<strong>Fe-BTC</strong>表面氨基化及对染料和重金属离子的吸附性能研究

doi:10.11900/0412.1961.2019.00079

金属学报

2019, Vol. 55

Issue (7): 821-830 DOI: 10.11900/0412.1961.2019.00079

本期目录 | 过刊浏览

Fe-BTC表面氨基化及对染料和重金属离子的吸附性能研究

曹梦薇,蔡桃,张霞(

)

东北大学理学院沈阳 110819

Study on Amination Modification of Fe-BTC and Their Adsorption for Dyes and Heavy Metal Ions

Mengwei CAO,Tao CAI,Xia ZHANG(

)

College of Sciences, Northeastern University, Shenyang 110819, China

引用本文:

曹梦薇,蔡桃,张霞. Fe-BTC表面氨基化及对染料和重金属离子的吸附性能研究[J]. 金属学报, 2019, 55(7): 821-830.
Mengwei CAO, Tao CAI, Xia ZHANG. Study on Amination Modification of Fe-BTC and Their Adsorption for Dyes and Heavy Metal Ions[J]. Acta Metall Sin, 2019, 55(7): 821-830.

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摘要:

利用二乙烯三胺(DETA)对Fe-BTC结构进行改性，并系统研究了其对刚果红(CR)和重金属离子Pb(II)的吸附性能。应用SEM、XRD、Fourier变换红外光谱仪(FT-IR)、N₂吸附-解吸实验、Zeta电位测定等方法对改性前后的Fe-BTC材料进行结构和表面性质表征。结果表明，在保持Fe-BTC晶体结构的前提下，DETA的掺杂可有效增加Fe-BTC表面—NH₂并改变其表面的电性。在对CR和Pb(II)的吸附实验中，DETA-Fe-BTC对CR和Pb(Ⅱ)的吸附量明显提高，对比实验证明了DETA-Fe-BTC对于CR和Pb(II)的吸附选择性。对吸附条件进行了优化并对于吸附的热力学和动力学数据进行了拟合。在循环吸附脱附实验中，DETA-Fe-BTC表现出对于CR和Pb(II)优秀的吸附性能稳定性。

关键词 ：固相吸附, 金属有机骨架材料, 表面功能化, 有机染料, 重金属离子

Abstract：

The efficient removal of synthetic organics and metal ions from wastewater is an urgent target in the environment remedy. Metal-organic frameworks (MOFs) have received extensive attention owing to their large surface area, tunable pore size and versatile composition of metal and organic ligand, which have presented potential applications in the adsorption/separation of gas, metal ions and also organic dyes. Furthermore, the surface functionalization with some special groups has been proved to be effective in improving the adsorption activity and selectivity. In this work, the diethylenetriamine (DETA) was used to modify the Fe-BTC, and then their adsorption properties toward Congo red (CR) and Pb(II) were studied systematically. SEM, XRD, Fourier transform infrared spectroscopy (FT-IR), N₂ adsorption-desorption experiments and Zeta potential measurements were employed to characterize the structure and surface properties of these modified Fe-BTC materials. The results showed that the incorporation of DETA maintained the crystal structure of Fe-BTC as while as effectively increased the surface—NH₂ group and also changed the surface charge properties. In the adsorption experiments of CR and Pb(II), the adsorption capacity on the DETA-Fe-BTC was significantly increased compared to that on original Fe-BTC, the adsorption conditions were optimized and the adsorption thermodynamics were analyzed. The adsorption selectivity of DETA-BTC for CR and Pb(II) was also determined through the contrast experiments. In the cyclic adsorption experiments, the DETA-Fe-BTC also exhibited the excellent adsorption stability for CR and Pb(II).

Key words： solid adsorption metal-organic framework surface functionalization organic dye heavy metal ion

收稿日期: 2019-03-25

ZTFLH:

TQ13

基金资助:中央高校基本科研业务专项资金项目(No.182410001);国家级大学生创新创业训练计划项目(No.201910145028)

作者简介: 曹梦薇，女，1998年生，本科生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2019.00079 或 https://www.ams.org.cn/CN/Y2019/V55/I7/821

图1 Fe-BTC和DETA-Fe-BTC的XRD谱以及Fourier变换红外光谱

图2 Fe-BTC和DETA-Fe-BTC表面Zeta电位随pH值变化曲线以及N2吸附-脱附曲线

图3 原始Fe-BTC和DETA-Fe-BTC的SEM像

图4 不同条件下，Fe-BTC和DETA-Fe-BTC对于CR和Pb(II)的平衡吸附量和吸附动力学曲线

图5 CR和 Pb(II)的吸附动力学拟合曲线

Adsorbate[border:border-top:solid;border-right:solid;]

