Accelerated generation and activation of H ₂ O ₂ by the synergetic effect of pyridine‐N protonation and Co ⁰ species toward efficient electro‐Fenton

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Designing highly effective cathodic catalysts that can efficiently generate H 2 O 2 in situ and promptly convert it to hydroxyl radicals (·OH) poses a significant challenge within the heterogeneous electro‐Fenton (EF) systems. Herein, we fabricate a bifunctional core–shell catalyst featuring Co 0 species encapsulated within N, P‐codoped carbon shells through a hydrothermal‐pyrolysis strategy, utilizing bamboo shoots as biomass‐derived precursors. Density functional theory (DFT) calculations elucidate that the protonation of pyridinic nitrogen modifies the adsorption energy of the OOH* intermediate, positioning it optimally at the peak (3.81 eV) on the two‐electron oxygen reduction reaction (2e − ORR) volcano plot, thereby significantly boosting H 2 O 2 production. Moreover, the Co 0 species embedded within the catalyst function as electron donors, catalyzing the activation of H 2 O 2 to produce ·OH by efficiently facilitating the transfer of electrons to Fe 3+ . Consequently, the synthesized catalyst exhibits a minimum electron transfer number of 2.06 and a maximum H 2 O 2 selectivity of 97.4%. Moreover, the degradation for the methylene blue solution exceeds 95% within 15 min, with only an 11.3% reduction in degradation efficiency after 180 min of continuous operation (9 cycles). This bifunctional catalyst design provides valuable insights that can accelerate the development of EF‐based degradation systems.