Molten Salt Synthesis of the Plate-Like ABi4Ti4O15 (A= Ba, and Pb) for Methylene Blue Removal via Phocatalysis Effect

Anton Prasetyo; Muhammad  Lathif Al-Abror; Usman Ali  Rouf; Erna  Hastuti; Widiya Nur  Safitri; Arie Hardian

doi:10.15408/jkv.v12i1.48900

Authors

Anton Prasetyo Department of Chemistry, Faculty of Science and Technology, Universitas Islam Negeri Maulana Malik Ibrahim Malang
Muhammad Lathif Al-Abror Department of Chemistry, Faculty of Science and Technology, Universitas Islam Negeri Maulana Malik Ibrahim Malang
Usman Ali Rouf Department of Chemistry, Faculty Science and Technology, Universitas Islam Negeri Maulana Malik Ibrahim Malang
Erna Hastuti Department of Physics, Faculty Science and Technology, Universitas Islam Negeri Maulana Malik Ibrahim Malang
Widiya Nur Safitri Department of Chemistry, Faculty of Science and Data Analytics, Institut Teknologi Sepuluh Nopember
Arie Hardian Department of Chemistry, Faculty of Sciences and Informatics, Universitas Jenderal Achmad Yani

DOI:

https://doi.org/10.15408/jkv.v12i1.48900

Keywords:

ABi4Ti4O15 (A= Ba and Pb), molten salt synthesis, methylene blue, photocatalysis

Abstract

One of the promising technologies for the treatment of dye-containing wastewater is photocatalysis. Among the compounds reported to exhibit good photocatalytic activity are Aurivillius compounds with plate-like morphology. In this study, the plate-like ABi₄Ti₄O₁₅ (A= Ba and Pb) compounds was synthesized using the molten salt method. Diffractogram confirmed that the target compounds BaBi₄Ti₄O₁₅ and PbBi₄Ti₄O₁₅ were successfully synthesized but still found the impurities compound. And also the differences in the type of A-site cation (Ba and Pb) also affect the local structure, meanwhile, the SEM image showed that the particle morphology of all samples is plate-like, however, the particle size obtained is not uniform and agglomerated. The plot tauc calculations showed that BaBi₄Ti₄O₁₅ has a band gap energy of 3.28 eV (378 nm), while that of PbBi₄Ti₄O₁₅ is 3.03 eV (409.19 nm). Differences in the type of A-site cation (Ba and Pb) affect the band gap energy of the four-layer Aurivillius compound ABi₄Ti₄O₁₅. Then the lower band gap energy of PbBi₄Ti₄O₁₅ results in a higher degradation capability toward methylene blue compared to BaBi₄Ti₄O₁₅. It also related to higher reaction rate constant of PbBi₄Ti₄O₁₅. In addition, the another factor also influences the yield of methylene blue degradation by PbBi₄Ti₄O₁₅ is its higher adsorption ability.

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References

1. Oladoye PO, Ajiboye TO, Omotola EO, Oyewola OJ. Methylene blue dye: Toxicity and potential elimination technology from wastewater. Results Eng. 2022;16:100678. doi:10.1016/j.rineng.2022.100678

2. Mulushewa Z, Dinbore WT, Ayele Y. Removal of methylene blue from textile waste water using kaolin and zeolite-x synthesized from Ethiopian kaolin. Environ Anal Heal Toxicol. 2021;36(1):e2021007-0. doi:10.5620/eaht.2021007

3. Fito J, Abewaa M, Mengistu MA. Adsorption of methylene blue from textile industrial wastewater using activated carbon developed from Rumex abyssinicus. Sci Rep. 2023;13:5427. doi:10.1038/s41598-023-32341-w

4. Sitompul DW, Kemala T, Darmawan N. Application of PAN/α-Fe2O3-Bentonite as a photocatalytic membrane for the photodegradation of methylene blue. J Kim Val. 2023;9(1):22-29. doi:10.15408/jkv.v9i1.28635

5. Mhaske S, Padwal Y, Chauhan R. Cu-doped TiO2 spheres: enhanced solar-driven photocatalysis for hydrogen generation and degradation of methylene blue and Congo red. J Mater Sci Mater Electron. 2024;35:1289. doi:10.1007/s10854-024-13067-5

6. Mohamadpour F, Amani AM. Photocatalytic systems: reactions, mechanism, and applications. RSC Adv. 2024;14:20609-20645. doi:10.1039/D4RA03259D

