Heterostructured Cobalt Silicide Nanocrystals: Synthesis in Molten Salts, Ferromagnetism, and Electrocatalysis

  1. Song, Yang 3
  2. Gómez-Recio, Isabel 3
  3. Ghoridi, Anissa 3
  4. Igoa Saldaña, Fernando 3
  5. Janisch, Daniel 3
  6. Sassoye, Capucine 3
  7. Dupuis, Vincent 1
  8. Hrabovsky, David 6
  9. Ruiz-González, M. Luisa 4
  10. González-Calbet, José M. 4
  11. Casale, Sandra 5
  12. Zitolo, Andrea 2
  13. Lassalle-Kaiser, Benedikt 2
  14. Laberty-Robert, Christel 3
  15. Portehault, David 3
  1. 1 Sorbonne Université, CNRS, Laboratoire de Physicochimie des Electrolytes et Nanosystèmes Interfaciaux (PHENIX), 4 place Jussieu, F-75005 Paris, France
  2. 2 Synchrotron SOLEIL, L’Orme des Merisiers, Départementale 128, 91190 Saint-Aubin, France
  3. 3 Sorbonne Université, CNRS, Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), 4 place Jussieu, F-75005 Paris, France
  4. 4 Dpto. de Química Inorgánica I, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid, Spain
  5. 5 Sorbonne Université, CNRS, Laboratoire de Réactivité de Surface (LRS), 4 place Jussieu, F-75005 Paris, France
  6. 6 Sorbonne Université, CNRS, Institut de Minéralogie de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu, F-75005 Paris, France
Journal of the American Chemical Society

ISSN: 0002-7863 1520-5126

Year of publication: 2023

Type: Article

DOI: 10.1021/JACS.3C01110 GOOGLE SCHOLAR lock_openOpen access editor

More publications in: Journal of the American Chemical Society


Nanoscale heterostructures of covalent intermetallics should give birth to a wide range of interface-driven physical and chemical properties. Such a level of design however remains unattainable for most of these compounds, due to the difficulty to reach a crystalline order of covalent bonds at the moderate temperatures required for colloidal chemistry. Herein, we design heterostructured cobalt silicide nanoparticles to trigger magnetic and catalytic properties in silicon-based materials. Our strategy consists in controlling the diffusion of cobalt atoms into silicon nanoparticles, by reacting these particles in molten salts. By adjusting the temperature, we tune the conversion of the initial silicon particles toward homogeneous CoSi nanoparticles and core–shell nanoparticles made of a CoSi shell and a silicon-rich core. The increased interface-to-volume ratio of the CoSi component in the core–shell particles yields distinct properties compared to the bulk and homogeneous nanoparticles. First, the core–shell particles exhibit increased ferromagnetism, despite the bulk diamagnetic properties of cobalt monosilicide. Second, the core–shell nanoparticles act as efficient precatalysts for alkaline water oxidation, where the nanostructure is converted in situ into a layered cobalt silicon oxide/(oxy)hydroxide with high and stable oxygen evolution reaction (OER) electrocatalytic activity. This work demonstrates a route to design heterostructured nanocrystals of covalent intermetallic compounds and shows that these new structures exhibit very rich, yet poorly explored, interface-based physical properties and reactivity.

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