Operando TEM study of a working copper catalyst during ethylene oxidation

Active catalysts are typically metastable, and their surface state depends on the gas-phase chemical potential and reaction kinetics. To gain relevant insights into structure-performance relationships, it is essential to investigate catalysts under their operational conditions. Here, we use operando TEM combining real-time observations with online mass spectrometry (MS) to study a Cu catalyst during ethylene oxidation. We identify three distinct regimes characterized by varying structures and states that show different selectivities with temperature, and elucidate the reaction pathways with the aid of theoretical calculations. Our findings reveal that quasi-static Cu2O at low temperatures is selective towards ethylene oxide (EO) and acetaldehyde (AcH) via an oxometallacycle (OMC) pathway. In the dynamic Cu0/Cu2O oscillation regime at medium temperatures, partially reduced and strained oxides decrease the activation energies associated with partial oxidation. At high temperatures, the catalyst is predominantly Cu0, partially covered by a monolayer Cu2O. While Cu0 is extremely efficient in dehydrogenation and eventual combustion, the monolayer oxide favors direct EO formation. These results challenge conclusions drawn from ultra-high vacuum studies that suggested metallic copper would be a selective epoxidation catalyst and highlight the need for operando study under realistic conditions.