Wu Jiaming, Li Keyan, Zhou Bing, Li Rui, Yan Siyang, Liu Jiaxu, Shi Hainan, Song Chunshan, Guo Xinwen
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, China.
School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029, China.
Angew Chem Int Ed Engl. 2025 Mar 3;64(10):e202421263. doi: 10.1002/anie.202421263. Epub 2024 Dec 9.
Poly(heptazine imide) (PHI), one of the crystalline or long-range ordered allotropes of polymeric carbon nitride, is a promising polymeric photocatalyst; however, preparation of highly crystalline PHI remains a challenge. Herein, through a bottom-up strategy involving repair of structural defects and increase of specific surface area of melon precursor, we prepared PHI nanorods with dramatically improved long-range order. The resulting PHI exhibited a shift of product selectivity in CO photoreduction from CO to CH with a high methanation activity in contrast to the pristine PHI with relatively low long-range order. The improvement of long-range order for PHI remarkably enhanced the separation efficiency and transfer kinetics of photogenerated charges as well as the adsorption for *CO intermediate. This study revealed the relationship between the precursor structure and PHI crystal growth in ionothermal synthesis, and also showcased the great potential of highly crystalline PHI in artificial photosynthesis.
聚（庚嗪酰亚胺）（PHI）是聚合氮化碳的晶体或长程有序同素异形体之一，是一种很有前景的聚合物光催化剂；然而，制备高结晶度的PHI仍然是一个挑战。在此，通过一种自下而上的策略，包括修复结构缺陷和增加瓜类前驱体的比表面积，我们制备了长程有序性显著提高的PHI纳米棒。与长程有序性相对较低的原始PHI相比，所得的PHI在CO光还原中表现出产物选择性从CO向CH的转变，具有较高的甲烷化活性。PHI长程有序性的提高显著增强了光生电荷的分离效率和转移动力学以及对*CO中间体的吸附。这项研究揭示了离子热合成中前驱体结构与PHI晶体生长之间的关系，也展示了高结晶度PHI在人工光合作用中的巨大潜力。
