Chen Minghui, Xiong Ji, Shi Quan, Zhang Weiwei, Chen Zhuoran, Wang Xiaolin, Zhu Xinyue, Guo Kai, Feng Yaqing, Zhang Bao
School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, P. R. China.
Collaborative Innovation Center of Chemical Science, Engineering (Tianjin), Tianjin, 300072, P. R. China.
Small. 2024 Dec;20(52):e2407782. doi: 10.1002/smll.202407782. Epub 2024 Oct 24.
Harsh synthetic conditions for crystalline covalent triazine frameworks (CTFs) and associated limitations on structural diversities impede not only further development of functional CTFs, but also practical large-scale synthesis. Herein, a mild and universal vapor-solid interface synthesis strategy is developed for highly crystalline CTFs employing trifluoromethanesulfonic acid vapor as catalysts. A series of highly ordered simple and functional CTFs (CTF-TJUs) can be facilely produced. In particular, the porphyrin-involved functional CTF (CTF-TJU-Por1) with high crystallinity is synthesized for the first time via this universal approach. The mechanism of vapor-catalyzed trimerization of nitrile monomers is thoroughly investigated through semi in situ characterizations. As a proof of concept, the photocatalytic performance of synthesized CTFs for water splitting is evaluated. CTF-TJU-133 exhibits significantly greater photocatalytic rates for hydrogen (4.35 µmol h) and oxygen (2.18 µmol h) evolutions during overall water splitting under visible light irradiations compared to other CTF-TJUs, representing one of the highest values among reported CTF photocatalysts. Further studies reveal that enhanced photocatalytic performance of CTF-TJU-133 results from optimized band structure, extended visible-light absorption, and high carrier separation efficiency. This study provides a promising strategy to synthesize various simple and functional CTFs, which significantly enriched diversities of CTF family for different application purposes.
结晶共价三嗪框架（CTF）苛刻的合成条件以及相关的结构多样性限制，不仅阻碍了功能性CTF的进一步发展，也阻碍了实际的大规模合成。在此，开发了一种温和且通用的气-固界面合成策略，以三氟甲磺酸蒸气为催化剂用于制备高结晶度的CTF。一系列高度有序的简单和功能性CTF（CTF-TJUs）能够轻松制备出来。特别地，首次通过这种通用方法合成了具有高结晶度的含卟啉功能CTF（CTF-TJU-Por1）。通过半原位表征深入研究了腈类单体的气相催化三聚反应机理。作为概念验证，评估了合成的CTF对水分解的光催化性能。与其他CTF-TJUs相比，CTF-TJU-133在可见光照射下整体水分解过程中表现出显著更高的氢气（4.35 μmol h）和氧气（2.18 μmol h）析出光催化速率，代表了已报道的CTF光催化剂中的最高值之一。进一步研究表明，CTF-TJU-133光催化性能的增强源于优化的能带结构、扩展的可见光吸收和高载流子分离效率。本研究提供了一种有前景的策略来合成各种简单和功能性CTF，这显著丰富了用于不同应用目的的CTF家族的多样性。
