and CPF. The key active species in the reaction are superoxide anions and hydroxyl radical, and the latter is the main species. TiO2 formed by the impregnation-calcination and the solvothermal exhibits different forms on the surface of the fiber, corresponding to film enclosed the fiber, and crystalline nanoparticles attached on the surface of the fiber, respectively.
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图 1 CPF和溶剂热法制备的纳米TiO2/CPF复合光催化剂的SEM图像
Figure 1. SEM images of CPF and nano TiO2/CPF composite photocatalysts prepared by solvothermal method ((a) CBF; (b) CCF; (c) CTF; (d) TiO2/CBF; (e) TiO2/CCF; (f) TiO2/CTF)
图 2 浸渍煅烧法制备的纳米TiO2/碳化楠竹纤维(CBF)复合光催化剂断面形貌的SEM图像
Figure 2. SEM images of section morphology of nano TiO2/carbonized bamboo fiber(CBF) composite photocatalysts prepared by impregnation-calcination method ((a) B1-TiO2/CBF; (b) C1-TiO2/CBF)
图 3 不同方法制备的纳米TiO2/CBF复合光催化剂的XRD图谱
Figure 3. XRD patterns of nano TiO2/CBF composite photocatalysts prepared by different methods
图 4 溶剂热法制备的不同TiO2与碳化纺织纤维(CTF)质量比的TiO2/CTF复合光催化剂的SEM图像
Figure 4. SEM images of nano TiO2/carbonized textile fiber(CTF) composite photocatalysts prepared by solvothermal method with different mass ratios of TiO2 to CTF ((a) B2-TiO2/CTF; (b) C2-TiO2/CTF; (c) D2-TiO2/CTF)
图 5 不同方法制备的纳米TiO2/CTF复合光催化剂的SEM图像
Figure 5. SEM images of nano TiO2/CTF composite photocatalysts prepared by different methods ((a) C1-TiO2/CTF ; (b) C2-TiO2/CTF)
图 6 不同方法制备的纳米TiO2/CTF复合光催化剂的HRTEM图像
Figure 6. HRTEM images of TiO2/CTF composite photocatalysts prepared by different methods ((a)–(c) Solvothermal; (d)–(f) Impregnation-calcination)
图 7 不同方法制备的纳米TiO2/CTF复合光催化剂的EDS图谱
Figure 7. EDS spectrum of TiO2/CTF composite photocatalysts prepared by different methods ((a)Impregnation-calcination; (b) Solvothermal)
图 8 CBF、碳化棉纤维(CCF)和CTF的拉曼图谱(a)及TiO2和不同TiO2与CTF质量比的纳米TiO2/CTF复合光催化剂的XRD图谱(b)
Figure 8. Raman spectra (a) of CBF, carbonized cotton fiber (CCF) and CTF and XRD patterns (b) of TiO2 and nano TiO2/CTF composite photocatalysts with different mass ratios of TiO2 to CTF (TiO2 nanoparticles prepared by sol-gel method, the dotted line is the standard card peak of anatase TiO2)
图 9 不同方法制备的纳米TiO2/CPF复合光催化剂(a) 及CTF、TiO2和不同TiO2与CTF质量比的纳米TiO2/CTF复合光催化剂光催化降解亚甲基蓝活性(b)
Figure 9. Photocatalytic degradation activity of methylene blue of nano TiO2/CPF composite photocatalysts prepared by different methods (a) and CTF, TiO2 and nano TiO2/CTF composite photocatalysts with different mass ratio of TiO2 to CTF(b)
图 10 C2-TiO2/CTF复合光催化剂降解亚甲基蓝的紫外光吸收曲线
Figure 10. UV absorption curves of photodegradation of methylene blue by C2-TiO2/CTF composite photocatalysts
图 11 超氧自由基在乙醇中捕获和羟基自由基在水中捕获的实验
Figure 11. Experiments of superoxide radical captured in ethanol and hydroxyl radical captured in water
图 12 TiO2和C2-TiO2/CTF复合光催化剂的荧光光谱
Figure 12. Photoluminescence spectra of TiO2 and C2-TiO2/CTF composite photocatalysts
图 13 C2-TiO2/CTF复合光催化剂降解亚甲基蓝的循环实验
Figure 13. Cycle experiments of C2-TiO2/CTF composite photocatalysts used for photocatalytic degradation of methylene blue
表 1 两种不同方法制备纳米TiO2/碳化植物纤维(CPF)复合光催化剂的名称
Table 1. Designations of nano TiO2/carbonized plant fiber(CPF) composite photocatalysts synthesized by two different methods
Method Mass ratio of TiO2 to CPF 2.5% 5% 10% 20% Impregnation-calcination A1-TiO2/CPF B1-TiO2/CPF C1-TiO2/CPF D1-TiO2/CPF Solvothermal A2-TiO2/CPF B2-TiO2/CPF C2-TiO2/CPF D2-TiO2/CPF Notes: CPF represents CBF, CCF and CTF, respectively; CBF—Carbonized bamboo fiber; CCF—Carbonized cotton fiber; CTF—Carbonized textile fiber. 
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