Wang Qian, Zhang Guigang, Xing Wandong, Pan Zhiming, Zheng Dandan, Wang Sibo, Hou Yidong, Wang Xinchen
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350108, P. R. China.
Angew Chem Int Ed Engl. 2023 Sep 11;62(37):e202307930. doi: 10.1002/anie.202307930. Epub 2023 Aug 4.
Poly (triazine imide) (PTI/Li Cl ), one of the crystalline versions of polymeric carbon nitrides, holds great promise for photocatalytic overall water splitting. In principle, the photocatalytic activity of PTI/Li Cl is closely related to the morphology, which could be reasonably tailored by the modulation of the polycondensation process. Herein, we demonstrate that the hexagonal prisms of PTI/Li Cl could be converted to hexagonal nanosheets by adjusting the binary eutectic salts from LiCl/KCl or NaCl/LiCl to ternary LiCl/KCl/NaCl. Results reveal that the extension of in-plane conjugation is preferred, when the polymerisation was performed in the presence of ternary eutectic salts. The hexagonal nanosheets bears longer lifetimes of charge carriers than that of hexagonal prisms due to lower intensity of structure defects and shorter hopping distance of charge carriers along the stacking direction of triazine nanosheets. The optimized hexagonal nanosheets exhibits a record apparent quantum yield value of 25 % (λ=365 nm) for solar hydrogen production by one-step excitation overall water splitting.
聚（三嗪酰亚胺）（PTI/Li Cl）作为聚合碳氮化物的晶体形式之一，在光催化全分解水方面具有巨大潜力。原则上，PTI/Li Cl的光催化活性与形貌密切相关，通过调节缩聚过程可以合理地对其进行调控。在此，我们证明，通过将二元共晶盐从LiCl/KCl或NaCl/LiCl调整为三元LiCl/KCl/NaCl，可以将PTI/Li Cl的六棱柱转化为六方纳米片。结果表明，当在三元共晶盐存在下进行聚合时，面内共轭的扩展更受青睐。由于结构缺陷强度较低且电荷载流子沿三嗪纳米片堆叠方向的跳跃距离较短，六方纳米片的电荷载流子寿命比六棱柱更长。通过一步激发全分解水制氢，优化后的六方纳米片展现出创纪录的25%（λ=365 nm）的表观量子产率值。
