壳聚糖功能化磁性氧化石墨烯复合材料的制备及对甲基橙的吸附

黄文涛; 邓呈逊; 吉宇尘; 张典雅; 俞志敏

doi:10.13801/j.cnki.fhclxb.20200723.003

壳聚糖功能化磁性氧化石墨烯复合材料的制备及对甲基橙的吸附

doi: 10.13801/j.cnki.fhclxb.20200723.003

合肥学院生物食品与环境学院，合肥 230601

基金项目: 安徽高校自然科学研究项目重点项目(KJ2019A0827)；安徽省重点研发计划面上攻关项目(1804a09020096)；合肥学院科研发展基金项目(自然科学•第一批)重大项目(18ZR03ZDA)

详细信息

通讯作者:
邓呈逊，硕士，教授，硕士生导师，研究方向为环境功能材料　 E-mail：dcx@hfuu.edu.cn

中图分类号: X703；TQ424；TQ127.11
计量
- 文章访问数: 1276
- HTML全文浏览量: 491
- PDF下载量: 87
- 被引次数: 0
出版历程
- 收稿日期: 2020-05-21
- 录用日期: 2020-07-13
- 网络出版日期: 2020-07-23
- 刊出日期: 2021-04-08

Synthesis of chitosan functionalized magnetic graphene oxide composite and adsorption on methyl orange

School of Biology, Food and Environment, Hefei University, Hefei 230601, China

摘要

摘要: 用改进Hummers方法和水热法制备壳聚糖功能化磁性氧化石墨烯(CS/MGO)复合材料，通过SEM、FTIR、XRD、BET和振动样品磁强计(VSM)对材料结构和性能进行表征和测试，并对水中甲基橙(Methyl orange，MO)吸附研究。结果表明：氧化石墨烯(Graphene oxide，GO)与壳聚糖(Chitosan，CS)成功键合，热稳定性好，被壳聚糖修饰后比表面积为36.873 m²·g⁻¹，磁性粒子均匀分布在GO表面，磁性响应明显。考察pH值、MO初始浓度、CS/MGO复合材料添加量及再生性能对MO去除率的影响，结果表明：在pH=3、MO初使浓度为20 mg·L⁻¹、吸附材料为0.12 g·L⁻¹时，210 min后达到吸附平衡，经5次循环后为初使吸附容量的83.7%。吸附过程符合拟二级动力学模型，吸附等温线符合Langmuir模型，在298.15、303.15、308.15 K温度下最大吸附量分别为129.96、138.94、145.03 mg·g⁻¹；吸附热力学表明，吸附过程为吸热、熵增自发的吸附过程。
- 水热法 /
- 壳聚糖 /
- 氧化石墨烯 /
- 复合材料 /
- 吸附 /
- 甲基橙
Abstract: The chitosan/magnetic graphene oxide (CS/MGO) composites were synthesized by the modified Hummers and hydrothermal methods and applied as an adsorbent for the removal of methyl orange (MO). CS/MGO composite was characterized by SEM, XRD, BET, FTIR and a vibrating sample magnetometer (VSM). Results show that Fe₃O₄ nanoparticles mainly exist on the surface of graphene oxide and chitosan (CS) composite with less aggregation and a good magnetic response. In addition, the thermal stability is good, and the specific surface area of CS/MGO is 36.873 m²·g⁻¹. CS/MGO composite could be easily separated by magnetic separation and demonstrates good stability and reusability. The effects of pH, initial concentration of MO, CS/MGO composite amount and regeneration on the removal of MO were systematically investigated. The results reveal that the initial MO concentration of 20 mg·L⁻¹, CS/MGO composite amount of 0.12 g·L⁻¹, and pH=3 lead to the adsorption equilibrium after 210 min. CS/MGO composite maintains 83.7% of its maximum MO adsorption capacity after five consecutive cycles. The adsorption process conforms to the pseudo-second-order kinetic model, and the adsorption isotherms conform to the Langmuir model. The maximum adsorption amounts at 298.15, 303.15 and 308.15 K are 129.96, 138.94 and 145.03 mg·g⁻¹, respectively. The adsorption thermodynamics indicate that the adsorption process is endothermic; entropy increases the spontaneous adsorption process.
- hydrothermal method /
- chitosan /
- grapheme oxide /
- composites /
- adsorption /
- methyl orange

