氧化石墨烯/海藻酸钙水凝胶复合膜对水中Cd(II)的吸附

白成玲; 王磊; 朱振亚; 王旭东

doi:10.13801/j.cnki.fhclxb.20191016.001

氧化石墨烯/海藻酸钙水凝胶复合膜对水中Cd(II)的吸附

doi: 10.13801/j.cnki.fhclxb.20191016.001

白成玲¹,
王磊¹,
朱振亚^{1, 2, ,},
王旭东¹

1.
西安建筑科技大学　环境与市政工程学院陕西省膜分离重点实验室，陕西省环境工程重点实验室，西安 710055
2.
河北地质大学　水资源与环境学院河北省水资源可持续利用与开发重点实验室，石家庄 050031

基金项目: 陕西省重点科技创新团队计划(2017KCT-19-01); 陕西省重点产业链(群)项目(2017ZDCXL-GY-07-03); 西安市科技计划项目(201805033YD11CG17(3)); 陕西省技术创新引导专项(2018HJCG-18); 陕西省自然科学基础研究计划课题(2017JM5110)

详细信息

通讯作者:
朱振亚，博士，讲师，研究方向为膜法水处理　E-mail：dgjj1982@163.com

中图分类号: TB332
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出版历程
- 收稿日期: 2019-07-07
- 录用日期: 2019-09-18
- 网络出版日期: 2019-10-16
- 刊出日期: 2020-06-15

Adsorption of Cd(II) in water by graphene oxide/calcium alginate hydrogel composite membrane

1.
Key Laboratory of Membrane Separation of Shaanxi Province, Shaanxi Key Laboratory of Environment Engineering, School of Environmental and Municipal Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China
2.
Province Key Laboratory of Sustained Utilization and Development of Water Resources, School of Water Resources and Environment, Hebei GEO University, Shijiazhuang 050031, China

摘要

摘要: 将氧化石墨烯(GO)、致孔剂与海藻酸钠共混后与CaCl₂交联制备的GO/海藻酸钙（CA）水凝胶复合膜作为含重金属废水的吸附材料。采用SEM和TEM表征了复合膜的表面形貌及透射性能，且分析了GO的加入对复合膜的力学性能、平均孔径、水通量及表面官能团的影响。为探究GO/CA水凝胶复合膜的吸附性能，考察了其吸附Cd(II)的影响因素：pH（6~7）值、初始离子浓度、接触时间、温度（三者均正相关）。用FTIR、XPS在吸附前后对复合膜进行了表征；引入了吸附动力学和等温线模型分析其吸附机制。探究结果表明GO的加入提高了复合膜的力学性能、平均孔径及水通量；吸附过程遵循Langmuir等温线，属于单层吸附，拟合得到的最大吸附量为173.61 mg/g；伪一级和伪二级吸附动力学分别在低浓度和高浓度时能较好地描述吸附过程的动力学行为；吸附机制主要为物理作用力吸附和离子交换。经过5个连续的吸附-解吸循环证明了GO/CA水凝胶复合膜的可重复利用性。
- 氧化石墨烯 /
- 水凝胶 /
- 复合膜 /
- 吸附 /
- Cd(II)
Abstract: The crosslinked graphene oxide (GO)/calcium alginate (CA) hydrogel composite membranes, prepared by blending GO, porogenas as well as Na alginate hydrogel (SA), cross-linking with CaCl₂, were used as adsorbent for wastewater containing heavy metal ions. SEM and TEM were used to characterize the composite membranes. The influences of GO on the mechanical properties, average pore diameter, water flux and surface functional groups of the composite membrane were analyzed. To explore the adsorption performance of GO/CA hydrogel composite membrane, the influencing factors of Cd(II) adsorption including pH (6-7), initial ion concentration, contact time and temperature (all positively correlated) were investigated. The composite membranes before and after adsorption of Cd(II) were characterized by FTIR and XPS; The adsorption kinetics and adsorption isotherm model were introduced to analyze the adsorption mechanism. The results show that the introduction of GO improves the mechanical properties, average pore diameter and water flux of the composite membrane. The adsorption process follows the Langmuir isotherm, belonging to the monolayer adsorption. The maximum adsorption capacity is 173.61 mg/g. The pseudo-first and pseudo-second adsorption kinetics could describe the adsorption process at low and high concentration, respectively. The adsorption mechanism is mainly physical force adsorption and ion exchange. The recyclability of the GO/CA hydrogel composite membranes was demonstrated by five successive adsorption-desorption cycles.
- graphene oxide /
- hydrogel /
- composite membrane /
- adsorption /
- Cd(II)

