Document Type : Original Research Paper


Department of Chemistry, Payame Noor University, Tehran, Iran


In this work, Fe3O4@TiO2@V2O5 is synthesized via functionalization of Fe3O4 with TiO2 and then modifying with V2O5. The characterization of the synthesized nano-catalyst is performed using several methods including XRD, TEM, SEM, EDS, TGA, and VSM. This nano-catalyst impressively catalyzes the synthesis of 3,3-di-indolyl oxindoles (with an 85-98% yield in 10-80 minutes). Furthermore, the introduced catalyst can be reused in at least five successive reactions with no significant catalytic activity loss. The effects of some influencing parameters on the catalytic efficacy of Fe3O4@TiO2@V2O5 are also assessed. The appropriate product is attained for a wide range of isatins and indoles. Using an inexpensive and reusable catalyst and using the H2O solvent puts this methodology in the green chemistry domain.


[1]. Palit, S. and Hussain, C.M. (2020). Nano-devices applications and recent advancements in nanotechnology and the global pharmaceutical industry. In:  Kanchi, S., Sharma, D. (Eds.). Nanomaterials in Diagnostic Tools and Devices, Elsevier, Amsterdam, the Netherlands, pp. 395–415.
[2]. Holmes, A.B., Ngan, A., Ye, J. and Gu, F. (2022). Selective photocatalytic reduction of selenate over TiO2 in the presence of nitrate and sulfate in mine-impacted water. Chemosphere. 287: 131951.
[3]. Chang, L., Pu, Y., Jing, P., Cui, Y., Zhang, G., Xu, Sh., Cao, B., Guo, J., Chen, F., and Qiao, Ch. (2021). Magnetic core-shell MnFe2O4@TiO2 nanoparticles decorated on reduced graphene oxide as a novel adsorbent for the removal of ciprofloxacin and Cu (II) from water. Applied Surface Science. 541:148400.
[4]. Yaqoob, A.A., Parveen, T., Umar, K., and Mohamad Ibrahim, M.N. (2020). Role of Nanomaterials in the Treatment of Wastewater: A Review. Water. 12 (2): 495.
[5]. Esmaeili, A. (2009). Applications of Nanotechnology in Oil and Gas Industry. Proc, AIP Conference Proceedings, PETROTECH–2009, P09–076, New Delhi, India, 11–15 January, 2-6.
[6]. Mohammed, M.I., Razak, A.A.A., and Shehab, M.A. (2017). Synthesis of nano-catalyst for hydro-desulfurization of gasoil using laboratory hydrothermal rig. Arabian Journal for Science and Engineering. 42 (4):1381–1387.
[7]. Farahbod, F. and Afkhami Karaei, M. (2021). Mathematical modeling and experimental study of sulfur removal process from light and heavy crude oil in a bed occupied by ferric oxide nano-catalysts. Environmental Technology and Innovation. 23: 101656.
[8]. Etim, U. J., Bai, P. and Yan, Z. (2018). Nanotechnology Applications in Petroleum Refining. In: Saleh, T. A. (Ed.). Nanotechnology in Oil and Gas Industries. Springer International Publishing AG, pp. 37-66.
[9]. Eljeeva Emerald, F.M., Pushpadass, H.A., Joseph, D. and Jaya, S.V. (2021). Impact of Nanotechnology in Beverage Processing. In: Muthukumarappan, K., Knoerzer, K. (Eds.). Innovative Food Processing Technologies. Elsevier E-book, Amsterdam, The Netherlands, pp. 688–700.
[10]. Ayatullah Hosne Asif, A.K.M., Zayedul Hasan, M.d. (2018). Application of Nanotechnology in Modern Textiles: A Review. International Journal of Engineering & Technology Sciences. 8 (02): 227–231.
[11]. Zhang, Yu., Zhao, B., Jiang, J., Zhuo, Y. and Wang, Sh. (2016). The use of TiO2 nanoparticles to enhance CO2 absorption. International Journal of Greenhouse Gas Control. 50: 49–56.
[12]. Feng, X., Liu, A. and Cheng, J. (2010). Applications and development of nanotechnology in machinery industry. Advanced Materials Research. 121: 5–10.
[13]. Li, J., Li, B., Sui, G., Du, L., Zhuang, Y., Zhang, Y. and Zou, Y. (2021). Removal of volatile organic compounds from air using supported ionic liquid membrane containing ultraviolet-visible light-driven Nd-TiO2 nanoparticles. Journal of Molecular Structure. 1231: 130023.
[14]. Durairajan, A., Kavitha, T., Rajendran, A., and Kumaraswamidhas, L.A. (2012). Design and manufacturing of nano-catalytic converter for pollution control in automobiles for green environment. Indian Journal of Innovations and Developments. 1 (5): 314-319.
[15]. Wang, B., Wu, T., Angaiah, S., Murugadoss, V., Ryu, J.E., Wujcik, E.K., Lu, N., Young, D.P., Gao, Q., and Guo, Z. (2018). Development of Nanocomposite Adsorbents for Heavy Metal Removal from Wastewater. ES Materials and Manufacturing. 2: 35–44.
