Vacuum Condensation of Hybrid Polymeric Graphitic Carbon Nitride for Extended Visible‐Light Photocatalytic Hydrogen Evolution

作者：Bo Lai, Xueqiang Ji, Nan Liu, Tong Li, Shuangtao Yuan, Xiaojia Zhao, Xiaoguang Luo, Dongli Yu, Yuanchun Zhao · 发表于：Chemistry - A European Journal · 年份：2025 · DOI：10.1002/chem.202501620 · 被引用次数：2 · 研究领域：Advanced Photocatalysis Techniques、Perovskite Materials and Applications、Covalent Organic Framework Applications

Abstract Polymeric graphitic carbon nitride (g‐CN) has attracted considerable attention as a promising photocatalyst; however, its practical application is still hindered by the poor visible‐light absorption and rapid recombination of photoinduced charge carriers. Herein, we report a vacuum‐condensation approach for synthesizing g‐CN with a hybrid polymeric structure that contains melon‐type chains combined with completely condensed domains, which induces a notable structural disorder with the N/C atomic ratio less than 1.5 (the nominal value of melon). This hybrid polymeric structure intrinsically extends the π‐conjugated system of the heptazine‐based framework, narrows its band gap, accelerates the exciton dissociation, and thus substantially improves its photocatalytic hydrogen evolution (PHE) performance. Compared to the counterparts synthesized under inert atmospheres (N 2 and Ar), the vacuum‐polycondensed g‐CN exhibits a threefold enhancement for visible‐light‐driven hydrogen production. In particular, its PHE activity can be effectively maintained under the light wavelength extended to 520 nm. This work presents a promising strategy to break through the limitation of linear polymerization pathway during the conventional g‐CN synthesis and offers new opportunities for rational design of more efficient g‐CN‐based photocatalysts.