海藻酸钠-羧甲基纤维素-氧化石墨烯复合气凝胶的制备及其对Pb(II)的吸附

田甜; 付义乐; 关丽; 王溢源; 周军

doi:10.13801/j.cnki.fhclxb.20230314.001

海藻酸钠-羧甲基纤维素-氧化石墨烯复合气凝胶的制备及其对Pb(II)的吸附

doi: 10.13801/j.cnki.fhclxb.20230314.001

西安建筑科技大学　化学与化工学院，西安 710055

基金项目: 国家自然科学基金(21807086)；陕西省自然科学基础研究计划项目(2022JM-096)

详细信息

通讯作者:
付义乐，博士，副教授，硕士生导师，研究方向为功能材料的制备及性能研究　E-mail: fuyile@xauat.edu.cn

中图分类号: X703；TQ424
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出版历程
- 收稿日期: 2022-11-29
- 修回日期: 2023-02-20
- 录用日期: 2023-03-03
- 网络出版日期: 2023-03-15
- 刊出日期: 2023-10-15

Preparation of sodium alginate-carboxymethyl cellulose-graphene oxide composite aerogel for adsorption of Pb(II) ion

School of Chemistry and Chemical Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China

Funds: National Natural Science Foundation of China (21807086); Natural Science Basic Research Program of Shaanxi (2022JM-096)

摘要

摘要: 目前，开发具有优异吸附性能、可持续使用和绿色环保的吸附剂仍然是水污染治理领域的焦点问题。因此，本研究以海藻酸钠(SA)、羧甲基纤维素(CMC)和氧化石墨烯(GO)为原料，通过简单的溶胶-凝胶法结合冷冻干燥，构建了具有三维多孔网络结构的SA-CMC-GO复合气凝胶。利用SEM、FTIR、XRD等对SA-CMC-GO复合气凝胶的微观形貌、官能团结构等进行表征分析。以水中Pb²⁺为吸附对象，通过一系列间歇吸附实验，探究了各种因素(pH、介质温度、接触时间等)对吸附剂去除水体中Pb²⁺的影响。结果表明，在pH值2~5的范围内，复合气凝胶对Pb²⁺的吸附量随着pH的升高而升高；复合气凝胶对于Pb²⁺的吸附过程属于自发放热过程并遵循Langmuir吸附等温模型，其最大吸附量为272.5 mg·g⁻¹；动力学研究表明，SA-CMC-GO复合气凝胶对Pb²⁺具有较快的吸附速率，可在60 min内达平衡并符合准二级动力学模型；此外，经过5次吸附-脱附试验，复合气凝胶仍对Pb²⁺保持较高的吸附性能。SA-CMC-GO复合气凝胶可以作为一种高效、快速的吸附剂用于从水体中去除Pb²⁺。
- 气凝胶 /
- 海藻酸钠 /
- 羧甲基纤维素 /
- 氧化石墨烯 /
- 吸附
Abstract: Exploiting adsorbents with excellent adsorption activity, good durability and environment friendly is still the core focus of water pollution treatment. Herein, in this study, sodium alginate (SA), carboxymethyl cellulose (CMC), and graphene oxide (GO) were used as raw materials to frame a SA-CMC-GO composite aerogel with a 3D network structure by a sol-gel and freeze-drying method. The functional group structure and microstructure of SA-CMC-GO composite aerogel were tested and analyzed by SEM, FTIR and XRD. Various parameters affecting the removal of Pb²⁺ such as pH, temperature and contact time were optimized by using a series of batch adsorption experiments. The results show that the adsorption amount of Pb²⁺ by the composite aerogel increases with the increase of pH=2-5. The adsorption process is a spontaneous exothermic process and the experimental data of the adsorption process are more fitted to Langmuir isotherm, the theoretical maximum adsorption capacity of Pb²⁺ on SA-CMC-GO composite aerogel is 272.5 mg·g⁻¹. Adsorption kinetics studies indicate the adsorption of Pb²⁺ by the SA-CMC-GO composite aerogel shows rapid uptake rates and reaches equilibrium within 60 min. The pseudo-second-order kinetic model coincides with the adsorption behavior of the composite aerogel. Furthermore, the composite aerogel exhibited better reusability for five adsorption and desorption cycles with highly adsorption properties. The results imply that the new SA-CMC-GO composite aerogel could be potentially applied as an effective and rapid adsorbent for Pb²⁺ removal from aqueous solutions.
- aerogel /
- sodium alginate /
- carboxymethyl cellulose /
- graphene oxide /
- adsorption

