Photothermal–Photoelectric Synergy in Prussian Blue/PEDOT for Efficient Fenton‐Like Catalysis

Fenton reactions are widely recognized as effective technologies for water remediation; however, their catalytic performance is often limited under near‐neutral aqueous conditions. In this study, Prussian blue/poly(3,4‐ethylenedioxythiophene) (PB/PEDOT) composites were synthesized via single‐source in situ growth and demonstrated significantly enhanced catalytic activity for dye degradation, achieving approximately fourfold improvement through synergistic photothermal and photoelectric effects. Experimental analyses and molecular dynamics simulations reveal that PEDOT incorporation enhances light‐harvesting capability and lowers thermal conductivity, thereby facilitating thermally driven catalytic processes. First‐principles calculations and experimental evidence confirm the formation of a heterojunction, which enables photogenerated electrons to possess a sufficiently negative potential to reduce dissolved oxygen to •O 2 − and to promote the reduction of Fe 3+ to Fe 2+ . The relative contributions of various mechanisms, including adsorption, photothermal Fenton catalysis, heterojunction‐driven photoelectric effects, and accelerated Fe redox cycling, were quantitatively evaluated. These findings provide valuable insights into advanced oxidation processes driven by multi‐field synergy and underscore the potential of coordination polymers/π‐conjugated polymer composites for efficient water remediation.