Abstract
A catalytic process for the selective formation of cis olefins would help minimize the production of unhealthy trans fats during the partial hydrogenation of edible oils. Here we report on the design of such a process on the basis of studies with model systems. Temperature programmed desorption data on single crystals showed that the isomerization of trans olefins to their cis counterparts is promoted by (111) facets of platinum, and that such selectivity is reversed on more open surfaces. Quantum mechanics calculations suggested that the extra stability of cis olefins seen on hydrogen-saturated Pt(111) surfaces may be due to a lesser degree of surface reconstruction, a factor found to be significant in the adsorption on close-packed platinum surfaces. Kinetic data using catalysts made out of dispersed tetrahedral Pt nanoparticles corroborated the selective promotion of the trans-to-cis isomerization on the (111) facets of the metal. Our work provides an example for how catalytic selectivity may be controlled by controlling the shape of the catalytic particles.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Taylor, H. S. A theory of the catalytic surface. Proc. R. Soc. A108, 105–111 (1925).
Sinfelt, J. H. Specificity in catalytic hydrogenolysis by metals. Adv. Catal. 23, 91–119 (1973).
Clarke, J. K. A. & Rooney, J. J. Stereochemical approach to mechanisms of hydrocarbon reactions on metal catalysts. Adv. Catal. 25, 125–183 (1976).
Bennett, C. O. & Che, M. Some geometric aspects of structure sensitivity. J. Catal. 120, 293–302 (1989).
Ertl, G. Surface science and catalysis—studies on the mechanism of ammonia synthesis: The P. H. Emmett Award address. Catal. Rev. Sci. Eng. 21, 201–223 (1980).
Somorjai, G. A. & Materer, N. Surface structures in ammonia synthesis. Top. Catal. 1, 215–231 (1994).
Simopoulos, A. P. in Handbook of Lipids in Human Nutrition (ed. Spiller, G. A.) 91–99 (CRC Press, 1996).
Scarbrough, F. E. Some food and drug administration perspectives of fat and fatty acids. Am. J. Clin. Nutr. 65, 1578S–1580S (1997).
Mercier, C. & Chabardes, P. Organometallic chemistry in industrial vitamin A and vitamin E synthesis. Pure Appl. Chem. 66, 1509–1518 (1994).
Rodriguez-Amaya, D. B. Food carotenoids: Analysis, composition and alterations during storage and processing of foods. Forum Nutr. 56, 35–37 (2003).
Dugave, C. & Demange, L. Cis–trans isomerization of organic molecules and biomolecules: Implications and applications. Chem. Rev. 103, 2475–2532 (2003).
Beller, M., Seayad, J., Tillack, A. & Jiao, H. Catalytic Markovnikov and anti-Markovnikov functionalization of alkenes and alkynes: Recent developments and trends. Angew. Chem. Int. Ed. 43, 3368–3398 (2004).
Schlatter, J. C. & Boudart, M. Hydrogenation of ethylene on supported platinum. J. Catal. 24, 482–492 (1972).
Dautzenberg, F. M. & Platteeuw, J. C. On the effect of metal particle size on the isomerization of n-hexane over supported platinum catalysts. J. Catal. 24, 364–365 (1972).
Gates, B. C., Katzer, J. R. & Schuit, G. C. A. Chemistry of Catalytic Processes (McGraw-Hill, 1979).
Yoshitake, H. & Iwasawa, Y. Electronic metal support interaction in platinum catalysts under deuterium–ethene reaction conditions and the microscopic nature of the active sites. J. Phys. Chem. 96, 1329–1334 (1992).
Lee, I. & Zaera, F. Selectivity in platinum-catalyzed cis–trans carbon–carbon double-bond isomerization. J. Am. Chem. Soc. 127, 12174–12175 (2005).
Polanyi, M. & Horiuti, J. Exchange reactions of hydrogen on metallic catalysts. Trans. Faraday Soc. 30, 1164–1172 (1934).
Zaera, F. On the mechanism for the hydrogenation of olefins on transition-metal surfaces: The chemistry of ethylene on Pt(111). Langmuir 12, 88–94 (1996).
Bond, G. C. in Metal-Catalysed Reactions of Hydrocarbons (eds Twigg, M. V. & Spencer, M. S.) (Springer, 2005).
Lee, I. & Zaera, F. Thermal chemistry of C4 hydrocarbons on Pt(111): Mechanism for double-bond isomerization. J. Phys. Chem. B 109, 2745–2753 (2005).
Lee, I. & Zaera, F. Infrared spectroscopy characterization of the chemistry of C4 hydrocarbons on Pt(111) single-crystal surfaces. J. Phys. Chem. C 111, 10062–10072 (2007).
