Magnetic and photocatalytic properties of BiFeO₃ nanoparticles formed during the heat treatment of hydroxides coprecipitated in a microreactor with intense swirling flows

   In this work, hydroxide deposition in a microreactor with intensively swirling flows was used to obtain BiFeO₃, followed by heat treatment of co-precipitated bismuth and iron hydroxides. The study of the formation of nanocrystalline bismuth orthoferrite was carried out using a set of methods: EDXMA, TEM, XRD, ⁵⁷Fe M¨ossbauer spectroscopy, DRS, etc. The photocatalytic activity and magnetic characteristics of the material were determined. It is shown that during heat treatment of hydroxide precipitation for 1 minute at a temperature of 530 ◦C, BiFeO₃ nanocrystals with an average crystallite size of 14 ± 7 nm are formed. It was found that the resulting BiFeO₃ nanopowder is represented by agglomerates of individual nanoparticles. The saturation magnetization and residual magnetization values of these bismuth orthoferrite nanoparticles are 2.31 and 0.48 emu/g, respectively. According to the DRS results, band gap energy for the samples calculated at 530, 515, and 500 ◦C were 1.82, 1.86, and 1.91 eV, respectively, which ensures strong absorption of visible light by the samples. The sample showed higher photocatalytic activity in the X-ray amorphous state compared with nanocrystalline BiFeO₃ in the process of Fenton-like discoloration of methyl violet under the action of visible light with reaction rate constants of the pseudo-first order 0.0256 and 0.0072 min⁻¹, respectively.

1. Kharbanda S., Dhanda N., Sun A.-C.A., Thakur A., Thakur P. Multiferroic perovskite bismuth ferrite nanostructures : A review on synthesis and applications. Journal of Magnetism and Magnetic Materials, 2023, 572, P. 170569.

2. Krishnamoorthy A., Hannah I., Maruthasalamoorthy S., Nirmala R., Punithavelan N., Navamathavan R. Review – State of the Art of the Multifunctional Bismuth Ferrite: Synthesis Method and Applications. ECS Journal of Solid State Science and Technology, 2022, 11, P. 043010.

3. Ghuge R.S., Shinde M.D., Rane S.B. Bismuth-Based Gas Sensors : A Comprehensive Review. Journal of Electronic Materials, 2021, 50(11), P. 6060–6072.

4. Gervits N.E., Tkachev A.V., Zhurenko S.V., Gunbin A.V., Bogach A.V., Lomanova N.A., Danilovich D.P., Pavlov I.S., Vasiliev A.L., Gippius A.A. The size effect of BiFeO3 nanocrystals on the spatial spin modulated structure. Physical Chemistry Chemical Physics, 2023, 25(37), P. 25526–25536.

5. Kravtsova P.D., Tomkovich M.V., Volkov M.P., Buryanenko I.V., Semenov V.G., Popkov V.I., Lomanova N.A. Magnetic properties of nanocrys-talline materials based on the system (1-x)BiFeO3-(x)YFeO₃. Physics of the Solid State, 2023, 65(12), P. 2120–2123.

6. Chinchay-Espino H.A., Montes-Albino G.M., Morales-Cruz C.M., Dobbertin-Sanchez S.E., Rojas-Flores S. Effect of Cobalt Substitution on the Structural and Magnetic Properties of Bismuth Ferrite Powders. Crystals, 2022, 12, P. 1058.

7. Zhao X., Menzel S., Polian I., Schmidt H., Du N. Review on Resistive Switching Devices Based on Multiferroic BiFeO₃. Nanomaterials, 2023, 13, P. 1325.

8. Dang T.T., Schell J., Boa A.G., Lewin D., Marschick G., Dubey A., Escobar-Castillo M., Noll C., Beck R., Zyabkin D.V., Glukhov K., Yap I.C.J., Mokhles G. A., Lupascu D.C. Temperature dependence of the local electromagnetic field at the Fe site in multiferroic bismuth ferrite. Physical Review B, 2022, 106(5), P. 054416.