HTML全文

图 1 氧化石墨烯(GO)、磁性氧化石墨烯(MGO)、壳聚糖功能化磁性氧化石墨烯(CS/MGO)复合材料、Fe₃O₄和CS的XRD图谱

Figure 1. XRD patterns of graphene oxide (GO), magnetic graphene oxide (MGO), chitosan/magnetic graphene oxide (CS/MGO) composite, Fe₃O₄ and CS

下载: 全尺寸图片幻灯片

图 2 GO、MGO、Fe₃O₄、CS/MGO复合材料和CS的FTIR图谱

Figure 2. FTIR spectra of GO, MGO, Fe₃O₄, CS/MGO composite and CS

下载: 全尺寸图片幻灯片

图 3 MGO、Fe₃O₄、CS/MGO复合材料的SEM图像

Figure 3. SEM images of MGO, Fe₃O₄, CS/MGO composite

下载: 全尺寸图片幻灯片

图 4 CS/MGO复合材料和GO的TGA曲线

Figure 4. TGA curves of CS/MGO composite and GO

下载: 全尺寸图片幻灯片

图 5 GO、CS/MGO复合材料的N₂吸附-脱附及BJH孔径分布曲线

Figure 5. N₂ adsorption desorption curve and BJH pore size distribution of GO and CS/MGO composite

下载: 全尺寸图片幻灯片

图 6 CS/MGO复合材料的VSM磁滞回线

Figure 6. VSM magnetization curve of CS/MGO composite

下载: 全尺寸图片幻灯片

图 7 CS/MGO复合材料磁性效果图

Figure 7. Photographs of CS/MGO composite attracted by a magnet

下载: 全尺寸图片幻灯片

图 8 不同材料对甲基橙(MO)的吸附效果

Figure 8. Adsorption effect of different materials on methyl orange (MO)

下载: 全尺寸图片幻灯片

图 9 pH值对CS/MGO复合材料吸附MO和Zata电位的影响

Figure 9. Effect of pH value on the adsorption potential of methyl orange and Zata by CS/MGO composite

下载: 全尺寸图片幻灯片

图 10 CS/MGO复合材料添加量对吸附MO的影响

Figure 10. Effect of CS/MGO composite amount on the adsorption of MO

下载: 全尺寸图片幻灯片

图 11 吸附时间对CS/MGO复合材料吸附MO的影响

Figure 11. Effect of time on methyl orange adsorption by CS/MGO composite

下载: 全尺寸图片幻灯片

图 12 循环次数对CS/MGO复合材料吸附MO的影响

Figure 12. Effect of cycle times on the adsorption of MO by CS/MGO composite

下载: 全尺寸图片幻灯片

图 13 颗粒内扩散模型

Figure 13. Intraparticle diffusion model

下载: 全尺寸图片幻灯片

表 1 CS/MGO复合材料吸附MO动力学拟合参数(T=298.15 K)

Table 1. Kinetic parameters of adsorption of MO onto CS/MGO composite (T=298.15 K)

Model	Parameter	Value
Pesudo-first-order	Q_e(cal)/(mg·g⁻¹)	91.922
	K₁/10⁻²min⁻¹	4.656
	R²	0.9449
Pesudo-second-order	Q_e(cal)/(mg·g⁻¹)	102.399
	K₂/(10⁻⁴g·mg⁻¹·min⁻¹)	6.437
	R²	0.9921
Intra-particle diffusion	K_p/(mg·g⁻¹·min^−0.5)	4.724
	C	35.5936
	R²	0.8409
Notes: K₁, K₂, K_p—Psudo-first-order kinetic constant and Psudo-second-order kinetic constant and Intra-particle diffusion rate constant, respectively; Q_e(cal)—Calculation amount of MO removed per unit mass of adsorbent; C—Adsorption constant.

