Conjugated microporous polymers (CMPs) and covalent triazine frameworks (CTFs) with conjugated linkages and nanochannels have been showcased as a new platform in extensive fields. Here, by tuning the geometry of the N-rich skeleton tricycloquinazoline (TQ) unit, isomers of the 3D amorphous conjugated microporous polymer (TQ-CMP) and 2D laminar covalent quinazoline network (TQ-CQN) are synthesized. The derived diverse microstructure and electrical conductivity related to the applications of gas adsorption and the hydrogen evolution reaction (HER) are systematically discussed. TQ-CMP fabricated with an internal crosslinking network reveals a notable uptake of 25.6 wt% CO₂ and of 2.91 wt% CH₄ at 273 K and 1 bar, higher than most reported POP materials, which could be attributed to the higher BET surface area (781.0 m² g⁻¹) and dispersed pore size (1.1 nm to 13.1 nm) for guest molecule absorption. In contrast, both the modulated electronic structure of the precise π-conjugate planes and the vertically ordered one-dimensional channels endow TQ-CQN with more built-in catalytic sites and rapid electron transmission for the HER. Without any noble metal doping, the excellent catalytic activity and faster reaction kinetics of TQ-CQN are epitomized by the achieved lower overpotential of 80 mV and the Tafel slope of 40 mV dec⁻¹. This work not only clarifies the interaction of the microstructure and conductivity of porous organic polymers for gas adsorption and the HER, but also provides flexible design guidance for future functional exploration.

中文翻译：

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含三环喹唑啉的3D共轭微孔聚合物和2D共价喹唑啉网络：微观结构和电导率

具有共轭键和纳米通道的共轭微孔聚合物（CMP）和共价三嗪骨架（CTF）已被展示为广泛领域中的新平台。在这里，通过调节富含N的骨架三环喹唑啉（TQ）单元的几何形状，可以合成3D非晶共轭微孔聚合物（TQ-CMP）和2D层状共价喹唑啉网络（TQ-CQN）的异构体。系统地讨论了与气体吸附和析氢反应（HER）的应用相关的各种微观结构和电导率。使用内部交联网络制造的TQ-CMP具有25.6 wt％的CO ₂和2.91 wt％的CH ₄显着吸收在273 K和1 bar的压力下，比大多数报道的POP材料要高，这可以归因于较高的BET表面积（781.0 m ² g ^-1）和用于客体分子吸收的分散孔径（1.1 nm至13.1 nm）。相反，精确的π共轭平面的调制电子结构和垂直有序的一维通道都使TQ-CQN具有更多的内置催化位点和快速的HER电子传输。在没有任何贵金属掺杂的情况下，TQ-CQN具有出色的催化活性和更快的反应动力学，体现在较低的80 mV过电势和40 mV dec ^-1的Tafel斜率。这项工作不仅阐明了用于气体吸附的多孔有机聚合物和HER的微观结构和导电性之间的相互作用，而且还为将来的功能探索提供了灵活的设计指南。