Relay Catalysis in Selective Transformations of C1 into C2+ Molecules

Abstract

C₁ molecules (e.g., CO, CO₂, CH₄, and CH₃OH) are pivotal platforms for synthesizing fuels and chemicals from nonpetroleum resources. However, the selective activation of C–O and C–H bonds, precise control of C–C formation, and preservation of functional groups are tough challenges in catalysis. Traditional routes like Fischer–Tropsch synthesis and methanol conversion often suffer from limited selectivity or require multiple processing steps. By using a relay catalysis strategy, a series of bifunctional or multifunctional catalysts composed of metals and acidic zeolites has been developed for the selective hydrogenation of CO to hydrocarbon fuels. Recently, this methodology has also been successfully applied for the precise synthesis of high-value chemicals, such as lower olefins, aromatic hydrocarbons, and higher alcohols from not only CO but also CO₂ and CH₄. The core of relay catalysis is integrating sequential reactions within one multifunctional catalyst or in a single reactor and providing controllable product selectivity. This review will analyze recent advances in C₁ chemistry using relay catalysis as well as tandem catalysis for the selective synthesis of hydrocarbon fuels and chemicals. We also detail the design principles of relay pathways, outlining the strengths, applications, and future potential of relay catalysis in C1 chemistry.