Preparation of titanium dioxide/ZIF-8 composite superhydrophobic sponge and its oil-water separation performance
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摘要: 含油废水的处理海上溢油问题及含油废水的排放对经济与环境带来了巨大的破坏。利用聚多巴胺将自制的双尺度ZIF-8/TiO2纳米粒子黏附到聚氨酯海绵，通过十八胺改性制备出超疏水油水分离海绵，通过FTIR、XRD等对其结构进行了表征分析；利用ZIF-8和TiO2两种纳米粒子构建双尺度粗糙结构，并深入探究了两种粒子的用量对复合涂层表面性能的影响。结果表明当纳米粒子ZIF-8和TiO2添加摩尔比为2∶1时，接触角达到最大值153°；复合海绵有良好的油水分离性能，吸收能力是其自重的40至118倍，分离效率平均在96%以上；在808 nm激光照射下10 s内温度可升高55.9℃，有良好的光热转换性能。Abstract: Treatment of oily wastewater problem of oil spills at sea and the discharge of oily wastewater have brought huge damage to the economy and the environment. This paper used polydopamine to adhere the self-made dual-scale ZIF-8/TiO2 nanoparticles to the polyurethane sponge, and prepared the superhydrophobic oil-water separation sponge by modification with octadecylamine. The structure was characterized and analyzed by FTIR, XRD, etc.. ZIF-8 and TiO2 two kinds of nano-particles constructed a two-scale rough structure, and the influence of the amount of the two kinds of particles on the surface performance of the composite coating was deeply explored. The results show that when the molar ratio of ZIF-8 and TiO2 nanoparticles is 2∶1, the contact angle reaches the maximum value of 153°.The composite sponge has good oil-water separation performance, the absorption capacity is 40 to 118 times its own weight, and the separation efficiency is on average more than 96%. The temperature can rise by 55℃ within 10 s under 808 nm laser irradiation, and it has good light-to-heat conversion performance.
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Key words:
- superhydrophobic /
- ZIF-8 /
- titanium dioxide /
- oil-water separation /
- polyurethane sponge
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图 1 TiO2/ZIF-8复合超疏水海绵制备
Figure 1. Preparation of TiO2/ZIF-8 composite superhydrophobic sponge
MOF—Metal-organic frameworks
图 2 (a) 不同温度的下TiO2的颜色变化照片；(b) 不同温度下的紫外-吸收图；(c) 不同时间下400℃烧结的TiO2的紫外-吸收图
Figure 2. (a) Optical photos of titanium dioxide fired at different temperatures; (b) Ultraviolet absorption curves of titanium dioxide fired at different temperatures; (c) Ultraviolet absorption curves of titanium dioxide fired at 400℃ at different time
图 4 TiO2 (a) 和ZIF-8 (b) 的XRD图谱
Figure 4. XRD patterns of TiO2 (a) and ZIF-8 (b)
W-TiO2—White-TiO2; B-TiO2—Black-TiO2
图 5 海绵水接触角随ZIF-8 (a)、十八胺(ODA) ((b)、(d)) 和TiO2 (c) 含量的变化
Figure 5. Change of sponge contact angles with ZIF-8 (a) and ODA content ((b), (d)) and TiO2 (c) content
图 6 海绵水接触角随TiO2和ZIF-8摩尔比的变化
Figure 6. Contact angle of the sponge changes with the TiO2 and ZIF-8 molar ratio
图 7 TiO2粒子 (a)、ZIF-8 粒子 (b)、未处理海绵 (c) 和双尺度海绵 (d) 的SEM图像
Figure 7. SEM images of TiO2 nanoparticles (a), ZIF-8 nanoparticles (b), untreated sponge (c) and two-scale sponge (d)
图 9 ((a)、(b)) TiO2/ZIF-8复合海绵的吸油过程；(c) 不同种类油的吸收容量；(d) 不同种类油的分离图；(e) 油水分离过程
Figure 9. ((a), (b)) Adsorption process of different oily substances in TiO2/ZIF-8 compound sponge; (c) Absorption capacity of different kinds of oil; (d) Separation efficiency of different types of oil; (e) Oil-water separation process
图 10 ((a)~(c)) 不同pH值下的TiO2/ZIF-8复合海绵超疏水效果；((d)~(f)) 疏水亲油现象的光学照片；(g) 摩擦100次后的SEM图像；(h) 吸油/回收循环图
Figure 10. ((a)-(c)) Superhydrophobic phenomenon under different pH of TiO2/ZIF-8 compound sponge; ((d)-(f)) Optical photographs of super-hydrophobic and super-lipophilic phenomena of composite sponge; (g) SEM image after 100 times of friction; (h) Diagram of the oil absorption/recovery cycle
图 11 吸油前后TiO2/ZIF-8复合海绵的光热曲线
Figure 11. Photothermal curves of TiO2/ZIF-8 compound sponge before and after absorpting oil
表 1 不同照射时间TiO2/ZIF-8复合海绵的温度
Table 1. Temperature of TiO2/ZIF-8 compound sponge before and after absorpting oil irradiating 10 s and 10 min
Sample Pure polyurethane sponge Super hydrophobic sponge
before oil absorptionSuper hydrophobic sponge
after oil absorptionTemperature (10 s)/℃ 20 75.9 58.1 Temperature (10 min)/℃ 25.9 90.3 68.3 
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