Engineering Co ⁰ –CoO _<i>x</i> Interfacial Sites in N-Doped Carbon for High-Efficiency Oxidative Carbonylation of Methanol to Dimethyl Carbonate

The pursuit of efficient catalysts for methanol oxidative carbonylation to dimethyl carbonate (DMC) is limited by the kinetic challenge of simultaneously activating CO and methanol on conventional single/mixed sites. Here, we demonstrate a Co 0 –CoO x interfacial engineering strategy via pyrolysis of bimetallic Zn/Co-ZIF to construct Co@NC catalysts. Systematic tuning of Zn/Co ratio and pyrolysis temperature controls nanoparticle size and oxidation state, yielding the optimal catalyst Co@NC-4, which exhibits a high DMC space-time yield (5.9 g DMC g –1 cat. h –1 ) and selectivity (97.8%). Through DFT and in situ spectroscopic investigations, we reveal a concentration-driven synergistic mechanism: Co 0 sites preferentially adsorb and enrich CO, while the adjacent Co 0 –CoO x interface activates methanol to form methoxy intermediates. The local high CO concentration ensures rapid coupling with methoxy groups at the interface, significantly boosting reaction efficiency. This work establishes a fundamental design principle of spatially resolved bifunctionality for enhanced catalysis in C1 transformations.