Abstract
In this study, a new magnetic ZrFe2O4@SiO2-TCPP nanocatalyst with high efficiency was used for the oxidation of cyclohexane to cyclohexanone (Ke) and cyclohexanol (Al). The mesoporous ZrFe2O4 nanoparticles, with a nanocauliflower structure was synthesized via solvothermal method and it was coated with SiO2 sell by tetraethyl orthosilicate (TEOS) to fabricate the ZrFe2O4@SiO2 core-shell. Then, this composite was modified by 5, 10, 15, 20-meso-tetrakis(4-carboxyphenyl) porphyrin (TCPP). FT-IR, XRD, XPS, FE-SEM, EDX, TEM, VSM, BET and fluorescence analyses were used to characterize the prepared nanomaterials. Optimization of the reaction conditions, as one of the most applicable Response Surface Methodologies (RSM), was executed by Central Composite Design (CCD) based on the applied mathematical modeling, and the results were analyzed by GC-Mass Analytical Testing Lab Services. The maximum Ke/Al products were 33.6 and 18.9%, respectively. Simple separation by a magnetic field, stability and recoverability, are the advantages of this new catalyst.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Tong J, Cai X, Wang H, Xia C (2013) Efficient magnetic CoFe2O4 nanocrystal catalyst for aerobic oxidation of cyclohexane prepared by sol–gel auto-combustion method: effects of catalyst preparation parameters. J Sol-Gel Sci Technol 66:452–459
Davis DD, and Kemp DR, in “Kirk–Othmer (1991) Encyclopedia of Chemical Technology” (J. I. Kroschwitz and M. Howe-Grant, Eds.), 1: 466
Castellan A, Bart JCJ, Cavallaro S (1991) Industrial production and use of adipic acid. Catal Today 9:237–254
Dumas T, Bulani W (1974) Oxidation of petrochemicals: chemistry and technology. Applied Science, London, pp 53–64
Chavan SA, Srinivas D, Ratnasamy P (2002) Oxidation of cyclohexane, cyclohexanone, and cyclohexanol to adipic acid by a non HNO3 route over Co/Mn cluster complexes. J Catal 212:39–45
Schuchardt U, Carvalho WA, Spinacé EV (1993) Why is it interesting to study cyclohexane oxidation? Synlett 10:713–718
Schuchardt U, Cardoso D, Sercheli R, Pereira R, Da Cruz RS, Guerreiro MC, Mandelli D, Spinacé EV, Pires EL (2001). Appl Catal A Gen 211:1–17
Suresh AK, Sharma MM, Sridhar T (2000) Engineering aspects of industrial liquid-phase air oxidation of hydrocarbons. Ind Eng Chem Res 39:3958–3997
Lang X, Chen X, Zhao J (2014) Heterogeneous visible light photocatalysis for selective organic transformations. Chem Soc Rev 43:473–486
Sideri IK, Voutyritsa E, Kokotos CG (2018) Photoorganocatalysis, small organic molecules and light in the service of organic synthesis: the awakening of a sleeping giant. Org Biomol Chem 16:4596–4614
Sankaranarayanapillai S, Sf V, Werner RT (2010) Magnetically separable nanocatalysts: bridges between homogeneous and heterogeneous catalysis. Angew Chem Int Ed 49:3428–3459
Ribeiro AP, Matias IA, Alegria EC, Ferraria AM, Botelho do Rego AM, Pombeiro AJ, Martins LM (2018) New trendy magnetic C-scorpionate iron catalyst and its performance towards cyclohexane oxidation. Catalysts 8:69
Maleki A, Hajizadeh Z (2019) Magnetic aluminosilicate nanoclay: a natural and efficient nanocatalystfor the green synthesis of 4H-Pyran derivatives. Silicon 11:2789–2798
Nabiyouni G, Ghanbari D, Ghasemi J, Yousofnejad A (2015) Microwave-assisted synthesis of MgFe2O4-ZnO nanocomposite and its photo-catalyst investigation in methyl orange degradation. J Nanostruct 5:289–295
