Effects of Sodium on the Catalytic Performance of CoMn Catalysts for Fischer–Tropsch to Olefin Reactions

The effects of a sodium (Na) promoter on the catalytic performance of cobalt-manganese (CoMn) catalysts for Fischer–Tropsch to olefin (FTO) reactions were investigated. For the sample without Na, Co0 was found to be the active phase for the traditional Co-based Fischer–Tropsch reaction with low CO2 selectivity. The olefin/paraffin (O/P) ratio was found to be low with a C2–4= selectivity of only 15.4 C%. However, with the addition of Na, cobalt carbide (Co2C) quadrangular nanoprisms with the (101) and (020) facets exposed were formed. The Co2C nanoprisms displayed a high C2–4= selectivity (54.2 C%) as well as a low methane selectivity (5.9 C%) under mild reaction conditions. The O/P ratio for C2–4 reached 23.9, and the product distribution deviated greatly from the classical Anderson–Schulz–Flory (ASF) distribution. Co2C nanoprisms were considered to be an effective FTO active phase with strong facet effects. The Na promoter played a key role in the evolution of the FTO catalysts. The addition of Na, which acted as an electronic donor to cobalt, resulted in stronger CO adsorption and enhanced CO dissociation, which also benefited the formation of the Co2C phase, leading to highly stable and active catalysts. The effects of other alkali promoters were also studied, and only the K promoter had an effect similar to that of Na on the CoMn catalysts for promoting the FTO reaction.