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
. 2019 Jun 20;9(6):901.
doi: 10.3390/nano9060901.

Removal of Phenolic Compounds from Water Using Copper Ferrite Nanosphere Composites as Fenton Catalysts

Carlos Moreno-Castilla  1 , María Victoria López-Ramón  2 , María Ángeles Fontecha-Cámara  3 , Miguel A Álvarez  4 , Lucía Mateus  5
Affiliations

Removal of Phenolic Compounds from Water Using Copper Ferrite Nanosphere Composites as Fenton Catalysts

Carlos Moreno-Castilla et al. Nanomaterials (Basel). .

Abstract

Copper ferrites containing Cu+ ions can be highly active heterogeneous Fenton catalysts due to synergic effects between Fe and Cu ions. Therefore, a method of copper ferrite nanosphere (CFNS) synthesis was selected that also permits the formation of cuprite, obtaining a CFNS composite that was subsequently calcined up to 400 °C. Composites were tested as Fenton catalysts in the mineralization of phenol (PHE), p-nitrophenol (PNP) and p-aminophenol (PAP). Catalysts were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and magnetic measurements. Degradation of all phenols was practically complete at 95% total organic carbon (TOC) removal. Catalytic activity increased in the order PHE < PNP < PAP and decreased when the calcination temperature was raised; this order depended on the electronic effects of the substituents of phenols. The as-prepared CFNS showed the highest catalytic activity due to the presence of cubic copper ferrite and cuprite. The Cu+ surface concentration decreased after calcination at 200 °C, diminishing the catalytic activity. Cuprite alone showed a lower activity than the CFNS composite and the homogeneous Fenton reaction had almost no influence on its overall activity. CFNS activity decreased with its reutilization due to the disappearance of the cuprite phase. Degradation pathways are proposed for the phenols.

Keywords: Fenton reaction; copper ferrite; cuprite; phenols; synergic effects.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
TEM micrographs of (A) copper ferrite nanosphere (CFNS); (B) CFNS200; (C) CFNS400 and SEM micrograph of (D) CFNS400.
Figure 2
Figure 2
XRD patterns of CFNS composites. (▲) cubic spinel; (♦) tenorite; (●) copper; (✚) cuprite.
Figure 3
Figure 3
FTIR spectra of CFNS composites.
Figure 4
Figure 4
XPS profiles of (A) Fe 2p and (B) Cu 2p region in: (a) CFNS; (b) CFNS200; (c) CFNS400. Continuous red line: experimental profile; discontinuous black line: fitted profile.
Figure 5
Figure 5
Magnetization versus applied magnetic field for: (□) CFNS; (△) CFNS200; (◇) CFNS400.
Figure 6
Figure 6
Degradation kinetics of phenols: (◇) phenol (PHE); (△) p-nitrophenol (PNP); (○) p-aminophenol (PAP). Reaction conditions: T = 35 °C; Mass of catalyst = 100 mg L−1, Cphenols = 0.107 mM, CH2O2(PHE) = 1.50 mM, CH2O2(PNP) = 1.45 mM, CH2O2(PAP) = 1.40 mM, pH 3, V = 0.1 L.
Figure 7
Figure 7
(A) Kinetics of total organic carbon (TOC) removal and (B) kinetics of H2O2 decomposition: (◇) PHE; (△) PNP; (○) PAP. Reaction conditions: T = 35 °C; Mass of catalyst = 100 mg L−1, Cphenols = 0.107 mM, CH2O2(PHE) = 1.50 mM, CH2O2(PNP) = 1.45 mM, CH2O2(PAP) = 1.40 mM, pH 3, V = 0.1 L.
Figure 8
Figure 8
Variations in the concentration of leached Cu ions at 35 °C from CFNS composites for different phenols: (◇) PHE; (△) PNP; (○) PAP.
Figure 9
Figure 9
PAP degradation kinetics with fresh and reutilized CFNS catalyst.
Figure 10
Figure 10
Proposed PHE degradation pathway.
Figure 11
Figure 11
Proposed PNP degradation pathway.
Figure 12
Figure 12
Proposed PAP degradation pathway.
See this image and copyright information in PMC

References

    1. Muñoz M., de Pedro Z.M., Casas J.A., Rodríguez J.J. Preparation of magnetite-based catalysts and their application in heterogeneous Fenton oxidation—A review. Appl. Catal. B Environ. 2015;176–177:249–265. doi: 10.1016/j.apcatb.2015.04.003. - DOI
    1. Pignatello J.J., Oliveros E., MacKay A. Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry. Crit. Rev. Environ. Sci. Technol. 2016;36:1–84. doi: 10.1080/10643380500326564. - DOI
    1. Sun Y., Yang Z., Tian P., Sheng Y., Xu J., Han Y.F. Oxidative degradation of nitrobenzene by a Fenton-like reaction with Fe-Cu bimetallic catalysts. Appl. Catal. B Environ. 2019;244:1–10. doi: 10.1016/j.apcatb.2018.11.009. - DOI
    1. Rigg T., Taylor W., Weiss J. The rate constant of the reaction between hydrogen peroxide and ferrous ions. J. Chem. Phys. 1954;22:575–577. doi: 10.1063/1.1740127. - DOI - PubMed
    1. Nichela D.A., Berkovic A.M., Costante M.R., Juliarena M.P., García Einschlag F.S. Nitrobenzene degradation in Fenton-like systems using Cu(II) as catalyst. Comparison between Cu(II)-and Fe(III)-based systems. Chem. Eng. J. 2013;228:1148–1157. doi: 10.1016/j.cej.2013.05.002. - DOI