Veldsink, J. W., Bouma, M. J., Schoon, N.-H. & Beenackers, A. A. C. M. Heterogeneous hydrogenation of vegetable oils: A literature review. Catal. Rev. Sci. Eng. 39, 253–318 (1997).
Gonzalez-Marcos, M. P., Gutierrez-Ortiz, J. I., De elguea, C. G.-O., Alvarez, J. I. & Gonzalez-Velasco, J. R. Control of the product distribution in the hydrogenation of vegetable oils over nickel on silica catalysts. Can. J. Chem. Eng. 76, 927–935 (1998).
Delbecq, F. & Zaera, F. Origin of the selectivity for trans-to-cis isomerization in 2-butene adsorbed on Pt(111) single crystal surfaces. J. Am. Chem. Soc. 130, 14924–14925 (2008).
Lee, I., Nguyen, M. K., Morton, T. H. & Zaera, F. Thermal chemistry of 1,4-difluoro-2-butenes on Pt(111) single crystal surfaces. J. Phys. Chem. C 112, 14117–14123 (2008).
Ahmadi, T. S., Wang, Z. L., Green, T. C., Henglein, A. & El-Sayed, M. A. Shape-controlled synthesis of colloidal platinum nanoparticles. Science 272, 1924–1926 (1996).
Lee, I., Morales, R., Albiter, M. A. & Zaera, F. Synthesis of heterogeneous catalysts with well-shaped platinum particles to control reaction selectivity. Proc. Natl Acad. Sci. 105, 15241–15246 (2008).
Song, H. et al. Hydrothermal growth of mesoporous SBA-15 silica in the presence of PVP-stabilized Pt nanoparticles: Synthesis, characterization, and catalytic properties. J. Am. Chem. Soc. 128, 3027–3037 (2006).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).
Kresse, G. & Hafner, J. Ab initio molecular dynamics for open-shell transition metals. Phys. Rev. B 48, 13115–13118 (1993).
Perdew, J. P. & Wang, Y. Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B 45, 13244–13249 (1992).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Valcárcel, A., Clotet, A., Ricart, J. M., Delbecq, F. & Sautet, P. Comparative DFT study of the adsorption of 1,3-butadiene, 1-butene and 2-cis/trans-butenes on the Pt(111) and Pd(111) surfaces. Surf. Sci. 549, 121–133 (2004).
Valcárcel, A., Clotet, A., Ricart, J. M., Delbecq, F. & Sautet, P. Selectivity control for the catalytic 1,3-butadiene hydrogenation on Pt(111) and Pd(111) surfaces: Radical versus closed-shell intermediates. J. Phys. Chem. B 109, 14175–14182 (2005).
Wilson, J. et al. Kinetic measurements of hydrocarbon conversion reactions on model metal surfaces. Phys. Chem. Chem. Phys. 9, 3830–3852 (2007).
Morales, R. & Zaera, F. Thermal chemistry of 1-methyl-1-cyclohexene and methylene cyclohexane on Pt(111) single crystal surfaces. J. Phys. Chem. C 111, 18367–18375 (2007).
Loaiza, A., Xu, M. & Zaera, F. On the mechanism of the H–D exchange reaction in ethane over platinum catalysts. J. Catal. 159, 127–139 (1996).
Loaiza, A. & Zaera, F. Regiospecificity in deuterium labeling determined by mass spectrometry. J. Am. Soc. Mass Spectrom. 15, 1366–1373 (2004).
Acknowledgements
Funding for this project was provided by the US National Science Foundation. We also wish to thank E. Montecino-Rodríguez for her help in editing the manuscript.
Author information
Authors and Affiliations
Contributions
I.L. carried out and helped analyse most of the experimental work; F.D. carried out and helped design the quantum mechanics calculations; R.M. and M.A.A. helped in the preparation and characterization of the supported catalysts; F.Z., the senior scientist, conceived and designed the study, helped analyse the data and wrote the paper.
Corresponding author
Rights and permissions
About this article
Cite this article
Lee, I., Delbecq, F., Morales, R. et al. Tuning selectivity in catalysis by controlling particle shape. Nature Mater 8, 132–138 (2009). https://doi.org/10.1038/nmat2371
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nmat2371
This article is cited by
-
Bioinspired nanomaterials for the treatment of bacterial infections
Nano Research (2024)
-
Boosting CO hydrogenation towards C2+ hydrocarbons over interfacial TiO2−x/Ni catalysts
Nature Communications (2022)
-
Metal nanoparticles: biomedical applications and their molecular mechanisms of toxicity
Chemical Papers (2022)
-
A modified method for morphology quantification and generation of 2D granular particles
Granular Matter (2022)
-
Design concept for electrocatalysts
Nano Research (2022)