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Precursor Nuclearity and Ligand Effects in Atomically‐Dispersed Heterogeneous Iron Catalysts for Alkyne Semi‐Hydrogenation
Author(s) -
Faust Akl Dario,
RuizFerrando Andrea,
Fako Edvin,
Hauert Roland,
Safonova Olga,
Mitchell Sharon,
López Núria,
PérezRamírez Javier
Publication year - 2021
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202100235
Subject(s) - catalysis , alkyne , mesoporous material , palladium , ligand (biochemistry) , metal , heterogeneous catalysis , adsorption , materials science , density functional theory , graphitic carbon nitride , chemistry , chemical engineering , chemical physics , nanotechnology , computational chemistry , organic chemistry , biochemistry , receptor , photocatalysis , engineering
Nanostructuring earth‐abundant metals as single atoms or clusters of controlled size on suitable carriers opens new routes to develop high‐performing heterogeneous catalysts, but resolving speciation trends remains challenging. Here, we investigate the potential of low‐nuclearity iron catalysts in the continuous liquid‐phase semi‐hydrogenation of various alkynes. The activity depends on multiple factors, including the nuclearity and ligand sphere of the metal precursor and their evolution upon interaction with the mesoporous graphitic carbon nitride scaffold. Density functional theory predicts the favorable adsorption of the metal precursors on the scaffold without altering the nuclearity and preserving some ligands. Contrary to previous observations for palladium catalysts, single atoms of iron exhibit higher activity than larger clusters. Atomistic simulations suggest a central role of residual carbonyl species in permitting low‐energy paths over these isolated metal centers.