Abstract
The selectivity and activity for the hydrogenation of crotonaldehyde to crotyl alcohol and butyraldehyde was studied over a series of Pt nanoparticles (diameter of 1.7, 2.9, 3.6, and 7.1 nm). The nanoparticles were synthesized by alcohol reduction of a Pt salt in the presence of poly(vinylpyrrolidone) (PVP), followed by incorporation into mesoporous SBA-15 silica. The rate of crotonaldehyde hydrogenation and selectivity towards crotyl alcohol both increase with increasing particle size. With an increase in particle size from 1.7 nm to 7.1 nm, the selectivity towards crotyl alcohol increases from 13.7% to 33.9% (8 Torr crotonaldehyde, 160 Torr H2 and 353 K). The turnover frequency increases from 2.1 × 10−2 s−1 to 4.8 × 10−2 s−1 with increasing particle size. Additionally, the decarbonylation pathway to form propene and CO is enhanced over smaller nanoparticles. The apparent activation energy remains constant (~16 kcal mol−1 for the formation of butyraldehyde and ~8 kcal mol−1 for the formation of crotyl alcohol) as a function of particle size as does the reaction order in H2, which is unity. In the presence of 130–260 mTorr CO, the reaction rate decreases for all products with a CO reaction order of −1 to −1.4 for crotyl alcohol and butyraldehyde. Hydrogen reduction at 673–723 K results in increased activity and selectivity relative to reduction at either higher or lower temperature; this is discussed with respect to the organic capping agent, PVP.
Similar content being viewed by others
References
Aiken JD, Finke RG (1999) J Mol Catal A: Chem 145:1
Roucoux A, Schulz J, Patin H (2002) Chem Rev 102:3757
Lang HF, May RA, Iversen BL, Chandler BD (2003) J Am Chem Soc 125:14832
Konya Z, Puntes VF, Kiricsi I, Zhu J, Ager JW, Ko MK, Frei H, Alivisatos P, Somorjai GA (2003) Chem Mater 15:1242
Rioux RM, Song H, Hoefelmeyer JD, Yang P, Somorjai GA (2005) J Phys Chem B 109:2192
Song H, Rioux RM, Hoefelmeyer JD, Komor R, Niesz K, Grass M, Yang PD, Somorjai GA (2006) J Am Chem Soc 128:3027
Rioux RM, Hoefelmeyer JD, Grass M, Song H, Niesz K, Yang PD, Somorjai GA (2008) Langmuir 24:198
Rioux RM, Komor R, Song H, Hoefelmeyer JD, Grass M, Niesz K, Yang PD, Somorjai GA (2008) J Catal 254:1
Grass ME, Yue Y, Habas SE, Rioux RM, Teall CI, Yang P, Somorjai GA (2008) J Phys Chem C 112:4797
Gallezot P, Richard D (1998) Cat Rev Sci Eng 40:81
Santori GF, Casella ML, Siri GJ, Aduriz HR, Ferretti OA (2002) React Kinet Catal Lett 75:225
Giroir-Fendler A, Richard D, Gallezot P (1990) Catal Lett 5:175
Englisch M, Jentys A, Lercher JA (1997) J Catal 166:25
Delbecq F, Sautet P (1995) J Catal 152:217
Venezia AM, Liotta LF, Pantaleo G, La Parola V, Deganello G, Beck A, Koppany Z, Frey K, Horvath D, Guczi L (2003) Appl Catal A: Gen 251:359
Deutsch DS, Siani A, Fanson PT, Hirata H, Matsumoto S, Williams CT, Amiridis MD (2007) J Phys Chem C 111:4246
Song H, Kim F, Connor S, Somorjai GA, Yang PD (2005) J Phys Chem B 109:188
Wang Y, Ren J, Deng K, Gui L, Tang Y (2000) Chem Mater 12:1622
Teranishi T, Hosoe M, Tanaka T, Miyake M (1999) J Phys Chem B 103:3818
Grubbs RB (2007) Polym Rev 47:197
Du YK, Yang P, Mou ZG, Hua NP, Jiang L (2006) J Appl Poly Sci 99:23
Birchem T, Pradier CM, Berthier Y, Cordier G (1994) J Catal 146:503
Waghray A, Blackmond DG (1993) J Phys Chem 97:6002
Singh UK, Vannice MA (2000) J Catal 191:165
Shekhar R, Barteau MA (1994) Surf Sci 319:298
Beccat P, Bertolini JC, Gauthier Y, Massardier J, Ruiz P (1990) J Catal 126:451
Boudart M (1972) AIChE J 18:465
Baker RTK, Prestridge EB, Garten RL (1979) J Catal 56:390
Coloma F, Sepulveda-Escribano A, Fierro JLG, Rodriguez-Reinoso F (1997) Appl Catal A: Gen 150:165
Borodko Y, Humphrey SM, Tilley TD, Frei H, Somorjai GA (2007) J Phys Chem C 111:6288
Acknowledgments
This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geological and Biosciences of the U.S. Department of Energy under Contract No. DE-AC03-76SF00098. This work was also supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Grass, M.E., Rioux, R.M. & Somorjai, G.A. Dependence of Gas-Phase Crotonaldehyde Hydrogenation Selectivity and Activity on the Size of Pt Nanoparticles (1.7–7.1 nm) Supported on SBA-15. Catal Lett 128, 1–8 (2009). https://doi.org/10.1007/s10562-008-9754-4
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10562-008-9754-4