Yu Jun-Jie, Huang Xin, Wang Li-Ying, Wu Yan-Ze, Huang Zhi-Wei, Su Ling-Ling, Wang Nan-Nan, Yu Ji-Pan, Shi Wei-Qun
Institute of Nuclear Fuel cycle and Materials, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China.
Adv Mater. 2025 Aug 21:e04808. doi: 10.1002/adma.202504808.
Two-dimensional covalent organic frameworks (2D-COFs) have emerged as prominent photocatalysts for photocatalytic hydrogen evolution. However, the exquisite design of linkage and topological structures is crucial for efficient charge generation, separation, and transfer in the planar periodic framework. Here, an imine-linked dibenzo[g,p]chrysene-based COF (DBC-Imine-COF) is presented as a template for topology-templated synthesis of two 2D sp carbon-linked COFs (dibenzo[g,p]chrysene-based DBC-spc-COF and tetraphenylethylene-based TPE-spc-COF) with Kagome lattice to boost photocatalytic hydrogen evolution. The fully conjugated DBC-spc-COF is highly luminescent and exhibits topology-dependent π-electron transmission and charge carrier mobility. Significantly, DBC-spc-COF exhibits an impressive photocatalytic hydrogen evolution rate of 172.93 mmol g h and excellent reusability in the presence of 0.8 wt.% Pt under light irradiation, with a remarkable apparent quantum yield of 14.9% at 420 nm. More importantly, DBC-spc-COF demonstrates a hydrogen evolution rate of 105.30 and 80.04 mmol g h in 3 wt.% saltwater and natural seawater, respectively, highlighting its potential in real-world scenarios. DFT calculations and various spectroscopic analyses reveal that the highly coplanar structure of DBC-spc-COF strengthens donor-acceptor interactions, facilitating charge generation and separation. In summary, this work provides an effective strategy to construct highly planar and full π-conjugated dibenzo[g,p]chrysene-based 2D sp carbon-linked COF as a promising platform for photocatalytic hydrogen evolution.
二维共价有机框架（2D-COF）已成为用于光催化析氢的重要光催化剂。然而，连接和拓扑结构的精确设计对于在平面周期性框架中高效产生、分离和转移电荷至关重要。在此，提出了一种基于亚胺连接的二苯并[g,p]并四苯的COF（DBC-亚胺-COF）作为拓扑模板合成两种具有Kagome晶格的二维sp碳连接COF（基于二苯并[g,p]并四苯的DBC-spc-COF和基于四苯乙烯的TPE-spc-COF）的模板，以促进光催化析氢。完全共轭的DBC-spc-COF具有高发光性，并表现出拓扑依赖性的π电子传输和电荷载流子迁移率。值得注意的是，DBC-spc-COF在光照下，在0.8 wt.% Pt存在的情况下，表现出令人印象深刻的172.93 mmol g h的光催化析氢速率和优异的可重复使用性，在420 nm处具有14.9%的显著表观量子产率。更重要的是，DBC-spc-COF在3 wt.%的盐水和天然海水中分别表现出105.30和80.04 mmol g h的析氢速率，突出了其在实际场景中的潜力。密度泛函理论（DFT）计算和各种光谱分析表明，DBC-spc-COF的高度共面结构增强了供体-受体相互作用，促进了电荷的产生和分离。总之，这项工作提供了一种有效的策略，来构建高度平面且完全π共轭的基于二苯并[g,p]并四苯的二维sp碳连接COF，作为光催化析氢的有前景的平台。
