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磁性氮掺杂石墨烯改性柿单宁复合材料对四环素的吸附行为

刘松林 王仲民 钱熹 王童 冉兆晋 黄志民 吴晨曦 李桂银

刘松林, 王仲民, 钱熹, 等. 磁性氮掺杂石墨烯改性柿单宁复合材料对四环素的吸附行为[J]. 复合材料学报, 2023, 40(7): 4048-4059. doi: 10.13801/j.cnki.fhclxb.20221021.001
引用本文: 刘松林, 王仲民, 钱熹, 等. 磁性氮掺杂石墨烯改性柿单宁复合材料对四环素的吸附行为[J]. 复合材料学报, 2023, 40(7): 4048-4059. doi: 10.13801/j.cnki.fhclxb.20221021.001
LIU Songlin, WANG Zhongmin, QIAN Xi, et al. Adsorption behaviors of magnetic nitrogen-doped graphene-modified persimmon tannins for tetracycline[J]. Acta Materiae Compositae Sinica, 2023, 40(7): 4048-4059. doi: 10.13801/j.cnki.fhclxb.20221021.001
Citation: LIU Songlin, WANG Zhongmin, QIAN Xi, et al. Adsorption behaviors of magnetic nitrogen-doped graphene-modified persimmon tannins for tetracycline[J]. Acta Materiae Compositae Sinica, 2023, 40(7): 4048-4059. doi: 10.13801/j.cnki.fhclxb.20221021.001

磁性氮掺杂石墨烯改性柿单宁复合材料对四环素的吸附行为

doi: 10.13801/j.cnki.fhclxb.20221021.001
基金项目: 国家自然科学基金(51961010);广西农业资源化学与生物技术重点实验室开放基金(2020KF07;2020KF05);广西重点研发项目(GuikeAB18281013;GuikeAB16380278)
详细信息
    通讯作者:

    王仲民,博士,教授,博士生导师,研究方向为生物质功能材料、氢能源材料 E-mail: zmwang@guet.edu.cn

    李桂银,博士,教授,博士生导师,研究方向为生物质功能材料 E-mail: liguiyin01@163.com

  • 中图分类号: X703;TB332

Adsorption behaviors of magnetic nitrogen-doped graphene-modified persimmon tannins for tetracycline

Funds: National Natural Science Foundation of China (51961010); Open Fund of Guangxi Key Laboratory of Agricultural Resources Chemistry and Biotechnology (2020KF07; 2020KF05); Guangxi Key Research and Development Program (GuikeAB18281013; GuikeAB16380278)
  • 摘要: 四环素(TC)作为广谱类抗生素药物被大量应用于养殖业,因其不易自然降解的特性,造成了严重的水污染。本文以柿单宁(PT)为基体,通过氮掺杂石墨烯(NG)对其改性,并以Fe3O4作为磁性功能,采用水热法制得磁性复合材料Fe3O4-NG/PT。并针对此复合材料在吸附TC方面的应用进行研究。NG以其疏水性和比表面积大的优势,弥补了PT在吸附上的不足,Fe3O4解决了吸附剂难以回收的问题。通过SEM、EDS、FTIR、XPS、BET、XRD等表明其机制主要是静电作用、孔填充、氢键作用和π-π相互作用;通过XRD与磁强计表明Fe3O4的成功引入及其高效回收性能。并对吸附条件优化,在Fe3O4∶PT质量比4∶1、pH为7、180 min、投加量为0.6 g/L时,吸附效果最佳。吸附动力学符合拟二级动力学模型,化学吸附为主;吸附等温符合Freundlich模型,表明其为多层吸附。318 K时吸附的最大容量达到315.65 mg/g,吸附效率达到94.5%。Fe3O4-NG/PT复合材料因其较大比表面积、多孔、回收方便、大量酚羟基结构的优点,在吸附领域有一定的应用前景。

     

  • 图  1  Fe3O4-氮掺杂石墨烯(NG)/柿单宁(PT)制备示意图

    Figure  1.  Schematic diagram of Fe3O4-nitrogen-doped graphene (NG)/persimmon tannin (PT) preparation

    图  2  Fe3O4-NG/PT吸附四环素(TC)初始条件优化:(a) Fe3O4∶PT质量比;(b) 吸附时间;(c) pH;(d) 吸附剂投放量

    Figure  2.  Optimization of the initial conditions for Fe3O4-NG/PT adsorption of tetracycline (TC): (a) Fe3O4∶PT mass ratios; (b) Adsorption time; (c) pH; (d) Adsorbent dosing

