Journal of Chemical Sciences

, Volume 129, Issue 5, pp 601–608 | Cite as

Studies on dehydrogenation of cyclohexanol to cyclohexanone over mesoporous \(\hbox {SiO}_{2}\) supported copper catalysts

  • B Sridevi
  • P Nagaiah
  • A H Padmasri
  • B David Raju
  • K S Rama Rao
Regular Article



SBA-15, KIT-6, \(\hbox {SiO}_{2}\) supported catalysts with 10% Cu loading have been prepared by impregnation techniques. The prepared catalysts have been characterized by BET technique, X-ray diffraction, Temperature programmed reduction (TPR), XPS and \(\hbox {N}_{2}\hbox {O}\) pulse chemisorption techniques. Dehydrogenation of cyclohexanol has been performed over these catalysts in vapour phase at 523 K. SBA-15 and KIT-6 supported copper catalysts showed higher activity than \(\hbox {SiO}_{2}\) supported Cu catalyst in dehydrogenation of cyclohexanol, which can be attributed to better Cu dispersion, small copper particle size and more number of Cu active species presented on the surface of mesoporous supported catalysts.

Graphical Abstract

SYNOPSIS Higher Cu-dispersion in 10%Cu/SBA-15 and 10%Cu/KIT-6 due to mesoporous nature of support is helpful in exhibiting higher cyclohexanol dehydrogenation ability than in \(10\%\hbox {Cu/SiO}_{2}\)


Cyclohexanol Cu/SBA-15 Cu/KIT-6 \(\hbox {Cu/SiO}_{2}\) dehydrogenation 



BS and PN thank CSIR and UGC, New Delhi, India for the award of Junior Research Fellowship.


