CaC<sub>2</sub>O<sub>4</sub>-直接枣红B/壳聚糖复合材料的制备及对乙基紫的吸附性能

赵丹华; 张少丽; 陈作义; 柳晓俊; 王柯; 王峰倩; 雷月清

doi:10.13801/j.cnki.fhclxb.20210506.003

CaC₂O₄-直接枣红B/壳聚糖复合材料的制备及对乙基紫的吸附性能

doi: 10.13801/j.cnki.fhclxb.20210506.003

广东第二师范学院　化学系，广州 510303

基金项目: 广东省普通高校特色创新项目(2019KTSCX118)；广东省大学生创新实验项目(S201914278027；S202014278021)；广东省普通高校进材料与节能减排工程技术开发中心(2016GCZX007)

详细信息

通讯作者:
赵丹华，博士，教授，研究方向为环境功能材料的结构设计与合成　E-mail：zhaodanhua@gdei.edu.cn

中图分类号: X131.2
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出版历程
- 收稿日期: 2021-02-25
- 修回日期: 2021-04-06
- 录用日期: 2021-04-12
- 网络出版日期: 2021-05-07
- 刊出日期: 2022-02-01

Preparation of CaC₂O₄-direct claret B/chitosan composite materials and adsorption properties for ethyl violet

Department of Chemistry, Guangdong University of Education, Guangzhou 510303, China

摘要

摘要: 以壳聚糖(CTS)和草酸钙-直接枣红B(CaC₂O₄-DB)杂化材料为原料，采用共混原位固载法制备草酸钙-直接枣红B/壳聚糖(CaC₂O₄-DB/CTS)复合材料。利用SEM、BET和FTIR对 CTS 和CaC₂O₄-DB/CTS的形貌及结构等进行表征分析，CaC₂O₄-DB的固载并未改变CTS的形貌结构，仅增加其比表面积和结合位点。详细考察了吸附时间、乙基紫 (Ethyl violet，EV)初始浓度、溶液pH及温度等因素对CaC₂O₄-DB/CTS吸附EV的影响，初步探讨了CaC₂O₄-DB/CTS对EV的吸附动力学和吸附热力学行为。结果表明，CaC₂O₄-DB/CTS吸附EV在3 h内达到吸附平衡，且pH=8、投加量为6 g/L时，25℃的100 mg/L EV溶液(化学需氧量(COD)为187 mg/L)染料去除率高达95%，COD去除率达90%以上。该吸附过程是自发进行的，符合Langmuir等温线模型和准二级动力学模型，其吸附过程由颗粒内扩散和化学吸附共同控制。
- 壳聚糖 /
- 复合材料 /
- 吸附 /
- 动力学 /
- 热力学 /
- 乙基紫
Abstract: A composite adsorbent of CaC₂O₄-DB/CTS was prepared using chitosan (CTS) and the hybrid materials of CaC₂O₄ and direct claret B (CaC₂O₄-DB/CTS) by the method of blending in-situ immobilization. CTS and CaC₂O₄-DB/CTS were characterized by SEM, BET and FTIR. The immobilization of CaC₂O₄-DB only increases the specific surface area and binding sites without changing the morphology and structure of CTS. The effects of adsorption time, the initial concentration of ethyl violet (EV), pH and temperature of the solution on the adsorption properties of CaC₂O₄-DB/CTS composite material were investigated in detail, and the adsorption kinetics and thermodynamic behavior of EV on CaC₂O₄-DB/CTS were preliminarily discussed. The results show that the removal rate of dye and chemical oxygen demand (COD) reach 95% and 90% for 100 mg/L EV solution (COD is 187 mg/L), respectively, under conditions of room temperature, CaC₂O₄-DB/CTS dosage of 6 g/L, adsorption time of 3 h and pH=8. The adsorption behavior of EV by the adsorbent is spontaneous and in accordance with Langmuir model and the quasi-second-order kinetic model. The adsorption process is controlled by intra-particle diffusion and the chemical adsorption.
- chitosan /
- composite materials /
- adsorption /
- kinetics /
- thermodynamics /
- ethyl violet