9. Taha G.M., Rashed M.N., El-Sadek M.S.A., Moghazy M.A.E. Multiferroic BiFeO₃ dithizone functionalized as optical sensor for detection and determination of some heavy metals in environmental samples. Bulletin of Materials Science, 2021, 44(2), P. 122.

10. Ahmed I., Naz I., Morley N., Shabbir S., Maraj M., Ismail A.G., Anwar H., Ahmad F. Experimental and DFT investigation of structural and optical properties of lanthanum substituted bismuth ferrites. Physica B: Condensed Matter., 2023, 661, P. 414927.

11. Nguyen K., Nguyen. C., Pham C., Lim D., Nguyen Q.-B., Le H., Mai N., Dao N. Kinetics and mechanism of photocatalytic degradation of rhodamine B on nanorod bismuth ferrite perovskite prepared by hydrothermal method. Research on Chemical Intermediates, 2022, 49, P. 57–72.

12. Cadenbach T., Sanchez V., Chiquito R´ıos D., Debut A., Vizuete K., Benitez M.J. Hydrothermal Synthesis of Bismuth Ferrite Hollow Spheres with Enhanced Visible-Light Photocatalytic Activity. Molecules, 2023, 28, P. 5079.

13. Zhou T., Zhai T., Shen H., Wang J., Min R., Ma K., Zhang G. Strategies for enhancing performance of perovskite bismuth ferrite photocatalysts (BiFeO₃) : A comprehensive review. Chemosphere, 2023, 339, P. 139678.

14. Mittal S., Garg S., Bhandari H., Sharma V. A review on recent progressions of Bismuth ferrite modified morphologies as an effective photocatalyst to curb water and air pollution. Inorganic Chemistry Communications, 2022, 144, P. 109834.

15. Ceballos-Sanchez O., Sanchez-Martinez A., Flores- Ruiz F.J., Huerta-Flores A.M., Torres-Mart´ınez L.M., Ruelas R, Garc´ıa-Guaderrama M. Study of BiFeO₃ thin film obtained by a simple chemical method forthe heterojunction-type solar cell design. Journal of Alloys and Compounds, 2020, 832, P. 154923.

16. Eshore A.N., Dey S., Goswami D.K., Guha P.K. Crystallographic Nanojunctions of Bismuth Ferrite for Unconventional Detection of Carbon Monoxide. ACS Applied Nano Materials, 2023, 6(11), P. 9397–9403.

17. Dmonte D.J., Bhardwaj A., Wilhelm M., Fischer T., Kuˇritka I., Mathur S. Sub PPM Detection of NO₂ Using Strontium Doped Bismuth Ferrite Nanostructures. Micromachines, 2023, 14, P. 644.

18. Ji H., Zhang L., Zhang R. Gas sensitive performance and mechanism of multiferroic BiFeO₃ under thermal-magnetic synergetic excitation. Inorganic Chemistry Communications, 2023, 150, P. 110491.

19. Zhang Y., Zhang H., Zhang J., Guo J., Zhang D. Fast Response and Low Detection Limit of Ammonia Sensor Based on WO₃ Nanoparticles-Decorated BiFeO₃ Nanoplates. IEEE Sensors Journal, 2022, 22(15), P. 14736–14742.

20. Egorysheva A.V., Kraev A.S., Gajtko O.M., Baranchikov A.E., Agafonov A.V., Ivanov V.K. Electrorheological Fluids Based on Bismuth Ferrites BiFeO₃ and Bi₂Fe₄O₉. Russian Journal of Inorganic Chemistry, 2020, 65(8), P. 1253–1263.

21. Li Y., Zhang X., Chen L., Sun H., Zhang H., Si W., Wang W., Wang L., Li J. Enhanced magnetic and photocatalytic properties of BiFeO₃ nanotubes with ultrathin wall thickness. Vacuum, 2021, 184, P. 109867.

