Skip to main content
SpringerLink
Log in

Poly(catechol) modified Fe3O4 magnetic nanocomposites with continuous high Fenton activity for organic degradation at neutral pH

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Fe3O4 magnetic nanoparticles (MNPs) have been widely used as a recyclable catalyst in Fenton reaction for organic degradation. However, the pristine MNPs suffer from the drawbacks of iron leaching in acidic conditions as well as the decreasing catalytic activity of organic degradation at a pH higher than 3.0. To solve the problems, Fe3O4 MNPs were modified by poly(catechol) (Fe3O4/PCC MNPs) using a facile chemical co-precipitation method. The poly(catechol) modification improved both the dispersity and the surface negative charges of Fe3O4/PCC MNPs, which are beneficial to the catalytic activity of MNPs for organic degradation. Moreover, the poly(catechol) modification enhanced the efficiency of Fe(II) regeneration during Fenton reaction due to the acceleration of Fe(III) reduction by the phenolic/quinonoid redox pair. As a result, the Fenton reaction with Fe3O4/PCC MNPs could efficiently degrade organic molecules, exampled by methylene blue (MB), in an expanded pH range between 3.0 and 10.0. In addition, Fe3O4/PCC MNPs could be reused up to 8 cycles for the MB degradation with negligible iron leaching of lower than 1.5 mg L−1. This study demonstrated Fe3O4/PCC MNPs are a promising heterogeneous Fenton catalysts for organic degradation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Scheme 2

Similar content being viewed by others

Data availability

All data generated or analyzed during this study are included in this published article and its supplementary information files.

References

  • Aktas N, Sahiner N, Kantoglu O, Salih B, Tanyolac A (2003) Biosynthesis and characterization of laccase catalyzed poly(catechol). J Polym Environ 11:123–128

    Article  CAS  Google Scholar 

  • Bai C, Xiao W, Feng D, Xian M, Guo D, Ge Z, Zhou Y (2013) Efficient decolorization of Malachite Green in the Fenton reaction catalyzed by [Fe(III)-salen]Cl complex. Chem Eng J 215(216):227–234

    Article  Google Scholar 

  • Baldi Marchetto F, Zanchettin D, Sartorato E, Paganelli S, Piccolo O (2010) A bio-generated Fe(III)-binding exopolysaccharide used as new catalyst for phenol hydroxylation. Green Chem 12:1405–1409

    Article  Google Scholar 

  • Cai HD, Li X, Ma DC, Feng QG, Wang DB, Liu Z, Wei X, Chen K, Lin HY, Qin SY, Lu FY (2021) Stable Fe3O4 submicrospheres with SiO2 coating for heterogeneous Fenton-like reaction at alkaline condition. Sci Total Environ 764:144200–144200

    Article  CAS  Google Scholar 

  • Chandra V, Park J, Chun Y, Lee JW, Hwang IC, Kim KS (2010) Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano 4:3979–3986

    Article  CAS  Google Scholar 

  • Chen F, Xie S, Huang X, Qiu X (2017) Ionothermal synthesis of Fe3O4 magnetic nanoparticles as efficient heterogeneous Fenton-like catalysts for degradation of organic pollutants with H2O2. J Hazard Mater 322:152–162

    Article  CAS  Google Scholar 

  • Contreras D, Oviedo C, Valenzuela R, Freer J, Rojo K, Rodriguez J (2009) Tribromophenol degradation by a catechol-driven Fenton reaction. J Chil Chem Soc 54:141–143

    Article  CAS  Google Scholar 

  • Dong YH, Fujii H, Hendrich MP, Leising RA, Pan GF, Randall CR, Wilkinson EC, Zang Y, Que L, Fox BG, Kauffmann K, Munck E (1995) A high-valent nonheme iron intermediate structure and properties of [Fe2(.mu.-O)2(5-Me-TPA)2](ClO4)3. J Am Chem Soc 117:2778–2792

    Article  CAS  Google Scholar 

  • Dubey S, Singh D, Misra RA (1998a) Enzymatic synthesis and various properties of poly(catechol). Enzyme Microb Tech 23:432–437

