Methylene migration and coupling on a non-reducible metal oxide: The reaction of dichloromethane on stoichiometric alpha -Cr sub(2)O sub(3)(0001)

The reaction of CH sub(2)Cl sub(2) over the nearly-stoichiometric alpha -Cr sub(2)O sub(3)(0001) surface produces gas phase ethylene, methane and surface chlorine adatoms. The reaction is initiated by the decomposition of CH sub(2)Cl sub(2) into surface methylene and chlorine. Photoemission indicates that surface cations are the preferred binding sites for both methylene and chlorine adatoms. Two reaction channels are observed for methylene coupling to ethylene in temperature-programmed desorption (TPD). A desorption-limited, low-temperature route is attributed to two methylenes bound at a single site. The majority of ethylene is produced by a reaction-limited process involving surface migration (diffusion) of methylene as the rate-limiting step. DFT calculations indicate the surface diffusion mechanism is mediated by surface oxygen anions. The source of hydrogen for methane formation is adsorbed background water. Chlorine adatoms produced by the dissociation of CH sub(2)Cl sub(2) deactivate the surface by simple site-blocking of surface Cr super(3+) sites. A comparison of experiment and theory shows that DFT provides a better description of the surface chemistry of the carbene intermediate than DFT+U using reported parameters for a best representation of the bulk electronic properties of alpha -Cr sub(2)O sub(3).