Operando Near-Ambient Pressure X-ray Photoelectron Spectroscopy Study of the CO Oxidation Reaction on the Oxide/Metal Model Catalyst ZnO/Pt(111)

The identification of the active sites in heterogeneous catalysis is important for a mechanistic understanding of the structure-reactivity relationship. Among others, the oxide/metal boundaries are expected to contain the active sites in various catalytic reactions. To reveal their nature and their chemical evolution under reaction conditions, the catalytic role of an oxide/metal system consisting of well-ordered ZnO nanoislands grown on Pt(111) in low-temperature CO oxidation was studied by near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) in operando conditions, and additionally by ultra-high vacuum scanning tunneling microscopy. To illustrate the special role played by the oxide/metal boundaries, a systematic comparative study of ZnO/Pt(111) with the pristine Pt(111) surface was undertaken. The regimes where mass transfer limitation starts to occur were identified using NAP-XPS and mass spectrometry measurements in combination, allowing a sound discussion on the relation between steady-state molar fractions of reactants/product and surface reactivity. Via the measurement of the steady-state CO₂ molar fraction, we observed that the CO oxidation reaction rate over the ZnO/Pt(111) system is superior to that over Pt(111) in a temperature range extending to 410 K. The pivotal, albeit unexpected, role of ZnO-bound hydroxyls was clearly highlighted by the observation of the chemical signature of the CO + OH associative reaction at the ZnO/Pt boundaries. The carboxyl formed at low temperature (410 K) can be the intermediate species in the CO oxidation reaction, the OHs at the Pt/ZnO boundary being the cocatalyst, which explains the synergistic effect of ZnO and Pt. However, the species formed at higher temperature (from 445 K) are formates that would essentially be spectators.