A Smart Catalytic System with In Situ Dynamic Current‐Tuned Pd‐Ce Diatomic Interactions for Enhanced Methane Oxidation

Abstract Enhancing catalytic performance through precise control of active site interactions still poses significant challenges. Diverging from conventional static methods, this study pioneers an innovative current‐assisted approach to achieve precise, in situ dynamic tuning of electron transfer specifically within Pd‐Ce diatomic sites. The groundbreaking current‐assisted Pd ₁ ‐Ce ₁ /ATO catalyst achieves unprecedentedly low‐temperature methane combustion performance, with a remarkable T ₅₀ of 181 °C and a record‐high turnover frequency (TOF _{260 °C} ) of 4.25 × 10 ⁻² s ⁻¹ . The current‐induced augmentation of electron transfer from Ce to Pd markedly elevates the electron density around Pd centers , orchestrating dynamic modulation to synergistically enhance catalysis. This modulation amplifies the electron backdonation from electron‐rich Pd to the methane C─H bond, facilitating efficient C─H bond scission, while promoting lattice oxygen mobility near Pd ₁ ‐Ce ₁ sites by tuning orbital energy matching, thus significantly amplifying the catalyst's oxidation capacity. The synergistic interplay of these electronically tuned factors promotes the formation of a four‐center transition state (H ₃ C ^{δ −} ‐Pd‐O‐H ^{δ +} ), effectively weakening the C─H bond and dramatically accelerating methane catalytic oxidation. This work not only achieves ultra‐low‐temperature catalytic activity with minimal noble metal loading but also establishes a paradigm shift in the rational design of advanced combustion catalysts, enabling on‐demand modulation of catalytic activity through real‐time regulation of inter‐site interactions .