Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 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.

PubMed Disclaimer

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.
See this image and copyright information in PMC

References

    1. Yu J., Tang L., Pang Y., Zeng G., Wang J., Deng Y., Liu Y., Feng H., Chen S., Ren X. Magnetic nitrogen-doped sludge-derived biochar catalysts for persulfate activation: Internal electron transfer mechanism. Chem. Eng. J. 2019;364:146–159. doi: 10.1016/j.cej.2019.01.163. - DOI
    1. Wang J., Tang L., Zeng G., Deng Y., Liu Y., Wang L., Zhou Y., Guo Z., Wang J., Zhang C. Atomic scale g-C3N4/Bi2WO6 2D/2D heterojunction with enhanced photocatalytic degradation of ibuprofen under visible light irradiation. Appl. Catal. B Environ. 2017;209:285–294. doi: 10.1016/j.apcatb.2017.03.019. - DOI
    1. Deng Y., Tang L., Zeng G., Zhu Z., Yan M., Zhou Y., Wang J., Liu Y., Wang J. Insight into highly efficient simultaneous photocatalytic removal of Cr(VI) and 2,4-diclorophenol under visible light irradiation by phosphorus doped porous ultrathin g-C3N4 nanosheets from aqueous media: Performance and reaction mechanism. Appl. Catal. B Environ. 2017;203:343–354. doi: 10.1016/j.apcatb.2016.10.046. - DOI
    1. Zhang X., Li Y., Wu M., Pang Y., Hao Z., Hu M., Qiu R., Chen Z. Enhanced adsorption of tetracycline by an iron and manganese oxides loaded biochar: Kinetics, mechanism and column adsorption. Bioresour. Technol. 2021;320:124264. doi: 10.1016/j.biortech.2020.124264. - DOI - PubMed
    1. Shah N.S., Ali Khan J., Sayed M., Ul Haq Khan Z., Sajid Ali H., Murtaza B., Khan H.M., Imran M., Muhammad N. Hydroxyl and sulfate radical mediated degradation of ciprofloxacin using nano zerovalent manganese catalyzed S2O82−. Chem. Eng. J. 2019;356:199–209. doi: 10.1016/j.cej.2018.09.009. - DOI

LinkOut - more resources