Revisiting the Impact of CO₂ on the Activity and Selectivity of Cobalt-Based Catalysts for Fischer–Tropsch Synthesis Under Industrial-Relevant Conditions

Understanding the impact of CO₂ on cobalt-based Fischer–Tropsch synthesis catalysts is critical for optimizing system efficiency, particularly in scenarios employing solid oxide electrolysis cells for syngas production, given the inevitable incorporation of CO₂ into syngas during the SOEC co-electrolysis process. In this study, we conducted comparative experiments using a Co-Re/γ-Al₂O₃ catalyst in a fixed-bed reactor under industrial conditions (2 MPa, 493 K, GHSV = 6000–8000 Ncm³/g_cat/h), varying the feed gas compositions of H₂, CO, CO₂, and Ar. At an H₂/CO ratio of 2, the addition of CO₂ led to a progressive decline in catalyst performance, attributed to carbon deposition and cobalt carbide formation, as confirmed by Raman spectroscopy, XRD analyses, and TPH. Furthermore, DFT calculations combined with ab initio atomistic thermodynamics (AIAT) were performed to gain molecular insights into the loss of catalyst activity arising from multiple factors, including (sub)surface carbon derived from CO or CO₂, polymeric carbon, and carbide formation.