Pressure-Mediated Cu Fragmentation and C1–C2 Intermediate Coupling in Electrocatalytic CO Reduction

Electrochemical carbon monoxide (CO) reduction to high-energy-density fuels, such as n-propanol, provides a potential route for chemical production and intermittent energy storage. However, challenges persist due to the weak adsorption of *C₂ intermediates and inefficient C₁–C₂ coupling on conventional Cu catalysts. To address this, we employ pressurized CO feedstock to amplify the near-surface CO concentration, which induces dynamic catalyst reconstruction, thereby generating more Cu(111)/Cu(100) interfaces to enhance C₁–C₂ coupling. Through systematic high-resolution transmission electron microscopy (HRTEM) analysis with quantified grain boundary statistics, we demonstrate that pressurized CO (1–10 atm) induces more Cu(111)/Cu(100) interface sites. When the CO reduction reaction (CORR) along with the in situ catalyst reconstruction is carried out with a 3-atm CO pressure, structural characterization reveals that a Cu(111)/Cu(100) catalytically active interface is 1.7 times more active than that under ambient conditions, and such a catalyst achieves a 28% Faradaic efficiency (FE) for n-propanol, surpassing the performance of catalysts reconstructed under other CO pressures. This work establishes that pressure-driven facet engineering offers a scalable pathway for CO upgrading, advancing the rational design of catalytic systems for multi-carbon synthesis.