Activation of Copper Species on Carbon Nitride for Enhanced Activity in the Arylation of Amines
Metadata only
Date
2020-10-02Type
- Journal Article
Citations
Cited 20 times in
Web of Science
Cited 18 times in
Scopus
ETH Bibliography
yes
Altmetrics
Abstract
We report the promoting effect of graphitic carbon nitride in Cu-catalyzed N-arylation. The abundance of pyridinic coordination sites in this host permits the adsorption of copper iodide from the reaction medium. The key to achieving high activity is to confine active Cu species on the surface, which is accomplished by introducing atomically dispersed metal dopants to block diffusion into the bulk of the carrier. The alternative route of incorporating metal during the synthesis of graphitic carbon nitride is ineffective as Cu is thermodynamically more stable in inactive subsurface positions. A combination of X-ray absorption, X-ray photoelectron, and electron paramagnetic resonance spectroscopy, density functional theory, and kinetic Monte Carlo simulations is employed to determine the location and associated geometry as well as the electronic structure of metal centers. N-Arylation activity correlates to the surface coverage by copper, which varies during the reaction due to an interplay between site formation via adsorption from the reaction medium and deactivation by diffusion into the bulk of the material, and is highest when an Fe dopant is used to hinder such movement through the lattice. © 2020 American Chemical Society Show more
Publication status
publishedExternal links
Journal / series
ACS CatalysisVolume
Pages / Article No.
Publisher
American Chemical SocietySubject
catalysts; metals; supports; C−N coupling; copper; carbon nitride; Catalyst deactivationOrganisational unit
03810 - Jeschke, Gunnar / Jeschke, Gunnar
03511 - Carreira, Erick M. / Carreira, Erick M.
03871 - Pérez-Ramírez, Javier / Pérez-Ramírez, Javier
More
Show all metadata
Citations
Cited 20 times in
Web of Science
Cited 18 times in
Scopus
ETH Bibliography
yes
Altmetrics