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Synthesis, structure, and visible-light-driven activity of o-YbFeO3/h-YbFeO3/CeO2 photocatalysts

Sofia M. Tikhanova, Lev A. Lebedev, Svetlana A. Kirillova, Maria V. Tomkovich, Vadim I. Popkov


Photo-Fenton-like oxidation of organic substances is one of the key advanced oxidation processes based on the reversible Fe2+↔Fe3+ transition and the generation of a strong oxidant ·OH in the presence of H2O2 and is currently considered as a promising method for the purification of polluted aqueous media. However, the absence of effective and stable photocatalysts of this process, operating under the action of visible light, necessitates the exploratory studies, mainly among iron oxides and ferrites of various compositions and structures. In this work, using the method of solution combustion followed by heat treatment in air the heterojunction nanocomposites based on ytterbium orthoferrite and cerium dioxide of the composition o-YbFeO3/h-YbFeO3/CeO2 (0–20 mol.%) with high absorption in the visible region and advanced photo-Fenton-like activity were obtained. The nanocomposites were studied by EDS, SEM, XRD, BET, and DRS methods. The photo-Fenton-like activity of the nanocomposites was investigated during the degradation of methyl violet under the action of visible (λmax = 410 nm) radiation. As a result, the formation of I-type heterojunction based on stable rhombic (55.4–79.0 nm) and metastable hexagonal (19.5–24.0 nm) modifications of ytterbium orthoferrite (o-YbFeO3 and h-YbFeO3, respectively) and cubic cerium dioxide CeO2 (13.2–19.2 nm) nanocrystals was established. It was shown that the obtained nanocomposites had foamy morphology and were characterized by a specific surface in the range of 9.1–25.0 m2/g, depending on the CeO2 content. It was found that nanocrystalline components were chemically and phase-pure, uniformly spatially distributed over the nanocomposite, and had multiple contacts with each other. Based on this fact and the established electronic structure of the nanocomposite components, the formation of I-type heterojunction with the participation of o-YbFeO3 (Eg = 2.15 eV), h-YbFeO3 (Eg = 2.08 eV), and CeO2 (Eg = 2.38 eV) was shown, the presence of which increased photocatalytic activity of the resulting nanocomposite. The optimal content of CeO2 in the nanocomposite was 5%, and the o-YbFeO3/h-YbFeO3/CeO2–5% sample was characterized by the highest rate constant of photo-Fenton-like degradation of methyl violet under the action of visible light equal to = 0.138 min–1, which was 2.5 to 5 times higher than for nanocomposites based on ytterbium orthoferrite. The obtained results obtained indicate that the developed nanocomposites can be considered as a promising basis for the advanced oxidation processes for the purification of aqueous media from organic pollutants.


ytterbium orthoferrite; cerium dioxide; solution combustion synthesis; heterojunction photocatalysts; Fenton-like process

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Matafonova G, Batoev V. Recent advances in application of UV light-emitting diodes for degrading organic pollutants in water through advanced oxidation processes: A review. Water Res. 2018;132:177–189. doi:10.1016/j.watres.2017.12.079

Skvortsova LN, Bolgaru KA, Sherstoboeva MV, Dychko KA. Degradation of diclofenac in aqueous solutions under con-ditions of combined homogeneous and heterogeneous pho-tocatalysis. Russ J Phys Chem A. 2020;94:1248–1253. doi:10.1134/S0036024420060242

Makhotkina OA, Preis SV, Parkhomchuk EV. Water deligni-fication by advanced oxidation processes: Homogeneous and heterogeneous Fenton and H2O2 photo-assisted reac-tions. Appl Catal B Environ. 2008;84:821–826. doi:10.1016/j.apcatb.2008.06.015

Hosokawa S, Jeon HJ, Inoue M. Thermal stabilities of hex-agonal and orthorhombic YbFeO3 synthesized by sol-vothermal method and their catalytic activities for me-thane combustion. Res Chem Intermed. 2011;37:291–296. doi:10.1007/s11164-011-0251-9

