A Solution-processable Porphyrin-based Hydrogen-bonded Organic Framework for Photoelectrochemical Sensing of Carbon Dioxide.
A Solution-processable Porphyrin-based Hydrogen-bonded Organic Framework for Photoelectrochemical Sensing of Carbon Dioxide.
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用于二氧化碳光电化学传感的可溶液加工的基于卟啉的氢键有机框架。
DOI：
10.1002/anie.202311482
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发表时间：
2023
影响因子：
--
通讯作者：
Peng Li
中科院分区：
文献类型：
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作者：
Chen Wang;Xiyu Song;Yao Wang;Rui Xu;Xiangyu Gao;Cheng Shang;Peng Lei;Qingdao Zeng;Yaming Zhou;Banglin Chen;Peng Li
由于环境大气中存在竞争性气体，因此检测复杂气体混合物中的CO2具有挑战性。光电化学（PEC）技术提供了一种解决方案，但材料选择和特异性仍然有限。在这里，我们发明了一种基于二氨基三嗪（DAT）修饰的卟啉结构的氢键有机框架材料。卟啉分子上的DAT基团不仅促进了结构间互补氢键的形成，而且在制备的多孔HOF材料中充当了选择性吸附CO2的识别位点。此外，通过简单的溶液处理方法，FDU-HOF-2可在平面内生长成面积可达23000 μm2、厚度可控制在0.298 ~ 2.407µm之间的各向异性分子片，产率超过89%。通过在甲酸中原位自组装，FDU-HOF-2可以直接生长并沉积在不同的基质上，包括二氧化硅、碳和金属氧化物。为了验证这一概念，制作了一种由FDU-HOF-2沉积的丝网印刷电极，作为二氧化碳检测的无标签光电化学（PEC）传感器。这样的信号关闭PEC传感器具有低二氧化碳检测限（2.3 ppm），可重复使用（至少30个循环）和长期工作稳定性（至少30天）。
Detecting CO2 in complex gas mixtures is challenging due to the presence of competitive gases in ambient atmosphere. Photoelectrochemical (PEC) techniques offer a solution, but material selection and specificity remain limiting. Here, we invented a hydrogen-bonded organic framework material based on a porphyrin tecton decorated with diaminotriazine (DAT) moieties. The DAT moieties on the porphyrin molecules not only facilitate the formation of complementary hydrogen-bonds between the tectons but also function as recognition sites in the resulting porous HOF materials for the selective CO2 adsorption. In addition, the in-plane growth of FDU-HOF-2 into anisotropic molecular sheets with large areas of up to 23,000 μm2 and controllable thickness between 0.298 and 2.407 µm were realized by a simple solution-processing method in over 89% yields. The FDU-HOF-2 can be directly grown and deposited onto different substrates including silica, carbon, and metal-oxides by self-assembly in situ in formic acid. As a proof of concept, a screen-printing electrode deposited with FDU-HOF-2 was fabricate as a label-free photoelectrochemical (PEC) sensor for CO2 detection. Such a signal-off PEC sensor exhibits low detection limit for CO2 (2.3 ppm), reusability (at least 30 cycles), and long-term working stability (at least 30 days).