Premium
Lewis Acid Strength of Interfacial Metal Sites Drives CH 3 OH Selectivity and Formation Rates on Cu‐Based CO 2 Hydrogenation Catalysts
Author(s) -
Noh Gina,
Lam Erwin,
Bregante Daniel T.,
Meyet Jordan,
Šot Petr,
Flaherty David W.,
Copéret Christophe
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202100672
Subject(s) - lewis acids and bases , catalysis , chemistry , formate , adsorption , pyridine , selectivity , inorganic chemistry , acid strength , metal , reactivity (psychology) , context (archaeology) , nanoparticle , medicinal chemistry , organic chemistry , materials science , nanotechnology , medicine , paleontology , zeolite , alternative medicine , pathology , biology
CH 3 OH formation rates in CO 2 hydrogenation on Cu‐based catalysts sensitively depend on the nature of the support and the presence of promoters. In this context, Cu nanoparticles supported on tailored supports (highly dispersed M on SiO 2 ; M=Ti, Zr, Hf, Nb, Ta) were prepared via surface organometallic chemistry, and their catalytic performance was systematically investigated for CO 2 hydrogenation to CH 3 OH. The presence of Lewis acid sites enhances CH 3 OH formation rate, likely originating from stabilization of formate and methoxy surface intermediates at the periphery of Cu nanoparticles, as evidenced by metrics of Lewis acid strength and detection of surface intermediates. The stabilization of surface intermediates depends on the strength of Lewis acid M sites, described by pyridine adsorption enthalpies and 13 C chemical shifts of ‐OCH 3 coordinated to M; these chemical shifts are demonstrated here to be a molecular descriptor for Lewis acid strength and reactivity in CO 2 hydrogenation.