Abstract
Selective hydrogenation of citral was investigated over Au-based bimetallic catalysts in the environmentally benign supercritical carbon dioxide (scCO2) medium. The catalytic performances were different in citral hydrogenation when Pd or Ru was mixed (physically and chemically) with Au. Compared with the corresponding monometallic catalyst, the total conversion and the selectivity to citronellal (CAL) were significantly enhanced over TiO2 supported Pd and Au bimetallic catalysts (physically and chemically mixed); however, the conversion and selectivity did not change when Ru was physically mixed with Au catalyst compared to the monometallic Ru/TiO2, and the chemically mixed Ru-Au/TiO2 catalyst did not show any activity. The effect of CO2 pressure on the conversion of citral and product selectivity was significantly different over the Au/TiO2, Pd-Au/TiO2, and Pd/TiO2 catalysts. It was assumed to be ascribed to the difference in the interactions between Au, Pd nanoparticles and CO2 under different CO2 pressures.
Similar content being viewed by others
References
Leitner W. Supercritical carbon dioxide as a green reaction medium for catalysis. Acc Chem Res, 2002, 35: 746–756
Jessop PG, Ikariya T, Noyori R. Homogeneous catalysis in supercritical fluids. Chem Rev, 1999, 99: 475–493
Baiker A. Supercritical fluids in heterogeneous catalysis. Chem Rev, 1999, 99: 453–473
Zhao F, Fujita S, Akihara S, Arai M. Hydrogenation of benzaldehyde and cinnamaldehyde in compressed CO2 medium with a Pt/C catalyst: A study on molecular interactions and pressure effects. J Phys Chem A, 2005, 109: 4419–4424
Nelson MR, Brokman RF. Ab initio calculations on CO2 binding to carbonyl groups. J Phys Chem A, 1998, 102: 7860–7863
Raveendran P, Wallen SL. Cooperative C…H…O hydrogen bonding in CO2 Lewis Base complexes: Implications for solvation in supercritical CO2. J Am Chem Soc, 2002, 124: 12590–2599
Milone C, Ingoglia R, Pistone A, Neri G, Frusteri F, Galvagno S. Selective hydrogenation of α,β-unsaturated ketones to α,β-unsaturated alcohols on gold-supported catalysts. J Catal, 2004, 222: 348–356
Mohr C, Hofmeister H, Radnik J, Claus P. Identification of active sites in gold-catalyzed hydrogenation of acrolein. J Am Chem Soc, 2003, 125: 1905–1911
Okumura M, Akita T, Haruta M. Hydrogenation of 1,3-butadiene and of crotonaldehyde over highly dispersed Au catalysts. Catal Today, 2002, 74: 265–269
Pawelec B, Venezia AM, La Parola V, Cano-Serrano E, Campos-Martin JM, Fierro JLG. AuPd alloy formation in Au-Pd/Al2O3 catalysts and its role on aromatics hydrogenation. Appl Surf Sci, 2005, 242: 380–391
Li XL, Li BZ, Cheng MH, Du YK, Wang XM, Yang P. Catalytic hydrogenation of phenyl aldehydes using bimetallic Pt/Pd and Pt/Au nanoparticles stabilized by cubic silsesquioxanes. J Mol Catal A, 2008, 284: 1–7
Pawelec B, Venezia AM, La Parola V, Thomas S, Fierro JLG. Factors influencing selectivity in naphthalene hydrogenation over Auand Pt-Au-supported catalysts. Appl Catal A, 2005, 283: 165–175
Claus P. Heterogeneously catalyzed hydrogenation using gold catalysts. Appl Catal A, 2005, 291: 222–229
Hammer B, Norskov JK. Why gold is the noblest of all the metals. Nature, 1995, 376: 238–240
