PT Journal
AU Schauermann, S
TI Partial Hydrogenation of Unsaturated Carbonyl Compounds: Towards Ligand-Directed Heterogeneous Catalysis
SO The journal of physical chemistry letters
PY 2018
BP 5555
EP 5566
VL 9
IS 18
PU Universitätsbibliothek
DI 10.1021/acs.jpclett.8b01782
WP https://macau.uni-kiel.de/receive/publ_mods_00002206
LA en
DE acrolein partial hydrogenation; Pd(111); Pd nanoparticles
SN 1948-7185
AB In this perspective, we report on the recent progress in atomistic-level understanding of selective partial hydrogenation of α,β-unsaturated carbonyl compounds, particularly acrolein, towards unsaturated alcohols over model single crystalline and nanostructured Pd catalysts. This reaction was observed to proceed with nearly 100% selectivity over Pd(111) but not over supported Pd nanoparticles. The origin of the high selectivity was related to formation of a dense overlayer of oxopropyl surface species occurring at the early reaction stages via partial hydrogenation of the C=C bond in acrolein with only one H atom. This oxopropyl overlayer strongly modifies the adsorption and reactive properties of Pd(111) turning it 100% selective towards C=O bond hydrogenation. The underlying reaction mechanism represents a particular case of ligand-directed heterogeneous catalysis, in which the surface adsorbates do not directly participate in the catalytic process as the reaction intermediates but strongly affect the elementary reaction steps via specific adsorbate-adsorbate interactions.
PI Kiel
ER