Zeolite‐Catalyzed Carbonylation of Dimethyl Ether

Syngas to ethanol, consisting of dimethyl ether (DME) carbonylation to methyl acetate (MA) over zeolites and MA hydrogenation to ethanol on copper catalysts, has been extensively investigated as new process in C1 chemistry. DME carbonylation over zeolites, as the key step, is featured by the high reaction efficiency and the promising industrial application. Continuous efforts have been made on improving the activity and stability of the catalysts, including both zeolites and metal-doped zeolites. From a mechanistic point of view, DME carbonylation to MA, involving the formation of CC bond, is achieved via CO insertion into DME within the 8-membered ring (8-MR) pores of zeolites, typically HMOR and HZSM-35. The unique geometric configuration of the 8-MR pore endowed the formation of the key intermediate (acetyl, CH 3 CO*), possibly by a spatial confinement of the transition state during CO insertion into the surface O-CH 3 group. Accordingly, populating acid sites and engineering pore structure of the zeolites, along with reaction kinetics and theoretical calculations, have been adopted to promote the overall reaction performance.