Preparation and Selective Adsorption Performance of Polyaniline Silicon Magnetic Composite by Multilayer Assembly for Sulfonic Dye†

doi:10.7503/cjcu20180259

Abstract

Abstract:

A multi-layer core-shell polyaniline silicon magnetic composite(Fe₃O₄@SiO₂@PANI) via in situ oxidation polymerization-coprecipitation of silicon magnetic particles(Fe₃O₄@SiO₂) as core at low temperature was prepared. The structure, surface morphology and properties of Fe₃O₄@SiO₂@PANI composites were characterized by means of X-ray means of diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). Using sulfonic azo dyes-methyl orange(MO), congo red(CR), and anthraquinone dye-alizarin red(AR) in aqueous solution, respectively, as an example for dyes in wastewaters, the effects of dyes adsorption pH, adsorption time, dyes concentration and amount of Fe₃O₄@SiO₂@PANI on the adsorption process were studied. The sulfonic dyes was more effective with weakly acidic(pH<6.0). The maximum adsorption capacity of MO, AR and CR on Fe₃O₄@SiO₂@PANI were 26.05, 69.58 and 34.0 mg/g, respectively, under optimized conditions. Analysis of the adsorption results demonstrated that the adsorption was better fit by Langmuir adsorption equation compared to Freundlich adsorption. The results suggested that the shell PANI of Fe₃O₄@SiO₂@PANI composite had good affinity for sulfonic dyes, and the removal efficiency of composites on dye wastewater reached up to 96.5%. In addition, the magnetic composite could be effectively and simply separated by using an external magnetic field and had good repeatability as sorbent of the sulfonic dye wastewater treatment.

Key words: Silicon magnetic particles, Polyaniline, Sulfonic dye, Selective adsorption

CLC Number:

O647

TrendMD:

ZHOU Yanfen,MENG Zhe,WANG Zelan,LI Jiguang,MEN Xiuqin,LIU Wanyi. Preparation and Selective Adsorption Performance of Polyaniline Silicon Magnetic Composite by Multilayer Assembly for Sulfonic Dye^†[J]. Chem. J. Chinese Universities, 2018, 39(10): 2253.

Figures/Tables 21

Scheme 1 Synthetic procedure of Fe3O4@SiO2@PANI core-shell microspheres and the adsorption of methyl orange

Fig.1 FTIR spectra of SiO2(a), Fe3O4@SiO2@PANI(b), Fe3O4@SiO2(c) and Fe3O4(d)

Fig.2 XRD patterns of Fe3O4@SiO2@PANI(a),Fe3O4@SiO2(b) and Fe3O4(c)

Fig.3 TG(a) and DSC(b) curves of Fe3O4@SiO2@PANI

Fig.4 Saturation magnetization intensity curves of Fe3O4@SiO2(a) and Fe3O4@SiO2@PANI(b)

Table 1 Structural properties of Fe3O4@SiO2 and Fe3O4@SiO2@PANI

Sample	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	D/nm
Fe₃O₄@SiO₂	490	0.599	1.94
Fe₃O₄@SiO₂@PANI	64.3	0.074	4.59

Fig.5 SEM images of Fe3O4@SiO2(A) and Fe3O4@SiO2@PANI(B)

Fig.6 TEM images of Fe3O4@SiO2(A) and Fe3O4@SiO2@PANI(B) Insets: magnified image.

Fig.7 UV-Vis absorption spectra obtained for AR(a, b), MO(c, d), CR(e, f) before(a, c, e) and after(b, d, f) absorption on Fe3O4@SiO2@PANI in weakly acidic solution(pH<6.0)

Fig.8 Effects of initial concentration of MO(A), AR(B) and CR(C) on the adsorption capacity

Fig.9 Effects of amount of MO(A), AR(B) and CR(C) on the removal rate(a) and adsorbing capacity(b)

Fig.10 Structural formulas of target dyes

Fig.11 Adsorption capacities of different dyes on Fe3O4@SiO2@PANI(A) and the images of adsorbents before(B) and after(C) adsorption

Fig.12 Adsorbing capacity of MO Fe3O4@SiO2@PANI(a), Fe3O4@SiO2(b) and Fe3O4(c)

Fig.13 Effect of adsorption time on the adsorption capacities of AR(a), CR(b) and MO(c)

Table 2 Pseudo-first order reaction kinetic parameter of adsorption

Sulfonic dye	Equation	k₁/min^-1	R²	Q_e,cal/(mg∙g^-1)	Q_e,exp/(mg∙g^-1)
MO	ln(1-Q_t/Q_e)=-0.0196t-0.2399	0.0195	0.9580	0.78	26.05
AR	ln(1-Q_t/Q_e)=-0.0276t-0.4038	0.0276	0.9412	0.67	69.58
CR	ln(1-Q_t/Q_e)=-0.0077t-0.8598	0.00775	0.8584	0.42	34.00

Table 3 Pseudo-second order reaction kinetic parameter of adsorption

Sulfonic dye	Equation	k₂/(g∙min∙mg^-1)	R²	Q_e,cal/(mg∙g^-1)	Q_e,exp/(mg∙g^-1)
MO	t/Q_t=0.0318t+0.6830	0.0015	0.9956	31.44	26.05
AR	t/Q_t=0.0125t+0.1297	0.0012	0.9987	80.06	69.58
CR	t/Q_t=0.0263t+0.2173	0.0032	0.9992	37.94	34.00

Fig.14 Effects of temperature on the adsorption of MO(A), AR(B) and CR(C) on Fe3O4@SiO2@PANI

Table 4 Correlated parameters of Langmuir and Freundlich isotherm models at 298 K

Sulfonic dye	Langmuir parameter				Freundlich parameter
Sulfonic dye	Equation, c_e/Q_e=(1/Q_max) c_e+ 1/(Q_maxK_L)	R²	Q_m/ (mg·g^-1)	K_L/ (L·mg^-1)	Equation, lnQ_e=(1/n)ln c_e+ lnK_F	R²	K_F/ (L·mg^-1)	n
MO	c_e/Q_e=0.0086c_e+0.0313	0.9991	31.95	3.62	lnQ_e=0.2706lnc_e+2.8389	0.8257	17.08	3.70
AR	c_e/Q_e=0.0157c_e+0.0565	0.9945	63.69	0.28	lnQ_e=1.255lnc_e+1.1768	0.9306	3.24	0.79
CR	c_e/Q_e=0.0210c_e+0.0118	0.9957	47.60	1.78	lnQ_e=1.0766lnc_e+1.4300	0.9084	4.18	0.93

Table 5 Thermodynamic parameters of adsorption

Temperature/K	Sulfonic dye	ΔG/(kJ·mol^-1)	ΔH/(kJ·mol^-1)	ΔS/(J·mol^-1·K^-1)
298	MO	-3.19	45.41	164.49
298	AR	-163.72	167.06	549.95
298	CR	-1.431	58.98	202.72

Fig.15 Reusability of Fe3O4@SiO2@PANI to adsorption of MO

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