Pan Zhiming, Zhang Guigang, Zhang Xirui, Xing Wandong, Zheng Dandan, Wang Sibo, Hou Yidong, Wang Xinchen
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350116, P. R. China.
Department College of Environment & Safety Engineering, Fuzhou University, Fuzhou, 350116, P. R. China.
Small. 2025 Jan;21(1):e2407307. doi: 10.1002/smll.202407307. Epub 2024 Oct 30.
Poly (heptazine imide) (PHI), a classic 2D polymeric photocatalyst, represents a promising organic semiconductor for photocatalytic overall water splitting (POWS). However, since the key bottleneck in POWS of PHI remains unclear, its quantum efficiency of POWS is extremely restrained. To identify the key obstacle in POWS on the PHI, a series of PHI with different stacking modes is synthesized by tuning interlayer cations. The structural characterizations revealed that tuning the interlayer cations of PHI can induce rearrangements in interlayer stacking modes. Additionally, charge carriers dynamics uncover that optimizing the interlayer stacking modes of PHI can promote exciton diffusion and prolong the photoexcited electron lifetimes, thus improving the concentration of surface-reaching charge. More importantly, this confirms that the POWS activity of PHI is closely correlated with the interlayer stacking modes. This work offers new insight into structural regulation for governing charge-transport dynamics and the activity of 2D polymeric photocatalysts.
聚（七嗪酰亚胺）（PHI）是一种经典的二维聚合物光催化剂，是用于光催化全水分解（POWS）的一种很有前景的有机半导体。然而，由于PHI在POWS中的关键瓶颈仍不明确，其POWS的量子效率受到极大限制。为了确定PHI在POWS中的关键障碍，通过调节层间阳离子合成了一系列具有不同堆积模式的PHI。结构表征表明，调节PHI的层间阳离子可以诱导层间堆积模式的重排。此外，电荷载流子动力学发现，优化PHI的层间堆积模式可以促进激子扩散并延长光激发电子寿命，从而提高表面到达电荷的浓度。更重要的是，这证实了PHI的POWS活性与层间堆积模式密切相关。这项工作为控制二维聚合物光催化剂的电荷传输动力学和活性的结构调控提供了新的见解。
