2025年2月25日，吉林大学化学学院刘晓明研究小组在《德国应用化学》杂志发表论文，报道了促进光催化析氢的全共轭苯并异恶唑桥接共价有机框架。

二维共价有机框架（2D-COFs）在太阳能到氢转化方面引起了广泛的兴趣。

然而，光捕获不足和激子解离困难严重限制了COFs光催化活性的提高，从而阻碍了这一先进领域的发展。本文首次通过Knoevenagel缩聚法制备了两个苯并异恶唑与三嗪（COF-JLU44）和芘（COF-JLU45）的桥接和全共轭2D-COFs，它们具有长程有序结构、很大程度上可接受的比表面积和优异的光电性能。值得注意的是，COF-JLU45表现出272.5 mmol g1 h 在1.0 wt% Pt存在下，在光照射下具有优异的可热性，在600nm长波长处具有12.9%的表观量子产率。多重光谱分析和理论模拟表明，COF-JLU45的设计巧妙地扩大了其光吸收，有效地促进了激子解离。这一发现为构建用于太阳能转换和利用的无金属光催化剂提供了有价值的见解。

附：英文原文

Title: Fully Conjugated Benzobisoxazole Bridged Covalent Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

Author: Xiaoming Liu, Si Ma, Zhongping Li, Yuxin Hou, Jiali Li, Zhenwei Zhang, Tianqi Deng, Gang Wu, Rui Wang, Shuo-wang Yang

Issue&Volume: 2025-02-25

Abstract: Two-dimensional covalent organic frameworks (2D-COFs) have attracted extensive interest in solar energy to hydrogen conversion. However, insufficient light harvesting and difficult exciton dissociation severely limit the improvement of photocatalytic activity for COFs, thereby impeding the progression of this advanced field. In this work, two benzobisoxazole bridged and fully conjugated 2D-COFs with triazine (COF-JLU44) and pyrene (COF-JLU45) units were constructed for the first time via Knoevenagel polycondensation, and they hold long-range ordered structures, largely acceptable surface area and fascinating photoelectric properties. Significantly, COF-JLU45 exhibits an impressive hydrogen evolution rate of 272.5 mmol g1 h1 and superior reusability in the presence of 1.0 wt% Pt under light irradiation, coupled with a remarkable apparent quantum yield of 12.9% at a long wavelength of 600 nm. Multiple spectroscopy and theoretical simulation demonstrate the ingenious design of COF-JLU45 widen its light absorption and effectively promote the exciton dissociation. This finding contributes valuable insights for constructing metal-free photocatalysts for solar energy conversion and utilization.

DOI: 10.1002/anie.202501869

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202501869