Lang Sandra M, Bernhardt Thorsten M, Bakker Joost M, Barnett Robert N, Landman Uzi
Institute of Surface Chemistry and Catalysis, University of Ulm, Albert-Einstein-Allee 47, 89069 Ulm, Germany.
Radboud University, Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.
J Phys Chem A. 2021 May 27;125(20):4435-4445. doi: 10.1021/acs.jpca.1c03195. Epub 2021 May 14.
We have employed infrared multiple-photon dissociation (IR-MPD) spectroscopy together with density functional theory (DFT) calculations to study the interaction of series of subnanometer sized manganese oxide clusters, MnO ( = 1-6, = 0-9) with acetic acid (HOAc) and methyl acetate (MeOAc). Reaction with HOAc leads to strongly cluster size and composition dependent IR-MPD spectra, indicating molecular adsorption on MnO clusters and thermodynamically favorable but kinetically hampered HOAc dissociation (deprotonation) on MnO and MnO. Other cluster sizes exhibit the preferred formation of a dissociative bidentate chelating structure. In contrast to HOAc, all clusters bind MeOAc via the carbonyl group as an intact molecule, and dissociation appears to be kinetically hindered under the given experimental conditions.
