Dual‐Exsolution Tailored Interfaces Boosts Bifunctional Catalysis for CH4‐Assisted CO2 Electrolysis

Abstract Replacing the sluggish oxygen evolution reaction (OER) with the partial oxidation of methane (POM) in solid oxide electrolysis cells (SOECs) offers a promising strategy to reduce energy consumption of the CO 2 reduction reaction (CO 2 RR), while converting methane into syngas. However, conventional perovskite electrodes exhibit limited bifunctional activity for both POM and CO 2 RR. Herein, a facile dual‐exsolution strategy is developed to fabricate RuFe@La 0.5 Sr 0.5 (Ru 0.25 Fe 0.75 ) 0.92 Nb 0.08 O 3‐δ /(Ru 0.25 Fe 0.75 ) 0.05 Gd 0.075 Ce 0.875 O 2‐δ (RuFe@LSFNR/RFGDC) symmetrical electrodes, enabling synergistic CH 4 ‐assisted CO 2 electrolysis. The tailored dual‐exsolved RuFe@LSFNR and RuFe@RFGDC interfaces exhibit significantly enhanced intrinsic bifunctional activity for both POM and CO 2 RR. At 800 °C, the energy consumption for CO production decreases markedly from 3.79 to 0.91 kWh m −3 . In situ characterizations and DFT calculations reveal that the in situ exsolved RuFe alloy nanoparticles facilitate CO 2 adsorption and CH 4 activation simultaneously, while AIMD simulations confirm heterostructure stability. This work highlights the feasibility of dual‐exsolution tailored interfaces for energy‐saving CO 2 electrolysis.