C,CO and CO2 hydrogenation on cobalt foil model catalysts: evidence for the need of CoO reduction

The hydrogenation of C, CO, and CO₂ has been studied on polycrystalline cobalt foils using a combination of UHV studies and atmospheric pressure reactions in temperature range from 475 to 575 K at 101 kPa total pressure. The reactions produce mainly methane but with selectivities of 98, 80, and 99 wt% at 525 K for C, CO, and CO₂, respectively. In the C and CO₂ hydrogenation the rest is ethane, whereas in CO hydrogenation hydrocarbons up to C₄ were detected. The activation energies of methane formation are 57, 86, and 158 kJ/mol from C, CO, and CO₂, respectively. The partial pressure dependencies of the CO and CO₂ hydrogenation indicate roughly first order dependence on hydrogen pressure (1.5 and 0.9), negative first order on CO (–0.75) and zero order on CO₂ (–0.05). Post reaction spectroscopy revealed carbon deposition from CO and oxygen deposition from CO₂ on the surface above 540 K. The reduction of cobalt oxide formed after dissociation of C-O bonds on the surface is proposed to be the rate limiting step in CO and CO₂ hydrogenation.