    图  3  ((a), (b)) NG/PT、Fe3O4-NG/PT的SEM图像;((c), (d)) Fe3O4-NG/PT吸附TC前后的SEM图像;((e), (i)) C元素吸附前后元素分布图;((f), (j)) O元素吸附前后元素分布图;((g), (k)) N元素吸附前后元素分布图;((h), (l)) Fe元素吸附前后元素分布图

    Figure  3.  ((a), (b)) SEM images of NG/PT and Fe3O4-NG/PT; ((c), (d)) SEM images of Fe3O4-NG/PT before and after TC adsorption; ((e), (i)) Elemental distribution before and after adsorption of element C; ((f), (j)) Elemental distribution before and after adsorption of element O; ((g), (k)) Elemental distribution before and after adsorption of element N; ((h), (l)) Elemental distribution before and after adsorption of element Fe

    图  4  (a) NG、PT、Fe3O4-NG/PT、Fe3O4-NG/PT吸附TC后的FTIR图谱;(b) Fe3O4-NG/PT和Fe3O4-NG/PT吸附TC后的XPS图谱;(c) C1s峰;(d) N1s峰;(e) O1s峰;(f) Fe2p峰

    Figure  4.  (a) FTIR spectra of NG, PT, Fe3O4-NG/PT and Fe3O4-NG/PT after TC adsorption; (b) XPS spectra of Fe3O4-NG/PT and Fe3O4-NG/PT after TC adsorption; (c) C1s peak; (d) N1s peak; (e) O1s peak; (f) Fe2p peak

    图  5  (a) Fe3O4-NG/PT和Fe3O4-NG/PT吸附TC后的孔径分布图;(b) N2吸脱附曲线

    Figure  5.  Pore size distribution diagram of Fe3O4-NG/PT and Fe3O4-NG/PT after TC adsorption; (b) Absorption and desorption curves of N2

    STP—Standard temperature and pressure

    图  6  (a) NG/PT、Fe3O4-NG/PT、Fe3O4-NG/PT吸附TC后的XRD图谱;(b) Fe3O4-NG/PT和Fe3O4-NG/PT吸附TC后的磁滞回归线

    Figure  6.  (a) XRD patterns of NG/PT, Fe3O4-NG/PT, Fe3O4-NG/PT after adsorbing TC; (b) Hysteresis regression line of Fe3O4-NG/PT and Fe3O4-NG/PT after TC adsorption

    图  7  Fe3O4-NG/PT吸附TC后的等温拟合:(a) 温度对吸附效果的影响;(b) Langmuir 拟合;(c) Freundlich 拟合;(d) Temkin拟合

    Figure  7.  Isothermal fitting of Fe3O4-NG/PT adsorption TC: (a) Influence of temperature on the adsorption effect; (b) Langmuir fitting; (c) Freundlich fitting; (d) Temkin fitting

    图  8  Fe3O4-NG/PT吸附TC的动力学拟合:(a) 不同TC浓度相同时间下对吸附量的影响;(b) Fe3O4-NG/PT吸附TC的拟一级动力学拟合图;(c) Fe3O4-NG/PT吸附TC的拟二级动力学拟合图;(d) Fe3O4-NG/PT吸附TC的内扩散拟合图

    Figure  8.  Kinetic fitting of TC adsorption by Fe3O4-NG/PT: (a) Effect of different TC concentrations for the same time on the amount of adsorption; (b) Proposed primary kinetic fitting plot of TC adsorption by Fe3O4-NG/PT; (c) Proposed secondary kinetic fitting plot of TC adsorption by Fe3O4-NG/PT; (d) Fitting of internal diffusion of TC adsorbed by Fe3O4-NG/PT

    qt—Adsorption capacity of time t

    图  9  Fe3O4-NG/PT吸附TC的吸附机制图

    Figure  9.  Adsorption mechanism diagram for TC adsorption by Fe3O4-NG/PT

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  • 收稿日期:  2022-07-18
  • 修回日期:  2022-09-04
  • 录用日期:  2022-09-24
  • 网络出版日期:  2022-10-24
  • 刊出日期:  2023-07-15

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