氨基功能化双醛淀粉吸附剂的制备及其对Pb(Ⅱ)的吸附行为

doi:10.16085/j.issn.1000-6613.2023-0123

摘要/Abstract

摘要：

以淀粉为原料，高碘酸钠为氧化剂，制备出双醛淀粉（DAS），然后与水合肼反应制备了氨基功能化双醛淀粉吸附剂（NH₂-DAS）。采用扫描电子显微镜、能量色散X射线光谱仪、X射线衍射仪、热重分析仪和X射线光电子能谱等表征手段对NH₂-DAS的形貌、元素组成、热稳定性和表面化学性质进行了分析。详细研究了NH₂-DAS吸附剂对水溶液中Pb(Ⅱ)离子的吸附行为和吸附机理。结果表明，NH₂-DAS对Pb(Ⅱ)的吸附符合Langmuir等温吸附模型和准二级吸附动力学模型。当吸附温度为45℃、pH为5.5、吸附时间为240min时，NH₂-DAS对Pb(Ⅱ)的吸附容量达到165mg/g。NH₂-DAS对Pb(Ⅱ)的吸附作用主要是利用其表面—C $̿$ N—和—NH₂与Pb(Ⅱ)的配位螯合作用实现的，且为自发、吸热的熵增过程。经过5次再生利用后，NH₂-DAS对Pb(Ⅱ)的吸附容量仍然能达到初始吸附容量的84.8%。该NH₂-DAS吸附剂在吸附Pb(Ⅱ)方面具有潜在的应用前景。

关键词: 双醛淀粉, 吸附剂, 铅离子, 吸附机理

Abstract:

Amino functionalized dialdehyde starch (NH₂-DAS) was successfully synthesized by Schiff base reaction of DAS with hydrazine hydrate. During the preparation process, dialdehyde starch (DAS) was firstly prepared using starch as raw material and NaIO₄ as oxidant. The morphology, element distribution, thermal stability and surface chemical property of the NH₂-DAS adsorbent were characterized by SEM, EDX, XRD, TGA, FTIR and XPS. The adsorption behavior and adsorption mechanism of NH₂-DAS adsorbent toward Pb(‍Ⅱ) from aqueous solution were studied. The results showed that the adsorption behavior of Pb(‍Ⅱ) onto NH₂-DAS adsorbent could be well described by Langmuir isotherm model and Pseudo-second-order kinetic mode. The NH₂-DAS exhibited a high adsorption capacity of 165mg/g toward Pb(‍Ⅱ) at adsorption temperature of 45℃, pH=5.5 and the adsorption time of 240min. The adsorption of NH₂-DAS on Pb(‍Ⅱ) mainly depended on the coordination bonds between—C $̿$ N—, —NH₂ groups and Pb(‍Ⅱ) ions. The adsorption process was a spontaneous, endothermic and entropy increase process. After five times of regeneration test, the adsorption capacity of NH₂-DAS for Pb(‍Ⅱ) was still above 84.8% of original adsorption capacity. Therefore, the NH₂-DAS adsorbent had potential application prospects in the removal of Pb(‍Ⅱ) ions from aqueous solution.

Key words: dialdehyde starch, adsorbent, lead(Ⅱ) ions, adsorption mechanism

中图分类号:

O647

郭宇, 佟民心, 吴红梅. 氨基功能化双醛淀粉吸附剂的制备及其对Pb(Ⅱ)的吸附行为[J]. 化工进展, 2023, 42(12): 6589-6599.

GUO Yu, TONG Minxin, WU Hongmei. Preparation of amino-functionalized dialdehyde starch adsorbent for adsorption of Pb(Ⅱ) ions[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6589-6599.

图/表 17

图1 NH2-DAS吸附剂的合成示意图

图2 淀粉、DAS、NH2-DAS的SEM图和EDX元素分析

图3 淀粉、DAS和NH2-DAS的XRD图和TGA曲线图

图4 淀粉、DAS和NH2-DAS的FTIR光谱分析和XPS谱图

图5 溶液pH对吸附Pb(Ⅱ)的影响

图6 NH2-DAS吸附Pb(Ⅱ)的等温线拟合曲线

表1 不同温度下NH2-DAS对Pb(Ⅱ)的吸附等温线拟合常数

温度/℃	Langmuir			Freundlich
温度/℃	q_m/mg·g^-1	K_L	R²	K_F	n	R²
25	139.86	0.029	0.982	19.55	2.77	0.816
35	162.07	0.0.38	0.991	31.68	3.29	0.814
45	177.93	0.122	0.998	78.63	6.19	0.555

