Competitive Molecular and Dissociative Hydrogen Chemisorption on Size Selected Doubly Rhodium Doped Aluminum Clusters
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 +.
KeywordsHydrogen storage Metal clusters Mass spectrometry IR spectroscopy Density functional theory calculations Ion-molecule reactions
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).
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