下载: 导出CSV

表 2 CS/MGO对MO吸附等温模型拟合结果

Table 2. Isotherm parameters for the adsorption of CS/MGO composite to MO

Temperature/K	Langmuir			Freundlich
Temperature/K	Q_m/(mg·g⁻¹)	K_L/(L·mg⁻¹)	R²	n/(mg·g⁻¹)	K_F/(mg·g⁻¹)	R²
298.15	129.96	0.228	0.996	1.993	29.865	0.972
303.15	138.94	0.247	0.996	2.051	34.479	0.984
308.15	145.03	0.263	0.996	2.156	38.205	0.983
Notes: Q_m—Langmuir adsorption maximum; K_L—Langmuir coefficient of distribution of the adsorption; K_F—Freundlich coefficient of distribution of the adsorption; n—Freundlich isotherm constant.

下载: 导出CSV

表 3 CS/MGO复合材料吸附MO热力学参数

Table 3. Thermodynamic parameters for the adsorption of MO onto CS/MGO composite

T/K	∆G^θ/(kJ·mol⁻¹)	∆H^θ/(kJ·mol⁻¹)	∆S^θ/(kJ·K⁻¹·mol⁻¹)
298.15	−7.92	16.60	82.34
303.15	−8.39
308.15	−8.74
Notes: ∆G^θ—Gibbs free energy variation of the adsorption process; ∆H^θ—Enthalpy change of the adsorption process; ∆S^θ—Entropy change of theadsorption process.

下载: 导出CSV

参考文献(28)

