A1 Journal article (refereed)
Selective Acrolein Hydrogenation over Ligand-Protected Gold Clusters : A Venus Flytrap Mechanism (2022)
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
JYU authors or editors
Publication details
All authors or editors: Mammen, Nisha; Malola, Sami; Honkala, Karoliina; Häkkinen, Hannu
Journal or series: ACS Catalysis
eISSN: 2155-5435
Publication year: 2022
Publication date: 01/02/2022
Volume: 12
Issue number: 4
Pages range: 2365-2374
Publisher: American Chemical Society (ACS)
Publication country: United States
Publication language: English
DOI: https://doi.org/10.1021/acscatal.1c04585
Publication open access: Openly available
Publication channel open access: Partially open access channel
Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/79639
Abstract
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.
Keywords: hydrogenation; reduction (chemistry); catalysis; catalysts; nanoparticles; gold; density functional theory
Free keywords: monolayer-protected clusters; acrolein reduction; catalysis; gold; nanoclusters; density functional theory
Contributing organizations
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Ministry reporting: Yes
Reporting Year: 2022
Preliminary JUFO rating: 2