Preparation of ZIF-67/waste cotton cellulose composite aerogels and the removal performance on dyes
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摘要: 为高效去除污水中的有机染料，以废旧棉织物为纤维素原材料，碱/尿素为溶解体系，N, N'-亚甲基双丙烯酰胺(MBA)作为交联剂，通过冷冻干燥技术制备了废棉纤维素气凝胶(WCCA)，在其表面原位生成钴基沸石咪唑酯有机框架(ZIF-67)，制备了ZIF-67/WCCA，用于吸附孔雀石绿(MG)和催化过硫酸氢钾(PMS)降解亚甲基蓝(MB)。借助SEM和XRD对ZIF-67/WCCA的结构和成分进行表征，并探讨了影响其染料吸附和催化降解性能的条件。结果表明，具有菱形十二面体结构的ZIF-67负载于WCCA网络框架上；在室温下，对MG吸附量达到1474.01 mg·g−1；在100 s左右催化PMS对MB的降解率可达100%。ZIF-67/WCCA可应用于污水中染料吸附和催化降解。Abstract: In order to efficiently remove organic dyes from waste water, ZIF-67/waste cotton cellulose composite aerogels (ZIF-67/WCCA) were prepared by freeze drying technology using waste cotton fabrics as cellulose raw materials, alkali/urea as dissolution system, N, N’-Methylenediacrylamide (MBA) as cross-linking agent, and cobalt-based zeolite imidazolate metal-organic framework (ZIF-67) nanoparticles were grown in situ on the surface of WCCA. ZIF-67/WCCA were prepared and used to adsorb malachite green (MG) and degrade methylene blue (MB) with peroxymonosulfate (PMS) activation. The structure and composition of the ZIF-67/WCCA were characterized by scanning electron microscopy and X-ray diffraction. The conditions affecting the adsorption and degradation properties of the dyes were also discussed. The results show that ZIF-67 nanoparticles of dodecahedron are loaded on the network framework of cellulose aerogels from waste cotton. The adsorption capacity of MG can reach 1474.01 mg·g−1 at room temperature, and the degradation rate of MB at 100 s can reach 100% by using ZIF-67/WCCA. ZIF-67/WCCA can be applied in fields of dye adsorption and catalytic degradation in sewage.
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Key words:
- waste cotton /
- cellulose aerogel /
- ZIF-67 /
- dye /
- adsorption /
- catalytic degradation
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图 1 ZIF-67/废棉纤维素复合气凝胶(WCCA)的合成路线
MBA—N,N’-Methylenediacrylamide
Figure 1. Route for the synthesis of ZIF-67/waste cotton cellulose composite aerogels (WCCA)
图 2 WCCA实物照片 (a)、WCCA的SEM图像 ((b)~(d))、ZIF-67/WCCA实物照片 (e) 和ZIF-67/WCCA的SEM图像 ((f)~(i))
Figure 2. Digital photograph of WCCA (a), SEM images of WCCA ((b)-(d)), digital photograph of ZIF-67/WCCA (e) and SEM images of ZIF-67/WCCA ((f)-(i))
图 4 时间对WCCA和ZIF-67/WCCA吸附量的影响
Figure 4. Effect of time on adsorption capacity of WCCA and ZIF-67/WCCA
图 5 ZIF-67/WCCA的动力学拟合曲线：(a) 准一级动力学模型；(b) 准二级动力学模型
Figure 5. Fitted adsorption kinetic plots of ZIF-67/WCCA: (a) Pseudo-first-order kinetic model; (b) Pseudo-second-order kinetic model
qe—Adsorption capacity at adsorption equilibrium; qt—Adsorption capacity of aerogels to dyes after a certain adsorption time t
图 6 ZIF-67/WCCA吸附MG的等温线
Figure 6. Adsorption isotherms plots for MG of ZIF-67/WCCA
Ce—Concentration of adsorption equilibrium
图 7 pH值对ZIF-67/WCCA吸附MG量的影响
Figure 7. Effect of pH value on adsorption capacity of MG on ZIF-67/WCCA
图 8 WCCA及ZIF-67/WCCA对MB的去除效率的影响 (a) 和相对应的一阶动力学方程的拟合曲线 (b)
Figure 8. Effect of WCCA and ZIF-67/WCCA on MB removal efficiency (a) and fitting curves of the corresponding first-order kinetic equation (b)
图 9 过硫酸氢钾(PMS)浓度 (a) 和pH (b) 对ZIF-67/WCCA去除MB效率的影响
Figure 9. Effects of potassium bisulfate (PMS) concentration (a) and pH (b) on MB removal efficiency of ZIF-67/WCCA
图 10 (a) 自由基清除剂对MB降解速率的影响；(b) MB降解的三次循环实验
Figure 10. (a) Effect of radical scavengers on MB degradation；(b) Degradation of MB within the successive three cycles
图 11 ZIF-67/WCCA活化PMS产生自由基的机制图
MB—Methylene blue; PMS—Peroxymonosulfate
Figure 11. Mechanism of PMS to generate free radicals on ZIF-67/WCCA
表 1 ZIF-67/WCCA吸附亚甲基蓝(MG)的动力学参数
Table 1. Adsorption kinetic parameters of methylene blue (MG) on ZIF-67/WCCA
Pseudo-first-order Pseudo-second-order k1/min−1 R12 k2/(min·g·mg−1) R22 0.0229 0.983 0.0000678 0.991 Notes: k1—Pseudo-first-order adsorption rate constants; R12—
Correlation coefficient of pseudo-first-order kinetics model; k2—Pseudo-second-order adsorption rate constants; R22—
Correlation coefficient of pseudo-second-order kinetics model.
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表 2 ZIF-67/WCCA吸附MG的等温线模型参数
Table 2. Parameters of adsorption isotherms model for MG on ZIF-67/WCCA
Langumir Freundlich Ce/qe=1/qmKL+Ce/qm lnqe=(1/n)lnCe+lnKF qe exp/(mg·g−1) qm/(mg·g−1) KL RL2 KF RF2 1474.01 1498.35 3.209 0.999 492.8 0.876 Notes: qe exp—Equilibrium adsorption capacities of the dyes; qm exp—Maximum adsorption capacities of the dyes; KL—Langmuir equilibrium adsorption constants; KF—Freundlich equilibrium adsorption constants; RL2—Correlation coefficient of Langumir model; RF2—Correlation coefficient of Freundlich model.
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