Phosphorus‐Alkynyl Functionalized Covalent Triazine/Heptazine‐Based Frameworks for High‐Performance Photocatalytic Hydrogen Peroxide Production

Abstract Identifying high‐efficiency photocatalysts for producing hydrogen peroxide from H₂O and O₂ is a promising yet challenging research direction for achieving solar‐to‐chemical energy conversion and storage. Herein, 14 experimentally feasible 2D covalent triazine/heptazine‐based frameworks (CTFs/CHFs) are constructed with phosphorus‐alkynyl/phosphorus‐alkynyl‐phenyl functional moieties through topological assembly and four promising visible‐light‐driven photocatalysts for H₂O₂ production from H₂O and O₂ via first‐principles computations are filtered out: CTF‐1 based on triazine and phosphorus‐acetylene, CTF‐2 based on triazine and phosphorus‐diacetylene, CHF‐1 based on heptazine and phosphorus‐acetylene, and CHF‐2 based on heptazine and phosphorus‐diacetylene. The computational results show that introducing electron‐rich phosphorus‐alkynyl moieties into CTFs/CHFs can effectively modulate their electronic structures, provide sufficient driving force for water oxidation, and facilitate O₂ adsorption and activation, thereby significantly boosting the overall photocatalytic process. Among them, CHF‐1 and CHF‐2 exhibit the highest photocatalytic activity for H₂O₂ production at pH 7, and their ideal solar‐to‐chemical conversion (SCC) efficiency for H₂O₂ generation are theoretically estimated to be 26.06% and 35.37%, respectively, implying their great promise as photocatalysts for industrialized production of H₂O₂. The work presents a promising way for rationally designing and developing novel photocatalysts for H₂O₂ production, and provides new inspiration and reference for experimental research in this field.