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

• DOI: 10.1002/anie.202301920
• Publication Date: 2023-04-19T17:09:09Z
• Authors: Ali M. Abdel‐Mageed; Bunyarat Rungtawe...; Sarawoot Impeng; Joachim Bansmann; Jabor Rabeah; Shilong Chen; Thomas Häring; Supawadee Namuangrak; Kajornsak Faungna...; Angelika Brückner; R. Jürgen Behm
• Keywords: Catalytic cycle; Reaction rate; Rate-determining step; Reaction intermediate; Oxidation state; Kinetic isotope effect

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