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图 1 海藻酸钠-羧甲基纤维素-氧化石墨烯(SA-CMC-GO)复合气凝胶制备流程

Figure 1. Sodium alginate-carboxymethyl cellulose-graphene oxide (SA-CMC-GO) composite aerogel preparation process

T—Temperature; t—Time

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图 2 ((a)、(b)) CMC-GO复合气凝胶的SEM图像；SA-CMC-GO复合气凝胶的SEM图像((c)、(d))和EDS能谱(e)

Figure 2. ((a), (b)) SEM images of CMC-GO composite aerogel; SEM images ((c), (d)) and EDS mapping (e) of SA-CMC-GO composite aerogel

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图 3 CMC、GO、SA、SA-CMC-GO复合气凝胶的FTIR图谱

Figure 3. FTIR spectra of CMC, GO, SA and SA-CMC-GO composite aerogel

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图 4 CMC气凝胶和SA-CMC-GO复合气凝胶的XRD图谱

Figure 4. XRD patterns of CMC aerogel and SA-CMC-GO composite aerogel

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图 5 SA-CMC-GO复合气凝胶的XPS图谱：(a) 全谱；(b) C1s；(c) O1s

Figure 5. XPS spectra of SA-CMC-GO composite aerogel: (a) Full spectrum; (b) C1s; (c) O1s

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图 6 溶液pH与SA-CMC-GO复合气凝胶吸附Pb²⁺去除率和吸附量的关系

Figure 6. Relationship between solution pH and removal rate and adsorption capacity of Pb²⁺ by SA-CMC-GO composite aerogel

q_e—Equilibrium adsorption capacity

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图 7 吸附时间与SA-CMC-GO复合气凝胶对Pb²⁺的吸附量的关系

Figure 7. Relationship between adsorption time and the adsorption capacity of Pb²⁺ adsorbed by SA-CMC-GO composite aerogel

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图 8 温度与SA-CMC-GO复合气凝胶对Pb²⁺的吸附量的关系

Figure 8. Relationship between temperature and the adsorption capacity of Pb²⁺ adsorbed by SA-CMC-GO composite aerogel

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图 9 SA-CMC-GO复合气凝胶吸附Pb²⁺：(a) 准一级动力学模型；(b) 准二级动力学模型；(c) 粒子内扩散模型

Figure 9. Pb²⁺ adsorption by SA-CMC-GO composite aerogel: (a) Pseudo-first-order kinetic model; (b) Pseudo-second-order kinetic model; (c) Intra-particle diffusion model

q_t—Adsorption capacity at time t

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图 10 SA-CMC-GO复合气凝胶吸附Pb²⁺：(a) Langmuir模型；(b) Freundlich模型

Figure 10. SA-CMC-GO composite aerogel on Pb²⁺: (a) Langmuir model; (b) Freundlich model

c_e—Concentration at adsorption equilibrium

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图 11 循环次数与SA-CMC-GO复合气凝胶对Pb²⁺去除率的关系

Figure 11. Relationship between cycle times and the Pb²⁺ removal rate of SA-CMC-GO composite aerogel

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图 12 SA-CMC-GO复合气凝胶对Pb²⁺的吸附原理图

Figure 12. Mechanism of the adsorption of Pb²⁺ by SA-CMC-GO composite aerogel

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表 1 元素的原子分数

Table 1. Atomic fraction of the element

Atomic fraction/at%
C		O			Na
C—C	C—O	C=O	C—O	COO⁻	—
65.55	10.63	4.88	19.23	1.83	1.87

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表 2 不同吸附剂对Pb²⁺的平衡吸附时间

Table 2. Equilibrium adsorption time of Pb²⁺ by different adsorbents

Adsorbent	Time/min	Ref.
DGO/CMC	550	[3]
GO/CMC	600	[21]
NSC	150	[25]
Cell@PEI	240	[26]
NPCS-PEI	120	[27]
SA-CMC-GO	60	This study
Notes: DGO—Functionalized graphene oxide; NSC—Nano-cellulose/sodium alginate/carboxymethyl chitosan aerogel; Cell@PEI—Amino-modified cellulose aerogel; NPCS-PEI—N-methylene phosphonic acid chitosan.

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表 3 SA-CMC-GO复合气凝胶对Pb²⁺的吸附热力学相关参数

Table 3. Thermodynamically relevant parameters for the adsorption of Pb²⁺ by SA-CMC-GO composite aerogel

T/K	ΔG/(kJ·mol⁻¹)	ΔS/(kJ·mol⁻¹·K⁻¹)	ΔH/(kJ·mol⁻¹)
303	−8.297	−0.08298	−33.44
308	−7.882
313	−7.467
Notes: T—Temperature; ΔH—Enthalpy change; ΔS—Entropy change; ΔG—Gibbs free energy change.