    Article  CAS  Google Scholar 

  • Dubey S, Singh D, Misra RA (1998b) Enzymatic synthesis and various properties of poly(catechol). Enzym Microb Technol 23(7-8):432–437

    Article  CAS  Google Scholar 

  • Elhabiri M, Carrer C, Marmolle F, Traboulsi H (2007) Complexation of iron(III) by catecholate-type polyphenols. Inorg Chim Acta 360:353–359

    Article  CAS  Google Scholar 

  • Fang GD, Dionysiou DD, Al Abed SR, Zhou DM (2013) Superoxide radical driving the activation of persulfate by magnetite nanoparticles: implications for the degradation of PCBs. Appl Catal B Environ 129:325–332

    Article  CAS  Google Scholar 

  • Faure E, Falentin Daudre C, Jerome C, Lyskawa J, Fournier D, Woisel P, Detrembleur C (2013) Catechols as versatile platforms in polymer chemistry. Prog Polym Sci 38:236–270

    Article  CAS  Google Scholar 

  • Feng Y, Wu D, Deng Y, Zhang T, Shih K (2016) Sulfate radical-mediated degradation of sulfadiazine by CuFeO2 rhombohedral crystal-catalyzed peroxymonosulfate: synergistic effects and mechanisms. Environ Sci Technol 50:3119–3127

    Article  CAS  Google Scholar 

  • Gao LZ, Zhuang J, Nie L, Zhang JB, Zhang Y, Gu N, Wang TH, Feng J, Yang DL, Perrett S, Yan X (2007) Intrinsic peroxidase-like activity of ferromagnetic nanoparticles. Nature Nanotech 2:577–583

    Article  CAS  Google Scholar 

  • Goncalves NPF, Minella M, Fabbri D, Calza P, Malitesta C, Mazzotta E, Prevot AB (2020) Humic acid coated magnetic particles as highly efficient heterogeneous photo-Fenton materials for wastewater treatments. Chem Eng J 390:124619

    Article  CAS  Google Scholar 

  • Gu L, Zhu N, Guo H, Huang S, Lou Z, Yuan H (2013) Adsorption and Fenton-like degradation of naphthalene dye intermediate on sewage sludge derived porous carbon. J Hazard Mater 246:145–153

    Article  Google Scholar 

  • Gulley Stahl H, Hogan PA, Schmidt WL II, Wall SJ, Buhrlage A, Bullen HA (2010) Surface complexation of catechol to metal oxides: an ATR-FTIR, adsorption, and dissolution study. Environ Sci Technol 44:4116–4121

    Article  CAS  Google Scholar 

  • Hammouda SB, Adhoum N, Monser L (2015) Synthesis of magnetic alginate beads based on Fe3O4 nanoparticles for the removal of 3-methylindole from aqueous solution using Fenton process. J Hazard Mater 294:128–136

    Article  CAS  Google Scholar 

  • He Y, Huang L, Cai JS, Zheng XM, Sun SG (2010) Structure and electrochemical performance of nanostructured Fe3O4/carbon nanotube composites as anodes for lithium ion batteries. Electrochim Acta 55:1140–1144

    Article  CAS  Google Scholar 

  • He J, Yang X, Men B, Bi Z, Pu Y, Wang D (2014) Heterogeneous Fenton oxidation of catechol and 4-chlorocatechol catalyzed by nano-Fe3O4: role of the interface. Chem Eng J 258:433–441

    Article  CAS  Google Scholar 

  • He J, Yang X, Men B, Yu L, Wang D (2015) EDTA enhanced heterogeneous Fenton oxidation of dimethyl phthalate catalyzed by Fe3O4: kinetics and interface mechanism. J Mol Catal A-Chem 408:179–188

    Article  CAS  Google Scholar 

  • Hu XB, Liu BZ, Deng YH, Chen HZ, Luo S, Sun C, Yang P, Yang SG (2011) Adsorption and heterogeneous Fenton degradation of 17 alpha-methyltestosterone on nano Fe3O4/MWCNTs in aqueous solution. Appl Catal B Environ 107:274–283

