磺酸基改性二维Ti3C2Tx纳米材料制备与Pb2+吸附性能

李晴晴; 蒋豪丽; 葛梦妮; 杨彦; 郭风; 龙云良; 张建峰

doi:10.13801/j.cnki.fhclxb.20210425.003

磺酸基改性二维Ti₃C₂T_x纳米材料制备与Pb²⁺吸附性能

doi: 10.13801/j.cnki.fhclxb.20210425.003

李晴晴^1,,
蒋豪丽^1,,
葛梦妮¹,
杨彦^{2, 3},
郭风^{2, 3},
龙云良^4,,
张建峰^{1, 3, 4, ,}

1.
河海大学　力学与材料学院，南京 210098
2.
南京水利科学研究院，南京 210029
3.
江苏省非常规水源开发及利用工程技术研究中心，南京 210000
4.
南京水联天下海水淡化研究院有限公司，南京 210000

基金项目: 国家重点研发计划(2018YFC1508704)

详细信息

通讯作者:
张建峰，博士，教授，博士生导师，研究方向为功能复合材料研发及应用　E-mail：jfzhang@hhu.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2020-12-02
- 录用日期: 2021-04-19
- 网络出版日期: 2021-04-26
- 刊出日期: 2021-11-01

Study on preparation of two-dimensional Ti₃C₂T_x nanomaterials modified by sulfonic acid groups and the adsorption performance of lead(II) ion

LI Qingqing^1
,,
JIANG Haoli^1
,,
GE Mengni¹,
YANG Yan^{2, 3},
GUO Feng^{2, 3},
LONG Yunliang^4
,,
ZHANG Jianfeng^{1, 3, 4
, ,}

1.
College of Mechanics and Materials, Hohai University, Nanjing 210098, China
2.
Nanjing Hydraulic Research Institute, Nanjing 210029, China
3.
Jiangsu Engineering Research Center on Utilization of Alternative Water Resources, Nanjing 210000, China
4.
Nanjing Aqua-world Institute of Seawater Desalination CO., LTD, Nanjing, 210000, China

摘要

摘要: 对二维Ti₃C₂T_x材料进行了磺酸基团接枝改性(Ti₃C₂T_x—SO₃H)，表征了改性前后微观结构的变化，研究了对重金属Pb²⁺的吸附行为与机制。XRD、FTIR及EDS表明磺酸基团在Ti₃C₂T_x表面成功接枝，而SEM则发现Ti₃C₂T_x−SO₃H呈现较Ti₃C₂T_x更轻薄的层状结构。改性后，Ti₃C₂T_x—SO₃H对重金属Pb²⁺20 min内达到吸附平衡，最大吸附量达到733.6 mg·g⁻¹，较Ti₃C₂T_x吸附量提升了23%，且吸附量随着pH(2~6)的增加而逐渐增大，在Mg²⁺、Ca²⁺、Co²⁺、Zn²⁺等共存离子的干扰下，仍保持较高的吸附水平。机制分析表明，改性前后吸附过程均符合准二级动力学模型和Langmuir吸附等温线拟合模型，以单分子层化学吸附为主，但由于磺酸基团提供了更多的吸附饱和活性位点，并提高了Ti₃C₂T_x在水溶液中的分散性，使改性后对Pb²⁺吸附性能更优异。
- Ti₃C₂T_x /
- Ti₃C₂T_x—SO₃H /
- 接枝改性 /
- Pb²⁺ /
- 吸附
Abstract: The two-dimensional Ti₃C₂T_x was modified by sulfonic acid group grafting (abbreviated as Ti₃C₂T_x—SO₃H), and its microstructure before and after the modification was characterized. The adsorption behavior and mechanism of heavy metal Pb²⁺ by the Ti₃C₂T_x—SO₃H were also investigated. XRD, FTIR and EDS analyses indicate that sulfonic acid group is successfully grafted on the surface of the Ti₃C₂T_x, while SEM shows that the Ti₃C₂T_x—SO₃H has a lighter and thinner layered structure than the Ti₃C₂T_x. Pb²⁺ adsorption by the Ti₃C₂T_x—SO₃H reaches equilibrium within 20 minutes. The maximum adsorption capacity of the Ti₃C₂T_x—SO₃H is 733.6 mg·g⁻¹, which is 23% higher than the Ti₃C₂T_x. And Pb²⁺ adsorption capacity by the Ti₃C₂T_x—SO₃H gradually increases with the increase of pH (2-6). Under the interference of coexisting ions such as Mg²⁺, Ca²⁺, Co²⁺ and Zn²⁺, the Ti₃C₂T_x-SO₃H still maintains a high level of Pb²⁺ adsorption. Pb²⁺ adsorption processes by both the Ti₃C₂T_x and the Ti₃C₂T_x—SO₃H fit well the pseudo second kinetic model and Langmuir isotherm model, suggesting that the adsorption processes are monolayer chemisorption. The Ti₃C₂T_x—SO₃H shows more excellent adsorption performance towards Pb²⁺ after adsorption mainly due to the more active sites provided by sulfonic acid group and the enhanced dispersion in aqueous solution.
- Ti₃C₂T_x /
- Ti₃C₂T_x—SO₃H /
- graft modification /
- Pb²⁺ /
- adsorption