$c 0$

mg·L^-1

$q$ _t_(max)

mg·g^-1

Pseudo-first order

Pseudo-second order

$q$ _e

mg·g^-1

k_l

min^-1

R²

$q$ _e

mg·g^-1

k₂

g·mg^-1·min^-1

R²

Pb(Ⅱ)

1500

100

2569.72

134.83

659.14

8.44

1.85×10^-2

4.29×10^-3

0.79551

0.78881

2696.43

135.32

4.48×10^-5

1.18×10^-2

0.99779

0.99998

表1 分别应用准一级和准二级动力学方程对于CR和Pb(II)的吸附动力学进行拟合的参数

图6 Fe-BTC 和DETA-Fe-BTC对于CR和Pb(II)的吸附等温线(25 ℃)

图7 分别应用Freundlich模型和Langmuir模型对DETA-Fe-BTC的吸附等温数据进行拟合的曲线

Adsorbate	Langmuir model			Freundlich model
	q_m	K_L	R²	$K$ _F	n	R²
	mg·g^-1	L·mg^-1		mg^1-1/ⁿ·L^1/ⁿ·g^-1
CR	3033.92	0.0623	0.97427	529.80	3.0733	0.88471
Pb(Ⅱ)	334.45	0.1397	0.98924	57.70	2.1204	0.92303

表2 应用Freundlich模型和Langmuir模型对DETA-Fe-BTC表面CR和Pb(II)吸附等温线进行拟合的参数

图8 DETA-Fe-BTC对于不同金属离子和染料的吸附量对比

表3 不同MOFs对CR的吸附容量对比[28,29,30,31,32,33,34,35]

表4 不同MOFs对Pb(II)的吸附容量对比[23,36,37]

