Preparation and photocatalytic properties TiO2/graphene nanocomposites with sandwich structure
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摘要: 以氧化石墨烯(GO)、1, 12-二氨基十二烷(C12H28N2)、TiO2溶胶为原料，通过预插层-离子交换-煅烧法制备TiO2/石墨烯夹层结构纳米复合材料。采用XRD、Raman、FTIR、TEM、TG、UV-Vis和PL对TiO2/石墨烯夹层结构纳米复合材料进行表征，并研究不同TiO2含量的TiO2/石墨烯纳米复合材料对环丙沙星(CIP)的光催化降解性能。在煅烧过程中，TiO2的晶化和GO的还原同时进行。根据XRD和FTIR结果推断，TiO2纳米颗粒在石墨烯层间原位生成，并通过化学键固定在石墨烯上，形成了石墨烯/TiO2/石墨烯夹层结构。当TiO2的质量分数为65.5wt%时，TiO2/石墨烯复合材料表现出对环丙沙星最佳的光催化活性，150 min光照后降解率为90%高于纯TiO2(28%、150 min)。这主要是特殊的夹层结构增强了光生电子-空穴分离。在光催化降解CIP的过程中，光生空穴和超氧自由基是主要的活性物质。此外，TiO2/石墨烯纳米复合材料具有较好的光稳定性和结构稳定性，在环境净化方面具有潜在的应用前景。Abstract: TiO2/graphene nanocomposites were synthesized from graphene oxide (GO), C12H28N2 and TiO2 sol by three-step method as follows: Dodecanediamine pre-intercalating, ion exchange, and interlayer in-situ formation of TiO2 by calcined. The properties and structures of TiO2/graphene nanocomposites with sandwich structure were characterized by XRD, Raman, FTIR, TEM, TG, UV-Vis and PL. The photocatalytic degradation performance of TiO2/graphene composites prepared with different amounts of TiO2 were investigated. The crystallization of TiO2 and the reduction of GO were significantly increased simultaneously during calcination. According to XRD and FTIR results, TiO2 nanoparticles have formed in situ between the interlayer of graphene and anchored on graphene with chemically-bonded. Therefore, it can be concluded that the TiO2/graphene nanocomposites with sandwich structure are prepared successfully. TiO2/graphene composites show the best photocatalytic degradation of ciprofloxacin (CIP) when the mass fraction of TiO2 is 65.5wt%, and the degradation rate reaches 90% after 150 min under visible light irradiation, which is higher than pure TiO2 nanoparticles (28%, 150 min). It can be mainly attributed to the special sandwich structure with enhanced photoinduced electron-hole separation. The photocatalyst stability test shows that TiO2/graphene nanocomposites possess high photostability and structure stability for potential practical applications in environmental purification.
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Key words:
- TiO2 /
- graphene /
- sandwich structure /
- composites /
- photocatalysis
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图 1 空气气氛中不同TiO2含量的TiO2/石墨烯纳米复合材料的TGA曲线
Figure 1. TGA curves in air of the TiO2/graphene nanocomposites with different TiO2 mass fractions
图 2 XRD图谱：(a) 氧化石墨烯(GO)、GO/dodecanediamine和GO/TiO2前驱体局部放大图[14]；(b) 不同TiO2含量TiO2/石墨烯复合材料
Figure 2. XRD patterns: (a) Partial enlarged drawing of graphene oxide (GO), dodecanediamine/GO and TiO2/GO precursor; (b) TiO2/graphene nanocomposites with different TiO2 contents
图 3 TiO2和TiO2/石墨烯纳米复合材料的拉曼光谱
Figure 3. Raman spectra of pure TiO2 and TiO2/graphene nanocomposites
图 4 GO、还原氧化石墨烯(rGO)、TiO2/石墨烯纳米复合材料和TiO2的FTIR图谱
Figure 4. FTIR spectra of GO, reduced graphene oxide (rGO), TiO2/graphene nanocomposites and pure TiO2
图 5 GO (a) 和TiO2/rGO(65.5wt%) (b) 的TEM图像((b)中插图为TiO2/rGO(65.5wt%)的HRTEM图像)
Figure 5. TEM images of GO (a) and TiO2/rGO(65.5wt%) (b) (Inset in (b) shows HRTEM image of TiO2/rGO(65.5wt%))
图 6 不同光催化剂对环丙沙星(CIP)的吸附
Figure 6. Adsorption of ciprofloxacin (CIP) at presence of different photocatalysts
图 7 不同催化剂光催化降解CIP曲线
Figure 7. Photocatalytic degradation rates of CIP at presence of different photocatalysts
图 8 TiO2/rGO(65.5wt%)光催化降解CIP的循环实验(每个循环照射时间150 min)
Figure 8. Photocatalytic degradation rates of CIP after repeated cycles by TiO2/rGO(65.5wt%) (Irradiation time lasted 150 min of each cycle)
图 9 TiO2和TiO2/rGO(65.5wt%)的PL曲线(激发波长380 nm)
Figure 9. PL curves of pure TiO2 and TiO2/rGO(65.5wt%) (Excitation: 380 nm)
图 10 牺牲剂对TiO2/rGO (65.5wt%)降解CIP的影响
Figure 10. Photocatalytic degradation rates of CIP for TiO2/rGO (65.5wt%) at presence of different scavengers
TEOA—Triethanolamine; BQ—Benzoquinone; IPA—Isopropanol
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