氧化石墨烯插层膨润土复合材料高效吸附碱性紫3染料

doi:10.16085/j.issn.1000-6613.2021-1356

摘要/Abstract

摘要：

通过超声途径，利用氧化石墨烯（GO）插层膨润土（Bent）制备复合材料（BGO），并评估对碱性紫3的吸附效果。采用XRD、FTIR、BET、SEM、XPS等检测手段表征了复合材料的结构特征，通过Langmuir、Freundlich模型和伪一级、伪二级模型拟合了等温吸附数据和动力学吸附数据，范特霍夫方程研究热力学过程。结果表明：GO成功插入Bent层间，XRD图谱显示膨润土层间距从1.35nm（Bent）扩大至1.6nm（BGO），BGO比表面积有大幅提升；吸附数据符合Langmuir等温线模型和伪二级动力学模型，在30℃、250mg/L初始浓度下，BGO最高吸附容量可达420.17mg/g，与Bent相比，BGO显示更强的吸附能力，吸附过程展现快速动态；热力学研究表明吸附过程是自发且吸热的。机理分析表明，高比表面积GO及所带含氧基团与Bent之间的协同作用共同决定BGO具有高吸附能力。

关键词: 氧化石墨烯, 膨润土, 插层复合材料, 碱性紫3, 吸附机理

Abstract:

The composite materials (BGO) prepared by graphene oxide (GO) and bentonite (Bent) through ultrasound method were tested for their ability to absorb Basic Violet 3. The materials structure were characterized by X-ray Diffraction, Fourier Transform Infra-Red Spectrophotometer, BET equation, Scanning Electron Microscope and X-ray Photoelectron Spectroscopy. The biosorption data were analyzed using Langmuir, Freundlich, pseudo-first-order kinetic model and pseudo-second-order kinetic model, and the thermodynamic parameters of the biosorption were determined by Van’t Hoff equation. XRD analysis indicated that the interlayer spacing of Bent increased from 1.35nm to 1.6nm after GO were inserted successfully, and the specific surface area of BGO were improved significantly. Langmuir model and pseudo-second-order kinetic model proved to be the best fit to the experimental data. BGO performed more significant adsorption capacity and adsorption speed. Compared with Bent, the maximum adsorption capacity of BGO was 420.17mg/g at an initial dye concentration of 250mg/L and 30℃. Thermodynamic analysis verified that BGO biosorption was spontaneous and endothermic. Mechanism analysis revealed that the synergy between GO with high specific surface area and oxygen-containing groups and Bent played a prominent role in adsorption ability of BGO.

Key words: graphene oxide, bentonite, intercalation composite, Basic Violet 3, adsorption mechanism

中图分类号:

TQ424.2

陈勇, 程宁, 杨育兵, 卢凯玲, 罗应, 易慧. 氧化石墨烯插层膨润土复合材料高效吸附碱性紫3染料[J]. 化工进展, 2022, 41(6): 3324-3332.

CHEN Yong, CHENG Ning, YANG Yubing, LU Kailing, LUO Ying, YI Hui. Highly efficient adsorption of Basic Violet 3 dye by composite material derived from graphene oxide intercalated bentonite[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3324-3332.

