Carbon　monoxide　hydrogenation　catalyzed　by　silica-supported　cobalt　catalysts　prepared　from　dicobalt　octacarbonyl　[Co2(CO)8]　yields　alcohols　with　greater　than　20%　selectivity　accompanied　by　80%　hydrocarbons.　Modification　by　alkaline　earth　metal　oxides　enhanced　the　formation　of　alcohols　in　the　order:　Mg　≪　Ca　<　Sr　≤　Ba.　A　maximum　selectivity　as　high　as　60%　for　oxygenated　compounds　was　observed　at　a　Ba:Co　mole　ratio　of　1.5　-　2.2.　Extended　X-ray　absorption　fine　structure　(EXAFS)　and　X-ray　diffraction　(XRD)　studies　of　these　catalysts　show　that　Co2(CO)2　supported　on　SiO2　changes　to　Co4(CO)12　in　vacuo,　and　then　to　highly　dispersed　cobalt　metal　when　heated　in　a　stream　of　hydrogen　at　673　K.　High-pressure　in　situ　FT-IR　studies　show　that　the　formation　of　alcohols　may　be　related　to　the　presence　of　bridged-CO　species　on　the　surface　of　the　catalysts.　©　1989.