Time-Resolved Formation and Operation Maps of Pd Catalysts Suggest a Key Role of Single Atom Centers in Cross-Coupling

Time-Resolved Formation and Operation Maps of Pd Catalysts Suggest a Key Role of Single Atom Centers in Cross-Coupling Full article

Journal

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Output data

Year: 2023, Volume: 145, Number: 16, Pages: 9092-9103 Pages count : 12 DOI: 10.1021/jacs.3c00645

Authors

Galushko Alexey S ¹ , Boiko Daniil A ¹ , Pentsak Evgeniy O ¹ , Eremin Dmitry B ^2,1 , Ananikov Valentine P ¹

Affiliations

1	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia
2	Bridge Institute and Department of Chemistry, University of Southern California, Los Angeles, California 90089-3502, United States

An approach to the spatially localized characterization of supported catalysts over a reaction course is proposed. It consists of a combination of scanning, transmission, and high-resolution scanning transmission electron microscopy to determine metal particles from arrays of surface nanoparticles to individual nanoparticles and individual atoms. The study of the evolution of specific metal catalyst particles at different scale levels over time, particularly before and after the cross-coupling catalytic reaction, made it possible to approach the concept of 4D catalysis–tracking the positions of catalytic centers in space (3D) over time (+1D). The dynamic behavior of individual palladium atoms and nanoparticles in cross-coupling reactions was recorded with nanometer accuracy via the precise localization of catalytic centers. Single atoms of palladium leach out into solution from the support under the action of the catalytic system, where they exhibit extremely high catalytic activity compared to surface metal nanoparticles. Monoatomic centers, which make up only approximately 1% of palladium in the Pd/C system, provide more than 99% of the catalytic activity. The remaining palladium nanoparticles changed their shape and could move over the surface of the support, which was recorded by processing images of the array of nanoparticles with a neural network and aligning them using automatically detected keypoints. The study reveals a novel opportunity for single-atom catalysis─easier detachment (capture) from (on) the carbon support surface is the origin of superior catalytic activity, rather than the operation of single atomic catalytic centers on the surface of the support, as is typically assumed.

Galushko A.S. , Boiko D.A. , Pentsak E.O. , Eremin D.B. , Ananikov V.P.
Time-Resolved Formation and Operation Maps of Pd Catalysts Suggest a Key Role of Single Atom Centers in Cross-Coupling
Journal of the American Chemical Society. 2023. V.145. N16. P.9092-9103. DOI: 10.1021/jacs.3c00645 WOS Scopus OpenAlex

Web of science:	WOS:000970846900001
Scopus:	2-s2.0-85153940686
OpenAlex:	W4365442777

DB	Citing
OpenAlex	32
Scopus	28
Web of science	23