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高粱秸秆负载HKUST-1对四环素的吸附行为与机制

谭浩 张文彬 卢文玉 祁志强 蔡红珍 杨科研

谭浩, 张文彬, 卢文玉, 等. 高粱秸秆负载HKUST-1对四环素的吸附行为与机制[J]. 复合材料学报, 2024, 42(0): 1-13.
引用本文: 谭浩, 张文彬, 卢文玉, 等. 高粱秸秆负载HKUST-1对四环素的吸附行为与机制[J]. 复合材料学报, 2024, 42(0): 1-13.
TAN Hao, ZHANG Wenbin, LU Wenyu, et al. Adsorption behaviour and mechanism of tetracycline by sorghum straw-loaded HKUST-1[J]. Acta Materiae Compositae Sinica.
Citation: TAN Hao, ZHANG Wenbin, LU Wenyu, et al. Adsorption behaviour and mechanism of tetracycline by sorghum straw-loaded HKUST-1[J]. Acta Materiae Compositae Sinica.

高粱秸秆负载HKUST-1对四环素的吸附行为与机制

基金项目: 山东省重点研发项目(2021SFGC0201,2021SFGC0203)
详细信息
    通讯作者:

    蔡红珍,二级教授,博导,研究方向为生物基材料 E-mail: chzh@sdut.edu.cn

    杨科研,博士,讲师,硕士生导师,研究方向为生物基材料 E-mail: ykysdut@163.com

  • 中图分类号: TQ424; TB332

Adsorption behaviour and mechanism of tetracycline by sorghum straw-loaded HKUST-1

Funds: Key R&D Projects of Shandong Province (2021SFGC0201, 2021SFGC0203)
  • 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。

     

  • 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
    kinetic
    Pseudo-second-order
    kinetic
    k1/
    min−1
    qe,cal /
    mg·g−1
    R2k2/
    (g·mg−1·min−1)
    qe,cal/
    mg·g −1
    R2
    95.440.00265.060.9470.0101.870.994
    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
    下载: 导出CSV

    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.
    下载: 导出CSV

    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.
    下载: 导出CSV
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  • 收稿日期:  2024-03-15
  • 修回日期:  2024-04-11
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