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表 4 SA-CMC-GO复合气凝胶对Pb²⁺的吸附动力学拟合参数

Table 4. Fitting parameters for the kinetics of Pb²⁺ adsorption by SA-CMC-GO composite aerogel

Pseudo-first-order kinetic model			Pseudo-second-order kinetic model
q_e/(mg·g⁻¹)	k₁/min⁻¹	R²	q_e/(mg·g⁻¹)	k₂/(g·mg⁻¹·min⁻¹)	R²
71.71	0.02374	0.7546	230.9	3.576×10⁻⁴	0.9942
Notes: R²—Linear correlation coefficient; k₁—Pseudo-first-order kinetic constant; k₂—Pseudo-second-order kinetic constant.

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表 5 SA-CMC-GO复合气凝胶吸附Pb²⁺的粒子内扩散模型拟合参数

Table 5. Fitting parameters for the intra-particle diffusion model for Pb²⁺ adsorption by SA-CMC-GO composite aerogel

k₁/ (mg·g⁻¹·min^0.5)	R₁²	k₂/ (mg·g⁻¹·min^0.5)	R₂²	k₃/ (mg·g⁻¹·min^0.5)	R₃²
37.70	0.9920	11.13	0.9917	0.5009	0.9923
Note: k_i—Intra-particle diffusion rate constant, i=1, 2, 3.

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表 6 SA-CMC-GO复合气凝胶吸附Pb²⁺的等温线吸附Langmuir模型和Freundlich模型参数

Table 6. Isothermal adsorption parameters of SA-CMC-GO composite aerogel for Pb²⁺ adsorption by Langmuir model and Freundlich model

Langmuir model			Freundlich model
q_e/ (mg·g⁻¹)	K_L	R²	K_F	n	R²
272.5	0.4809	0.9974	155.1	7.125	0.6719
Notes: K_L—Langmuir adsorption coefficient; K_F—Freundlich adsorption coefficient; n—Adsorption strength constant.

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参考文献(33)

