Please wait a minute...
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 |
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
全文: PDF(8080 KB)   HTML


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    

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 wordssolid adsorption    metal-organic framework    surface functionalization    organic dye    heavy metal ion
收稿日期: 2019-03-25     
ZTFLH:  TQ13  
通讯作者: 张霞     E-mail:
Corresponding author: Xia ZHANG     E-mail:
作者简介: 曹梦薇,女,1998年生,本科生


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. Acta Metall Sin, 2019, 55(7): 821-830.

链接本文:      或

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






Pseudo-first orderPseudo-second order





























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
AdsorbateLangmuir modelFreundlich model
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
Solid adsorbentAdsorptionRef.
DETA-Fe-BTC3033.92This work
MIL-68 (In) microrods318[30]
Ce(III)-doped UiO-66826[35]
MIL-68(In) nanorods1204[30]
表3  不同MOFs对CR的吸附容量对比[28,29,30,31,32,33,34,35]
Solid adsorbentAdsorptionRef.
DETA-Fe-BTC334.45This work
ED-MIL-101(2 mmol)25.6[23]
ED-MIL-101(5 mmol)81.1[23]
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
[1] 张 霞 宋 扬 王 誉 纪逯鹤 杨 媚 孟 皓. 超声共混合成Ni(HNCN)2/BiVO4复合可见光催化剂[J]. 金属学报, 0, (): 0-0.
[2] 荣凤鸣, 王誉, 张霞. 基于氰胺锌的复合光催化剂的结构与可见光催化性能[J]. 金属学报, 2018, 54(1): 76-82.
[3] 杨晓丹, 姜春海, 杨振明, 张劲松. 泡沫SiC负载钴基结构化催化剂的制备及其催化性能*[J]. 金属学报, 2014, 50(6): 762-768.
[4] 王盈, 邹兵林, 曹学强. Al-Ti-B4C体系熔体内燃烧合成TiC-TiB2颗粒局部增强钢基复合材料*[J]. 金属学报, 2014, 50(3): 367-372.
[5] 李合琴; 陈志宝 . 低掺杂La0.82Sr0.18MnO3巨磁电阻块材的低频内耗[J]. 金属学报, 2003, 39(11): 1170-1172 .
[6] 金海波; 邹宗树 . 原位自反应合成A1N粉体[J]. 金属学报, 2000, 36(7): 775-779 .
[7] 陈建峰; 王玉红 . 超重力反应结晶法制备纳米立方形CaCO3颗粒:I.实验研究[J]. 金属学报, 1999, 35(2): 179-182 .
[8] 王玉红; 陈建峰 . 超重力反应结晶法制备纳米立方形CaCO3颗粒:II.模型化研究[J]. 金属学报, 1999, 35(2): 183-186 .