木质素-聚苯胺复合材料的制备及对刚果红的吸附

doi:10.16085/j.issn.1000-6613.2022-1441

摘要/Abstract

摘要：

以木质素磺酸盐（Lig）为原料，采用化学聚合法与聚苯胺（PANI）复合制备出木质素/聚苯胺（Lig/PANI）复合材料。利用扫描电子显微镜、透射电镜、红外光谱等手段对材料的形貌、结构进行了表征，并研究了复合材料对刚果红（CR）的吸附性能，探究了吸附剂用量、染料初始浓度和吸附时间等因素对吸附性能的影响。结果表明，在20mg的吸附剂用量和350mg/L的起始浓度下，刚果红在200min内的吸附效果最佳，最高吸附量为431.17mg/g。该吸附过程遵循Freundlich吸附模型和准二级吸附动力模型，以化学吸附为主，属于多分子层吸附。刚果红的吸附机制主要存在着静电吸引、孔隙吸附，且吸附过程中存在电子的转移，内扩散模型表明粒子内扩散不是控制吸附速率的唯一因素；整个吸附过程是熵增、自发进行的。

关键词: 木质素, 聚苯胺, 刚果红, 吸附性能

Abstract:

Lignin/polyaniline(Lig/PANI) composite material was prepared by chemical polymerization with polyaniline(PANI) and lignosulfonate(Lig). The morphology, structure and properties of the materials were characterized by scanning electron microscopy, transmission electron microscopy and infrared spectroscopy. The adsorption properties of composite materials on Congo red was studied, and the effects of the amounts of adsorbent, initial concentration of dye, and adsorption time on the adsorption properties were investigated. The results showed that under the dosage of 20mg adsorbent and the initial concentration of 350mg/L, Congo red had the best adsorption effect within 200min and the highest adsorption capacity was 431.17mg/g. The adsorption process followed the Freundlich adsorption model and the quasi-second-order adsorption dynamic model, in which chemisorption was dominant and belonged to multi-molecular layer adsorption. The adsorption mechanism of Congo red mainly included electrostatic attraction, pore adsorption and electron transfer during the adsorption process. The internal diffusion model indicated that the internal diffusion was not the only factor controlling the adsorption rate, and the whole process of adsorption was spontaneous and entropic.

Key words: lignin, polyaniline, Congo red, adsorption performance

中图分类号:

X793

任建鹏, 吴彩文, 刘慧君, 吴文娟. 木质素-聚苯胺复合材料的制备及对刚果红的吸附[J]. 化工进展, 2023, 42(6): 3087-3096.

REN Jianpeng, WU Caiwen, LIU Huijun, WU Wenjuan. Preparation of lignin-polyaniline composites and adsorption of Congo red[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3087-3096.

图/表 26

图1 木质素/聚苯胺的合成示意图

图2 Lig/PANI复合材料吸附CR示意图

图3 刚果红染料的标准曲线

图4 木质素复合材料投入量对CR吸附量的影响

图5 木质素复合材料投入量对CR去除率的影响

图6 初始浓度对CR吸附量的影响

图7 初始浓度CR去除率的影响

表1 木质素复合材料吸附CR的Langmuir模型参数和Freundlich模型参数

样品	Langmuir吸附等温模型			Freundlich吸附等温模型
样品	$K L$ /g·L^-1	$Q m$ /mg·g^-1	R²	$K F$ / $m g 1 - 1 / n · L - 1 / n$	$n$	R²
PANI	3.39×10^-3	538.46	0.91	21.14	2.26	0.98
Lig/PANI	3.31×10^-3	608.76	0.93	22.94	2.23	0.98

表1 木质素复合材料吸附CR的Langmuir模型参数和Freundlich模型参数

样品	Langmuir吸附等温模型			Freundlich吸附等温模型
样品	$K L$ /g·L^-1	$Q m$ /mg·g^-1	R²	$K F$ / $m g 1 - 1 / n · L - 1 / n$	$n$	R²
PANI	3.39×10^-3	538.46	0.91	21.14	2.26	0.98
Lig/PANI	3.31×10^-3	608.76	0.93	22.94	2.23	0.98

图8 木质素复合材料吸附CR的Langmuir和Freundlich非线性拟合曲线

图9 木质素复合材料吸附CR的Langmuir线性拟合曲线

图10 木质素复合材料吸附CR的Freundlich线性拟合曲线

表2 木质素复合材料吸附CR的热力学参数

样品	$Δ G ϴ / k J · m o l - 1$						$Δ H ϴ$ $/ k J · m o l - 1$	$Δ S ϴ$ $/ J · m o l - 1 · K - 1$
样品	283K	298K	313K	328K	343K	358K	$Δ H ϴ$ $/ k J · m o l - 1$	$Δ S ϴ$ $/ J · m o l - 1 · K - 1$
PANI	-3.73	-4.28	-4.83	-5.38	-5.93	-6.48	6.63	36.62
Lig/PANI	-4.62	-5.26	-5.90	-6.54	-7.18	-7.82	7.48	42.74

