卟啉
光催化
堆积
共价键
催化作用
钴
析氧
离解(化学)
材料科学
化学工程
聚合
齿合度
氧气
煅烧
化学
光化学
纳米技术
无机化学
结晶学
有机化学
聚合物
物理化学
晶体结构
电化学
工程类
电极
作者
Donglin Jiang,Shuailei Xie,Ruoyang Liu,Nengyi Liu,Hetao Xu,Xiong Chen,Wei Wang
标识
DOI:10.1002/anie.202416771
摘要
Covalent organic frameworks with unique π architectures and pores could be developed as photocatalysts for transformations. However, they usually form π‐stacking layers, so that only surface layers function in photocatalysis. Here we report a strategy for developing vertically expanded frameworks to expose originally inaccessible active sites hidden in layers to catalysis. We designed covalently linked two‐dimensional cobalt(II) porphyrin layers and explored coordination bonds to connect the cobalt(II) porphyrin layers with bidentate ligands via a three‐component one‐pot polymerization. The frameworks expand the interlayer space greatly, where both the up and down faces of each cobalt(II) porphyrin layer are exposed to reactants. Unexpectedly, the vertically expanded frameworks increase skeleton oxidation potentials, decrease exciton dissociation energy, improve pore hydrophilicity and affinity to water, and facilitate water delivery. Remarkably, these positive effects work collectively in the photocatalysis of water oxidation into oxygen, with an oxygen production rate of 1155 µmol g−1 h−1, a quantum efficiency of 1.24% at 450 nm, and a turnover frequency of 1.39 h−1, which is even 5.1‐fold as high as that of the π‐stacked frameworks and ranks them the most effective photocatalysts. This strategy offers a new platform for designing layer frameworks to build various catalytic systems for chemical transformations.
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