Zanella R, Louis C, Giorgio S, Touroude R. Crotonaldehyde hydrogenation by gold supported on TiO2: Structure sensitivity and mechanism. J Catal, 2004, 223: 328–339
Liu F, Wechsler D, Zhang P. Alloy-structure-dependent electronic behavior and surface properties of Au-Pd nanoparticles. Chem Phys Lett, 2008, 461: 254–259
Cardenas-Lizana F, Gomez-Quero S, Keane M. Gas phase hydrogenation of m-dinitrobenzene over alumina supported Au and Au-Ni alloy. Catal Lett, 2009, 127: 25–32
Pawelec B, Cano-Serrano E, Campos-Martin JM, Navarro RM, Thomas S, Fierro JLG. Deep aromatics hydrogenation in the presence of DBT over Au-Pd/gamma-alumina catalysts. Appl Catal A, 2004, 275: 127–139
Venezia AM, La Parola V, Pawelec B, Fierro JLG. Hydrogenation of aromatics over Au-Pd/SiO2-Al2O3 catalysts; Support acidity effect. Appl Catal A, 2004, 264: 43–51
Sarkany A, Geszti O, Safran G. Preparation of Pd-shell-Au-core/SiO2 catalyst and catalytic activity for acetylene hydrogenation. Appl Catal 0A, 2008, 350: 157–163
Sarkany A, Hargittai P, Horvath A. Controlled synthesis of PDDA stabilized Au-Pd bimetallic nanostructures and their activity in hydrogenation of acetylene. Top Catal, 2007, 46: 121–128
Malinowski A. Hydrodechlorination of dichlorodifluoromethane (CFC-12) on silica-supported palladium and palladium-gold catalysts. Pol J Chem, 2002, 76: 1461–1466
Bonarowska M, Pielaszek J, Semikolenov VA, Karpinski Z. Pd-Au/Sibunit carbon catalysts: Characterization and catalytic activity in hydrodechlorination of dichlorodifluoromethane (CFC-12). J Catal, 2002, 209: 528–538
Nutt MO, Heck KN, Alvarez P, Wong MS. Improved Pd-on-Au bimetallic nanoparticle catalysts for aqueous-phase trichloroethene hydrodechlorination. Appl Catal B, 2006, 69: 115–125
Venezia AM, La Parola V, Deganello G, Pawelec B, Fierro JLG. Synergetic effect of gold in Au/Pd catalysts during hydrodesulfurization reactions of model compounds. J Catal, 2003, 215: 317–325
Sarkany A, Horvath A, Beck A. Hydrogenation of acetylene over low loaded Pd and Pd-Au/SiO2 catalysts. Appl Catal A, 2002, 229: 117–125
Liu R, Yu Y, Yoshida K, Li G, Jiang H, Zhang M, Zhao F, Fujita S, Arai M. Physically and chemically mixed TiO2-supported Pd and Au catalysts: unexpected synergistic effects on selective hydrogenation of citral in supercritical CO2. J Catal, 2010, 269: 191–200
Hao J, Xi C, Cheng H, Liu R, Cai S, Arai M, Zhao F. Influence of compressed carbon dioxide on hydrogenation reactions in cyclohexane with a Pd/C catalyst. Ind Eng Chem Res, 2008, 47: 6796–6800
Schwank J. Gold in bimetallic catalysts. Gold Bull, 1985, 18: 2–10
Milone C, Tropeano ML, Gulino G, Neri G, Ingoglia R, Galvagno S. Selective liquid phase hydrogenation of citral on Au/Fe2O3 catalysts. Chem Commun, 2002, 868–869
Liu R, Zhao F, Fujita S, Arai M. Selective hydrogenation of citral with transition metal complexes in supercritical carbon dioxide. Appl Catal A, 2007, 316: 127–133
Liu R, Wu C, Wang Q, Ming J, Hao Y, Yu Y, Zhao F. Selective hydrogenation of citral catalyzed with palladium nanoparticles in CO2-in-water emulsion. Green Chem, 2009, 11: 979–985
