纳米碳酸钙掺杂纤维素基水凝胶制备及其对铜离子吸附性能研究

doi:10.19964/j.issn.1006-4990.2024-0046

Abstract

Abstract:

Natural cellulose-based hydrogels have strong adsorption properties and are excellent adsorbent for removing heavy metal ions，but hydrogels strength is weak.Through free radical polymerization，acrylic acid（AA） and acrylamide（AM） were grafted onto sodium carboxymethyl cellulose（CMC），and further self-made nano-calcium carbonate（NCC） was doped into the cellulose hydrogel，successfully preparing NCC/CMC composite hydrogel.The pressive performance test results showed that the maximum stress was 48.52 kPa when the maximum strain was 80% and the mass fraction of NCC was 2.5%，and it still reached 39.64 kPa after 20 cycles.The morphology and structure of the hydrogel were characterized using SEM，FT-IR，XRD，and N₂ adsorption-desorption test.The results showed that the composite hydrogel had an abundant surface porous structure with a specific surface area of 7.775 m²/g，which was belonged to mesoporous materials.The effects of pH，initial mass concentration of copper ion solution，and temperature on the adsorption amount of copper ions were investigated.The results showed that when the pH of the copper ion solution was 5.5，the temperature was 30 ℃，and the initial mass concentration of the copper ion solution was 150 mg/L，the maximum adsorption capacity of NCC/CMC composite hydrogel for copper ions reached 178 mg/g，and the adsorption capacity was 30 mg/g higher than that of CMC hydrogel.The adsorption process was followed the Langmuir model and the Pseudo-second order.After 5 consecutive adsorption-desorption cycles，the composite hydrogel still has good regeneration performance.

Key words: hydrogel, sodium carboxymethyl cellulose, nano-calcium carbonate, adsorption, Cu²⁺

CLC Number:

TB332

BAI Xingxing, LI Hanfei, TANG Yong, ZHANG Jun, ZHU Guangkai, LI Lishuo, TONG Zhangfa. Study on preparation of cellulose based hydrogel doped with nano-calcium carbonate and its adsorption properties of copper ions[J]. Inorganic Chemicals Industry, 2025, 57(2): 83-91.

