磁性Fe<sub>3</sub>O<sub>4</sub>纳米复合材料的制备及其对Pb(II)的吸附

包国庆; 吴纯鑫; 赵德明

doi:10.13801/j.cnki.fhclxb.20220117.001

磁性Fe₃O₄纳米复合材料的制备及其对Pb(II)的吸附

doi: 10.13801/j.cnki.fhclxb.20220117.001

浙江工业大学　化学工程学院，杭州 310032

基金项目: 浙江省自然科学基金项目(LY19B070006)；浙江省基础公益研究计划项目(LGF20B070003)

详细信息

通讯作者:
赵德明，博士，副教授，硕士生导师，研究方向为清洁生产工艺、环境污染治理技术　E-mail: dmzhao@zjut.edu.cn

中图分类号: X78；TQ138.1
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出版历程
- 收稿日期: 2021-12-13
- 修回日期: 2022-01-04
- 录用日期: 2022-01-07
- 网络出版日期: 2022-01-18
- 刊出日期: 2023-01-15

Preparation of magnetic Fe₃O₄ nanocomposites and their adsorption to Pb(II)

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Funds: Zhejiang Natural Science Foundation (LY19B070006); Zhejiang Basic Public Welfare Research Program (LGF20B070003)

摘要

摘要: 为解决磁性纳米Fe₃O₄易被腐蚀、团聚等问题，可对其进行功能化修饰。在超声波辐照下首先制备磁性纳米Fe₃O₄颗粒，然后选用2,5-二氨基苯磺酸(SP)和间苯二胺(mPD)单体为引入剂进行功能化修饰，制备得到富含氨基、磺酸基和亚氨基活性官能团的金属基复合材料Fe₃O₄-mPD/SP(95∶5)，并采用FTIR、TEM、XRD等手段对其进行表征，证实了超声波辐照法制得的磁性纳米复合材料具有稳定性好、反应活性高、粒径小和比表面积更大等特点。同时考察其对Pb(II)的吸附性能，结果表明：mPD和SP摩尔比、溶液pH值、竞争性阳离子种类和反应温度等因素均会影响吸附效果；等温吸附过程符合Freundlich模型，吉布斯自由能∆G⁰<0，吸附是一个自发过程；Pb(II)的吸附行为符合准二级动力学，速率常数k₂=3.61×10⁻³ g·mg⁻¹·min⁻¹，平衡吸附量q_e=63.297 mg·g⁻¹；推测得到吸附机制主要为离子交换、络合吸附和静电引力等。
- 超声波 /
- 磁性 /
- 金属基复合材料 /
- 吸附 /
- Freundlich模型 /
- 纳米Fe₃O₄
Abstract: In order to solve the problem that Fe₃O₄ nanoparticles were easy to be corroded and agglomerated, it was decided to functionalize it. Magnetic nano-Fe₃O₄ particles were prepared under ultrasonic irradiation, then 2-diaminobenzenesulfonic acid (SP) and m-phenylenediamine (mPD) monomers were selected as introduction agents to prepare metal matrix composites Fe₃O₄-mPD/SP(95∶5), which were rich in amino, sulfonic acid and imine active functional groups, and nanocomposites were characterized by FTIR, TEM, XRD and other methods. The characterized results show that the magnetic nanocomposites prepared by ultrasonic strengthening method have the characteristics of good stability, high reaction activity, small particle size and larger specific surface area. The adsorption properties of Pb(II) by Fe₃O₄-mPD/SP were investigated which showed that the molar percentage of SP and mPD, reaction temperature, sorts of competitive cations and the pH value of solution all had effect on the adsorption of Pb(II). The adsorption isotherm conforms to the Freundlich model, and the adsorption of Pb(II) is a spontaneous process, Gibbs free energy ∆G⁰<0. It is found that the adsorption behavior of Pb(II) on nanocomposites can be well described by quasi secondary dynamics equation, kinetic constant k₂=3.61×10⁻³ g·mg⁻¹·min⁻¹, equilibrium adsorption capacity q_e=63.297 mg·g⁻¹. It is speculated that the adsorption mechanism of this adsorbent includes ion exchange, complex adsorption and electrostatic adsorption.
- ultrasound /
- magnetic properties /
- metal-matrix composites /
- adsorption /
- freundlich model /
- Fe₃O₄ nanoparticles

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图 1 磁性纳米Fe₃O₄颗粒的表面功能化

Figure 1. Surface functionalization of magnetic Fe₃O₄ nanoparticles

SP—2-diaminobenzenesulfonic acid; mPD—m-phenylenediamine

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图 2 Fe₃O₄和无超声波辐照、引入超声波辐照制备的Fe₃O₄-mPD/SP(95∶5)的XRD图谱

