Catalytic study of highly recoverable chitosan supported Cu(II) Schiff base complex for alkanes oxidation

We have synthesized a chitosan anchored Cu(II) Schiff base heterogeneous catalyst. Schiff base ligand was prepared by condensation of chitosan (Cs) with ortho-hydroxyl acetophenone (OHACP).It is abbreviated as [Cs-OHACP]. Then Cu(II) heterogeneous catalyst2> was prepared by the reaction of [Cs-OHACP] and cupric chloride. The synthesized catalyst, 2> was characterized byscanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), Brunauer–Emmett–Teller (BET) surface area, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), Ultraviolet visible near-infrared (UV–VIS–NIR), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) studies. The catalytic performance of heterogeneous catalyst was tested for alkane oxidation using 70% tert-butylhydroperoxide (TBHP) as an oxidant. The influencing factors that affect the rate of reaction such as various oxidants, solvents, reaction time, molar ratio of tetralin to oxidant, catalyst amount and reaction temperature were investigated for optimization of alkane oxidation. The heterogeneous catalyst 2> is easy to separate, handle and recover. It was recycled seven times.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save

Springer+ Basic €32.70 /Month

Buy Now

Price includes VAT (France)

Instant access to the full article PDF.

Rent this article via DeepDyve

Similar content being viewed by others

Synthesis and DFT studies of robust heterogeneous Co(III) catalyst for liquid phase oxidation of tetralin

Article 01 April 2024

Epoxidation of alkenes with NaIO4 catalyzed by an efficient and reusable natural polymer-supported ruthenium(III) salophen catalyst

Article Open access 17 November 2015

Copper(II)-Ethanolamine Triazine Complex on Chitosan-Functionalized Nanomaghemite for Catalytic Aerobic Oxidation of Benzylic Alcohols