HTML全文

图 1 各种材料SEM图像：(a) 壳聚糖(CTS)材料表面；(b) CTS材料切面；(c) CaC₂O₄-直接枣红B(DB)/CTS材料表面；(a₁) CTS材料表面局部放大图；(b₁) CTS材料切面局部放大图；(c₁) CaC₂O₄-DB/CTS材料切面；(d) CaC₂O₄-DB材料

Figure 1. SEM images of chitosan (CTS) ((a), (b)), CaC₂O₄-direct claret B (DB)/CTS (c) and CaC₂O₄-DB (d), area of CaC₂O₄-DB materials (a₁), CTS materials (b₁), CaC₂O₄-DB/CTS materials (c₁)

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图 2 CTS及CaC₂O₄-DB/CTS材料的FTIR图谱

Figure 2. FTIR spectra of CTS and CaC₂O₄-DB/CTS materials

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图 3 CaC₂O₄-DB/CTS投加量对乙基紫(EV)吸附的影响(100 mg·L⁻¹ EV)

Figure 3. Effect of CaC₂O₄-DB/CTS dosage on adsorption of ethyl violet (EV) (100 mg·L⁻¹ EV)

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图 4 EV初始浓度对CaC₂O₄-DB/CTS吸附的影响

Figure 4. Effect of initial concentration of EV on CaC₂O₄-DB/CTS adsorption

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图 5 吸附时间对CaC₂O₄-DB/CTS吸附效果的影响

Figure 5. Effect of contact time on CaC₂O₄-DB/CTS adsorption

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图 6 温度对CaC₂O₄-DB/CTS吸附效果的影响

Figure 6. Effect of temperature of EV on CaC₂O₄-DB/CTS adsorption

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图 7 pH对CaC₂O₄-DB/CTS吸附效果的影响

Figure 7. Effect of pH of EV on CaC₂O₄-DB/CTS adsorption

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图 8 CaC₂O₄-DB/CTS对EV吸附颗粒内扩散动力学模型拟合曲线

Figure 8. Fitting curve of intra-particle kinetic model for the adsorption of EV on CaC₂O₄-DB/CTS

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表 1 动边界模型拟合参数

Table 1. Parameters of moving boundary model Rate controlling step

Moving boundary model Rate controlling step	k	R²
Liquid film diffusion	0.01217	0.9643
Intraparticle diffusion	0.00280	0.9341
Chemical reaction	0.00196	0.9319
Notes: k—Constant of rate; R²—Fitting coefficients.

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表 2 CaC₂O₄-DB/CTS吸附EV各吸附动力学方程的参数

Table 2. Kinetics parameters of kinetic models for the adsorption of EV on CaC₂O₄-DB/CTS

First-order kinetic model			Second-order kinetic model			Elovich model
q_e/(mg·g⁻¹)	K₁/min⁻¹	R²	q_e/(mg·g⁻¹)	K₂/(g·mg⁻¹·min⁻¹)	R²	q_e/(mg·g⁻¹)	α/(g·mg ⁻¹·min⁻¹)	R²
13.22	0.0204	0.9682	32.15	0.0311	0.9995	30.63	109.57	0.9858
Notes：q_e—Equilibrium adsorption capacity; q_t—Adsorption capacity at time t; k_l—Rate constant of the pseudo-first-order model; k₂—Rate constant of the pseudo-second-order model; β—Desorption constant.

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表 3 CaC₂O₄-DB/CTS对EV吸附颗粒内扩散模型参数

Table 3. Parameters of intra-particle kinetic model for the adsorption of EV on CaC₂O₄-DB/CTS

The first step			>The second step			>The third step
>q_t=1.765t^1/2+14.51			>q_t=0.942t^1/2+19.45			>q_t=0.209t^1/2+28.19
k_p	C	R²	k_p	C	R²	k_p	C	R²
1.765	14.51	0.9933	0.942	19.45	0.9915	0.209	28.19	0.9999
Notes：k_p—Constant intra-particle diffusion rate; C—Constant of the reaction boundary layer effect.

