GO/AT复合材料的制备及其吸附性能分析

doi:10.19491/j.issn.1001-9278.2020.05.008

中国塑料 ›› 2020, Vol. 34 ›› Issue (5): 45-51.DOI: 10.19491/j.issn.1001-9278.2020.05.008

GO/AT复合材料的制备及其吸附性能分析

刘佳衡, 王冬琴, 胡盛(), 胡卫兵

湖北民族大学生物资源保护与利用湖北省重点实验室，化学与环境工程学院，湖北恩施 445000

收稿日期:2020-01-06 出版日期:2020-05-26 发布日期:2020-05-26
基金资助:
国家自然科学基金项目(21461008);恩施州科技计划项目(D20180027);湖北民族大学博士启动基金项目(MY2017B023)

Preparation and Adsorption Performance of Graphene Oxide/Attapulgite Composites

Jiaheng LIU, Dongqin WANG, Sheng HU(), Weibing HU

Key Laboratory of Biologic Resources Protection and Utilization of Hubei Province, School of Chemical and Environment Engineering, Hubei Minzu University, Enshi 445000, China

Received:2020-01-06 Online:2020-05-26 Published:2020-05-26
Contact: Sheng HU E-mail:cailiaoxue007@126.com

摘要/Abstract

摘要：

采用溶液共混法制备氧化石墨烯（GO）/凹凸棒石（AT）复合材料，探讨GO含量对复合材料吸附性能的影响，并对复合材料的组成和微观结构进行了表征和分析。结果表明，当GO/AT的质量比为3/4时，复合材料对盐酸四环素的吸附效果最佳，吸附率达到93.06 %。进一步探讨了吸附时间、盐酸四环素初始浓度和溶液pH条件对复合材料吸附性能的变化，分析了复合材料吸附盐酸四环素的过程；GO/AT复合材料对盐酸四环素的吸附过程符合准二级动力学方程，其表观吸附活化能为37.19 kJ/mol，此吸附过程以静电吸附为主；对盐酸四环素的吸附行为符合Langmuir等温式，在研究的温度范围，吸附焓变（ΔH^O）为7.77 kJ/mol，吸附自由能变（ΔG^O）<0，吸附熵变（ΔS^O）为57.62 J/(mol·K)，表明该吸附是吸热、自发、熵增过程。

关键词: 凹凸棒石, 氧化石墨烯, 复合材料, 吸附性能

Abstract:

Graphene oxide (GO)/attapulgite (AT) composites were prepared by a solution blending method. The effect of the mass ratio of GO/AT on the adsorption capacity of the composites was investigated, and the phase composition and microstructure of the composites were analyzed. The results indicated that the composites gained a maximum adsorption capacity when the mass ratio of GO/AT was 3/4, and their adsorption rate reached 93.06 %. The effects of adsorption time, the initial concentration of tetracycline hydrochloride, and the pH values on the removal of tetracycline hydrochloride from aqueous solution were further investigated, and the mechanism and process of tetracycline hydrochloride adsorption were explored. The adsorption behavior of the composites for tetracycline hydrochloride was found to comply with the Langmuir isothermal equation and quasi second?order kinetic model with apparent adsorption activation energy of 37.19 kJ/mol. This indicated that the adsorption behavior was dominated by electrostatic adsorption. Moreover, the adsorption process was determined as an endothermic, spontaneous and entropy increasing process in the temperature range of this study according to the important parameters of ΔH^O=7.77 kJ/mol, ΔG^O＜0 and ΔS^O=57.62 J/(mol·K).

Key words: attapulgite, graphene oxide, composite, adsorption performance

中图分类号:

TQ327

刘佳衡, 王冬琴, 胡盛, 胡卫兵. GO/AT复合材料的制备及其吸附性能分析[J]. 中国塑料, 2020, 34(5): 45-51.

Jiaheng LIU, Dongqin WANG, Sheng HU, Weibing HU. Preparation and Adsorption Performance of Graphene Oxide/Attapulgite Composites[J]. China Plastics, 2020, 34(5): 45-51.