Rahimi R, Kerdari H, Rabbani M, Shafiee M (2011) Synthesis, characterization and adsorbing properties of hollow Zn-Fe2O4 nanospheres on removal of Congo red from aqueous solution. Desalination 280:412–418
Jiang W, Zhang X, Gong X, Yan F, Zhang Z (2010) Sonochemical synthesis and characterization of magnetic separable Fe3O4–TiO2 nanocomposites and their catalytic properties. Inter J Smart Nano Mater 1:278–287
Wu W, Xiao X, Zhang S, Ren F, Jiang C (2011) Facile method to synthesize magnetic iron oxides/TiO2 hybrid nanoparticles and their photodegradation application of methylene blue. Nanoscale Res Lett 6:533
Soltani RDC, Mashayekhi M, Khataee A, Ghanadzadeh MJ, Sillanpää M (2018) Hybrid sonocatalysis/electrolysis process for intensified decomposition of amoxicillin in aqueous solution in the presence of magnesium oxide nanocatalyst. J Ind Eng Chem 64:373–382
Gangwar A, Alla S, Srivastava M, Meena S, Prasadrao E, Mandal R, Yusuf S, Prasad N (2016) Structural and magnetic characterization of Zr-substituted magnetite (ZrxFe3− xO4, 0≤ x≤ 1). J Magn Magn Mater 401:559–566
Zhang L, Hp S, Zheng H, Lin T, Guo Z (2016) Synthesis and characterization of Fe3O4@SiO2 magnetic composite nanoparticles by a one-pot process. Int J Miner Metall Mater 23:1112–1118
Hajizadeh Z, Maleki A, Rahimi R, Eivazzadeh-Keihan R (2019) Halloysite nanotubes modified by Fe3O4 nanoparticles and applied as a natural and efficient nanocatalyst for the symmetrical Hantzsch reaction. Silicon:1–10. https://doi.org/10.1007/s12633-019-00224-3
Maleki A, Kari T, Aghaei M (2017) Fe3O4@SiO2@TiO2-OSO3H: an efficient hierarchical nanocatalyst for the organic quinazolines syntheses. J Porous Mater 24:1481–1496
Groves, JT, Shalyaev K, Lee J, Kadish KM, Smith KM, Guilard R (2000) The Porphyrin handbook, Eds. Academic Press 4: 17–40
Stephenson NA, Bell AT (2007) Effects of porphyrin composition on the activity and selectivity of the iron (III) porphyrin catalysts for the epoxidation of cyclooctene by hydrogen peroxide. J Mol Catal A Chem 272:108–117
Laybourn A, Dawson R, Clowes R, Hasell T, Cooper AI, Khimyak YZ, Adams DJ (2014) Network formation mechanisms in conjugated microporous polymers. Polym Chem 5:6325–6333
Monnereau C, Gomez J, Blart E, Odobel F (2005) Photoinduced electron transfer in platinum (II) terpyridinyl acetylide complexes connected to a porphyrin unit. Inorg Chem 44:4806–4817
Kira A, Umeyama T, Matano Y, Yoshida K, Isoda S, Park JK, Kim D, Imahori HJ (2009) Supramolecular donor−acceptor Heterojunctions by Vectorial stepwise assembly of Porphyrins and coordination-bonded fullerene arrays for photocurrent generation. Am Chem Soc 131:3198–3200
Liu CY, Bard A (1999) Optoelectronic properties and memories based on organic single-crystal thin films. J Acc Chem Res 32(3):235–245
Fungo F, Otero L, Borsarelli CD, Durantini EN, SilberJJ SLJ (2002) Optoelectronic properties and memories based on organic single-crystal thin films. Phys Chem B 106:4070–4078
Gervaldo M, Fungo F, Durantini EN, Silber JJ, Sereno L, Otero L (2005) Carboxyphenyl metalloporphyrins as photosensitizers of semiconductor film electrodes. A study of the effect of different central metals. J Phys Chem B 109:20953–20962
Drain CM, Varotto A, Radivojevic I (2009) Self-organized porphyrinic materials. Chem Rev 109:1630–1658
Liu Q, Yang Y, Li H, Zhu R, Shao Q, Yang S, Xu J (2015) NiO nanoparticles modified with 5,10,15,20-tetrakis (4-carboxyl pheyl) porphyrin promising peroxidase mimetics for H2O2 and glucose detection. Biosens Bioelectron 64:147–153
