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Catalysis to discriminate single atoms from subnanometric ruthenium particles in ultra-high loading catalysts

Rivera-Cárcamo, C., Leng, F., Gerber, I. C., del Rosal, I., Poteau, R., Collière, V., Lecante, P., Nechiyil, D., Bacsa, W., Corrias, A., and others. (2020) Catalysis to discriminate single atoms from subnanometric ruthenium particles in ultra-high loading catalysts. Catalysis Science and Technology, 10 . pp. 4673-4683. ISSN 2044-4753. E-ISSN 2044-4761. (doi:10.1039/D0CY00540A) (KAR id:81677)

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Abstract

We report a procedure for preparing ulta-high metal loading (10-20 % w/w Ru) Ru@C60 nanostructured catalysts comprising exclusively Ru single atoms. We show that by changing the Ru/C60 ratio and the nature of the solvent used during the synthesis, it is possible to increase the Ru loading up to 50% w/w, and to produce hetero-structures containing subnanometric Ru nanoparticles. Several techniques such as high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy – high angle annular dark field (STEM-HAADF), Raman spectroscopy, wideangle X-ray scattering (WAXS), extended X-ray absorption fine structure (EXAFS) and X-ray photoelectron spectroscopy (XPS) together with theoretical calculations were used to characterize these materials. At such high metal loading, the distinction between Ru single atoms and clusters is not trivial, even with this combination of techniques. We evaluated the catalytic properties of these materials for the hydrogenation of nitrobenzene and 2,3-dimethyl-2-butene. The catalysts containing only Ru single atoms are much less active for these reactions than the ones containing clusters. For nitrobenzene hydrogenation, this is because electro-deficient Ru single atoms and few atom Run clusters are not performant for H2 activation compared to larger clusters (n ≥ 13), as shown by density functional theory (DFT) calculations. For the more crowded substrate 2,3-dimethyl-2-butene, DFT calculations have shown that this is due to steric hindrance. These simple tests can thus been used to distinguish samples containing metallic sub-nanometer nanoparticles. These novel catalysts are also extremely active for the hydrogenation of -substituted 2,3-dimethyl-2-butene.

Item Type: Article
DOI/Identification number: 10.1039/D0CY00540A
Uncontrolled keywords: Materials for Energy and Electronics
Subjects: Q Science
Divisions: Faculties > Sciences > School of Physical Sciences
Depositing User: Anna Corrias
Date Deposited: 12 Jun 2020 09:55 UTC
Last Modified: 21 Aug 2020 15:19 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/81677 (The current URI for this page, for reference purposes)
Corrias, A.: https://orcid.org/0000-0002-5190-8196
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