Cao S, Sinha K, Zhang X, Zhang X, Wang X, Yin Y. Electronic structure and direct observation of ferrimagnetism in mul-tiferroic hexagonal YbFeO3. Phys Rev B. 2017;95.doi:10.1103/PhysRevB.95.224428

Albadi Y, Sirotkin AA, Semenov VG, Abiev RS, Popkov VI. Synthesis of superparamagnetic GdFeO3 nanoparticles us-ing a free impinging-jets microreactor. Russ Chem Bull. 2020;69:1290–1295. doi:10.1007/s11172-020-2900-x

Sklyarova A, Popkov VI, Pleshakov IV, Matveev VV, Štěpánková H, Chlan V. Peculiarities of 57Fe NMR Spectrum in micro- and nanocrystalline europium orthoferrites. Appl Magn Reson. 2020. doi:10.1007/s00723-020-01224-y

Shen T, Hu C, Yang WL, Liu HC, Wei XL. Theoretical inves-tigation of magnetic, electronic and optical properties of or-thorhombic YFeO3: A first-principle study. Mater Sci Semicond Process. 2015;34:114–120. doi:10.1016/j.mssp.2015.02.015

Makoed II, Liedienov NA, Pashchenko AV, Levchenko GG, Tatarchuk DD, Didenko YV. Influence of rare-earth doping on the structural and dielectric properties of orthoferrite La0.5R0.5FeO3 ceramics synthesized under high pressure. J Alloys Compd. 2020;842:155859. doi:10.1016/j.jallcom.2020.155859

Downie LJ, Goff RJ, Kockelmann W, Forder SD, Parker JE, Morrison FD. Structural, magnetic and electrical properties of the hexagonal ferrites MFeO3 (M=Y, Yb, In). J Solid State Chem. 2012;190:52–60. doi:10.1016/j.jssc.2012.02.004

Polat O, Coskun M, Coskun FM, Zlamal J, Kurt BZ, Durmus Z. Co doped YbFeO3: exploring the electrical properties via tuning the doping level. Ionics.2019;25:4013–4029. doi:10.1007/s11581-019-02934-5

Dhinesh Kumar R, Thangappan R, Jayavel R. Synthesis and characterization of LaFeO3/TiO2 nanocomposites for visible light photocatalytic activity. J Phys Chem Solids. 2017;101:25–33. doi:10.1016/j.jpcs.2016.10.005

Martinson KD, Kondrashkova IS, Omarov SO, Sladkovskiy DA, Kiselev AS, Kiseleva TY. Magnetically recoverable cata-lyst based on porous nanocrystalline HoFeO3 for processes of n-hexane conversion. Adv Powder Technol. 2020;31:402–408. doi:10.1016/j.apt.2019.10.033

Baeissa ES. Environmental remediation of aqueous methyl orange dye solution via photocatalytic oxidation using Ag-GdFeO3 nanoparticles. J Alloys Compd. 2016;678:267–272. doi:10.1016/j.jallcom.2016.04.007

Liu J, He F, Chen L, Qin X, Zhao N, Huang Y. Novel hexago-nal-YFeO3/α-Fe2O3 heterojunction composite nanowires with enhanced visible light photocatalytic activity. Mater Lett. 2016;165:263–266. doi:10.1016/j.matlet.2015.12.008

Yang Z, Wu H, Liao J, Li W, Song Z, Yang Y. Infrared to visi-ble upconversion luminescence in Er3+/Yb3+ co-doped CeO2 inverse opal. Mater Sci Eng B. 2013;178:977–981. doi:10.1016/j.mseb.2013.06.007

Shao Z, Meng X, Lai H, Zhang D, Pu X, Su C. Coralline-like Ni2P decorated novel tetrapod-bundle Cd0.9Zn0.1S ZB/WZ homojunctions for highly efficient visible-light photocata-lytic hydrogen evolution. Chinese J Catal. 2021;42:439–449. doi:10.1016/S1872-2067(20)63597-5

Hosokawa S, Matsumoto S, Tada R, Shibano T, Tanaka T. Development of Mn-modified hexagonal YbFeO3 catalyst for reducing the use of precious metal resources. J Japan Soc Powder Powder Metall. 2017;64:583–588. doi:10.2497/jjspm.64.583

