Liu Jianchuan, Tuo Chao, Xiao Wei-Yun, Qi Ming-Yu, Yusran Yusran, Wang Zitao, Li Hui, Guo Chunsheng, Song Jialong, Qiu Shilun, Xu Yi-Jun, Fang Qianrong
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry, Jilin University, Changchun, 130012, P.R. China.
School of Life Sciences, Zhuhai College of Science and Technology, Zhuhai, 519040, P.R. China.
Angew Chem Int Ed Engl. 2025 Feb 24;64(9):e202416240. doi: 10.1002/anie.202416240. Epub 2025 Feb 5.
The development of photocatalytic systems that enable the simultaneous production of HO and value-added organic chemicals presents a dual advantage: generating valuable products while maximizing the utilization of solar energy. Despite the potential, there are relatively few reports on photocatalysts capable of such dual functions. In this study, we synthesized a series of donor-acceptor covalent organic frameworks (COFs), designated as JUC-675 to JUC-677, to explore their photocatalytic efficiency in the co-production of HO and N-benzylbenzaldimine (BBAD). Among them, JUC-675 exhibited exceptional performance, achieving a HO production rate of 22.8 mmol g h with an apparent quantum yield of 15.7 %, and its solar-to-chemical conversion efficiency was calculated to be 1.09 %, marking it as the most effective COF-based photocatalyst reported to date. Additionally, JUC-675 demonstrated a high selectivity (99.9 %) and yield (96 %) for BBAD in the oxidative coupling of benzylamine. The underlying reaction mechanism was thoroughly investigated through validation experiments and density functional theory (DFT) calculations. This work represents a significant advancement in the design of COF-based photocatalysts and the development of efficient dual-function photocatalytic platforms, offering new insights and methodologies for enhanced solar energy utilization and the synthesis of value-added products.
能够同时产生羟基自由基（HO）和增值有机化学品的光催化系统的开发具有双重优势：在最大化太阳能利用的同时生成有价值的产品。尽管具有潜力，但关于能够实现这种双重功能的光催化剂的报道相对较少。在本研究中，我们合成了一系列供体-受体共价有机框架（COF），命名为JUC-675至JUC-677，以探索它们在协同生产HO和N-苄基苯甲亚胺（BBAD）中的光催化效率。其中，JUC-675表现出卓越的性能，羟基自由基的产率为22.8 mmol g h，表观量子产率为15.7 %，其太阳能到化学能的转换效率经计算为1.09 %，这使其成为迄今为止报道的最有效的基于COF的光催化剂。此外，JUC-675在苄胺的氧化偶联反应中对BBAD表现出高选择性（99.9 %）和高产率（96 %）。通过验证实验和密度泛函理论（DFT）计算对潜在的反应机理进行了深入研究。这项工作代表了基于COF的光催化剂设计和高效双功能光催化平台开发的重大进展，为提高太阳能利用和增值产品合成提供了新的见解和方法。