HTML全文

图 1 Ti₃C₂T_x表面接枝磺酸基团(Ti₃C₂T_x—SO₃H)示意图

Figure 1. Schematic diagram of grafting sulfonic acid groups on the surface of Ti₃C₂T_x(Ti₃C₂T_x—SO₃H)

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图 2 Ti₃C₂T_x和Ti₃C₂T_x—SO₃H的XRD图谱 (a) 和FTIR图谱 (b)

Figure 2. XRD patterns (a) and FTIR spectra (b) of Ti₃C₂T_x and Ti₃C₂T_x—SO₃H

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图 3 Ti₃C₂T_x((a), (c)) 和Ti₃C₂T_x—SO₃H ((b),(d)) 的SEM图像和EDS图谱

Figure 3. SEM images and EDS patterns of Ti₃C₂T_x ((a), (c)) and Ti₃C₂T_x—SO₃H ((b),(d))

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图 4 不同质量Ti₃C₂T_x (a) 和Ti₃C₂T_x—SO₃H (b) 吸附30 mg·L⁻¹ Pb²⁺的相对浓度对比图

Figure 4. Comparison diagrams of the relative concentration of 30 mg·L⁻¹ Pb²⁺ adsorbed by Ti₃C₂T_x (a) and Ti₃C₂T_x—SO₃H (b) of different weights

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图 5 Ti₃C₂T_x (a) 和Ti₃C₂T_x—SO₃H (b) 对低浓度Pb²⁺的吸附量曲线

Figure 5. Adsorption capacity curves of low concentration Pb²⁺ by Ti₃C₂T_x (a) and Ti₃C₂T_x—SO₃H (b)

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图 6 Ti₃C₂T_x (a) 和Ti₃C₂T_x—SO₃H (b) 对高浓度Pb²⁺的吸附量曲线

Figure 6. Adsorption capacity curves of high concentration Pb²⁺ by Ti₃C₂T_x (a) and Ti₃C₂T_x—SO₃H (b)

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图 7 Ti₃C₂T_x—SO₃H在不同pH下对30 mg·L⁻¹ Pb²⁺的吸附量曲线

Figure 7. Adsorption capacity diagrams of 30 mg·L⁻¹ Pb²⁺ by Ti₃C₂T_x—SO₃H at different pH

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图 8 溶液中共存离子对Ti₃C₂T_x—SO₃H吸附Pb²⁺的影响([Pb²⁺]=30 mg·L⁻¹, [M²⁺]=30 mg·L⁻¹, M=Mg, Ca, Co, Zn)

Figure 8. Effect of coexisting cations in solution on Ti₃C₂T_x—SO₃H adsorbing Pb²⁺ ([Pb²⁺]=30 mg·L⁻¹, [M²⁺]=30 mg·L⁻¹, M= Mg, Ca, Co, Zn)

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图 9 Ti₃C₂T_x—SO₃H吸附Pb²⁺后的SEM图像 ((a), (b)) 和EDS图谱 ((d)~(h))

Figure 9. SEM images ((a), (b)) and EDS patterns ((d)-(h)) of Ti₃C₂T_x—SO₃H after adsorbing Pb²⁺

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图 10 Ti₃C₂T_x (a) 和Ti₃C₂T_x—SO₃H (b) 吸附Pb²⁺的等温吸附曲线拟合曲线

Figure 10. Fitting curves of adsorption isotherm curves of Pb²⁺ adsorbed by Ti₃C₂T_x (a) and Ti₃C₂T_x—SO₃H (b)

