Materials containing organic-inorganic interfaces usually display a combination of molecular and solid-state properties, which are of interest for applications ranging from chemical sensing to microelectronics and catalysis. Thiols--organic compounds carrying a SH group--are widely used to anchor organic layers to gold surfaces, because gold is catalytically sufficiently active to replace relatively weak S-H bonds with Au-S bonds, yet too inert to attack C-C and C-H bonds in the organic layer. But although several methods of functionalizing the surfaces of semiconductors, oxides and metals are known, it remains difficult to attach a wide range of more complex organic species. Organic layers could, in principle, be formed on the surfaces of metals that are capable of inserting into strong bonds, but such surfaces catalyse the decomposition of organic layers at temperatures above 400 to 600 K, through progressive C-H and C-C bond breaking. Here we report that cycloketones adsorbed on molybdenum carbide, a material known to catalyse a variety of hydrocarbon conversion reactions, transform into surface-bound alkylidenes stable to above 900 K. We expect that this chemistry can be used to create a wide range of exceptionally stable organic layers on molybdenum carbide.

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Atomic nitrogen and oxygen were deposited on -Mo 2 C through dissociative adsorption of NO. Reflectance absorbance infrared spectroscopy (RAIRS), thermal desorption, and synchrotron X-ray photoelectron spectroscopy (XPS) measurements were used to investigate the interplay between atomic nitrogen, carbon, and oxygen in the 400-1250 K region. The combination of the high resolution and high surface sensitivity offered by the synchrotron XPS technique was used to show that atomic nitrogen displaces interstitial carbon onto the carbide surface. Thermal desorption measurements show that the burnoff of the displaced carbon occurs at approximately 890 K. The incorporation of nitrogen into interstitial sites inhibits oxygen dissolution into the bulk. RAIRS spectroscopy was used to identify surface oxo, terminal oxygen, species formed from O 2 and NO on -Mo 2 C.

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