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图 1 氧化石墨烯/海藻酸钙水凝胶( GO/CA)复合膜的表面形貌(a)、透视特征(b)及官能团的变化(c)

Figure 1. Surface morphology (a), perspective characteristics (b) and functional groups (c) of graphene oxide/calcium alginate hydrogel( GO/CA) hydrogel composite membrane

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图 2 GO (a)、pH ((b)、(c))、初始浓度(d)、温度(e)和循环次数(f)对GO/CA 膜吸附容量的影响

Figure 2. Effect of GO (a), pH ((b), (c)), initial concentration (d), temperature (e), cycle times (f) on adsorption capacity of GO/CA hydrogel composite membrane

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图 3 GO/CA水凝复合膜吸附动力学((a)~(d))及等温线((e)、(f))模型拟合图

Figure 3. Adsorption kinetics((a)-(d))and isotherm ((e), (f)) model fitting diagram of GO/CA hydrogel composite membrane

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图 4 GO/CA水凝胶复合膜的FTIR图谱

Figure 4. FTIR spectra of GO/CA hydrogel composite membrane

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图 5 GO/CA水凝胶复合膜吸附Cd(II)的XPS能谱

Figure 5. XPS spectra of GO/CA hydrogel composite membrane adsorption of Cd(II)

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表 1 CA膜和GO/CA水凝复合膜的渗透性能

Table 1. Permeability of CA membrane and GO/CA hydrogel composite membrane

Membrane	Mean pore size/nm	Poriness/%	Water flux/(L·m^-2h^-1)
CA	10.6	86.5	14.7
GO/CA	12.6	90.1	18.1

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表 2 CA膜和GO/CA水凝复合膜的力学性能

Table 2. Mechanical properties of the CA membrane and GO/CA hydrogel composite membrane

Membrane	Elongation at break/%	Fracture energy/(kJ·m⁻²)	Stress/MPa
CA	95	34	914
GO/CA	143	65	1 725

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表 3 Cd(II)的初始浓度C₀不同时GO/CA水凝复合膜吸附性能的动力学模型拟合参数

Table 3. Kinetic model parameters of GO/CA hydrogel composite membrane adsorption at different initial concentration C₀ of Cd(II)

C₀/(mg·L⁻¹)	Pseudo-first order kinetic model			Pseudo-second order kinetic model			Elovich model
C₀/(mg·L⁻¹)	k₁/min⁻¹	Q_e/(mg·g⁻¹)	R²	k₂/min⁻¹	Q_e/(mg·g⁻¹)	R²	A	B	R²
10	0.1530	51.37	0.9999	0.0826	57.28	0.9874	34.53	−4.497	0.964 1
40	0.3131	140.0	0.9919	0.0116	147.5	0.9993	113.7	−7.579	0.9785
80	0.4497	211.9	0.9804	0.0066	224.1	0.9993	135.3	−22.17	0.9714
Notes: C₀—Initial concentration of Cd(II); R²—Goodness; Q_e—Adsorption capacity at adsorption equilibrium; k₁, k₂ and A—Constant of kinetic models, respectively; B—Coefficient of elovich kinetic models.

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表 4 GO/CA水凝胶复合膜吸附Cd(II)的吸附等温线模型参数

Table 4. Isothermal adsorption model parameters of Cd(II) adsorbed by GO/CA hydrogel composite membrane

Temper- ature/K	Freundlich isotherm			Langmuir isotherm
Temper- ature/K	k_f	N	R²	k_l	Q_m/(mg·g⁻¹)	R²
288	13.81	1.787	0.9445	0.1766	85.40	0.9914
303	47.99	2.770	0.9618	0.2168	161.8	0.9952
318	47.67	3.147	0.9589	0.3146	173.6	0.9981
Notes: k_f—Capacity factor of Freundlich; N—Liquid phase adsorption isotherm index of Freundlich; k₁—Langmuir constant of affinity point; Q_m—Adsorption capacity of single layer.

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