View More View Less
  • 1 Catalysis and Nanomaterials Research Laboratory, Department of Chemistry, Loyola College, Chennai 600 034, India
  • | 2 Materials Division, School of Advanced Sciences, VIT-University, Chennai Campus, Chennai, India
Restricted access

Abstract

Strontium added CoAl2O4 nanocatalysts with spinel structure were prepared by a modified sol–gel method using ethylene diamine followed by sintering at 900 °C. The samples were labeled as CoSA1-900, CoSA2-900, CoSA3-900, CoSA4-900, CoSA5-900, CoSA6-900, where the molar ratios of Co:Sr were 1.0:0.0, 0.9:0.1, 0.8:0.2, 0.7:0.3, 0.6:0.4 and 0.5:0.5 and the aluminum molar ratio was kept constant, 900 referring to the sintering temperature. The effect of Sr addition on the structural and morphological properties of cobalt aluminate nanocatalysts was investigated by X-ray diffraction, Fourier transform infrared spectra, high resolution scanning electron microscopy, energy dispersive X-ray analysis, nitrogen adsorption/desorption isotherms, temperature dependent conductance measurements and thermoelectric power measurements. The addition of Sr improves the performance of the nano cobalt aluminate catalyst towards the selective oxidation of alcohols and decreases the grain size. The effect of solvent, oxidant and reaction time on the Sr(II)-added cobalt aluminate nanocatalysts for the oxidation of benzyl alcohol was studied. Higher activity was obtained for the conversion of benzyl alcohol to benzaldehyde for 0.3 molar percentage Sr(II) added cobalt aluminate catalyst (CoSA4-900) which was used for the selective oxidation of other alcohols. The stability and reusability of the catalyst were also investigated.

  • 1. Timofeev VS , Serafimov LA (2003) Principles of technology of basic organic and petrochemical synthesis, Vysshaya Shkola, Moscow.

  • 2. Zayat, M, Levy, D 2000 Blue CoAl2O4 particles prepared by the sol–gel and citrate–gel methods. Chem Mater 12:27632769 .

  • 3. Suciu, C, Mindru, I, Marinescu, G, Patron, L, Carp, O, Teodorescu, VS 2008 Nanospinel mixed oxides obtained by self-propagating combustion. Blue cobalt aluminate. J Optoelectron Adv Mater 10:27032707.

    • Search Google Scholar
    • Export Citation
  • 4. Ji, L, Tang, S, Zeng, HC, Lin, J, Tan, KL 2001 CO2 reforming of methane to synthesis gas over sol–gel-made Co/γ-Al2O3 catalysts from organometallic precursors. Appl Catal A 207:247255 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Bolt, PH, Habraken, FHPM, Geus, JW 1998 Formation of nickel, cobalt, copper, and iron aluminates from α- and γ-alumina-supported oxides: a comparative study. J Solid State Chem 135:5969 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6. Schmidt, W, Weidenthaler, C 2001 A novel synthesis route for high surface area spinels using ion exchanged zeolites as precursors. Microporous Mesoporous Mater 48:8994 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. Vijaya, JJ, Kennedy, LJ, Sekaran, G, Meenakshisundaram, A, Kumar, RT, Amalthi, P Nagaraja 2008 Alcohol sensing properties of sol–gel prepared Sr(II)-added cobalt aluminate spinel composites. Sens Actuators B 129:741749 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. Rojanapipatkul, S, Jongsomjit, B 2008 Synthesis of cobalt on cobalt-aluminate via solvothermal method and its catalytic properties for carbon monoxide hydrogenation. Catal Commun 10:232236 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. Chen, ZZ, Shi, EW, Li, WJ, Zheng, YQ, Zhuang, JY, Xiao, B, Tang, LA 2004 Preparation of nanosized cobalt aluminate powders by a hydrothermal method. Mater Sci Eng 107:217223 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 10. Kroschwitz, JI 1992 Kirk-othmer encyclopedia of chemical technology, vol 4 4 Wiley-Intersciences New York.

