Ma Tiantian, Liu Zhijie, Deng Jiaqi, Han Enshan, Liang Jun, Wang Ruihu
Hebei Key Laboratory of Functional Polymer, School of Chemical Engineering and Technology, Hebei University of Technology, 300401, Tianjin, China.
College of Chemical and Textile Engineering, Xinjiang University of Science and Technology, Korla, China.
ChemSusChem. 2024 Nov 25;17(22):e202400987. doi: 10.1002/cssc.202400987. Epub 2024 Jul 15.
Covalent organic frameworks (COFs) are one type of promising polymer semiconductors in solar-driven hydrogen production, but majority of COFs-based photocatalytic systems show low photocatalytic efficiency owing to lack of metal active sites. Herein, we reported II-Scheme heterojunction frameworks based on COF (TpPa-1) and metal-organic framework (HKUST-1) for highly efficient hydrogen production. The coordination bonding directed self-assembly of HKUST-1 on the surface of TpPa-1 endows the heterojunction frameworks (HKUST-1/TpPa-1) with strong interface interaction, optimized electronic structures and abundant redox active sites, thus remarkably boosting photocatalytic hydrogen evolution. The hydrogen evolution rate for optimal HKUST-1/TpPa-1 is as high as 10.50 mmol g h, which is significantly enhanced when compared with that of their physical mixture (4.13 mmol g h), TpPa-1 (0.013 mmol g h) and Pt-based counterpart (6.70 mmol g h). This work offers a facile approach to the construction of noble-metal-free II-Scheme heterojunctions based on framework materials for efficient solar energy conversion.
共价有机框架（COF）是太阳能驱动制氢领域中一类很有前景的聚合物半导体，但大多数基于COF的光催化体系由于缺乏金属活性位点，光催化效率较低。在此，我们报道了基于COF（TpPa-1）和金属有机框架（HKUST-1）的II型异质结框架用于高效制氢。HKUST-1在TpPa-1表面通过配位键导向的自组装，赋予了异质结框架（HKUST-1/TpPa-1）强界面相互作用、优化的电子结构和丰富的氧化还原活性位点，从而显著提高了光催化析氢性能。最优的HKUST-1/TpPa-1的析氢速率高达10.50 mmol g h，与它们的物理混合物（4.13 mmol g h）、TpPa-1（0.013 mmol g h）和基于Pt的对应物（6.70 mmol g h）相比有显著提高。这项工作为基于框架材料构建无贵金属的II型异质结以实现高效太阳能转换提供了一种简便方法。