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表 4 CaC₂O₄-DB/CTS对EV等温吸附线参数

Table 4. Isotherm parameters for adsorption of EV on CaC₂O₄-DB/CTS

T/K	Langmuir model			Freundlich model			D-R model
T/K	q_m/(mg·g⁻¹)	K_L/(L·mg⁻¹)	R²	K_F/(mg·g⁻¹)· (L·mg⁻¹)^1/ⁿ	n	R²	k/(mol²·kJ⁻²)	R²	ε/(kJ·mol⁻¹)
288.15	40.65	0.0768	0.9964	7.72	2.75	0.9842	0.4671	0.9429	5.17
298.15	45.25	0.0959	0.9952	8.85	2.64	0.9285	0.4046	0.9794	5.96
308.15	51.81	0.1092	0.9980	9.62	2.40	0.9458	0.3054	0.9883	7.92
Notes: T—Temperature; q_m—Maximumadsorption capacity; K_L—Langmuir characteristic constant; K_F—Freundlich characteristic constant; n—Freundlich characteristic constant; k—Constant of adsorption energy; ε—Adsorption potential energy.

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表 5 CaC₂O₄-DB/CTS材料吸附EV的热力学参数

Table 5. Isotherm parameters for adsorption of EV on CaC₂O₄-DB/CTS

C₀/(mg·L⁻¹)	T/K	ΔG/(kJ·mol⁻¹)	ΔH/(kJ·mol⁻¹)	ΔS/(J·(mol·K)⁻¹)
125	288.15-308.15	−2.204 - −4.412	27.5228	0.1031
150		−1.598 - −3.393	22.5636	0.0839
175		−0.9234 - −2.810	24.5821	0.0887
Notes: C₀—Initial concentration; ΔG—Gibbs free energy change; ΔH—Enthalpy change; ΔS—Entropy change.

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参考文献(34)

