Gallium-rich Pd–Ga phases as supported liquid metal catalysts

Abstract

A strategy to develop improved catalysts is to create systems that merge the advantages of heterogeneous and molecular catalysis. One such system involves supported liquid-phase catalysts, which feature a molecularly defined, catalytically active liquid film/droplet layer adsorbed on a porous solid support. In the past decade, this concept has also been extended to supported ionic liquid-phase catalysts. Here we develop this idea further and describe supported catalytically active liquid metal solutions (SCALMS). We report a liquid mixture of gallium and palladium deposited on porous glass that forms an active catalyst for alkane dehydrogenation that is resistant to coke formation and is thus highly stable. X-ray diffraction and X-ray photoelectron spectroscopy, supported by theoretical calculations, confirm the liquid state of the catalytic phase under the reaction conditions. Unlike traditional heterogeneous catalysts, the supported liquid metal reported here is highly dynamic and catalysis does not proceed at the surface of the metal nanoparticles, but presumably at homogeneously distributed metal atoms at the surface of a liquid metallic phase.

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Figure 1: Section of the Ga-Pd phase diagram.
Figure 2: SEM images of Ga- and Pd/Ga-decorated porous glass.
Figure 3: XPS and AR-XPS of Pd/Ga-SCALMS materials.
Figure 4: Ab initio molecular dynamic simulation of a Pd/Ga slab as a model for SCALMS.
Figure 5: Catalytic performance of Pd/Ga SCALMS for BDH.

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Acknowledgements

The Cluster of Excellence-Engineering of Advanced Material is acknowledged for financial support.

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Contributions

N.T, J.D. and P.W. conceived and designed the experiments. N.T. synthesized the catalytic materials and J.D. performed the catalytic testing. M.D. and W.P. contributed the electron microscopic analysis, M.B. and R.H. the XRD characterization and M.G., C.P., F.M., H.-P.S. the XPS characterization of the materials and the XPS measurements of the model system. J.E., C.N. and A.G. performed the molecular dynamic simulations. All the authors discussed the results and co-wrote the paper.

Corresponding author

Correspondence to P. Wasserscheid.

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The authors declare no competing financial interests.

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Taccardi, N., Grabau, M., Debuschewitz, J. et al. Gallium-rich Pd–Ga phases as supported liquid metal catalysts. Nature Chem 9, 862–867 (2017). https://doi.org/10.1038/nchem.2822

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