Copper (II) supported on a post-modified Magnetic pectin Fe3O4@Pectin~Imidazole~SO3H-Cu(II): An efficient biopolymer-based catalyst for selective oxidation of alcohols with aqueous TBHP

Document Type : Article


Department of Chemistry, Faculty of Sciences, University of Birjand, Birjand, P.O. Box 97175-615, Iran


Designing a catalyst that combines the activity, selectivity, simple recovery, and follows the green chemistry instructions is of great importance. In the present study, Fe3O4@Pectin~Imidazole~SO3H-Cu(II) was synthesized as an efficient and biopolymer-based magnetic catalyst for the oxidation of benzyl alcohols to aldehydes using tert-butyl hydroperoxide (TBHP) as an oxidant under solvent-free conditions. The catalyst was characterized using Fourier Transform Infrared Spectroscopy (FT-IR), Powder X-Ray Diffraction (XRD), Vibrating Sample Magnetometer (VSM), Field Emission scanning electron microscopy (FE-SEM), Energy dispersive spectroscopy (EDX), Transmission electron microscopy (TEM), and inductively coupled plasma (ICP) atomic emission spectroscopy. The results indicated that our catalyst was quite active in oxidizing the benzyl alcohols to their corresponding aldehydes in the presence of TBHP. The efficiency with low catalyst loading, convenient work-up, isolation of pure products, use of inexpensive metal instead of precious metals, solvent-free condition, use of eco-friendly support, and also the sustainability of catalyst up to at least 5 consecutive runs without a special drop-in activity are some of the remarkable advantages of this protocol.


[1] Ghamari Kargar, P., Bakherad, M., Keivanloo, and et al. "Silica-anchored Cu (I) aminothiophenol complex: An efficient heterogeneous catalyst for synthesis of 1, 4-disubstituted 1, 2, 3-triazoles in water", Iranian Journal of Catalysis, 8(3), 179-187 (2018).
[2] Ghamari Kargar, P., Aryanejad, S., & Bagherzade, G. "Simple synthesis of the novel Cu‐MOF catalysts for the selective alcohol oxidation and the oxidative cross‐coupling of amines and alcohols", Applied Organometallic Chemistry., 34(12), e5965 (2020). 
[3] Khashei Siuki, H., Bagherzade, G., & Ghamari Kargar, P. "A Green Method for Synthesizing Nickel Nanoparticles Supported by Magnetized Pectin: Applied as a Catalyst for Aldehyde Synthesis as a Precursor in Xanthan Synthesis", ChemistrySelect, 5(43), 13537-13544 (2020).
[4] Wathoni, N., Nguyen, A.N., Rusdin, A., and et al. "Enteric-Coated Strategies in Colorectal Cancer Nanoparticle Drug Delivery System",  Drug Des Devel Ther.,14, p.4387 (2020).
[5] Pettignano, A., Aguilera, D.A., Tanchoux, N., and et al. "Alginate: a Versatile Biopolymer for Functional Advanced Materials for Catalysis", Stud Surf Sci Catal., 178, pp. 357-375 (2019).
[6] Nasrollahzadeh, M., Shafiei, N., Nezafat, Z., and et al. "Recent progresses in the application of cellulose, starch, alginate, gum, pectin, chitin and chitosan based (nano) catalysts in sustainable and selective oxidation reactions: A review", Carbohydr. Polym. , pp. 116353 (2020).
[7] Ghamari kargar, P. Noorian, M. Chamani, E. and et al. " Synthesis, characterization and cytotoxicity evaluation of a novel magnetic nanocomposite with iron oxide deposited on cellulose nanofibers with nickel (Fe3O4@NFC@ONSM-Ni)", RSC Adv., 11, pp. 17413-17430 (2021).
[8] Marcon, M. V., Vriesmann, L. C., Wosiacki, G., and et al. "Pectins from apple pomace", Polímeros., 15(2), pp.127-129 (2005).
[9] Cervenka, L., Zachova, I., Minarikova, P. and et al. "Effect of pH and water activity on the growth of Arcobacter sp. in culture", Czech J. Food Sci., 15(2), pp.112 (2003).
[10] Sriamornsak, P."Chemistry of pectin and its pharmaceutical uses: A review", SUSTJ. , 3(1-2), pp.206-228 (2003).
[11] Akansha A, Deepali A, Anamika B, and et al. "A Mild and environmentally benign Synthesis of Benzimidazoles: Relevance to the pectin hetero Polysaccharide as a Catalyst", Res. J. Recent Sci., pp.2277-2502 (2014).
[12] Kangani, M., Hazeri, N. and Maghsoodlou, M.T."A mild and environmentally benign synthesis of tetrahydrobenzo [b] pyrans and pyrano [c] chromenes using pectin as a green and biodegradable catalyst", J Chin Chem Soc., 63(11), pp.896-901 (2016).