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图 11 Ti₃C₂T_x ((a1), (a2), (a3)) 和Ti₃C₂T_x—SO₃H ((b1), (b2), (b3))吸附Pb²⁺的动力学模型拟合曲线((a1,b1) 准一级吸附动力学模型；(a2,b2) 准二级吸附动力学模型；(a3, b3) 颗粒内扩散模型)

Figure 11. Kinetic equation fitting curves of Pb²⁺ adsorbed by Ti₃C₂T_x ((a1), (a2), (a3)) and Ti₃C₂T_x—SO₃H ((b1), (b2), (b3)) ((a1, b1) Pseudo-first-order adsorption kinetic model; (a2, b2) Pseudo-second-order adsorption kinetic model; (a3, b3) Intra-particle diffusion model)

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图 12 Ti₃C₂T_x—SO₃H材料对Pb²⁺的吸附机制图

Figure 12. Adsorption mechanism of Ti₃C₂T_x—SO₃H on Pb²⁺

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表 1 不同吸附剂对Pb²⁺的吸附量对比表

Table 1. Comparison table of Pb²⁺ adsorption capacity of different adsorbents

Adsorbents	q_max/(mg·g⁻¹)	pH	T/℃	Ref.
Amino-modified attapulgite	49.0	6.0	25	[26]
CNFs/GO/Fe₃O₄ composite materials	126.5	6.0	25	[27]
Saponified muskmelon peel	167.9	4-6.4	25	[28]
Seaweed laminaria japonica	279.5	3-4.8	25	[29]
Silanized red mud	361.0	6	25	[30]
GO-LDH composite materials	387.7	5.2	25	[31]
GO	757.6	3.0	25	[32]
Ti₃C₂T_x	38.5	6.0	40	[16]
Ti₃C₂T_x	594.3	6.0	25	This work
Ti₃C₂T_x—SO₃H	733.6	5.9	25	This work
Notes: q_max—maximum adsorption capacity; CNFs—Cellulose nanofibrills; GO—Graphene oxide; GO-LDH—Graphene oxide-double layer magnesium & aluminum hydroxide.

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表 2 25℃下二维Ti₃C₂T_x和Ti₃C₂T_x—SO₃H吸附Pb²⁺的吸附等温式参数表

Table 2. Ti₃C₂T_x and Ti₃C₂T_x—SO₃H adsorption isotherm parameters of Pb²⁺ at 25℃

Sample	Dosage/g	Langmuir			Freundlich
Sample	Dosage/g	q_m/(mg·g⁻¹)	K_L/(L·mg⁻¹)	R²	n	k_F/(mg^1-(1/n) ·L^1/n·g⁻¹)	R²
Ti₃C₂T_x	0.02	793.65	0.0001	0.9604	0.0039	1.2616	0.9817
Ti₃C₂T_x	0.04	300.48	0.0229	0.9338	0.0001	1.0442	0.9694
Ti₃C₂T_x—SO₃H	0.005	199.01	0.0073	0.9366	−	−	−
Ti₃C₂T_x—SO₃H	0.01	811.10	0.0003	0.9309	−	−	−
Notes: q_m—Maximum saturation adsorption capacity; R—Correlation coefficient; K_L—Langmuir adsorption equilibrium constant; K_F, n—Freundlich adsorption equilibrium constant, denotes adsorption capacity and density in adsorption, respectively.

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参考文献(32)

