How Rh surface breaks CO2 molecules under ambient pressure.

Utilization of carbon dioxide (CO₂) molecules leads to increased interest in the sustainable synthesis of methane (CH₄) or methanol (CH₃OH). The representative reaction intermediate consisting of a carbonyl or formate group determines yields of the fuel source during catalytic reactions. However, their selective initial surface reaction processes have been assumed without a fundamental understanding at the molecular level. Here, we report direct observations of spontaneous CO₂ dissociation over the model rhodium (Rh) catalyst at 0.1 mbar CO₂. The linear geometry of CO₂ gas molecules turns into a chemically active bent-structure at the interface, which allows non-uniform charge transfers between chemisorbed CO₂ and surface Rh atoms. By combining scanning tunneling microscopy, X-ray photoelectron spectroscopy at near-ambient pressure, and computational calculations, we reveal strong evidence for chemical bond cleavage of O‒CO* with ordered intermediates structure formation of (2 × 2)-CO on an atomically flat Rh(111) surface at room temperature. Direct observation of carbon dioxide dissociation provides an origin of catalytic conversion for industrial chemical reactions. Here, the authors reveal their molecular interactions on the rhodium catalyst at near-ambient pressure by interface science techniques and computational calculations. [ABSTRACT FROM AUTHOR]