  1. 1.
    Koc S N, Dayioglu K and Ozdemir H 2016 Oxidative dehydrogenation of propane with \(\text{ K-MoO }_{3}\text{/MgAl2O }_{4}\) catalysts J. Chem. Sci. 128 67CrossRefGoogle Scholar
  2. 2.
    Pochamoni R, Narani A, Varkolu M, Muralidhar G, Sai Prasad P S, David Raju B and Rama Rao K S 2015 Studies on dehydrogenation with \(\text{ CO }_{2}\) as soft oxidant over \(\text{ Co }_{3}\text{ O }_{4}\text{/COK-12 }\) catalysts J. Chem. Sci. 127 701CrossRefGoogle Scholar
  3. 3.
    Jing F, Zhang Y, Luo S, Chu W, Zhang H and Shi X 2010 Catalytic synthesis of 2-methylpyrazine over Cr-promoted copper based catalyst via a cyclo-dehydrogenation reaction route J. Chem. Sci. 122 621CrossRefGoogle Scholar
  4. 4.
    Chen W S and Lee M D 1992 Nonoxidative dehydrogenation of cyclohexanol over copper-iron binary oxides Appl. Catal. 83 201Google Scholar
  5. 5.
    Jeon G S and Chung J S 1994 Preparation and characterization of silica-supported copper catalysts for the dehydrogenation of cyclohexanol to cyclohexanone Appl. Catal. 29 115Google Scholar
  6. 6.
    Krishna G, Rama Rao K S and Kanta Rao P 1999 Effect of support modification by carbon coverage in the dehydrogenation activity of \(\text{ Cu/Al }_{2}\text{ O }_{3}\) Catalyst Catal. Lett. 59 157Google Scholar
  7. 7.
    Mendes F M T and Schmal M 1997 The cyclohexanol dehydrogenation on \(\text{ Rh-Cu } \text{ Al }_{2}\text{ O }_{3}\) catalysts PART 1: Characterization of catalysts Appl. Catal. A 151 393CrossRefGoogle Scholar
  8. 8.
    Nikiforova N N and Gavrenko K A 1974 \(4^{{\rm th}}\) EFCATS School on Catalysis catalyst design – from molecular to industrial level Petrochemisry (in Russian) 14 11Google Scholar
  9. 9.
    Sing K S W, Everett D H, Haul R A W, Moscou L, Pierotti R A, Rouquerol J and Siemieniewska T 1985 Hybrid inorganic–organic mesoporous silicates—nanoscopic reactors coming of age Pure Appl. Chem. 57 603Google Scholar
  10. 10.
    Chang H F and Saleque M A 1993 Surface Structure and Catalytic Properties of \(\text{ Cu/SiO }_{2}\) Catalysts Prepared by Different Methods Appl. Catal. A 103 233CrossRefGoogle Scholar
  11. 11.
    Burri D R, Jun K W, Kim Y H, Kim J M, Park S E and Yoo J S 2002 Oxidative Cleavage of C=C Bond of Styrene and Its Derivatives with \(\text{ H }_{2}\text{ O }_{2}\) using Vanadyl (IV) Acetylacetonate Anchored SBA-15 Catalyst Chem. Lett. 31 212Google Scholar
  12. 12.
    Huizhen L, Jiang T, Han B, Liang S and Zhou Y 2009 Selective phenol hydrogenation to cyclohexanone over a Dual Supported Pd-Lewis Acid Catalyst Science 326 1250CrossRefGoogle Scholar
  13. 13.
    Chag H F, Salequ M A, Hsu W S and Lin W H 1996 Characterization and dehydrogenation activity of \(\text{ CuAl }_{2}\text{ O }_{3}\) catalysts prepared by electroless plating technique J. Mol. Catal. 109 249CrossRefGoogle Scholar
  14. 14.
    Nagaraja B M, Siva Kumar V, Shashikala V, Padmasri A H, Sreevardhan Reddy B, Reddy S, David Raju B and Rama Rao K S 2004 Effect of method of preparation of copper–magnesium oxide catalyst on the dehydrogenation of cyclohexanol J. Mol. Catal. A 223 339CrossRefGoogle Scholar
  15. 15.
    Reddy S S, Burri D R, Kumar S V, Padmasri A H, Narayanan S and Rama Rao K S 2007 Sulfonic acid functionalized mesoporous SBA-15 for selective synthesis of 4-phenyl-1, 3-dioxane Catal. Commun. 8 261Google Scholar
  16. 16.
    Zhao D, Feng J, Huo Q, Melossh N, Fredrickson G H, Chmelka B F and Stucky G D 1998 Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores Science 279 548CrossRefGoogle Scholar
  17. 17.
    Zhao D, Huo Q, Feng J, Chmelka B F and Stucky G D 1998 Mesocellular Siliceous Foams with Uniformly Sized Cells and Windows J. Am. Chem. Soc. 120 6024CrossRefGoogle Scholar
  18. 18.
    Wang H, Li L, Bai X F, Shang J Y, Yang K F and Xu L W 2013 Efficient Palladium-Catalyzed C-O Hydrogenolysis of Benzylic Alcohols and Aromatic Ketones with Polymethylhydrosiloxane Adv. Synth. Catal. 355 341Google Scholar
