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Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH ARTICLE

Adsorption-enhanced catalytic wet peroxide oxidation of aromatic compounds on ionothermally synthesised copper-doped magnetite magnetic nanoparticles

Xuanlin Huang A , Wei Du A , Rong Chen A and Fengxi Chen https://orcid.org/0000-0002-1097-2036 A B
+ Author Affiliations
- Author Affiliations

A School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan 430073, China.

B Corresponding author. Email: fxchen@wit.edu.cn

Environmental Chemistry 17(6) 426-435 https://doi.org/10.1071/EN19245
Submitted: 3 September 2019  Accepted: 27 November 2019   Published: 20 February 2020

Environmental context. Aromatic compounds are major organic pollutants that are hard to clean up by either adsorption or biological treatment processes. We synthesised Cu-doped Fe3O4 magnetic nanoparticles and showed that they efficiently degrade various aromatic compounds with H2O2 under mild conditions. This active and stabile heterogeneous Fenton-like catalyst has the potential for various environmental applications.

Abstract. Magnetite magnetic nanoparticles (Fe3O4 MNPs) have great potential in environmental remediation owing to the intrinsic peroxidase-like activity, which is unfortunately not strong enough to activate H2O2 for practical applications. Herein, Cu-doped Fe3O4 MNPs (Fe2.88Cu0.12O4) were ionothermally synthesised and demonstrated as a highly efficient and stable heterogeneous Fenton-like catalyst for the catalytic wet peroxide oxidation of aromatic compounds with H2O2 at pH ~7 and 25 °C. Theoretical calculations found that the interaction between aromatic compounds (e.g. orange G) and Cu2+ through a terminal end-on binding mode with moderate strength was favourable to enhance their adsorption on Fe2.88Cu0.12O4. In addition, copper dopants increased the decomposition rate of H2O2 at 25 °C about four-fold (0.584 h−1 on Fe2.88Cu0.12O4 versus 0.153 h−1 on Fe3O4), which is attributed to efficient redox cycling of iron and copper ions for synergistic activation of H2O2. Copper-enhanced adsorption of aromatic compounds, together with synergistic activation of H2O2 by surface iron and copper active sites, explained the higher catalytic activity of Fe2.88Cu0.12O4. This study provided new insight for improving the catalytic performance of magnetite-based heterogeneous catalysts for various environmental and biomedical applications.

Additional keywords: ionothermal synthesis.


References

Amaniampong PN, Trinh QT, Varghese JJ, Behling R, Valange S, Mushrif SH, Jérôme F (2018). Unraveling the mechanism of the oxidation of glycerol to dicarboxylic acids over a sonochemically synthesized copper oxide catalyst. Green Chemistry 20, 2730–2741.
Unraveling the mechanism of the oxidation of glycerol to dicarboxylic acids over a sonochemically synthesized copper oxide catalystCrossref | GoogleScholarGoogle Scholar |

Amaniampong PN, Trinh QT, De Oliveira Vigier K, Dao DQ, Tran NH, Wang Y, Sherburne MP, Jérôme F (2019). Synergistic effect of high-frequency ultrasound with cupric oxide catalyst resulting in a selectivity switch in glucose oxidation under argon. Journal of the American Chemical Society 141, 14772–14779.
Synergistic effect of high-frequency ultrasound with cupric oxide catalyst resulting in a selectivity switch in glucose oxidation under argonCrossref | GoogleScholarGoogle Scholar | 31450888PubMed |

Barros WRP, Steter JR, Lanza MRV, Tavares AC (2016). Catalytic activity of Fe3−xCuxO4 (0 ≤ x ≤ 0.25) nanoparticles for the degradation of Amaranth food dye by heterogeneous electro-Fenton process. Applied Catalysis B: Environmental 180, 434–441.
Catalytic activity of Fe3−xCuxO4 (0 ≤ x ≤ 0.25) nanoparticles for the degradation of Amaranth food dye by heterogeneous electro-Fenton processCrossref | GoogleScholarGoogle Scholar |

