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Control of Reactivity through Chemical Order in Very Small RuRe Nanoparticles

Abstract

The choice of adequate organometallic precursors, [Re2(C3H5)4] and [Ru(Me Allyl)2COD] or [Ru(COD)(COT)], allows to synthesize polyvinylpyrrolidone (PVP) stabilized bimetallic RuRe nanoparticles of ca. 1.3nm with narrow size dispersity, displaying the hcp crystal structure and to control their chemical order : alloy or Re rich surface. The structural features of these NPs was determined using complementary characterization techniques (TEM, HRTEM, STEM-HAADF, EDX, WAXS, FT IR, MAS-NMR and ICP). In particular, surface state investigation based on CO adsorption and oxidation reactions provided useful information on the chemical order in these nanoparticles. The RuRe NPs were obtained as stable colloidal solutions or powders. Surface reactivity studies demonstrated that the alloy type RuRe/PVP NPs can better resist to oxidation than the ones displaying a Re enriched surface and are more active towards CO dissociation than monometallic Re/PVP NPs as the result of a synergic effect between Ru and Re. Interestingly, the dissociation of CO was not observed with RuRe/PVP NPs displaying a Re enriched surface. Besides the synthetic aspect, this work hightlights the crucial influence of the chemical order resulting from the choice of the metal sources in the control of the reactivity of ultra-small metal nanoparticles.

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Publication details

The article was received on 23 Jun 2017, accepted on 05 Oct 2017 and first published on 05 Oct 2017


Article type: Paper
DOI: 10.1039/C7DT02287E
Citation: Dalton Trans., 2017, Accepted Manuscript
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    Control of Reactivity through Chemical Order in Very Small RuRe Nanoparticles

    T. AYVALI, P. Fazzini, P. Lecante, A. Mayoral, K. Philippot and B. Chaudret, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT02287E

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