Relay Catalysis for Highly Selective Conversion of Methanol to Ethylene in Syngas

The precise C–C coupling is a challenging goal in C1 chemistry. The conversion of methanol, a cheap and easily available C1 feedstock, into value-added and largely demanded olefins has been playing a game-changing role in the production of olefins. The current methanol-to-olefin (MTO) process, however, suffers from limited selectivity to a specific olefin. Here, we present a relay-catalysis route for the high-selective conversion of methanol to ethylene in syngas (H₂/CO) typically used for methanol synthesis. A bifunctional catalyst composed of selectively dealuminated H-MOR zeolite and ZnO–TiO₂, which implemented methanol carbonylation with CO to acetic acid and selective acetic acid hydrogenation to ethylene in tandem, offered ethylene selectivity of 85% at complete methanol conversion at 583 K. The selective removal of Brønsted acid sites in the 12-membered ring channel of H-MOR favors the selectivity of acetic acid in CH₃OH carbonylation. The high capabilities of ZnO–TiO₂ in the adsorption of acetic acid and the activation of H₂ play key roles in selective hydrogenation of acetic acid to ethylene. Our work provides a promising relay-catalysis strategy for precise C–C coupling of C1 to C2 molecules.