This research, for the first time, reports the design and development of a heterogeneous nano-catalyst based on sodium ions (Na+) incorporation in Technical University of Delft (TUD-1) mesoporous silica for Knoevenagel condensation reaction. Facile one-step fabrication of Na-TUD-1 nano-catalysts (varying Si/Na ratio as 100–5) was demonstrated using the sol–gel route. The catalytic performance of Na-TUD-1 was evaluated as a base heterogeneous catalyst in Knoevenagel condensation reaction, which took place under conventional and microwave irradiations conditions using ethanol as a solvent. Na-TUD-1 exhibited superior catalytic activity in comparison to available homogeneous base catalysts such as sodium ethoxide. The Na-TUD-1 nano-catalyst demonstrated identical performance till the fourth run along with high stability and negligible leaching of Na. Moreover, the use of microwave heating reduced the reaction time from 240 to 20 min only with a TOF of 0.58 min−1. Such excellent performance of Na-TUD-1 heterogeneous nano-catalysts will certainly increase its industrial acceptability to achieve affordable and efficient waste-effluent treatments.
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Sheldon, R., Arend, I., Hanefeld, U.: Catalysis in Novel Reaktion Media, pp. 295–328. Wiley, Weinheim (2007)
Prout, F.S., Abdel-Latif, A.A., Kamal, M.R.: Catalyst study of the Knoevenagel condensation. J. Chem. Eng. Data. 8(4), 597–599 (1963)
Villemin, D., Jullien, A., Bar, N.: Optimisation of solvent free parallel synthesis under microwave irradiation: synthesis of new arylacrylonitriles. Green Chem. 5(4), 467–469 (2003)
Bogdał, D.: Coumarins: fast synthesis by Knoevenagel condensation under microwave irradiation. J. Chem. Res. Synopses. 9, 468–469 (1998)
Wada, S., Suzuki, H.: Calcite and fluorite as catalyst for the Knövenagel condensation of malononitrile and methyl cyanoacetate under solvent-free conditions. Tetrahed. Lett. 44(2), 399–401 (2003)
Hangarge, R.V., Jarikote, D.V., Shingare, M.S.: Knoevenagel condensation reactions in an ionic liquid. Green Chem. 4(3), 266–268 (2002)
Sebti, S.D., Smahi, A., Solhy, A.: Natural phosphate doped with potassium fluoride and modified with sodium nitrate: efficient catalysts for the Knoevenagel condensation. Tetrahed. Lett. 43(10), 1813–1815 (2002)
Amantini, D., Fringuelli, F., Piermatti, O., Pizzo, F., Vaccaro, L.: Water, a clean, inexpensive, and re-usable reaction medium. One-pot synthesis of (E)-2-aryl-1-cyano-1-nitroethenes. Green Chem. 3(5), 229–232 (2001)
Zhang, X., Man Lai, E.S., Martin-Aranda, R., Yeung, K.L.: An investigation of Knoevenagel condensation reaction in microreactors using a new zeolite catalyst. Appl. Catal. A Gen. 261(1), 109–118 (2004)
Martins, L., Vieira, K.M., Rios, L.M., Cardoso, D.: Basic catalyzed Knoevenagel condensation by FAU zeolites exchanged with alkylammonium cations. Catal. Today 133–135, 706–710 (2008)
Mondal, J., Modak, A., Bhaumik, A.: Highly efficient mesoporous base catalyzed Knoevenagel condensation of different aromatic aldehydes with malononitrile and subsequent noncatalytic Diels-Alder reactions. J. Mo. Catal. A Chem. 335(1), 236–241 (2011)
Ruiz, N., del Rio, I., Jiménez, J.L., Claver, C., Forniés-Cámer, J., Cardin, C.C.J., et al.: High-branched selectivity in the palladium-catalysed alkoxycarbonylation of styrene in the presence of thiol–thioether atropisomeric ligands. J. Mol. Catal. A Chem. 143(1), 171–180 (1999)
