Enhanced heterogeneous Fenton-like activity by Cu-doped BiFeO₃ perovskite for degradation of organic pollutants

Abstract

OH played a key role in heterogeneous Fenton-like catalytic oxidation of organic pollutants.

Doping Cu into BiFeO₃ promoted the generation of Fe²⁺ and then facilitated the effective formation of •OH.

Cu-doped BiFeO₃ exhibited higher catalytic performance for phenol degradation than non-doped BiFeO₃.

Heterogeneous Fenton-like reaction has been extensively investigated to eliminate refractory organic contaminants in wastewater, but it usually shows low catalytic performance due to difficulty in reduction from Fe(III) to Fe(II). In this study, enhanced catalytic efficiency was obtained by employing Cu-doped BiFeO₃ as heterogeneous Fenton-like catalysts, which exhibited higher catalytic performance toward the activation of H₂O₂ for phenol degradation than un-doped BiFeO₃. BiFe_0.8Cu_0.2O₃ displayed the best performance, which yielded 91% removal of phenol (10 mg L⁻¹) in 120 min. The pseudo first-order kinetic rate constant of phenol degradation in BiFe_0.8Cu_0.2O₃ catalyzed heterogeneous Fenton-like reaction was 5 times higher than those of traditional heterogeneous Fenton-like catalysts, such as Fe₃O₄ and goethite. The phenol degradation efficiency could still reach 83% after 4 cycles, which implied the good stability of BiFe_0.8Cu_0.2O₃. The high catalytic activity of BiFe_0.8Cu_0.2O₃ was attributed to the fact that the doping Cu into BiFeO₃ could promote the generation of Fe(II) in the catalyst and then facilitate the activation of H₂O₂ to degrade the organic pollutants.

Graphical abstract

Keywords

Cu doped BiFeO ₃ / Heterogeneous Fenton-like catalysts / Oxidative degradation

References

[1] Afzal S, Quan X, Zhang J L (2017). High surface area mesoporous nanocast LaMO₃ (M= Mn, Fe) perovskites for efficient catalytic ozonation and an insight into probable catalytic mechanism. Applied Catalysis B: Environmental, 206: 692–703

[2] An J J, Zhu L, Wang N, Song Z, Yang Z, Du D, Tang H (2013). Photo-Fenton like degradation of tetrabromobisphenol A with graphene-BiFeO₃ composite as a catalyst. Chemical Engineering Journal, 219(3): 225–237

[3] Bobu M, Yediler A, Siminiceanu I, Schulte-Hostede S (2008). Degradation studies of ciprofloxacin on a pillared iron catalyst. Applied Catalysis B: Environmental, 83(1): 15–23

[4] Eberhardt M K, Ramirez G, Ayala E (1989). Does the reaction of Cu⁺ with H₂O₂ give OH radicals? A study of aromatic hydroxylation. Journal of Organic Chemistry, 54(25)

[5] El-Desoky M M, Mostafa M M, Ayoub M S, Ahmed M A (2015). Transport properties of Ba-doped BiFeO₃ multiferroic nanoparticles. Journal of Materials Science Materials in Electronics, 26(9): 6793–6800

[6] Gao C, Chen S, Quan X, Yu H T, Zhang Y B (2017). Enhanced Fenton-like catalysis by iron-based metal organic frameworks for degradation of organic pollutants. Journal of Catalysis, 356: 125–132

[7] Gao F, Chen X Y, Yin K B, Dong S, Ren Z F, Yuan F, Yu T, Zou Z G, Liu J M (2007). Visible-light photocatalytic properties of weak magnetic BiFeO₃ nanoparticles. Advanced Materials, 19(19): 2889–2892

[8] Ghodselahi T, Vesaghi M A, Shafiekhani A, Baghizadeh A, Lameii M (2008). XPS study of the Cu@Cu₂O core-shell nanoparticles. Applied Surface Science, 255(5): 2730–2734

[9] Guo R Q, Fang L, Dong W, Zheng F G, Shen M R (2010). Enhanced photocatalytic activity and ferromagnetism in Gd doped BiFeO₃ nanoparticles. Journal of Physical Chemistry C, 114(49): 21390–21396

[10] Han Z B, Dong Y C, Dong S M (2011). Copper-iron bimetal modified PAN fiber complexes as novel heterogeneous Fenton catalysts for degradation of organic dye under visible light irradiation. Journal of Hazardous Materials, 189(1–2): 241–248

[11] Jin H, Tian X K, Nie Y L, Zhou Z X, Yang C, Li Y, Lu L Q (2017). Oxygen vacancy promoted heterogeneous Fenton-like degradation of ofloxacin at pH 3.2–9.0 by Cu substituted magnetic Fe₃O₄@FeOOH nanocomposite. Environmental Science & Technology, 51(21): 12699–12706

[12] Li H, Shang J, Yang Z P, Shen W J, Ai Z H, Zhang L Z (2017). Oxygen vacancy associated surface Fenton chemistry: surface structure dependent hydroxyl radicals generation and substrate dependent reactivity. Environmental Science & Technology, 51(10): 5685–5694

