Ag 2 O Merged in Potassium‐Incorporated Polymeric Carbon Nitride Photoanodes with Efficient Charge Transfer for Photoelectrochemical Water Splitting

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Escalating energy demands and environmental imperatives necessitate sustainable hydrogen production, with photoelectrochemical (PEC) water splitting emerging as a vital approach. Though polymeric carbon nitride (PCN)‐based photoanodes offer enormous promise, their efficacy is hampered by the inadequate charge transfer efficiency. Herein, Ag 2 O was in situ integrated into potassium‐incorporated PCN (KCN) photoanodes (AgKCN), primarily forming the intimate heterojunctions at the KCN/FTO interface. Importantly, AgKCN maintains a 2.56 eV bandgap while preserving the crystalline architecture of KCN. Within this structure, Ag 2 O establishes a thermodynamically favorable band alignment that enables the directional hole transfer from the valence band of KCN to that of Ag 2 O, thereby mitigating charge carrier recombination and lowering charge transfer resistance. Consequently, the optimized AgKCN achieves a benchmark photocurrent density of 378 μA cm −2 at 1.23 V versus reversible hydrogen electrode (RHE) in a 1.0 M NaOH electrolyte under AM1.5G illumination, which is ca. 4 times that of the pristine KCN, accompanied by a 90.5% surface charge injection efficiency. This work highlights the transformative role of Ag 2 O in enhancing PEC performance via heterojunction‐mediated carrier regulation, providing the design principles for advanced PCN‐based photoanodes.

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