Catalysis Letters

, Volume 149, Issue 6, pp 1611–1620 | Cite as

Mixed Oxides of Hydrotalcites as Catalysts for Nopol Epoxidation

  • Diana L. Hoyos-Castaño
  • Edwin AlarcónEmail author
  • Aída Luz Villa


Mixed oxides catalysts derived from Mg/Al hydrotalcite-type materials with molar ratios of 1, 2, 3 and 4 were synthesized, characterized and tested in nopol epoxidation. A combined oxidant of hydrogen peroxide and acetonitrile was used in the presence of acetone and water as solvents. Catalysts were characterized by X-ray diffraction (XRD), N2 adsorption, scanning electron microscopy (SEM), atomic absorption spectrophotometry (AAS), basicity by CO2-TPD, and infrared spectroscopy (FTIR). SEM analysis showed in all materials irregular non-homogeneous aggregates. Basicity of mixed oxides increased with Mg/Al ratio. The effect of temperature and basicity of the catalysts on the catalytic activity was analyzed. The best conversion and selectivity were obtained (60 °C, 2 h) over the most basic catalyst HT4C (mixed oxide Mg/Al = 4), with 99% conversion, epoxide selectivity of 38% and a selectivity of 36% to a campholenic aldehyde analogue compound, which duplicate the activity reported over a heterogeneous catalyst based on askanite–bentonite solid starting from nopol epoxide. In terms of TOF the most active catalyst, which also combines an acceptable conversion, was mixed oxide HT3C (mixed oxide Mg/Al = 3).

Graphical Abstract


Hydrotalcite-type-materials Hydrogen peroxide Nopol epoxide Campholenic aldehyde analogue 



The authors thank financial support from Universidad de Antioquia and Patrimonio Autónomo Fondo Nacional de Financiamiento para la Ciencia, la Tecnología y la Innovación, Francisco José de Caldas, Contrato RC-0572-2012 and the Project PRG2014-1091.