Biache C, Ouali S, Cébron A, Lorgeoux C, Colombano S, Faure P (2017). Bioremediation of PAH-contamined soils: Consequences on formation and degradation of polar-polycyclic aromatic compounds and microbial community abundance. Journal of Hazardous Materials 329, 1–10.
Bioremediation of PAH-contamined soils: Consequences on formation and degradation of polar-polycyclic aromatic compounds and microbial community abundanceCrossref | GoogleScholarGoogle Scholar | 28119192PubMed |

Bokare AD, Choi W (2014). Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes. Journal of Hazardous Materials 275, 121–135.
Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processesCrossref | GoogleScholarGoogle Scholar | 24857896PubMed |

Buda F, Ensing B, Gribnau M, Baerends EJ (2001). DFT study of the active intermediate in the Fenton reaction. Chemistry – A European Journal 7, 2775–2783.
DFT study of the active intermediate in the Fenton reactionCrossref | GoogleScholarGoogle Scholar |

Chen F, Xie S, Zhang J, Liu R (2013). Synthesis of spherical Fe3O4 magnetic nanoparticles by co-precipitation in choline chloride/urea deep eutectic solvent. Materials Letters 112, 177–179.
Synthesis of spherical Fe3O4 magnetic nanoparticles by co-precipitation in choline chloride/urea deep eutectic solventCrossref | GoogleScholarGoogle Scholar |

Chen F, Liu R, Xiao S, Lin M (2014a). One-step solvothermal synthesis of epichlorohydrin-modified magnetic Fe3O4 microspheres in ethylene glycol. Materials Letters 130, 101–103.
One-step solvothermal synthesis of epichlorohydrin-modified magnetic Fe3O4 microspheres in ethylene glycolCrossref | GoogleScholarGoogle Scholar |

Chen F, Liu R, Xiao S, Zhang C (2014b). Solvothermal synthesis in ethylene glycol and adsorption property of magnetic Fe3O4 microspheres. Materials Research Bulletin 55, 38–42.
Solvothermal synthesis in ethylene glycol and adsorption property of magnetic Fe3O4 microspheresCrossref | GoogleScholarGoogle Scholar |

Chen F, Xie S, Huang X, Qiu X (2017a). Ionothermal synthesis of Fe3O4 magnetic nanoparticles as efficient heterogeneous Fenton-like catalysts for degradation of organic pollutants with H2O2. Journal of Hazardous Materials 322, 152–162.
Ionothermal synthesis of Fe3O4 magnetic nanoparticles as efficient heterogeneous Fenton-like catalysts for degradation of organic pollutants with H2O2Crossref | GoogleScholarGoogle Scholar | 26952081PubMed |

Chen W, Xiong L, Chen F (2017b). Solvothermal synthesis of sub-200 nm Fe3O4 submicrospheres with enhanced catalytic performances by using acicular goethite as solid precursor. Micro & Nano Letters 12, 711–713.
Solvothermal synthesis of sub-200 nm Fe3O4 submicrospheres with enhanced catalytic performances by using acicular goethite as solid precursorCrossref | GoogleScholarGoogle Scholar |

Chen W, Zhang J, Chen F (2019). Glycothermal synthesis of fluorinated Fe3O4 microspheres with distinct peroxidase-like activity. Advanced Powder Technology 30, 999–1005.
Glycothermal synthesis of fluorinated Fe3O4 microspheres with distinct peroxidase-like activityCrossref | GoogleScholarGoogle Scholar |

dos Santos PL, Guimarães IR, Mesquita AM, Guerreiro MC (2016). Copper-doped akaganeite: Application in catalytic Cupro-Fenton reactions for oxidation of methylene blue. Journal of Molecular Catalysis A: Chemical 424, 194–202.
Copper-doped akaganeite: Application in catalytic Cupro-Fenton reactions for oxidation of methylene blueCrossref | GoogleScholarGoogle Scholar |

Feng Y, Liao C, Shih K (2016). Copper-promoted circumneutral activation of H2O2 by magnetic CuFe2O4 spinel nanoparticles: Mechanism, stoichiometric efficiency, and pathway of degrading sulfanilamide. Chemosphere 154, 573–582.
Copper-promoted circumneutral activation of H2O2 by magnetic CuFe2O4 spinel nanoparticles: Mechanism, stoichiometric efficiency, and pathway of degrading sulfanilamideCrossref | GoogleScholarGoogle Scholar | 27085318PubMed |