[1]	任春溶. 磁性纳米复合材料的制备及其对重金属离子的吸附性能研究[D]. 杭州: 浙江大学, 2017. REN Chunrong. Preparation of magnetic nanocomposites for adsorption of heavy metal ions[D]. Hangzhou: Zhe-jiang University, 2017(in Chinese).
[2]	LIANG Qianqian, YU Liuhua, JIANG Wei, et al. One-pot synthesis of magnetic graphitic carbon nitride photocatalyst with synergistic catalytic performance under visible-light irradiation[J]. Journal of Photochemistry and Photobiology A: Chemistry,2017,335:165-173. doi: 10.1016/j.jphotochem.2016.11.012
[3]	洪亚军, 冯承莲, 徐祖信, 等. 重金属对水生生物的毒性效应机制研究进展[J]. 环境工程, 2019, 37(11):1-9. HONG Yajun, FENG Chenglian, XU Zuxin, et al. Advances on ecotoxicity effects of heavy metals to aquatic organisms and the mechanisms[J]. Environmental Engineering,2019,37(11):1-9(in Chinese).
[4]	SONG Yueqin, ZHOU Xiaolong, WANG Jin an. Adsorption performance of activated carbon for methane with low concentration at atmospheric pressure[J]. Energy Sources Part A Recovery Utilization and Environmental Effects,2021,43(11):1337-1347. doi: 10.1080/15567036.2019.1636903
[5]	武雪梅. 天然矿物类吸附剂的复合改性及脱氮除磷性能研究[D]. 武汉: 华中科技大学, 2019. WU Xuemei. Study on the compound modification of natural mineral adsorbents to remove nitrogen and phosphorus[D]. Wuhan: Huazhong University of Science & Technology, 2019(in Chinese).
[6]	林驰浩, 徐劼, 王嘉俊, 等. 生物质材料在重金属废水处理中的应用及其研究进展[J]. 广州化工, 2020, 48(5):24-26, 104. doi: 10.3969/j.issn.1001-9677.2020.05.014 LIN Chihao, XU Jie, WANG Jiajun, et al. Application and research progress on biomass materials in heavy metal wastewater treatment[J]. Guangzhou Chemical Industry,2020,48(5):24-26, 104(in Chinese). doi: 10.3969/j.issn.1001-9677.2020.05.014
[7]	ZHOU Dawei. Multifunctional MXene nanosheets as host materials with superior adsorption ability for enhanced electrochemical performance[J]. Ionics,2021,27:1291-1296. doi: 10.1007/s11581-020-03863-4
[8]	ZHANG Shan, TIAN Lidong, CHEN Xiaohu, et al. Ultralight graphene/carbon nanofibers/carbon nanotubes aerogels with thermal insulating and hot-oil adsorption performance[J]. Journal of Materials Science,2021,56(11):7409-7419.
[9]	ABGHOUI Y, SIGTRYGGSSON S B, EGILL S. Biomimetic nitrogen fixation catalyzed by transition metal sulfide surfaces in an electrolytic cell[J]. ChemSusChem,2019,12(18):4265-4273. doi: 10.1002/cssc.201901429
[10]	SUN Yingzhu, CHEN Ming, LIU Hao, et al. Adsorptive removal of dye and antibiotic from water with functionalized zirconium-based metal organic framework and graphene oxide composite nanomaterial UiO-66-(OH)₂/GO[J]. Applied Surface Science,2020,525:146614. doi: 10.1016/j.apsusc.2020.146614
[11]	HE Peng, CAO Maosheng, CAI Yongzhu, et al. Self-assembling flexible 2D carbide MXene film with tunable integrated electron migration and group relaxation toward energy storage and green EMI shielding[J]. Carbon,2020,157:80-89. doi: 10.1016/j.carbon.2019.10.009
[12]	YASAEI P, TU Qing, XU Yaobin, et al. Mapping hot spots at heterogeneities of few-layer Ti₃C₂ MXene Sheets[J]. ACS Nano,2019,13(3):3301-3309. doi: 10.1021/acsnano.8b09103
[13]	周晓伟. Ti₃C₂T_x的制备表征及其SERS应用研究[D]. 天津: 天津大学, 2018. ZHOU Xiaowei. The synthesis, characterization of Ti₃C₂T_x and applying on SERS study[D]. Tianjin: Tianjin University, 2018(in Chinese).
[14]	ZHANG Yujuan, LAN Jianhui, WANG Lin et al. Adsorption of uranyl species on hydroxylated titanium carbide nanosheet: A first-principles study[J]. Journal of Hazardous Materials,2016,308(308):402-410.
[15]	FARD A K, MCKAY G, CHAMOUN R, et al. Barium removal from synthetic natural and produced water using MXene as two dimensional (2D) nanosheet adsorbent[J]. Chemical Engineering Journal,2017,317:331-342. doi: 10.1016/j.cej.2017.02.090
[16]	JUN B M, HER N G, PARK C M, et al. Effective removal of Pb (II) from synthetic wastewater using Ti₃C₂T_x MXene[J]. Environmental Science: Water Research & Technology,2020,6(1):173-180.
