Design of Single Gold Atoms on Nitrogen‐Doped Carbon for Molecular Recognition in Alkyne Semi‐Hydrogenation. Issue 2 (21st November 2018)

• Record Type: Journal Article
• Authors: Lin, Ronghe; Albani, Davide; Fako, Edvin; Kaiser, Selina K.; Safonova, Olga V.; López, Núria; Pérez‐Ramírez, Javier
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 2(2019)
• Page Start: 504
• Page End: 509
• Publication Date: 2018-11-21
• Subjects: alkyne semi-hydrogenation -- gold -- molecular recognition -- N-doped carbon -- single-atom catalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201805820
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Single‐atom heterogeneous catalysts with well‐defined architectures are promising for deriving structure–performance relationships, but the challenge lies in finely tuning the structural and electronic properties of the metal. To tackle this point, a new approach based on the surface diffusion of gold atoms on different cavities of N‐doped carbon is presented. By controlling the activation temperature, the coordination neighbors (Cl, O, N) and the oxidation state of the metal can be tailored. Semi‐hydrogenation of various alkynes on the single‐atom gold catalysts displays substrate‐dependent catalytic responses; structure insensitive for alkynols with γ‐OH and unfunctionalized alkynes, and sensitive for alkynols with α‐OH. Density functional theory links the sensitivity for alkynols to the strong interaction between the substrate and specific gold‐cavity ensembles, mimicking a molecular recognition pattern that allows to identify the cavity site and to enhance the catalytic activity. Abstract : Finding the right spot : The stabilization of single gold atoms on nitrogen‐doped carbon allows fine tailoring of the structural and electronic properties of the metal centers and thus enables identification of the most active site for the semi‐hydrogenation of functionalized alkynes.