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. 2022 Feb 9;12(4):579.
doi: 10.3390/nano12040579.

Adsorption and Fenton-like Degradation of Ciprofloxacin Using Corncob Biochar-Based Magnetic Iron-Copper Bimetallic Nanomaterial in Aqueous Solutions

Hongrun Liu  1 , Yuankun Liu  1 , Xing Li  1 , Xiaoying Zheng  1 , Xiaoying Feng  1 , Aixin Yu  1
Affiliations

Adsorption and Fenton-like Degradation of Ciprofloxacin Using Corncob Biochar-Based Magnetic Iron-Copper Bimetallic Nanomaterial in Aqueous Solutions

Hongrun Liu et al. Nanomaterials (Basel). .

Abstract

An economical corncob biochar-based magnetic iron-copper bimetallic nanomaterial (marked as MBC) was successfully synthesized and optimized through a co-precipitation and pyrolysis method. It was successfully used to activate H2O2 to remove ciprofloxacin (CIP) from aqueous solutions. This material had high catalytic activity and structural stability. Additionally, it had good magnetic properties, which can be easily separated from solutions. In MBC/H2O2, the removal efficiency of CIP was 93.6% within 360 min at optimal reaction conditions. The conversion of total organic carbon (TOC) reached 51.0% under the same situation. The desorption experiments concluded that adsorption and catalytic oxidation accounted for 34% and 66% on the removal efficiency of CIP, respectively. The influences of several reaction parameters were systematically evaluated on the catalytic activity of MBC. OH was proved to play a significant role in the removal of CIP through electron paramagnetic resonance (EPR) analysis and a free radical quenching experiment. Additionally, such outstanding removal efficiency can be attributed to the excellent electronic conductivity of MBC, as well as the redox cycle reaction between iron and copper ions, which achieved the continuous generation of hydroxyl radicals. Integrating HPLC-MS, ion chromatography and density functional theory (DFT) calculation results, and possible degradation of the pathways of the removal of CIP were also thoroughly discussed. These results provided a theoretical basis and technical support for the removal of CIP in water.

Keywords: AOPs; adsorption; advanced oxidation process; catalytic activity; ciprofloxacin; corncob biochar-based magnetic iron–copper bimetallic nanomaterial; fenton-like catalyst.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
(a) The preparation route of MBC catalyst; (b) the schematic diagram of the experimental parameters.
Figure 2
Figure 2
The SEM images of (a) BC and (b) MBC; (c) Nitrogen adsorption–desorption isotherms of MBC and BC (inset); (d) the corresponding pore size distribution of MBC; (e) XRD pattern; (f) FTIR spectra.
Figure 2
Figure 2
The SEM images of (a) BC and (b) MBC; (c) Nitrogen adsorption–desorption isotherms of MBC and BC (inset); (d) the corresponding pore size distribution of MBC; (e) XRD pattern; (f) FTIR spectra.
Figure 3
Figure 3
(a) Wide-scan XPS spectra, and high-resolution XPS spectra of MBC and used MBC: (b) C1s; (c) O1s; (d) Fe2p; (e) Cu2p.
Figure 4
Figure 4
Magnetization curves of MBC and used MBC. The illustration is separation of used MBC from the solution under external magnetic field.
Figure 5
Figure 5
(a) Removal of CIP at various mass of biomass. (b) Removal of CIP at different Fe/Cu molar ratios. Reaction conditions: pH, 6.4; initial CIP, 10 mg/L; catalyst dosage, 0.4 g/L.
Figure 6
Figure 6
(a) Removal of CIP in different systems. (b) The removal efficiency of TOC in the MBC/H2O2. Reaction conditions: pH, 6.4; initial CIP, 10 mg/L; catalyst dosage, 0.6 g/L; H2O2, 10 mM.
Figure 7
Figure 7
(a) Adsorption isotherm of CIP on the MBC. (b) The removal efficiency of CIP was compared between adsorption–catalytic oxidation process and adsorption and catalytic oxidation process. Reaction conditions: pH = 6.4; initial CIP, 10 mg/L; catalyst dosage, 0.6 g/L; H2O2, 10 mM.
Figure 8
Figure 8
The influence of different parameters on the CIP removal in MBC/H2O2: (a) H2O2 concentration, (b) catalyst dosage, (c) initial pH value, and (d) initial CIP concentration. Except for the studied parameter, the other settings were as follows: pH, 6.4; initial CIP, 10 mg/L; catalyst dosage, 0.6 g/L; H2O2, 10 mM.
Figure 9
Figure 9
(a) Removal efficiency of CIP and the corresponding coppers and irons leaching concentration without washing in three cycles. (b) Three consecutive experiments under four conditions.
Figure 10
Figure 10
(a) Comparison of EPR spectra at 1min and 10min in the MBC/H2O2. (b) Effect of TBA or KI scavengers on the removal of CIP in the MBC/H2O2. (c) Mechanisms of CIP removal in the MBC/H2O2.
Figure 11
Figure 11
Defluorination and denitrification efficiencies in the MBC/H2O2 condition. Reaction conditions: pH = 6.4; initial CIP, 10 mg/L; catalyst dosage, 0.6 g/L; H2O2, 10mM.
Figure 12
Figure 12
Degradation pathways of the CIP degradation products.
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