[13] Nabi, S.A., Shahadat, M., Bushra, R., and et al."Development of composite ion-exchange adsorbent for pollutants removal from environmental wastes", Chem. Eng. J., 165(2), pp.405-412 (2010).
[14] Pathania, D., Sarita, S. and Rathore, B.S. "Synthesis, characterization and photocatalytic application of bovine serum albumin capped cadmium sulphide nanopartilces", Chalcogenide Lett., 8(6), pp.396-404 (2011).
[15] Baran, T."Bio-synthesis and structural characterization of highly stable silver nanoparticles decorated on a sustainable bio-composite for catalytic reduction of nitroarenes", J. Mol. Struct., 1182, pp.213-218 (2019).
[16] Pathania, D., Sharma, G. and Thakur, R. "Pectin@ zirconium (IV) silicophosphate nanocomposite ion exchanger: photo catalysis, heavy metal separation and antibacterial activity", Chem. Eng. J.,pp. 235-244 (2015).
[17] Baran, T. "Pd (0) nanocatalyst stabilized on a novel agar/pectin composite and its catalytic activity in the synthesis of biphenyl compounds by Suzuki-Miyaura cross coupling reaction and reduction of o-nitroaniline", Carbohydr. Polym., 195, pp.45-52 (2018).
[18] Khazaei, A., Rahmati, S., Hekmatian, Z. and et al. "A green approach for the synthesis of palladium nanoparticles supported on pectin: Application as a catalyst for solvent-free Mizoroki–Heck reaction", J. Mol. Catal. A Chem., 372, pp.160-166 (2013).
[19] Wang, X., Hu, P., Xue, F. and et al. "Cellulose-supported N-heterocyclic carbene-palladium catalyst: Synthesis and its applications in the Suzuki cross-coupling reaction", Carbohydr. Polym., 114, pp.476-483 (2014).
[20] Rostamnia, S., Doustkhah, E., Baghban, A. and et al. "Seaweed‐derived κ‐carrageenan: Modified κ‐carrageenan as a recyclable green catalyst in the multicomponent synthesis of aminophosphonates and polyhydroquinolines", J. Appl. Polym. Sci., 133(11), pp. 43190 (2016).
[21] Ghamari kargar, P. Bagherzade, G. and Eshghi, H. "Novel biocompatible core/shell Fe3O4@NFC@Co (ii) as a new catalyst in a multicomponent reaction: an efficient and sustainable methodology and novel reusable material for one-pot synthesis of 4 H-pyran and pyranopyrazole in aqueous media", RSC Adv., 10(61), pp.37086-37097 (2020).
[22] Ghamari kargar, P. Bagherzade, G. and Eshghi, H. "Introduction of a trinuclear manganese (iii) catalyst on the surface of magnetic cellulose as an eco-benign, efficient and reusable novel heterogeneous catalyst for the multi-component synthesis of new derivatives of xanthene", RSC Adv., 11(8), pp.4339-4355 (2021).
[23] Ghamari kargar, P. Bagherzade, G. and Eshghi, H. "Design and synthesis of magnetic Fe3O4@ NFC-ImSalophCu nanocatalyst based on cellulose nanofibers as a new and highly efficient, reusable, stable and green catalyst for the synthesis of 1, 2, 3-triazoles", RSC Adv., 10(54), pp.32927-32937 (2020).
[24] Doustkhah, E., Heidarizadeh, M., Rostamnia, S. and et al. "Copper immobilization on carboxylic acid-rich Fe3O4-Pectin: Cu2+@ Fe3O4-Pectin a superparamagnetic nanobiopolymer source for click reaction",Mater. Lett.,216, pp.139-143 (2018).
[25] Gong, J.L., Wang, X.Y., Zeng, G.M., and et al. "Copper (II) removal by pectin–iron oxide magnetic nanocomposite adsorbent", Chem. Eng. Sci., 185, pp.100-107(2012).
[26] Ma, C.Y., Dou, B.J., Li, J.J. and et al. "Catalytic oxidation of benzyl alcohol on Au or Au–Pd nanoparticles confined in mesoporous silica", Appl. Catal. B., 92(1-2), pp.202-208 (2009).
[27] Zhan, G., Huang, J., Du, M., and et al. "Liquid phase oxidation of benzyl alcohol to benzaldehyde with novel uncalcined bioreduction Au catalysts: high activity and durability", Chem. Eng. J., 187,pp.232-238 (2012).
[28] Palermo, V., Villabrille, P.I., Vazquez, P.G., and et al. "Role of vanadium and pyridine in heteropolycompounds for selective oxidation of alcohols with hydrogen peroxide", J. Chem. Sci., 125(6), 1375-1383 (2013).
[29] Holum, J.R. "Study of the chromium (VI) oxide-pyridine complex", J. Org. Chem., 26(12), 4814-4816 (1961).
[30] Renuka, M.K. and Gayathri, V. "A polymer supported Cu (II) catalyst for oxidative amidation of benzyl alcohol and substituted amines in TBHP/H2O", Catal. Commun., 104, 71-77 (2018).