Opanasenko, M., Dhakshinamoorthy, A., Shamzhy, M., Nachtigall, P., Horacek, M., Garcia, H., et al.: Catalytic performance of metal–organic-frameworks in Knoevenagel condensation. Catal. Sci. Technol. 3, 500–507 (2013)
Choudary, B.M., Kantam, M.L., Sreekanth, P., Bandopadhyay, T., Figueras, F., Tuel, A.: Knoevenagel and aldol condensations catalysed by a new diamino-functionalised mesoporous material. J. Mol. Catalysis A Chem. 142(3), 361–365 (1999)
Xue, B., Wen, L.-Z., Ma, D., Li, M.-M., Xu, J.: Knoevenagel condensation reactions catalyzed by nitrogen-containing mesoporous carbon materials under mild reaction conditions. Res. Chem. Intermed. 44(12), 7641–7655 (2018)
Jansen, J., Shan, Z., Marchese, L., Zhou, W., vd Puil, N., Maschmeyer, T.: A new templating method for three-dimensional mesopore networks. Chem. Commun. 8, 713–714 (2001)
Hamdy, M., Mul, G., Jansen, J., Ebaid, A., Shan, Z., Overweg, A., et al.: Synthesis, characterization, and unique catalytic performance of the mesoporous material Fe-TUD-1 in Friedel-Crafts benzylation of benzene. Catal. Today 100(3–4), 255–260 (2005)
Saputera, W.H., Mul, G., Hamdy, M.S.: Ti3+-containing titania: synthesis tactics and photocatalytic performance. Catal. Today 246, 60–66 (2015)
Anand, R., Hamdy, M., Hanefeld, U., Maschmeyer, T.: Liquid-phase oxidation of cyclohexane over Co-TUD-1. Catal. Lett. 95(3–4), 113–117 (2004)
Hamdy, M.S., Mul, G.: Synthesis, characterization and catalytic performance of Mo-TUD-1 catalysts in epoxidation of cyclohexene. Catal. Sci. Tech. 2(9), 1894–1900 (2012)
Hamdy, M.S.: Au-TUD-1: a new catalyst for aerobic oxidation of cyclohexene. Microp. Mesop. Mater. 220, 81–87 (2016)
Al-Shehri, B.M., Shkir, M., Khder, A.E.R.S., Kaushik, A., Hamdy, M.S.: Noble metal nanoparticles incorporated siliceous TUD-1 mesoporous nano-catalyst for low-temperature oxidation of carbon monoxide. Manomater. 10, 1067 (2020)
Hamdy, M.S., Eissa, M.A., Keshk, S.M.A.S.: New catalyst with multiple active sites for selective hydrogenolysis of cellulose to ethylene glycol. Green Chem. 19(21), 5144–5151 (2017)
Al-Shehri, B., Altass, H.M., Ashour, S.S., Shkir, M., Abd El Rahman, S.K., Hamdy, M.S.: Enhancement the photocatalytic performance of semiconductors through composite formation with Eu-TUD-1. Optik. 202, 163522 (2020)
Sun, H., Han, J., Ding, Y., Li, W., Duan, J., Chen, P., et al.: One-pot synthesized mesoporous Ca/SBA-15 solid base for transesterification of sunflower oil with methanol. Appl. Catal. A Gen. 390(1), 26–34 (2010)
Sing, K.S., Everett, D.H., Haul, R., Moscou, L., Pierotti, R.A., Rouquerol, J., et al.: International union of pure commission on colloid and surface chemistry including catalysis* reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl. Chem. 57(4), 603–619 (1985)
Adam, F., Chew, T.-S., Andas, J.: A simple template-free sol–gel synthesis of spherical nanosilica from agricultural biomass. J. Sol-Gel Sci. Techn. 59(3), 580–583 (2011)
Shan, Z., Jansen, J.C., Marchese, L., Maschmeyer, T.: Synthesis, characterization and catalytic testing of a 3-D mesoporous titanosilica, Ti–TUD-1. Microp. Mesop. Mater. 48(1), 181–187 (2001)
Jin H. Synthesis of NaOH-impregnated Calcined Oyster Shell for Transesterification Reaction. (PhD Thesis) (2017)
Kumar, S., Kishore, B., Munichandraiah, N.: Electrochemical studies of non-aqueous Na–O2 cells employing Ag-RGO as the bifunctional catalyst. RSC Adv. 6(68), 63477–63479 (2016). https://doi.org/10.1039/C6RA13596J
Yadegari, H., Li, Y., Banis, M.N., Li, X., Wang, B., Sun, Q., et al.: On rechargeability and reaction kinetics of sodium–air batteries. Energy Environ. Sci. 7(11), 3747–3757 (2014)
