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

doi:10.11900/0412.1961.2019.00079

Acta Metall Sin

2019, Vol. 55

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

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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

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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.

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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

Received: 25 March 2019

ZTFLH:

TQ13

Fund: Fundamental Research Funds for the Central Universities(No.182410001);National Undergraduate Innovation and Entrepreneurship Training Program(No.201910145028)

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	Mengwei CAO
	Tao CAI
	Xia ZHANG

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https://www.ams.org.cn/EN/10.11900/0412.1961.2019.00079 OR https://www.ams.org.cn/EN/Y2019/V55/I7/821

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 (q_e) of CR (a) and Pb(II) (b) on Fe-BTC and DETA-Fe-BTC, q_e 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) (q_e—equilibrium adsorption amount, q_t—adsorption amount at time t, R²—correlation coefficient)

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

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) ( c_e—equilibrium concentration of solution)

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

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

Table 3 Comparison of adsorption capacities of CR on different metal organic frameworks (MOFs) adsorbents^{[28,29,30,31,32,33,34,35]}

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)

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