Article 02 July 2020

Explore related subjects

Data availability

References

  1. Debono N, Iglesias M, Sanchez F (2007) New pyridine ONN-pincer gold and palladium complexes: synthesis, characterization and catalysis in hydrogenation, hydrosilylation and C–C cross-coupling reactions. Adv Synth Cata 349:2470–2476 ArticleCASGoogle Scholar
  2. Nomura N, Ishii R, Akakura M, Aoi K (2002) Stereoselective ring-opening polymerization of racemic lactide using aluminum-achiral ligand complexes: exploration of a chain-end control mechanism. Am Chem Soc 124:5938–5939 ArticleCASGoogle Scholar
  3. Miller JA, Jin W, Nguyen ST (2002) An efficient and highly enantio- and diastereoselective cyclopropanation of olefins catalyzed by schiff-base ruthenium(II) complexes. Angew Chem 114:3077–3080 ArticleGoogle Scholar
  4. Abu-Dief AM, Mohamed IMA (2015) A review on versatile applications of transition metal complexes incorporating Schiff bases. Beni-Suef Univ J Basic App Sci 4(2):119–133 Google Scholar
  5. Dhakshinamoorthy A, Alvaro M, Garcia H (2011) Metal–organic frameworks as heterogeneous catalysts for oxidation reactions. Catal Sci Technol 1:856–867 ArticleCASGoogle Scholar
  6. Khare S, Kirar JS, Parashar S (2019) Solvent-free oxidation of ethylbenzene over LDH-hosted Co(II) Schiff base of 2-hydroxy-1- naphthaldehyde and 4-amino benzoic acid. Inorg Nano-Met Chem 49:204–216 ArticleCASGoogle Scholar
  7. Al Zoubi W, Ko YG (2016) Organometallic complexes of Schiff bases: Recent progress in oxidation catalysis. J Organomet Chem 822:173–188 ArticleCASGoogle Scholar
  8. Khare S, Chokhare R, Shrivastava P, Kirar JS, Parashar (2017) α-Zirconium phosphate supported metal–salen complex: synthesis, characterization and catalytic activity for cyclohexane oxidation. J Porous Mater 24:855–866 ArticleCASGoogle Scholar
  9. Frank HG, Stadelhofer JW (1988) Industrial Aromatic Chemistry. Springer-Verlag, Berlin BookGoogle Scholar
  10. Mizukami F, Imamura J (1979) US 4 175 098
  11. Groggins PH, Nagel RH (1934) Studies in the Friedel and Crafts reaction preparation of ketones and keto acids. Ind Eng Chem 26:1313–1316 ArticleCASGoogle Scholar
  12. Feldberg L, Sasson Y (1996) Copper catalyzed oxidation of tetralin to 1-(tert-butylperoxy)-tetralin by aqueous tert-butylhydroperoxide under phase transfer conditions. Tetrahedron Lett 37:2063–2066 ArticleCASGoogle Scholar
  13. Navarro M, Escobar A, Landaeta VR, Visbal G, Lopez-Linares F, Luis ML, Fuentes A (2009) Catalytic oxidation of tetralin by biologically active copper and palladium complexes. Appl Catal A-Gen 363:27–31 ArticleCASGoogle Scholar
  14. Kharat AN, Jahromi BT, Bakhoda A (2012) Manganese(II), cobalts (II) and nickel(II) complexes of tris(2-pyridyl) phosphine and their catalytic activity toward oxidation of tetralin. Transition Met Chem 37:63–69 ArticleCASGoogle Scholar
  15. Khare S, Shrivastava P (2016) liquid phase solvent-less cyclohexane oxidation catalyzed by covalently anchored transition-metal schiff base complexon a-titanium phosphate. Catal Lett 146:319–332 ArticleCASGoogle Scholar
  16. Sheldon RA, Kochi JK (1981) Metal-catalyzed oxidation of organic compounds. Academic, New York, p 34 Google Scholar
  17. Guibal E (2005) Heterogeneous catalysis on chitosan-based materials: a review. Prog Polym Sci 30:71–109 ArticleCASGoogle Scholar
  18. Kirar JS, Khare S, Tiwari N (2021) Fabrication and characterization of Cu nanoparticles dispersed on Zn Al-layered double hydroxide nanocatalysts for the oxidation of cyclohexane. Chem Sel 6:11557–11568 CASGoogle Scholar
