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

来源：ACS Sustainable Chemistry & Engineering

发表年代：2022

作者：Qiang Nie, Jiaqi Si, Chao Meng, Tian Lan, Weidong Sun, Guofeng Zhao, Ye Liu, Yong Lu*

Abstract：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 molMA kgcat⁻¹ h⁻¹ is 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 Cu⁰ dehydrogenation, 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 Cu⁰ site to form MA.