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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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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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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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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DOI: https://doi.org/10.1038/nmat2849
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