Characterization of oxide surfaces and zeolites by carbon monoxide as an IR probe molecule

The review is a summary and analysis of the data characterizing CO adsorption on surface cationic sites of oxides including supported materials and microporous and mesoporous materials. The contributions of various types of CO bonding to the IR frequency shifts of carbon-bonded molecules are analyzed, namely, the increase of the CO stretching frequency in cases of electrostatic and σ bonding and the decrease of the frequency with π bonding. Polycarbonyls, bridging CO, oxygen-bonded CO, and tilted CO are also considered. The main part of the review is a collection of the experimental results characterizing carbonyls of individual metal ions. The spectral behavior of CO bonded to metal atoms is also assessed in the cases when the metal ions are easily reduced to metal (Cu, Ag, Au, Pd, or Pt) or cationic carbonyls are produced after CO adsorption on supported metals (Ru, Rh, Ir, and Os). The interaction of CO with surface OH groups is also considered. It is demonstrated that IR spectroscopy of adsorbed CO is an efficient methodology to characterize cationic surface sites in terms of their nature, oxidation states, coordination environment and coordinative unsaturation, and location at faces, edges or corners of microcrystallites. When applied to materials with surface hydroxyl groups CO undergoes hydrogen bonding and information can be collected on the proton acid strength. © 2002.