[1]	YANG X Y, CHEN L H, LI Y, et al. Hierarchically porous materials: Synthesis strategies and structure design[J]. Che-mical Society Reviews,2017,46(2):481-558. doi: 10.1039/C6CS00829A
[2]	BHATNAGAR A, SILLANPAA M, WITEK A. Agricultural waste peels as versatile biomass for water purification-A review[J]. Chemical Engineering Journal,2015,270:244-271. doi: 10.1016/j.cej.2015.01.135
[3]	KAYAN A. Inorganic-organic hybrid materials and their adsorbent properties[J]. Advanced Composite and Hybrid Materials,2019,2:34. doi: 10.1007/s42114-018-0073-y
[4]	NF N T, KAMARUDDIN A F, WAN I. Advances in organic-inorganic hybrid sorbents for the extraction of organic and inorganic pollutants in different types of food and environmental samples[J]. Journal of Separation Science,2018,41:195-208. doi: 10.1002/jssc.201700689
[5]	PARISA M P, SEYED J P. Review on recent progress in chitosan-based hydrogels for wastewater treatment application[J]. Carbohydrate Polymers,2018,201:264-279. doi: 10.1016/j.carbpol.2018.08.070
[6]	牛耀岚. 新型壳聚糖纤维材料的制备及其对重金属离子的吸附研究[D]. 上海: 上海交通大学, 2017. NIU Yaolan. The preparation of chitosan-based fibrous materials and research of adsorption performance for metal ions[D]. Shanghai: Shanghai Jiaotong University, 2017(in Chinese).
[7]	ZHANG Q S, ZHANG T T, HE T, et al. Removal of crystal violet by clay/PNIPAm nanocomposite hydrogels with various clay contents[J]. Applied Clay Science,2014,90:1-5. doi: 10.1016/j.clay.2014.01.003
[8]	赵丹华. CaF₂-WAGGS杂化吸附材料的制备及应用研究[J]. 水处理技术, 2012, 8(8):51-54. doi: 10.3969/j.issn.1000-3770.2012.08.014 ZHAO Danhua. Preparation of the calcium fluoride-weak acid green as hybrid absorption material and application to dye wastewater treatment[J]. Technology of Water Treatment,2012,8(8):51-54(in Chinese). doi: 10.3969/j.issn.1000-3770.2012.08.014
[9]	MOHAMMED E K, EI M N, BAHCINE B, et al. Study of removal of Congo red by local natural clay[J]. Scientific Study and Research,2016,17(3):295-307.
[10]	KANNAN K P, GEORGE T S, GURU K S. Extraction, purification and characterization of chitosan from endophytic fungi isolated from medicinal plants[J]. World Journal of Science and Technology,2011,1(4):43-48.
[11]	马建青. 基于壳聚糖和石墨相氮化碳的净水材料制备及其机理研究[D]. 杭州: 浙江大学, 2018. MA Jianqing. Preparation and mechanism study of water purification materials based on chitosan and graphitic carbon nitride[D]. Hangzhou: Zhejiang University, 2018(in Chinese).
[12]	MRIDUSMITA G, PRODEEP P. Enhanced adsorption of cationic dyes using sulfonic acid modified activated carbon[J]. Journal of Environmental Chemical Engineering,2017,5:3508-3517. doi: 10.1016/j.jece.2017.07.016
[13]	FAN L, LU Y, YANG L Y, et al. Fabrication of polyethylenimine-functionalized sodium alginate/cellulose nanocrystal/polyvinyl alcohol core-shell microspheres ((PVA/SA/CNC)@PEI) for diclofenac sodium adsorption[J]. Journal of Colloid and Interface Science,2019,554:48-58. doi: 10.1016/j.jcis.2019.06.099
[14]	SAYED G O. Removal of methylene blue and crystal violet from aqueous solutions by palm kernel fiber[J]. Desalination,2011,272:225-232. doi: 10.1016/j.desal.2011.01.025
[15]	谭忠祥. 高堆积密度壳聚糖及其制备方法: 中国, ZL02110716.5[P]. 2002-8-21. TAN Zhongxiang. High bulk density chitosan and its preparation method: China, ZL02110716.5[P]. 2002-8-21(in Chinese).
[16]	HUI K S, CHO C Y N, KOT S C. Removal of mixed heavy metal ions in wastewater by zeolite 4A and residual products from recycled coal fly ash[J]. Journal of Hazardous Materials,2005,127(13):89-101.
[17]	SILVIA P D, FABIANO B S, APARECIDO N M, et al. Kinetic, equilibrium and thermodynamic phenomenological modeling of reactive dye adsorption onto polymeric adsorbent[J]. Chemical Engineering Journal,2017,307:466-475. doi: 10.1016/j.cej.2016.08.104