Fontecha-Cámara MA, Moreno-Castilla C, López-Ramón MV, Álvarez MA (2016). Mixed iron oxides as Fenton catalysts for gallic acid removal from aqueous solutions. Applied Catalysis B: Environmental 196, 207–215.
Mixed iron oxides as Fenton catalysts for gallic acid removal from aqueous solutionsCrossref | GoogleScholarGoogle Scholar |

Gao L, Zhuang J, Nie L, Zhang J, Zhang Y, Gu N, Wang T, Feng J, Yang D, Perrett S, Yan X (2007). Intrinsic peroxidase-like activity of ferromagnetic nanoparticles. Nature Nanotechnology 2, 577–583.
Intrinsic peroxidase-like activity of ferromagnetic nanoparticlesCrossref | GoogleScholarGoogle Scholar | 18654371PubMed |

Huang R, Fang Z, Yan X, Cheng W (2012). Heterogeneous sono-Fenton catalytic degradation of bisphenol A by Fe3O4 magnetic nanoparticles under neutral condition. Chemical Engineering Journal 197, 242–249.
Heterogeneous sono-Fenton catalytic degradation of bisphenol A by Fe3O4 magnetic nanoparticles under neutral conditionCrossref | GoogleScholarGoogle Scholar |

Huang X, Xu C, Ma J, Chen F (2018). Ionothermal synthesis of Cu-doped Fe3O4 magnetic nanoparticles with enhanced peroxidase-like activity for organic wastewater treatment. Advanced Powder Technology 29, 796–803.
Ionothermal synthesis of Cu-doped Fe3O4 magnetic nanoparticles with enhanced peroxidase-like activity for organic wastewater treatmentCrossref | GoogleScholarGoogle Scholar |

Kwan WP, Voelker BM (2002). Decomposition of hydrogen peroxide and organic compounds in the presence of dissolved iron and ferrihydrite. Environmental Science & Technology 36, 1467–1476.
Decomposition of hydrogen peroxide and organic compounds in the presence of dissolved iron and ferrihydriteCrossref | GoogleScholarGoogle Scholar |

Li K, Zhao Y, Janik MJ, Song C, Guo X (2017). Facile preparation of magnetic mesoporous Fe3O4/C/Cu composites as high performance Fenton-like catalysts. Applied Surface Science 396, 1383–1392.
Facile preparation of magnetic mesoporous Fe3O4/C/Cu composites as high performance Fenton-like catalystsCrossref | GoogleScholarGoogle Scholar |

Lin S-S, Gurol MD (1998). Catalytic decomposition of hydrogen peroxide on iron oxide: Kinetics, mechanism, and implications. Environmental Science & Technology 32, 1417–1423.
Catalytic decomposition of hydrogen peroxide on iron oxide: Kinetics, mechanism, and implicationsCrossref | GoogleScholarGoogle Scholar |

Munoz M, de Pedro ZM, Casas JA, Rodriguez JJ (2015). Preparation of magnetite-based catalysts and their application in heterogeneous Fenton oxidation – A review. Applied Catalysis B: Environmental 176–177, 249–265.
Preparation of magnetite-based catalysts and their application in heterogeneous Fenton oxidation – A reviewCrossref | GoogleScholarGoogle Scholar |

Nie G, Huang J, Hu Y, Ding Y, Han X, Tang H (2017). Heterogeneous catalytic activation of peroxymonosulfate for efficient degradation of organic pollutants by magnetic Cu0/Fe3O4 submicron composites. Chinese Journal of Catalysis 38, 227–239.
Heterogeneous catalytic activation of peroxymonosulfate for efficient degradation of organic pollutants by magnetic Cu0/Fe3O4 submicron compositesCrossref | GoogleScholarGoogle Scholar |

Nihei M, Ida H, Nibe T, Moeljadi AMP, Trinh QT, Hirao H, Ishizaki M, Kurihara M, Shiga T, Oshio H (2018). Ferrihydrite particle encapsulated within a molecular organic cage. Journal of the American Chemical Society 140, 17753–17759.
Ferrihydrite particle encapsulated within a molecular organic cageCrossref | GoogleScholarGoogle Scholar | 30474980PubMed |