  19. Chakraborty T, Chakraborty A, Maity S, Das D, Chattopadhyay T (2019) Conglomerated system of Ag nanoparticles decorated Al2O3 supported cobalt and copper complexes with enhanced catalytic activity for oxidation reactions. Mol Catal 462:104–113 ArticleCASGoogle Scholar
  20. Ispir E (2014) Synthesis and characterization of silica–supported Schiff base ligands and their metal complexes: applications as catalysts for the oxidation of alkanes. Phosphorus Sulfur Silicon 189:1644–1655 ArticleCASGoogle Scholar
  21. Kumari S, Ray S (2020) Zeolite encapsulated Ni(II) Schiff-base complexes: improved catalysis and site isolation. New J Chem 44:14953–14963 ArticleCASGoogle Scholar
  22. Antony R, Arun T, Theodore David Manickam S (2019) A review on applications of chitosan-based Schiff bases. Int J Biol Macromo 129:615–633 ArticleCASGoogle Scholar
  23. Lee M, Den CB, W, (2015) Chitosan as a natural polymer for heterogeneous catalysts support: a short review on its applications. Appl Sci 5:1272–1283 ArticleCASGoogle Scholar
  24. Baran T, Menteş A (2016) Polymeric material prepared from Schiff base based on O-carboxymethyl chitosan and its Cu(II) and Pd(II) complexes. J Mol Struct 1115:220–227 ArticleCASGoogle Scholar
  25. Kramareva NV, Stakheev AY, Tkachenko OP, Klementiev KV, Grunert W, Finashina ED, Kustov LM (2004) Heterogenized palladium chitosan complexes as potentialcatalysts in oxidation reactions: study of the structure. J Mol Catal 209:97 ArticleCASGoogle Scholar
  26. Li-xia W, Zi-wei W, Guo-song W, Xiao-dong L, Jian-guo R (2010) Catalytic performance of Chitosan-Schiff basesupported Pd/Co bimetallic catalyst for acrylamide with phenyl halide. Polym Adv Technol 21:244 ArticleGoogle Scholar
  27. Reddy KR, Rajgopal K, Maheshwari CU, Katam ML (2006) Chitosan hydrogel: a green and recyclable biopolymer catalyst for aldol and Knoevenagel reactions. New J Chem 30:1549–1552 ArticleCASGoogle Scholar
  28. Demetgul C, Serin S (2008) Synthesis and characterization of a new vic-dioxime derivative of chitosan and its transition metal complexes. Carbohydr Polym 72:506–512 ArticleGoogle Scholar
  29. Chang Y, Wang Y, Zha F, Wang R (2004) Preparation and catalytic properties of chitosan bound Schiff base copper complexes. Polym Adv Technol 15:284–286 ArticleCASGoogle Scholar
  30. Tong J, Li Z, Xia C (2005) Highly efficient catalysts of Chitosan-Schiff base Co(II) and Pd(II) complexes for aerobic oxidation of cyclohexane in the absence of reductants and solvents. J Mol Catal 231:197–203 ArticleCASGoogle Scholar
  31. Xue L, Zhou DJ, Tang L (2004) The asymmetric hydration of 1-octene to (S)-(+)-2-octanol with a biopolymer–metal complex, silica-supported chitosan–cobalt complex. React Funct Polym 58:117–121 ArticleCASGoogle Scholar
  32. Hu DD, Cui YL, Dong XL (2001) Studies on Co-Salen immobilized onto N-(4-pyridylmethylidene)–chitosan. React Funct Polym 48:201–207 ArticleCASGoogle Scholar
  33. Baran T, Açıksöz E, Menteş A (2015) Carboxymethyl chitosan Schiff base supported heterogeneous palladium(II) catalysts for Suzuki cross-coupling reaction. J Mol Catal A Chem 407:47–52 ArticleCASGoogle Scholar
  34. Sun W, Xia CG, Wang HW (2002) Efficient heterogeneous catalysts for the cyclopropanation of olefins. New J Chem 226:755–758 ArticleGoogle Scholar
  35. Baran T (2019) Highly recoverable, reusable, cost-effective, and Schiff base functionalized pectin supported Pd(II) catalyst for microwave-accelerated Suzuki cross-coupling reactions. Int J Biol Macromol 127:232–239 ArticleCASPubMedGoogle Scholar
  36. Shafiei N, Nasrollahzadeh M, Baran T, Baran NY (2021) Pd nanoparticles loaded on modified chitosan-Unye bentonite microcapsules: a reusable nanocatalyst for Sonogashira coupling reaction. Carbohy Polym 262:117920 ArticleCASGoogle Scholar
