Promotional Effects on the Catalytic Activity of Co-Fe Alloy Supported on Graphitic Carbon for CO₂ Hydrogenation

Starting from the reported activity of Co-Fe nanoparticles wrapped onto graphitic carbon (Co-Fe@C) as CO₂ hydrogenation catalysts, the present article studies the influence of a series of metallic (Pd, Ce, Ca, Ca, and Ce) and non-metallic (S in various percentages and S and alkali metals) elements as Co-Fe@C promoters. Pd at 0.5 wt % somewhat enhances CO₂ conversion and CH₄ selectivity, probably due to H₂ activation and spillover on Co-Fe. At similar concentrations, Ce does not influence CO₂ conversion but does diminish CO selectivity. A 25 wt % Fe excess increases the Fe-Co particle size and has a detrimental effect due to this large particle size. The presence of 25 wt % of Ca increases the CO₂ conversion and CH₄ selectivity remarkably, the effect being attributable to the CO₂ adsorption capacity and basicity of Ca. Sulfur at a concentration of 2.1% or higher acts as a strong poison, decreasing CO₂ conversion and shifting selectivity to CO. The combination of S and alkali metals as promoters maintain the CO selectivity of S but notably increase the CO₂ conversion. Overall, this study shows how promoters and poisons can alter the catalytic activity of Co/Fe@C catalysts, changing from CH₄ to CO. It is expected that further modulation of the activity of Co/Fe@C catalysts can serve to drive the activity and selectivity of these materials to any CO₂ hydrogenation products that are wanted.