[13] Liao Q, Sun J, Gao L (2009). Degradation of phenol by heterogeneous Fenton reaction using multi-walled carbon nanotube supported Fe₂O₃ catalysts. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 345(1–3): 95–100

[14] Luo W, Zhu L H, Wang N, Tang H Q, Cao M J, She Y B (2010). Efficient removal of organic pollutants with magnetic nanoscaled BiFeO₃ as a reusable heterogeneous Fenton-like catalyst. Environmental Science & Technology, 44(5): 1786–1791

[15] Matta R, Hanna K, Kone T, Chiron S (2008). Oxidation of 2,4,6-trinitrotoluene in the presence of different iron-bearing minerals at neutral pH. Chemical Engineering Journal, 144(3): 453–458

[16] Nie Y L, Hu C, Qu J H, Zhao X (2009). Photoassisted degradation of endocrine disruptors over CuO_x-FeOOH with H₂O₂ at neutral pH. Applied Catalysis B: Environmental, 87(1–2): 30–36

[17] Patel K B, Willson R L (1973). Semiquinone free radicals and oxygen. Pulse radiolysis study of one electron transfer equilibria. Journal of the Chemical Society, Faraday Transactions, 69(4): 814–825

[18] Pham L T, Lee C, Doyle F M, Sedlak D L (2009). A silica-supported iron oxide catalyst capable of activating hydrogen peroxide at neutral pH values. Environmental Science & Technology, 43(23): 8930–8935

[19] Ramadan W, Parves A, Shaikh , Ebrahim S, Ramadan A, Hannoyer B, Jouen S, Sauvage X, Ogale S (2013). Highly efficient photocatalysis by BiFeO₃/a(g)-Fe₂O₃ ferromagnetic nano P/N junctions formed by dopant-induced phase separation. Journal of Nanoparticle Research, 15(15): 1–10

[20] Sedlak D L, Hoigne J (1994). Oxidation of S(IV) in atmospheric water by photooxidants and iron in the presence of copper. Environmental Science & Technology, 28(11): 1898–1906

[21] Soltani T, Lee B K (2016). Novel and facile synthesis of Ba-doped BiFeO₃ nanoparticles and enhancement of their magnetic and photocatalytic activities for complete degradation of benzene in aqueous solution. Journal of Hazardous Materials, 316: 122–133

[22] Soltani T, Lee B K (2017a). Comparison of benzene and toluene photodegradation under visible light irradiation by Ba-doped BiFeO₃ magnetic nanoparticles with fast sonochemical synthesis. Photochemical & Photobiological Sciences, 16(1): 86–95

[23] Soltani T, Lee B K (2017b). Enhanced formation of sulfate radicals by metal-doped BiFeO₃ under visible light for improving photo-Fenton catalytic degradation of 2-chlorophenol. Chemical Engineering Journal, 313: 1258–1268

[24] Xia M, Long M C, Yang Y D, Chen C, Cai W M, Zhou B X (2011). A highly active bimetallic oxides catalyst supported on Al-containing MCM-41 for Fenton oxidation of phenol solution. Applied Catalysis B: Environmental, 110: 118–125

[25] Xu L J, Wang J L (2012). Magnetic nanoscaled Fe₃O₄/CeO₂ composite as an efficient Fenton-like heterogeneous catalyst for degradation of 4-chlorophenol. Environmental Science & Technology, 46(18): 10145–10153

[26] Yin Y H, Liu W F, Huo N N, Yang S T (2017). High rate capability and long cycle stability of Fe₂O₃/MgFe₂O₄ anode material synthesized by gel-cast processing. Chemical Engineering Journal, 307: 999–1007

[27] Zaki M I, Ramadan W, Katrib A, Rabee A I M (2014). Surface chemical and photocatalytic consequences of Ca-doping of BiFeO₃ as probed by XPS and H₂O₂ decomposition studies. Applied Surface Science, 317: 929–934

[28] Zhang C Y, Sun H J, Chen W, Zhou J, Li B, Wang Y B (2009). Hydrothermal synthesis and photo-catalytic property of Bi25FeO40 powders: Applications of Ferroelectrics. IEEE International Symposium on the IEEE,1–3

[29] Zhang J B, Zhuang J, Gao L Z, Zhang Y, Gu N, Feng J, Yang D L, Zhu J D, Yan X Y (2008). Decomposing phenol by the hidden talent of ferromagnetic nanoparticles. Chemosphere, 73(9): 1524–1528

[30] Zhang X Y, Ding Y B, Tang H Q, Han X Y, Zhu L H, Wang N (2014). Degradation of bisphenol A by hydrogen peroxide activated with CuFeO₂ microparticles as a heterogeneous Fenton-like catalyst: Efficiency, stability and mechanism. Chemical Engineering Journal, 236: 251–262

[31] Zhu J J, Li H L, Zhong L Y, Xiao P, Xu X L, Yang X G, Zhao Z, Li J L (2014). Perovskite oxides: Preparation, characterizations, and applications in heterogeneous catalysis. ACS Catalysis, 4(9): 2917–2940

[32] Zhu J J, Thomas (2009). A Perovskite-type mixed oxides as catalytic material for NO removal. Applied Catalysis B: Environmental, 92(3–4): 225–233

RIGHTS & PERMISSIONS

Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature