Lei Longfei, Liu Yuanyuan, Zhang Yujia, Zhang Caiyun, Li Yujie, Wang Zeyan, Wang Peng, Zheng Zhaoke, Cheng Hefeng, Dai Ying, Huang Baibiao
State Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, P.R. China.
School of Physics, Shandong University, Jinan, 250100, P.R. China.
Chemistry. 2023 Jul 20;29(41):e202300843. doi: 10.1002/chem.202300843. Epub 2023 Jun 6.
In this work, a new method to extend the light absorption and improve the photocatalytic activity of metal-organic frameworks (MOFs) with nitrogen-containing ligand is reported, namely, the protonation of nitrogen. Specifically, a protonated Bi-based MOF synthesized by a hydrothermal method (Bi-MMTAA-H, MMTAA=2-mercapto-4-methyl-5-thiazoleacetic acid) displays a wider visible light absorption than Bi-MMTAA-R with the same single-crystal structure, but synthesized by a reflux method. The redshifted light absorption was confirmed to be caused by the protonation of nitrogen in the thiazolyl ring in MMTAA. Moreover, this protonation also facilitates the charge separation and transfer and improves the photocatalytic activity of selective oxidation of α-terpinene to p-cymene. Our results provide a new idea for nitrogen-containing Bi-based MOFs to extend the light absorption and improve the photocatalytic performance.
在这项工作中，报道了一种通过含氮配体来扩展光吸收并提高金属有机框架（MOF）光催化活性的新方法，即氮的质子化。具体而言，通过水热法合成的质子化铋基MOF（Bi-MMTAA-H，MMTAA = 2-巯基-4-甲基-5-噻唑乙酸）与具有相同单晶结构但通过回流法合成的Bi-MMTAA-R相比，显示出更宽的可见光吸收。红移的光吸收被证实是由MMTAA中噻唑环上氮的质子化引起的。此外，这种质子化还促进了电荷分离和转移，并提高了α-萜品烯选择性氧化为对异丙基甲苯的光催化活性。我们的结果为含氮铋基MOF扩展光吸收和提高光催化性能提供了新思路。
