Lu Meng, Zhang Shuai-Bing, Yang Ming-Yi, Liu Yu-Fei, Liao Jia-Peng, Huang Pei, Zhang Mi, Li Shun-Li, Su Zhong-Min, Lan Ya-Qian
School of Chemistry, South China Normal University, Guangzhou, 510006, P. R. China.
School of Chemistry and Environment Engineering, Changchun University of Science and Technology, Changchun, 130022, P. R. China.
Angew Chem Int Ed Engl. 2023 Aug 1;62(31):e202307632. doi: 10.1002/anie.202307632. Epub 2023 Jun 23.
In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy) /Fe(bpy) ) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series of dual photosensitizer-based three-dimensional metal-covalent organic frameworks (3D MCOFs), which behaved strong visible light-absorbing ability, efficient electron transfer and suitable band gap for highly efficient photocatalytic hydrogen (H ) evolution. Rubpy-ZnPor COF achieved the highest H yield (30 338 μmol g h ) with apparent quantum efficiency (AQE) of 9.68 %@420 nm, which showed one of the best performances among all reported COF based photocatalysts. Furthermore, the in situ produced H was successfully tandem used in the alkyne hydrogenation with ≈99.9 % conversion efficiency. Theoretical calculations reveal that both the two photosensitizer units in MCOFs can be photoexcited and thus contribute optimal photocatalytic activity. This work develops a general strategy and shows the great potential of using multiple photosensitive materials in the field of photocatalysis.
在本工作中，我们创新性地通过共价连接组装了两种传统光敏剂，即吡啶钌/铁（Ru(bpy) /Fe(bpy) ）和卟啉/金属卟啉配合物（2HPor/ZnPor），得到了一系列基于双光敏剂的三维金属共价有机框架（3D MCOF），其具有很强的可见光吸收能力、高效的电子转移以及适合高效光催化析氢（H ）的带隙。Rubpy-ZnPor COF实现了最高的H产率（30 338 μmol g h ），在420 nm处的表观量子效率（AQE）为9.68 %，这是所有报道的基于COF的光催化剂中表现最好的之一。此外，原位产生的H成功地串联用于炔烃加氢，转化效率约为99.9 %。理论计算表明，MCOF中的两个光敏剂单元均可被光激发，从而贡献最佳的光催化活性。这项工作开发了一种通用策略，并展示了在光催化领域使用多种光敏材料的巨大潜力。