表2 木质素复合材料吸附CR的热力学参数

样品	$Δ G ϴ / k J · m o l - 1$						$Δ H ϴ$ $/ k J · m o l - 1$	$Δ S ϴ$ $/ J · m o l - 1 · K - 1$
样品	283K	298K	313K	328K	343K	358K	$Δ H ϴ$ $/ k J · m o l - 1$	$Δ S ϴ$ $/ J · m o l - 1 · K - 1$
PANI	-3.73	-4.28	-4.83	-5.38	-5.93	-6.48	6.63	36.62
Lig/PANI	-4.62	-5.26	-5.90	-6.54	-7.18	-7.82	7.48	42.74

图11 木质素复合材料吸附CR的热力学曲线

图12 吸附时间对CR吸附量的影响

图13 吸附时间对CR去除率的影响

图14 木质素复合材料吸附CR的准一级和准二级动力学模型非线性拟合曲线

表3 木质素复合材料吸附CR的准一级动力学模型和准二级动力学模型相关参数

样品	准一级吸附动力学模型			准二级吸附动力学模型
样品	$Q 1$ /mg·g^-1	$k 1$ /min^-1	R²	$Q 2$ /mg·g^-1	$k 2$ /g·mg^-1min^-1	R²
PANI	201.39	3.42×10^-2	0.80	220.94	2.50×10^-4	0.96
Lig/PANI	219.95	5.03×10^-2	0.76	233.22	4.30×10^-4	0.97

表3 木质素复合材料吸附CR的准一级动力学模型和准二级动力学模型相关参数

样品	准一级吸附动力学模型			准二级吸附动力学模型
样品	$Q 1$ /mg·g^-1	$k 1$ /min^-1	R²	$Q 2$ /mg·g^-1	$k 2$ /g·mg^-1min^-1	R²
PANI	201.39	3.42×10^-2	0.80	220.94	2.50×10^-4	0.96
Lig/PANI	219.95	5.03×10^-2	0.76	233.22	4.30×10^-4	0.97

图15 木质素复合材料吸附CR的准二级动力学模型

表4 木质素复合材料吸附CR的内扩散模型相关参数

样品	$K i 1$ /mg·g^-1·min^-1/2	$C 1$ /mg·g^-1	$R 12$	$K i 2$ /mg·g^-1·min^-1/2	$C 2$ /mg·g^-1	$R 12$
PANI	7.19	107.23	0.96	1.06	191.99	0.79
Lig/PANI	5.80	149.60	0.98	0.42	219.31	0.56

表4 木质素复合材料吸附CR的内扩散模型相关参数

样品	$K i 1$ /mg·g^-1·min^-1/2	$C 1$ /mg·g^-1	$R 12$	$K i 2$ /mg·g^-1·min^-1/2	$C 2$ /mg·g^-1	$R 12$
PANI	7.19	107.23	0.96	1.06	191.99	0.79
Lig/PANI	5.80	149.60	0.98	0.42	219.31	0.56

图16 木质素复合材料吸附CR的颗粒内扩散模型

图17 PANI和Lig/PANI的SEM图和TEM图[20]

图18 Lig/PANI吸附CR前SEM图和高倍数SEM图

图19 Lig/PANI吸附CR后的SEM图和高倍数SEM图

表5 Lig、PANI、Lig/PANI谱峰对应的特定官能团

振动基团	波数/cm^-1
振动基团	PANI	Lig/PANI	Lig
O—H 伸缩振动	—	—	3432
N—H 面外弯曲振动	3421	3421	—
C—H 伸缩振动	2931	2931	2931
C $̿$ C醌环骨架振动	1563	1565	1600
C $̿$ C苯环骨架振动	1481	1486	1506
C—N 苯型结构拉伸	1301	1301	—
C—N 醌型结构拉伸	1249	1245	—
N—(B)—N 伸缩振动	1128	1133	—
S $̿$ O 对称伸缩振动	—	1041	1039
C—H 面外芳环弯曲振动	802	808	—