  • 11. Sheldon, RA, Arends, IWCE GJ Ten Brink Dijksman, A 2002 Green, catalytic oxidation of alcohols. Acc Chem Res 35:774781 .

  • 12. Muzart, J 2003 Palladium-catalysed oxidation of primary and secondary alcohols. Tetrahedron 59:57895816 .

  • 13. Peterson, KP, Larock, RC 1998 Palladium-catalyzed oxidation of primary and secondary allylic and benzylic alcohols. J Org Chem 63:31853189 .

  • 14. Dijksman, A, Mario-González, A, Payeras, AM, Arends, IWCE, Sheldon, RA 2001 Palladium-catalyzed oxidation of primary and secondary allylic and benzylic alcohols. J Am Chem Soc 123:68266833 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 15. Stahl, SS 2003 Angew Chem Int Ed 43:34003420 .

  • 16. Mallat, T, Baiker, A 1994 Oxidation of alcohols with molecular oxygen on platinum metal catalysts in aqueous solutions. Catal Today 19:247283 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17. Mallat, T, Bodnar, Z, Baiker, A, Greis, O, Strubig, H, Reller, A 1993 Preparation of promoted platinum catalysts of designed geometry and the role of promoters in the liquid-phase oxidation of 1-methoxy-2-propanol. J Catal 142:237253 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Mallat, T, Bodnar, Z, Hug, P, Baiker, A 1995 Selective oxidation of cinnamyl alcohol to cinnamaldehyde with air over Bi-Pt/alumina catalysts. J Catal 153:131143 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19. Mori, K, Hara, T, Mizugaki, T, Ebitani, K, Kaneda, K 2004 Hydroxyapatite-supported palladium nanoclusters: a highly active heterogeneous catalyst for selective oxidation of alcohols by use of molecular oxygen. J Am Chem Soc 126:1065710666 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 20. Sheldon, RA, Arends, IWCE, Dijksman, A 2000 New developments in catalytic alcohol oxidations for fine chemicals synthesis. Catal Today 57:157166 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 21. Zhan, BZ, Thomson, A 2004 Recent developments in the aerobic oxidation of alcohols. Tetrahedron 60:29172935 .

  • 22. Petrov, AN, Kononchuk, OF, Andreev, AV, Cherepanov, VA, Kofstad, P 1995 Crystal structure, electrical and magnetic properties of La1−xSrxCoO3−y. Solid States Ion 80:189199 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 23. Remmel, J, Geerk, J, Linker, G, Meyer, O, Smithey, R, Strehlau, B, Xiong, GC 1990 Superconductivity and structure of ion irradiated LaSrCuO thin films. Physica C 165:212220 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Brunauer, S, Emmett, PH, Teller, EJ 1938 Adsorption of gases in multimolecular layers. J Am Chem Soc 60:309319 .

  • 25. Adamson, AW 1960 Physical chemistry of surfaces Interscience Publishers New York.

  • 26. Viswanathan, B, Sivasankar, S, Ramasamy, AV 2002 Catalysis: principles and applications Narosa Publishing House New Delhi.

  • 27. Greg, SJ, Sing, KSW 1982 Adsorption surface area and porosity Academic Press London.

  • 28. Bouberki, R, Beji, Z, Elkabous, K, Herbst, F, Viau, G, Ammar, S, Fievet, F, Bardeleben, JHV, Mauger, A 2009 Annealing effects on Zn(Co)O: from para- to ferromagnetic behavior. Chem Mater 21:843855 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 29. Sundaram, R, Raj, ES, Nagaraja, KS 2004 Nonstoichiometric orthorhombic titanium oxide, TiO2−δ and its thermochromic properties. Mater Res Bull 39:17371744 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 30. Bhandari, CM, Rowe, DM 1995 RC handbook of thermoelectric CRC Press Boca Raton.

