Probing Basal and Prismatic Planes of Graphitic Materials for Metal Single Atom and Subnanometer Cluster Stabilization

• Published in: Chemistry : a European journal Vol. 30; no. 50; pp. e202400669 - n/a
• Main Authors: Vidal, Mathieu, Pandey, Jyoti, Navarro‐Ruiz, Javier, Langlois, Joris, Tison, Yann, Yoshii, Takeharu, Wakabayashi, Keigo, Nishihara, Hirotomo, Frenkel, Anatoly I., Stavitski, Eli, Urrutigoïty, Martine, Campos, Cristian H., Godard, Cyril, Placke, Tobias, Rosal, Iker, Gerber, Iann C., Petkov, Valeri, Serp, Philippe
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 19.08.2024; Wiley-VCH Verlag; Wiley Blackwell (John Wiley & Sons)
• Subjects: Analytical chemistry; Carbon; Carbon materials; Catalysis; Catalysts; Chemical reactions; Chemical Sciences; Chemical synthesis; Cluster analysis; Hydroformylation; Hydrogenation; Material chemistry; Metal clusters; Metals; or physical chemistry; Oxygen; Polymers; Rhodium; Single atom catalysis; Single atom catalysts; Speciation; Stabilization; Theoretical and; Single atom catalysis; Rhodium; Hydrogenation; Carbon materials; Hydroformylation
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.202400669

Supported metal single atom catalysis is a dynamic research area in catalysis science combining the advantages of homogeneous and heterogeneous catalysis. Understanding the interactions between metal single atoms and the support constitutes a challenge facing the development of such catalysts, since these interactions are essential in optimizing the catalytic performance. For conventional carbon supports, two types of surfaces can contribute to single atom stabilization: the basal planes and the prismatic surface; both of which can be decorated by defects and surface oxygen groups. To date, most studies on carbon‐supported single atom catalysts focused on nitrogen‐doped carbons, which, unlike classic carbon materials, have a fairly well‐defined chemical environment. Herein we report the synthesis, characterization and modeling of rhodium single atom catalysts supported on carbon materials presenting distinct concentrations of surface oxygen groups and basal/prismatic surface area. The influence of these parameters on the speciation of the Rh species, their coordination and ultimately on their catalytic performance in hydrogenation and hydroformylation reactions is analyzed. The results obtained show that catalysis itself is an interesting tool for the fine characterization of these materials, for which the detection of small quantities of metal clusters remains a challenge, even when combining several cutting‐edge analytical methods. The detection of small quantities of metal clusters in single atom catalysts remains a challenge even when combining electron microscopy (EM), X‐ray absorption spectroscopy (XAS) and X‐ray photoelectron spectroscopy (XPS). The results obtained demonstrate that Rh single atoms are mainly present on materials presenting prismatic surface, and that catalysis itself constitutes a valuable tool for the characterization of these materials.