[1]	SUBBAIAHM V, KIM D S. Adsorption of methyl orange from aqueous solution by aminated pumpkin seed powder: Kinetics, isotherms, and thermodynamic studies[J]. Ecotoxicology and Environmental Safety,2016,128:109-117. doi: 10.1016/j.ecoenv.2016.02.016
[2]	FU L, BAI Y N, LU Y Z, et al. Degradation of organic pollutants by anaerobic methane-oxidizing microorganisms using methyl orange as example[J]. Journal of Hazardous Materials,2019,364:264-271. doi: 10.1016/j.jhazmat.2018.10.036
[3]	GAO M, WANG Z, YANG C, et al. Novel magnetic graphene oxide decorated with persimmon tannins for efficient adsorption of malachite green from aqueous solutions[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects,2019,566:48-57.
[4]	毕玉玺, 凌辉, 唐振平, 等. 磁性介孔TiO₂/氧化石墨烯复合材料的制备及其对U(Ⅵ)的吸附[J]. 复合材料学报, 2019, 36(9):2176-2186. BI Y X, LING H, TANG Z P, et al. Preparation of magnetic mesoporous TiO₂/graphene oxide composites and their adsorption for U(Ⅵ)[J]. Acta Materiae Compositae Sinica,2019,36(9):2176-2186(in Chinese).
[5]	CHENG Z, LIAO J, HE B, et al. One-step fabrication of graphene oxide enhanced magnetic composite gel for highly efficient dye adsorption and catalysis[J]. ACS Sustainable Chemistry & Engineering,2015,3(7):1677-1685.
[6]	OTHMANN H, ALIAS N H, SHAHRUDDIN M. Z, et al. Adsorption kinetics of methylene blue dyes onto magnetic grapheneoxide[J]. Journal of Environmental Chemical Engineering,2018,6(2):2803-2811. doi: 10.1016/j.jece.2018.04.024
[7]	LIU S, HUANG B, CHAI L, et al. Enhancement of As (V) ad-sorption from aqueous solution by a magnetic chitosan/biochar composite[J]. RSC Advances,2017,7(18):10891-10900. doi: 10.1039/C6RA27341F
[8]	LE T T N, LE V T, DAO M U, et al. Preparation of magnetic graphene oxide/chitosan composite beads for effective removal of heavy metals and dyes from aqueous solutions[J]. Chemical Engineering Communications,2019,206(10):1337-1352. doi: 10.1080/00986445.2018.1558215
[9]	XU, L, HUANG Y A, ZHU Q J, et al. Chitosan in molecularly-imprinted polymers: Current and future prospects[J]. International Journal of Molecular Sciences,2015,16(8):18328-18347. doi: 10.3390/ijms160818328
[10]	SUN L, YUAN Z, GONG W, et al. The mechanism study of trace Cr (VI) removal from water using Fe⁰nanorods modified with chitosan in porous anodic alumina[J]. Applied Surface Science,2015,328:606-613. doi: 10.1016/j.apsusc.2014.12.094
[11]	郜玉楠, 周历涛, 王静, 等. 壳聚糖/沸石分子筛复合吸附颗粒的制备与性能[J]. 复合材料学报, 2019, 36(3):701-707. GAO Y N, ZHOU L T, WANG J, et al. Preparation and performances of chitosan/zeolite molecular sieve composite adsorbed particles[J]. Acta Materiae Compositae Sinica,2019,36(3):701-707(in Chinese).
[12]	FAN L, LUO C, SUN M, et al. Preparation of novel magnetic chitosan/graphene oxide composite as effective adsorbents toward methylene blue[J]. Bioresource Technology,2012,114:703-706. doi: 10.1016/j.biortech.2012.02.067
[13]	丁杰, 沙焕伟, 赵双阳, 等. 磁性氧化石墨烯/壳聚糖制备及其对磺胺嘧啶吸附性能研究[J]. 环境科学学报, 2016, 36(10):3691-3700. DING J, SHA H W, ZHAO S Y, et al. Synthesis of graphene oxide/magnetite chitosan composite and adsorption performance for sulfadiazine[J]. Acta Scientiae Circumstantiae,2016,36(10):3691-3700(in Chinese).
[14]	李林波, 马键. 氧化石墨烯/改性磁性壳聚糖复合材料对Cu²⁺的吸附研究[J]. 化工新型材料, 2019, 47(8):261-264. LI L B, MA J. Study on adsorption of Cu²⁺by GO/modified magnetic chitosan composite[J]. New Chemical Materials,2019,47(8):261-264(in Chinese).
[15]	MARCANO D C, KOSYNKIN D V, BERLIN J M, et al. Improved synthesis of graphene oxide[J]. ACS Nano,2010,4(8):4806-4814. doi: 10.1021/nn1006368
