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

DOI: 10.1002/cctc.201901955 DOI Help

Authors: Rosa Arrigo (University of Salford; Diamond Light Source) , Simone Gallarati (University of St Andrews) , Manfred E. Schuster (Diamond Light Source; Johnson Matthey Technology Centre) , Jake Seymour (University of Reading) , Diego Gianolio (Diamond Light Source) , Ivan Da Silva (ISIS Facility) , June Callison (University College London; UK Catalysis Hub) , Haosheng Feng (University of Cambridge) , John E. Proctor (University of Salford) , Pilar Ferrer (Diamond Light Source) , Federica Venturini (Diamond Light Source) , Dave Grinter (Diamond Light Source) , Georg Held (Johnson Matthey Technology Centre; Diamond Light Source)
Co-authored by industrial partner: Yes

Type: Journal Paper
Journal: Chemcatchem

State: Published (Approved)
Published: December 2019

Open Access Open Access

Abstract: Unsupported and SiO 2 ‐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 there was no impact of particle size on the selectivity. ( R )‐selectivity was very high only on catalysts containing positively charged Ni species such as over the SiO 2 ‐supported NiO 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.

Journal Keywords: Nanoparticles; Ni phosphides; Hot-injection; hydrogenation; XPS; XAFS; HRTEM

Subject Areas: Chemistry

Diamond Offline Facilities: Electron Physical Sciences Imaging Centre (ePSIC)
Instruments: B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS , B18-Core EXAFS , E01-JEM ARM 200CF