WATER-ADSORPTION AND COADSORPTION WITH POTASSIUM ON GRAPHITE(0001)

Water and water coadsorbed with potassium on the basal plane of graphite were studied with thermal desorption spectroscopy (TDS) and high-resolution electron energy loss spectroscopy (HREELS) in the temperature range 85-900 K. Water alone adsorbs nondissociatively on the clean graphite surface at 85 K, forming hydrogen bonded aggregates. Its structure depends both on the coverage and on substrate temperature. With increasing coverage at 85 K(0.5-1.0 monolayer (ML)) the libration mode at similar to 86 meV shows a rapid upward shift, indicating a phase transition from a 2D to a 3D structure. The transition can also be induced by annealing the low coverage structure. Water coadsorption with potassium is nonreactive or reactive, depending on temperature and potassium coverage. The nonreactive coadsorption at T-s = 85 K occurs only below a critical potassium coverage of BK less than or equal to 0.3 ML. It is characterized by substantial symmetry changes of the adsorbed water molecules, compared to the pure water adsorption, and is attributed to formation of hydrated-ion species on the surface. The surface solvation number at the lowest K coverage is three to four H2O molecules per potassium atom. K and H2O react at submonolayer coverages at 120-160 K to form surface KOH, KH, KxOy, and volatile products. The surface species gradually transforms/decomposes at elevated temperatures (200-500 K) to first form potassium-oxygen complexes that then serve as precursors to graphite oxidation to CO2 at similar to 750 K.