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Towards Atomically Precise Supported Catalysts from Monolayer‐Protected Clusters: The Critical Role of the Support
Author(s) -
Longo Alessandro,
Boed Ewoud J. J.,
Mammen Nisha,
Linden Marte,
Honkala Karoliina,
Häkkinen Hannu,
Jongh Petra E.,
Donoeva Baira
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000637
Subject(s) - monolayer , cluster (spacecraft) , nanomaterials , catalysis , density functional theory , chemical physics , cluster size , metal , nanotechnology , materials science , ligand (biochemistry) , fragmentation (computing) , chemistry , computational chemistry , electronic structure , computer science , organic chemistry , biochemistry , receptor , programming language , operating system , metallurgy
Controlling the size and uniformity of metal clusters with atomic precision is essential for fine‐tuning their catalytic properties, however for clusters deposited on supports, such control is challenging. Here, by combining X‐ray absorption spectroscopy and density functional theory calculations, it is shown that supports play a crucial role in the evolution of monolayer‐protected clusters into catalysts. Based on the acidic nature of the support, cluster‐support interactions lead either to fragmentation of the cluster into isolated Au–ligand species or ligand‐free metallic Au 0 clusters. On Lewis acidic supports that bind metals strongly, the latter transformation occurs while preserving the original size of the metal cluster, as demonstrated for various Au n sizes. These findings underline the role of the support in the design of supported catalysts and represent an important step toward the synthesis of atomically precise supported nanomaterials with tailored physico‐chemical properties.