蛋黄-壳介孔磁性炭微球的制备及其对红霉素的高效吸附

doi:10.16085/j.issn.1000-6613.2022-1230

摘要/Abstract

摘要：

以溶剂热法制得的Fe₃O₄纳米颗粒为磁核，正硅酸四乙酯（TEOS）为造孔前体，间苯二酚-甲醛树脂（RF）为碳源，一步法制备蛋黄-壳介孔磁性炭微球（Fe₃O₄@C），并将其作为吸附剂用于去除水中的红霉素。采用TEM、XRD、FTIR、BET和VSM对Fe₃O₄@C进行表征。结果表明，Fe₃O₄@C核壳之间具有大空腔，比表面积为444m²/g，平均孔径为7.7nm，具有超顺磁性。通过静态吸附实验研究了Fe₃O₄@C对红霉素的吸附平衡和速率，并确定了优化的操作条件。结果表明，在吸附剂投加量为1.0g/L、初始红霉素浓度为300mg/L、pH为10的优化条件下，Fe₃O₄@C对红霉素的吸附量为210mg/g。Fe₃O₄@C对红霉素的吸附过程是自发的、吸热的和不可逆的，遵循准二级动力学和Langmuir等温线模型。经3次循环再生后，Fe₃O₄@C吸附量仍能维持在初始吸附量的86%以上。

关键词: 介孔, 磁性碳微球, 复合材料, 吸附, 红霉素, 分离

Abstract:

With Fe₃O₄ nanoparticles prepared by solvothermal method as magnetic cores, tetraethyl orthosilicate as the pore-forming precursor, and resorcinol-formaldehyde resin as the carbon source, yolk-shell mesoporous magnetic carbon microspheres (abbreviated as Fe₃O₄@C) were prepared by one-step method, and used as adsorbent to remove erythromycin from water. It was characterized by TEM, XRD, FTIR, BET and VSM. The results demonstrated that the prepared Fe₃O₄@C core-shell had a large cavity, with specific surface area of 444m²/g and average pore diameter of 7.7nm, and exhibits superparamagnetic properties. The adsorption equilibrium and rate of Fe₃O₄@C to erythromycin were studied by batch experiments, and the optimal operating conditions were determined. The results indicated that the adsorption capacity of Fe₃O₄@C for erythromycin was 210mg/g under the optimized conditions of adsorbent dosage of 1.0g/L, initial erythromycin concentration of 300mg/L and pH of 10. The adsorption process of Fe₃O₄@C to erythromycin was spontaneous, endothermic and irreversible, following pseudo-second-order kinetics and Langmuir isotherm models. After three cycles of regeneration, the adsorption capacity of Fe₃O₄@C still remained above 86% of the initial adsorption capacity.

Key words: mesoporous, magnetic carbon microspheres, composites, adsorption, erythromycin, separation

中图分类号:

TB333

刘念, 陈葵, 武斌, 纪利俊, 吴艳阳, 韩金玲. 蛋黄-壳介孔磁性炭微球的制备及其对红霉素的高效吸附[J]. 化工进展, 2023, 42(5): 2724-2732.

LIU Nian, CHEN Kui, WU Bin, JI Lijun, WU Yanyang, HAN Jinling. Preparation of yolk-shell mesoporous magnetic carbon microspheres and its efficient adsorption of erythromycin[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2724-2732.

图/表 20

图1 蛋黄-壳介孔磁性炭微球的制备工艺图

图2 Fe3O4@C的TEM图

图3 Fe3O4@C的XRD图

图4 Fe3O4和Fe3O4@C及其制备阶段产物的红外光谱图

图5 Fe3O4@C的N2等温吸脱附曲线和孔径分布曲线

表1 Fe3O4@C的孔结构数据

比表面积/m²·g^-1	总孔容/cm³·g^-1	介孔孔容占比/%	平均孔径/nm
444	0.637	74	7.7

图6 Fe3O4和Fe3O4@C的磁化曲线（1Oe=79.6A/m）

图7 吸附剂投加量对Fe3O4@C吸附红霉素的影响

图8 溶液初始pH对Fe3O4@C吸附红霉素的影响

图9 初始红霉素浓度对Fe3O4@C吸附红霉素的影响

图10 Fe3O4@C吸附红霉素的吸附动力学曲线

图11 红霉素在Fe3O4@C上的吸附动力学模型拟合图

表2 Fe3O4@C吸附红霉素的动力学常数

准一级动力学模型

准二级动力学模型

实验值q_e

/mg·g^-1

q_e,cal

/mg·g^-1

k₁

/min^-1

R²

q_e,cal

/mg·g^-1

k₂

/mg·g^-1·min^-1

R²

图12 Fe3O4@C对红霉素的吸附等温线

图13 红霉素在Fe3O4@C上的吸附等温线模型拟合图

表3 Fe3O4@C对红霉素的吸附等温线模型拟合数据

温度/K	Langmuir等温模型 c_e/q_e=c_e/q_m+1/ (k_Lq_m)			Freundlich等温模型 lnq_e=lnk_F+1/(nlnc_e)
温度/K	q_m/mg·g^-1	k_L/L·mg^-1	R²	k_F/L·g^-1	n	R²
303	227.3	0.00782	0.992	41.72	4.854	0.895
313	263.2	0.00801	0.991	52.51	5.435	0.838
323	277.8	0.01293	0.995	37.08	4.027	0.990

表4 红霉素对Fe3O4@C的热力学参数

温度/K	lnK_d	$Δ G$ /kJ·mol^-1	$Δ H$ /kJ·mol^-1	$Δ S$ /kJ·mol^-1·K^-1
303	2.62	-6.60
313	3.02	-7.87	12.12	0.0639
323	5.11	-13.74

表4 红霉素对Fe3O4@C的热力学参数

温度/K	lnK_d	$Δ G$ /kJ·mol^-1	$Δ H$ /kJ·mol^-1	$Δ S$ /kJ·mol^-1·K^-1
303	2.62	-6.60
313	3.02	-7.87	12.12	0.0639
323	5.11	-13.74

图14 再生次数对Fe3O4@C的吸附性能的影响

图15 Fe3O4@C吸附前后的FTIR光谱图a—吸附前；b—再生后；c—吸附后；d—红霉素标准品

表5 不同吸附剂对红霉素的吸附

吸附剂	吸附量/mg·g^-1	参考文献
SBA-15	172.4	[19]
分子印迹聚合物	87.1	[20]
磁性印迹聚合物	38.4	[21]
磁性活性炭/壳聚糖	178.6	[22]
Fe₃O₄@C	255.0	本文

参考文献 22

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