Pham AL-T, Lee C, Doyle FM, Sedlak DL (2009). A silica-supported iron oxide catalyst capable of activating hydrogen peroxide at neutral pH values. Environmental Science & Technology 43, 8930–8935.
A silica-supported iron oxide catalyst capable of activating hydrogen peroxide at neutral pH valuesCrossref | GoogleScholarGoogle Scholar |

Pham TD, Bui TT, Nguyen VT, Bui TKV, Tran TT, Phan QC, Pham TD, Hoang TH (2018). Adsorption of polyelectrolyte onto nanosilica synthesized from rice husk: Characteristics, mechanisms, and application for antibiotic removal. Polymers 10, 220
Adsorption of polyelectrolyte onto nanosilica synthesized from rice husk: Characteristics, mechanisms, and application for antibiotic removalCrossref | GoogleScholarGoogle Scholar |

Pham TD, Tran TT, Le VA, Pham TT, Dao TH, Le TS (2019). Adsorption characteristics of molecular oxytetracycline onto alumina particles: The role of surface modification with an anionic surfactant. Journal of Molecular Liquids 287, 110900
Adsorption characteristics of molecular oxytetracycline onto alumina particles: The role of surface modification with an anionic surfactantCrossref | GoogleScholarGoogle Scholar |

Qi Z, Lan H, Joshi TP, Liu R, Liu H, Qu J (2016). Enhanced oxidative and adsorptive capability towards antimony by copper-doping into magnetite magnetic particles. RSC Advances 6, 66990–67001.
Enhanced oxidative and adsorptive capability towards antimony by copper-doping into magnetite magnetic particlesCrossref | GoogleScholarGoogle Scholar |

Rahim Pouran S, Abdul Raman AA, Wan Daud WMA (2014). Review on the application of modified iron oxides as heterogeneous catalysts in Fenton reactions. Journal of Cleaner Production 64, 24–35.
Review on the application of modified iron oxides as heterogeneous catalysts in Fenton reactionsCrossref | GoogleScholarGoogle Scholar |

Ribeiro RS, Silva AMT, Figueiredo JL, Faria JL, Gomes HT (2016). Catalytic wet peroxide oxidation: a route towards the application of hybrid magnetic carbon nanocomposites for the degradation of organic pollutants. A review. Applied Catalysis B: Environmental 187, 428–460.
Catalytic wet peroxide oxidation: a route towards the application of hybrid magnetic carbon nanocomposites for the degradation of organic pollutants. A reviewCrossref | GoogleScholarGoogle Scholar |

Sarkar C, Pendem S, Shrotri A, Dao DQ, Pham Thi Mai P, Nguyen Ngoc T, Chandaka DR, Rao TV, Trinh QT, Sherburne MP, Mondal J (2019). Interface engineering of graphene-supported Cu nanoparticles encapsulated by mesoporous silica for size-dependent catalytic oxidative coupling of aromatic amines. ACS Applied Materials & Interfaces 11, 11722–11735.
Interface engineering of graphene-supported Cu nanoparticles encapsulated by mesoporous silica for size-dependent catalytic oxidative coupling of aromatic aminesCrossref | GoogleScholarGoogle Scholar |

Sasaki T, Tanaka S (2011). Adsorption behavior of some aromatic compounds on hydrophobic magnetite for magnetic separation. Journal of Hazardous Materials 196, 327–334.
Adsorption behavior of some aromatic compounds on hydrophobic magnetite for magnetic separationCrossref | GoogleScholarGoogle Scholar | 21962863PubMed |

Singuru R, Trinh QT, Banerjee B, Govinda Rao B, Bai L, Bhaumik A, Reddy BM, Hirao H, Mondal J (2016). Integrated experimental and theoretical study of shape-controlled catalytic oxidative coupling of aromatic amines over CuO nanostructures. ACS Omega 1, 1121–1138.
Integrated experimental and theoretical study of shape-controlled catalytic oxidative coupling of aromatic amines over CuO nanostructuresCrossref | GoogleScholarGoogle Scholar | 31457184PubMed |