Figure 2. XRD patterns of Fe₃O₄ and Fe₃O₄-mPD/SP(95∶5) prepared without ultrasonic irradiation and introducing ultrasonic irradiation

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图 3 不同方法制备的Fe₃O₄-mPD/SP(95∶5)纳米复合材料反应前的TEM图像

Figure 3. TEM images of Fe₃O₄-mPD/SP(95∶5) nanocomposites prepared by different methods before reaction

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图 4 Fe₃O₄和无超声波辐照、引入超声波辐照制备的Fe₃O₄-mPD/SP(95∶5)和Fe₃O₄-mPD/SP(50∶50)反应前红外图谱

Figure 4. Infrared spectra of fresh Fe₃O₄ and Fe₃O₄-mPD/SP(95∶5) and Fe₃O₄-mPD/SP(50∶50) prepared without ultrasonic irradiation and introducing ultrasonic irradiation before reaction

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图 5 Fe₃O₄和无超声波辐照、引入超声波辐照制备的Fe₃O₄-mPD/SP(95∶5)反应前热重图

Figure 5. Thermogravimetric spectra of fresh Fe₃O₄ and Fe₃O₄-mPD/SP(95∶5) prepared without ultrasonic irradiation and introducing ultrasonic irradiation before reaction

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图 6 Fe₃O₄和无超声波辐照、引入超声波辐照制备的Fe₃O₄-mPD/SP(50∶50)和Fe₃O₄-mPD/SP(95∶5)磁滞回线图谱

Figure 6. Hysteresis loop spectra of Fe₃O₄ and Fe₃O₄-mPD/SP(50∶50) and Fe₃O₄-mPD/SP(95∶5) prepared without ultrasonic irradiation and introducing ultrasonic irradiation

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图 7 无超声波辐照、引入超声波辐照制备的Fe₃O₄-mPD/SP(95∶5)对Pb(II)的吸附效果

Figure 7. Adsorption effect of Fe₃O₄-mPD/SP(95∶5) prepared without ultrasonic irradiation and introducing ultrasonic irradiation on Pb(II)

q_t—Adsorption capacity at time t; t—Reaction time

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图 8 不同mPD/SP单体比例对Fe₃O₄-mPD/SP吸附 Pb(II)影响

Figure 8. Effects of different mPD/SP monomer ratios on Pb(II) adsorption by Fe₃O₄-mPD/SP

q_e—Equilibrium adsorption capacity

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图 9 pH值对Fe₃O₄-mPD/SP(95∶5)吸附Pb(II)的影响

Figure 9. Effect of pH value on Pb(II) adsorption by Fe₃O₄-mPD/SP(95∶5)

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图 10 竞争性离子对Fe₃O₄-mPD/SP(95∶5)吸附Pb(II)的影响

Figure 10. Effect of competitive ions on Pb(II) adsorption by Fe₃O₄-mPD/SP(95∶5)

C_e—Equilibrium concentration

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图 11 Fe₃O₄-mPD/SP(95∶5)吸附Pb(II)的量随时间变化曲线及吸附动力学模型拟合

Figure 11. Time-dependent curve of Pb(II) amount by Fe₃O₄-mPD/SP(95∶5) and the fitting of adsorption kinetic model

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图 12 Fe₃O₄-mPD/SP(95∶5)对Pb(II)的吸附等温线及吸附等温线拟合

Figure 12. Adsorption isotherm and adsorption isotherm fitting of Pb(II) adsorption by Fe₃O₄-mPD/SP(95∶5)

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图 13 温度对Fe₃O₄-mPD/SP(95∶5)吸附Pb(II)的影响

Figure 13. Effect of temperature on the adsorption of Pb(II) by Fe₃O₄-mPD/SP(95∶5)

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图 14 不同Pb(II)初始浓度下lnK₀对1/T作图

Figure 14. lnK₀ plots of 1/T under different initial Pb(II) concentrations

K₀—Thermodynamic equilibrium constant

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图 15 Fe₃O₄-mPD/SP(95∶5)循环使用次数对吸附Pb(II)的影响

Figure 15. Effect of Fe₃O₄-mPD/SP(95∶5) recycling times on Pb(II) adsorption

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图 16 磁性纳米复合材料Fe₃O₄-mPD/SP(95∶5)吸附Pb(II)前后的红外图谱

Figure 16. Infrared spectra of magnetic nanocomposites Fe₃O₄-mPD/SP(95∶5) before and after adsorption of Pb(II)