[16]. Sagir, M., Tahir, M.B., Akram, J., Tahir, M.S. and Waheed, U. (2021). Nanoparticles and Significance of Photocatalytic Nanoparticles in Wastewater Treatment: A Review. Current Analytical Chemistry. 17: 38-48.
[17]. Siddeeg, S.M., Tahoon, M.A., Alsaiari, N.S., Shabbir, M., and Rebah, F.B. (2021). Application of Functionalized Nanomaterials as Effective Adsorbents for the Removal of Heavy Metals from Wastewater: A Review. Current Analytical Chemistry. 17: 1-19.
[18]. Akhbarizadeh, R., Shayestefar, M.R. and Darezereshki, E. (2013). Competitive Removal of Metals from Wastewater by Maghemite Nanoparticles: A Comparison between Simulated Wastewater and AMD. Mine Water Environ. Doi: 10.1007/s10230-013-0257-1.
[19]. Mashkour, M., Rahimnejad, M., Raouf, F. and Navidjouy, N. (2021). A review on the application of nanomaterials in improving microbial fuel cells, Biofuel Research Journal. 8 (2): 1400-1416.
[20]. Kouzu, M., Kasuno, T. and Tajika, M., (2008). Active phase of calcium oxide used as solid base catalyst or transesterification of soybean oil with refluxing methanol, Journal of Applied Catalyst, 334: 357-365.
[21]. Saththasivam, J., Yiming, W., Wang, K., Jin, J. and Liu, Z. (2018). A Novel Architecture for Carbon Nanotube Membranes towards Fast and Efficient Oil/water Separation. Scientific Reports. 8: 7418.
[22]. Mustapha, M.H., Azizi, A.K., Aini, W.N., Mokhtar, W. and Mohamed, A.M. (2021). Application of Nanoparticles for the Enhanced Production of Biodiesel. In: Editor(s): Inamuddin, Ahamed, M. I., Boddula, R., Rezakazemi, M. (Eds). Biodiesel Technology and Applications. Scrivener Publishing LLC, pp. 465-480.
[23]. Ziarani, G.M., Gholamzadeh, P., Lashgari, N. and Hajiabbasi, P. (2013). Oxindole as starting material in organic synthesis. ARKIVOC: Online Journal of Organic Chemistry. 2013 (1): 470-535.
[24]. Peddibhotla, S. (2009). 3-Substituted-3-hydroxy-2-oxindole, an emerging new scaffold for drug discovery with potential anti-cancer and other biological activities. Current Bioactive Compounds. 5 (1): 20-38.
[25]. Kang, T. H., Murakami, Y., Matsumoto, K., Takayama, H., Kitajima, M., Aimi, N. and Watanabe, H. (2002). Rhynchophylline and isorhynchophylline inhibit NMDA receptors expressed in Xenopus oocytes. European journal of pharmacology. 455 (1): 27-34.
[26]. Praveen, C., Ayyanar, A. and Perumal, P.T. (2011). Practical synthesis, anti-convulsant, and anti-microbial activity of N-allyl and N-propargyl di (indolyl) indolin-2-ones. Bioorganic and medicinal chemistry letters. 21 (13): 4072-4077.
[27]. Paira, P., Hazra, A., Kumar, S., Paira, R., Sahu, K.B., Naskar, S., Mondal, S., Maity, A., Banerjee, S. and Mondal, N.B. (2009). Efficient synthesis of 3, 3-diheteroaromatic oxindole analogues and their in vitro evaluation for spermicidal potential. Bioorganic and medicinal chemistry letters. 19 (16): 4786-4789.
[28]. Reddy, B.S., Rajeswari, N., Sarangapani, M., Prashanthi, Y., Ganji, R.J. and Addlagatta, A. (2012). Iodine-catalyzed condensation of isatin with indoles: a facile synthesis of di (indolyl) indolin-2-ones and evaluation of their cytotoxicity. Bioorganic and medicinal chemistry letters. 22 (7): 2460-2463.
[29]. Natarajan, A., Fan, Y. H., Chen, H., Guo, Y., Iyasere, J., Harbinski, F., Christ, W.J., Aktas, H., and Halperin, J.A. (2004). 3,3-diaryl-1, 3-dihydroindol-2-ones as anti-proliferatives mediated by translation initiation inhibition. Journal of medicinal chemistry. 47 (8): 1882-1885.
[30]. Azizian, J., Mohammadi, A.A., Karimi, N., Mohammadizadeh, M.R. and Karimi, A.R. (2006). Silica sulfuric acid a novel and heterogeneous catalyst for the synthesis of some new oxindole derivatives. Catalysis Communications. 7 (10): 752-755.
[31]. Wu, C., Liu, J., Kui, D., Lemao, Y., Yingjie, X., Luo, X., Meiyang, X. and Shen, R. (2020). Efficient Multicomponent Synthesis of Spirooxindole Derivatives Catalyzed by Copper Triflate. Polycyclic Aromatic Compounds. 1-13.
[32]. Kamal, A., Srikanth, Y., Khan, M.N.A., Shaik, T.B. and Ashraf, M. (2010). Synthesis of 3,3-diindolyl oxyindoles efficiently catalysed by FeCl3 and their in vitro evaluation for anticancer activity. Bioorganic and medicinal chemistry letters. 20: 5229-5231.
