Facile soft-chemistry synthesis of Co-Ru nanoalloys: influence of the composition on the catalytic activity for the acceptorless dehydrogenation of alcohols.

08 February 2022, Version 1

Abstract

The synthesis of Co-Ru bimetallic nanoparticles was performed by co-reduction of Co(II) and Ru(III) salts in octan-1-ol, acting both as a solvent and a mild reducing agent. The metal composition was varied in the entire range, from pure Co to pure Ru. Although Co and Ru are miscible in the bulk, the formation of nanoalloys is not straightforward and requires selecting carefully reaction parameters such as the nature of the solvent and that of the metal precursors. The formation of nanoalloys was unambiguously evidenced by HAADF STEM–EDX analyses. The particle size and the size dispersity were found to decrease with increasing Ru amount, yielding very small and monodisperse particles for the richest compositions in Ru. The unsupported particles were tested for the acceptorless alcohol dehydrogenation using (±)-octan-2-ol and octan-1-ol as model substrates. The results clearly show a synergetic effect since the bimetallic particles exhibit better performances than their monometallic counterparts.

Keywords

nanoparticles
alloys
cobalt
ruthenium
alcohols
catalytic acceptorless dehydrogenation of alcohols

Supplementary materials

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Figure S1. TEM images and X-ray diffraction pattern of samples prepared with different Co and Ru precursors in butane-1,2-diol or in octane-1-ol. Figure S2. Size distributions measured by TEM for the CoxRu100-x samples Figure S3. X-ray diffraction pattern of the pure Ru sample. Figure S4. (a) Thermogravimetric (TG) and thermodifferential (TD) analyses of the sample Co80Ru20; (b) IR spectra recorded with time during the TG-TD analysis; (c) IR spectra obtained at 28 min and (d) associated mass spectra. Figure S5. Gas chromatograms of: (a) the liquid phase recovered after completion of the synthesis of the Co80Ru20 sample and (b) of the gas phase after 1 h reaction time. Figure S6. Conversion and yield vs time measured in the acceptorless dehydrogenation of (±)-octan-2-ol at 145°C with the catalysts: a) pure Co, b) Co80Ru20, c) Co50Ru50, d) Co20Ru80 and e) pure Ru. Specific surface area calculations Turnover number calculations
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