Adsorption behaviour and mechanism of tetracycline by sorghum straw-loaded HKUST-1
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摘要: 四环素(TC)是一种难降解广谱抗生素，广泛存在于畜牧业排放的污废中，排放后会对水体生态环境造成严重的污染，通过吸附法可有效去除。本研究以高粱秸秆(SS)为基材，通过原位生长法在SS表面负载MOFs(HKUST-1)制备SS@HKUST-1复合材料，用于对TC的吸附去除，探究复合材料对TC的吸附行为及吸附机制。研究表明：当pH=7、T=25°C、HKUST-1的负载量为31%时，吸附容量达到95 mg/g。吸附过程符合准二级动力学模型，吸附等温线符合Freundlich模型，表明复合材料对TC吸附属于多分子层化学吸附。因此，SS@HKUST-1对水中TC的去除具有良好的应用前景。Abstract: Tetracycline (TC) is a refractory broad-spectrum antibiotic, that is widely present in the waste discharged from animal husbandry, which will cause serious pollution to the ecological environment of water bodies after discharge, and it can be effectively removed by adsorption. In this work, sorghum straw (SS) was used as the substrate to prepare SS@HKUST-1 composites by in-situ growth of MOFs (HKUST-1) on the surface of SS for the adsorption and removal of TC, investigating the adsorption behaviour and adsorption mechanism of composites on TC. The results showed that the adsorption capacity reached 95mg/g when pH=7, T=25℃ and the load capacity of HKUST-1 is 31%. The adsorption process conforms to the pseudo-second-order kinetic model, and the adsorption isotherm conforms to the Freundlich model, which suggested the existence of multimolecular layer chemisorption between TC and adsorbent. Therefore, SS@HKUST-1 had a good application prospect for tetracycline removal in water.
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Key words:
- sorghum straw /
- HKUST-1 /
- In-situ growth /
- tetracycline /
- adsorption
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图 1 高粱秸秆(SS)@HKUST-1复合材料的制备流程示意图
Figure 1. Schematic for the preparation process of sorghum straw (SS)@HKUST-1 composite
图 2 (a) SS的SEM图像; (b) HKUST-1的SEM图像; (c) SS@HKUST-1的SEM图像; (d-f) SS@HKUST-1的EDS图像
Figure 2. (a) SEM image of SS; (b) SEM image of HKUST-1; (c) SEM image of SS@HKUST-1; (d-f) EDS image of SS@HKUST-1
图 3 (a) SS、HKUST-1和SS@HKUST-1的FT-IR图谱; (b) SS、HKUST-1和SS@HKUST-1的XRD图谱; SS@HKUST-1复合材料的XPS图谱：(c) Cu2p； (d) C1s； (e) O1s
Figure 3. (a) FT-IR of SS、HKUST-1 and SS@HKUST-1; (b) XRD patterns of SS、HKUST-1 and SS@HKUST-1; XPS of SS@HKUST-1 composite: (c) Cu2p； (d) C1s； (e) O1s
图 4 SS、HKUST-1和SS@HKUST-1的热重图
Figure 4. Thermogravimetric spectra of SS、HKUST-1 and SS@HKUST-1
图 5 SS、HKUST-1、SS@HKUST-1的N2吸附脱附等温线和孔径分布
Figure 5. N2 adsorption-desorption isotherm and pore size distribution of SS, HKUST-1 and SS@HKUST-1
图 6 (a) 不同Cu(NO3)2质量对TC吸附的影响; (b) SS与HKUST-1对TC的吸附效果 (c) 吸附剂用量对SS@HKUST-1 TC吸附的影响; (d) 不同溶液pH值对SS@HKUST-1 TC吸附的影响； (e) 不同pH值下SS@HKUST-1的Zeta电位
Figure 6. (a) Effects of different Cu(NO3)2 monomer rations on TC adsorption; (b) Adsorption effects of SS and HKUST-1 on TC (c) Effects of adsorbent dosages on TC adsorption by SS@HKUST-1 composites; (d) Effects of different pH values on TC adsorption by SS@HKUST-1 composites; (e) Zeta potential of SS@HKUST-1 under different pH values
qe—Equilibrium adsorption capacity
图 7 (a) 吸附时间对SS@HKUST-1去除TC效率的影响；(b)准一级动力学模拟；(c)准二级动力学模拟；
