2D spatial structure-favored, tandem catalysis-boosted direct transformation of methane to methanol over Cu-FER

Abstract

The direct transformation of methane into methanol (DMTM) remains a significant challenge of C1 chemistry. Herein, we investigate continuous N₂O-DMTM over Cu-FER zeolite. A two-dimensional (2D) spatial structure-favored tandem catalysis is for the first time elucidated, which leads to boosted (CH₃OH + DME) productivity, corresponding to 2736 μmol g_cat⁻¹ h⁻¹ or 58 368 mmol per mol_Cu per h of CH₃OH, and improved reaction stability (passing through a 100 h long-term test). A unique dual Cu single-atom site located at the parallel 6-membered ring (MR) of the 8 MR channel could be generated, which serves as the primary CH₃OH production active site exhibiting much higher activity than the traditional monomeric [Cu]⁺ and Cu dimer sites. The generated CH₃OH can subsequently diffuse from the 8 MR channel into a 10 MR main channel and directly react with the radicals of CH₃⁻ and OH⁻ to produce DME not only favoring DME production but also efficiently preventing carbon deposition. The present work highlights a tandem catalysis over Cu-FER that would substantially favor the design of other efficient catalysts for N₂O-DMTM.