H<sub>2</sub>O‐Built Proton Transfer Bridge Enhances Continuous Methane Oxidation to Methanol over Cu‐BEA Zeolite
Ruinian Xu, Ning Liu, Chengna Dai, Yan Li, Jie Zhang, Bin Wu, Gangqiang Yu, Biaohua Chen
Abstract
Abstract Direct oxidation of methane to methanol (DMTM) is a big challenge in C 1 chemistry. We present a continuous N 2 O‐DMTM investigation by simultaneously introducing 10 vol % H 2 O into the reaction system over Cu‐BEA zeolites. Combining a D 2 O isotopic tracer technique and ab initio molecular dynamics (AIMD) simulation, we for the first time demonstrate that the H 2 O molecules can participate in the reaction through a proton transfer route, wherein the H 2 O molecules can build a high‐speed proton transfer bridge between the generated moieties of CH 3 − and OH − over the evolved mono(μ‐oxo) dicopper ([Cu‐O‐Cu] 2+ ) active site, thereby pronouncedly boosting the CH 3 OH selectivity (3.1→71.6 %), productivity (16.8→242.9 μmol g cat −1 h −1 ) and long‐term reaction stability (10→70 h) relative to the scenario of absence of H 2 O. Unravelling the proton transfer of H 2 O over the dicopper [Cu‐O‐Cu] 2+ site would substantially contribute to highly efficient catalyst designs for the continuous DMTM.