[16]	CUI L M, WANG Y G, GAO L, et al. EDTA functionalized magnetic graphene oxide for removal of Pb(II), Hg(II) and Cu(II) in water treatment: Adsorption mechanism and separation property[J]. Chemical Engineering Journal,2015,281:1-10. doi: 10.1016/j.cej.2015.06.043
[17]	DUANH, LI L, WANG X, et al. β-Cyclodextrin/chitosan-magnetic graphene oxide-surface molecularly imprinted polymer nanocomplex coupled with chemiluminescence biosensing of bovine serum albumin[J]. RSC Advances,2015,5(84):68397-68403. doi: 10.1039/C5RA11061K
[18]	SUTAR D S, NARAYANAM P K, SINGH G, et al. Spectroscopic studies of large sheets of graphene oxide and reduced graphene oxide monolayers prepared by Langmuir-Blodgett technique[J]. Thin Solid Films,2012,520(18):5991-5996. doi: 10.1016/j.tsf.2012.05.018
[19]	常会, 范文娟, 曾成华, 等. 氨基功能化磁性氧化石墨烯吸附亚甲基蓝的性能探讨[J]. 冶金分析, 2019, 39(8):52-60. CHANG H, FAN W J, ZENG C H, et al. Discussion on adsorption property of amino-functionalized magnetic graphene oxide to methylene blue[J]. Metallurgical Analysis,2019,39(8):52-60(in Chinese).
[20]	龚新怀, 辛梅华, 李明春, 等. 磁性响应茶渣制备及其对水溶液中亚甲基蓝的吸附[J]. 化工进展, 2019, 38(2):1113-1121. GONG X H, XIN M H, LI M C, et al. Preparationof magnetically responsive tea waste andit's adsorption of methylene blue from aqueous[J]. Chemical Industry and Engineering Progress,2019,38(2):1113-1121(in Chinese).
[21]	ZHANG, Y, WEN, G, FAN, S, et al. Partially reduced and nitrogen-doped graphene oxides with phenylethylamine for high-performance supercapacitors[J]. Journal of Materials Science,2018,53(16):11715-11727. doi: 10.1007/s10853-018-2471-5
[22]	于长江, 王苗, 董心雨, 等. 海藻酸钙@Fe₃O₄/生物碳磁性复合材料的制备及其对Co(Ⅱ)的吸附性能和机制[J]. 复合材料学报, 2018, 35(6):1549-1557. YU C J, WANG M, DONG X Y, et al. Preparationand characterization of calcium alginate@Fe₃O₄/biochar magnetic microsphereand its adso[J]. Acta Materiae Compositae Sinica,2018,35(6):1549-1557(in Chinese).
[23]	姚时, 张鸣帅, 李林璇, 等. 茶渣负载纳米四氧化三铁复合材料制备及其对亚甲基蓝的吸附机理[J]. 环境化学, 2018, 37(1):96-107. doi: 10.7524/j.issn.0254-6108.2017050401 YAO S, ZHANG M S, LI L X, et al. Preparationof tea waste-nano Fe₃O₄ composite and its removal mechanism of methylene blue from aqueous solution[J]. Environmental Cheistry,2018,37(1):96-107(in Chinese). doi: 10.7524/j.issn.0254-6108.2017050401
[24]	朱脉勇, 陈齐, 童文杰, 等. 四氧化三铁纳米材料的制备与应用[J]. 化学进展, 2017, 29(11):1366-1394. ZHU M Y, CHEN Q, TONG W J, et al. Preparation and application of Fe₃O₄nanomaterials[J]. Progress in Chemistry,2017,29(11):1366-1394(in Chinese).
[25]	史月月, 单锐, 袁浩然. 改性稻壳生物炭对水溶液中甲基橙的吸附效果与机制[J]. 环境科学, 2019, 40(6):2783-2792. SHI Y Y, SHAN R, YUAN H R. Effect and mechanisms of methyl orange removal from aqueous solutions by modified riceshell biochar[J]. Environmental Science,2019,40(6):2783-2792(in Chinese).
[26]	常春, 刘天琪, 王瑀婷, 等. 水热法制备玉米叶基生物炭对亚甲基蓝的吸附性能研究[J]. 环境科学学报, 2017, 37(7):2680-2690. CHANG C, LIU T Q, WANG Y T, etal. Hydrothermal preparation of maize leaf based biochar and its adsorption performance for methylene blue[J]. Acta Scientiae Circumstantiae,2017,37(7):2680-2690(in Chinese).
[27]	吴艳, 罗汉金, 王侯. 改性木屑对水中刚果红的吸附性能研究[J]. 环境科学学报, 2014, 34(7):1680-1688. WU Y, LUO H J, WANG H. Adsorption properties of modified sawdust for conge red removal from wastewater[J]. Acta Scientiae Circumstantiae,2014,34(7):1680-1688(in Chinese).
[28]	布林朝克, 郭婷, 张邦文, 等. 部分还原氧化石墨烯-Fe₃O₄对水中Mn(Ⅱ)的快速去除[J]. 高等学校化学学报, 2017, 38(2):217-224. doi: 10.7503/cjcu20160664 BULIN C K, GUO T, ZHANG B W, et al. Fast removal of aqueous Mn(II) using partially reduced graphene oxide-Fe₃O₄[J]. Chemical Journal of Chinese Universities,2017,38(2):217-224(in Chinese). doi: 10.7503/cjcu20160664