表5 Lig、PANI、Lig/PANI谱峰对应的特定官能团

振动基团	波数/cm^-1
振动基团	PANI	Lig/PANI	Lig
O—H 伸缩振动	—	—	3432
N—H 面外弯曲振动	3421	3421	—
C—H 伸缩振动	2931	2931	2931
C $̿$ C醌环骨架振动	1563	1565	1600
C $̿$ C苯环骨架振动	1481	1486	1506
C—N 苯型结构拉伸	1301	1301	—
C—N 醌型结构拉伸	1249	1245	—
N—(B)—N 伸缩振动	1128	1133	—
S $̿$ O 对称伸缩振动	—	1041	1039
C—H 面外芳环弯曲振动	802	808	—

图20 CR和Lig/PANI吸附CR前后的红外光谱图

表6 Lig/PANI复合材料与其他材料吸附CR的性能比较

吸附剂	污染物	吸附量/mg·g^-1	文献
改性纤维素气凝胶	刚果红	478.00	[23]
L-半胱氨酸/rGO/PANI	刚果红	56.57	[24]
PANI/羧甲基纤维素/二氧化钛	刚果红	119.90	[18]
钛酸锌/PANI	刚果红	64.51	[25]
马酸铝-MOF硅藻	刚果红	181.82	[26]
硬硅钙石纤维	刚果红	574.71	[27]
MOF-5/Cu	刚果红	357.42	[28]
Lig/PANI	刚果红	431.17	本研究

