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Control of selectivity in heterogeneous catalysis by tuning nanoparticle properties and reactor residence time

Nature Chemistry volume 4, pages 947–952 (2012)Cite this article

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Abstract

A combination of the advantages of homogeneous and heterogeneous catalysis could enable the development of sustainable catalysts with novel reactivity and selectivity. Although heterogeneous catalysts are often recycled more easily than their homogeneous counterparts, they can be difficult to apply in traditional organic reactions and modification of their properties towards a desired reactivity is, at best, complex. In contrast, tuning the properties of homogeneous catalysts by, for example, modifying the ligands that coordinate a metal centre is better understood. Here, using olefin cyclopropanation reactions catalysed by dendrimer-encapsulated Au nanoclusters as examples, we demonstrate that changing the dendrimer properties allows the catalytic reactivity to be tuned in a similar fashion to ligand modification in a homogeneous catalyst. Furthermore, we show that these heterogeneous catalysts employed in a fixed-bed flow reactor allow fine control over the residence time of the reactants and thus enables the control over product distribution in a way that is not easily available for homogeneous catalysts.

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Figure 1: Batch measurements of cyclopropane 2 yield as function of reaction time at r.t.
Figure 2: Flow measurements of cyclopropane 2 yield as function of time on-stream.
Figure 3: Flow measurements of the conversion and selectivity of the cascade cyclopropanation-rearrangement reaction as a function of reactant residence time.

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Acknowledgements

We acknowledge support from the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geological and Biosciences of the US Department of Energy (DOE) under contract DE-AC02-05CH11231. Nanoparticle TEM imaging was performed by S. Alayoglu at the Molecular Foundry Imaging Facility, Lawrence Berkeley National Laboratory, which is supported by the Office of Science, Office of Basic Energy Sciences of the US DOE under contract DE-AC02-05CH11231.

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  1. Chemical Sciences Division, California and Department of Chemistry, Lawrence Berkeley National Laboratory, Berkeley, University of California, Berkeley, 94720, California, USA

    Elad Gross, Jack Hung-Chang Liu, F. Dean Toste & Gabor A. Somorjai

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  1. Elad Gross
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  2. Jack Hung-Chang Liu
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Contributions

E.G. and J.H.L. performed the experiments and synthesized materials, substrates and catalysts. F.D.T. and G.A.S. supervised the research. All authors contributed to the conception of the experiments, discussed the results and commented on the manuscript.

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Correspondence to F. Dean Toste or Gabor A. Somorjai.

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The authors declare no competing financial interests.

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Gross, E., Liu, JC., Toste, F. et al. Control of selectivity in heterogeneous catalysis by tuning nanoparticle properties and reactor residence time. Nature Chem 4, 947–952 (2012). https://doi.org/10.1038/nchem.1465

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