  19. 19.
    Takahashi T, Yoshimura M, Suzuka H, Maegawa T, Sawama Y and Monguci Sajiki H 2012 Chemoselective hydrogenation using molecular sieves-supported Pd catalysts: Pd/MS3A and Pd/MS5A Tetrahedron 68 8293CrossRefGoogle Scholar
  20. 20.
    Rodiansono, Khairi S, Hara T, Ichikuni N and Shimazu S 2012 Highly efficient and selective hydrogenation of unsaturated carbonyl compounds using Ni–Sn alloy catalysts Catal. Sci. Technol. 2 2139Google Scholar
  21. 21.
    Mirkhani V, Moghadam M, Tangestaninejad S, Mohammadpoor-Baltork I and Rasouli N 2008 A comparative study of oxidation of alkanes and alkenes by hydrogen peroxide catalyzed by Cu(salen) complex covalently bound to a Keggin type polyoxometalate and its neat counterpart Catal. Commun. 9 2411Google Scholar
  22. 22.
    Anand N, Reddy H P K, Swapna V, Rama Rao K S and Burri D R 2011 Fe(III) complex anchored SBA-15 is a new heterogeneous catalyst for the cleavage of aliphatic C-C bond of styrene and its derivatives Micropor. Mesopor. Mater. 143 132CrossRefGoogle Scholar
  23. 23.
    Qiu T, Xua X and Qian X 2009 Fluorous biphase oxidation of ethyl benzene and benzyl alcohol catalyzed by perfluoroalkyl phthalocyanine complexes J. Chem. Technol. Biotechnol. 84 1051CrossRefGoogle Scholar
  24. 24.
    Tanase S, Reedijk J, Hage R and Rothenberg G 2010 Hydrocarbon oxidation with \(\text{ H }_{2}\text{ O }_{2}\), catalyzed by iron complexes with a polydentate pyridine-based ligand Top. Catal. 53 1039Google Scholar
  25. 25.
    Mishra G S, Anil Kumar and Tavaresa P B 2012 Single site anchored novel Cu (II) catalysts for selective liquid–gas phase \(\text{ O }_{2}\) oxidation of n-alkanes J. Mol. Catal. A: Chem. 357 125CrossRefGoogle Scholar
  26. 26.
    Rioux R M, Song H, Hoefelmeyer J D, Yang P and Somorjai G A 2005 High surface area catalyst design: synthesis, characterization, and reaction studies of platinum nanoparticles in mesoporous SBA-15 silica J. Phys. Chem. 109 2192CrossRefGoogle Scholar
  27. 27.
    Sun J, Ma D, Zhang H, Liu X, Han X, Bao X, Weinberg G, Pfander N and Su D 2006 Toward monodispersed silver nanoparticles with unusual thermal stability J. Am. Chem Soc. 128 15756CrossRefGoogle Scholar
  28. 28.
    Lopes I, Hassan N E, Guerba H, Wallez G and Davidson A 2006 Size-induced structural modifications affecting \(\text{ Co }_{3}\text{ O }_{4}\) nanoparticles patterned in SBA-15 silicas Chem. Mater. 18 5826Google Scholar
  29. 29.
    Segura Y, Cool P, Kustrowski P, Chmielarz L, Dziembaj R and Vansant E F 2005 Characterization of vanadium and titanium oxide supported SBA-15 J. Phys. Chem. B 109 12071CrossRefGoogle Scholar
  30. 30.
    Yang C M, Liu P H, Ho Y F, Chiu C Y and Chao K J 2003 Highly dispersed metal nanoparticles in functionalized SBA-15 Chem. Mater. 15 275Google Scholar
  31. 31.
    Feng X, Yan M, Zhang T, Liu Y and Bao M 2010 Preparation and application of SBA-15-supported palladium catalyst for Suzuki reaction in supercritical carbon dioxide Green Chem.12 1758CrossRefGoogle Scholar
  32. 32.
    Zhao M, Church T L and Harris A T 2011 SBA-15 supported Ni-Co bimetallic catalysts for enhanced hydrogen production during cellulose decomposition Appl. Catal. B 101 522CrossRefGoogle Scholar
  33. 33.
    Wang H and Liu C J 2011 Preparation and characterization of SBA-15 supported Pd catalyst for CO oxidation Appl. Catal. B 106 672CrossRefGoogle Scholar
  34. 34.
    Palcheva R, Spojakina A, Dimitrov L and Jiratovac K 2009 12-Tungstophosphoric heteropolyacid supported on modified SBA-15 as catalyst in HDS of thiophene Micropor. Mesopor. Mater. 122 128CrossRefGoogle Scholar
  35. 35.
    Zukal A, Pastva J and Cejka J 2013 MgO-Modified Mesoporus Silicas impregnated by potassium Micropor. Mesopor. Mater. 167 44CrossRefGoogle Scholar