图7 NH2-DAS对Pb(Ⅱ)吸附热力学拟合曲线图

表2 NH2-DAS吸附Pb(Ⅱ)的热力学方程拟合参数

温度/K	K_c	ΔG/kJ·mol^-1	ΔH/kJ·mol^-1	ΔS/kJ·mol·K^-1	R²
298	1.289	-0.629	25.28	0.087	0.979
303	1.494	-1.011
308	1.667	-1.308
313	2.042	-1.858
318	2.463	-2.583

图8 NH2-DAS吸附Pb(Ⅱ)的动力学分析图

表3 NH2-DAS吸附铅(Ⅱ)动力学方程拟合参数

吸附剂	q_e（实验）/mg·g^-1	准一级动力学模型			准二级动力学模型
吸附剂	q_e（实验）/mg·g^-1	k₁/min^-1	q_e（计算）/mg·g^-1	R²	k₂/g·mg^-1·min^-1	q_e（计算）/mg·g^-1	R²
NH₂-SBA-15	165	0.009	119.42	0.952	1.24×10^-5	177.62	0.988

表4 各种吸附剂对Pb(Ⅱ)的吸附性能

吸附剂	q_m/mg·g^-1	参考文献
氧化淀粉	48.27	[36]
淀粉-FeS@PSB	90.15	[37]
MMT/淀粉	21.5	[38]
交联两性淀粉	152.74	[39]
氧化淀粉纳米颗粒	110.9	[16]
双醛淀粉	38.25	本工作
NH₂-DAS	165	本工作

