Atom‐by‐Atom Resolution of Structure–Function Relations over Low‐Nuclearity Metal Catalysts

Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom-efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non-scalable regime in which each atom counts. Almost all trends in this ultra-small frontier derive from...

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Detalles Bibliográficos
Autores: Vorobyeva, Evgeniya, Fako, Edvin, Chen, Zupeng, Collins, Sean M., Johnstone, Duncan, Midgley, Paul A., Hauert, Roland, Safonova, Olga V., Vilé, Gianvito, López, Núria, Mitchell, Sharon, Pérez-Ramírez, Javier
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/359797
Acceso en línea:http://hdl.handle.net/2072/359797
https://doi.org/10.1002/anie.201902136
Access Level:acceso abierto
Palabra clave:54
Descripción
Sumario:Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom-efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non-scalable regime in which each atom counts. Almost all trends in this ultra-small frontier derive from surface science approaches using model systems, because of both synthetic and analytical challenges. Exploiting the unique coordination chemistry of carbon nitride, we discriminate through experiments and simulations the interplay between the geometry, electronic structure, and reactivity of palladium atoms, dimers, and trimers. Catalytic tests evidence applicationdependent requirements of the active ensemble. In the semihydrogenation of alkynes, the nuclearity primarily impacts activity, whereas the selectivity and stability are affected in Suzuki coupling. This powerful approach will provide practical insights into the design of heterogeneous catalysts comprising well-defined numbers of atoms.