图/表 16

参考文献 25

1	KARIMIFARD S, ALAVI MOGHADDAM M R. Application of response surface methodology in physicochemical removal of dyes from wastewater: a critical review[J]. Science of the Total Environment, 2018, 640/641: 772-797.
2	LI W, MU B N, YANG Y Q. Feasibility of industrial-scale treatment of dye wastewater via bio-adsorption technology[J]. Bioresource Technology, 2019, 277: 157-170.
3	ZHANG P, LO I, O'CONNOR D, et al. High efficiency removal of methylene blue using SDS surface-modified ZnFe₂O₄ nanoparticles[J]. Journal of Colloid and Interface Science, 2017, 508: 39-48.
4	THAKUR S, PANDEY S, AROTIBA O A. Development of a sodium alginate-based organic/inorganic superabsorbent composite hydrogel for adsorption of methylene blue[J]. Carbohydrate Polymers, 2016, 153: 34-46.
5	LIU C, OMER A M, OUYANG X K. Adsorptive removal of cationic methylene blue dye using carboxymethyl cellulose/k-carrageenan/activated montmorillonite composite beads: isotherm and kinetic studies[J]. International Journal of Biological Macromolecules, 2018, 106: 823-833.
6	LIU C, ZHU G L, SONG S X, et al. Flotation separation of smithsonite from quartz using calcium lignosulphonate as a depressant and sodium oleate as a collector[J]. Minerals Engineering, 2019, 131: 385-391.
7	ZHU Y, FAN W H, ZHOU T T, et al. Removal of chelated heavy metals from aqueous solution: a review of current methods and mechanisms[J]. Science of the Total Environment, 2019, 678: 253-266.
8	宋晓东, 程昌敬, 余海溶. 阴离子聚电解质修饰磁性氧化石墨烯对碱性品红的吸附性能[J]. 化工进展, 2016, 35(9): 2973-2981.
	SONG Xiaodong, CHENG Changjing, YU Hairong. Adsorption performance of an anionic polyelectrolyte-functionalized magnetic graphene oxide for basic fuchsin[J]. Chemical Industry and Engineering Progress, 2016, 35(9): 2973-2981.
9	BAI H Y, ZHAO Y L, ZHANG X, et al. Correlation of exfoliation performance with interlayer cations of montmorillonite in the preparation of two-dimensional nanosheets[J]. Journal of the American Ceramic Society, 2019, 102(7): 3908-3922.
10	ZHAO Y L, KANG S C, QIN L, et al. Self-assembled gels of Fe-chitosan/montmorillonite nanosheets: dye degradation by the synergistic effect of adsorption and photo-Fenton reaction[J]. Chemical Engineering Journal, 2020, 379: 122322.
11	FARROKHI-RAD M, MOHAMMADALIPOUR M, SHAHRABI T. Electrophoretically deposited halloysite nanotubes coating as the adsorbent for the removal of methylene blue from aqueous solution[J]. Journal of the European Ceramic Society, 2018, 38(10): 3650-3659.
12	LI Y H, DU Q J, LIU T H, et al. Comparative study of methylene blue dye adsorption onto activated carbon, graphene oxide, and carbon nanotubes[J]. Chemical Engineering Research and Design, 2013, 91(2): 361-368.
13	KYZAS G Z, FU J, MATIS K A. The change from past to future for adsorbent materials in treatment of dyeing wastewaters[J]. Materials, 2013, 6(11): 5131-5158.
14	杜夕铭, 卢钧, 陈泉源. 氧化石墨对活性红X-3B的吸附特性及再生性能[J]. 水处理技术, 2019, 45(8): 35-39, 44.
	DU Ximing, LU Jun, CHEN Quanyuan. Adsorption characteristics of reactive red X-3B by graphite oxide and its regeneration[J]. Technology of Water Treatment, 2019, 45(8): 35-39, 44.
15	王希越, 明明, 连丽丽, 等. 磁性氧化石墨烯纳米粒子的制备及其对大红染料的去除[J]. 应用化工, 2019, 48(10): 2324-2327.
	WANG Xiyue, MING Ming, LIAN Lili, et al. Preparation of magnetic graphene oxide nanoparticles and its application for red dye removal[J]. Applied Chemical Industry, 2019, 48(10): 2324-2327.
16	LIU L, ZHANG Y R, HE Y J, et al. Preparation of montmorillonite-pillared graphene oxide with increased single- and co-adsorption towards lead ions and methylene blue[J]. RSC Advances, 2015, 5(6): 3965-3973.
17	ZHANG Z L, LUO H J, JIANG X L, et al. Synthesis of reduced graphene oxide-montmorillonite nanocomposite and its application in hexavalent chromium removal from aqueous solutions[J]. RSC Advances, 2015, 5(59): 47408-47417.
18	王志明, 吕宪俊, 渠美云. 膨润土提纯工艺研究[J]. 现代矿业, 2013, 29(3): 26-29, 50.
	WANG Zhiming, Xianjun LYU, QU Meiyun. Research on purification technology of montmorillonite[J]. Modern Mining, 2013, 29(3): 26-29, 50.
19	MUNIR M, AHMAD M, SAEED M, et al. Sustainable production of bioenergy from novel non-edible seed oil (Prunus cerasoides) using bimetallic impregnated montmorillonite clay catalyst[J]. Renewable and Sustainable Energy Reviews, 2019, 109: 321-332.
20	WANG J Q, HAN Z D. The combustion behavior of polyacrylate ester/graphite oxide composites[J]. Polymers for Advanced Technologies, 2006, 17(4): 335-340.
21	TYAGI B, CHUDASAMA C D, JASRA R V. Determination of structural modification in acid activated montmorillonite clay by FT-IR spectroscopy[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2006, 64(2): 273-278.
22	ZHANG X L, CHENG L P, WU X P, et al. Activated carbon coated palygorskite as adsorbent by activation and its adsorption for methylene blue[J]. Journal of Environmental Sciences, 2015, 33: 97-105.
23	BRADDER P, LING S K, WANG S B, et al. Dye adsorption on layered graphite oxide[J]. Journal of Chemical & Engineering Data, 2011, 56(1): 138-141.
24	TEKIN N, ŞAFAKLI A, BINGÖL D. Process modeling and thermodynamics and kinetics evaluation of Basic Yellow 28 adsorption onto sepiolite[J]. Desalination and Water Treatment, 2015, 54(7): 2023-2035.
25	DERAKHSHAN Z, BAGHAPOUR M A, RANJBAR M, et al. Adsorption of methylene blue dye from aqueous solutions by modified pumice stone: kinetics and equilibrium studies[J]. Health Scope, 2013, 2(3): 136-144.

样品	元素质量分数/%
样品	C	O	N	Al	Si
Bent	20.71	51.54	0.93	8.64	18.17
BGO	40.09	35.71	0.58	6.05	13.57

样品	元素质量分数/%
样品	C	O	N	Al	Si
Bent	20.71	51.54	0.93	8.64	18.17
BGO	40.09	35.71	0.58	6.05	13.57

样品	总比表面积S_BET/m²·g^-1	孔径D_BJH/nm	孔容/cm³·g^-1
Bent	79.28	4.04	0.1513
GO	44.80	3.34	0.1069
BGO	95.79	3.88	0.1637

样品	总比表面积S_BET/m²·g^-1	孔径D_BJH/nm	孔容/cm³·g^-1
Bent	79.28	4.04	0.1513
GO	44.80	3.34	0.1069
BGO	95.79	3.88	0.1637

初始浓度 /mg·L^-1	伪一级反应速率模型			伪二级反应速率模型
初始浓度 /mg·L^-1	q_e/mg·g^-1	k₁/min^-1	r₁²	q_e/mg·g^-1	k₂/g·mg^-1·min^-1	r₂²
200	10.22	0.04	0.8691	199.60	0.290	0.99999
250	3.30	0.08	0.9640	248.76	0.010	0.99999
300	29.52	0.06	0.8951	299.40	0.007	0.99998