Preferential Dual‐Site Synergy in Pyrolyzed Bimetallic Catalysts for NO Reduction by CO

Abstract The development of highly efficient Copper (Cu)‐based catalysts for the selective catalytic reduction of NO by CO remains challenging due to their insufficient catalytic activity at low to medium temperatures. Herein, bimetallic CuX‐MOF‐74 catalysts (X = Co, Ni, Ce) were synthesized via hydrothermal–pyrolysis strategy, which effectively retains high surface area, promotes better metal dispersion, and enhances bimetallic synergy, thereby addressing key limitations of conventional Cu‐based catalysts. It is found that CuCo/C presents more outstanding catalytic efficiency, with > 9% NO conversion at 250 °C, complete conversion (100%) at 300 °C and 100% N 2 selectivity. The hierarchical micro–mesoporous architecture of CuCo/C not only provides a high specific surface area but also facilitates efficient reactant diffusion. More importantly, the unique “bulk alloy phase‐surface oxide phase” heterostructure, successfully constructed through the designed synthesis route, establishes a continuous Co 3+ /Co 2+ –Cu 2+ /Cu 0 redox cycle, which promotes the formation of oxygen vacancies and significantly enhances oxygen mobility and catalytic durability. The Langmuir–Hinshelwood (L–H) pathway validated by in situ DRIFTS analysis confirms coadsorption of NO/CO at adjacent sites with oxygen vacancy facilitated N‐O bond cleavage. This work provides comprehensive insights for the design of high‐efficiency CO‐SCR catalysts.