Sun Lijuan, Yan Weicheng, Wang Weikang, Wang LeLe, Osella Silvio, Liang Guijie, Goddard William A, Zbořil Radek, Zhou Yazhou, Yang Juan, Liu Qinqin
School of Materials Science and Engineering, Jiangsu University, Zhenjiang, Jiangsu, 212013, P.R. China.
School of Chemistry & Chemical Engineering, Jiangsu University, Zhenjiang, Jiangsu, 212013, P.R. China.
Angew Chem Int Ed Engl. 2025 Aug 18;64(34):e202511080. doi: 10.1002/anie.202511080. Epub 2025 Jul 9.
Covalent organic frameworks (COFs) have shown promise as photocatalysts for chemical transformations. However, their dense micropores and poor pore connectivity hinder mass transport and charge separation/transfer, limiting their efficiency. Herein, we develop a one-step self-sacrificing template strategy to synthesize three-dimensional ordered macroporous COFs (3DOM-COFs). This approach uniquely integrates in situ Tp-Tta COF crystallization with synchronized degradation of polystyrene templates under solvothermal conditions. This method introduces unreported kinetic match between template decomposition and framework growth. Such a confined growth mechanism leads to structurally robust and highly ordered macroporosity without post-processing. 3DOM architecture enables uniform dispersion of fine ZnCdS nanoparticles for the generation a 3DOM-COF based S-scheme heterojunction, which exhibits remarkable performance in the oxidation of benzylamine (BA) for simultaneous N-benzylbenzaldimine production with 99% selectivity at a rate of 15.1 mmol g h and H generation with a rate of 17.8 mmol g h. The 3DOM architecture confers 50-fold faster mass transport than bulk COFs, while the heterojunction facilitates directional charge separation and interface charge transfer. Density functional theory calculations confirm that the heterojunction optimizes reaction thermodynamics by lowering the potential energy barriers of BA activation. The work pioneers a template-concurrent synthesis paradigm, resolving COFs' critical pore engineering challenges.
共价有机框架（COFs）已显示出作为化学转化光催化剂的潜力。然而，它们密集的微孔和较差的孔连通性阻碍了质量传输以及电荷分离/转移，限制了它们的效率。在此，我们开发了一种一步自牺牲模板策略来合成三维有序大孔COFs（3DOM-COFs）。这种方法独特地将原位Tp-Tta COF结晶与溶剂热条件下聚苯乙烯模板的同步降解相结合。该方法引入了模板分解与框架生长之间未报道的动力学匹配。这种受限生长机制导致结构坚固且高度有序的大孔结构，无需后处理。3DOM结构能够使细小的ZnCdS纳米颗粒均匀分散，从而生成基于3DOM-COF的S型异质结，该异质结在苄胺（BA）氧化反应中表现出卓越性能，能够以15.1 mmol g⁻¹ h⁻¹的速率同时以99%的选择性生成N-苄基苯甲亚胺，并以17.8 mmol g⁻¹ h⁻¹的速率生成H₂。3DOM结构赋予的质量传输速度比块状COFs快50倍，而异质结则促进了定向电荷分离和界面电荷转移。密度泛函理论计算证实，该异质结通过降低BA活化的势能垒优化了反应热力学。这项工作开创了一种模板并行合成范式，解决了COFs关键的孔工程挑战。