Zhao F, Ikushima Y, Shirai M, Ebina T, Arai M. Influence of electronic state and dispersion of supported platinum particles on the conversion and selectivity of selective hydrogenation of α,β-unsaturated aldehyde in supercritical carbon dioxide. J Mol Catal A, 2002, 180: 259–265
Arai M, Nishiyama Y, Ikushima Y. Optical absorption of fine gold particles in supercritical carbon dioxide for the characterization of solvent properties. J Supercrit Fluid, 1998, 13: 149–153
Bhanage BM, Ikushima Y, Shirai M, Arai M. The selective formation of unsaturated alcohols by hydrogenation of α,β-unsaturated aldehydes in supercritical carbon dioxide using unpromoted Pt/Al2O3 catalyst. Catal Lett, 1999, 62: 175–177
Zhao F, Ikushima Y, Shirai M, Ebina T, Arai M. Influence of electronic state and dispersion of supported platinum particles on the conversion and selectivity of selective hydrogenation of α,β-unsaturated aldehyde in supercritical carbon dioxide. J Mol Catal A, 2002, 180: 259–265
Meric P, Yu KMK, Kong ATS, Tsang SC. Pressure-dependent product distribution of citral hydrogenation over micelle-hosted Pd and Ru nanoparticles in supercritical carbon dioxide. J Catal, 2006, 237: 330–336
Poliakoff M, Howdle S. Supercritical chemistry: Synthesis with a spanner. Chem Ber, 1995, 31: 118–121
Hiyoshi NV. Rode C, Sato O, Tetsuka H, Shirai M. Stereoselective hydrogenation of tert-butylphenols over charcoal-supported rhodium catalyst in supercritical carbon dioxide solvent. J Catal, 2007, 252: 57–68
Hiyoshi N, Inoue TV. Rode C, Sato O, Shirai M. Tuning cis-decalin selectivity in naphthalene hydrogenation over carbon-supported rhodium catalyst under supercritical carbon dioxide. Catal Lett, 2006, 106: 133–138
Hiyoshi N, Mine EV, Rode C, Sato O, Shirai M. Stereoselective hydrogenation of tetralin to cis-decalin over a carbon-supported rhodium catalyst in supercritical carbon dioxide solvent. Chem Lett, 2006, 35: 188–189
Hiyoshi N, Mine EV, Rode C, Sato O, Shirai M. Low temperature hydrogenation of tetralin over supported rhodium catalysts in supercritical carbon dioxide solvent. Appl Catal A, 2006, 310: 194–198
Chatterjee M, Kawanami H, Sato M, Chatterjee A, Yokoyama T, Suzuki T. Hydrogenation of phenol in supercritical carbon dioxide catalyzed by palladium supported on Al-MCM-41: A facile route for one-pot cyclohexanone formation. Adv Synth Catal, 2009, 351: 1912–1924
Ichikawa S, Tada M, Iwasawab Y, Ikariya T. The role of carbon dioxide in chemoselective hydrogenation of halonitroaromatics over supported noble metal catalysts in supercritical carbon dioxide. Chem Commun, 2005, 924–926
Liu H, Jiang T, Han B, Liang S, Zhou Y. Selective phenol hydrogenation to cyclohexanone over a dual supported Pd-Lewis acid catalyst. Science, 2009, 326: 1250–1252
Augustine RL. Dekker Inc M, New York, 1996
Chatterjee M, Chatterjee A, Ikushima Y. Pd-catalyzed completely selective hydrogenation of conjugated and isolated C=C of citral (3,7-dimethyl-2,6-octadienal) in supercritical carbon dioxide. Green Chem, 2004, 6: 114–118
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Liu, R., Zhao, F. Selective hydrogenation of citral over Au-based bimetallic catalysts in supercritical carbon dioxide. Sci. China Chem. 53, 1571–1577 (2010). https://doi.org/10.1007/s11426-010-3205-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-010-3205-y