2D covalent organic frameworks (COFs) could have well‐defined arrangements of photo‐ and electro‐active units that serve as electron or hole transport channels for solar energy harvesting and conversion, but their insufficient charge transfer and rapid charge recombination impede the sunlight‐driven photocatalytic performance. We report a new donor–acceptor (D–A) system, PyTz‐COF that was constructed from the electron‐rich pyrene (Py) and electron‐deficient thiazolo[5,4‐d]thiazole (Tz). With its bicontinuous heterojunction, PyTz‐COF demonstrated exceptional optoelectronic properties, photocatalytic ability in superoxide anion radical‐mediated coupling of (arylmethyl)amines and photoelectrochemical activity in sunlight‐driven hydrogen evolution. Remarkably, PyTz‐COF exhibited a photocurrent up to 100 μA cm⁻² at 0.2 V vs. RHE and could reach a hydrogen evolution rate of 2072.4 μmol g⁻¹ h⁻¹. This work is paving the way for reticular design of highly efficient and highly active D–A systems for solar energy harvesting and conversion.

中文翻译：

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噻唑并[5,4-d]噻唑为基础的供体-受体共价有机框架，用于阳光驱动的氢气释放

二维共价有机框架（COF）可能具有明确定义的光敏和电活性单元排列，这些单元用作太阳能或电子的空穴传输通道，用于太阳能的收集和转换，但是它们的电荷转移不足和电荷快速重组会阻碍阳光驱动光催化性能。我们报告了一种新的供体-受体（DA）系统PyTz-COF，该系统由富电子pyr（Py）和电子不足的噻唑并[5,4- d ]噻唑（Tz）构成。通过其双连续异质结，PyTz-COF表现出卓越的光电性能，在超氧阴离子自由基介导的（芳基甲基）胺偶联中的光催化能力以及在阳光驱动的氢气释放过程中的光电化学活性。值得注意的是，PyTz-COF的光电流高达100μAcm在相对于RHE的0.2 V下为^-2，并且可以达到2072.4μmolg ^-1  h ^-1的析氢速率。这项工作为高效，高活性的D-A系统的网状设计铺平了道路，以进行太阳能的收集和转化。