Topics in Catalysis

, Volume 61, Issue 1–2, pp 62–70 | Cite as

Competitive Molecular and Dissociative Hydrogen Chemisorption on Size Selected Doubly Rhodium Doped Aluminum Clusters

  • Jan Vanbuel
  • Mei-ye Jia
  • Piero Ferrari
  • Sandy Gewinner
  • Wieland Schöllkopf
  • Minh Tho Nguyen
  • André Fielicke
  • Ewald Janssens
Original Paper

Abstract

The interaction of hydrogen with Al n Rh2 + (n = 10–13) clusters is studied by mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. Comparing the IRMPD spectra with predictions obtained using density functional theory calculations allows for the identification of the hydrogen binding geometry. For n = 10 and 11, a single H2 molecule binds dissociatively, whereas for n = 12 and 13, it adsorbs molecularly. Upon adsorption of a second H2 to Al12Rh2 +, both hydrogen molecules dissociate. Theoretical calculations suggest that the molecular adsorption for n = 12 and 13 is not due to kinetic impediment of the hydrogenation reaction by an activation barrier, but due to a higher binding energy of the molecularly adsorbed hydrogen–cluster complex. Inspection of the highest occupied molecular orbitals shows that the hydrogen molecule initially forms a strongly bound Kubas complex with the Al11–13Rh2 + clusters, whereas it only binds weakly with Al10Rh2 +.

Keywords

Hydrogen storage Metal clusters Mass spectrometry IR spectroscopy Density functional theory calculations Ion-molecule reactions 

Notes

Acknowledgements

This work is supported by the KU Leuven Research Council (GOA/14/007). J.V. would like to thank the FWO—Research Foundation Flanders for a PhD fellowship. P.F. acknowledges CONICyT for a Becas Chile scholarship. A.F. thanks the Deutsche Forschungsgemeinschaft for a Heisenberg grant (FI 893/5).

Supplementary material

11244_2017_878_MOESM1_ESM.docx (11.9 mb)
Supplementary material 1 (DOCX 12200 KB)

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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2017

Authors and Affiliations

  1. 1.Laboratory of Solid State Physics & MagnetismKU LeuvenLeuvenBelgium
  2. 2.Fritz-Haber-Institut der Max-Planck-GesellschaftBerlinGermany
  3. 3.Department of ChemistryKU LeuvenLeuvenBelgium
  4. 4.Institut für Optik und Atomare PhysikTU BerlinBerlinGermany

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