Issue 20, 2024

Hydrogen spillover through hydride transfer: the reaction of ZnO and ZrO2 with strong hydride donors

Abstract

Hydrogen spillover, transfer of H2 from a metal surface to a support (often metal oxides), is pivotal for many heterogeneous catalytic processes, including Cu/ZnO and Cu/ZrO2 catalyzed methanol synthesis. Little is known about hydrogen spillover on ZnO or ZrO2, due to the high complexity of the metal–metal oxide interface. Here, we model hydrogen spillover on ZnO and ZrO2 by reacting them with molecular metal hydrides to see how the properties of the hydrides affect hydrogen spillover. While the good H· donors HV(CO)4dppe (1) and CpCr(CO)3H (2) do not react with the metal oxide surfaces, the strong hydride donors iBu2AlH (3), Cp2ZrHCl (4), and [HCu(PPh3)]6 (5) do reduce ZnO and ZrO2 to give defect sites with the same EPR signatures as obtained via hydrogen spillover. We also observe new M–O bonds to the surface using X-ray absorption spectroscopy (XAS). We propose that these metal oxides undergo hydrogen spillover via initial hydride transfer followed by tautomerization of the surface hydride, giving reduced sites and OH bonds. This mechanism is in contrast to the traditional spillover mechanism involving discrete proton- and electron transfer steps. We also observe that ZnO is easier to reduce than ZrO2, explaining the difficulty observing spillover on Cu/ZrO2.

Graphical abstract: Hydrogen spillover through hydride transfer: the reaction of ZnO and ZrO2 with strong hydride donors

Supplementary files

Article information

Article type
Paper
Submitted
19 Apr 2024
Accepted
04 Jul 2024
First published
19 Aug 2024
This article is Open Access
Creative Commons BY license

Catal. Sci. Technol., 2024,14, 5854-5863

Hydrogen spillover through hydride transfer: the reaction of ZnO and ZrO2 with strong hydride donors

M. Benz, O. Bunjaku, M. Nowakowski, A. Allgaier, I. Biswas, J. van Slageren, M. Bauer and D. P. Estes, Catal. Sci. Technol., 2024, 14, 5854 DOI: 10.1039/D4CY00504J

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