Preparation of Pd/TiO2 Catalyst Using Room Temperature Ionic Liquids for Aerobic Benzyl Alcohol Oxidation

상온 이온성액체를 이용한 호기성 벤질 알코올 산화반응용 Pd/TiO2 촉매 제조

  • Cho, Tae Jun (Department of Chemical & Biomolecular Engineering, Seoul National University of Science & Technology) ;
  • Yoo, Kye Sang (Department of Chemical & Biomolecular Engineering, Seoul National University of Science & Technology)
  • 조태준 (서울과학기술대학교 화공생명공학과) ;
  • 유계상 (서울과학기술대학교 화공생명공학과)
  • Received : 2015.04.01
  • Accepted : 2015.04.21
  • Published : 2015.06.10


$Pd/TiO_2$ catalysts for aerobic benzyl alcohol oxidation were synthesized and eight different room temperature ionic liquids were used to control the palladium properties as active sites. $Pd/TiO_2$ particles were also calcined at 300, 400 and $500^{\circ}C$ to obtain an optimum catalyst. As the calcination temperature increased, the surface area and pore volume of catalyst decreased, but negligible changes were observed for the pore size of catalyst. However, the structural properties of catalyst varied with respect to the type of ionic liquids. Under identical reaction conditions, different catalytic activities were obtained depending upon the calcination temperature and type of ionic liquids. Mostly, the catalyst calcined at $400^{\circ}C$ showed higher catalytic activity than those at other temperatures. However, the catalyst prepared with 1-octyl-3-methylimidazolium hexafluorophosphate and 1-octyl-3-methylimidazolium trifluoromethanesulfonate showed good catalytic performance after calcination at $300^{\circ}C$. Among the catalyst, $Pd/TiO_2$ prepared with 1-octyl-3-methylimidazolium tetrafluoroborate and calcined at $400^{\circ}C$ showed the highest catalytic activity.


$Pd/TiO_2$;aerobic benzyl alcohol oxidation;room temperature ionic liquids


Supported by : 서울과학기술대학교


  1. R. V. Stevens, K. T. Chapman, and H. N. Weller, Convenient and inexpensive procedure for oxidation of secondary alcohols to ketones, J. Org. Chem., 45, 2030-2032 (1980).
  2. J. R. Holum, Study of the chromium (VI) oxide-pyridine complex, J. Org. Chem., 26, 4814-4816 (1961).
  3. D. G. Lee and U. A. Spitzer, Aqueous dichromate oxidation of primary alcohols, J. Org. Chem., 35, 3589-3590 (1970).
  4. R. J. Highet and W. C. Wildman, Solid manganese dioxide as an oxidizing agent, J. Am. Chem. Soc., 77, 4399-4401 (1955).
  5. F. M. Menger and C. Lee, Synthetically useful oxidations at solid sodium permanganate surfaces, Tetrahedron Lett., 22, 1655-1656 (1981).
  6. G. J. Hutchings, Nanocrystalline gold and gold palladium alloy catalysts for chemical synthesis, Chem. Commun., 1148-1164 (2008).
  7. K. Mori, T. Hara, T. Mizugaki, K. Ebitani, and K. Kaneda, Hydroxyapatite-supported palladium nanoclusters: a highly active heterogeneous catalyst for selective oxidation of alcohols by use of molecular oxygen, J. Am. Chem. Soc., 126, 10657-10666 (2004).
  8. A. Abad, P. Concepcion, A. Corma, and H. Garcia, A collaborative effect between gold and a support induces the selective oxidation of alcohols, Angew. Chem. Int. Ed., 44, 4066-4069 (2005).
  9. A. Arcadi and S. Di Giuseppe, Recent applications of gold catalysis in organic synthesis, Curr. Org. Chem., 8, 795-812 (2004).
  10. P. Vonmatt and A. Pfaltz, Chiral phosphinoaryldihydrooxazoles as ligands in asymmetric catalysis: Pd-catalyzed allylic substitution, Angew. Chem. Int. Ed., 32, 566-568(1993).
  11. D. Astruc, F. Lu, and J. R. Aranzaes, Nanoparticles as recyclable catalysts: the frontier between homogeneous and heterogeneous catalysis, Angew. Chem. Int. Ed., 44, 7852-7872 (2005).
  12. R. Narayanan and M. A. El-Sayed, Shape-dependent catalytic activity of platinum nanoparticles in colloidal solution, Nano Lett., 4, 1343-1348 (2004).
  13. S. E. Habas, H. Lee, V. Radmilovic, G. A. Somorjai, and P. Yang, Shaping binary metal nanocrystals through epitaxial seeded growth, Nat. Mater., 6, 692-697 (2007).
  14. K. M. Bratlie, H. Lee, K. Komvopoulos, P. Yang, and G. A. Somorjai, Platinum nanoparticle shape effects on benzene hydrogenation selectivity, Nano Lett., 7, 3097-3101 (2007).
  15. C. Wang, H. Daimon, T. Onodera, T. Koda, and S. Sun, A general approach to the size-and shape-controlled synthesis of platinum nanoparticles and their catalytic reduction of oxygen, Angew. Chem, Int. Ed., 47, 3588-3591 (2008).
  16. W. Fang, J. Chen, Q. Zhang, W. Deng, and Y. Wang, Hydrotalcite-supported gold catalyst for the oxidant-free dehydrogenation of benzyl alcohol: studies on support and gold size effects, Chem. Eur. J., 17, 1247-1256 (2011).
  17. N. Lopez, T. V. W. Janssens, B. S. Clausen, Y. Xu, M. Mavrikakis, T. Bligaard, and J. K. Norskov, On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidation, J. Catal., 223, 232-235 (2004).
  18. T. V. W. Janssens, B. S. Clausen, B. Hvolbaek, H. Falsig, C. H. Christensen, T. Bligaard, and J. K. Norskov, Insights into the reactivity of supported Au nanoparticles: combining theory and experiments, Top. Catal., 44, 15-26 (2007).
  19. C. N. R. Rao, G. U. Kulkarni, P. J. Thomas, and P. P. Edwards, Size dependent chemistry: Properties of nanocrystals, Chem. Eur. J., 8, 29-35 (2002).
  20. E. Roduner, Size matters: why nanomaterials are different, Chem. Soc. Rev., 35, 583-592 (2006).
  21. P. Wasserscheid and W. Keim, Ionic liquids-new "solutions" for transition metal catalysis, Angew. Chem. Int. Ed., 39, 3773-3789 (2000).
  22. T. Welton, Room-temperature ionic liquids. Solvents for synthesis and catalysis, Chem. Rev., 99, 2071-2083 (1999).
  23. T. J. Cho and K. S. Yoo, Synthesis of $Pd/TiO_2$ catalyst for aerobic benzyl alcohol dxidation, App. Chem. Eng., 25, 281-285 (2014).