[1]	YANG W X, HAN Y, LI C H, et al. Shapeable three-dimensional CMC aerogels decorated with Ni/Co-MOF for rapid and highly efficient tetracycline hydrochloride removal[J]. Chemical Engineering Journal,2019,375:122076. doi: 10.1016/j.cej.2019.122076
[2]	ZHANG S Y, HAN X S, CAI H Z, et al. Aramid nanofibers/WS₂ nanosheets co-assembled aerogels for efficient and stable Pb (II) adsorption in harsh environments[J]. Chemical Engineering Journal,2022,450:138268. doi: 10.1016/j.cej.2022.138268
[3]	LUO J Q, FAN C J, ZHOU X D. Functionalized graphene oxide/carboxymethyl chitosan composite aerogels with strong compressive strength for water purification[J]. Journal of Applied Polymer Science,2020,138(12):50065-50079.
[4]	李继丰, 闫文静, 方婷, 等. C6位羧基纤维素制备及其对Cu²⁺吸附性能[J]. 复合材料学报, 2022, 39(3):1280-1290. LI Jifeng, YAN Wenjing, FANG Ting, et al. Preparation of C6 carboxylic cellulose and adsorption for Cu²⁺[J]. Acta Materiae Compositae Sinica,2022,39(3):1280-1290(in Chinese).
[5]	LIU Q, LI S S, YU H H, et al. Covalently crosslinked zirconium-based metal-organic framework aerogel monolith with ultralow-density and highly efficient Pb(II) removal[J]. Journal of Colloid and Interface Science,2020,561:211-219. doi: 10.1016/j.jcis.2019.11.074
[6]	徐晓燕, 张鹏, 朱静, 等. 水环境中天然有机物对纳米颗粒吸附铅和镉的不同作用[J]. 环境化学, 2021, 40(2):571-582. doi: 10.7524/j.issn.0254-6108.2020052501 XU Xiaoyan, ZHANG Peng, ZHU Jing, et al. The varying roles of natural organic matters on nanoparticles adsorbing Cd²⁺ and Pb²⁺ in water environment[J]. Environmental Chemistry,2021,40(2):571-582(in Chinese). doi: 10.7524/j.issn.0254-6108.2020052501
[7]	牛乙涛, 包国庆, 吴纯鑫, 等. 功能化纳米复合材料Fe₃O₄@SiO₂-3-氨丙基三甲氧基硅烷的制备及其对Pb(II)的吸附[J]. 复合材料学报, 2023, 40(6): 3350-3365. NIU Yitao, BAO Guoqing, WU Chunxin, et al. Preparation of functionalized nanocomposites Fe₃O₄@SiO₂-3-aminopropyltrimethoxysilane and its adsorption to Pb(II)[J]. Acta Materiae Compositae Sinica, 2023, 40(6): 3350-3365(in Chinese).
[8]	JIAO G J, MA J L, ZHANG J Q, et al. High-efficiency capture and removal of phosphate from wastewater by 3D hierarchical functional biomass-derived carbon aerogel[J]. Science of the Total Environment,2022,827:154343. doi: 10.1016/j.scitotenv.2022.154343
[9]	MO L T, TAN Y, SHEN Y L, et al. Highly compressible nanocellulose aerogels with a cellular structure for high-performance adsorption of Cu(II)[J]. Chemosphere,2022,291:132887. doi: 10.1016/j.chemosphere.2021.132887
[10]	LEI C Y, WEN F B, CHEN J M, et al. Mussel-inspired synthesis of magnetic carboxymethyl chitosan aerogel for removal cationic and anionic dyes from aqueous solution[J]. Polymer,2021,213:123316. doi: 10.1016/j.polymer.2020.123316
[11]	GE X S, SHAN Y N, WU L, et al. High-strength and morphology-controlled aerogel based on carboxymethyl cellulose and graphene oxide[J]. Carbohydrate Polymers,2018,197:277-283. doi: 10.1016/j.carbpol.2018.06.014
[12]	QIANG X H, GUO X, SU H X, et al. In situ nanoarchitectonics of magnesium hydroxide particles for property regulation of carboxymethyl cellulose/poly(vinyl alcohol) aerogels[J]. RSC Advances,2021,11(56):35197-35204. doi: 10.1039/D1RA06556D
[13]	翟红侠, 赵越, 李超凡, 等. 氨基改性SiO₂气凝胶去除Cu(II)的性能与机制[J]. 复合材料学报, 2023, 40(8): 3981-3992. ZHAI Hongxia, ZHAO Yue, LI Chaofan, et al. Performance and mechanism of the amine-modified silica aerogel for the removal of Cu(II)[J]. Acta Materiae Compositae Sinica, 2023, 40(8): 3981-3992(in Chinese).
[14]	张春梅, 杨婷婷, 陆桂花, 等. 纳米纤维素/壳聚糖气凝胶对六价铬的吸附性能[J]. 功能材料, 2022, 53(10):10180-10184. ZHANG Chunmei, YANG Tingting, LU Guihua, et al. Adsorption properties of cellulose nanocrystalline/chitosan aerogels for hexavalent chromium[J]. Journal of Functional Materials,2022,53(10):10180-10184(in Chinese).
[15]	HAN X H, LIANG J C, FUKUDA S, et al. Sodium alginate-silica composite aerogels from rice husk ash for efficient absorption of organic pollutants[J]. Biomass and Bioenergy,2022,159:106424. doi: 10.1016/j.biombioe.2022.106424
[16]	DONG K Q, XU K J, WEI N S, et al. Three-dimensional porous sodium alginate/gellan gum environmentally friendly aerogel: Preparation, characterization, adsorption, and kinetics studies[J]. Chemical Engineering Research and Design,2022,179:227-236. doi: 10.1016/j.cherd.2022.01.027
