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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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Front. Environ. Sci. Eng.    2020, Vol. 14 Issue (2) : 22    https://doi.org/10.1007/s11783-019-1201-9
RESEARCH ARTICLE
Enhancement of the electrocatalytic oxidation of antibiotic wastewater over the conductive black carbon-PbO2 electrode prepared using novel green approach
Xiangyu Wang1, Yu Xie1, Guizhen Yang1, Jiming Hao1,2, Jun Ma3, Ping Ning1()
1. Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China
2. School of Environment, Tsinghua University, Beijing 100084, China
3. State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
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Abstract

• A novel conductive carbon black modified lead dioxide electrode is synthesized.

• The modified PbO2 electrode exhibits enhanced electrochemical performances.

• BBD method could predict optimal experiment conditions accurately and reliably.

• The modified electrode possesses outstanding reusability and safety.

The secondary pollution caused by modification of an electrode due to doping of harmful materials has long been a big concern. In this study, an environmentally friendly material, conductive carbon black, was adopted for modification of lead dioxide electrode (PbO2). It was observed that the as-prepared conductive carbon black modified electrode (C-PbO2) exhibited an enhanced electrocatalytical performance and more stable structure than a pristine PbO2 electrode, and the removal efficiency of metronidazole (MNZ) and COD by a 1.0% C-PbO2 electrode at optimal conditions was increased by 24.66% and 7.01%, respectively. Results revealed that the electrochemical degradation of MNZ wastewater followed pseudo-first-order kinetics. This intimates that the presence of conductive carbon black could improve the current efficiency, promote the generation of hydroxyl radicals, and accelerate the removal of MNZ through oxidation. In addition, MNZ degradation pathways through a C-PbO2 electrode were proposed based on the identified intermediates. To promote the electrode to treat antibiotic wastewater, optimal experimental conditions were predicted through the Box-Behnken design (BBD) method. The results of this study suggest that a C-PbO2 electrode may represent a promising functional material to pretreat antibiotic wastewaters.
Keywords Conductive carbon black      PbO2 electrode      Metronidazole      Electrochemical oxidation      Box-Behnken design-response surface method     
Corresponding Author(s): Ping Ning   
Issue Date: 27 December 2019
 Cite this article:   
Xiangyu Wang,Yu Xie,Guizhen Yang, et al. Enhancement of the electrocatalytic oxidation of antibiotic wastewater over the conductive black carbon-PbO2 electrode prepared using novel green approach[J]. Front. Environ. Sci. Eng., 2020, 14(2): 22.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-019-1201-9
https://academic.hep.com.cn/fese/EN/Y2020/V14/I2/22
Fig.1  Graphical illustration of the synthesis of C-PbO2 electrode (a); SEM surface images of different PbO2 electrodes (b); The comparison of XRD patterns of PbO2 electrode and C-PbO2 electrode (c).
Fig.2  Linear scan voltammograms of PbO2 electrode and C-PbO2 electrode (a); Fluorescence spectra changes based on PbO2 electrode (b) and C-PbO2 electrode (c) in the electrolysis time of 45 min; (d) Fluorescence intensity versus time fitting curves for PbO2 electrode and C-PbO2 electrode.
