Structural insight into palladium-nickel clusters over mordenite zeolite for carbene-insertion reaction

Abstract

The advancement of heterogeneous catalysts incorporating metal clusters in the nanometric size range has garnered significant attention due to their extraordinary catalytic activity and selectivity. The detailed characterization and understanding of the atomic structure of these metal clusters within catalysts is crucial for elucidating the underlying reaction mechanisms. In the present study, a distinctive three-atom PdNi cluster, characterized by two Pd atoms at terminal positions and a central Ni atom, was synthesized over mordenite zeolite. The presence of atomic PdNi clusters within the eight-membered ring side pocket area was confirmed by multiple advanced analytical techniques, including magic-angle spinning nuclear magnetic resonance spectroscopy, synchrotron X-ray powder diffraction, extended X-ray absorption fine structure spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy. The catalytic activity of the confined active species was examined by the carbene-mediated reactions of ethyl-2-diazoacetate to ethyl-2-methoxyacetate as a model reaction. Compared to the Pd-mordenite and Ni-mordenite, the PdNi-mordenite catalyst incorporates a PdNi cluster, which demonstrates a superior performance, achieving 100% conversion and high selectivity under the same reaction conditions. Our study elucidates the potential of constructing bimetallic clusters in zeolites, providing valuable insights for developing new heterogeneous catalysts applicable to a wide range of catalytic processes.

Graphical abstract

Keywords

zeolite / metal cluster / synchrotron X-ray diffraction / carbene-mediated reaction

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Competing interests

The authors declare that they have no competing interests.

Acknowledgements

GL would like to thank the University Research Facility in Chemical and Environmental Analysis at The Hong Kong Polytechnic University for providing access to the solid-state NMR instrument and the financial support from the Department of Applied Biology and Chemical Technology (PolyU P0049034). The synchrotron radiation experiments were performed at BL02B2 in SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2455-8 and is accessible for authorized users.

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