  • 31. Park, K, Jang, KU, Kwon, HC, Kim, JG, Cho, WS 2006 Influence of partial substitution of Cu for Co on the thermoelectric properties of NaCo2O4. J Alloys Compd 419:213219 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 32. Park, K, Seong, JK, Nahm, S 2008 Improvement of thermoelectric properties with the addition of Sb to ZnO. J Alloys Compd 455:331335 .

  • 33. Park, K, Ko, KY, Seo, WS 2006 Effect of partial substitution of Ca for Al on the microstructure and high-temperature thermoelectric properties of CuAlO2. Mater Sci Eng 129:15 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 34. Itoh, T, Terasaki, I 2000 Thermoelectric properties of Bi2.3−xPbxSr2.6Co2Oy single crystals. Jpn J Appl Phys 39:66586660 .

  • 35. Vijaya, JJ, Kennedy, LJ, Sekaran, G, Jeyaraj, B, Nagaraja, KS 2007 Effect of Sr addition on the humidity sensing properties of CoAl2O4 composites. Sens Actuators B 123:211217 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 36. Chroma, M, Pinkas, J, Pakutinskiene, I, Beganskiene, A, Kareiva, A 2005 Processing and characterization of sol–gel fabricated mixed metal aluminates. Ceram Int 31:11231130 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 37. Guo, J, Lou, H, Zhao, H, Wangg, X, Zheng, X 2004 Novel synthesis of high surface area MgAl2O4 spinel as catalyst support. Mater Lett 58:19201923 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 38. Naskar, MK, Chatterjee, M 2004 A novel process for the synthesis of cordierite (Mg2Al4Si5O18) powders from rice husk ash and other sources of silica and their comparative study. J Eur Ceram Soc 24:34993508 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 39. Ouahdi, N, Guillemet, S, Demai, JJ, Durand, B, Rakho, LE, Mousa, R, Samdi, A 2005 Investigation of the reactivity of AlCl3 and CoCl2 toward molten alkali-metal nitrates in order to synthesize CoAl2O4. Mater Lett 59:334340 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 40. Pillai, UR, Sahle-Demessie, E 2004 Selective oxidation of alcohols over vanadium phosphorus oxide catalyst using hydrogen peroxide. Appl Catal A 276:139144 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 41. Hou, Z, Theyssen, N, Brinkmann, A, Leitner, W 2005 Biphasic aerobic oxidation of alcohols catalyzed by poly(ethylene glycol)-stabilized palladium nanoparticles in supercritical carbon dioxide. Angew Chem Int Ed 44:13461349 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 42. Karimi, B, Abedi, S, Clark, JH, Budarin, V 2006 Highly efficient aerobic oxidation of alcohols using a recoverable catalyst: the role of mesoporous channels of SBA-15 in stabilizing palladium nanoparticles. Angew Chem Int Ed 45:47764779 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 43. Yamaguchi, K, Mori, K, Mizugaki, T, Ebitani, K, Kaneda, K 2000 Creation of a monomeric Ru species on the surface of hydroxyapatite as an efficient heterogeneous catalyst for aerobic alcohol oxidation. J Am Chem Soc 122:71447145 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 44. Xiao-Mei, Z, Jiang-Min, C, Middleton, K, Zhdankin, VV 2011 Recyclable silica-supported iodoarene–RuCl3 bifunctional catalysts for oxidation of alcohols and alkylarenes. Tetrahedron Lett 52:56525655 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 45. Shi, Y, Yang, H, Zhao, X, Cao, T, Chen, J, Zhu, W, Yu, Y, Hou, Z 2012 Au–Pd nanoparticles on layered double hydroxide: highly active catalyst for aerobic oxidation of alcohols in aqueous phase. Catal Commun 18:142146 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 46. Wang, L, Zhang, J, Meng, X, Zheng, D, Xiaoa, FS 2011 Superior catalytic properties in aerobic oxidation of alcohols over Au nanoparticles supported on layered double hydroxide. Catal Today 175:404410 .

    • Crossref
    • Search Google Scholar
    • Export Citation