Figure 7. (a) Influence of adsorption time on the removal efficiency of TC by SS@HKUST-1; (b) Pseudo first-order; (c) Pseudo second-order;
qt—Adsorption capacity at t time; t—Adsorption time
图 8 (a) TC在SS@HKUST-1表面的吸附等温线; (b) Langmuir吸附等温线; (c) Freundlich吸附等温线; (d) 不同温度处理SS@HKUST-1对吸附TC的影响
Figure 8. (a) Adsorption isotherms of TC onto the surfaces of SS@HKUST-1; (b) Langmuir adsorption isotherm; (c) Freundlich adsorption isotherm; (d) Effect of different temperature treatment SS@HKUST-1 on adsorbed TC
Ce—concentration at adsorption equilibrium; T—Temperature
图 9 SS@HKUST-1循环次数对吸附TC的影响
Figure 9. Effect of SS@HKUST-1 recycling times on TC adsorption
图 10 共存离子对SS@HKUST-1吸附四环素的影响
Figure 10. The effect of coexisting ions on the adsorption of TC by SS@HKUST-1
图 11 (a) SS@HKUST-1吸附TC前后的FT-IR差谱图; (b) SS@HKUST-1吸附TC前后XPS图谱； (c) TC的吸附机制示意图
Figure 11. (a) Infrared difference spectra of SS@HKUST-1 before and after adsorption of TC; (b) XPS of SS@HKUST-1 before and after adsorption of TC; (c) Schematic diagram of adsorption mechanism of TC
表 1 SS@HKUST-1吸附TC的动力学模型拟合参数
Table 1. parameters of kinetic model fitting for SS@HKUST-1 adsorbed TC
qe,exp/
(mg·g−1)Pseudo-first-order
kineticPseudo-second-order
kinetick1/
min−1qe,cal /
mg·g−1R2 k2/
(g·mg−1·min−1)qe,cal/
mg·g −1R2 95.44 0.002 65.06 0.947 0.010 1.87 0.994 Notes: qe,exp—The actual adsorption capacity at adsorption equilibrium; qe,cal—The calculated adsorption capacity at adsorption equilibrium; k1—Pseudo-first-order adsorption rate constant; k2—Pseudo-second-order adsorption rate constant; R2—The Correlation coefficient of Langmuir and Freundlich models 
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表 2 SS@HKUST-1的吸附等温线的拟合参数
Table 2. Fitting parameters to SS@HKUST-1 adsorption isotherms
Temperature/°C Langmuir model Freundlich model $ {q}_{\mathrm{m}} $/
(mg·g−1)b/
(L·mg−1)R2 $ {K}_{\mathrm{f}} $/
(mg·g−1)1/n R2 25 119.10 0.686 0.901 3.88 0.7291 0.989 35 120.00 0.335 0.987 4.69 0.7302 0.991 45 194.97 0.220 0.926 10.03 0.6453 0.997 Notes: qm—Maximum adsorption capacity; b—$ \dfrac{1}{{q}_{\mathrm{m}}{k}_{\mathrm{L}}} $, kL—Adsorption coefficient of Langmuir; Kf—Adsorption coefficient of Freundlich; 1/n—Empirical parameter varied with the degree of heterogeneity of adsorbing sites.
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表 3 不同吸附剂对TC的吸附去除效果对比
Table 3. Comparison of adsorption and removal effects of different adsorbents for TC
Sample qe(mg·g−1) Reference SS@HKUST-1 95 This work ZIF-8/CMC 78.75 37 CS biochar 53.191 38 WS biochar 66.67 38 MIL-100(Fe)/PEO 85.02 39 Fe3O4@RGO@C18 77.56 40 AG(Mn)-88 B-C 53.07 41 Notes: ZIF-8/CMC—The metal-organic skeleton hybrid foam ZIF-8/CMC with cellulose; CS biochar—Corn straw biochar; WS biochar—Wheat straw biochar; MIL-100(Fe)/PEO—Polyethylene oxide modified MIL-100(Fe); Fe3O4@RGO@C18—Fe3O4 magnetic particles were coated with a layer of RGO (graphene),and C18 was further modified on the surface of Fe3O4@RGO material; AG(Mn)-88 B-C—MIL-88 B(Fe)/sodium alginate composite aerogel.
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