7. Hassaan MA, El-Nemr MA, Elkatory MR. Principles of photocatalysts and their different applications: A Review. Top Curr Chem. 2023;381:31. doi:10.1007/s41061-023-00444-7

8. Chakravorty A, Roy S. A review of photocatalysis, basic principles, processes, and materials. Sustain Chem Environ. 2024;8:100155. doi:10.1016/j.scenv.2024.100155

9. Malini B, Gandhimathi R. Benefits and challenges of nanotechnology-based photocatalysts in achieving a pollution free environment. J Environ Anal Chem. 2025;105(17):5110-5132. doi:10.1080/03067319.2024.2384653

10. Bekele T, Alamnie G. The photocatalytic degradation of organic pollutants-a comprehensive overview. Results Chem. 2025;18:102758. doi:10.1016/j.rechem.2025.102758

11. Li Z, Zhu X, Chen Z. Novel Br-doped Bi2WO6 photocatalyst for high-efficiency removal of norfloxacin: mechanism and photocatalytic activity. Environ Sci Pollut Res. 2024;31:56210-56226. doi:10.1007/s11356-024-34908-0

12. Halili R, Li Z. Synergizing photocatalysis with Aurivillius-phase Bi4Ti3O12: current insights and emerging trends. J Mater Chem A. 2025;13:16345-16381. doi:10.1039/D4TA07986H

13. Supriya S. Tailoring layered structure of bismuth-based Aurivillius perovskites: Recent advances and future aspects. Coord Chem Rev. 2023;479:215010. doi:10.1016/j.ccr.2022.215010

14. Khan MA, Nadeem MA, Idriss H. Ferroelectric polarization effect on surface chemistry and photo-catalytic activity: A review. Surf Sci Rep. 2016;71(1):1-31. doi:10.1016/j.surfrep.2016.01.001

15. Wang Y, Zhang M, Wu J, Hu Z, Zhang H, Yan H. Ferroelectric and photocatalytic properties of Aurivillius phase Ca2Bi4Ti5O18. J Am Ceram Soc. 2021;104(1):322-328. doi:10.1111/jace.17466

16. He R, Xu D, Cheng B, Yu J, Ho W. Review on nanoscale Bi-based photocatalysts. Nanoscale Horizons. 2018;3:464-504. doi:10.1039/C8NH00062J

17. Huang X, Soomro RA, Shen H, Guo L, Yang C, Wang D. Bi2MO6 (M = Mo, W) Aurivillius oxides for efficient photocatalytic N2-to-NH3 conversion: a perspective review. Inorg Chem Front. 2025;12:1773-1797. doi:10.1039/D4QI03182B

18. Kumar A, Sharma P, Wang T, Lai CW, Sharma G, Dhiman P. Recent progresses in improving the photocatalytic potential of Bi4Ti3O12 as emerging material for environmental and energy applications. J Ind Eng Chem. 2024;138:1-16. doi:10.1016/j.jiec.2024.03.054

19. al-Abrar ML, Hastuti E, Prasetyo A. Molten salt synthesis of photocatalyst material SrBi4Ti4O15 for methylene blue degradation. J Rekayasa Kim dan Lingkung. 2023;17(2):182-189. doi:10.23955/rkl.v17i2.25288

20. Febrianti A, Prasetyo A. Ciprofloxacin removal by adsorption photocatalysis effect of SrBi4Ti4O15. In: IOP Conference Series: Earth and Environmental Science. Vol 1574. ; 2025:12006. doi:10.1088/1755-1315/1574/1/012006

21. Qi W, Wang Y, Wu J, Hu Z, Jia C, Zhang H. Relaxor ferroelectric and photocatalytic properties of BaBi4Ti4O15. Adv Appl Ceram. 2019;118(7):418-424. doi:10.1080/17436753.2019.1634943

22. Kumar P, Vaish R, Sung TH, et al. Effect of poling on photocatalysis, piezocatalysis, and photo-piezo catalysis performance of BaBi4Ti4O15 ceramics. Glob Challenges. 2023;7:2200142. doi:10.1002/gch2.202200142

23. Zulhadjri, Prijamboedi B, Nugroho AA, et al. Aurivillius phases of PbBi4Ti4O15 doped with Mn3+ synthesized by molten salt technique: Structure, dielectric, and magnetic properties. J Solid State Chem. 2011;184(5):1318-1323. doi:10.1016/j.jssc.2011.03.044