Tang H, Dai Z, Xie X, Wen Z, Chen R (2019). Promotion of peroxydisulfate activation over Cu0.84Bi2.08O4 for visible light induced photodegradation of ciprofloxacin in water matrix. Chemical Engineering Journal 356, 472–482.
Promotion of peroxydisulfate activation over Cu0.84Bi2.08O4 for visible light induced photodegradation of ciprofloxacin in water matrixCrossref | GoogleScholarGoogle Scholar |

Thi TM, Trang NTH, Van Anh NT (2015). Effects of Mn, Cu doping concentration to the properties of magnetic nanoparticles and arsenic adsorption capacity in wastewater. Applied Surface Science 340, 166–172.
Effects of Mn, Cu doping concentration to the properties of magnetic nanoparticles and arsenic adsorption capacity in wastewaterCrossref | GoogleScholarGoogle Scholar |

Trinh QT, Banerjee A, Yang Y, Mushrif SH (2017). Sub-surface boron-doped copper for methane activation and coupling: First-principles investigation of the structure, activity, and selectivity of the catalyst. The Journal of Physical Chemistry C 121, 1099–1112.
Sub-surface boron-doped copper for methane activation and coupling: First-principles investigation of the structure, activity, and selectivity of the catalystCrossref | GoogleScholarGoogle Scholar |

Trinh QT, Bhola K, Amaniampong PN, Jérôme F, Mushrif SH (2018). Synergistic application of XPS and DFT to investigate metal oxide surface catalysis. The Journal of Physical Chemistry C 122, 22397–22406.
Synergistic application of XPS and DFT to investigate metal oxide surface catalysisCrossref | GoogleScholarGoogle 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. Ultrasonics Sonochemistry 17, 526–533.
Sono-assisted preparation of highly-efficient peroxidase-like Fe3O4 magnetic nanoparticles for catalytic removal of organic pollutants with H2O2Crossref | GoogleScholarGoogle Scholar | 19945901PubMed |

Wang T, Yang W, Song T, Li C, Zhang L, Wang H, Chai L (2015a). Cu doped Fe3O4 magnetic adsorbent for arsenic: synthesis, property, and sorption application. RSC Advances 5, 50011–50018.
Cu doped Fe3O4 magnetic adsorbent for arsenic: synthesis, property, and sorption applicationCrossref | GoogleScholarGoogle Scholar |

Wang Y, Zhao H, Zhao G (2015b). Iron-copper bimetallic nanoparticles embedded within ordered mesoporous carbon as effective and stable heterogeneous Fenton catalyst for the degradation of organic contaminants. Applied Catalysis B: Environmental 164, 396–406.
Iron-copper bimetallic nanoparticles embedded within ordered mesoporous carbon as effective and stable heterogeneous Fenton catalyst for the degradation of organic contaminantsCrossref | GoogleScholarGoogle Scholar |

Wen Z, Zhang Y, Wang Y, Li L, Chen R (2017). Redox transformation of arsenic by magnetic thin-film MnO2 nanosheet-coated flowerlike Fe3O4 nanocomposites. Chemical Engineering Journal 312, 39–49.
Redox transformation of arsenic by magnetic thin-film MnO2 nanosheet-coated flowerlike Fe3O4 nanocompositesCrossref | GoogleScholarGoogle Scholar |

Xiao S, Liu R, Ma J, Chen F (2015a). Adsorption of Cu2+ on epichlorohydrin-modified magnetic Fe3O4 microspheres prepared via one-step solvothermal synthesis. Adsorption Science and Technology 33, 25–35.
Adsorption of Cu2+ on epichlorohydrin-modified magnetic Fe3O4 microspheres prepared via one-step solvothermal synthesisCrossref | GoogleScholarGoogle Scholar |

Xiao S, Zhang C, Chen R, Chen F (2015b). Selective oxidation of benzyl alcohol to benzaldehyde with H2O2 in water on epichlorohydrin-modified Fe3O4 microspheres. New Journal of Chemistry 39, 4924–4932.
Selective oxidation of benzyl alcohol to benzaldehyde with H2O2 in water on epichlorohydrin-modified Fe3O4 microspheresCrossref | GoogleScholarGoogle Scholar |

