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

Mammen, Nisha
Malola, Sami
Honkala, Karoliina
Häkkinen, Hannu

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