  1. 1.
    Hoegaerts D, Sels BF, De Vos DE et al (2000) Heterogeneous tungsten-based catalysts for the epoxidation of bulky olefins. Catal Today 60:209–218. CrossRefGoogle Scholar
  2. 2.
    Oyama ST (2008) Rates, kinetics, and mechanisms of epoxidation: homogeneous, heterogeneous, and biological routes. In: Oyama ST (ed) Mechanisms in homogeneous and heterogeneous epoxidation catalysis, 1st edn. Elsevier B.V, Amsterdam, pp 3–99CrossRefGoogle Scholar
  3. 3.
    De Vos DE, Sels BF, Jacobs PA (2002) Heterogeneous enzyme mimics based on zeolites and layered hydroxides. CATTECH 6:14–29. CrossRefGoogle Scholar
  4. 4.
    Lane BS, Burgess K (2003) Metal-catalyzed epoxidations of alkenes with hydrogen peroxide. Chem Rev 103:2457–2473. CrossRefGoogle Scholar
  5. 5.
    Yamaguchi K, Ebitani K, Kaneda K (1999) Hydrotalcite-catalyzed epoxidation of olefins using hydrogen peroxide and amide compounds. J Org Chem 2:2966–2968. CrossRefGoogle Scholar
  6. 6.
    Kirm I, Medina F, Rodrı́guez X et al (2004) Epoxidation of styrene with hydrogen peroxide using hydrotalcites as heterogeneous catalysts. Appl Catal A Gen 272:175–185. CrossRefGoogle Scholar
  7. 7.
    Swift KAD (2004) Catalytic transformations of the major terpene feedstocks. Top Catal 27:143–155. CrossRefGoogle Scholar
  8. 8.
    Monteiro J, Veloso C (2004) Catalytic conversion of terpenes into fine chemicals. Top Catal 27:169–180. CrossRefGoogle Scholar
  9. 9.
    Salakhutdinov N, Volcho K, Yarovaya O (2017) Monoterpenes as a renewable source of biologically active compounds. Pure Appl Chem 89:1105–1117. CrossRefGoogle Scholar
  10. 10.
    Chapuis C, Brauchli R (1992) Preparation of Campholenal Analogues: chirons for the lipophilic moiety of sandalwood-like odorant alcohols. Helv Chim Acta 75:1527–1546. CrossRefGoogle Scholar
  11. 11.
    Bruno SM, Pillinger M, Kühn FE et al (2013) Isomerization of α-pinene oxide in the presence of methyltrioxorhenium(VII). Catal Commun 35:40–44. CrossRefGoogle Scholar
  12. 12.
    Selvaraj M, Kawi S (2006) Highly selective synthesis of nopol over mesoporous and microporous solid acid catalysts. J Mol Catal A Chem 246:218–222. CrossRefGoogle Scholar
  13. 13.
    Lei J, Xia QH, Lu XH et al (2015) Selectively catalytic epoxidation of α-pinene with dry air over the composite catalysts of Co-MOR(L) with Schiff-base ligands. J Mol Catal A Chem 400:71–80. CrossRefGoogle Scholar
  14. 14.
    Hajian R, Tangestaninejad S, Moghadam M et al (2012) [PZnMo2W9O39]5− immobilized on ionic liquid-modified silica as a heterogeneous catalyst for epoxidation of olefins with hydrogen peroxide. Comptes Rendus Chim 15:975–979. CrossRefGoogle Scholar
  15. 15.
    Yu N, Ding Y, Lo A-Y et al (2011) Gold nanoparticles supported on periodic mesoporous organosilicas for epoxidation of olefins: effects of pore architecture and surface modification method of the supports. Microporous Mesoporous Mater 143:426–434. CrossRefGoogle Scholar
  16. 16.
    Qi B, Lu XH, Fang SY et al (2011) Aerobic epoxidation of olefins over the composite catalysts of Co-ZSM-5(L) with bi-/tridentate Schiff-base ligands. J Mol Catal A Chem 334:44–51. CrossRefGoogle Scholar
  17. 17.
    Hatefi M, Moghadam M, Mirkhani V, Sheikhshoaei I (2010) Silica supported Ru(salophen)Cl: an efficient and robust heterogeneous catalyst for epoxidation of alkenes with sodium periodate. Polyhedron 29:2953–2958. CrossRefGoogle Scholar
  18. 18.
    Gupta KC, Kumar Sutar A, Lin C-C (2009) Polymer-supported Schiff base complexes in oxidation reactions. Coord Chem Rev 253:1926–1946. CrossRefGoogle Scholar
  19. 19.
    Mora CC (1987) Derivative of (-)-6,6-dimethylbicyclo [3.1.1]hept-2-ene-2-ethanol having mucosecretolytic activity, a process for its preparation and pharmaceutical compositions containing the same. US Patent 4644087Google Scholar
  20. 20.
    Kover A, Hoffmann HMR (1988) Synthesis and π-facially selective cycloadditions of pinofurans. Tetrahedron 44:6831–6840. CrossRefGoogle Scholar
  21. 21.
    Satoh T, Kinugawa Y, Tamaki M et al (2008) Synthesis, structure, and characteristics of hyperbranched polyterpene alcohols. Macromolecules 41:5265–5271. CrossRefGoogle Scholar
  22. 22.
    Stapleton AJ, Sloan ME, Napper NJ, Burns RC (2009) Transition metal-substituted Dawson anions as chemo- and regio-selective oxygen transfer catalysts for H2O2 in the epoxidation of allylic alcohols. Dalton Trans. Google Scholar
  23. 23.
    Chen Y, Reymond J (1995) Epoxidation of olefins with formamide-hydrogen peroxide. Tetrahedron Lett 36:4015–4018. CrossRefGoogle Scholar
  24. 24.
    Villa AL, De Vos DE, Verpoort F et al (2001) A study of V-pillared layered double hydroxides as catalysts for the epoxidation of terpenic unsaturated alcohols. J Catal 198:223–231. CrossRefGoogle Scholar
  25. 25.
    Grison C, Escande V (2015) Use of certain manganese-accumulating plants for carrying out organic chemistry reactions. US Patent 2015/0174566 A1Google Scholar
  26. 26.
