Computational and experimental insights into reactive forms of oxygen species on dynamic Ag surfaces under ethylene epoxidation conditions

The partial oxidation of ethylene to ethylene oxide (EO) proceeds over supported Ag particles. Adsorption of molecular oxygen upon Ag forms the reactive oxygen species responsible for both epoxidation and combustion reactions, however, the catalyst surface structure and the molecular structure and identity of the reactive oxygen species present remain debated despite past use of appropriate forms of in situ spectroscopy. Specifically, there is no consensus for the molecular origin of widely reported Raman features that appear on contact with only O₂ or in reactant mixtures of C₂H₄ and O₂ at pressures and temperatures relevant for the industrial process, in part, due to the lack of concerted ab initio studies that compute vibrational frequencies for oxygen-containing Ag surfaces. Here, we elucidate the molecular structure of the catalyst surface and reactive oxygen species by coordinating spectral deconvolution of transient and steady-state surface-enhanced Raman spectroscopy of Ag catalysts exposed to oxygen (2 – 101 kPa O₂, 523 – 673 K) and mixtures of oxygen and ethylene (2 – 101 kPa O₂, 0.5 – 9.8 kPa C₂H₄, 523 K) with ab initio thermodynamic modeling and vibrational frequency calculations. These comparisons suggest that during EO catalysis reconstructed surface oxides form and partially or completely encase metallic Ag particles. Raman features near 600 cm⁻¹ that persist in O₂ or cofed C₂H₄ represent O–Ag–O structural motifs that form only on surface oxides and high oxygen-coverage reconstructed Ag_xO_y surfaces. We assign features centered near 810 – 840 cm⁻¹ and at higher frequencies, which are ubiquitous throughout the literature, to dioxygen complexes partially embedded within an oxide-like overlayer that forms during exposure either to O₂ or during steady-state epoxidations. Taken together our results implicate the presence of a combination of monatomic and diatomic surface oxygen species, which emerge with appreciable quantities of subsurface oxygen at temperatures and O₂ pressures representative of EO catalysis.