AEP作用下溶胶-凝胶法制备纤维素基炭气凝胶及其对水溶液中Cu2+吸附性能

doi:10.15541/jim20170053

摘要/Abstract

摘要：

以微晶纤维素为前驱物, 在表面活性剂异辛醇聚氧乙烯醚磷酸酯(AEP)作用下进行溶胶-凝胶反应, 经过真空冷冻干燥后得到纤维素气凝胶, 再在600℃惰性气氛中碳化反应制备成炭气凝胶。通过扫描电镜、BET比表面测定和红外光谱表征制备的炭气凝胶孔隙结构及表面官能团, 并采用静态吸附法考察了炭气凝胶对水溶液中铜离子的吸附性能。结果表明, 溶胶-凝胶反应中的AEP能够有效调节和改进制备的炭气溶胶孔隙结构及其吸附性能。添加2%的AEP得到的纤维素凝胶制备炭气凝胶CCA₂孔隙结构发达、均匀, 具有655.4 m²/g的比表面积和0.73 cm³/g的孔容, 对水溶液中Cu²⁺的吸附容量最大可达到86.27 mg/g, 吸附等温线符合Langmiur模型, 吸附过程遵循准二级动力学方程。

关键词: 纤维素, 溶胶-凝胶, 炭气凝胶, 表面活性剂, 铜离子

Abstract:

A novel cellulose-based carbon aerogel with well-developed porous structure and surface group of hydroxyl was synthesized from cellulose aerogel by means of Sol-Gel reaction, freeze-drying and carbonization. In this preparation, cellulose was taken as carbon precursor and phosphate of polyoxyethylene isooctyl ether (AEP) was chosen as structure inducer of micelle in cellulose colloid. Thermal decomposition of the prepared cellulose aerogel was studied by TG technique; the properties of the prepared carbon aerogel, such as porous structure and function groups were characterized with SEM, N₂ adsorption-desorption isotherms and Fourier-transform infrared spectroscopy (FT-IR). Adsorption of copper ion onto the test samples in aqueous solution was investigated through a static adsorption method. Results show that AEP can obviously regulate the porous structure and improve the adsorption performance of the prepared samples. The optimal sample of the prepared carbon aerogel possesses predominant pore structure of three-dimensional network, with a surface area of 655.4 m²/g and total pore volume of 0.73 cm³/g. The maximum copper ion adsorption capacity reached 86.27 mg/g in aqueous solution. In adsorption process, it is also found that the kinetics nicely follows pseudo-second-order rate expression, while the isotherm fits Langmuir model, displaying good adsorption properties. Therefore, the prepared carbon aerogel may have potential application in treatment of metal ion pollution in water. Meanwhile, the preparation strategies in this study provides a novel pathway for preparing carbon adsorbent with specific pore structure and functional groups on the surface.

Key words: cellulose, Sol-Gel, carbon aerogel, surfactant, copper ion

中图分类号:

TQ174

郑磊, 李劲, 刘洪波. AEP作用下溶胶-凝胶法制备纤维素基炭气凝胶及其对水溶液中Cu²⁺吸附性能[J]. 无机材料学报, 2017, 32(11): 1159-1164.

ZHENG Lei, LI Jin, LIU Hong-Bo. Carbon Aerogels Prepared Based on Sol-Gel Reaction of Cellulose Colloid with AEP and Its Adsorption of Copper Ions in Aqueous Solution[J]. Journal of Inorganic Materials, 2017, 32(11): 1159-1164.

图/表 9

图1 CAx的热重分析图(a)和CCAx红外光谱图(b)

Fig. 1 TGA curves of CAx (a) and FTIR spectrum of CCAx (b)

图2 溶胶-凝胶反应中不同百分量(w/v)AEP制备CCAx的SEM照片

Fig. 2 SEM images of CCAx prepared from different ratios (w/v) of AEP in Sol-Gel reaction (a) 0; (b) 2%; (c) 4%; (d) 6%

图3 样品的N2吸脱附曲线(a)和孔径分布图(b)

Fig. 3 Nitrogen adsorption isotherms (a) and the pore size distribution curve (b) of samples

表1 样品的物理性质分析

Table 1 Analysis of the physical properties of samples after carbonization

Sample	S_BET/(m²·g^-1)	V_tot/(cm³·g^-1)	V_mic/(cm³·g^-1)	V_mes/(cm³·g^-1)	D_a*/nm
CCA₀	476.9	0.2580	0.1777	0.0803	2.16
CCA₂	655.4	0.7324	0.3137	0.4187	4.87
CCA₄	523.5	0.5106	0.1740	0.3366	3.94
CCA₆	401.2	0.4875	0.1654	0.3221	3.21
AC	2729.8	1.8130	1.7672	0.0458	2.65

图4 AC和CCAx对Cu2+的吸附等温线

Fig. 4 Adsorption isotherm of Cu2+ on CCAx and AC

图5 CCA2吸附Cu2+的Langmuir和Freundlich等温吸附方程拟合曲线

Fig. 5 Langmuir and Freundlich isotherms for adsorption of Cu2+ onto the CCA2

图6 不同温度下CCA2吸附Cu2+的吸附容量与吸附时间的关系

Fig. 6 Effect of contact time on adsorption of Cu2+ onto CCA2 at different temperatures

图7 Cu2+在CCA2上的准一级(a)和准二级方程吸附曲线图(b)

Fig. 7 Pseudo-first-order model (a) and pseudo-second- order model (b) for the adsorption of Cu2+ onto the CCA2

表2 准一级和准二级的反应速率常数

Table 2 Constants of pseudo-first-order and pseudo-second-order models

Temp./K	Q_e,exp/(mg•g)^-1	Pseudo-first order			Pseudo-second order
Temp./K	Q_e,exp/(mg•g)^-1	k₁/min^-1	Q_e,cal/(mg•g)^-1	R²	k₂/(g•mg^-1•min^-1)	Q_e,cal/(mg•g)^-1	R²
298	86.27	0.0552	69.57	0.8758	0.00333	90.91	0.9998
308	61.34	0.0675	42.57	0.7534	0.00302	65.24	0.9998
318	30.02	0.0984	40.12	0.7018	0.00319	32.25	0.9996

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AEP作用下溶胶-凝胶法制备纤维素基炭气凝胶及其对水溶液中Cu²⁺吸附性能

Carbon Aerogels Prepared Based on Sol-Gel Reaction of Cellulose Colloid with AEP and Its Adsorption of Copper Ions in Aqueous Solution

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