22. Egorysheva A.V., Milenov T.I., Ellert O.G., Avdeev G.V., Rafailov P.M., Efimov N.N., Novotortsev V.M. Magnetic glasseceramics containing multiferroic BiFeO₃ crystals. Solid State Science, 2015, 40, P. 31–35.

23. Gao X., Wang Y., Wang Q., Wu X., Zhang W., Zong M., Zhang L. Facile synthesis of a novel flower-like BiFeO₃ microspheres/graphene with superior electromagnetic wave absorption performances. Ceramics International, 2019, 45(3), P. 3325–3332.

24. Yastrebov S.G., Lomanova N.A. Specific Features in the Interaction between BiFeO₃ Nanoclusters Synthesized by Solution Combustion. Technical Physics Letters, 2021, 47(1), P. 1–4.

25. Alikhanov N.M.-R., Rabadanov M.Kh., Orudzhev F.F., Gadzhimagomedov S.Kh., Emirov R.M., Sadykov S.A., Kallaev S.N., Ramazanov S.M., Abdulvakhidov K.G., Sobola D. Size-dependent structural parameters, optical, and magnetic properties of facile synthesized pure-phase BiFeO₃. Journal of Materials Science: Materials in Electronics, 2021, 32, P. 13323–13335.

26. Mhamad S.A., Ali A.A., Mohtar S.S., Aziz F., Aziz M., Jaafar J., Yusof N., Salleh W.N.W., Ismail A.F., Chandren S. Synthesis of bismuth ferrite by sol-gel auto combustion method: Impact of citric acid concentration on its physicochemical properties. Materials Chemistry and Physics, 2022, 282, P. 125983.

27. Proskurina O.V., Tomkovich M.V., Bachina A.K., Sokolov V.V., Danilovich D.P., Panchuk V.V., Semenov V.G., Gusarov V.V. Formation of Nanocrystalline BiFeO₃ under Hydrothermal Conditions. Russian Journal of General Chemistry, 2017, 87(11), P. 2507–2515.

28. Rouhani Z., Karimi-Sabet J., Mehdipourghazi M., Hadi A., Dastbaz A. Response surface optimization of hydrothermal synthesis of Bismuth ferrite nanoparticles under supercritical water conditions: Application for photocatalytic degradation of Tetracycline. Environmental Nanotechnology, Monitoring & Management, 2019, 11, P. 100198.

29. Wang Z.-B., Aldalbahi A., Ahamad T., Alshehri S.M., Feng P.X. Preparation of BiFeO<sub3</sub> and its photoelectric performance as photoanode of DSSC. Ceramics International, 2021, 47(19), P. 27565–27570.

30. Xiaoyan Sun, Zhongwu Liu, Hongya Yu, Zhigang Zheng, Dechang Zeng, Facile synthesis of BiFeO₃ nanoparticles by modified microwave-assisted hydrothermal method as visible light driven photocatalysts. Materials Letters, 2018, 219, P. 225–228.

31. Tuluk A., Brouwer H., van der Zwaag S. Controlling the Oxygen Defects Concentration in a Pure BiFeO₃ Bulk Ceramic. Materials, 2022, 15, P. 6509.

32. Gil-Gonz´alez E., Perej´on A., S´anchez-Jim´enez P.E., Sayagu´es M.J., Raj R., P´erez-Maqueda L.A. Phase-pure BiFeO₃ produced by reaction flash-sintering of Bi₂O₃ and Fe₂O₃. Journal of Materials Chemistry A, 2018, 6(13), P. 5356–5366.

33. Carranza-Celis D., Cardona-Rodr´ıguez A., Narv´aez J., Moscoso-Londono O., Muraca D., Knobel M., Ornelas-Soto N., Reiber A., Ram´ırez J.G. Control of Multiferroic properties in BiFeO₃ nanoparticles. Scientific Reports, 2019, 9, P. 3182.

34. Pedro-Garc´ıa F., S´anchez-De Jes´us F., Cort´es-Escobedo C.A., Barba-Pingarr´on A., Bolar´ın-Mir´o A.M. Mechanically assisted synthesis of multiferroic BiFeO₃: Effect of synthesis parameters. Journal of Alloys and Compounds, 2017, 711(2004), P. 77–84.