Hamdy, M.S., Mul, G., Wei, W., Anand, R., Hanefeld, U., Jansen, J.C., et al.: Fe, Co and Cu-incorporated TUD-1: synthesis, characterization and catalytic performance in N2O decomposition and cyclohexane oxidation. Catal. Today 110(3), 264–271 (2005)
Hamdy, M.S.: One-step synthesis of M-doped TiO2 nanoparticles in TUD-1 (M-TiO2-TUD-1, M=Cr or V) and their photocatalytic performance under visible light irradiation. J. Mol. Catal. A Chem. 393, 39–46 (2014)
Benaissa, M., Alhanash, A.M., Eissa, M., Hamdy, M.S.: Solvent-free selective hydrogenation of 1,5-cyclooctadiene catalyzed by palladium incorporated TUD-1. Catal. Comm. 101, 62–65 (2017)
Mubarak, A.T., Alhanash, A.M., Benaissa, M., Hegazy, H.H., Hamdy, M.S.: In-situ activation of Pd-TUD-1 during the selective reduction of 1,5-cyclooctadiene. Microp. Mesop. Mater. 278, 225–231 (2019)
Song, H., Zhang, F., Jiang, N., Chen, M., Li, F., Yan, Z.: Synthesis of an Ni2P catalyst supported on Na-MCM-41 with highly activity for dibenzothiophene HDS under mild conditions. Res. Chem. Intermed. 44(9), 5285–5299 (2018)
Michalska, A., Daturi, M., Saussey, J., Nowak, I., Ziolek, M.: The role of MCM-41 composition in the creation of basicity by alkali metal impregnation. Microp. Meso. Mater. 90(1), 362–369 (2006)
Albayati, T.M., Doyle, A.M.: Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel. J. Nanop. Res. 17(2), 109 (2015)
Chen, W.-K., Tseng, H.-H., Wei, M.-C., Su, E.-C., Chiu, I.C.: Transesterification of canola oil as biodiesel over Na/Zr-SBA-15 catalysts: Effect of zirconium content. Intern. J. Hydrog. Energy. 39(34), 19555–19562 (2014)
Shen, Z.-L., Xu, X.-P., Ji, S.-J.: Brønsted base-catalyzed one-pot three-component biginelli-type reaction: an efficient synthesis of 4,5,6-triaryl-3,4-dihydropyrimidin-2(1H)-one and mechanistic study. The J. Org. Chem. 75(4), 1162–1167 (2010)
Kamal Raj, M., Rao, H.S.P., Manjunatha, S.G., Sridharan, R., Nambiar, S., Keshwan, J., et al.: A mechanistic investigation of Biginelli reaction under base catalysis. Tetrahed. Lett. 52(28), 3605–3609 (2011)
Shen, Z.L., Xu, X.P., Ji, S.J.: Brønsted Base-Catalyzed One-Pot Three-Component Biginelli-Type Reaction: An Efficient Synthesis of 4,5,6-Triaryl-3,4-dihydropyrimidin-2(1H)-one and Mechanistic Study. J. Org. Chem. 75, 1162 (2010)
Raj, M.K., Rao, H.S.P., Manjunatha, S.G., Sridharan, R., Nambiar, S., Keshwan, J., Rappai, J., Bhagat, S., Shwetha, B.S., Hegde, D., Santhosh, U.: A mechanistic investigation of Biginelli reaction under base catalysis. Tetrahed. Lett. 52, 3605 (2011)
Albayati, T.M., Aidan, M.D.: Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel. J. Nano Res. 17, 109 (2015)
Chen, W., Tseng, H., Wei, M., Su, E., Chiu, I.: Transesterification of canola oil as biodiesel over Na/Zr-SBA-15 catalysts: Effect of zirconium content. Intern. J. Hydrog. Energ. 39, 19555 (2014)
B. M. Al-Shehri thanks Chemistry Department, College of Science, Umm Al-Qura University for personal fellowship. The authors also acknowledge the Deanship of Scientific Research at King Khalid University for funding this work through the research group program under Grant number R.G.P.1/172/41.
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Al-Shehri, B.M., Shabaan, M.R., Shkir, M. et al. Single-step fabrication of Na-TUD-1 novel heterogeneous base nano-catalyst for Knoevenagel condensation reaction. J Nanostruct Chem (2020). https://doi.org/10.1007/s40097-020-00364-8
- Knoevenagel condensation
- Conventional heating
- Base catalyst