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Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

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Front. Mater. Sci.    2016, Vol. 10 Issue (1) : 45-55    https://doi.org/10.1007/s11706-016-0326-z
RESEARCH ARTICLE
Heterogeneous Fenton-like discoloration of methyl orange using Fe3O4/MWCNTs as catalyst: process optimization by response surface methodology
Huan-Yan XU(),Tian-Nuo SHI,Hang ZHAO,Li-Guo JIN,Feng-Chun WANG,Chun-Yan WANG,Shu-Yan QI
School of Materials Science and Engineering, Harbin University of Science and Technology, Harbin 150040, China
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Abstract

Fe3O4/MWCNTs nanocomposites were prepared by chemical oxidation coprecipitation method and developed as highly efficient heterogeneous Fenton-like catalyst. XRD results revealed that Fe3O4 nanoparticles deposited onto MWCNTs surface remained the inverse spinel crystal structure of cubic Fe3O4 phase. The FTIR characteristic peaks of MWCNTs weakened or disappeared due to the anchor of Fe3O4 nanoparticles and Fe–O peak at 570 cm−1 was indicative of the formation of Fe3O4. TEM observation revealed that Fe3O4 nanoparticles were tightly anchored by MWCNTs. The Fenton-like catalytic activity of Fe3O4/MWCNTs nanocomposites for the discoloration of methyl orange (MO) was much higher than that of Fe3O4 nanoparticles. The process optimization of this heterogeneous Fenton-like system was implemented by response surface methodology (RSM). The optimum conditions for MO discoloration were determined to be of 12.3 mmol/L H2O2 concentration, 2.9 g/L catalyst dosage, solution pH 2.7 and 39.3 min reaction time, with the maximum predicted value for MO discoloration ratio of 101.85%. The corresponding experimental value under the identical conditions was obtained as 99.86%, which was very close to the predicted one with the absolute deviation of 1.99%.
Keywords Fe3O4/MWCNTs      Fenton-like catalyst      azo dye      response surface methodology     
Corresponding Author(s): Huan-Yan XU   
Online First Date: 29 December 2015    Issue Date: 15 January 2016
 Cite this article:   
Huan-Yan XU,Tian-Nuo SHI,Hang ZHAO, et al. Heterogeneous Fenton-like discoloration of methyl orange using Fe3O4/MWCNTs as catalyst: process optimization by response surface methodology[J]. Front. Mater. Sci., 2016, 10(1): 45-55.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-016-0326-z
https://academic.hep.com.cn/foms/EN/Y2016/V10/I1/45
Coded level Variables
Solution pH, X1 H2O2 concentration, X2 /(mmol·L−1) Catalyst dosage, X3 /(g·L−1) Reaction time, X4 /min
−2 1 9.69 1.0 10
−1 2 19.35 2.0 20
0 3 29.07 3.0 30
1 4 38.76 4.0 40
2 5 48.45 5.0 50
Tab.1  Variables and their codes and real experimental values used in CCD
Fig.1  XRD patterns of acid-treated MWCNTs, Fe3O4 nanoparticles and Fe3O4/MWCNTs nanocomposites.
Fig.2  FTIR spectra of acid-treated MWCNTs and Fe3O4/MWCNTs nanocomposites.
Fig.3  TEM images of (a) acid-treated MWCNTs and (b) Fe3O4/MWCNTs nanocomposites.
Fig.4  Contrast experiments of 50 mg/L MO discoloration at room temperature in Fe3O4–H2O2 system (pH= 2, [H2O2]0 = 19.38 mmol/L, Fe3O4 dosage= 2.0 g/L), Fe3O4/MWCNTs system (pH= 2, Fe3O4/MWCNTs dosage= 2.0 g/L), Fe3O4/MWCNTs–H2O2 system (pH= 2, [H2O2]0 = 19.38 mmol/L, Fe3O4/MWCNTs dosage= 2.0 g/L), MWCNTs system (pH= 2, MWCNTs dosage= 2.0 g/L), MWCNTs–H2O2 system (pH= 2, [H2O2]0 = 19.38 mmol/L, MWCNTs dosage= 2.0 g/L) and Fe3O4 system (pH= 2, Fe3O4 dosage= 2.0 g/L).