  37. Hamed AA, Abdelhamid IA, Saad GR, Elkady NA, Elsabee MZ (2020) Synthesis, characterization and antimicrobial activity of a novel chitosan Schiff bases based on heterocyclic moieties. Int J Biol Macromol 153:492–501 ArticleCASPubMedGoogle Scholar
  38. Kamiya Y, Ingold K (1964) The Metal-catalyzed autoxidation of Tetralin: III. catalysis by manganese, copper, nickel, and iron. Can J Chem 42:1027–1043 ArticleCASGoogle Scholar
  39. Mizukami F, Imamura J (1978) Liquid-phase oxidation of hydrocarbons with molecular oxygen. I. the effects of metal ions and their ligands on product distribution in the oxidation of tetralin in acetic acid. Bull Chem Soc Jpn 51:1404–1412 ArticleCASGoogle Scholar
  40. Frank HG, Stadelhofer JW (1988) Industrial Aromatic Chemistry. Springer-Verlag, Heidelberg, p 313 BookGoogle Scholar
  41. Dhakshinamoorthy A, Alvaro M, Garcia H (2009) Metal organic frameworks as efficient heterogeneous catalysts for the oxidation of benzylic compounds with t-butylhydroperoxide. J Cat 267(1):1–4 ArticleCASGoogle Scholar
  42. Bhattacharjee S, Lee YR, Ahn WS (2017) Oxidation of tetraline to 1-tetralone over CrAPO-5. Korean J Chem Eng 34(3):701–705 ArticleCASGoogle Scholar
  43. Bhattacharjee S, Jeong KE, Jeong SY, Ahn WS (2010) Synthesis of a sulfonato-salen-nickel (II) complex immobilized in LDH for tetralin oxidation. New J Chem 34:156–162 ArticleCASGoogle Scholar
  44. Kim J, Bhattacharjee S, Jeong KE, Jeong SY, Ahn WS (2009) Selective oxidation of tetraline over a chromium terephthalate metal organic framework, MIL-101. Chem Commun 26:3904–3906 ArticleGoogle Scholar
  45. Neeli CKP, Kannapu HPR, Kalevaru VN, Kamaraju SRR, Burri DR (2018) An efficient and selective benzylic oxidation of tetralin to 1-tetralone on Cu (II) immobilized γ-Fe2O3@SBA-15 magnetic Nano catalyst in green water medium without base or additives. Mol Catal 45:74–84 ArticleGoogle Scholar
  46. Wan C, Zhu M, Du L, Xu L, Ye M, An Y (2019) Highly efficient aerobic oxidation of tetralin to α-tetralone over MnOx–CoOy/γ-Al2O3 catalysts. Catal Commun 125:87–92 ArticleCASGoogle Scholar
  47. LlabrésIXamena FX, Casanova O, Galiasso Tailleur R, Garcia H, Corma A (2008) Metal organic frameworks (MOFs) as catalysts: a combination of Cu2+ and Co2+ MOFs as an efficient catalyst for tetralin oxidation. J Catal 255:220–227 ArticleGoogle Scholar
  48. Louis B, Detoni C, Carvalho NMF, Duarte CD, Antunes OAC (2009) Cu(II) bipyridine and phenantroline complexes: Tailor-made catalysts for the selective oxidation of tetralin. Appl Catal A: Gen 360:218–225 ArticleCASGoogle Scholar
  49. Ma Y, Zeng M, He J, Duana L, Wang J, Li J, Wang J (2011) Syntheses and characterizations of cobalt doped mesoporous alumina prepared using natural rubber latex as template and its catalytic oxidation of tetralin to tetralone. Appl Catal A: Gen 396:123–128 ArticleCASGoogle Scholar
  50. Shaikh RA, Chandrasekar G, Biswas K, Choi JS, Son WJ, Jeong SY, Ahn WS (2008) Tetralin oxidation over chromium-containing molecular sieve catalysts. Catal Today 132:52–57 ArticleCASGoogle Scholar
  51. Razi R, Abedini M, Kharat AN, Amini MM (2008) Oxidation of tetralin with molecular oxygen by vanadium-substituted polyoxometalate. Catal Commun 9:245–249 ArticleCASGoogle Scholar
  52. Parashar S, Khare S (2019) Transition metal Schiff base complexes supported on layered double hydroxide: synthesis, characterization and catalytic activity for the oxidation of toluene. Reac Kinet Mech Cat 127:469–488 ArticleCASGoogle Scholar