图/表 14

图1 AT和GO的SEM照片

Fig.1 SEM of AT and GO

样品编号	GO的质量/g	AT的质量/g	GO/AT的质量比
1^#	0.3	1.2	1/4
2^#	0.6	1.2	1/2
3^#	0.9	1.2	3/4
4^#	1.2	1.2	1/1
5^#	1.5	1.2	5/4
6^#	1.8	1.2	3/2

表1 样品配方表

Tab.1 Formulation of the samples

图2 GO/AT的质量比对复合材料吸附性能的影响

Fig.2 Effect of the mass ratio of GO/AT on adsorption capacity of the composites

图3 GO/AT复合材料的FTIR谱图

Fig.3 FTIR of GO/AT composites

图4 GO/AT复合材料的XRD曲线

Fig.4 XRD curves of GO/AT composites

图5 GO/AT质量比对复合材料微观结构的影响

Fig.5 Effect of the mass ratio of GO/AT on the microstructure of the composites

图6 复合材料吸附性能与pH值间的关系

Fig.6 Effect of pH on the adsorption capacity of GO/AT composites

温度/ K	准一级动力学方程			准二级动力学方程
温度/ K	K₁	R²	q_e(cal)	K₂	R²	q_e(cal)
298	0.057 85	0.910 00	160.19	0.000 233 8	0.991 29	166.15
308	0.068 84	0.766 36	178.41	0.000 354 6	0.982 99	188.08
318	0.080 12	0.912 34	198.15	0.000 601 9	0.981 44	211.71

表2 吸附动力学拟合相关系数

Tab.2 Adsorption kinetic model correlation coefficient

图7 吸附速率曲线拟合

Fig.7 The adsorption rate fitting curves of the pseudo?first?order model and the pseudo?second?order model

图8 lnK2与1/T 的关系

Fig.8 The relationship between lnK2 and 1/T

图9 吸附等温线

Fig.9 The adsorption isotherm of Langmuir and Freundlich

T/K	Langmuir吸附等温式			Freundlich吸附等温式
T/K	K₁	R²	q_m	K_f	R²	1/n
298	0.044 313	0.993 91	203.33	51.511 20	0.918 98	0.257 95
308	0.049 423	0.994 72	221.92	51.718 82	0.930 36	0.272 77
318	0.053 969	0.985 54	248.52	51.042 62	0.917 41	0.295 79

表3 吸附常数及相关系数

Tab.3 Adsorption constants and correlation coefficients

图10 lnK1与1/T的关系

Fig.10 The relationship between lnK1 and 1/T

T/K	ΔH^O/kJ·mol^-1	ΔG^O/kJ·mol^-1	ΔS^O/J·（mol·K）^-1
298	-	-9.39	-
308	7.77	-9.99	57.62
318	-	-10.54	-

表4 吸附热力学参数

Tab.4 Adsorption thermodynamic parameters

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GO/AT复合材料的制备及其吸附性能分析

Preparation and Adsorption Performance of Graphene Oxide/Attapulgite Composites

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参考文献 18

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样品编号	GO的质量/g	AT的质量/g	GO/AT的质量比
1^#	0.3	1.2	1/4
2^#	0.6	1.2	1/2
3^#	0.9	1.2	3/4
4^#	1.2	1.2	1/1
5^#	1.5	1.2	5/4
6^#	1.8	1.2	3/2

样品编号	GO的质量/g	AT的质量/g	GO/AT的质量比
1^#	0.3	1.2	1/4
2^#	0.6	1.2	1/2
3^#	0.9	1.2	3/4
4^#	1.2	1.2	1/1
5^#	1.5	1.2	5/4
6^#	1.8	1.2	3/2

样品编号	GO的质量/g	AT的质量/g	GO/AT的质量比
1^#	0.3	1.2	1/4
2^#	0.6	1.2	1/2
3^#	0.9	1.2	3/4
4^#	1.2	1.2	1/1
5^#	1.5	1.2	5/4
6^#	1.8	1.2	3/2

样品编号	GO的质量/g	AT的质量/g	GO/AT的质量比
1^#	0.3	1.2	1/4
2^#	0.6	1.2	1/2
3^#	0.9	1.2	3/4
4^#	1.2	1.2	1/1
5^#	1.5	1.2	5/4
6^#	1.8	1.2	3/2

样品编号	GO的质量/g	AT的质量/g	GO/AT的质量比
1^#	0.3	1.2	1/4
2^#	0.6	1.2	1/2
3^#	0.9	1.2	3/4
4^#	1.2	1.2	1/1
5^#	1.5	1.2	5/4
6^#	1.8	1.2	3/2

样品编号	GO的质量/g	AT的质量/g	GO/AT的质量比
1^#	0.3	1.2	1/4
2^#	0.6	1.2	1/2
3^#	0.9	1.2	3/4
4^#	1.2	1.2	1/1
5^#	1.5	1.2	5/4
6^#	1.8	1.2	3/2