Premium
Atom‐by‐Atom Resolution of Structure–Function Relations over Low‐Nuclearity Metal Catalysts
Author(s) -
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,
PérezRamírez Javier
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201902136
Subject(s) - catalysis , atom (system on chip) , palladium , chemical physics , electronic structure , chemistry , reactivity (psychology) , metal , function (biology) , materials science , computational chemistry , nanotechnology , computer science , organic chemistry , pathology , embedded system , evolutionary biology , biology , medicine , alternative medicine
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 application‐dependent requirements of the active ensemble. In the semi‐hydrogenation 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.