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图 17 功能化磁性纳米复合材料Fe₃O₄-mPD/SP(95∶5)吸附Pb(II)的机制图

Figure 17. Mechanism diagram of adsorption of Pb(II) by functionalized magnetic nanocomposite Fe₃O₄-mPD/SP(95∶5)

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表 1 不同吸附剂对Pb(II)的吸附容量比较

Table 1. Comparison of adsorption capacity of Pb(II) by different adsorbents

Adsorbent	Saturated adsorption capacity/(mg·g⁻¹)	Ref.
Magnetic ion-imprinted and —SH functionalized polymer	32.58	[3]
MNPs-Ca-alginate immobilized Phanerochaete chrysosporium	56.18	[6]
Magnetic alginate beads	50.00	[7]
Fe₃O₄@SiO₂-NH₂	40.10	[8]
Fe₃O₄@SiO₂-NH-COOH	34.27	[9]
Magnetic chitosan/graphene oxide	76.94	[13]
Fe₃O₄-mPD/SP(95∶5)	95.24	This study
Note: MNPs—Magnetic nanoparticles.

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表 2 Pb(II)吸附动力学方程拟合及各参数值

Table 2. Pb(II) adsorption kinetic equation fitting and parameters

Dynamics model	R²	Rate constant	q_e,cal/(mg·g⁻¹)	q_e,exp/(mg·g⁻¹)
Quasi-first-order kinetics	0.627	k₁=1.65×10⁻² min⁻¹	—	—
Quasi-second-order kinetics	0.999	k₂=3.61×10⁻³ g·mg⁻¹·min⁻¹	63.297	62.493
Internal diffusion equation	0.557	k_p=2.005 mg·(g·min^1/2)⁻¹	—	—
Notes: q_e,cal—Theoretical saturated adsorption capacity; q_e,exp—Experimental saturated adsorption capacity; k₁—Quasi-first-order kinetic constant; k₂—Quasi-second-order kinetic constant; k_p—Internal diffusion coefficient; R²—Correlation coefficient.

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表 3 Fe₃O₄-mPD/SP(95∶5)对Pb(II)各吸附动力学模型参数

Table 3. Kinetic model parameters of adsorption of Pb(II) by Fe₃O₄-mPD/SP(95∶5)

Model	Parameters and values
Langmuir model	K_L/(L·mg⁻¹)	q_m/(mg·g⁻¹)	R²
Langmuir model	0.068	95.24	0.979
Freundlich model	K_F/(mg^1−(1/n)·L^1/n·g⁻¹)	1/n	R²
Freundlich model	23.53	0.268	0.994
Temkin model	K_t	B_l	R²
Temkin model	3.513	13.55	0.952
Notes: K_L—Langmuir adsorption constant; K_F—Freundlich adsorption coefficient; K_t, B_l—Temkin adsorption isotherm; q_m—Saturated adsorption capacity; R²—Linear correlation coefficient; n—Empirical constant.

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表 4 Fe₃O₄-mPD/SP(95∶5)吸附Pb(II)热力学常数

Table 4. Thermodynamic constants of Fe₃O₄-mPD/SP(95∶5) adsorption of Pb(II)

C₀/(mg·L⁻¹)	∆G⁰/(kJ·mol⁻¹)				∆H⁰/(kJ·mol⁻¹)	∆S⁰/(J·mol⁻¹·K⁻¹)
C₀/(mg·L⁻¹)	293 K	303 K	313 K	323 K	∆H⁰/(kJ·mol⁻¹)	∆S⁰/(J·mol⁻¹·K⁻¹)
90	3.404	−4.570	5.561	6.807	30.766	116.620
100	3.342	4.197	4.768	5.542	21.703	85.479
110	2.937	−3.677	−4.361	−5.183	18.749	74.014
Notes: C₀—Initial concentration of solution; ∆G⁰—Gibbs free energy; ∆H⁰—Enthalpy change; ∆S⁰—Entropy change.

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表 5 Fe₃O₄和Fe₃O₄-mPD/SP(95∶5)抗氧化性实验

Table 5. Antioxidant activity of Fe₃O₄ and Fe₃O₄-mPD/SP(95∶5)

Sample	Sample state during adsorption	q_e/(mg·g⁻¹)
Fe₃O₄	Fresh preparation	23.19
Fe₃O₄	Exposed to air for 48 h	17.51
Fe₃O₄-mPD/SP(95∶5)	Fresh preparation	40.46
Fe₃O₄-mPD/SP(95∶5)	Exposed to air for 48 h	37.73

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