35. Selbach S.M., Einarsrud M.-A., Grande T. On the Thermodynamic Stability of BiFeO₃. Chemistry of Materials, 2009, 21(1), P. 169–173.

36. Denisov V.M., Belousova N.V., Zhereb V.P., Denisova L.T., Skorikov V.M. Oxide Compounds of Bi₂O₃−Fe₂O₃ System I. The Obtaining and Phase Equilibriums. Journal of Siberian Federal University. Chemistry, 2012, 5(2), P. 146–167.

37. Pikula T., Szumiata T., Siedliska K., Mitsiuk V.I., Panek R., Kowalczyk M., Jartych E. The Influence of Annealing Temperature on the Structure and Magnetic Properties of Nanocrystalline BiFeO₃ Prepared by Sol–Gel Method. Metallurgical and Materials Transactions A, 2022, 53, P. 470–483.

38. Stankiewicz A.I., Moulijn J.A. Process intensification: Transforming chemical engineering. Chemical Engineering Progress, 2000, 96(1), P. 22–34.

39. Abiev R.S. Impinging-Jets Micromixers and Microreactors: State of the Art and Prospects for Use in the Chemical Technology of Nanomaterials (Review). Theoretical Foundations of Chemical Engineering, 2020, 54(6), P. 1131–1147.

40. Proskurina O.V., Sivtsov E.V., Enikeeva M.O., Sirotkin A.A., Abiev R.Sh., Gusarov V.V. Formation of rhabdophane-structured lanthanum orthophosphate nanoparticles in an impinging-jets microreactor and rheological properties of sols based on them. Nanosystems: Physics, Chemistry, Mathematics, 2019, 10(2), P. 206–214.

41. Bałdyga J., Jasi´nska M., Orciuch W. Barium Sulphate Agglomeration in a Pipe – An Experimental Study and CFD Modeling. Chemical Engineering & Technology, 2003, 26(3), P. 334–340.

42. Almjasheva O.V., Popkov V.I., Proskurina O.V., Gusarov V.V. Phase formation under conditions of self-organization of particle growth restrictions in the reaction system. Nanosystems: Physics, Chemistry, Mathematics, 2022, 13(2), P. 164–180.

43. Proskurina O.V., Abiev R.S., Danilovich D.P., Panchuk V.V., Semenov V.G., Nevedomsky V.N., Gusarov V.V. Formation of nanocrystalline BiFeO₃ during heat treatment of hydroxides co-precipitated in an impinging-jets microreactor. Chemical Engineering and Processing – Process Intensification, 2019, 143, P. 107598.

44. Lomakin M.S., Proskurina O.V., Abiev R.Sh., Leonov A.A., Nevedomskiy V.N., Voznesenskiy S.S., Gusarov V.V. Pyrochlore phase in the Bi₂O₃–Fe₂O₃–WO₃–(H₂O) system: physicochemical and hydrodynamic aspects of its production using a microreactor with intensively swirled flows. Advanced Powder Technology, 2023, 34, P. 104053.

45. Abiev R.Sh., Makusheva I.V. Effect of Macro- and Micromixing on Processes Involved in Solution Synthesis of Oxide Particles in High-Swirl Microreactors. Theoretical Foundations of Chemical Engineering, 2022, 56(2), P. 141–151.

46. Proskurina O.V., Sokolova A.N., Sirotkin A.A., Abiev R.Sh., Gusarov V.V. Role of Hydroxide Precipitation Conditions in the Formation of Nanocrystalline BiFeO₃. Russian Journal of Inorganic Chemistry, 2021, 66(2), P. 163–169.

47. Proskurina O.V., Abiev R.Sh., Nevedomskiy V.N. Influence of using different types of microreactors on the formation of nanocrystalline BiFeO₃. Nanosystems: Physics, Chemistry, Mathematics, 2023, 14(1), P. 120–126.

