Reticular Synthesis of 3D Metal Cluster‐Based COFs With Record High‐Connectivity for Efficient Photocatalytic H <sub>2</sub> O <sub>2</sub> Synthesis
Mi Zhang, Pei Huang, Run‐Han Li, Yingying Huang, Minghao Qin, Yan‐Yu Peng, Si‐Miao Wang, Yong Yan, Meng Lu, Ya‐Qian Lan
Abstract
Abstract The assembly of metal clusters with organic building units by covalent bonds to form metal cluster‐based covalent‐organic frameworks (MCCOFs) material is a novel strategy in reticular synthesis. However, only 2, 3, and 6 connectivity of MCCOFs have been achieved in reported structures. Developing a higher connectivity remains a great challenge in the MCCOFs due to the difficulties in introducing multiple connecting nodes to the metal cluster. In this work, two 3D [8 + 2]‐connected MCCOFs were synthesized by condensing an 8‐connectivity aluminum cluster‐based building block (termed Al 8 ‐8c) with linear dialdehyde linkers. Furthermore, these AlCCOFs showed efficient photocatalytic O 2 ‐to‐H 2 O 2 conversion due to the suitable energy band structure, efficient photoelectron conversion capability and the AlCCOF‐1 showed H 2 O 2 photosynthetic efficiency of 16794.69 µmol g −1 h −1 using water and benzyl alcohol reaction system. The in situ EPR, in situ FTIR, and DFT calculations were then performed to study the structure‐function relationships on the two AlCCOFs for H 2 O 2 photosynthesis. This work is the first report of high‐connectivity MCCOFs bearing 8‐connected cluster units, showing the great potential of using metal clusters to construct complicate reticular frameworks by covalent linkage.