Selectivity Control by Relay Catalysis in CO and CO2 Hydrogenation to Multicarbon Compounds

ConspectusThe hydrogenative conversion of both CO and CO₂ into high-value multicarbon (C₂₊) compounds, such as olefins, aromatic hydrocarbons, ethanol, and liquid fuels, has attracted much recent attention. The hydrogenation of CO is related to the chemical utilization of various carbon resources including shale gas, biomass, coal, and carbon-containing wastes via syngas (a mixture of H₂ and CO), while the hydrogenation of CO₂ by green H₂ to chemicals and liquid fuels would contribute to recycling CO₂ for carbon neutrality. The state-of-the-art technologies for the hydrogenation of CO/CO₂ to C₂₊ compounds primarily rely on a direct route via Fischer-Tropsch (FT) synthesis and an indirect route via two methanol-mediated processes, i.e., methanol synthesis from CO/CO₂ and methanol to C₂₊ compounds. The direct route would be more energy- and cost-efficient owing to the reduced operation units, but the product selectivity of the direct route via FT synthesis is limited by the Anderson-Schulz-Flory (ASF) distribution. Selectivity control for the direct hydrogenation of CO/CO₂ to a high-value C₂₊ compound is one of the most challenging goals in the field of C1 chemistry, i.e., chemistry for the transformation of one-carbon (C1) molecules.We have developed a relay-catalysis strategy to solve the selectivity challenge arising from the complicated reaction network in the hydrogenation of CO/CO₂ to C₂₊ compounds involving multiple intermediates and reaction channels, which inevitably lead to side reactions and byproducts over a conventional heterogeneous catalyst. The core of relay catalysis is to design a single tandem-reaction channel, which can direct the reaction to the target product controllably, by choosing appropriate intermediates (or intermediate products) and reaction steps connecting these intermediates, and arranging optimized yet matched catalysts to implement these steps like a relay. This Account showcases representative relay-catalysis systems developed by our group in the past decade for the synthesis of liquid fuels, lower (C₂-C₄) olefins, aromatics, and C₂₊ oxygenates from CO/CO₂ with selectivity breaking the limitation of conventional catalysts. These relay systems are typically composed of a metal or metal oxide for CO/CO₂/H₂ activation and a zeolite for C-C coupling or reconstruction, as well as a third or even a fourth catalyst component with other functions if necessary. The mechanisms for the activation of H₂ and CO/CO₂ on metal oxides, which are distinct from that on the conventional transition or noble metal surfaces, are discussed with emphasis on the role of oxygen vacancies. Zeolites catalyze the conversion of intermediates (including hydrocracking/isomerization of heavier hydrocarbons, methanol-to-hydrocarbon reactions, and carbonylation of methanol/dimethyl ether) in the relay system, and the selectivity is mainly controlled by the Brønsted acidity and the shape-selectivity or the confinement effect of zeolites. We demonstrate that the thermodynamic/kinetic matching of the relay steps, the proximity and spatial arrangement of the catalyst components, and the transportation of intermediates/products in sequence are the key issues guiding the selection of each catalyst component and the construction of an efficient relay-catalysis system. Our methodology would also be useful for the transformation of other C1 molecules via controlled C-C coupling, inspiring more efforts toward precision catalysis.