图9 离子强度对NH2-DAS吸附Pb(Ⅱ)的影响

图10 NH2-DAS和Pb-NH2-DAS的FTIR谱图、EDX面扫描图和XPS谱图

图11 NH2-DAS吸附Pb(Ⅱ)的机理示意图

图12 NH2-DAS吸附剂的再生性能图

图13 再生后的NH2-DAS吸附剂的SEM图、XRD图和FTIR谱图

参考文献 42

1	CHAPLYGIN Victor A, RAJPUT Vishnu D, MANDZHIEVA Saglara S, et al. Comparison of heavy metal content in Artemisia austriaca in various impact zones[J]. ACS Omega, 2020, 5(36): 23393-23400.
2	MAO Changping, SONG Yinxian, CHEN Lingxiao, et al. Human health risks of heavy metals in paddy rice based on transfer characteristics of heavy metals from soil to rice[J]. CATENA, 2019, 175: 339-348.
3	NARANJO Valeria I, HENDRICKS Michael, JONES Kimberly S. Lead toxicity in children: An unremitting public health problem[J]. Pediatric Neurology, 2020, 113: 51-55.
4	BANSOD BabanKumar, KUMAR Tejinder, THAKUR Ritula, et al. A review on various electrochemical techniques for heavy metal ions detection with different sensing platforms[J]. Biosensors and Bioelectronics, 2017, 94: 443-455.
5	Rahul RAM, MORRISROE Liam, ETSCHMANN Barbara, et al. Lead (Pb) sorption and co-precipitation on natural sulfide, sulfate and oxide minerals under environmental conditions[J]. Minerals Engineering, 2021, 163: 106801.
6	TAVAKOLI Omid, GOODARZI Vahabodin, SAEB Mohammad Reza, et al. Competitive removal of heavy metal ions from squid oil under isothermal condition by CR11 chelate ion exchanger[J]. Journal of Hazardous Materials, 2017, 334: 256-266.
7	CUI Lin, WU Jie, JU Huangxian. Electrochemical sensing of heavy metal ions with inorganic, organic and bio-materials[J]. Biosensors and Bioelectronics, 2015, 63: 276-286.
8	MONDAL Somen, KUMAR MAJUMDER Subrata. Fabrication of the polysulfone-based composite ultrafiltration membranes for the adsorptive removal of heavy metal ions from their contaminated aqueous solutions[J]. Chemical Engineering Journal, 2020, 401: 126036.
9	WU Hongmei, XIAO Yu, GUO Yu, et al. Functionalization of SBA-15 mesoporous materials with 2-acetylthiophene for adsorption of Cr(Ⅲ) ions[J]. Microporous and Mesoporous Materials, 2020, 292: 109754.
10	GHAHREMANI Parastoo, VAKILI Mohammad Hassan, Alireza NEZAMZADEH-EJHIEH. Optimization of Pb(Ⅱ) removal by a novel modified silica aerogel using Quince seed mucilage with response surface methodology[J]. Journal of Environmental Chemical Engineering, 2021, 9(6): 106648.
11	姜晓庆, 郭宇, 吴红梅. 2-吡啶甲醛功能化SBA-15介孔材料的制备及其对Cr(Ⅲ)离子的吸附[J]. 化工进展, 2022, 41(7): 3915-3924.
	JIANG Xiaoqing, GUO Yu, WU Hongmei. Synthesis of 2-pyridinecarboxaldehyde functionalized SBA-15 mesoporous material for the adsorption of Cr(Ⅲ) ions from aqueous solution[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3915-3924.
12	GUO Y, WU D F, WU H M, et al. Efficient removal of Pb(Ⅱ) ions by using 2-acetylthiophene-modified graphene oxide from aqueous solution[J]. Materials Today Sustainability, 2022, 20: 100212.
13	WANG Wenyong, WU Guohao, ZHU Tao, et al. Synthesis of-thiazole Schiff base modified SBA-15 mesoporous silica for selective Pb(Ⅱ) adsorption[J]. Journal of the Taiwan Institute of Chemical Engineers, 2021, 125: 349-359.
14	周丽莎, 李若男, 卞雨洁, 等. TOCNF与磁性羧甲基壳聚糖纳米粒子复合物的制备及吸附Pb²⁺的特性[J]. 化工进展, 2022, 41(2): 901-910.
	ZHOU Lisha, LI Ruonan, BIAN Yujie, et al. Preparation of TOCNF and magnetic carboxymethyl chitosan nanoparticles composite and adsorption properties of Pb²⁺ [J]. Chemical Industry and Engineering Progress, 2022, 41(2): 901-910.
15	WANG Anqi, ZHENG Zhikeng, LI Ruiqi, et al. Biomass-derived porous carbon highly efficient for removal of Pb(Ⅱ) and Cd(Ⅱ)[J]. Green Energy & Environment, 2019, 4(4): 414-423.
16	AWOKOYA Kehinde N, ONINLA Vincent O, BELLO Dolapo J. Synthesis of oxidized Dioscorea dumentorum starch nanoparticles for the adsorption of lead(Ⅱ) and cadmium(Ⅱ) ions from wastewater[J]. Environmental Nanotechnology, Monitoring & Management, 2021, 15: 100440.
17	GUO Yu, XIAO Yu, WU Hongmei, et al. Efficient removal of Pb(Ⅱ) ions from aqueous solution by using a novel functionalized bio-material with two tridentate coordinated units[J]. Journal of Chemical Technology & Biotechnology, 2021, 96(6): 1709-1719.
18	WANG Rou, DONG Zhengping, WANG Renqi, et al. Efficient removal of Cd²⁺ by dialdehyde phenylhydrazine starch from aqueous solution[J]. RSC Advances, 2013, 3(43): 20480.
19	WANG Yang, ZHANG Yun, HOU Chen, et al. Facile synthesis of monodisperse functional magnetic dialdehyde starch nano-composite and used for highly effective recovery of Hg(Ⅱ)[J]. Chemosphere, 2015, 141: 26-33.
20	ZHANG Yaoyao, MAGAGNIN Luca, YUAN Kangze, et al. Highly-efficient removal of Pb (Ⅱ) from water by mesoporous amino functionalized silica aerogels: Experimental, DFT investigations and life cycle assessment[J]. Microporous and Mesoporous Materials, 2022, 345: 112280.
