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

DOI: 10.1039/D0CY00540A DOI Help

Authors: Camila Rivera-cárcamo (LCC-CNRS, Université de Toulouse) , Faqiang Leng (LCC-CNRS, Université de Toulouse) , Iann C. Gerber (Université de Toulouse; INSA, UPS, CNRS; LPCNO (IRSAMC)) , Iker Del Rosal (Université de Toulouse; INSA, UPS, CNRS; LPCNO (IRSAMC)) , Romuald Poteau (Université de Toulouse; INSA, UPS, CNRS; LPCNO (IRSAMC)) , Vincent Collière (LCC-CNRS, Université de Toulouse) , Pierre Lecante (Centre d’élaboration des matériaux et d’études structurales UPR CNRS 8011) , Divya Nechiyil (Centre d’élaboration des matériaux et d’études structurales UPR CNRS 8011) , Wolfgang Bacsa (Centre d’élaboration des matériaux et d’études structurales UPR CNRS 8011) , Anna Corrias (University of Kent) , M. Rosa Axet (LCC-CNRS, Université de Toulouse) , Philippe Serp (LCC-CNRS, Université de Toulouse)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Catalysis Science & Technology

State: Published (Approved)
Published: June 2020
Diamond Proposal Number(s): 14239

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, wide-angle 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.

Subject Areas: Chemistry

Instruments: B18-Core EXAFS