纳米Fe<sub>3</sub>O<sub>4</sub>@茶渣/海藻酸钙磁性复合材料制备及其对亚甲基蓝的吸附性能与吸附机制

龚新怀; 李明春; 杨坤; 吴珠海; 王兆礼; 吕橄; 吴振增

doi:10.13801/j.cnki.fhclxb.20200507.002

纳米Fe₃O₄@茶渣/海藻酸钙磁性复合材料制备及其对亚甲基蓝的吸附性能与吸附机制

doi: 10.13801/j.cnki.fhclxb.20200507.002

龚新怀^{1, 2, ,},
李明春²,
杨坤¹,
吴珠海¹,
王兆礼¹,
吕橄¹,
吴振增¹

1.
武夷学院　生态与资源工程学院福建省生态产业绿色技术重点实验室，武夷山 354300
2.
华侨大学　材料科学与工程学院环境友好功能材料教育部工程研究中心，厦门 361021

基金项目: 福建省自然科学基金(2018J01445)；福建省高校杰出青年科研人才计划(闽科教[2018]47号)；福建省中青年教师教育科研项目(JAT170594；JT180555)；武夷学院引进人才科研项目(YJ201810)；福建省生态产业绿色技术重点实验室项目(WYKF2018-5)

详细信息

通讯作者:
龚新怀，博士，副教授，研究方向为生物质高值化利用与高分子复合材料　Email：wyu_gxh@163.com

中图分类号: TQ424.3；X712；TB332
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出版历程
- 收稿日期: 2020-02-17
- 录用日期: 2020-04-15
- 网络出版日期: 2020-05-07
- 刊出日期: 2021-02-15

Preparation of nano-Fe₃O₄@tea waste/calcium alginate magnetic composited bead and it’s adsorption characteristics and mechanisms for methylene blue from aqueous solution

1.
Fujian Provincial Key Laboratory of Eco-Industrial Green Technology, Ecology and Resources Engineering College, Wuyi University, Wuyishan 354300, China
2.
Engineering Research Center of Environment-Friendly Functional Materials, College of Material Science and Engineering, Huaqiao University, Xiamen 361021, China

摘要

摘要: 采用离子共沉淀技术在茶渣(Tea waste, TW)表面沉积纳米Fe₃O₄粒子(TW@nano-Fe₃O₄)，用溶胶凝胶法制备茶渣@纳米Fe₃O₄/海藻酸钙(TW@nano-Fe₃O₄/CA)磁性复合微球，通过SEM、XPS、XRD、振动样品磁强计(VSM)及万能试验机对材料结构和性能进行了表征与测试，并研究了其对水溶液中亚甲基蓝(Methylene blue, MB)的吸附性能与机制。结果表明，TW@nano-Fe₃O₄/CA复合微球磁性响应明显，粒径为1.2~1.7 mm。微球表面粗糙、褶皱，内部为疏松多孔道结构。随TW@nano-Fe₃O₄含量增加，微球粒径增加，磁响应增强，但对MB的吸附量缓慢下降；TW@nano-Fe₃O₄/CA微球对MB的吸附动力学数据与准二级动力学方程拟合较好，等温吸附过程符合Langmuir模型，对MB的吸附过程是自发性和熵减小的放热过程。在303 K下，质量配比为TW@nano-Fe₃O₄∶CA=4∶1的复合微球对MB的Langmuir最大吸附量为272.5 mg·g⁻¹，比TW提高86.7%，并具有良好的再生与循环使用性能。
- 茶渣 /
- 海藻酸钠 /
- 微球 /
- 磁性分离 /
- 吸附 /
- 亚甲基蓝
Abstract: Nano-Fe₃O₄ particles were deposited on the surface of tea waste (TW) by co-precipitation method to form tea waste@nano-Fe₃O₄ magnetic composited material, and then spherical tea waste@nano-Fe₃O₄/calcium algnate (TW@nano-Fe₃O₄/CA) magnetic beads were prepared by sol-gel approach. The magnetic composites were characterized by SEM, XPS, XRD, vibrating sample magnetometer (VSM) and universal testing machine. The adsorption properties and mechanism of methylene blue (MB) from aqueous solution onto the beads were studied. The results show that the TW@nano-Fe₃O₄/CA beads possess a good magnetic response, with the diamters ranges from 1.2 mm to 1.7 mm. The composited beads display a rough and folded surface morphology and porous inner structure. The diameters and magnetic response of the beads increase while the adsorption abilities of MB decrease with the increasing content of TW@nano-Fe₃O₄ in the beads. The adsorption kinetics followed is second order, and the adsorption isotherm data are well fitted to Langmuir model. The adsorption process of MB onto the beads is spontaneous, entropy decreased and exothermic process. The Langmuir maximum adsorption capacity of MB onto the beads with 80% mass fraction of TW@nano-Fe₃O₄ is found to be 272.5 mg·g⁻¹ at 303 K, which is increased by 86.7% than TW. The adsorbent shows satisfactory regeneration and recycling utiliziation performance.
- tea waste /
- sodium alginate /
- beads /
- magnetic separation /
- adsorption /
- methylene blue

