Design and preparation of TiO2-based environmentally stable photocatalytic self-cleaning coatings
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摘要: 将光催化活性与超疏水性相结合，一方面，涂层利用表面超疏水作用能够将污染物通过水珠带走；另一方面，光催化作用能够对有机污染物进行降解，同时维持材料的超疏水特性。通过洞渣制石英砂(Quartz Sand)协同TiO2构筑微纳米粗糙结构，以聚甲基氢硅氧烷(PMHS)和钛酸四丁酯(TBT)作为低表面能物质，制备了坚固耐磨的PMHS/TBT-Quartz Sand-TiO2光催化自清洁成膜涂层。结果表明，涂层接触角为 154.4°，滚动角小于 10°。TiO2有效地负载到石英砂表面，构造了优异的微纳米粗糙结构。涂层具有优良的光催化活性，可降解表面有机物小分子去除空气中的氮氧化物。此外，涂层在经过连续摩擦损伤、长期紫外暴露、冻融循环等不同的破坏形式后，仍能保持环境稳定性。Abstract: Combining photocatalytic activity with superhydrophobicity, on the one hand, the surface superhydrophobicity can be utilized to carry away pollutants through water droplets, and on the other hand, photocatalysis can degrade organic pollutants and maintain the superhydrophobicity of the materials. A robust and wear-resistant PMHS/TBT-Quartz Sand-TiO2 photocatalytic self-cleaning film-forming coating was prepared by constructing a micro- and nano-scrubber structure with Quartz Sand made from cave slag in synergy with TiO2, and using poly(methylhydrosiloxane) (PMHS) and tetrabutyl titanate (TBT) as the low-surface-energy substances. The results show that the contact angle of the coating is 154.4°, and the rolling angle is less than 10°. TiO2 is effectively loaded onto the surface of quartz sand, and an excellent micro and nano rough structure is constructed. The coating has excellent photocatalytic activity, which can degrade small organic molecules on the surface to remove nitrogen oxides in the air. In addition, the coating remains environmentally stable after continuous friction damage, long-term UV exposure, freeze-thaw cycles and other forms of damage.
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Key words:
- superhydrophobic /
- photocatalysis /
- micro-nano rough structure /
- self-cleaning /
- composite coating
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图 1 光催化自清洁涂层的制备流程
Figure 1. Preparation process for the photocatalytic self-cleaning coating
图 2 聚甲基氢硅氧烷(PMHS)/钛酸四丁酯(TBT)-Quartz Sand-TiO2涂层的SEM照片以及AFM粗糙度分析
Figure 2. The SEM photos of the poly(methylhydrosiloxane) (PMHS)/tetrabutyl titanate (TBT)-Quartz Sand-TiO2 coating as well as the AFM roughness analysis
图 3 TiO2疏水化改性前后的红外光谱图
Figure 3. Infrared spectra of TiO2 before and after hydrophobic modification
图 4 PMHS/TBT-Quartz Sand-TiO2涂层的X射线光电子能谱
Figure 4. The X-ray photoelectron energy spectrum of the PMHS/TBT-Quartz Sand-TiO2 coating
图 5 PMHS/TBT-Quartz Sand-TiO2涂层的热重分析
Figure 5. A thermogravimetric analysis of the PMHS/TBT-Quartz Sand-TiO2 coating
图 6 PMHS/TBT-Quartz Sand-TiO2涂层表面的超疏水性能
Figure 6. Superhydrophobic properties of the PMHS/TBT-Quartz Sand-TiO2 coating surface
图 7 PMHS/TBT-Quartz Sand-TiO2涂层的耐油酸降解性能
Figure 7. The oleic acid-resistant degradation properties of the PMHS/TBT-Quartz Sand-TiO2 coating
图 8 在光降解试验的9 h过程中，通过照片表征MB脱色的变化情况
(插图为色度计对中间位置颜色的测量结果)
Figure 8. Changes in MB decolorization during the 9 h course of the photodegradation test, characterized by photographs
(The inset shows the results of colorimeter measurement of the color at the middle position)
图 9 PMHS/TBT-Quartz Sand-TiO2涂层的光催化降解MB性能
Figure 9. Photocatalytic degradation of the MB properties of the PMHS/TBT-Quartz Sand-TiO2 coating
图 10 PMHS/TBT-Quartz Sand-TiO2涂层的光催化降解氮氧化合物性能
Figure 10. Photocatalytic degradation performance of PMHS/TBT-Quartz Sand-TiO2 coatings for nitrogen oxides
图 11 每个磨损循环后的接触角滚动角变化，插图为第 10 次磨损后染色水滴在PMHS/TBT-Quartz Sand-TiO2涂层上的光学图片
Figure 11. Contact angle rolling angle change after each wear cycle, and the inset is the optical picture of the stained water droplets on the PMHS/TBT-Quartz Sand-TiO2 coating after the 10 th wear
图 12 PMHS/TBT-Quartz Sand-TiO2涂层的耐紫外老化性能
Figure 12. The UV-aging resistance of the PMHS/TBT-Quartz Sand-TiO2 coating
图 13 PMHS/TBT-Quartz Sand-TiO2涂层的抗硫酸盐侵蚀能力测试
Figure 13. Sulfate attack resistance test of PMHS/TBT-Quartz Sand-TiO2 coatings
图 14 PMHS/TBT-Quartz Sand-TiO2涂层的抗冻融侵蚀能力测试
Figure 14. Sulfate attack resistance test of PMHS/TBT-Quartz Sand-TiO2 coatings
图 15 PMHS/TBT- Quartz sand-TiO2光催化协同超疏水涂层模型
Figure 15. Model of PMHS/TBT- Quartz sand-TiO2 photocatalytic synergistic superhydrophobic coating
表 1 砂浆配合比
Table 1. Mortar mix ratio
/(kg·m−3) Water cement ratio Cement Sand Water 0.46 450 1350 225 
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