A1 Journal article (refereed)
Atomically Precise, Thiolated Copper–Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions (2019)

Sun, C., Mammen, N., Kaappa, S., Yuan, P., Deng, G., Zhao, C., . . . Zheng, N. (2019). Atomically Precise, Thiolated Copper–Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions. ACS Nano, 13 (5), 5975-5986. doi:10.1021/acsnano.9b02052

JYU authors or editors

Publication details

All authors or editors: Sun, Cunfa; Mammen, Nisha; Kaappa, Sami; Yuan, Peng; Deng, Guocheng; Zhao, Chaowei; Yan, Juanzhu; Malola, Sami; Honkala, Karoliina; Häkkinen, Hannu; et al.

Journal or series: ACS Nano

ISSN: 1936-0851

eISSN: 1936-086X

Publication year: 2019

Volume: 13

Issue number: 5

Pages range: 5975-5986

Publisher: American Chemical Society

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acsnano.9b02052

Open Access: Open access publication published in a hybrid channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/67697

Abstract

Copper-hydrides are known catalysts for several technologically important reactions such as hydrogenation of CO, hydroamination of alkenes and alkynes, and chemoselective hydrogenation of unsaturated ketones to unsaturated alcohols. Stabilizing copper-based particles by ligand chemistry to nanometer scale is an appealing route to make active catalysts with optimized material economy; however, it has been long believed that the ligand-metal interface, particularly if sulfur-containing thiols are used as stabilizing agent, may poison the catalyst. We report here a discovery of an ambient-stable thiolate-protected copper-hydride nanocluster [Cu25H10(SPhCl2)18]3- that readily catalyzes hydrogenation of ketones to alcohols in mild conditions. A full experimental and theoretical characterization of its atomic and electronic structure shows that the 10 hydrides are instrumental for the stability of the nanocluster and are in an active role being continuously consumed and replenished in the hydrogenation reaction. Density functional theory computations suggest, backed up by the experimental evidence, that the hydrogenation takes place only around a single site of the 10 hydride locations, rendering the [Cu25H10(SPhCl2)18]3- one of the first nanocatalysts whose structure and catalytic functions are characterized fully to atomic precision. Understanding of a working catalyst at the atomistic level helps to optimize its properties and provides fundamental insights into the controversial issue of how a stable, ligand-passivated, metal-containing nanocluster can be at the same time an active catalyst.

Keywords: nanoparticles; copper; hydrides; catalysts; density functional theory

Free keywords: catalytic hydrogenation; Cu nanocluster; hydride; single-site catalyst; thiolate

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Ministry reporting: Yes

Reporting Year: 2019

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