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Influence of synthesis conditions on the structure of nickel nanoparticles and their reactivity in selective asymmetric hydrogenation

Arrigo, R; Gallarati, S; Schuster, ME; Seymour, J; Gianolio, D; da Silva, I; Callison, J; Feng, H; Proctor, JE; Ferrer, P; Venturini, F; Grinter, D; Held, G

Authors

S Gallarati

ME Schuster

J Seymour

D Gianolio

I da Silva

J Callison

H Feng

P Ferrer

F Venturini

D Grinter

G Held



Abstract

Unsupported and SiO2-supported Ni nanoparticles (NPs), were synthesised via hot-injection colloidal route using oleylamine (OAm) and trioctylphosphine (TOP) as reducing and protective agents, respectively. By adopting a multi-length scale structural characterization, it was found that by changing equivalents of OAM and TOP not only the size of the nanoparticles is affected but also the Ni electronic structure. The synthetized NPs were modified with (R,R)-tartaric acid (TA) and investigated in the asymmetric hydrogenation of methyl acetoacetate to chiral methyl-3-hydroxy butyrate. The comparative analysis of structure and catalytic performance for the synthetized catalysts has enabled us to identify a Ni metallic active surface, whereby the activity increases with the size of the metallic domains. Conversely, at the high conversion obtained for the unsupported NPs no impact of particle size on the selectivity was observed. (R)-selectivity was very high only on catalysts containing positively charged Ni species such as over the SiO2-supported Ni oxide NPs. This work shows that the chiral modification of metallic Ni NPs with TA is insufficient to maintain high selectivity towards the (R)-enantiomer at long reaction time and provide guidance for the engineering of long-term stable enantioselective catalysts.

Citation

Arrigo, R., Gallarati, S., Schuster, M., Seymour, J., Gianolio, D., da Silva, I., …Held, G. (2020). Influence of synthesis conditions on the structure of nickel nanoparticles and their reactivity in selective asymmetric hydrogenation. ChemCatChem, 12(5), 1491-1503. https://doi.org/10.1002/cctc.201901955

Journal Article Type Article
Acceptance Date Dec 10, 2019
Online Publication Date Dec 11, 2019
Publication Date Mar 6, 2020
Deposit Date Jan 2, 2020
Publicly Available Date Feb 4, 2020
Journal ChemCatChem
Print ISSN 1867-3880
Publisher Wiley
Volume 12
Issue 5
Pages 1491-1503
DOI https://doi.org/10.1002/cctc.201901955
Publisher URL https://doi.org/10.1002/cctc.201901955
Related Public URLs https://onlinelibrary.wiley.com/journal/18673899
Additional Information Funders : Engineering and Physical Sciences Research Council (EPSRC)
Grant Number: EP/K014706/1
Grant Number: EP/K014668/1
Grant Number: EP/K014714/1
Grant Number: EP/I019693/1

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