[17]	田程程. 新型多功能纳米复合材料的合成及其催化性能研究[D]. 上海: 华东理工大学, 2014. TIAN Chengcheng. Synthesis and catalytic performance of novel multifunctional nanocomposites[D]. Shanghai: East China University of Science and Technology, 2014(in Chinese).
[18]	ZHANG Pengcheng, WANG Lin, HUANG Zhiwei, et al. Aryl diazonium-assisted amidoximation of MXene for boosting water stability and uranyl sequestration via electrochemical sorption[J]. ACS Applied Materials & Interfaces,2020,12:15579-15587.
[19]	SEHYEONG L, HYUNSU P, JIN H K, et al. Polyelectrolyte-grafted Ti₃C₂-MXenes stable in extreme salinity aquatic conditions for remediation of contaminated subsurface environments[J]. RSC Advances,2020,10:25966-25978. doi: 10.1039/D0RA04348F
[20]	LI Yahui, DENG Yanan, ZHANG Jianfeng, et al. Synthesis of restacking-free wrinkled Ti₃C₂T_x monolayers by sulfonic acid group grafting and N-doped carbon decoration for enhanced supercapacitor performance[J]. Journal of Alloys and Compounds,2020,842:155985. doi: 10.1016/j.jallcom.2020.155985
[21]	LI Yahui, DENG Yanan, ZHANG Jianfeng, et al. Tunable energy storage capacity of two-dimensional Ti₃C₂T_x modified by a facile two-step pillaring strategy for high performance supercapacitor electrodes[J]. Nanoscale,2019,11(45):21981-21989. doi: 10.1039/C9NR07259D
[22]	OBAID S A. Langmuir, Freundlich and Tamkin adsorption isotherms and kinetics for the removal aartichoke tournefortii straw from agricultural waste[J]. Journal of Physics Conference Series,2020,1664:012011. doi: 10.1088/1742-6596/1664/1/012011
[23]	MARCU C, VARODI C, BALLA A. Adsorption kinetics of chromium (VI) from aqueous solution using an anion exchange resin[J]. Analytical Letters,2020,54:140-149.
[24]	SI Y C, SAMULSKI E T. Synthesis of water soluble graphene[J]. Nano Letters,2008,8:1679-1682. doi: 10.1021/nl080604h
[25]	SUGANUMA S, NAKAJIMA K, KITANO M et al. SO₃H-bearing mesoporous carbon with highly selective catalysis[J]. Microporous and Mesoporous Materials,2011,143(2-3):443-450. doi: 10.1016/j.micromeso.2011.03.028
[26]	XU Lei, LIU Yani, WANG Jingang, et al. Selective adsorption of Pb²⁺ and Cu²⁺ on amino-modified attapulgite: kinetic, thermal dynamic and DFT studies[J]. Journal of Hazardous Materials,2021,404:124140. doi: 10.1016/j.jhazmat.2020.124140
[27]	HOSSEINI M, DIZAJI H Z, TAGHAVI M, et al. Preparation of ultra-lightweight and surface-tailored cellulose nanofibril composite cryogels derived from date palm waste as powerful and low-cost heavy metals adsorbent to treat aqueous medium[J]. Industrial Crops and Products,2020,154:112696. doi: 10.1016/j.indcrop.2020.112696
[28]	HUANG Kai, ZHU Hongmin. Removal of Pb²⁺ from aqueous solution by adsorption on chemically modified muskmelon peel[J]. Environmental Science and Pollution Research International,2013,20(7):4424-4434. doi: 10.1007/s11356-012-1361-7
[29]	GHIMIRE K N, INOUE K, OHTO K, et al. Adsorption study of metal ions onto crosslinked seaweed Laminaria japonica[J]. Bioresource Technology,2008,99(1):32-37. doi: 10.1016/j.biortech.2006.11.057
[30]	刘江龙, 郭焱, 何小山, 等. 硅烷化赤泥的制备及其对水中铅离子吸附性能分析[J]. 环境工程, 2019, 37(11):36-44. LIU Jianglong, GUO Yan, HE Xiaoshan, et al. Preparation of silanized red mud and its adsorption properties for lead ions in water[J]. Environmental Engineering,2019,37(11):36-44(in Chinese).
[31]	周博秋, 李慧强, 廖维, 等. GO-LDH复合材料对水中铅离子的吸附性能[J]. 中国给水排水, 2019, 35(17):105-111. ZHOU Boqiu, LI Huiqiang, LIAO Wei, et al. Adsorption properties of GO-LDH composite materials to lead ion in water[J]. China Water & Wastewater,2019,35(17):105-111(in Chinese).
[32]	梁程. 还原条件下氧化石墨烯对铅离子吸附/解吸附性能的研究[D]. 西安: 西安建筑科技大学, 2016. LIANG Cheng. A study on oxide graphene’s adsorption and desorption property of lead in the reductive condition[D]. Xi’an: Xi’an University of Architecture and Technology, 2016(in Chinese).