Ring-opening polymerization affords an extremely powerful driver for large-scale delocalization of π-electrons and good charge transport via incorporating aromatic repeat units and rigid molecular skeleton. Herein, we first developed a branched six functional benzoxazine monomer (BZ) through Mannich condensation reaction. The rigid chain segment structure of crosslinked polybenzoxazine (PBZ) penetrated into the π-conjugated planes of C₃N₄ via the room-temperature HCl-catalyzed polymerization of the monomer, leading to the formation of a range of 3D C₃N₄ monolithic aerogels embedded with carbon aerogel. High nitrogen self-doped carbon aerogels were flexibly embedded in situ into the C₃N₄ matrix during the heat curing process, leading to the redshift of the C₃N₄ absorption edge and the increase of electrical conductivity. The special framework of the NC/C₃N₄ monolithic aerogels can tremendously enrich the electron-trapping sites through the generation of delocalized big π bonds. This work provides new insights into the understanding of polymer chemistry and photocatalysis mechanism.

开环聚合通过结合芳族重复单元和刚性分子骨架，为π电子的大规模离域化和良好的电荷传输提供了极为强大的驱动力。本文中，我们首先通过曼尼希缩合反应开发了一种支链的六官能度苯并恶嗪单体（BZ）。交联的聚苯并恶嗪（PBZ）的刚性链段结构通过室温HCl催化的单体聚合反应渗入C ₃ N ₄的π共轭平面，从而导致形成一系列3D C ₃ N ₄单片含碳气凝胶的气凝胶。高氮自掺杂碳气凝胶可灵活地原位嵌入C ₃ N _4中基体在热固化过程中，导致C ₃ N ₄吸收边缘的红移和电导率的增加。NC / C ₃ N ₄整体气凝胶的特殊框架可通过产生离域大π键极大地丰富电子俘获位点。这项工作为了解聚合物化学和光催化机理提供了新的见解。