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Oil has long been the dominant feedstock for producing fuels and chemicals, but coal, natural gas and biomass are increasingly explored alternatives1–3. Their conversion first generates syngas, a mixture of CO and H2, which is then processed further using Fischer–Tropsch (FT) chemistry. However, although commercial FT technology for fuel production is established, using it to access valuable chemicals remains challenging. A case in point is linear α-olefins (LAOs), which are important chemical intermediates obtained by ethylene oligomerization at present4–8. The commercial high-temperature FT process and the FT-to-olefin process under development at present both convert syngas directly to LAOs, but also generate much CO2 waste that leads to a low carbon utilization efficiency9–14. The efficiency is further compromised by substantially fewer of the converted carbon atoms ending up as valuable C5–C10 LAOs than are found in the C2–C4 olefins that dominate the product mixtures9–14. Here we show that the use of the original phase-pure χ-iron carbide can minimize these syngas conversion problems: tailored and optimized for the process of FT to LAOs, this catalyst exhibits an activity at 290 °C that is 1–2 orders higher than dedicated FT-to-olefin catalysts can achieve above 320 °C (refs. 12–15), is stable for 200 h, and produces desired C2–C10 LAOs and unwanted CO2 with carbon-based selectivities of 51% and 9% under industrially relevant conditions. This higher catalytic performance, persisting over a wide temperature range (250–320 °C), demonstrates the potential of the system for developing a practically relevant technology.When used in its phase-pure form, iron carbide catalyses the conversion of syngas to linear α-olefins with high activity and selectivity under industrially relevant conditions. [ABSTRACT FROM AUTHOR]

Structure sensitivity in heterogeneous catalysis dictates the overall activity and selectivity of a catalyst whose origins lie in the atomic configurations of the active sites. We explored the influence of the active site geometry on the dissociation activity of CO by investigating the electronic structure of CO adsorbed on 12 different Co sites and correlating its electronic structure features to the corresponding C-O dissociation barrier. By including the electronic structure analyses of CO adsorbed on step-edge sites, we expand upon the current models that primarily pertain to flat sites. The most important descriptors for activation of the C-O bond are the decrease in electron density in CO's 1π orbital , the occupation of 2π anti-bonding orbitals and the redistribution of electrons in the 3σ orbital. The enhanced weakening of the C-O bond that occurs when CO adsorbs on sites with a step-edge motif as compared to flat sites is caused by a distancing of the 1π orbital with respect to Co. This distancing reduces the electron-electron repulsion with the Co d -band. These results deepen our understanding of the electronic phenomena that enable the breaking of a molecular bond on a metal surface., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Developing highly active cluster catalysts for the bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is significant for future renewable energy technology. Here, we employ first-principles calculations combined with a genetic algorithm to explore the activity trends of transition metal clusters supported on C 2 N. Our results indicate that the supported clusters, as bifunctional catalysts for the OER and the ORR, may outperform single-atom catalysts. In particular, the C 2 N-supported Ag 6 cluster exhibits outstanding bifunctional activity with low overpotentials. Mechanistic analysis indicates that the activity of the cluster is related to the number of atoms in the active site as well as the interaction between the intermediate and the cluster. Accordingly, we identify a descriptor that links the intrinsic properties of the clusters with the activity of both the OER and the ORR. This work provides guidelines and strategies for the rational design of highly efficient bifunctional cluster catalysts.