近日，哈尔滨理工大学张凤鸣团队实现了共价有机框架锚定单原子Pt用于三相界面辅助光催化全面水分解。2025年9月18日，《德国应用化学》杂志发表了这项成果。

共价有机骨架（COFs）由于其高结晶度、孔隙度和结构可调等特点，是一种很有前途的光催化剂。然而，目前基于COF的体系依赖于助催化剂，而助催化剂存在原子利用率低和聚集性差的问题。此外，氧还原反应（ORR）逆向反应严重影响了长时间反应的催化效率和稳定性。

研究组提出了一种策略，结合了三嗪基COFs中通过N/O配位锚定的原子分散Pt位点和气-液-固三相界面辅助光催化系统，以提高性能和耐久性。结果表明，Pt-TBPyT-COF的H₂和O₂析出速率分别为469.8和234.9 μmol·g^-1·h^-1，在450 nm处的表观量子产率为8.91%。值得注意的是，通过气-液-固三相界面辅助方法制备的OWS有效抑制了ORR的逆向反应，在5 h内对H2和O2的催化平均反应速率分别高达568.7和284.3 μmol·g^-1·h^-1?，并在30 h的连续反应中保持稳定的光催化活性。此外，密度泛函理论计算和原位实验表明，单原子Pt配位加速了*H的脱附，而COFs中的三嗪单元有利于电荷分离，降低了OER速率决定步骤的能量势垒。

附：英文原文

Title: Covalent Organic Frameworks Anchoring Single-Atom Pt for Three-Phase Interface-Assisted Photocatalytic Overall Water Splitting

Author: Ting-Ting Sun, Hao Zhang, Ya Wang, Nan-Nan Zhang, Lu-Hua Shao, Hong Dong, Feng-Ming Zhang

Issue&Volume: 2025-09-18

Abstract: Covalent organic frameworks (COFs) are promising photocatalysts for overall water splitting (OWS) due to their high crystallinity, porosity and tunable structures. However, current COF-based systems rely on cocatalysts, which suffer from low atomic utilization and poor distribution due to aggregation. In addition, the oxygen reduction reaction (ORR) backward reaction severely undermines catalytic efficiency and stability in long time reaction. Herein, we present a strategy that combines atomically dispersed Pt sites anchored via N/O coordination within triazine-based COFs and a gas-liquid-solid three-phase interface-assisted photocatalytic system to enhance both performance and durability. As a result, the Pt-TBPyT-COF achieves superior OWS performance with H2 and O2 evolution rates of 469.8 and 234.9 μmol·g1·h1, respectively, and an apparent quantum yield of 8.91% at 450 nm. Notably, the OWS via gas-liquid-solid three-phase interface-assisted method effectively suppresses ORR backward reaction and reaches average rates as high as 568.7 and 284.3 μmol·g1·h1 for H2 and O2 in 5 h, respectively, and maintained stable photocatalytic activity over a 30 h continuous reaction. Further, density functional theory calculations and in situ experiments reveal that the single-atoms Pt coordination accelerates *H desorption, while the triazine units in COFs benefits charge separation and reduced energy barriers of OER rate-determining step.

DOI: 10.1002/anie.202515397

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202515397