  53. Khare S, Shrivastava P, Chokhare R, Kirar JS, Parashar S (2018) Catalytic liquid phase oxidation of cyclohexane with tert-butylhydroperoxide over transition metal exchanged α-zirconium phosphate. Indian J Chem Sect A 57:427–443 Google Scholar
  54. Kirar JS, Khare S, Tiwari N (2021) Transition metal Schiff base complexes supported on layered double hydroxide: synthesis, characterization and catalytic activity for the oxidation of toluene. Reac Kinet Mech Cat 132:1025–1046 ArticleCASGoogle Scholar
  55. Parashar S, Khare S (2019) Synthesis, characterization and catalytic activity of Cu(II) Schiff base complexes intercalated in layered double hydroxide for the oxidation of styrene. Indian J Chem 58A:753–762 CASGoogle Scholar
  56. Sagunthala Devi PR, Theodore David S, Biju Bennie R, Joel C, Daniel Abraham S (2023) Investigation on the effect of electron beam impact on chitosan anchored mixed ligand Schif base complexes for cyclohexane oxidation. Reac Kinet Mech Cat 136:963–979 ArticleGoogle Scholar
  57. Inukai Y, Chinen T, Matsuda T, Kaida Y, Yasuda S (1998) Selective separation of germanium(IV) by 2,3-dihydroxypropyl chitosan resin. J Analytica Chimica Acta 371:187–193 ArticleCASGoogle Scholar
  58. El-Atawy MA, Khalil KD, Bashal AH (2022) Chitosan capped copper oxide nanocomposite: efficient, recyclable, heterogeneous base catalyst for synthesis of nitroolefins. Catalysts 12:964 ArticleCASGoogle Scholar
  59. Khan A, Toufiq AM, Tariq F, Khan Y, Hussain R, Akhtar N, Rahman S (2019) Influence of Fe doping on the structural, optical and thermal properties of α-MnO2 nanowires. Mater Res Express 6:6 Google Scholar
  60. Antony R, Manickam STD, Saravanan K, Karuppasamy K, Balakumar S (2013) Synthesis, spectroscopic and catalytic studies of Cu(II), Co(II) and Ni(II) complexes immobilized on Schiff base modified chitosan. J Mol Stru 1050:53–60 ArticleCASGoogle Scholar
  61. Nakamoto K (1986) Coordination compounds, Infrared and Raman spectra of inorganic and coordination compounds, 4th edn. Wiley, NewYork Google Scholar
  62. Baran T, Mentes A, Arslan H (2015) Synthesis and characterization of water soluble O-carboxymethyl chitosan Schiff bases and Cu(II) complexes. Int J Bio Macromol 72:94–103 ArticleCASGoogle Scholar
  63. Khare S, Chokhare R (2012) Oxidation of cyclohexene catalyzed by Cu(Salen) intercalated α-zirconium phosphate using dry tert-butylhydroperoxide. J Mol Catal A Chem 353–354:138–147 ArticleGoogle Scholar
  64. Arshad F, Munir A, Kashif QQ, ulHaq T, Iqbal J, Sher F, Hussain I (2020) Controlled development of higher-dimensional nanostructured copper oxide thin films as binder free electrocatalysts for oxygen evolution reaction. Int J hydrog energy 45:16583–16590 ArticleCASGoogle Scholar
  65. Mondal P, Sinha A, Salam N, Roy AS, Jana NR, Islam SM (2013) Enhanced catalytic performance by copper nanoparticle–graphene based composite. RSC Adv 3:5615–5623 ArticleCASGoogle Scholar
  66. Moulder JF., Stickle WF., Peter E. Sob (BookZZ.org)
  67. Frisch, MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JJE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2010) Gaussian 09 Revision B.01 Gaussian Inc Wallingford CT
  68. Abdel-Rahman LH, Ismail NM, Ismael M, Abu-Dief AM, Abdel- Hameed Ahmed E (2017) Synthesis, characterization, DFT calculations and biological studies of Mn(II), Fe(II), Co(II) and Cd(II) complexes based on a tetradentate ONNO donor Schiff base ligand. J Mol Struct 1134:851–862 ArticleCASGoogle Scholar
  69. Shimizu I, Morimoto Y, Faltermeier D, Kerscher M, Paria S, Abe T, Sugimoto H, Fujieda N, Asano K, Suzuki T, Comba P, Itoh S (2017) Tetrahedral copper(II) complexes with a labile coordination site supported by a tris-tetramethylguanidinato, Ligand. Inorg Chem 56:9634–9645 ArticleCASPubMedGoogle Scholar
