Xu Shiwen, Gao Wenqian, Lu Jun, Liang Xiaolong, Xu Ke, Liang Jing, Li Fei, Liu Jinxuan
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 116024, Dalian, China.
Leicester International Institute, Dalian University of Technology, 116024, Dalian, China.
ChemSusChem. 2024 Dec 6;17(23):e202400936. doi: 10.1002/cssc.202400936. Epub 2024 Aug 7.
The limited visible light response is a critical drawback that hampers the photocatalytic efficacy of Ti-MOFs. However, study concerning the enhancement of the visible-light response of Ti-MOFs is still in its nascent stage. In this study, we employ the 'dual-ligand decrystallization strategy' to manipulate the electronic environment of Ti, leading to the synthesis of three ester-functionalized bidentate Ti-MOFs with enhanced visible light response. Our findings reveal that this approach not only reduces the bandgap of Ti-MOFs but also enhances their photocatalytic activity for carbon dioxide reduction. Specifically, compared to the bandgap of Ti-BPDC at 2.98 eV, the bandgap of Ti-BPDC-CA 1 : 2 has been reduced to 2.14 eV. Moreover, Ti-BPDC-CA 1 : 2 exhibits extraordinary photocatalytic activity with the formic acid (HCOOH) production rate of 617 μmol g h with over 99.5 % selectivity, which is 3.47 times higher than that of Ti-BPDC. Besides providing a cost-effective strategy for enhancing the visible light response of Ti-MOFs, our study also serves as an illustrative example for establishing the correlation between electronic structure and optical properties.
有限的可见光响应是阻碍钛基金属有机框架材料（Ti-MOFs）光催化效率的一个关键缺陷。然而，关于增强Ti-MOFs可见光响应的研究仍处于起步阶段。在本研究中，我们采用“双配体去结晶策略”来调控Ti的电子环境，从而合成了三种具有增强可见光响应的酯官能化双齿Ti-MOFs。我们的研究结果表明，这种方法不仅降低了Ti-MOFs的带隙，还提高了它们对二氧化碳还原的光催化活性。具体而言，与Ti-BPDC的带隙2.98 eV相比，Ti-BPDC-CA 1 : 2的带隙已降至2.14 eV。此外，Ti-BPDC-CA 1 : 2表现出非凡的光催化活性，甲酸（HCOOH）产率为617 μmol g h，选择性超过99.5 %，这是Ti-BPDC的3.47倍。除了为增强Ti-MOFs的可见光响应提供一种经济有效的策略外，我们的研究还为建立电子结构与光学性质之间的关联提供了一个示例。
