A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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., Yan, J., Malola, S., Honkala, K., Häkkinen, H., Teo, B. K., & 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. https://doi.org/10.1021/acsnano.9b02052

JYU-tekijät tai -toimittajat

Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Sun, Cunfa; Mammen, Nisha; Kaappa, Sami; Yuan, Peng; Deng, Guocheng; Zhao, Chaowei; Yan, Juanzhu; Malola, Sami; Honkala, Karoliina; Häkkinen, Hannu; et al.

Lehti tai sarja: ACS Nano

ISSN: 1936-0851

eISSN: 1936-086X

Julkaisuvuosi: 2019

Volyymi: 13

Lehden numero: 5

Artikkelin sivunumerot: 5975-5986

Kustantaja: American Chemical Society

Julkaisumaa: Yhdysvallat (USA)

Julkaisun kieli: englanti

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

Julkaisun avoin saatavuus: Avoimesti saatavilla

Julkaisukanavan avoin saatavuus: Osittain avoin julkaisukanava

Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/67697

Tiivistelmä

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.

YSO-asiasanat: nanohiukkaset; kupari; hydridit; katalyytit; tiheysfunktionaaliteoria

Vapaat asiasanat: catalytic hydrogenation; Cu nanocluster; hydride; single-site catalyst; thiolate

Liittyvät organisaatiot

Hankkeet, joissa julkaisu on tehty

OKM-raportointi: Kyllä

Raportointivuosi: 2019

JUFO-taso: 3