Kathiravan A, Renganathan R (2009) Effect of anchoring group on the photosensitization of colloidal TiO2 nanoparticles with porphyrins. J Colloid Interface Sci 331:401–407
Darvishi Cheshmeh Soltani R, Rezaee A, Khataee RA, Godini H (2014) Optimisation of the operational parameters during a biological nitrification process using response surface methodology. Can J Chem Eng 92:13–22
Shaykhi ZM, Zinatizadeh AAL (2014) Statistical modeling of photocatalytic degradation of synthetic amoxicillin wastewater (SAW) in an immobilized TiO2 photocatalytic reactor using response surface methodology (RSM). J Taiwan Inst Chem Eng 45:1717–1726
Hassani A, Soltani RDC, Karaca S, Khataee A (2015) Preparation of montmorillonite–alginate nanobiocomposite for adsorption of a textile dye in aqueous phase: isotherm, kinetic and experimental design approaches. J Ind Eng Chem 21:1197–1207
Roosta M, Ghaedi M, Daneshfar A, Sahraei R, Asghari A (2015) Optimization of combined ultrasonic assisted/tin sulfide nanoparticle loaded on activated carbon removal of erythrosine by response surface methodology. J Ind Eng Chem 21:459–469
Weissman SA, Anderson NG (2015) Design of Experiments (DoE) and process optimization. Org Process Res Dev 19:1605–1633
Adler AD, Longo FR, Finarelli JD, Goldmacher J, Assour J, Korsakoff L (1967) A simplified synthesis for meso-tetraphenylporphine. J Organomet Chem 32:476–476
Li D, Dong W, Sun S, Shi Z, Feng S (2008) Photocatalytic degradation of acid chrome blue K with porphyrin-sensitized TiO2 under visible light. J Phys Chem C 112:14878–14882
Wang W, Ma R, Wu Q, Wang C, Wang Z (2013) Magnetic microsphere-confined graphene for the extraction of polycyclic aromatic hydrocarbons from environmental water samples coupled with high performance liquid chromatography–fluorescence analysis. J Chromatogr A 1293:20–27
Rahimi R, Zargari S, Yousefi A, Berijani MY, Ghaffarinejad A, Morsali A (2015) Visible light photocatalytic disinfection of E. coli with TiO2–graphene nanocomposite sensitized with tetrakis (4-carboxyphenyl) porphyrin. Appl Surf Sci 355:1098–1106
Yua J, Zhua S, Panga L, Chena P, Zhu GT (2018) Porphyrin-based magnetic nanocomposites for efficient extraction of polycyclic aromatic hydrocarbons from water samples. J Chromatogr A 1540:1–10
Bassiouk M, Basiuk VA, Basiuk EV, Álvarez-Zauco E, Martínez-Herrera M, Rojas-Aguilar A, Puente-Lee I (2013) Noncovalent functionalization of single-walled carbon nanotubes with porphyrins. Appl Surf Sci 275:168–177
Bosi F, Hålenius U, Skogby H (2009) Crystal chemistry of the magnetite-ulvospinel series. Am Min 94:181–189
Sorescu M, Xu T, Wise A, Díaz-Michelena M, McHenry ME (2012) Studies on structural, magnetic and thermal properties of xFe2TiO4-(1− x) Fe3O4 (0≤ x≤ 1) pseudo-binary system. J Magn Magn Mater 324:1453–1462
Yan D, Xin J, Zhao Q, Gao K, Lu X, Wang G, Zhang S (2018) Fe-Zr-O catalyzed base-free aerobic oxidation of 5-HMF to 2,5-FDCA as a bio-based polyester monomer. Catal Sci Technol 8:164–175
Subramanian A, Annamalai A, Lee HH, Choi SH, Ryu J, Park JH, Jang JS (2016) Trade-off between Zr passivation and Sn doping on hematite nanorod photoanodes for efficient solar water oxidation: effects of a ZrO2 underlayer and FTO deformation. ACS Appl Mater Interfaces 8:19428–19437
Luo JM, Luo XB, Hu CZ, Crittenden JC, Qu JC (2016) Zirconia (ZrO2) embedded in carbon nanowires via electrospinning for efficient arsenic removal from water combined with DFT studies. ACS Appl Mater Interfaces 8:18912–18921