Tang P, Yu L, Min J, Yang J, Chen H. Preparation of nano-crystalline YbFeO3 by sol-gel method and its visible-light photocatalytic activities. Ferroelectrics. 2017;521:71–76. doi:10.1080/00150193.2017.1390962

Jia LX, Zhu JY, Lin TT, Jiang Z, Tang CW, Tang PS. Prepara-tion YbFeO3 by microwave assisted method and its visible-light photocatalytic activity. Adv Mater Res. 2013;699:708–711. doi:10.4028/

Kondrashkova IS, Martinson KD, Zakharova NV, Popkov VI. Synthesis of Nanocrystalline HoFeO3 Photocatalyst via Heat Treatment of Products of Glycine-Nitrate Combustion. Russ J Gen Chem. 2018;88:2465–2471. doi:10.1134/S1070363218120022

Petschnig LL, Fuhrmann G, Schildhammer D, Tribus M, Schottenberger H, Huppertz H. Solution combustion synthe-sis of CeFeO3 under ambient atmosphere. Ceram Int. 2016;42:4262–4267. doi:10.1016/j.ceramint.2015.11.102

Tikhanova SM, Lebedev LA, Martinson KD, Chebanenko MI, Buryanenko IV, Semenov VG. The synthesis of novel het-erojunction h-YbFeO3/o-YbFeO3 photocatalyst with en-hanced Fenton-like activity under visible-light. New J Chem. Royal Society of Chemistry. 2021;45:1541–1550. doi:10.1039/d0nj04895j

Popkov VI, Almjasheva OV, Nevedomskiy VN, Sokolov VV, Gusarov VV. Crystallization behavior and morphological features of YFeO3 nanocrystallites obtained by glycine-nitrate combustion. Nanosyst Physics, Chem Math. 2015;6:866–874. doi:10.17586/2220-8054-2015-6-6-866-874

Popkov VI, Almjasheva OV, Nevedomskiy VN, Panchuk VV, Semenov VG, Gusarov VV. Effect of spatial constraints on the phase evolution of YFeO3-based nanopowders under heat treatment of glycine-nitrate combustion products. Ce-ram Int. 2018;44:20906–20912. doi:10.1016/j.ceramint.2018.08.097

Kusmierek E. A CeO2 semiconductor as a photocatalytic and photoelectrocatalytic material for the remediation of pollu-tants in industrial wastewater: A review. Catalysts. 2020;10:1–54.

Fan X, Hao H, Shen X, Chen F, Zhang J. Removal and degra-dation pathway study of sulfasalazine with Fenton-like re-action. J Hazard Mater. 2011;190:493–500. doi:10.1016/j.jhazmat.2011.03.069

Wu S, Lin Y, Yang C, Du C, Teng Q, Ma Y. Enhanced activa-tion of peroxymonosulfte by LaFeO3 perovskite supported on Al2O3 for degradation of organic pollutants. Chemo-sphere. 2019;237:124478. doi:10.1016/j.chemosphere.2019.124478

Saeed K, Khan I, Gul T, Sadiq M. Efficient photodegradation of methyl violet dye using TiO2/Pt and TiO2/Pd photocata-lysts. Appl Water Sci. 2017;7:3841–3848. doi:10.1007/s13201-017-0535-3

Mazarji M, Esmaili H, Bidhendi GN, Mahmoodi NM, Minki-na T, Sushkova S. Green synthesis of reduced graphene ox-ide-CoFe2O4 nanocomposite as a highly efficient visible-light-driven catalyst in photocatalysis and photo Fenton-like reaction. Mater Sci Eng B. 2021;270:115223. doi:10.1016/j.mseb.2021.115223


Copyright (c) 2021 Sofia M. Tikhanova, Lev A. Lebedev, Svetlana A. Kirillova, Maria V. Tomkovich, Vadim I. Popkov

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Chimica Techno Acta, 2014-2022
ISSN 2411-1414 (Online)