21	TANG Ni, LIU Xue, JIA Mengru, et al. Amine- and thiol-bifunctionalized mesoporous silica material for immobilization of Pb and Cd: Characterization, efficiency, and mechanism[J]. Chemosphere, 2022, 291: 132771.
22	HERNÁNDEZ-MORALES V, NAVA R, ACOSTA-SILVA Y J, et al. Adsorption of lead (Ⅱ) on SBA-15 mesoporous molecular sieve functionalized with-NH₂ groups[J]. Microporous and Mesoporous Materials, 2012, 160: 133-142.
23	YIN Qiangfeng, JU Benzhi, ZHANG Shufen, et al. Preparation and characteristics of novel dialdehyde aminothiazole starch and its adsorption properties for Cu (Ⅱ) ions from aqueous solution[J]. Carbohydrate Polymers, 2008, 72(2): 326-333.
24	HOFREITER B T, ALEXANDER B H, WOLFF I A. Rapid estimation of dialdehyde content of periodate oxystarch through quantitative alkali consumption[J]. Analytical Chemistry, 1955, 27(12): 1930-1931.
25	YU Jiugao, CHANG Peter R, MA Xiaofei. The preparation and properties of dialdehyde starch and thermoplastic dialdehyde starch[J]. Carbohydrate Polymers, 2010, 79(2): 296-300.
26	WANG Shujun, YU Jinglin, GAO Wenyuan, et al. Granule structural changes in native Chinese Yam (Dioscorea opposita Thunb var. Anguo) starch during acid hydrolysis[J]. Carbohydrate Polymers, 2007, 69(2): 286-292.
27	FIEDOROWICZ Maciej, PARA Andrzej. Structural and molecular properties of dialdehyde starch[J]. Carbohydrate Polymers, 2006, 63(3): 360-366.
28	DING Wen, ZHAI Shenyong, LIU Juntao, et al. Preparation and adsorption properties of dialdehyde 8-aminoquinoline starch[J]. Water Science and Technology, 2013, 67(2): 306-310.
29	JIANG Yijun, GAO Qiuming, YU Huaguang, et al. Intensively competitive adsorption for heavy metal ions by PAMAM-SBA-15 and EDTA-PAMAM-SBA-15 inorganic-organic hybrid materials[J]. Microporous and Mesoporous Materials, 2007, 103(1/2/3): 316-324.
30	RAHMAN Noor Hidayah ABD, JAAFAR Nardiah Rizwana, SHAMSUL ANNUAR Nur Arbainah, et al. Efficient substrate accessibility of cross-linked levanase aggregates using dialdehyde starch as a macromolecular cross-linker[J]. Carbohydrate Polymers, 2021, 267: 118159.
31	ZHANG Liming, YAN Pengchao, LI Yan, et al. Preparation and antibacterial activity of a cellulose-based Schiff base derived from dialdehyde cellulose and L-lysine[J]. Industrial Crops and Products, 2020, 145: 112126.
32	HE Panyang, ZHANG Yaojun, ZHANG Xiaomin, et al. Diverse zeolites derived from a circulating fluidized bed fly ash based geopolymer for the adsorption of lead ions from wastewater[J]. Journal of Cleaner Production, 2021, 312: 127769.
33	TOUIHRI Manel, GUESMI Fatma, HANNACHI Chiraz, et al. Single and simultaneous adsorption of Cr(Ⅵ) and Cu(‍Ⅱ) on a novel Fe₃O₄/pine cones gel beads nanocomposite: Experiments, characterization and isotherms modeling[J]. Chemical Engineering Journal, 2021, 416: 129101.
34	XU Hao, HU Xinjiang, CHEN Yonghua, et al. Cd(Ⅱ) and Pb(Ⅱ) absorbed on humic acid-iron-pillared bentonite: Kinetics, thermodynamics and mechanism of adsorption[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 612: 126005.
35	MOHAN Sweta, KUMAR Vijay, SINGH Devendra Kumar, et al. Effective removal of lead ions using graphene oxide-MgO nanohybrid from aqueous solution: Isotherm, kinetic and thermodynamic modeling of adsorption[J]. Journal of Environmental Chemical Engineering, 2017, 5(3): 2259-2273.
36	D-K KWEON, J-K CHOI, KIM E-K, et al. Adsorption of divalent metal ions by succinylated and oxidized corn starches[J]. Carbohydrate Polymers, 2001, 46(2): 171-177.
37	WANG Hai, LIU Renrong, CHEN Qian, et al. Biochar-supported starch/chitosan-stabilized nano-iron sulfide composites for the removal of lead ions and nitrogen from aqueous solutions[J]. Bioresource Technology, 2022, 347: 126700.
38	Tam Hoang LUU, VAN NGUYEN Hung, Nhan Thuc Chi HA, et al. Synthesis of starch modified montmorillonite as an effective adsorbent for Pb(‍Ⅱ) removal from water[J]. Vietnam Journal of Science and Technology, 2019, 57(3A): 94-102.
39	XU Shimei, FENG Shun, PENG Gui, et al. Removal of Pb(Ⅱ) by crosslinked amphoteric starch containing the carboxymethyl group[J]. Carbohydrate Polymers, 2005, 60(3): 301-305.
40	SHI Tianzhu, XIE Zhengfeng, MO Xinliang, et al. Adsorption behaviors of heavy metal ions by different hydrazone-modified sodium alginate in aqueous medium: Experimental and DFT studies[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 659: 130754.
41	NAUSHAD Mu, AHAMAD Tansir, SHARMA Gaurav, et al. Synthesis and characterization of a new starch/SnO₂ nanocomposite for efficient adsorption of toxic Hg²⁺ metal ion[J]. Chemical Engineering Journal, 2016, 300: 306-316.
42	ZHANG Wei, WANG Hongyu, HU Xiaoling, et al. Multicavity triethylenetetramine-chitosan/alginate composite beads for enhanced Cr(Ⅵ) removal[J]. Journal of Cleaner Production, 2019, 231: 733-745.