[31] Azeredo, J., Schwab, R., Braga, A. B., and et al. "Synthesis of Biologically Active Selenium-Containing Molecules From Greener Perspectives", Chem.Comm., pp.3352-3365 (2008).
[32] Brink, G.J., Arends, I.W. and Sheldon, R.A. "Green, catalytic oxidation of alcohols in water", sci., 287(5458), pp.1636-1639 (2000).
[33] Nasrollahzadeh, M., Bagherzadeh, M. and Karimi, H. "Preparation, characterization and catalytic activity of CoFe2O4 nanoparticles as a magnetically recoverable catalyst for selective oxidation of benzyl alcohol to benzaldehyde and reduction of organic dyes", J. Colloid Interface Sci., 465, 271-278 (2016).
[34] Tamizhdurai, P., Sakthinathan, S., Krishnan, P.S., and et al. "Catalytic activity of ratio-dependent SBA-15 supported zirconia catalysts for highly selective oxidation of benzyl alcohol to benzaldehyde and environmental pollutant heavy metal ions detection", J. Mol. Struct., 1176, pp.650-661 (2019).
[35] Singh, S.J. and Jayaram, R.V. "Oxidation of Alcohols to Aldehydes and Ketones Using TBHP as an Oxidant over LaMO3 (M˭ Cr, Mn, Co, Ni, Fe) Perovskites",Synth. Commun., 42(3), pp.299-308 (2018).
[36] Fukahori, S., Morikawa, M. and Ninomiya, J.I. "Preparation of ruthenium-containing sheet composites using a papermaking technique for selective oxidation of alcohol", Chem. Eng. Sci., 157(2-3), pp.311-315 (2010).
[37] Villa, A., Wang, D., Dimitratos, N., and et al. "Pd on carbon nanotubes for liquid phase alcohol oxidation", Catal. Today., 150(1-2), pp.8-15 (2010).
[38] Yamamoto, R., Sawayama, Y.S., Shibahara, H., and et al. "Promoted partial oxidation activity of supported Ag catalysts in the gas-phase catalytic oxidation of benzyl alcohol", J. Catal., 234(2), pp.308-317 (2005).
[39] Choudhary, V.R., Dhar, A., Jana, P., and et al. "A green process for chlorine-free benzaldehyde from the solvent-free oxidation of benzyl alcohol with molecular oxygen over a supported nano-size gold catalyst", Green Chem., 7(11), pp.768-770 (2005).
[40] Bullock, R.M."Reaction: earth-abundant metal catalysts for energy conversions", Chem., 2(4), pp.444-446 (2017).
[41] Torii, H., Nakadai, M., Ishihara, K., and et al. "Asymmetric direct aldol reaction assisted by water and a proline‐derived tetrazole catalyst", Angew. Chem., Int. Ed. Engl., 43(15), pp.1983-1986 (2004).
[42] Gogoi, N., Begum, T., Dutta, S., and et al. "Rice husk derived nanosilica supported Cu (II) complex: an efficient heterogeneous catalyst for oxidation of alcohols using TBHP", RSC Adv., 5(115), pp.95344-95352 (2015).
[43] An, T.T., Zheng, T.Y., Yu, Y.Q. and et al. RSC Adv., 2017, 7, 15176–15180;(b) JR Luque-Ortega, P. Reuther, L. Rivas and C. Rivas, J. Med. Chem., 53, pp.1788-1798 (2010).
[44] Rahman, T., Borah, G. and Gogoi, P.K. "Hybrid composite of CuO with hbox {g}hbox {-C}_{3}hbox {N}_{4} as a photoactive catalyst: an efficient approach for the oxidation of alcohols", J. Chem. Sci., 131(1), pp.1-9 (2019).
[45] Khodamorady, M. and Bahrami, K. "Fe3O4@ BNPs‐CPTMS‐Chitosan‐Pd (0) as an efficient and stable heterogeneous magnetic nanocatalyst for the chemoselective oxidation of alcohols and homoselective synthesis of 5‐subestituted 1H‐tetrazoles", ChemistrySelect., 4(28), pp.8183-8194 (2019).
[46] Sarmah, P., Das, B.K. and Phukan, P. "Novel dicopper (II)-tetracarboxylates as catalysts for selective oxidation of benzyl alcohols with aqueous TBHP", Catal. Commun., 11(10), pp.932-935 (2010).
[47] Baskaran, T., Kumaravel, R., Christopher, J., and et al. "Synthesis and Heterogenization of Siloxane Functionalized Cobalt Complex: Potential Catalyst for Oxidation of Alcohols", Catal. Lett., 145(3), pp.851-859 (2015).
[48] Jiang, Y.W., Chai, K., Wang, Y.Q., and et al. "Mesoporous silica-supported CuCo2O4 mixed-metal oxides for the aerobic oxidation of alcohols", ACS Appl. Nano Mater., 2(7), pp.4435-4442 (2019).