Figures/Tables 18

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References 25

1	GUAN Xian， YUAN Xingzhong， ZHAO Yanlan，et al.Adsorption behaviors and mechanisms of Fe/Mg layered double hydroxide loaded on bentonite on Cd（Ⅱ） and Pb（Ⅱ） removal［J］.Journal of Colloid and Interface Science，2022，612：572-583.
2	王勇力，刘妮，李海洋，等.硅胶改性壳聚糖膜的制备及其对Cu²⁺的吸附性能［J］.无机盐工业，2019，51（8）：60-63.
	WANG Yongli， LIU Ni， LI Haiyang，et al.Preparation of chitosan membrane modified by silica gel and its absorption properties for Cu²⁺ removal［J］.Inorganic Chemicals Industry，2019，51（8）：60-63.
3	侯文静，何彩庆，陈文清.农业固废基水凝胶用于水体中重金属吸附的研究进展［J］.复合材料学报，2024，41（7）：3322-3334.
	HOU Wenjing， HE Caiqing， CHEN Wenqing.Adsorption of heavy metals by agricultural solid waste based hydrogel：A review［J］.Acta Materiae Compositae Sinica，2024，41（7）：3322-3334.
4	HE Xiaoyan， JIA Hui， SUN Nan，et al.Fluorescent hydrogels based on oxidized carboxymethyl cellulose with excellent adsorption and sensing abilities for Ag⁺ ［J］.International Journal of Biological Macromolecules，2022，213：955-966.
5	崔香梅，潘彤彤，罗清龙，等.氨基醇改性GO/CNTs复合气凝胶的制备及对盐湖卤水硼的吸附［J］.无机盐工业，2023，55（12）：59-65，101.
	CUI Xiangmei， PAN Tongtong， LUO Qinglong，et al.Preparation of amino alcohol modified GO/CNTs composite aerogel and boron adsorption from salt lake brines［J］.Inorganic Chemicals Industry，2023，55（12）：59-65，101.
6	YANG Lingze， BAO Lei， DONG Tong，et al.Adsorption properties of cellulose/guar gum/biochar composite hydrogel for Cu²⁺，Co²⁺ and methylene blue［J］.International Journal of Biological Macromolecules，2023，242：125021.
7	刘学，张璐，高鸣霞，等.磁性羧甲基纤维素基水凝胶的制备及其对Cu²⁺的吸附行为［J］.东北林业大学学报，2020，48（4）：109-113，124.
	LIU Xue， ZHANG Lu， GAO Mingxia，et al.Preparation of magnetic carboxymethyl cellulose-based hydrogels and adsorption behavior of Cu²⁺ ［J］.Journal of Northeast Forestry University，2020，48（4）：109-113，124.
8	DOU Detian， WEI Donglai， GUAN Xin，et al.Adsorption of copper （Ⅱ） and cadmium（Ⅱ） ions by in situ doped nano-calcium carbonate high-intensity chitin hydrogels［J］.Journal of Hazardous Materials，2022，423：127137.
9	何天娇.纳米碳酸钙对聚丙烯酰胺/纳米纤维素/淀粉复合水凝胶改性研究［D］.南京：南京林业大学，2021.
	HE Tianjiao.Study on modification of polyacrylamide/nano-cellulose/starch composite hydrogel by nano-CaCO₃ ［D］.Nanjing：Nanjing Forestry University，2021.
10	焦妍惠，季军荣，韦德恩，等.纺锤状磁性碳酸钙复合材料的制备及其表征［J］.广西大学学报（自然科学版），2023，48（6）：1456-1465.
	JIAO Yanhui， JI Junrong， WEI Deen，et al.Preparation and characterization of fusiform magnetic calcium carbonate composites［J］.Journal of Guangxi University（Natural Science Edition），2023，48（6）：1456-1465.
11	杨润萍，李晓霞，丁磊，等.污染水中铜离子浓度的快速测定［J］.中国卫生检验杂志，2007，17（12）：2217-2218，2345.
	YANG Runping， LI Xiaoxia， DING Lei，et al.Determination of copper ions in polluted water［J］.Chinese Journal of Health Laboratory Technology，2007，17（12）：2217-2218，2345.
12	CACCAVO D， CASCONE S， LAMBERTI G，et al.Hydrogels：Experimental characterization and mathematical modelling of their mechanical and diffusive behaviour［J］.Chemical Society Reviews，2018，47（7）：2357-2373.
13	DAI Hongjie， CHEN Yuan， MA Liang，et al.Direct regeneration of hydrogels based on lemon peel and its isolated microcrystalline cellulose：Characterization and application for methylene blue adsorption［J］.International Journal of Biological Macromolecules，2021，191：129-138.
14	CHENG Yi， LU Lingbin， ZHANG Wuyuan，et al.Reinforced low density alginate-based aerogels：Preparation，hydrophobic modification and characterization［J］.Carbohydrate Polymers，2012，88（3）：1093-1099.
15	FANG Shixin， WANG Guangjian， XING Ronge，et al.Synthesis of superabsorbent polymers based on chitosan derivative graft acrylic acid-co-acrylamide and its property testing［J］.International Journal of Biological Macromolecules，2019，132：575- 584.
16	USMAN A， HUSSAIN Z， RIAZ A，et al.Enhanced mechanical，thermal and antimicrobial properties of poly（vinyl alcohol）/graphene oxide/starch/silver nanocomposites films［J］.Carbohydrate Polymers，2016，153：592-599.
17	YAP J X， GAN W C， LEO C P.Porous cellulose beads intercalated with calcium carbonate nanoparticles for dye adsorption［J］.Desalination and Water Treatment，2022，277：206-214.
18	MALLAKPOUR S， ABDOLMALEKI A， TABESH F.Ultrasonic-assisted manufacturing of new hydrogel nanocomposite biosorbent containing calcium carbonate nanoparticles and tragacanth gum for removal of heavy metal［J］.Ultrasonics Sonochemistry，2018，41：572-581.
19	CHANG Chunyu， PENG Na， HE Meng，et al.Fabrication and properties of chitin/hydroxyapatite hybrid hydrogels as scaffold nano-materials［J］.Carbohydrate Polymers，2013，91（1）：7-13.
20	WU Wenqin， YANG Yan， ZHOU Haihui，et al.Highly efficient removal of Cu（Ⅱ） from aqueous solution by using graphene oxide［J］.Water，Air，& Soil Pollution，2012，224（1）：1372.
21	TRAN V V， PARK D， LEE Y C.Hydrogel applications for adsorption of contaminants in water and wastewater treatment［J］.Environmental Science and Pollution Research International，2018，25（25）：24569-24599.
22	FAN Xiangbo， WANG Xiaohong， CAI Yaotao，et al.Functionalized cotton charcoal/chitosan biomass-based hydrogel for capturing Pb²⁺，Cu²⁺ and MB［J］.Journal of Hazardous Materials，2022，423：127191.
23	朱伟志，李雯静，贺媚，等.各向异性纤维素双交联水凝胶的制备与应用研究［J］.化工新型材料，2024，52（3）：226-230，235.
	ZHU Weizhi， LI Wenjing， HE Mei，et al.Preparation and application of anisotropic cellulose double-crosslinked hydrogels［J］.New Chemical Materials，2024，52（3）：226-230，235.
24	LI Peiyi， LIU Hezhen， ZHOU Miaomiao，et al.Preparation of green magnetic hydrogel from cellulose nanofibril（CNF） originated from soybean residue for effective and rapid removal of copper ions from waste water［J］.Industrial Crops and Products，2022，186：115257.
25	LIANG Lili， YANG Xingbao， LIANG Xuan，et al.Synergistic improvement of mechanical and adsorption properties by constructing physical multiple-network hydrogel for removing uranium［J］.Journal of Molecular Structure，2024，1298：137046.

吸附剂	准一级动力学模型				准二级动力学模型
吸附剂	k₁/ min^‒1	q_e/ （mg·g^-1）	R²	k₂/ （g·mg^-1·min^-1）	q_e/ （mg·g^-1）	R²
CMC	0.018	141.444	0.968	2.153×10^-4	151.351	0.993
2.5% NCC/CMC	0.014	166.510	0.984	1.293×10^-4	180.878	0.998
5.0% NCC/CMC	0.018	151.917	0.987	2.042×10^-4	162.105	0.998

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Study on preparation of cellulose based hydrogel doped with nano-calcium carbonate and its adsorption properties of copper ions

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