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图 1 茶渣(TW)及TW@nano-Fe₃O₄的SEM图像

Figure 1. SEM images of tea waste (TW) and TW@nano-Fe₃O₄

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图 2 TW及TW@nano-Fe₃O₄的XPS图谱

Figure 2. XPS spectra of TW and TW@nano-Fe₃O₄

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图 3 海藻酸钙微球(CA)和TW@nano-Fe₃O₄/CA(4∶1)复合微球的SEM图像

Figure 3. SEM images of the calcium algnate(CA) and TW@nano-Fe₃O₄/CA(4∶1) composite beads

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图 4 TW@nano-Fe₃O₄/CA(4∶1)复合微球的XRD图谱

Figure 4. XRD spectra of TW@nano-Fe₃O₄/CA(4∶1) composited beads

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图 5 TW@nano-Fe₃O₄/CA(4∶1)复合微球粒径分布

Figure 5. Size distribution of TW@nano-Fe₃O₄/CA(4∶1) composited beads

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图 6 TW和TW@nano-Fe₃O₄的磁性效果对比

Figure 6. Photographs of TW andTW@nano-Fe₃O₄ attracted by a magnet

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图 7 TW@nano-Fe₃O₄/CA复合微球的磁性效果图

Figure 7. Photographs of TW@nano-Fe₃O₄/CA beads attracted by a magnet

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图 8 TW@nano-Fe₃O₄/CA(4∶1)复合微球的磁化曲线

Figure 8. Magnetization curves of TW@nano-Fe₃O₄/CA(4∶1)

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图 9 TW@nano-Fe₃O₄质量比对复合微球吸附亚甲基蓝(MB)效果影响

Figure 9. Effects of TW@nano-Fe₃O₄ mass ratio on the adsorption capacity of methylene blue (MB) onto the beads

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图 10 pH对TW@nano-Fe₃O₄/CA(4∶1)复合微球吸附MB效果的影响

Figure 10. Effects of pH on the adsorption capacity of MB onto TW@nano-Fe₃O₄/CA(4∶1) beads

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图 11 接触时间对TW@nano-Fe₃O₄和TW@nano-Fe₃O₄/CA(4∶1)复合微球吸附MB效果的影响

Figure 11. Effects of time on adsorption capacity of MB onto TW@nano-Fe₃O₄ and TW@nano-Fe₃O₄/CA(4∶1) beads

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图 12 TW@nano-Fe₃O₄/CA(4∶1)复合微球吸附MB的动力学方程拟合曲线

Figure 12. Kinetic fitting curves of adsorption data of MB onto TW@nano-Fe₃O₄/CA(4∶1) beads

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图 13 TW@nano-Fe₃O₄和nTW@nano-Fe₃O₄/CA(4∶1)复合微球对MB的等温吸附曲线

Figure 13. Adsorption isothermal curves of TW@nano-Fe₃O₄ and TW@nano-Fe₃O₄/CA(4∶1) beads

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图 14 TW、TW@nano-Fe₃O₄及nTW@nano-Fe₃O₄/CA(4∶1)复合微球对MB的等温吸附模型拟合曲线

Figure 14. Langmuir model fitting curves for TW, TW@nano-Fe₃O₄, TW@nano-Fe₃O₄/CA(4∶1) beads, Freundlich model fitting curves for TW@nano-Fe₃O₄/CA(4∶1) beads

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图 15 TW、TW@nano-Fe₃O₄及TW@nano-Fe₃O₄/CA(4∶1)复合微吸附MB热力学拟合曲线

Figure 15. Thermodynamic fitting curves of adsorption data of MB onto TW, TW@nano-Fe₃O₄ and TW@nano-Fe₃O₄/CA(4∶1)

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图 16 TW@nano-Fe₃O₄/CA(4∶1)复合微球再生与吸附循环使用前后外观形态

Figure 16. Appearances of the TW@nano-Fe₃O₄/CA(4∶1) beads during the regeneration and recycling utiliziation process

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图 17 TW@nano-Fe₃O₄/CA(4∶1)复合微球的压缩应力-应变曲线

Figure 17. Stress-strain curves of compression test of the TW@nano-Fe₃O₄/CA(4∶1) beads