    Kuśtrowski P, Sułkowska D, Chmielarz L et al (2005) Influence of thermal treatment conditions on the activity of hydrotalcite-derived Mg-Al oxides in the aldol condensation of acetone. Microporous Mesoporous Mater 78:11–22. CrossRefGoogle Scholar
  27. 27.
    Di Cosimo JI, Dı́ez VK, Xu M et al (1998) Structure and surface and catalytic properties of Mg-Al Basic oxides. J Catal 178:499–510. CrossRefGoogle Scholar
  28. 28.
    Dumitru O, Tichit D, Marcu I (2012) Acido-basic and catalytic properties of transition-metal containing Mg–Al hydrotalcites and their corresponding mixed oxides. Appl Clay Sci 61:52–58. CrossRefGoogle Scholar
  29. 29.
    Comelli NA, Ruiz ML, Merino NA et al (2013) Preparation and characterisation of calcined Mg/Al hydrotalcites impregnated with alkaline nitrate and their activities in the combustion of particulate matter. Appl Clay Sci 80–81:426–432. CrossRefGoogle Scholar
  30. 30.
    Wang B, Xiong X, Ren H, Huang Z (2017) Preparation of MgO nanocrystals and catalytic mechanism on phenol ozonation. RSC Adv 7:43464–43473. CrossRefGoogle Scholar
  31. 31.
    Wang L, Ma Y, Wang Y et al (2011) Efficient synthesis of glycerol carbonate from glycerol and urea with lanthanum oxide as a solid base catalyst. Catal Commun 12:1459–1462. Google Scholar
  32. 32.
    Kumar P, With P, Srivastava VC et al (2017) Efficient ceria-zirconium oxide catalyst for carbon dioxide conversions: characterization, catalytic activity and thermodynamic study. J Alloys Compd 696:718–726. CrossRefGoogle Scholar
  33. 33.
    Liu P, Derchi M, Hensen EJM (2014) Promotional effect of transition metal doping on the basicity and activity of calcined hydrotalcite catalysts for glycerol carbonate synthesis. Appl Catal B Environ 144:135–143. CrossRefGoogle Scholar
  34. 34.
    Díez VK, Apesteguía CR, Di Cosimo JI (2000) Acid-base properties and active site requirements for elimination reactions on alkali-promoted MgO catalysts. Catal Today 63:53–62. CrossRefGoogle Scholar
  35. 35.
    Climent MJ, Corma A, Iborra S et al (2004) Increasing the basicity and catalytic activity of hydrotalcites by different synthesis procedures. J Catal 225:316–326. CrossRefGoogle Scholar
  36. 36.
    Dębek R, Motak M, Galvez ME et al (2018) Promotion effect of zirconia on Mg(Ni, Al)O mixed oxides derived from hydrotalcites in CO2 methane reforming. Appl Catal B Environ 223:36–46. CrossRefGoogle Scholar
  37. 37.
    Di Serio M, Ledda M, Cozzolino M et al (2006) Transesterification of soybean oil to biodiesel by using heterogeneous basic catalysts. Ind Eng Chem Res 45:3009–3014. CrossRefGoogle Scholar
  38. 38.
    Navarro RM, Guil-Lopez R, Fierro JLG et al (2018) Catalytic fast pyrolysis of biomass over Mg-Al mixed oxides derived from hydrotalcite-like precursors: influence of Mg/Al ratio. J Anal Appl Pyrolysis 134:362–370. CrossRefGoogle Scholar
  39. 39.
    Il’ina IV, Volcho KP, Korchagina DV et al (2004) Transformations of epoxide derived from nopol over askanite-bentonite clay. Russ J Org Chem 40:1432–1436. CrossRefGoogle Scholar
  40. 40.
    Jones CW, Clark JH (1999) Application of hydrogen peroxide for the synthesis of fine chemicals. In: Jones CW (ed) Applications of hydrogen peroxide and derivatives. Royal Society of Chemistry, London, pp 79–178CrossRefGoogle Scholar
  41. 41.
    Payne GB, Deming PH, Williams PH (1961) Reactions of hydrogen peroxide. VII. Alkali-catalyzed epoxidation and oxidation using a nitrile as co-reactant. J Org Chem 26:659–663. CrossRefGoogle Scholar
  42. 42.
    Aramendía MA, Borau V, Jiménez C et al (2001) Epoxidation of limonene over hydrotalcite-like compounds with hydrogen peroxide in the presence of nitriles. Appl Catal A Gen 216:257–265. CrossRefGoogle Scholar
  43. 43.
    Chen J, Tian S, Lu J, Xiong Y (2015) Catalytic performance of MgO with different exposed crystal facets towards the ozonation of 4-chlorophenol. Appl Catal A Gen 506:118–125. CrossRefGoogle Scholar
  44. 44.
    Da Silva Rocha KA, Kozhevnikov IV, Gusevskaya EV (2005) Isomerisation of a-pinene oxide over silica supported heteropoly acid H3PW12O40. Appl Catal A Gen 294:106–110. CrossRefGoogle Scholar
  45. 45.
    Flores-Moreno JL, Baraket L, Figueras F (2001) Isomerisation of α-pinene oxide on sulfated oxides. Catal Lett 77:113–117. CrossRefGoogle Scholar
  46. 46.
    Stekrova M, Kumar N, Aho A et al (2014) Isomerization of α-pinene oxide using Fe-supported catalysts: selective synthesis of campholenic aldehyde. Appl Catal A Gen 470:162–176. CrossRefGoogle Scholar
  47. 47.
    Padmasri AH, Venugopal A, Kumari VD et al (2002) Calcined Mg–Al, Mg–Cr and Zn–Al hydrotalcite catalysts for tert -butylation of phenol with iso-butanol—a comparative study. J Mol Catal A Chem 188:255–265. CrossRefGoogle Scholar
  48. 48.
    Costa VV, da Silva Rocha KA, de Sousa LF et al (2011) Isomerization of α-pinene oxide over cerium and tin catalysts: selective synthesis of trans-carveol and trans-sobrerol. J Mol Catal A Chem 345:69–74. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Environmental Catalysis Research Group, Chemical Engineering DepartmentUniversidad de AntioquiaMedellínColombia

Personalised recommendations