Theoretical Insights into the Formation Mechanism of Methane, Ethylene and Methanol in Fischer‐Tropsch Synthesis at Co₂C Surfaces

Abstract

Fischer‐Tropsch synthesis (FTS) is an attractive opportunity to prepare fuels and chemicals, avoiding fossil resources exploration. Co2C was recently demonstrated to exhibit outstanding properties in Fischer‐Tropsch to olefins (FTO) reaction, inhibiting methane formation. However, the exact mechanisms have not been entirely revealed yet. Here we are proposing a study combining DFT calculations and microkinetic modelling (MKM) in order to unveil the dominant reaction pathways of three products of interest in FTS, namely methane, ethylene, and methanol, over (020), (101) and (111) facets of Co2C. We found methane and ethylene share the same determining states, being responsible for the competition between the two species. Since our MKM gives results suggesting the surface is fully covered with CO at the steady‐state, we expect that including adsorbate‐adsorbate interactions both in DFT calculations and MKM simulations would be important in the future studies of FTS over Co2C surfaces.

Promoting jet fuel production by utilizing a Ru-doped Co-based catalyst of Ru-Co@C(Z-d)@Void@CeO2 in Fischer Tropsch synthesis

“…Hence, it was predicted that the selectivity towards jet fuel (C 8 –C 16 ) at the RNC catalyst would be greater in comparison to the FTS products, in particular, liquid fuels. Besides, from a thermodynamic point of view, methane is the most probable product in FTS, which is according to the reports by Davies et al and Zaffran et al , 47,48 and the Δ G results that were extracted from MD computations confirm this. The MD simulation results illustrate that Δ G for methane formation, 0.29 and 0.26 kcal mol −1 in NC and RNC catalysts, respectively, have the lowest values and Ru boosts its formation.…”

Visualization of the Active Sites of Zinc–Chromium Oxides and the CO/H2 Activation Mechanism in Direct Syngas Conversion

“…Fu et al theoretically predicted a higher concentration of CH 2 * than CH* and CH 3 * over the ZnO surface . Zaffran and Yang reported a lowest energy barrier for CH 2 –CH 2 coupling among CH x –CH x ( x = 0–3) couplings over Co 2 C . Ohta et al showed ready coupling of two ground-state methylene without a barrier …”

A Critical Review of the Sustainable Production and Application of Methanol as a Biochemical and Bioenergy Carrier

“…Increasing reaction temperature decreased methanol selectivity while increasing the ethanol content. Zaffran et al [67] reported the formation mechanism of methanol in FTS at Co 2 C surfaces using combined density functional theory and microkinetic modeling. Density functional theory modeling was employed for vibrational calculations, and it suggests that (101) and (111) facets are more favorable to methanol formation.…”