Xing S, Hu C, Qu J, He H, Yang M (2008). Characterization and reactivity of MnOx supported on mesoporous zirconia for herbicide 2,4-D mineralization with ozone. Environmental Science & Technology 42, 3363–3368.
Characterization and reactivity of MnOx supported on mesoporous zirconia for herbicide 2,4-D mineralization with ozoneCrossref | GoogleScholarGoogle Scholar |

Xiong L, Chen R, Chen F (2016). One-step solvothermal synthesis of Al-promoted Fe3O4 magnetic catalysts for the selective oxidation of benzyl alcohol to benzaldehyde with H2O2 in water. RSC Advances 6, 101048–101060.
One-step solvothermal synthesis of Al-promoted Fe3O4 magnetic catalysts for the selective oxidation of benzyl alcohol to benzaldehyde with H2O2 in waterCrossref | GoogleScholarGoogle Scholar |

Xu L, Wang J (2012). Magnetic nanoscaled Fe3O4/CeO2 composite as an efficient Fenton-like heterogeneous catalyst for degradation of 4-chlorophenol. Environmental Science & Technology 46, 10145–10153.
Magnetic nanoscaled Fe3O4/CeO2 composite as an efficient Fenton-like heterogeneous catalyst for degradation of 4-chlorophenolCrossref | GoogleScholarGoogle Scholar |

Xu J, Li Y, Yuan B, Shen C, Fu M, Cui H, Sun W (2016a). Large scale preparation of Cu-doped α-FeOOH nanoflowers and their photo-Fenton-like catalytic degradation of diclofenac sodium. Chemical Engineering Journal 291, 174–183.
Large scale preparation of Cu-doped α-FeOOH nanoflowers and their photo-Fenton-like catalytic degradation of diclofenac sodiumCrossref | GoogleScholarGoogle Scholar |

Xu Y, Ai J, Zhang H (2016b). The mechanism of degradation of bisphenol A using the magnetically separable CuFe2O4/peroxymonosulfate heterogeneous oxidation process. Journal of Hazardous Materials 309, 87–96.
The mechanism of degradation of bisphenol A using the magnetically separable CuFe2O4/peroxymonosulfate heterogeneous oxidation processCrossref | GoogleScholarGoogle Scholar | 26875144PubMed |

Xu C, Zhang J, Huang X, Chen F (2019). One-step nonaqueous synthesis of modified magnetic Fe3O4 microspheres by using epichlorohydrin as functional solvent. Chemistry Letters 48, 22–25.
One-step nonaqueous synthesis of modified magnetic Fe3O4 microspheres by using epichlorohydrin as functional solventCrossref | GoogleScholarGoogle Scholar |

Xue X, Hanna K, Deng N (2009). Fenton-like oxidation of Rhodamine B in the presence of two types of iron (II, III) oxide. Journal of Hazardous Materials 166, 407–414.
Fenton-like oxidation of Rhodamine B in the presence of two types of iron (II, III) oxideCrossref | GoogleScholarGoogle Scholar | 19167810PubMed |

Zhang S, Zhao X, Niu H, Shi Y, Cai Y, Jiang G (2009). Superparamagnetic Fe3O4 nanoparticles as catalysts for the catalytic oxidation of phenolic and aniline compounds. Journal of Hazardous Materials 167, 560–566.
Superparamagnetic Fe3O4 nanoparticles as catalysts for the catalytic oxidation of phenolic and aniline compoundsCrossref | GoogleScholarGoogle Scholar | 19201085PubMed |

Zhang J, Xiao S, Chen R, Chen F (2019). Promotional effect of short-chain saturated alcohols on Fe3O4-catalyzed decomposition of H2O2 and its application in selective oxidation of benzyl alcohol. Journal of Chemical Technology and Biotechnology 94, 1613–1621.
Promotional effect of short-chain saturated alcohols on Fe3O4-catalyzed decomposition of H2O2 and its application in selective oxidation of benzyl alcoholCrossref | GoogleScholarGoogle Scholar |