Cu/Sn-β Catalyst Enabling the One-Step Synthesis of Methyl Acetate from Methanol Alone via Dehydrogenation Coupling

Methyl acetate (MA) can be directly synthesized via a methanol dehydrocoupling reaction, which is attractive but urgently calls for a groundbreaking catalyst. Herein, we report a Cu/Sn-β system with Sn-Cu synergistic catalysis, enabling the one-step MA synthesis from methanol alone. Over the 3Cu/Sn-β-30 (Si/Sn molar ratio of 33, Cu loading of 3 wt %), a maximum MA space-Time yield of 1.4 mol_MAkg_cat^-1h^-1is obtained with 4.1% methanol conversion and 56.4% MA selectivity at 220 °C. Electron transfer from Cu species to framework-confined Sn occurs and thus increases and stabilizes Cu⁺sites. Lewis-Acidic Sn(framework)/Cu⁺pairs, with the assistance of Cu⁰dehydrogenation, can transform a methanol molecule into bridged-Adsorbed CH₂O*. The C-C coupling of CH₂O∗ with CH₃O∗ on another Sn site proceeds to form CH₃CHO∗ by leaving H on Cu⁺and O (C-O bond cleavage of CH₃O*) on that Sn site. The CH₃CHO∗ subsequently condenses with CH₃O∗ adsorbed on the Cu⁰site to form MA.