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图 18 TW@nano-Fe₃O₄/CA(4∶1)复合微球的循环使用

Figure 18. Recycling utilization of TW@nano-Fe₃O₄/CA(4∶1)

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表 1 TW@nano-Fe₃O₄/CA(4∶1)复合微球吸附MB的动力学模型拟合参数(C₀=200 mg·L⁻¹)

Table 1. Parameters of kinetic adsorption models for MB adsorption onto TW@nano-Fe₃O₄/CA(4∶1) beads ( C₀=200 mg·L⁻¹)

Model	Parameter	Value
	Q_e(exp)/(mg·g⁻¹)	171.3
Pesudo- first- order	k₁/min⁻¹	8.0×10⁻³
	Q_e(cal)/(mg·g⁻¹)	123.8
	R²	0.9542
Pesudo- second- order	k₂/(g·mg⁻¹·min⁻¹)	1.0×10⁻⁴
	Q_e(cal)/(mg·g⁻¹)	185.2
	R²	0.9985
Notes: k₁, k₂—Psudo-first-order kinetic constant and Psudo-second-order kinetic constant, respectively; Q_e(cal)—Calculation amount of MB removed per unit mass of adsorbent; Q_e(exp)—Experimental amount of MB removed per unit mass of adsorbent.

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表 2 TW、TW@nano-Fe₃O₄及TW@nano-Fe₃O₄/CA(4∶1)对MB的吸附等温式拟合结果

Table 2. Isothermal parameters for the adsorption of MB onto TW, TW@nano-Fe₃O₄ and TW@nano-Fe₃O₄/CA(4∶1) beads

Adsorbent	Model	Parameter	T/K
Adsorbent	Model	Parameter	303	313	323
TW	Langmuir	Q_m/(mg·g⁻¹)	146.0	145.3	143.3
		K_L×10⁻²/(L·mg⁻¹)	5.2	4.4	4.2
		R²	0.9995	0.9992	0.9989
TW@nano-Fe₃O₄	Langmuir	Q_m/(mg·g⁻¹)	160.5	154.8	152.0
		K_L×10⁻²/(L·mg⁻¹)	9.1	8.1	7.4
		R²	0.9993	0.9996	0.9998
TW@nano-Fe₃O₄/CA	Langmuir	Q_m/(mg·g⁻¹)	272.5	266.0	261.8
		K_L×10⁻²/(L·mg⁻¹)	5.1	4.8	4.2
		R²	0.9949	0.9971	0.9952
	Fredudlich	K_F/(L·mg⁻¹)	26.0	25.6	24.3
		n	2.0	2.1	2.1
		R²	0.9089	0.9482	0.9718
Notes: Q_m—Langmuir adsorption maximum; K_L—Langmuir coefficient of distribution of the adsorption; K_F—Freundlich coefficient of distribution of the adsorption; n—Empirical constant related to temperature and system.

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表 3 TW、TW@nano-Fe₃O₄及TW@nano-Fe₃O₄/CA(4∶1)复合微球吸附MB的热力学参数分析

Table 3. Values of thermodynamic parameters for the adsorption of MB onto TW, TW@nano-Fe₃O₄ andTW@nano-Fe₃O₄/CA(4∶1) beads

Adsorbent	T/K	∆G^θ/(kJ·mol⁻¹)	∆H^θ/(kJ·mol⁻¹)	∆S^θ/(J·mol⁻¹·K⁻¹)	R²
TW	303	−0.9
	313	−0.8	−4.4	−11.7	0.9943
	323	−0.7
TW@nano-Fe₃O₄	303	−1.6
	313	−1.5	−5.9	−13.9	0.9960
	323	−1.4
TW@nano-Fe₃O₄/CA beads	303	−4.8
	313	−4.4	−20.5	−51.7	0.9952
	323	−3.8
Notes: ∆G^θ—Gibbs free energy variation of the adsorption process; ∆H^θ—Enthalpy change of the adsorption process; ∆S^θ—Entropy change of the adsorption process.; R²—Linear correlation coefficient.

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表 4 不同处理方法后TW@nano-Fe₃O₄/CA(4∶1)复合微球的力学性能

Table 4. Mechanical properties of TW@nano-Fe₃O₄/CA(4∶1) composites with different treatments

TW@nano-Fe₃O₄/CA beads	Compressive strength/MPa	Compression modulus/MPa
Before adsorption of MB	6.2±0.5	41.1±4.7
After adsorption of MB	6.5±0.4	42.2±4.6
Regeneration for 2 times	6.3±0.3	44.7±3.4
Regeneration for 4 times	6.2±0.2	42.2±3.1

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