Unveiling the CO Oxidation Mechanism over a Molecularly Defined Copper Single‐Atom Catalyst Supported on a Metal–Organic Framework

Catalytic cycle Reaction rate Rate-determining step Reaction intermediate Oxidation state Kinetic isotope effect
DOI: 10.1002/anie.202301920 Publication Date: 2023-04-19T17:09:09Z
ABSTRACT
Elucidating the reaction mechanism in heterogeneous catalysis is critically important for catalyst development, yet remains challenging because of often unclear nature active sites. Using a molecularly defined copper single-atom supported by UiO-66 metal-organic framework (Cu/UiO-66) allows detailed mechanistic elucidation CO oxidation reaction. Based on combination situ/operando spectroscopies, kinetic measurements including isotope effects, and density-functional-theory-based calculations, we identified site, intermediates, transition states dominant cycle as well changes oxidation/spin state during The involves continuous reactive dissociation adsorbed O2 , O2,ad with COad leading to formation an O atom connecting Cu center neighboring Zr4+ ion rate limiting step. This removed second activated
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