Highly efficient CO ₂ hydrogenation to long-chain linear α-olefins <i>via</i> CO intermediate enrichment over Na/FeMn/ZrO ₂ catalysts

Although significant progress has been made in the oriented conversion of CO₂ to long-chain linear α-olefins (LAOs), cooperatively regulating C-O bond activation and C-C coupling <i>via</i> tailored catalyst microstructures remains a persistent challenge. Herein, a highly efficient Na/FeMn/ZrO₂ catalyst has been fabricated through a covalent anchoring strategy, which achieves a LAOs/C₄₊ selectivity of 68% and an O/P ratio of 5.1 in CO₂ hydrogenation to LAOs. There is a pronounced interaction between Fe species and MnCO₃ in Na/FeMn/ZrO₂ catalysts, which promotes the formation and stabilization of iron carbides. Meanwhile, Fe₅C₂-ZrO₂ interfaces possess strong adsorption capacity for CO intermediates, resulting in the accumulation of generated CO on the Fe₅C₂ active sites. The higher CO concentration on the Fe₅C₂-ZrO₂ interface is beneficial to the C-C coupling reaction, thereby significantly improving the production of high-value olefins. These results will provide a theoretical basis and guidance for developing efficient catalysts for the oriented conversion of CO₂ to LAOs.