000K  utf8
1100  $c2018
1500  eng
2050  urn:nbn:de:gbv:8-publ-22068
2051  10.1021/acs.jpclett.8b01782
3000  Schauermann, Swetlana
4000  Partial Hydrogenation of Unsaturated Carbonyl Compounds: Towards Ligand-Directed Heterogeneous Catalysis  [Schauermann, Swetlana]
4209  In this perspective, we report on the recent progress in atomistic-level understanding of selective partial hydrogenation of α,β-unsaturated carbonyl compounds, particularly acrolein, towards unsaturated alcohols over model single crystalline and nanostructured Pd catalysts. This reaction was observed to proceed with nearly 100% selectivity over Pd(111) but not over supported Pd nanoparticles. The origin of the high selectivity was related to formation of a dense overlayer of oxopropyl surface species occurring at the early reaction stages via partial hydrogenation of the C=C bond in acrolein with only one H atom. This oxopropyl overlayer strongly modifies the adsorption and reactive properties of Pd(111) turning it 100% selective towards C=O bond hydrogenation. The underlying reaction mechanism represents a particular case of ligand-directed heterogeneous catalysis, in which the surface adsorbates do not directly participate in the catalytic process as the reaction intermediates but strongly affect the elementary reaction steps via specific adsorbate-adsorbate interactions.
4950  https://doi.org/10.1021/acs.jpclett.8b01782$xR$3Volltext$534
4950  https://nbn-resolving.org/urn:nbn:de:gbv:8-publ-22068$xR$3Volltext$534
4961  https://macau.uni-kiel.de/receive/publ_mods_00002206
5051  540
5550  acrolein partial hydrogenation
5550  Pd(111)
5550  Pd nanoparticles