    Article  CAS  Google Scholar 

  • Jho E, Singhal N, Turner S (2012) Tetrachloroethylene and hexachloroethane degradation in Fe(III) and Fe(III)-citrate catalyzed Fenton systems. J Chem Technol Biotechnol 87:1179–1186

    Article  CAS  Google Scholar 

  • Jubb AM, Allen HC (2010) Vibrational spectroscopic characterization of hematite, maghemite, and magnetite thin films produced by vapor deposition. ACS Appl Mater Interfaces 2:2804–2812

    Article  CAS  Google Scholar 

  • Kang SH, Choi W (2009) Oxidative degradation of organic compounds using zero-valent iron in the presence of natural organic matter serving as an electron shuttle. Environ Sci Technol 43:878–883

    Article  CAS  Google Scholar 

  • Kong Y, Mu SF, Mao BW (2002) Synthesis of polycatechol with electrochemical activity and its properties. Chin J Polym Sci 20:517–524

    CAS  Google Scholar 

  • Leng Y, Guo W, Shi X, Li Y, Xing L (2013) Polyhydroquinone-coated Fe3O4 nanocatalyst for degradation of Rhodamine B based on sulfate radicals. Ind Eng Chem Res 52:13607–13612

    Article  CAS  Google Scholar 

  • Li GY, Huang KL, Jiang YR, Ding P, Yang DL (2008) Preparation and characterization of carboxyl functionalization of chitosan derivative magnetic nanoparticles. Biochem Eng J 40:408–414

    Article  CAS  Google Scholar 

  • Li K, Zhao Y, Song C, Guo X (2017) Magnetic ordered mesoporous Fe3O4/CeO2 composites with synergy of adsorption and Fenton catalysis. Appl Surf Sci 425:526–534

    Article  CAS  Google Scholar 

  • Li W, Wu X, Li S, Tang W, Chen Y (2018) Magnetic porous Fe3O4/carbon octahedra derived from iron-based metal-organic framework as heterogeneous Fenton-like catalyst. Appl Surf Sci 436:252–262

    Article  CAS  Google Scholar 

  • Luo W, Zhu L, Wang N, Tang H, Cao M, She Y (2010) Efficient removal of organic pollutants with magnetic nanoscaled BiFeO3 as a reusable heterogeneous Fenton-Like catalyst. Environ Sci Technol 44:1786–1791

    Article  CAS  Google Scholar 

  • Ma Z, Ren L, Xing S, Wu Y, Gao Y (2015) Sodium dodecyl sulfate modified FeCo2O4 with enhanced Fenton-like activity at neutral pH. J Phys Chem C 119:23068–23074

    Article  CAS  Google Scholar 

  • Magnacca G, Allera A, Montoneri E, Celi L, Benito DE, Gagliardi LG, Gonzalez MC, Mártire DO, Carlos L (2014) Novel magnetite nanoparticles coated with waste-sourced biobased substances as sustainable and renewable adsorbing materials. ACS Sustain Chem Eng 2:1518–1524

    Article  CAS  Google Scholar 

  • Melin V, Henriquez A, Freer J, Contreras D (2015) Reactivity of catecholamine-driven Fenton reaction and its relationships with iron(III) speciation. Redox Rep 20:89–96

    Article  CAS  Google Scholar 

  • Mercado DF, Weiss RG (2018) Polydimethylsiloxane as a matrix for the stabilization and immobilization of zero-valent iron nanoparticles. J Braz Chem Soc 29:1427–1439

    CAS  Google Scholar 

  • Mercado DF, Magnacca G, Malandrino M, Rubert A, Montoneri E, Celi L, Prevot AB, Gonzalez MC (2014) Paramagnetic iron-doped hydroxyapatite nanoparticles with improved metal sorption properties. a bioorganic substrates mediated synthesis. ACS Appl Mater Interfaces 6:3937–3946