Fig.3  The effect of different anode materials on MNZ removal (a) concentration; (b) COD; (c) ICE (initial neutral pH; initial MNZ concentration 200 mg/L; current density 20 mA/cm2; electrolyte concentration 0.1 mol/L); The effect of current density on MNZ removal (d) concentration; (e) COD; (f) ICE (initial MNZ concentration 200 mg/L, initial electrolyte concentration 0.1 mol/L, initial neutral pH; 1.0% C-PbO2 electrode).
Parameters Values Removal of MNZ
(%)		 Removal of COD
(%)		 ICE
(%)		 Rate constants
(k, s?1)		 Half-lives
(t1/2, min)		 R2
Electrolyte concentration (mol/L) 0.02 82.87 23.25 12.22?20.83 2.80 × 10?4 24.75 0.999
0.05 85.10 27.26 16.45?25.06 3.20 × 10?4 21.66 0.998
0.1 97.65 37.65 18.12?43.67 4.10 × 10?4 16.90 0.998
0.2 90.35 32.38 18.68?35.46 3.50 × 10?4 19.80 0.999
0.5 94.35 34.68 19.60?32.38 3.80 × 10??4 18.24 0.997
Initial concentration (C0, mg/L) 50 97.52 36.56 10.05?27.64 4.40 × 10?4 15.75 0.997
100 89.49 29.36 16.52?43.64 4.60 × 10?4 15.07 0.997
200 82.10 20.56 28.74?51.15 4.80 × 10?4 14.44 0.995
500 59.22 12.25 49.18?82.23 5.00 × 10?4 13.86 0.999
Current density (mA/cm2) 50 80.10 27.84 26.06?82.80 2.40 × 10?4 28.88 0.999
100 86.67 30.13 13.86?44.83 2.70 × 10?4 25.67 0.996
150 89.55 32.45 9.78?32.18 2.90 × 10?4 23.90 0.998
200 92.52 34.65 7.63?25.77 3.10 × 10?4 22.35 0.995
400 99.95 49.66 6.22?19.95 4.80 × 10?4 14.44 0.993
pH 3.80 91.70 35.56 49.56?66.57 4.00 × 10?4 17.33 0.998
6.20 92.89 32.36 44.20?60.54 4.20 × 10?4 16.50 0.996
8.20 95.36 29.66 39.68?57.01 4.30 × 10?4 16.12 0.997
10.40 96.10 27.85 36.65?51.16 4.60 × 10?4 15.07 0.995
Tab.1  The efficiency and kinetics for the MNZ degradation on different parameters with C-PbO2 electrode (electrolysis time: 120 min)
Fig.4  The effect of supporting electrolyte (Na2SO4) concentration on the MNZ removal of (a) concentration, (b) COD (initial neutral pH; initial MNZ concentration 200 mg/L; current density 20 mA/cm2; 1.0% C-PbO2 electrode); The effect of initial concentration on MNZ removal (c) concentration, (d) COD (initial neutral pH; current density 20 mA/cm2; initial electrolyte concentration 0.1 mol/L; 1.0% C-PbO2 electrode); The effect of pH on the MNZ removal (e) concentration; (f) COD (MNZ concentration 200 mg/L, electrolyte concentration 0.1 mol/L, current density 20 mA/cm2).
Runs Factors Response
MNZ removal efficiency
(%)
A:Doping ratio
(%)		 B:Electrolyte concentration
(Mol/L)		 C:Current density
(mA/cm2)
1 0 0 0 86.05
2 0 0 0 85.96
3 1 1 0 64.45
4 0 0 0 85.5
5 1 0 1 87.65
6 0 1 1 73.2
7 0 0 0 86.28
8 1 0 1 80.45
9 0 1 1 68.23
10 0 0 0 85.27
11 1 0 1 74.75
12 1 1 0 72.35
13 1 1 0 77.45
14 1 1 0 70.25
15 0 1 1 85.85
16 1 0 1 67.15
17 0 1 1 80.78
Tab.2  Experimental runs and observed responses for the Box-Behnken design
Source Sum of Squares Df Mean of Square F-value P-value
Model 994.19 9 110.47 842.90 <0.0001 Significant
A-Doping ratio 111.75 1 111.75 852.71 <0.0001
B-Electrolyte concentration 54.81 1 54.81 418.23 <0.0001
C-Current density 330.25 1 330.25 2519.91 <0.0001
AB 0.12 1 0.12 0.93 0.3658
AC 0.040 1 0.040 0.31 0.5978
BC 2.500 × 10?3 1 2.500 × 10?3 0.019 0.8940
A2 212.31 1 212.31 1620.03 <0.0001
B2 242.30 1 242.30 1848.89 <0.0001
C2 6.17 1 6.17 47.12 0.0002
Residual 0.92 7 0.13
Lack of Fit 0.23 3 0.076 0.44 0.7354 Not significant
Pure Error 0.69 4 0.17
R2 0.9991
Adjusted R2 0.9979
Predicted R2 0.9952
Tab.3  Statistical analysis results of MNZ removal efficiency
Fig.5  2D-Contour plots and 3D-Response surface plots show the effect of different factors on MNZ removal efficiency.
Fig.6  The removal efficiencies of MNZ for eight successive reactions using different electrodes (a); degradation mechanism diagram for MNZ by electrochemical oxidation (b).
Fig.7  Possible degradation pathway for MNZ by electrochemical oxidation.
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