[17]	GAO C, WANG X L, AN Q D, et al. Synergistic preparation of modified alginate aerogel with melamine/chitosan for efficiently selective adsorption of lead ions[J]. Carbohydrate Polymers,2021,256:117564. doi: 10.1016/j.carbpol.2020.117564
[18]	KONG Y, ZHUANG Y, HAN K, et al. Enhanced tetracycline adsorption using alginate-graphene-ZIF67 aerogel[J]. Colloids and Surfaces A,2020,588:124360. doi: 10.1016/j.colsurfa.2019.124360
[19]	CHEN P, XIE F W, TANG F Z, et al. Glycerol plasticisation of chitosan/carboxymethyl cellulose composites: Role of interactions in determining structure and properties[J]. International Journal of Biological Macromolecules,2020,163:683-693. doi: 10.1016/j.ijbiomac.2020.07.004
[20]	ELTAWEIL A S, ELGARHY G S, EL-SUBRUITI G M, et al. Carboxymethyl cellulose/carboxylated graphene oxide composite microbeads for efficient adsorption of cationic methylene blue dye[J]. International Journal of Biological Macromolecules,2020,154:307-318. doi: 10.1016/j.ijbiomac.2020.03.122
[21]	LUO J Q, FAN C J, XIAO Z, et al. Novel graphene oxide/carboxymethyl chitosan aerogels via vacuum-assisted self-assembly for heavy metal adsorption capacity[J]. Colloids and Surfaces A,2019,578:123584. doi: 10.1016/j.colsurfa.2019.123584
[22]	LI J J, TAN S C, XU Z Y. Anisotropic nanocellulose aerogel loaded with modified UiO-66 as efficient adsorbent for heavy metal ions removal[J]. Nanomaterials,2020,10(6):1114. doi: 10.3390/nano10061114
[23]	XU W L, CHEN S, ZHU Y N, et al. Preparation of hyperelastic graphene/carboxymethyl cellulose composite aerogels by ambient pressure drying and its adsorption applications[J]. Journal of Materials Science,2020,55(24):10543-10557. doi: 10.1007/s10853-020-04720-5
[24]	LIU P, CHEN M G, XIONG C G, et al. Flexible and highly sensitive graphene/carboxymethyl cellulose films for bending sensing[J]. Journal of Materials Science: Materials in Electronics,2020,31(17):14118-14127. doi: 10.1007/s10854-020-03966-8
[25]	LI W Q, ZHANG L P, HU D, et al. A mesoporous nanocellulose/sodium alginate/carboxymethyl-chitosan gel beads for efficient adsorption of Cu²⁺ and Pb²⁺[J]. International Journal of Biological Macromolecules,2021,187:922-930. doi: 10.1016/j.ijbiomac.2021.07.181
[26]	李琦琪, 杨桂芳, 刘以凡, 等. 氨基改性纤维素气凝胶吸附Pb²⁺的研究[J]. 纤维素科学与技术, 2022, 30(1):34-46. LI Qiqi, YANG Guifang, LIU Yifan, et al. Adsorption behavior of Pb²⁺ on amino-modified cellulose aerogel[J]. Journal of Cellulose Science and Technology,2022,30(1):34-46(in Chinese).
[27]	LIU T, GOU S H, HE Y, et al. N-methylene phosphonic chitosan aerogels for efficient capture of Cu²⁺ and Pb²⁺ from aqueous environment[J]. Carbohydrate Polymers,2021,269:118355. doi: 10.1016/j.carbpol.2021.118355
[28]	张宏伟, 谢鸿, 肖欣荣, 等. 不同氧化程度氧化石墨烯/聚乙烯醇气凝胶对亚甲基蓝的吸附[J]. 复合材料学报, 2021, 38(9):2788-2795. doi: 10.13801/j.cnki.fhclxb.20201203.002 ZHANG Hongwei, XIE Hong, XIAO Xinrong, et al. Adsorption of methylene blue by graphene oxide/polyvinyl alcohol aerogels with different oxidation degrees[J]. Acta Materiae Compositae Sinica,2021,38(9):2788-2795(in Chinese). doi: 10.13801/j.cnki.fhclxb.20201203.002
[29]	YANG P, YANG L, WANG Y, et al. An indole-based aerogel for enhanced removal of heavy metals from water via the synergistic effects of complexation and cation-π interactions[J]. Journal of Materials Chemistry A,2019,7(2):531-539. doi: 10.1039/C8TA07326K
[30]	WANG Z G, SONG L, WANG Y Q, et al. Lightweight UiO-66/cellulose aerogels constructed through self-crosslinking strategy for adsorption applications[J]. Chemical Engineering Journal,2019,371:138-144. doi: 10.1016/j.cej.2019.04.022
[31]	HOSSEINI H, ZIRAKJOU A, MCCLEMENTS D J, et al. Removal of methylene blue from wastewater using ternary nanocomposite aerogel systems: Carboxymethyl cellulose grafted by polyacrylic acid and decorated with graphene oxide[J]. Journal of Hazardous Materials,2022,421:126752. doi: 10.1016/j.jhazmat.2021.126752
[32]	ZHOU Y Q, GAO Y, WANG H L, et al. Versatile 3D reduced graphene oxide/poly(amino-phosphonic acid) aerogel derived from waste acrylic fibers as an efficient adsorbent for water purification[J]. Science of the Total Environment,2021,776:145973. doi: 10.1016/j.scitotenv.2021.145973
[33]	XIANG C, WANG C, GUO R H, et al. Synthesis of carboxymethyl cellulose-reduced graphene oxide aerogel for efficient removal of organic liquids and dyes[J]. Journal of Materials Science,2019,54(2):1872-1883. doi: 10.1007/s10853-018-2900-5