CO₂ hydrogenation to chemicals and fuels has the potential to alleviate CO₂ emissions and displace fossil resources simultaneously via consecutive RWGS and FTS reactions, also known as CO₂-FTS. As Fe-based catalysts are active and selective for both reactions, their bifunctionality requires a delicate balance between the RWGS and FTS. In this work, we investigated the thermodynamic constraints of RWGS and CO₂-FTS, the influence of CO₂ conversion on selectivity and the influence of Fe nanoparticle size within the range of 4.7 to 10.3 nm. An inert carbon support was selected to rule out metal-support interaction and promoting effects of the support. Catalytic performance was evaluated at 300 °C, 11 bar, H₂/CO₂/Ar = 3/1/1, 600 to 72000 mL·g_cat^-1·h^-1. At a CO₂ conversion level below RWGS equilibrium conversion of 23 %, RWGS was found to be the primary and dominant reaction. No primary Sabatier reaction was observed. At higher CO₂ conversion till the CO₂-FTS threshold of 42 %, the secondary FTS reaction became dominant. Notably, a non-linear relation between CO₂ conversion and CO selectivity was discovered. Comparing two catalysts with identical 5 wt% Fe loading but different average Fe nanoparticle size (6.6 and 8.4 nm), the 8.4 nm Fe catalyst was at least two times more active than the 6.6 nm Fe catalyst. In situ Mössbauer spectroscopy suggested a positive correlation between particle size, carburization and selectivity towards long-chain hydrocarbons. For these potassium-promoted carbon-supported Fe-based catalysts, nanoparticles of at least 8 nm are required for the formation of Fe carbides and improved reactivity.

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The attachment of colloidal iron‐oxide nanoparticles (designated Fe‐NPs) to pristine and surface‐oxidized carbon nanotubes (CNTs and CNT‐Ox, respectively) was investigated. The loadings of Fe‐NPs (size 7 nm) on the CNT and CNT‐Ox supports amounted to 3.4 and 2.3 wt. %, respectively; the difference was attributed to weaker van der Waals interactions between the colloidal Fe‐NPs and the surface of CNT‐Ox. Fischer–Tropsch to olefins (FTO) synthesis was performed to investigate the impact of support functionalization on catalyst performance. Weak interactions between the Fe‐NPs and the CNT‐Ox support facilitated particle growth and led to substantial deactivation of the Fe/CNT‐Ox catalysts. The addition of promoters (Na+S) to Fe/CNT resulted in remarkable activity, selectivity to lower olefins, and stability, making colloidal iron nanoparticles on pristine CNTs a suitable catalyst for FTO synthesis.@en

The fundamentals of structure sensitivity and promoter effects in the Fischer–Tropsch synthesis of lower olefins have been studied. Steady state isotopic transient kinetic analysis, switching 12CO to 13CO and H2 to D2, was used to provide coverages and residence times for reactive species on supported iron carbide particles of 2–7 nm with and without promoters (Na + S). CO coverages appeared to be too low to be measured, suggesting dissociative adsorption of CO. Fitting of CH4 response curves revealed the presence of parallel side-pools of reacting carbon. CHx coverages decreased with increasing particle size, and this is rationalized by smaller particles having a higher number of highly active low coordination sites. It was also established that the turnover frequency increased with CHx coverage. To calculate H coverages, new equations were derived to fit HD response curves, again leading to a parallel side-pool model. The H coverages appeared to be lower for bigger particles. The H coverage was suppressed upon addition of promoters in line with lower methane selectivity and higher lower olefin selectivity. Density functional theory (DFT) was applied on H adsorption for a fundamental understanding of this promoter effect on the selectivities, with a special focus on counterion effects. Na2S is a better promoter than Na2O due to both a larger negative charge donation and a more effective binding configuration. On the unpromoted Fe5C2 (111) surface, H atoms bind preferably on C after dissociation on Fe. On Na2S-promoted Fe5C2 surfaces, adsorption on carbon sites weakens, and adsorption on iron sites strengthens, which fits with lower H coverage, less CH4 formation, and more olefin formation.@en

The Fischer−Tropsch Synthesis converts synthesis gas from alternative carbon resources, including natural gas, coal, and biomass, to hydrocarbons used as fuels or chemicals. In particular, iron-based catalysts at elevated temperatures favor the selective production of C2−C4 olefins, which are important building blocks for the chemical industry. Bulk iron catalysts (with promoters) were conventionally used, but these deactivate due to either phase transformation or carbon deposition resulting in disintegration of the catalyst particles. For supported iron catalysts, iron particle growth may result in loss of catalytic activity over time. In this work, the effects of promoters and particle size on the stability of supported iron nanoparticles (initial sizes of 3−9 nm) were investigated at industrially relevant conditions (340 °C, 20 bar, H2/CO = 1). Upon addition of sodium and sulfur promoters to iron nanoparticles supported on carbon nanofibers, initial catalytic activities were high, but substantial deactivation was observed over a period of 100 h. In situ Mössbauer spectroscopy revealed that after 20 h time-on-stream, promoted catalysts attained 100% carbidization, whereas for unpromoted catalysts, this was around 25%. In situ carbon deposition studies were carried out using a tapered element oscillating microbalance (TEOM). No carbon laydown was detected for the unpromoted catalysts, whereas for promoted catalysts, carbon deposition occurred mainly over the first 4 h and thus did not play a pivotal role in deactivation over 100 h. Instead, the loss of catalytic activity coincided with the increase in Fe particle size to 20−50 nm, thereby supporting the proposal that the loss of active Fe surface area was the main cause of deactivation.@en

The Fe-catalyzed Fischer–Tropsch to olefins (FTO) synthesis is a non-oil-based route for the production of C2–C4 olefins. The understanding of the interplay between the catalytically active species, promoters, and support materials has improved over the last years, but the nanostructures of the various supports used are often not comparable. Several ordered mesoporous materials with a comparable pore size and pore symmetry are used as model supports for Fe-based FTO catalysts. Ammonium iron citrate is used as the Fe source for all supports, and Na and S are added as promoters. The formation of catalytically active iron carbide species is suppressed within the strongly interacting mesoporous silica support, but the weakly interacting carbon and silicon carbide supports yield highly active FTO catalysts. Carbon-supported catalysts show a high selectivity towards lower olefins, low methane production, and stable operation for up to 140 h under industrially relevant FTO conditions.@en