Lu Yang, Li Wenyan, Sun Chenyu, Tang Yawen, Cheng Lei, Sun Hanjun
School of Chemistry and Materials Science, Jiangsu Key Laboratory of New Power Batteries, Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Nanjing Normal University, Nanjing, 210023, P. R. China.
Chemistry. 2024 Dec 13;30(70):e202402930. doi: 10.1002/chem.202402930. Epub 2024 Oct 29.
Sp-carbon (sp-c) covalent organic frameworks (COFs), featuring distinctive π-conjugated network structures, facilitate the migration of photo-generated carriers, rendering them exceptionally appealing for applications in photoelectrochemical water splitting. However, owing to the powdery nature of COFs, leaving anchor the sp-c COFs powder tightly onto a conductive substrate challenging. Here, we propose a method for preparing photoactive substance-conductive substrate integrated photocathodes through copper surface-mediated knoevenagel polycondensation (Cu-SMKP), this approach results in a uniform and stable sp-c COF film, directly grown on commercial copper foam (COFTh-Cu). The COFTh-Cu demonstrates a high H-evolution photocurrent density of 56 μA cm at 0.3 V vs. RHE, sustaining stability for 12 h. The as-prepared COFTh-Cu represents a 4.5-fold increase in current density compared to traditional spin-coating methods and outperforms most COF photocathodes without cocatalysts. This innovative copper surface-mediated approach for preparing photocathodes opens up a crucial pathway towards the realization of highly active COF photocathodes.
具有独特π共轭网络结构的sp-碳（sp-c）共价有机框架（COF），促进了光生载流子的迁移，使其在光电化学水分解应用中极具吸引力。然而，由于COF的粉末性质，将sp-c COF粉末牢固地锚定在导电基底上具有挑战性。在此，我们提出一种通过铜表面介导的克诺文纳格尔缩聚反应（Cu-SMKP）制备光活性物质-导电基底集成光阴极的方法，该方法可直接在商用泡沫铜（COFTh-Cu）上生长出均匀且稳定的sp-c COF薄膜。COFTh-Cu在相对于可逆氢电极（RHE）为0.3 V时，表现出56 μA cm的高析氢光电流密度，并保持12小时的稳定性。与传统旋涂方法相比，所制备的COFTh-Cu的电流密度提高了4.5倍，并且在没有助催化剂的情况下优于大多数COF光阴极。这种创新的铜表面介导制备光阴极的方法为实现高活性COF光阴极开辟了一条关键途径。