24. Bella I, Wendari TP, Jamarun N, Mufti N, Zulhadjri. Hydrothermal synthesis of ABi2Ta2O9 Aurivillius phase: A comparative study of A-site cation size on structure, dielectric, optical properties. J Adv Dielectr. 2022;12(2):2150030. doi:10.1142/S2010135X21500302

25. Zhang Z, Yang Y, Wang Y, et al. Revealing the A-site effect of lead-free A3Sb2Br9 Perovskite in photocatalytic C(sp3)-H bond activation. Angew Chemie. 2020;132:18293. doi:10.1002/anie.202005495

26. Tian W, Wang R, Yang D. Organic A-cations in metal halide perovskite photovoltaics. Nat Rev Chem. 2026;10:50-71. doi:10.1038/s41570-025-00774-8

27. Collu DA, Carucci C, Piludu M, Parsons DF, Salis A. Aurivillius oxides nanosheets-based photocatalysts for efficient oxidation of malachite green dye. Int J Mol Sci. 2022;23(10):5422. doi:10.3390/ijms23105422

28. Shetty M, Muniyappa M, Rani MN, Gangaraju V, Shivaramu P, Rangappa D. Photocatalytic efficiency of Bi-based Aurivillius compounds: critical review and discernment of the factors involved. In: Balakumar S, Keller V, Shankar M, eds. Nanostructured Materials for Environmental Applications. Cham: Springer; 2021. doi:10.1007/978-3-030-72076-6_6

29. Ozaki D, Suzuki H, Tomita O. A new lead-free Sillén-Aurivillius oxychloride Bi5SrTi3O14Cl with triple-perovskite layers for photocatalytic water splitting under visible light. J Photochem Photobiol A Chem. 2021;408:113095. doi:10.1016/j.jphotochem.2020.113095

30. Chen Z, Jiang H, Jin W, Shi C. Enhanced photocatalytic performance over Bi4Ti3O12 nanosheets with controllable size and exposed {001} facets for Rhodamine B degradation. Appl Catal B Environ. 2016;180:698-706. doi:10.1016/j.apcatb.2015.07.022

31. Zhao Z, Li X, Ji H, Deng M. Formation mechanism of plate-like Bi4Ti3O12 particles in molten salt fluxes. Integr Ferroelectr. 2014;154(1):154-158. doi:10.1080/10584587.2014.904705

32. Maryani K, Anwari NS, Safitri WN, Hardian A, Inggarwati ED, Prasetyo A. The effect of synthesis temperature on structural, morphological, and band gap energy of plate-like Bi4Ti2.95V0.05O12 prepared by molten NaCl/KCl salt method. Commun Sci Technol. 2024;9(1):1-6. doi:10.21924/cst.9.1.2024.1279

33. Wang Z, Wang Z, Feng Y, et al. Plate-like multiprincipal cation ceramic powders with Aurivillius and Perovskite structures fabricated by molten salt synthesis. Inorg Chem. 2025;64(23):11721-11730. doi:10.1021/acs.inorgchem.5c01197

34. Nurcahyaningtyas D, Prasetyo A. Synthesis and characterization Fe doped BaBi4Ti4O15 prepared via molten salt method. In: AIP Conference Proceedings. Vol 3106. ; 2024:20005. doi:10.1063/5.0214994

35. Toby BH. R factors in rietveld analysis: How good is good enough? Powder Diffr. 2006;21(1):67-70. doi:10.1154/1.2179804

36. García-Guaderrama M, Fuentes L, Márquez-Lucero A, Blanco O. Structural stability and cation disorder in Aurivillius phases. Mater Res Bull. 2012;47(11):3850-3854. doi:10.1016/j.materresbull.2012.08.038

37. Hervoches CH, Lightfoot P. Cation Disorder in Three-Layer Aurivillius Phases: Structural Studies of Bi2-xSr2+xTi1-xNb2+xO12 (0

38. Prasetyo A, Guntur ANM, Himmah SN, Aini N, Rouf UA, Aziz A. Synthesis of microsheets Bi4Ti3O12, and Bi4Ti2.95V0.05O12 via molten NaCl-KCl salt method. J Pure Appl Chem Res. 2022;11(3):207-213. doi:10.21776/ub.jpacr.2022.011.03.703