[33]. Yadav, J.S., SubbaReddy, B.V., Gayathri, K.U., Meraj, S. and Prasad, A.R. (2006). Bismuth (III) triflate catalyzed condensation of isatin with indoles and pyrroles: a facile synthesis of 3,3-diindolyl-and 3,3-dipyrrolyl oxindoles. Synthesis. 2006 (24): 4121-4123.
[34]. Nasseri, M.A. and Zakerinasab, B. (2013). Sulfonated polyethylene glycol as a reusable and efficient catalytic system for the synthesis of diindolyl oxindole derivatives under ambient conditions. Iranian Journal of Organic Chemistry. 5 (2): 1021-1025.
[35]. Khorshidi, A. and Tabatabaeian, K. (2010). Ru(III)-exchanged FAU-Y zeolite as an efficient heterogeneous catalyst for preparation of oxindoles. Oriental Journal of Chemistry. 26 (3): 837-841.
[36]. Wang, S.Y. and Ji, S.J. (2006). Facile synthesis of 3,3-di (heteroaryl) indolin-2-one derivatives catalyzed by ceric ammonium nitrate (CAN) under ultrasound irradiation. Tetrahedron. 62 (7): 1527-1535.
[37]. Adibian, F., Pourali, A.R., Maleki, B., Baghayeri, M. and Amiri, A. (2020). One‐pot synthesis of dihydro-1H-indeno [1, 2-b] pyridines and tetrahydrobenzo [b] pyran derivatives using a new and efficient nanocomposite catalyst based on N‐butylsulfonate‐functionalized MMWCNTs-D-NH2. Polyhedron. 175: 114179.
[38]. Moqadam, Z.A., Allahresani, A. and Hassani, H. (2020). An efficiently and quickly synthesized NiO@ gC 3 N 4 nanocomposite-catalyzed green synthesis of spirooxindole derivatives. Research on Chemical Intermediates. 46: 299-311.
[39]. Hassani, H. and Jahani, Z. (2020). Synthesis of 1,3,5-Trisubstituted Pyrazoles and Hydrazones Using Fe3O4@ CeO2 Nanocomposite as an Efficient Heterogeneous Nanocatalyst. Russian Journal of Organic Chemistry. 56 (3): 485-490.
[40]. Bahri-Laleh, N., Hanifpour, A., Mirmohammadi, S.A., Poater, A., Nekoomanesh-Haghighi, M., Talarico, G. and Cavallo, L. (2018). Computational modeling of heterogeneous Ziegler-Natta catalysts for olefins polymerization. Progress in Polymer Science. 84: 89-114.
[41]. Li, C.J. (2005). Organic reactions in aqueous media with a focus on carbon−carbon bond formations: a decade update. Chemical Reviews. 105 (8): 3095-3166.
[42]. Bazi, F., El Badaoui, H., Tamani, S., Sokori, S., Solhy, A., Macquarrie, D. and Sebti, S. (2006). A facile synthesis of amides by selective hydration of nitriles using modified natural phosphate and hydroxyapatite as new catalysts. Applied Catalysis A-General. 301 (2): 211-214.
[43]. Hassani, H., Zakerinasab, B., and Nozarie, A. (2018). Sulfonic acid supported on Fe2O3/VO2 nanocatalyst: a highly efficient and reusable nanocatalyst for synthesis of spirooxindole derivatives. Asian Journal of Green Chemistry. 2: 59-69.
[44]. Wei, Y., Han, B., Hu, X., Lin, Y., Wang, X., and Deng, X. (2012). Synthesis of Fe3O4 nanoparticles and their magnetic properties. Procedia Engineering. 27: 632-637.
[45]. Tan, L., Zhang, X., Liu, Q., Jing, X., Liu, J., Song, D., Hu, S., Liu, L., and Wang, J. (2015). Synthesis of Fe3O4@TiO2 core–shell magnetic composites for highly efficient sorption of uranium (VI). Colloids and Surfaces A: Physicochemical and Engineering Aspects. 469: 279-286.
[46]. Theivasanthi, T. and Alagar, M. (2013). Titanium dioxide (TiO2) nanoparticles XRD analyses: an insight. arXiv preprint arXiv. 1307. 1091.
[47]. Pratheepa, M.I. and Lawrence, M. (2018). X-Ray Diffraction Analyses of Titanium Dioxide Nanoparticles. International Journal of Scientific Research in Science and Technology. 3 (11): 83-88.
[48]. Chan, Y.L., Pung, S.Y. and Sreekantan, S. (2014). Synthesis of V2O5 nanoflakes on PET fiber as visible-light-driven photocatalysts for degradation of RhB dye. Journal of Catalysts. 2014 (1): 1-7.
[49]. Kandathil, V., Fahlman, B.D., Sasidhar, B., Patil, S.A., and Patil, S.A. (2017). A convenient, efficient and reusable N-heterocyclic carbene-palladium(II)-based catalyst supported on magnetite for Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions. New Journal of Chemistry. 41: 9531-9545.