  36. 36.
    Burri D R, Choi K M, Lee J H, Han D S and Bark S E 2007 Influence of SBA-15 support on \(\text{ CeO }_{2}-\text{ ZrO }_{2}\) catalyst for the dehydrogenation of ethylbenzene to styrene with \(\text{ CO }_{2}\) Catal. Commun. 8 43Google Scholar
  37. 37.
    Burri D R, Shaikh I R, Choi K M and Park S E 2007 Facile heterogenization of homogeneous ferrocene catalyst on SBA-15 and its hydroxylation activity Catal. Commun. 8 731Google Scholar
  38. 38.
    Kleitz F, Choi S H and Ryoo R 2003 Cubic Ia3d large mesoporous silica: Synthesis and replication to platinum nanowires, carbon nanorods and carbon nanotubes Chem. Commun. 17 2136Google Scholar
  39. 39.
    Kim T W, Kleitz F, Paul B and Ryoo R 2005 MCM-48-like large mesoporous silicas with tailored pore structure: Facile synthesis domain in a ternary triblock copolymer- butanol- water system J. Am. Chem. Soc. 127 7601Google Scholar
  40. 40.
    Venkateswarlu V, Saidulu G, Ravikumar M, Rama Rao K S and David Raju B 2014 Vapor phase chemoselective conjugate hydrogenation of isophorone over Pd/SBA-15 catalysts Ind. J. Chem. 53A 557Google Scholar
  41. 41.
    Wang Z, Liu Q, Yu J, Wu T and Wang G 2003 Surface structure and catalytic behavior of silica-supported copper catalysts prepared by impregnation and sol–gel methods Appl. Catal. A: Gen. 239 187Google Scholar
  42. 42.
    Fridman V Z and Davydov A A 2000 Dehydrogenation of cyclohexanol on copper-containing catalysts: I. The influence of the oxidation state of copper on the activity of copper sites J. Catal. 195 20CrossRefGoogle Scholar
  43. 43.
    Rioux R M and Vannice M A 2003 Hydrogenation/dehydrogenation reactions: Isopropanol dehydrogenation over copper catalysts J. Catal. 216 362CrossRefGoogle Scholar
  44. 44.
    Chang F W, Yang H C, Roselin L S and Lee W Y 2006 Ethanol Dehydrogenation Over copper Catalysts on Rice husk ash prepared by ion exchange Appl. Catal. 304 30Google Scholar
  45. 45.
    Frost D C, Ishitani A and McDowell C A 1972 X-ray photoelectron spectroscopy of copper compounds Mol. Phys. 24 861Google Scholar
  46. 46.
    Carlson T A 1975 In Photoelectron and Auger Spectroscopy (New York: Plenum Press)Google Scholar
  47. 47.
    Kim K S 1974 Charge transfer transition accompanying X-ray photoionization in transition-metal compounds J. Electron Spectrosc. Relat. Phenom. 3 217CrossRefGoogle Scholar
  48. 48.
    Lin Y M, Wang I and Yeh C T 1988 Activity stability of a copper (II) oxide—zinc (II) oxide catalyst for oxidative dehydrogenation of cyclohexanol to cyclohexanone Appl. Catal. 41 53Google Scholar
  49. 49.
    Martin J M C, Guerrero-Ruiz A and Fierro J L G 1995 Structural and surface properties of \(\text{ CuO-ZnO-Cr }_{2}\text{ O }_{3}\) catalysts and their relationship with selectivity to higher alcohol synthesis J. Catal. 156 208Google Scholar
  50. 50.
    Sivaraj C, Srinvas S T, Rao V N and Rao P K 1990 Selectivity dependence on the acidity of copper-alumina catalysts in the dehydrogenation of cyclohexanol J. Mol. Catal. 60 L23CrossRefGoogle Scholar
  51. 51.
    Sivaraj C, Reddy B M and Rao P K 1988 Selective dehydrogenation of cyclohexanol to cyclohexanone on \(\text{ Cu-ZnO-Al }_{2}\text{ O }_{3}\) catalysts Appl. Catal. 45 LllGoogle Scholar
  52. 52.
    Popova M, Domitrov M, Dal Santo V, Ravasio N and Scotti N 2012 Dehydrogenation of cyclohexanol on copper containing catalysts: The role of the support and the preparation method Catal. Commun. 17 150Google Scholar

Copyright information

© Indian Academy of Sciences 2017

Authors and Affiliations

  1. 1.Inorganic and Physical Chemistry DivisionCSIR-Indian Institute of Chemical TechnologyHyderabadIndia
  2. 2.Government Degree CollegeGambhiraopet, KarimnagarIndia
  3. 3.Government College for WomenOsmania University, KotiHyderabadIndia

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