H2O‐Built Proton Transfer Bridge Enhances Continuous Methane Oxidation to Methanol over Cu‐BEA Zeolite

Direct oxidation of methane to methanol (DMTM) is a big challenge in C1 chemistry. We present a continuous N2O‐DMTM investigation by simultaneously introducing 10 vol % H2O into the reaction system over Cu‐BEA zeolites. Combining a D2O isotopic tracer technique and ab initio molecular dynamics (AIMD) simulation, we for the first time demonstrate that the H2O molecules can participate in the reaction through a proton transfer route, wherein the H2O molecules can build a high‐speed proton transfer bridge between the generated moieties of CH3− and OH− over the evolved mono(μ‐oxo) dicopper ([Cu‐O‐Cu]2+) active site, thereby pronouncedly boosting the CH3OH selectivity (3.1→71.6 %), productivity (16.8→242.9 μmol gcat−1 h−1) and long‐term reaction stability (10→70 h) relative to the scenario of absence of H2O. Unravelling the proton transfer of H2O over the dicopper [Cu‐O‐Cu]2+ site would substantially contribute to highly efficient catalyst designs for the continuous DMTM.