Selective Acrolein Hydrogenation over Ligand-Protected Gold Clusters : A Venus Flytrap Mechanism
Mammen, N., Malola, S., Honkala, K., & Häkkinen, H. (2022). Selective Acrolein Hydrogenation over Ligand-Protected Gold Clusters : A Venus Flytrap Mechanism. ACS Catalysis, 12(4), 2365-2374. https://doi.org/10.1021/acscatal.1c04585
Julkaistu sarjassa
ACS CatalysisPäivämäärä
2022Tekijänoikeudet
© 2022 the Authors
The catalytic partial hydrogenation of α,β-unsaturated aldehydes is an ideal reaction to understand the selectivity between two different functional groups Here the two functional groups are C═C and C═O, and the hydrogenation of C═O is preferentially desired due to the importance of the issuing products, unsaturated alcohols, in fine-chemical industries. Using density functional theory calculations, we investigate the catalytic competency toward this reaction of a Au nanocluster in the presence of protecting ligands that offer higher stability and the possibility for the uniform distribution of size-selected clusters in the catalytic system. meta-Mercaptobenzoic-acid-protected-protected Au clusters exhibit special (bidentate) ligand–metal interactions: two weak interactions, O═C–OH···Au and Ph(π)···Au, in addition to the strong S–Au covalent bonds. We find that Ph(π)···Au interactions break (or open) to expose unprotected, low-coordinated Au sites on the cluster, which have a high propensity for trapping incoming reactant molecules. We study the partial hydrogenation of acrolein at these sites and find that the unsaturated alcohol, 1-propenol, is selectively favored over possible products. The opening of the π···Au interaction and the trapping of reactant molecules at Au sites are similar to a Venus flytrap mechanism where the flowers in the plant exhibit motion to actively trap its prey.
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Julkaisija
American Chemical Society (ACS)ISSN Hae Julkaisufoorumista
2155-5435Asiasanat
Julkaisu tutkimustietojärjestelmässä
https://converis.jyu.fi/converis/portal/detail/Publication/104121915
Metadata
Näytä kaikki kuvailutiedotKokoelmat
Rahoittaja(t)
Suomen AkatemiaRahoitusohjelmat(t)
Akatemiaohjelma, SA; Akatemiahanke, SA; Akatemiaprofessorin tutkimuskulut, SA; Tutkijatohtori, SALisätietoja rahoituksesta
This work was supported by the Academy of Finland (grants 319208 and 317739 to H.H., 307623 to K.H., and 332290 to N.M.). The computations were performed at the CSC center in Finland and at the Barcelona Supercomputing Center in Spain (PRACE project no. 2018194723).Lisenssi
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