    Article  CAS  Google Scholar 

  • Mercado DF, Cipollone M, González MC, Sánchez FH (2018a) Yerba Mate applications: magnetic response of powders and colloids of iron oxide nanoparticles coated with Ilex paraguariensis derivatives. J Magn Magn Mater 462:13–21

    Article  CAS  Google Scholar 

  • Mercado DF, Caregnato P, Villatal LS, Gonzalez MC (2018b) Ilex paraguariensis extract-coated magnetite nanoparticles: a sustainable nano-adsorbent and antioxidant. J Inorg Organo met P 28:519–527

    Article  CAS  Google Scholar 

  • Mondal P, Anweshan A, Purkait MK (2020) Green synthesis and environmental application of iron-based nanomaterials and nanocomposite: a review. Chemosphere:259

  • Niu H, Zhang D, Zhang S, Zhang X, Meng Z (2011) Humic acid coated Fe3O4 magnetic nanoparticles as highly efficient Fenton-like catalyst for complete mineralization of sulfathiazole. J Hazard Mater 190:559–565

    Article  CAS  Google Scholar 

  • Noorjahan A, Kumari VD, Subrahmanyam A, Panda L (2005) Immobilized Fe(III)-HY: an efficient and stable photo-Fenton catalyst. Appl Catal B Environ 57:91–298

    Article  Google Scholar 

  • Pu J, Shen L, Zhu S, Wang J, Zhang W, Wang Z (2014) Fe3O4@C core-shell microspheres: synthesis, characterization, and application as supercapacitor electrodes. J. Solid State Electron 18:1067–1076

    Article  CAS  Google Scholar 

  • Rahhal S, Richter HW (1988) Reduction of hydrogen-peroxide by the ferrous iron chelate of diethylenetriamine-N,N,N,N,N-pentaacetate. J Am Chem Soc 110:3126–3133

    Article  CAS  Google Scholar 

  • Slikboer S, Grandy L, Blair SL, Nizkorodov SA, Smith RW, Al-Abadleh HA (2015) Formation of light absorbing soluble secondary organics and insoluble polymeric particles from the dark reaction of catechol and guaiacol with Fe(III). Environ Sci Technol 49:7793–7801

    Article  CAS  Google Scholar 

  • Wang N, Zhu L, Wang D, Wang M, Lin Z, Tang H (2010) Sono-assisted preparation of highly-efficient peroxidase-like Fe3O4 magnetic nanoparticles for catalytic removal of organic pollutants with H2O2. Ultrason Sonochem 17:526–533

    Article  CAS  Google Scholar 

  • Wang W, Wang Y, Liu Y, Li T (2012) Synthesis of novel pH-responsive magnetic nanocomposites as highly efficient heterogeneous Fenton catalysts. Chem Lett 41:897–899

    Article  CAS  Google Scholar 

  • Wang W, Liu Y, Li T, Zhou M (2014) Heterogeneous Fenton catalytic degradation of phenol based on controlled release of magnetic nanoparticles. Chem Eng J 242:1–9

    Article  CAS  Google Scholar 

  • Wang J, Cao ZF, Ren H, Yu C, Wang S, Li L, Zhong H (2020) Reactivation of Fenton catalytic performance for Fe3O4 catalyst: optimizing the cyclic performance by low voltage electric field. Appl Surf Sci 500:144045

    Article  CAS  Google Scholar 

  • Xiang HL, Ren GK, Zhong YJ, Xu DH, Zhang ZY, Wang XL, Yang XS (2021) Fe3O4@C nanoparticles synthesized by in situ solid-phase method for removal of methylene blue. Nanomaterials:11

  • Xiao J, Wang C, Lyu SS, Liu H, Jiang CC, Lei YM (2016) Enhancement of Fenton degradation by catechol in a wide initial pH range. Sep Purif Technol 169:202–209

    Article  CAS  Google Scholar 

  • Xie G, Xi P, Liu H, Chen F, Huang L, Shi Y, Hou F, Zeng Z, Shao C, Wang J (2012) A facile chemical method to produce superparamagnetic graphene oxide-Fe3O4 hybrid composite and its application in the removal of dyes from aqueous solution. J Mater Chem 22:1033–1039