参考文献 28

1	MINISY I M, SALAHUDDIN N A, AYAD M M. Chitosan/polyaniline hybrid for the removal of cationic and anionic dyes from aqueous solutions[J]. Journal of Applied Polymer Science, 2019, 136(6): 47056.
2	SUN Chencheng, XIONG Bowen, PAN Yang, et al. Adsorption removal of tannic acid from aqueous solution by polyaniline: Analysis of operating parameters and mechanism[J]. Journal of Colloid and Interface Science, 2017, 487: 175-181.
3	YAN Bo, CHEN Zhonghui, CAI Lu, et al. Fabrication of polyaniline hydrogel: Synthesis, characterization and adsorption of Methylene blue[J]. Applied Surface Science, 2015, 356: 39-47.
4	DUHAN Monika, KAUR Raminder. Nano-structured polyaniline as a potential adsorbent for Methylene blue dye removal from effluent[J]. Journal of Composites Science, 2020, 5(1): 7.
5	BHAUMIK Madhumita, MCCRINDLE Rob I, MAITY Arjun, et al. Polyaniline nanofibers as highly effective re-usable adsorbent for removal of Reactive black 5 from aqueous solutions[J]. Journal of Colloid and Interface Science, 2016, 466: 442-451.
6	LI Changzhi, ZHAO Xiaochen, WANG Aiqin, et al. Catalytic transformation of lignin for the production of chemicals and fuels[J]. Chemical Reviews, 2015, 115(21): 11559-11624.
7	XU Wenjing, CHEN Yizhen, KANG Jianxun, et al. Synthesis of polyaniline/lignosulfonate for highly efficient removal of Acid red 94 from aqueous solution[J]. Polymer Bulletin, 2019, 76(8): 4103-4116.
8	DEBNATH Sushanta, BALLAV Niladri, MAITY Arjun, et al. Development of a polyaniline-lignocellulose composite for optimal adsorption of Congo red[J]. International Journal of Biological Macromolecules, 2015, 75: 199-209.
9	贾羽洁, 孙康, 陈超. 聚苯胺-改性木质素磺酸的制备及电化学性能[J]. 电源技术, 2018, 42(8): 1204-1208.
	JIA Yujie, SUN Kang, CHEN Chao. Synthesis and electrochemical performance of polyaniline doped with sulfonation modified lignosulfonate[J]. Chinese Journal of Power Sources, 2018, 42(8): 1204-1208.
10	Qiufeng LYU, HE Zhiwei, ZHANG Jiayin, et al. Preparation and properties of nitrogen-containing hollow carbon nanospheres by pyrolysis of polyaniline-lignosulfonate composites[J]. Journal of Analytical and Applied Pyrolysis, 2011, 92(1): 152-157.
11	Zümriye AKSU. Biosorption of reactive dyes by dried activated sludge: Equilibrium and kinetic modelling[J]. Biochemical Engineering Journal, 2001, 7(1): 79-84.
12	ZAIR Zyad R, ALISMAEEL Ziad T, EYSSA Mohammed Y, et al. Optimization, equilibrium, kinetics and thermodynamic study of Congo red dye adsorption from aqueous solutions using Iraqi porcelanite rocks[J]. Heat and Mass Transfer, 2022, 58(8): 1393-1410.
13	ALSENANI Ghadah. Removal of Congo red dye from aqueous solution by date palm leaf base[J]. American Journal of Applied Sciences, 2014, 11(9): 1553-1557.
14	MEHRIZAD Ali, BEHNAJADY Mohammad A, GHARBANI Parvin, et al. Sonocatalytic degradation of Acid Red 1 by sonochemically synthesized zinc sulfide-titanium dioxide nanotubes: Optimization, kinetics and thermodynamics studies[J]. Journal of Cleaner Production, 2019, 215: 1341-1350.
15	HU Lishuang, GUANG Chunyu, LIU Yang, et al. Adsorption behavior of dyes from an aqueous solution onto composite magnetic lignin adsorbent[J]. Chemosphere, 2020, 246: 1-12.
16	ASEFA Misikir Tamiru, FEYISA Gebisa Bekele. Comparative investigation on two synthesizing methods of zeolites for removal of Methylene blue from aqueous solution[J]. International Journal of Chemical Engineering, 2022, 2022: 9378712.
17	WU Chung Hsin. Adsorption of reactive dye onto carbon nanotubes: Equilibrium, kinetics and thermodynamics[J]. Journal of Hazardous Materials, 2007, 144(1/2): 93-100.
18	TANZIFI Marjan, TAVAKKOLI YARAKI Mohammad, KARAMI Mojtaba, et al. Modelling of dye adsorption from aqueous solution on polyaniline/carboxymethyl cellulose/TiO₂ nanocomposites[J]. Journal of Colloid and Interface Science, 2018, 519: 154-173.
19	陈凤贵, 李娇, 黄露, 等. 木质素改性及其对染料的吸附性能[J]. 中山大学学报(自然科学版), 2019, 58(2): 103-109.
	CHEN Fenggui, LI Jiao, HUANG Lu, et al. The application of freeze-dried and cross-linked lignin in water treatment[J]. Acta Scientiarum Naturalium Universitatis Sunyatseni, 2019, 58(2): 103-109.
20	LI Penghui, WEI Yumeng, WU Caiwen, et al. Lignin-based composites for high-performance supercapacitor electrode materials[J]. RSC Advances, 2022, 12(30): 19485-19494.
21	BHAUMIK Madhumita, MCCRINDLE Rob, MAITY Arjun. Efficient removal of Congo red from aqueous solutions by adsorption onto interconnected polypyrrole-polyaniline nanofibres[J]. Chemical Engineering Journal, 2013, 228: 506-515.
22	Alica BARTOŠOVÁ, Lenka BLINOVÁ, SIROTIAK Maroš, et al. Usage of FTIR-ATR as non-destructive analysis of selected toxic dyes[J]. Research Papers Faculty of Materials Science and Technology Slovak University of Technology, 2017, 25(40): 103-111.
23	宋文琦, 霍文娟, 杨金腾, 等. 氨丙基咪唑离子液体修饰纤维素气凝胶吸附剂对刚果红的清除研究：高性能与吸附机理[J]. 材料导报, 2022, 36(12): 202-208.
	SONG Wenqi, HUO Wenjuan, YANG Jinteng, et al. Aminopropyl imidazolium ionic liquid modified cellulosic aerogel adsorbent for Congo red removal: High-performance and adsorption mechanism[J]. Materials Reports, 2022, 36(12): 202-208.
24	RAZZAQ Saba, AKHTAR Mehwish, ZULFIQAR Sonia, et al. Adsorption removal of Congo red onto L-cysteine/rGO/PANI nanocomposite: Equilibrium, kinetics and thermodynamic studies[J]. Journal of Taibah University for Science, 2021, 15(1): 50-62.
25	SINGH Somendra, PERWEEN Shama, RANJAN Amit. Dramatic enhancement in adsorption of Congo red dye in polymer-nanoparticle composite of polyaniline-zinc titanate[J]. Journal of Environmental Chemical Engineering, 2021, 9(3): 105149.
26	HEGDE Vinayak, UTHAPPA U T, ARVIND SWAMI O R, et al. Sustainable green functional nano aluminium fumarate-MOF decorated on 3D low-cost natural diatoms for the removal of Congo red dye and fabric whitening agent from wastewater: Batch & continuous adsorption process[J]. Materials Today Communications, 2022, 32: 103887.
27	HAN Mingyu, SHEN Xiaoyi, SHAO Hongmei, et al. Adsorption of Congo red by fibrous xonotlite prepared from waste silicon residue[J]. Water Science and Technology, 2022, 85(11): 3159-3168.
28	MOSAVI S H, ZARE‐DORABEI R, BEREYHI M. Rapid and effective ultrasonic-assisted adsorptive removal of Congo red onto MOF‐5 modified by CuCl₂ in ambient conditions: Adsorption isotherms and kinetics studies[J]. ChemistrySelect, 2021, 6(18):4432-4439.

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