[1]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[2]	张雪伟, 黄亚继, 许月阳, 程好强, 朱志成, 李金壘, 丁雪宇, 王圣, 张荣初. 碱性吸附剂对燃煤烟气中SO₃的吸附特性[J]. 化工进展, 2023, 42(7): 3855-3864.
[3]	陆洋, 周劲松, 周启昕, 王瑭, 刘壮, 李博昊, 周灵涛. CeO₂/TiO₂吸附剂煤气脱汞产物的浸出规律[J]. 化工进展, 2023, 42(7): 3875-3883.
[4]	王久衡, 荣鼐, 刘开伟, 韩龙, 水滔滔, 吴岩, 穆正勇, 廖徐情, 孟文佳. 水蒸气强化纤维素模板改性钙基吸附剂固碳性能及强度[J]. 化工进展, 2023, 42(6): 3217-3225.
[5]	赵重阳, 赵磊, 石详文, 黄俊, 李治尧, 沈凯, 张亚平. O₂/H₂O/SO₂ 对改性富铁凹凸棒石高温吸附PbCl₂ 的影响[J]. 化工进展, 2023, 42(4): 2190-2200.
[6]	郭帅帅, 陈锦路, 金梁程龙, 陶醉, 陈小丽, 彭国文. 基于海水提铀的多孔芳香框架材料研究进展[J]. 化工进展, 2023, 42(3): 1426-1436.
[7]	叶沁辉, 陈红, 于鑫, 王凯, 于露滢, 曾可佳. 沼渣生物炭的制备及资源化利用研究进展[J]. 化工进展, 2023, 42(12): 6554-6566.
[8]	柯玉鑫, 朱晓丽, 司绍诚, 张婷, 王军强, 张子夜. 废白土衍生吸附剂协同去除水中的四环素和铜[J]. 化工进展, 2023, 42(11): 5981-5992.
[9]	伍岳, 李晓宇, 陶春珲, 张莹, 李印辉, 张文祥, 杨伯伦, 马和平. 离子改性的CON材料用于吸附分离NF₃[J]. 化工进展, 2023, 42(11): 6076-6085.
[10]	王胜楠, 郑旭. 空气取水用活性炭纤维复合吸附剂的研究[J]. 化工进展, 2023, 42(10): 5567-5573.
[11]	王子航, 梁瑞升, 邓超和, 王佳韵. 离子凝胶复合吸附剂的制备及空气取水性能[J]. 化工进展, 2022, 41(S1): 389-396.
[12]	曹正凯, 米晓斌, 吴子明, 孙士可, 曹均丰, 彭德强, 梁相程. 煤合成气净化除尘装置压降问题分析及应用优化[J]. 化工进展, 2022, 41(S1): 15-21.
[13]	王一茹, 宋小三, 水博阳, 王三反. 胺功能化介孔二氧化硅捕集CO₂的研究进展[J]. 化工进展, 2022, 41(S1): 536-544.
[14]	李兴, 黄宏宇, 大坂侑吾, 呼和涛力, 肖林发, 李军. 碳材料吸附脱除二氧化硫性能的影响因素[J]. 化工进展, 2022, 41(9): 4963-4972.
[15]	张雨珂, 刘倩, 段媛媛, 赵英杰, 崔阳, 史利娟, 李向远, 李剑川, 范海明, 易群. 基于MOFs材料的低碳烃（C₁~C₃）分离研究进展[J]. 化工进展, 2022, 41(8): 4288-4302.