    Article  CAS  Google Scholar 

  • Xu L, Wang J (2012) Fenton-like degradation of 2,4-dichlorophenol using Fe3O4 magnetic nanoparticles. Appl Catal B Environ 123:117–126

    Article  Google Scholar 

  • Xu CJ, Xu KM, Gu HW, Zheng RK, Liu H, Zhang XX, Guo ZH, Xu B (2004) Dopamine as a robust anchor to immobilize functional molecules on the iron oxide shell of magnetic nanoparticles. J Am Chem Soc 126:9938–9939

    Article  CAS  Google Scholar 

  • Xue X, Hanna K, Abdelmoula M, Deng N (2009) Adsorption and oxidation of PCP on the surface of magnetite: kinetic experiments and spectroscopic investigations. Appl Catal B Environ 89:432–440

    Article  CAS  Google Scholar 

  • Ye Q, Zhou F, Liu W (2011) Bioinspired catecholic chemistry for surface modification. Chem Soc Rev 40:4244–4258

    Article  CAS  Google Scholar 

  • Zhang X, Ding Y, Tang H, Han X, Zhu L, Wang N (2014a) Degradation of bisphenol A by hydrogen peroxide activated with CuFeO2 microparticles as a heterogeneous Fenton-like catalyst: Efficiency, stability and mechanism. Chem Eng J 236:251–262

    Article  CAS  Google Scholar 

  • Zhang X, He M, Liu JH, Liao R, Zhao L, Xie J, Wang R, Yang ST, Wang H, Liu Y (2014b) Fe3O4@C nanoparticles as high-performance Fenton-like catalyst for dye decoloration. Chin Sci Bull 59:3406–3412

    Article  CAS  Google Scholar 

  • Zhang JW, Azam MS, Shi C, Huang J, Bin B, Liu QX, Zeng HB (2015) Poly (acrylic acid) functionalized magnetic graphene oxide nanocomposite for removal of methylene blue. RSC Adv 5:32272–32282

    Article  CAS  Google Scholar 

  • Zubir NA, Yacou C, Motuzas J, Zhang X, da Costa JCD (2014) Structural and functional investigation of graphene oxide-Fe3O4 nanocomposites for the heterogeneous Fenton-like reaction. Sci Rep 4

Download references

Funding

The present research is supported by the Natural Science Foundation of China (No. 51678554, No. 51978181).

Author information

Authors and Affiliations

  1. School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an, 710049, People’s Republic of China

    Yani Hua

  2. Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Institute of Environmental Research at Greater Bay, Guangzhou University, Guangzhou, 510006, China

    Yani Hua & Chuan Wang

  3. Key Laboratory of Reservoir Aquatic Environment, Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing, 400714, China

    Yani Hua & Sha Wang

  4. School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou, 510275, China

    Juan Xiao

Authors
  1. Yani Hua
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chuan Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sha Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Juan Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

NH conducted the experiment and experimental analysis, contributed to the discussion of the study, and wrote the original draft of the manuscript. CW supervised the research, conducted the experimental analysis, funding acquisition, and reviewed and edited the manuscript. SW and JX contributed to the discussion of the study and wrote the original draft of the manuscript.

Corresponding author

Correspondence to Chuan Wang.

Ethics declarations

Ethics approval

Not applicable.

Consent to participate

Not applicable.

Consent for publication

Not applicable.

Competing interests

The authors declare no competing interests.

Additional information

Responsible Editor: Ricardo Torres-Palma

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supporting Information

ESM 1

(DOC 828 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Hua, Y., Wang, C., Wang, S. et al. Poly(catechol) modified Fe3O4 magnetic nanocomposites with continuous high Fenton activity for organic degradation at neutral pH. Environ Sci Pollut Res 28, 62690–62702 (2021). https://doi.org/10.1007/s11356-021-15088-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-021-15088-7

Keywords

Search

Navigation