48. Li X., Tang Z., Ma H., Wu F., Jian R. PVP-assisted hydrothermal synthesis and photocatalytic activity of single-crystalline BiFeO₃ nanorods. Applied Physics A, 2019, 125, P. 598.

49. Ortiz-Qui˜nonez J.L., D´ıaz D., Zumeta-Dub´e I., Arriola-Santamar´ıa H., Betancourt I., Santiago-Jacinto P., Nava-Etzana N. Easy Synthesis of High-Purity BiFeO₃ Nanoparticles: New Insights Derived from the Structural, Optical, and Magnetic Characterization. Inorganic Chemistry, 2013, 52(18), P. 10306–10317.

50. Park T.-J., Papaefthymiou G.C., Viescas A.J., Moodenbaugh A.R., Wong S.S. Size-Dependent Magnetic Properties of Single-Crystalline Multiferroic BiFeO₃. Nanoparticles, 2007, 7(3), P. 766–772.

51. Lomanova N.A., Tomkovich M.V., Sokolov V.V., Ugolkov V.L., Panchuk V.V., Semenov V.G., Pleshakov I.V., Volkov M.P., Gusarov V.V. Thermal and magnetic behavior of BiFeO₃ nanoparticles prepared by glycine-nitrate combustion. Journal of Nanoparticle Research, 2018, 20, P. 17.

52. Freitas V.F., Grande H.L.C., de Medeiros S.N., Santos I.A., C´otica L.F., Coelho A.A. Structural, microstructural and magnetic investigations in high-energy ball milled BiFeO₃ and Bi_0.95Eu_0.05FeO₃ powders. Journal of Alloys and Compounds, 2008, 461(1-2), P. 48–52.

53. Lomanova N.A., Panchuk V.V., Semenov V.G., Pleshakov I.V., Volkov M.P., Gusarov V.V. Bismuth orthoferrite nanocrystals: magnetic characteristics and size effects. Ferroelectrics, 2020. 569(1), P. 240–250.

54. Juwita E., Sulistiani F.A., Darmawan M.Y., Istiqomah N.I., Suharyadi E. Microstructural, optical, and magnetic properties and specific absorption rate of bismuth ferrite/SiO₂ nanoparticles. Materials Research Express, 2022, 9, P. 076101.

55. Ramazanov S., Sobola D., Orudzhev F., Knapek A., Polcak J., Potocek M., Kaspar P., Dallaev R. Surface Modification and Enhancement of Ferromagnetism in BiFeO₃ Nanofilms Deposited on HOPG. Nanomaterials, 2020, 10(10), P. 1990.

56. Thamizharasan G., Eithiraj R.D., Enhtuwshin E., Kim S.J., Sahu N.K., Nayak A.K., Han H.S. Computational and Experimental Study on Electronic Band Structure of Bismuth Ferrite: A Promising Visible Light Photocatalyst. Ceramist, 2020, 23(4), P. 350–357.

57. Wang N., Zheng T., Zhang G., Wang P. A review on Fenton-like processes for organic wastewater treatment. Journal of Environmental Chemical Engineering, 2016, 4(1), P. 762–787.

58. Mao J., Quan X., Wang J., Gao C., Chen S., Yu H., Zhang Y. Enhanced heterogeneous Fenton-like activity by Cu-doped BiFeO₃ perovskite for degradation of organic pollutants. Frontiers of Environmental Science & Engineering, 2018, 12(6), P. 10.

59. Dhanalakshmi R., Muneeswaran M., Vanga P.R.; Ashok M.; Giridharan N.V. Enhanced photocatalytic activity of hydrothermally grown BiFeO₃ nanostructures and role of catalyst recyclability in photocatalysis based on magnetic framework. Applied Physics A, 2016, 122(1), P. 13.

60. Liang C., Liu Y., Li K., Wen J., Xing S., Ma Z., Wu Y. Heterogeneous photo-Fenton degradation of organic pollutants with amorphous Fe-Zn-oxide/hydrochar under visible light irradiation. Separation and Purification Technology, 2017, 188, P. 105–111.