Run X1 X2 X3 X4 MO discoloration ratio, Y /%
Experimental Predicted
1 0 2 0 0 63.35 64.91
2 0 0 0 −2 15.09 15.32
3 0 0 0 0 89.73 89.20
4 1 −1 −1 −1 38.10 35.95
5 1 1 1 1 86.77 84.16
6 −1 1 −1 1 74.57 70.23
7 1 −1 1 1 97.48 98.32
8 0 −2 0 0 92.77 90.55
9 2 0 0 0 79.98 78.99
10 −1 −1 −1 1 85.68 84.59
11 −1 1 1 −1 85.43 82.48
12 1 1 −1 −1 11.67 8.94
13 −1 1 1 1 98.42 102.61
14 0 0 0 0 90.42 89.20
15 1 −1 1 −1 69.88 72.84
16 −1 −1 1 1 98.98 100.78
17 1 1 −1 1 63.99 66.07
18 0 0 0 0 88.76 89.20
19 0 0 0 0 89.18 89.20
20 −1 1 −1 −1 13.92 15.11
21 0 0 2 0 92.08 88.76
22 −1 −1 −1 −1 25.34 26.58
23 0 0 0 2 96.79 95.91
24 0 0 0 0 90.42 89.20
25 −1 −1 1 −1 77.82 77.77
26 0 0 0 0 86.70 89.20
27 0 0 -2 0 16.83 19.49
28 −2 0 0 0 87.73 88.06
29 1 1 1 −1 58.44 61.57
30 1 −1 −1 1 94.85 96.42
Tab.2  Central composite design matrix along with the experimental and predicted values of MO discoloration ratio
Source Sum of squares Degree of freedom Mean square F value p-value(Prob>F)
Model 23580.71 14 1684.34 184.14 <0.0001 Significant
X1 123.67 1 123.67 13.52 0.0022
X2 985.09 1 985.09 107.69 <0.0001
X3 7196.81 1 7196.81 786.79 <0.0001
X4 9742.12 1 9742.12 1065.05 <0.0001
X1X2 255.68 1 255.68 27.95 <0.0001
X1X3 204.35 1 204.35 22.34 0.0003
X1X4 6.08 1 6.08 0.66 0.4278
X2X3 261.79 1 261.79 28.62 <0.0001
X2X4 8.35 1 8.35 0.91 0.3544
X3X4 1224.65 1 1224.65 133.88 <0.0001
X12 55.23 1 55.23 6.04 0.0267
X22 225.57 1 225.57 24.66 0.0002
X32 2109.11 1 2109.11 230.58 <0.0001
X42 1934.30 1 1934.30 211.47 <0.0001
Residual 137.21 15 9.15
R2 0.9942
Adj R2 0.9888
Tab.3  ANOVA for the obtained quadratic polynomial model
Fig.5  Predicted vs. actual values plot for MO discoloration.
Fig.6  Normal plot of residuals for MO discoloration.
Fig.7  The 3D response surface diagram of MO discoloration as the interaction of solution pH (X1) and H2O2 concentration (X2).
Fig.8  The 3D response surface diagram of MO discoloration as the interaction of solution pH (X1) and catalyst dosage (X3).
Fig.9  The 3D response surface diagram of MO discoloration as the interaction of solution pH (X1) and reaction time (X4).
Fig.10  The 3D response surface diagram of MO discoloration as the interaction of H2O2 concentration (X2) and catalyst dosage (X3).
Fig.11  The 3D response surface diagram of MO discoloration as the interaction of H2O2 concentration (X2) and reaction time (X4).
Fig.12  The 3D response surface diagram of MO discoloration as the interaction of catalyst dosage (X3) and reaction time (X4).
3Dthree-dimensional
ANOVAanalysis of variance
AOPadvanced oxidation process
ATZatrazine
BPAbisphenol A
CCDcentral composite design
CNTcarbon nanotube
EDCendocrine disrupting compound
FTIRFourier transform infrared spectroscopy
MOmethyl orange
MT17α-methyltestosterone
MWCNTmulti-walled carbon nanotube
RSMresponse surface methodology
SWCNTsingle-walled carbon nanotube
TBBPAtetrabromobisphenol A
TEMtransmission electron microscopy
UVultraviolet
XRDX-ray diffraction
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[1] Huan-Yan XU, Yuan WANG, Tian-Nuo SHI, Hang ZHAO, Qu TAN, Bo-Chao ZHAO, Xiu-Lan HE, Shu-Yan QI. Heterogeneous Fenton-like discoloration of methyl orange using Fe3O4/MWCNTs as catalyst: combination mechanism and affecting parameters[J]. Front. Mater. Sci., 2018, 12(1): 21-33.
[2] Hang ZHAO,Ling WENG,Wei-Wei CUI,Xiao-Rui ZHANG,Huan-Yan XU,Li-Zhu LIU. In situ anchor of magnetic Fe3O4 nanoparticles onto natural maifanite as efficient heterogeneous Fenton-like catalyst[J]. Front. Mater. Sci., 2016, 10(3): 300-309.
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