High-capacity Polyvinyltetrazole-grafted Chelating Resin for Adsorption of Heavy Metal Ions†

doi:10.7503/cjcu20140029

Abstract

Abstract:

A novel polyvinyltetrazole-grafted chelating resin was prepared by grafting poly(acrylonitrile) onto the chloromethylated polystyrene beads via surface-initiated atom transfer radical polymerization(SI-ATRP), and followed by the reaction of cyano-tetrazole conversion under microwave assistance. The structure of the resin was characterized by Fourier transform infrared spectroscopy and elemental analysis, and the adsorption properties were evaluated with Pb(Ⅱ), Ni(Ⅱ) and Cd(Ⅱ). It was found that an increase in the polymerization time leads to the increases in grafting degree of acrylonitrile, the binding amount of tetrazoles and adsorption capacities of Pb(Ⅱ), Ni(Ⅱ), and Cd(Ⅱ). The results suggested that the polymerization of acrylonitrile on the resin surface was a controllable living polymerization, and the binding amount of tetrazoles on the resin surface and adsorption capacity of the resins could be adjusted by the polymerization time. The adsorption of three metal ions was mainly regarded as chemical adsorption based on the coordinating effect by analyzing the relationship between adsorption capacity with the solution pH, adsorption isotherm and adsorption kinetics. At the polymerization time of 10 h, the maximum sorption capacities of Pb(Ⅱ), Ni(Ⅱ) and Cd(Ⅱ) were 1.57, 1.68 and 1.92 mmol/g, respectively. Ten adsorption-desorption cycles demonstrated that the resin possessed high recycling efficiency and stability and was suitable for efficient removal of metal ions from aqueous solution.

Key words: Chloromethylated polystyrene bead, Surface-initiated atom transfer radical polymerization, Tetrazole, Heavy metal ion, Adsorption property

CLC Number:

O631
O647.3

TrendMD:

CHEN Youning, GAO Li, HE Maofang, WEI Yinmao. High-capacity Polyvinyltetrazole-grafted Chelating Resin for Adsorption of Heavy Metal Ions^†[J]. Chem. J. Chinese Universities, 2014, 35(7): 1596.

Figures/Tables 12

Scheme 1 Synthetic routes of polyvinyltetrazole-grafted PS resins

Fig.1 Relationship between the grafting degree of GMA with ATRP time

Table 1 Elemental composition and physical structure parameters of PS-CH2Cl and chelating resins

ATRP time /h	N content(%) (Calculated from GD)	Elemental ananlysis(%)			Surface area/ ( m²·g^-1)	BJH cumulative volume/ (cm³·g^-1 )	Average pore diameter/nm
ATRP time /h	N content(%) (Calculated from GD)	C			Surface area/ ( m²·g^-1)	H	N
1	1.40	70.38	4.963	1.14	47.35	0.24	32.24
3	4.07	69.20	5.381	3.14	45.14	0.23	25.06
5	6.45	69.20	5.210	5.04	40.06	0.21	23.65
10	9.19	65.54	4.305	8.61	28.81	0.20	19.71

Fig.2 SEM surface images of PS-CH2Cl(A), PAN-g-PS(B), PVT-g-PS(C) and photo of PVT-g-PS beads(D)

Fig.3 FTIR spectra of PS-CH2Cl(a), PAN-g-PS(b) and PVT-g-PS resins(c)

Fig.4 Effects of ATRP times on the content of tetrazole and on the sorption capacities

Fig.5 Effects of pH on the adsorption of PVT-g-PS resin for Pb(Ⅱ)(a), Ni(Ⅱ)(b) and Cd(Ⅱ)(c)

Fig.6 Adsorption kinetics of PVT-g-PS resin for Pb(Ⅱ)(a), Ni(Ⅱ)(b) and Cd(Ⅱ)(c)

Fig.7 Adsorption isotherms of PVT-g-PS resin for Pb(Ⅱ)(a), Ni(Ⅱ)(b) and Cd(Ⅱ)(c) at 25 ℃ pH=5.0; contact time: 12 h; adsorbent dose: 0.1 g.

Metal ion	Langmuir parameter				Freundlich parameter
Metal ion	Q₀/(mmol·g^-1)	b	K_c	$R L 2$	K_F	1/n	$R F 2$
Pb(Ⅱ)	1.57	0.589	33. 72	0.9902	1.068	0.563	0.9740
Ni(Ⅱ)	1.68	0.645	36.83	0.9876	1.165	0.526	0.9642
Cd(Ⅱ)	1.92	0.723	41.17	0.9890	1.339	0.534	0.9731

Metal ion	Langmuir parameter				Freundlich parameter
Metal ion	Q₀/(mmol·g^-1)	b	K_c	$R L 2$	K_F	1/n	$R F 2$
Pb(Ⅱ)	1.57	0.589	33. 72	0.9902	1.068	0.563	0.9740
Ni(Ⅱ)	1.68	0.645	36.83	0.9876	1.165	0.526	0.9642
Cd(Ⅱ)	1.92	0.723	41.17	0.9890	1.339	0.534	0.9731

Table 3 Comparison of heavy metal ions adsorption capacity of various adsorbents

Adsorbent	Metal ion	Sorption capacity/ (mmol·g^-1)	Ref.
Poly(hydroethylacrylate)-grafted crosslinked poly(vinyl chloride) particles	Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ)	(35—60)×10^-3	[26]
Amine and thio chelating resins	Hg(Ⅱ), Cd(Ⅱ), Zn(Ⅱ)	1.73,0.69,0.65	[27]
Amine-functionalised SBA-15	Pb(Ⅱ), Cd(Ⅱ)	39×10³, 41×10³	[28]
N,N'-di(carboxymethyl) dithiocarbamate chelating resin	Pb(Ⅱ), Cu(Ⅱ), Ni(Ⅱ)	1.40,1.08,0.97	[29]
Magnetic beads with amino groups	Cu(Ⅱ), Ni(Ⅱ)	0.814,0.845	[30]
Poly(amidoxime)/SiO₂	Ni(II), Pb(Ⅱ), Cd(Ⅱ)	0.55,0.42,0.35	[15]
Poly(Hydroxyethyl methacrylate/Maleamic acid)[p(HEA/MALA)] hydrogel	Ni(II), Pb(Ⅱ), Cd(Ⅱ)	0.2,0.244,0.18	[31]
PVT-g-PS resin	Pb(Ⅱ), Ni(Ⅱ), Cd(Ⅱ)	1.57,1.68,1.92	This study

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