  70. Mathammal R, Sangeetha K, Sangeetha M, Mekala R, Gadheeja S (2016) Molecular structure, vibrational, UV, NMR, HOMO-LUMO, MEP, NLO, NBO analysisof 3, 5 di tert butyl 4 Hydroxy benzoic acid. J Mol Struct 1120:1–14 ArticleCASGoogle Scholar
  71. Basha MT, Alghanmi RM, Shehata MR, Abdel-Rahman LH (2019) Synthesis, structural characterization, DFT calculations, biological investigation, molecular docking and DNA binding of Co(II), Ni(II) and Cu(II) nanosized Schiff base complexes bearing pyrimidine moiety. J Mol Struct 1183:298–312 ArticleCASGoogle Scholar
  72. Hossain MS, Khushy KA, Latif MA, Hossen MF, Asraf MA, Zahan MKE, Abdou A (2022) Co (II), Ni (II), and Cu (II) complexes containing isatin-based Schiff Base ligand: synthesis, physicochemical characterization, DFT calculations, antibacterial Activity, and molecular docking analysis. Russ J Gen Chem 92:2723–2733 ArticleCASGoogle Scholar
  73. Yousef TA (2020) Structural, optical, morphology characterization and DFT studies of nano sized Cu(II) complexes containing schiff base using green synthesis. J Mol Struct 1215:128180 ArticleCASGoogle Scholar
  74. Abdou A, Mawgoud MA (2022) Synthesis, structural elucidation, and density functional theory investigation of new mononuclear Fe (III), Ni (II), and Cu (II) mixed-ligand complexes: biological and catalase mimicking activity exploration. Appl Organomet Chem 36:6600 ArticleGoogle Scholar
  75. Elkanzi NAA, Hrichi H, Salah H, Albqmi MA, Abdou A (2023) Synthesis, physicochemical properties, biological, molecular docking and DFT investigation of Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of the 4-[(5-oxo-4,5-dihydro-1,3-thiazol-2-yl)hydrazono]methyl>phenyl 4-methylbenzenesulfonate Schiff-base ligand. Polyhedron 230:116219 ArticleCASGoogle Scholar
  76. Abdou A, Mostafa HM, Abdel-Mawgoud AM (2022) Seven metal-based bi-dentate NO azocoumarine complexes: synthesis, physicochemical properties, DFT calculations, drug-likeness, in vitro antimicrobial screening and molecular docking analysis. Inorg Chim Acta 539:121043 ArticleCASGoogle Scholar
  77. Abdou A, Mostafa HM, Abdel-Mawgoud MA, Sohag (2022) Molecular modeling, breast cancer, and hepatitis a, b, c molecular docking investigation of (2E)-1-phenyl-butane-1, 2, 3-trione 2-[(2-oxo-2H-chromene-6-yl) hydrazone. Sohag J Sci 7:167–173 Google Scholar
  78. Elkanzi NAA, Ali AM, Albqmi M, Abdou A (2022) New Benzimidazole-based Fe (III) and Cr (III) complexes: characterization, bioactivity screening, and theoretical implementations using DFT and molecular docking analysis. Appl Organomet Chem 36:6868 ArticleGoogle Scholar
  79. Shukla N, Gaur P, Raidas ML, Chaurasia B (2020) Tailored synthesis of unsymmetrical tetradentate ONNO schiff base complexes of Fe(IIl), Co(II) and Ni(II): Spectroscopic characterization, DFT optimization, oxygen-binding study, antibacterial and anticorrosion activity. J Mol Struct 1202:127362 ArticleCASGoogle Scholar

Acknowledgements

We are very thankful to Head, School of Chemical Sciences, DAVV, Indore. UGC-DAE Consortium of Scientific Research, D AVV, Indore for providing analytical facilities such as XRD and XPS. STIC Cochin for SEM and EDX facilities, IIT Madras for DRUV-Vis facility, Material analysis and research centre (MARC) Bangalore for BET surface area and IISER Bhopal for GC-MS facility.

Author information

Authors and Affiliations

  1. School of Chemical Sciences, Devi Ahilya Vishwavidyalaya, Takshashila Campus, Khandwa Road, Indore, MP, 452001, India Savita Khare & Neha Tiwari