Kouotou PM, Vieker H, Tian ZY, Ngamou PHT, El Kasmi A, Beyer A, Golzhauser A, KohseHoinghaus K (2014) Structure activity relation of spinel type Co–Fe oxides for low-temperature CO oxidation. Catal Sci Technol 4:3359–3367
Nie JF, Liu HC (2014) Efficient aerobic oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran on manganese oxide catalysts. J Catal 316:57–66
Deng H, Li X, Peng Q, Wang X, Chen J, Li Y (2005) Monodisperse magnetic single-crystal ferrite microspheres. Angew Chem 117:2842–2845
Yu BY, Kwak SY (2011) Self-assembled mesoporous Co and Ni-ferrite spherical clusters consisting of spinel nanocrystals prepared using a template-free approach. Dalton Trans 40:9989–9998
Wang Y, Zhao H, Li M, Fan J, Zhao G (2014) Magnetic ordered mesoporous copper ferrite as a heterogeneous Fenton catalyst for the degradation of imidacloprid. Appl Catal B-Environ 147:534–545
Abbas M, Torati S, Lee C, Rinaldi C, Kim C (2014) Fe3O4/SiO2 core/shell nanocubes: novel coating approach with tunable silica thickness and enhancement in stability and biocompatibility. J Nanomed Nanotechnol 5:1–8
Issa B, Obaidat I, Albiss B, Haik Y (2013) Magnetic nanoparticles: surface effects and properties related to biomedicine applications. Int J Mol Sci 14:21266–21305
Sun L, Li Y, Sun M, Wang H, Xu S, Zhang C, Yang Q (2011) Porphyrin-functionalized Fe3O4@SiO2 core/shell magnetic colorimetric material for detection, adsorption and removal of Hg2+ in aqueous solution. New J Chem 35:2697–2270
Li L, Yang Q, Chen S, Hou X, Liu B, Lua J, Jiang H-L (2017) Boosting selective oxidation of cyclohexane over a metal–organic framework by hydrophobicity engineering of pore walls. Chem Commun 53(72):10026–10029
Bezaatpour A, Khatami S, Nejati K (2017) Cis-dioxo-Mo (VI) salophen complex supported on Fe3O4@SiO2 nanoparticles as an efficient magnetically separable and reusable nanocatalyst for selective epoxidation of olefins. J Iran Chem Soc 14(10):2105–2115
Pires E-L, Wallau M, Schuchardt U (1997) Selective oxidation of cyclohexane over rare earth exchanged zeolite Y. Stud Surf Sci Catal 110:1025–1027
Xie Y, Zhang F, Liu P, Hao F, Luo H (2013) Synthesis and catalytic properties of trans-A2B2-type metalloporphyrins in cyclohexane oxidation. Can J Chem 92(1):49–53
Zhang Q, Chen C, Wang M, Cai J, Xu J, Xia C (2011) Facile preparation of highly-dispersed cobalt-silicon mixed oxide nanosphere and its catalytic application in cyclohexane selective oxidation. Nanoscale Res Lett 6(1):586
Zhao H, Zhou J, Luo H, Zen C (2006) Synthesis, characterization of Ag/MCM-41 and the catalytic performance for liquid-phase oxidation of cyclohexane. Catal Lett 108:1–2
Maleki A, Aghaei M, Hafizi-Atabak H-R, Ferdowsi M (2017) Ultrasonic treatment of CoFe2O4@B2O3-SiO2 as a new hybrid magnetic composite nanostructure and catalytic application in the synthesis of dihydroquinazolinones. Ultrason Sonochem 37:260–266
Acknowledgements
The authors gratefully acknowledge the partial support by Iran University of Science and Technology.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Disclosure Statement
No potential conflict of interest was reported by the authors.
Additional information
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Khosravi, H.B., Rahimi, R., Rabbani, M. et al. Design, Facile Synthesis and Characterization of Porphyrin-Zirconium-Ferrite@SiO2 Core-Shell and Catalytic Application in Cyclohexane Oxidation. Silicon 13, 451–465 (2021). https://doi.org/10.1007/s12633-020-00454-w
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12633-020-00454-w