图9 DETA-Fe-BTC去除CR和Pb(II)的循环性能测试

[1]	Gao Q, Xu J, Bu X H. Recent advances about metal-organic frameworks in the removal of pollutants from wastewater [J]. Coord. Chem. Rev., 2019, 378: 17
[2]	Ahmad A, Mohd-Setapar S H, Chuong C S, et al. Recent advances in new generation dye removal technologies: Novel search for approaches to reprocess wastewater [J]. RSC Adv., 2015, 5: 30801
[3]	Yagub M T, Sen T K, Afroze S, et al. Dye and its removal from aqueous solution by adsorption: A review [J]. Adv. Colloid Interface Sci., 2014, 209: 172
[4]	Kadirvelu K, Kavipriya M, Karthika C, et al. Utilization of various agricultural wastes for activated carbon preparation and application for the removal of dyes and metal ions from aqueous solutions [J]. Bioresourc. Technol., 2003, 87: 129
[5]	Wen J, Fang Y, Zeng G M. Progress and prospect of adsorptive removal of heavy metal ions from aqueous solution using metal-organic frameworks: A review of studies from the last decade [J]. Chemosphere, 2018, 201: 627
[6]	Sun D T, Peng L, Reeder W S, et al. Rapid, selective heavy metal removal from water by a metal-organic framework/polydopamine composite [J]. ACS Cent. Sci., 2018, 4: 349
[7]	Haque E, Lee J E, Jang I T, et al. Adsorptive removal of methyl orange from aqueous solution with metal-organic frameworks, porous chromium-benzenedicarboxylates [J]. J. Hazard. Mater., 2010, 181: 535
[8]	Bolto B, Gregory J. Organic polyelectrolytes in water treatment [J]. Water Res., 2007, 41: 2301
[9]	Savage N, Diallo M S. Nanomaterials and water purification: Opportunities and challenges [J]. J. Nanopart. Res., 2005, 7: 331
[10]	Cao Y, Li X B. Adsorption of graphene for the removal of inorganic pollutants in water purification: A review [J]. Adsorption, 2014, 20: 713
[11]	Dias J M, Alvim-Ferraz M C M, Almeida M F, et al. Waste materials for activated carbon preparation and its use in aqueous-phase treatment: A review [J]. J. Environ. Manage., 2007, 85: 833
[12]	Tao Y S, Kanoh H, Abrams L, et al. Mesopore-modified zeolites: Preparation, characterization, and applications [J]. Chem. Rev., 2006, 106: 896
[13]	Lee B, Kim Y, Lee H, et al. Synthesis of functionalized porous silicas via templating method as heavy metal ion adsorbents: The introduction of surface hydrophilicity onto the surface of adsorbents [J]. Micropor. Mesopor. Mater., 2001, 50: 77
[14]	Hua M, Zhang S J, Pan B C, et al. Heavy metal removal from water/wastewater by nanosized metal oxides: A review [J]. J. Hazard. Mater., 2012, 211-212: 317
[15]	Zhang W X, Liao P Q, Lin R B, et al. Metal cluster-based functional porous coordination polymers [J]. Coord. Chem. Rev, 2015, 293: 263
[16]	Eddaoudi M, Kim J, Rosi N, et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage [J]. Science, 2002, 295: 469
[17]	Wu Y N, Zhou M M, Li S, et al. Magnetic metal-organic frameworks: γ-Fe2O3@ MOFs via confined in situ pyrolysis method for drug delivery [J]. Small, 2014, 10: 2927
[18]	Li Y W, Li J R, Wang L F, et al. Microporous metal-organic frameworks with open metal sites as sorbents for selective gas adsorption and fluorescence sensors for metal ions [J]. J. Mater. Chem., 2013, 1A: 495
[19]	Xu Y, Jin J J, Li X L, et al. Magnetization of a Cu (II)-1, 3, 5-benzenetricarboxylate metal-organic framework for efficient solid-phase extraction of Congo Red [J]. Microchim. Acta, 2015, 182: 2313
[20]	Haque E, Jun J W, Jhung S H. Adsorptive removal of methyl orange and methylene blue from aqueous solution with a metal-organic framework material, iron terephthalate (MOF-235) [J]. J. Hazard. Mater., 2011, 185: 507
[21]	Li Z Q, Yang J C, Sui K W, et al. Facile synthesis of metal-organic framework MOF-808 for arsenic removal [J]. Mater. Lett., 2015, 160: 412
[22]	Bai Z Q, Yuan L Y, Zhu L, et al. Introduction of amino groups into acid-resistant MOFs for enhanced U (VI) sorption [J]. J. Mater. Chem., 2015, 3A: 525
[23]	Luo X B, Ding L, Luo J M. Adsorptive removal of Pb (II) ions from aqueous samples with amino-functionalization of metal-organic frameworks MIL-101 (Cr) [J]. J. Chem. Eng. Data, 2015, 60: 1732
[24]	Martínez F, Leo P, Orcajo G, et al. Sustainable Fe-BTC catalyst for efficient removal of mehylene blue by advanced fenton oxidation[J]. Cataly. Today, 2018, 313: 6
[25]	Thommes M, Kaneko K, Neimark A V, et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report) [J]. Pure Appl. Chem., 2015, 87: 1051
[26]	Ma W, Lv T F, Song X Y, et al. Characteristics of selective fluoride adsorption by biocarbon-Mg/Al layered double hydroxides composites from protein solutions: Kinetics and equilibrium isotherms study [J]. J. Hazard. Mater., 2014, 268: 166
[27]	Kumar K V, Sivanesan S. Comparison of linear and non-linear method in estimating the sorption isotherm parameters for safranin onto activated carbon [J]. J. Hazard. Mater., 2005, 123: 288
[28]	Quan X P, Sun Z Q, Meng H, et al. Polyethyleneimine (PEI) incorporated Cu-BTC composites: Extendedapplications in ultra-high efficient removal of congo red [J]. J. Solid State Chem., 2019, 270: 231
[29]	Namasivayam C, Kavitha D. Removal of Congo red from water by adsorption onto activated carbon prepared from coir pith, an agricultural solid waste [J]. Dyes Pigments, 2002, 54: 47
[30]	Masoomi M Y, Morsali A, Junk P C, et al. Ultrasonic assisted synthesis of two new coordination polymers and their applications as precursors for preparation of nano-materials [J]. Ultrason. Sonochem., 2017, 34: 984
[31]	Zhang X Q, Gao Y F, Liu H T, et al. Fabrication of porous metal-organic frameworks via a mixed-ligand strategy for highly selective and efficient dye adsorption in aqueous solution [J]. CrystEngComm., 2015, 17: 6037
[32]	Yang Q F, Wang Y, Wang J, et al. High effective adsorption/removal of illegal food dyes from contaminated aqueous solution by Zr-MOFs (UiO-67) [J]. Food Chem., 2018, 254: 241
[33]	Abdi J, Vossoughi M, Mahmoodi N M, et al. Synthesis of metal-organic framework hybrid nanocomposites based on GO and CNT with high adsorption capacity for dye removal [J]. Chem. Eng. J., 2017, 326: 1145
[34]	Xiao S L, Li Y H, Ma P J, et al. Synthesis and characterizations of two bis (benzimidazole)-based cobaltous coordination polymers with high adsorption capacity for congo red dye [J]. Inorg. Chem. Commun., 2013, 37: 54
[35]	Yang J M, Ying R J, Han C X, et al. Adsorptive removal of organic dyes from aqueous solution by a Zr-based metal-organic framework: Effects of Ce(III) doping [J]. Dalton Trans, 2018, 47: 3913
[36]	Saleem H, Rafique U, Davies R P. Investigations on post-synthetically modified UiO-66-NH2 for the adsorptive removal of heavy metal ions from aqueous solution [J]. Micropor. Mesopor. Mater., 2016, 221: 238
[37]	Yin N, Wang K, Li Z Q. Rapid microwave-promoted synthesis of Zr-MOFs: An efficient adsorbent for Pb (II) removal [J]. Chem. Lett., 2016, 45: 625

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