39. Garcia MAP, Gupta SK, Mao Y. Effects of molten-salt processing parameters on the structural and optical properties of preformed La2Zr2O7: Eu3+ nanoparticles. Ceram Int. 2020;46(2):1352-1361. doi:10.1016/j.ceramint.2019.09.098

40. Zuniga JP, Abdou M, Gupta SK, Mao Y. Molten-salt synthesis of complex metal oxide nanoparticles. J Vis Exp. 2018;140:58482. doi:10.3791/58482

41. Marela SD, Aini N, Hardian A, Suendo V, Prasetyo A. The effect of synthesis temperature on the plate-like particle of Bi4Ti3O12 obtained by molten NaCl salt method. J Pure Appl Chem Res. 2021;10(1):64-71. doi:10.21776/ub.jpacr.2021.010.01.570

42. Hur SG, Kim TW, Hwang SJ, Choy JH. Influences of A- and B-site cations on the physicochemical properties of Perovskite-structured A(In1/3Nb1/3B1/3)O3 (A= Sr, Ba; B= Sn, Pb) photocatalysts. J Photochem Photobiol A Chem. 2006;183(1-2):176-181. doi:10.1016/j.jphotochem.2006.03.014

43. Cahyo IN, Aini N, Steky F V, Suendo V, Safitri WN, Prasetyo A. Synthesis of plate-like Fe-doped SrBi4Ti4O15 using Na2SO4/K2SO4 molten salt method: XRD, Raman spectroscopy, SEM, and Uv-Vis DRS studies. J Iran Chem Soc. 2023;20:3079-3085. doi:10.1007/s13738-023-02899-3

44. Banerjee S, Debnath A, Allam BK, Musa N. Adsorptive and photocatalytic performance of perovskite material for the removal of food dye in an aqueous solution. Environ Challenges. 2021;5:100240. doi:10.1016/j.envc.2021.100240

45. Huang L, Huang X, Yan J. Research progresses on the application of perovskite in adsorption and photocatalytic removal of water pollutants. J Hazard Mater. 2023;442:130024. doi:10.1016/j.jhazmat.2022.130024

46. Kusiak-Nejman E, Sienkiewicz A, Wanag A, Rokicka-Konieczna P, Morawski AW. The role of adsorption in the photocatalytic decomposition of dyes on APTES-modified TiO2 nanomaterials. Catalysts. 2021;11(2):172. doi:10.3390/catal11020172

47. Bekhit SM, Zaki SA, Hassouna MSD. Combined effect of adsorption and photocatalytic degradation using magnesium oxide nano-flowers for tetracycline removal. J Inorg Organomet Polym Mater. 2024;34:5006-5019. doi:10.1007/s10904-024-03138-9

48. Kalaycıoğlu Z, Özuğur U, Bengü P, Önder E, Erim FB. Efficient photocatalytic degradation of methylene blue dye from aqueous solution with cerium oxide nanoparticles and graphene oxide-doped polyacrylamide. ACS Omega. 2023;8(14):13004-13015. doi:10.1021/acsomega.3c00198

49. Kumar A, Pandey G. A review on the factors affecting the photocatalytic degradation of hazardous materials. Mater Sci Eng Int J. 2017;1(3):106-114. doi:10.15406/mseij.2017.01.00018

50. Li X, Chen Y, Tao Y, et al. Challenges of photocatalysis and their coping strategies. Chem Catal. 2022;2(6):1315-1345. doi:10.1016/j.checat.2022.04.007

51. Pellegrino F, Pellutiè L, Sordello F. Influence of agglomeration and aggregation on the photocatalytic activity of TiO2 nanoparticles. Appl Catal B Environ. 2017;216:80-87. doi:10.1016/j.apcatb.2017.05.046

52. Tran HD, Nguyen DQ, Do PT, Tran UNP. Kinetics of photocatalytic degradation of organic compounds: a mini-review and new approach. RSC Adv. 2023;13:16915-16925. doi:10.1039/D3RA01970E

53. Naseri A, Samadi M, Mahmoodi NM, Pourjavadi A, Mehdipour H, Moshfegh AZ. Tuning composition of electrospun ZnO/CuO nanofibers: toward controllable and efficient solar photocatalytic degradation of organic pollutants. J Phys Chem C. 2017;121(6):3327-3338. doi:10.1021/acs.jpcc.6b10414