Adsorption behaviors of magnetic nitrogen-doped graphene-modified persimmon tannins for tetracycline
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摘要:
磁性氮掺杂石墨烯改性柿单宁材料对四环素的吸附行为研究柿单宁材料以其比表面积大、表面官能团丰富、成本低廉、环保等优点，在吸附领域吸引了越来越多的研究。但由于其具有亲水性，导致其在吸附过程的分离较差，回收困难，阻碍了其吸附领域的应用。以柿单宁(PT)为基体，通过氮掺杂石墨烯(NG)对其改性，并以四氧化三铁(Fe3O4)作为磁性功能，采用水热法制得磁性复合材料(Fe3O4-NG/PT)。氮掺杂石墨烯以其疏水性和比表面积大的优势，弥补了柿单宁在吸附上的不足，四氧化三铁解决了吸附剂难以回收的问题。针对此复合材料在吸附四环素方面的应用进行研究，通过SEM、EDS、FTIR、XPS、BET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-NG/PT 的成功引入以及其高效回收性能。并对吸附条件优化，在Fe3O4:PT为4 :1，PH为7，投加量为0.6 g/L，吸附180min吸附效果最佳。研究其磁性复合材料对四环素的吸附过程符合拟二级动力学模型和Freundlich模型，其主要为化学吸附为主的多层吸附，308K时吸附的饱和容量达到315.65 mg/g，吸附效率达到94.5%。 (A)NG、PT、Fe3O4-NG/PT以及Fe3O4-NG/PT吸附TC之后的红外图谱(B)Fe3O4-NG/PT和Fe3O4-NG/PT吸附TC之后的XPS图谱(C)C1s峰(D)N1s峰(E)O1s峰(F)Fe2p峰(A) FTIR profiles of NG, PT, Fe3O4-NG/PT and Fe3O4-NG/PT after TC adsorption (B) XPS profiles of Fe3O4-NG/PT and Fe3O4-NG/PT after TC adsorption (C) C1s peak (D) N1s peak (E) O1s peak (F) Fe2p -
关键词:
- 柿单宁(PT) /
- 氮掺杂石墨烯(NG) /
- 吸附 /
- 四环素(TC) /
- 吸附模型
Abstract: Tetracycline, as a broad-spectrum class of antibiotics, is used in large quantities in the farming industry and has caused serious water pollution due to its characteristics of not being easily degraded naturally.In this paper, a magnetic composite (Fe3O4-NG/PT) was produced by hydrothermal method, persimmon tannin (PT) was as the matrix, and modified by nitrogen-doped graphene (NG), ferric tetroxide (Fe3O4) was as a magnetic filler. The application of the composite in tetracycline adsorption was also investigated.Nitrogen-doped graphene with its hydrophobicity and the large specific surface area made up for the lack of persistent tannin in adsorption, and Fe3O4 solved the problem of difficult recovery of adsorbent.The mechanism was shown by SEM, chemisorption was dominant; the adsorption isotherm was consistent with the Freundlich model, indicating that it was multilayer adsorption. the maximum capacity of adsorption at 308 K reached 315.65 mg/g, and the adsorption efficiency reached 94.5%. The Fe3O4-NG/PT composites have the advantages of large specific surface area, high porosity, and phenolic hydroxyl groups, which will broaden their application fields.-
Key words:
- Persimmon tannin (PT) /
- Nitrogen-doped graphene (NG) /
- Adsorption /
- Tetracycline (TC) /
- Adsorption model
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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TC初始条件优化: (a) 不同Fe3O4∶PT质量比对于吸附效果的影响;(b)不同吸附时间对吸附的影响; (c) pH对于吸附效果的影响; (d) 吸附剂投放量对吸附效果的影响
Figure 2. Optimization of the initial conditions for Fe3O4-NG/PT adsorption of TC: (a) Effect of different Fe3O4∶PT mass ratios on the adsorption effect; (b) Effect of different adsorption times on the adsorption; (c) pH The influence of the adsorption effect; (d) effect of adsorbent dosing on adsorption effectiveness
图 3 (a) NG/PT的SEM图；(b)Fe3O4-NG/PT的SEM图；(c) Fe3O4-NG/PT吸附前的SEM图；(d)Fe3O4-NG/PT吸附TC后的SEM图；(e) C元素吸附前元素分布图；(f) O元素吸附前元素分布图；(g) N元素吸附前元素分布图；(h) Fe元素吸附前元素分布图；(i) C元素吸附后元素分布图；(j) N元素吸附后元素分布图；(k) N元素吸附后元素分布图；(l) N元素吸附后元素分布图
Figure 3. (a) SEM image of NG/PT; (b) SEM image of Fe3O4-NG/PT; (c) SEM image ofFe3O4-NG/PT before TC adsorption; (d) SEM image of Fe3O4-NG/PT after TC adsorption；(e) Elemental distribution before adsorption of element C; (f) Elemental distribution before adsorption of element O; (g) Elemental distribution before adsorption of element N; (h) Elemental distribution before adsorption of element Fe; (i) Elemental distribution after adsorption of element C; (j) Elemental distribution after adsorption of element N; (k) Elemental distribution after adsorption of element N; (l) Elemental distribution after adsorption of element N
图 4 (a)NG、PT、Fe3O4-NG/PT以及Fe3O4-NG/PT吸附TC之后的红外图谱(b)Fe3O4-NG/PT和Fe3O4-NG/PT吸附TC之后的XPS图谱(c)C1 s峰(d)N1 s峰(e)O1 s峰(f)Fe2 p峰
Figure 4. (a) FTIR profiles of NG, PT, Fe3O4-NG/PT and Fe3O4-NG/PT after TC adsorption (b) XPS profiles of Fe3O4-NG/PT and Fe3O4-NG/PT after TC adsorption (c) C1 s peak (d) N1 s peak (e) O1 s peak (f) Fe2 p peak
图 5 (a) Fe3O4-NG/PT和Fe3O4-NG/PT吸附TC之后的孔径分布图; (b) N2吸脱附曲线
Figure 5. Pore size distribution diagram of Fe3O4-NG/PT andFe3O4-NG/PT after TC adsorption Adsorption; (b) Absorption and desorption curves of N2
图 6 (a)NG/PT、Fe3O4-NG/PT、Fe3O4-NG/PT吸附TC之后的XRD图; (b)Fe3O4-NG/PT和Fe3O4-NG/PT吸附TC之后的磁滞回归线图谱
Figure 6. (a)XRD patterns of NG/PT, Fe3O4-NG/PT, Fe3O4-NG/PT after adsorbing TC;(b) The hysteresis regression line graph of Fe3O4-NG/PT and Fe3O4-NG/PT after TC adsorption.
图 7 e3O4-NG/PT吸附TC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。Fig.7 Isothermal fitting ofFe3O4-NG/PT adsorption TC ：(a) the 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 byFe3O4-NG/PT; (d) Fitting of internal diffusion of TC adsorbed by Fe3O4-NG/PT.
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