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Hydrogen Chemisorption on Singly Vanadium‐Doped Aluminum Clusters
Author(s) -
Vanbuel Jan,
Fernández Eva M.,
Ferrari Piero,
Gewinner Sandy,
Schöllkopf Wieland,
Balbás Luis C.,
Fielicke André,
Janssens Ewald
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704361
Subject(s) - chemisorption , vanadium , hydrogen , doping , materials science , aluminium , inorganic chemistry , chemistry , metallurgy , adsorption , optoelectronics , organic chemistry
The effect of vanadium doping on the hydrogen adsorption capacity of aluminum clusters (Al n + , n =2–18) is studied experimentally by mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. We find that vanadium doping enhances the reactivity of the clusters towards hydrogen, albeit in a size‐dependent way. IRMPD spectra, which provide a fingerprint of the hydrogen binding geometry, show that H 2 dissociates upon adsorption. Density functional theory (DFT) calculations for the smaller Al n V + ( n =2–8,10) clusters are in good agreement with the observed reactivity pattern and underline the importance of activation barriers in the chemisorption process. Orbital analysis shows that the activation barriers are due to an unfavorable overlap between cluster and hydrogen orbitals.