[18]	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. doi: 10.1016/j.ijbiomac.2017.08.084
[19]	KUMARI H J, KRISHNAMOORTHY P, ARUMUGAM T K, et al. An efficient removal of crystal violet dye from waste water by adsorption onto TLAC/Chitosan composite: A novel low-cost adsorbent[J]. International Journal of Biological Macromolecules,2017,96:324-333. doi: 10.1016/j.ijbiomac.2016.11.077
[20]	SONG X, AN J L, HE C, et al. A bioinspired strategy towards super-adsorbent hydrogel spheres via self-sacrificing micro-reactors for robust wastewater remediation[J]. Jour-nal of Materials Chemistry,2019,7:21386-21403. doi: 10.1039/C9TA05550A
[21]	HO Y S, MCKAY G. Pseudo-second order model for sorption processes[J]. Process Biochemistry,1999,34(5):451-465. doi: 10.1016/S0032-9592(98)00112-5
[22]	万骏. 基于功能设计的水凝胶对水中磷酸盐去除研究[D]. 武汉: 华中科技大学, 2018. WAN Jun. Hydrogels based on functional design for phosphorous removal from water[D]. Wuhan: Huazhong University of Science and Technology, 2018(in Chinese).
[23]	HU X, ZHANG H, SUN Z R. Adsorption of low concentration ceftazidime from aqueous solutions using impregnated activated carbon promoted by iron copper and aluminum[J]. Applied Surface Science,2017,392:332-341. doi: 10.1016/j.apsusc.2016.09.047
[24]	AHMED M J. Adsorption of quinolone, tetracycline from aqueous solutions onto multi-walled carbon nanotubes with different oxygen contents[J]. Scientific Reports,2014,4(3):4326-4332.
[25]	KAUSHAL S, BADRU R, KUMAR S, et al. Efficient removal of cationic and anionic dyes from their binary mixtures by organic-inorganic hybrid material[J]. Journal of Inorganic and Organometallic Polymers and Materials,2018,28(3):968-977. doi: 10.1007/s10904-018-0817-8
[26]	INYINBOR A A, ADEKOLA F A, OLATUNJI G A. Kinetics, isotherms and thermodynamic modeling of liquid phase adsorption of Rhodamine B dye onto Raphia hookerie fruit epicarp[J]. Water Resources and Industry,2016,15:14-27. doi: 10.1016/j.wri.2016.06.001
[27]	SANGHWA O, KAWK M Y, SHIN W S. Competitive sorption of lead and cadmium onto sediments[J]. Chemical Engineering Journal,2009,152(23):376-388.
[28]	SCHEUFELE F B, MODENEDS A N, BORBA C E, et al. Monolayer-multilayer adsorption phenome-nological model: Kinetics, equilibrium and thermodynamics[J]. Chemical Engineering Journal,2016,284:1328-1341. doi: 10.1016/j.cej.2015.09.085
[29]	ISAH U A, ABDULRAHEEM G, BALA S, et al. Kinetics, equilibrium and thermodynamics studies of Reactive Blue 19 dye adsorption on coconut shell based activated carbon[J]. International Biodeterioration Biodegradation,2015,102:265-273. doi: 10.1016/j.ibiod.2015.04.006
[30]	AHMAD A, MOHD-SETAPAR S H, AHMAD A, et al. Recent advances in new generation dye removal technologies: Novel search for approaches to reprocess wastewater[J]. RSC Advances,2015,5(39):30801-30818. doi: 10.1039/C4RA16959J
[31]	OEPEN B V, KORDEL W, KLEIN W. Sorption of nonpolar and polar compounds to soils: Processes, measurements and experience with the applicability of the modified OECD-Guideline 106[J]. Chemosphere,1991,22(3-4):285-304. doi: 10.1016/0045-6535(91)90318-8
[32]	NOLLET H, ROELS M, LUTGEN P, et al. Removal of PCBs from wastewater using fly ash[J]. Chemosphere, 2003, 53: 655-665.
[33]	国家环境保护局. 水质化学需氧量的测定−重铬酸盐法: GB/T 11914—1989[S]. 北京: 中国标准出版社, 1989. National Environmental Protection Agency. Water quality-Determination of the chemical oxygen demand-Dichromate method: GB/T 11914—1989[S]. Beijing: China Standards Press, 1989(in Chinese).
[34]	陈锦诗, 孙诗乐, 黄文海, 等. CaF₂-CR杂化吸附材料对乙基紫的吸附性能研究[J]. 化学试剂, 2018, 40(10):937-942, 970. CHEN Jinshi, SUN Shile, HUANG Wenhai, et al. Adsorption of ethylene violet on hybrid adsorption material of CaF₂-CR[J]. Chemical Reagents,2018,40(10):937-942, 970(in Chinese).