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
Cite this article:
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.
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).
Fund: Fundamental Research Funds for the Central Universities(No.182410001);National Undergraduate Innovation and Entrepreneurship Training Program(No.201910145028)
Fig.1 XRD spectra (a) and Fourier transform infrared (FT-IR) spectra (b) of pristine Fe-BTC and DETA-Fe-BTC
Fig.2 The dependence of Zeta potentials upon different pH values (a) and N2 adsorption-desorption isotherms (b) for original Fe-BTC and DETA-Fe-BTC (P—partial pressure of adsorbate, P0—saturated vapor pressure of adsorbent)
Fig.3 SEM images of original Fe-BTC (a) and DETA-Fe-BTC (b) particles
Fig.4 Effects of pH values on the adsorption capacities (qe) of CR (a) and Pb(II) (b) on Fe-BTC and DETA-Fe-BTC, qe of CR (c) and Pb(II) (d) by DETA-Fe-BTC under different temperatures, adsorption kinetics of CR (e) and Pb(II) (f) on Fe-BTC and DETA-Fe-BTC
Fig.5 Fitting curves of adsorption kinetics data of CR (a, b) and Pb(II) (c, d) using pseudo-first-order kinetic model (a, c) and pseudo-second-order kinetic model (b, d) (qe—equilibrium adsorption amount, qt—adsorption amount at time t, R2—correlation coefficient)
Table 1 Simulating parameters of adsorption kinetics for CR and Pb(Ⅱ) on DETA-Fe-BTC
Fig.6 Adsorption isotherm of CR (a) and Pb (b) on Fe-BTC and DETA-Fe-BTC at 25 ℃
Fig.7 Fitting curves of adsorption isotherm data of CR (a, b) and Pb(II) (c, d) using Freundlich model (a, c) and Langmuir model (b, d) ( ce—equilibrium concentration of solution)
Adsorbate
Langmuir model
Freundlich model
qm
KL
R2
F
n
R2
mg·g-1
L·mg-1
mg1-1/n·L1/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
Table 2 Simulating parameters using Langmuir and Freundlich models based on the adsorption isotherm of CR and Pb(Ⅱ) on DETA-Fe-BTC
Fig.8 Comparison of adsorption capacity of three metal ions and three dyes using DETA-Fe-BTC as adsorbents
Solid adsorbent
Adsorption
Ref.
capacity
mg·g-1
DETA-Fe-BTC
3033.92
This work
Ni-MOFs
2046
[29]
MIL-68 (In) microrods
318
[30]
[Zn(BDC)(TIB)]·3H2O
60
[31]
UiO-67
1237
[32]
PEI-Cu-BTC
2578
[28]
GO/ZIF8
2489
[33]
[Co(L1)(tp)]n
928.4
[34]
Ce(III)-doped UiO-66
826
[35]
MIL-68(In) nanorods
1204
[30]
Table 3 Comparison of adsorption capacities of CR on different metal organic frameworks (MOFs) adsorbents[28,29,30,31,32,33,34,35]
Solid adsorbent
Adsorption
Ref.
capacity
mg·g-1
DETA-Fe-BTC
334.45
This work
MIL-101
15.8
[23]
ED-MIL-101(2 mmol)
25.6
[23]
ED-MIL-101(5 mmol)
81.1
[23]
UiO-66
8.4
[36]
UiO-66-NH2
31.2
[36]
Zr-MOFs
72.1
[37]
Melamine-Zr-MOFs
122
[37]
Table 4 Comparison of adsorption capacities of Pb(II) on different MOFs adsorbents[23,36,37]
Fig.9 Reusability of DETA-Fe-BTC in the cyclic removal of CR and Pb(II)
[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
