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Controlled selectivity for palladium catalysts using self-assembled monolayers

Nature Materials volume 9, pages 853–858 (2010)Cite this article

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Abstract

The selective reaction of one part of a bifunctional molecule is a fundamental challenge in heterogeneous catalysis and for many processes including the conversion of biomass-derived intermediates. Selective hydrogenation of unsaturated epoxides to saturated epoxides is particularly difficult given the reactivity of the strained epoxide ring, and traditional platinum group catalysts show low selectivities. We describe the preparation of highly selective Pd catalysts involving the deposition of n-alkanethiol self-assembled monolayer (SAM) coatings. These coatings improve the selectivity of 1-epoxybutane formation from 1-epoxy-3-butene on palladium catalysts from 11 to 94% at equivalent reaction conditions and conversions. Although sulphur species are generally considered to be indiscriminate catalyst poisons, the reaction rate to the desired product on a catalyst coated with a thiol was 40% of the rate on an uncoated catalyst. Interestingly the activity decreased for less-ordered SAMs with shorter chains. The behaviour of SAM-coated catalysts was compared with catalysts where surface sites were modified by carbon monoxide, hydrocarbons or sulphur atoms. The results suggest that the SAMs restrict sulphur coverage to enhance selectivity without significantly poisoning the activity of the desired reaction.

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Figure 1
Figure 2: The structure of a propanethiol SAM on Pd(111).
Figure 3: Epoxybutane selectivity and formation rate for different thiol coatings at 313 K.
Figure 4: DRIFT spectra of SAM-coated catalysts.
Figure 5: Epoxybutane selectivity and formation rate versus 1,000 ppm H2S exposure at 313 K.

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Acknowledgements

This research was supported by the Renewable and Sustainable Energy Institute, a joint institute of the University of Colorado and the National Renewable Energy Laboratory. S.T.M. thanks the Department of Education Graduate Assistantships in Areas of National Need and Peter and Vivian Teets for additional funding.

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Authors and Affiliations

  1. Department of Chemical and Biological Engineering, University of Colorado at Boulder, UCB 424. Boulder, Colorado 80309, USA

    Stephen T. Marshall, Marykate O’Brien, Brittany Oetter, Daniel K. Schwartz & J. William Medlin

  2. Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, Colorado 80401, USA

    April Corpuz & Ryan M. Richards

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  1. Stephen T. Marshall
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Contributions

S.T.M., M.O. and B.O. carried out the catalysis and surface science experiments; A.C. carried out DRIFT spectroscopy experiments; S.T.M., D.K.S. and J.W.M. wrote the manuscript; and R.M.R., D.K.S. and J.W.M. supervised the project.

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Correspondence to J. William Medlin.

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Marshall, S., O’Brien, M., Oetter, B. et al. Controlled selectivity for palladium catalysts using self-assembled monolayers. Nature Mater 9, 853–858 (2010). https://doi.org/10.1038/nmat2849

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