Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, China.
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, China; Zhejiang Engineering Laboratory for Green Syntheses and Applications of Fluorine-Containing Specialty Chemicals, Institute of Advanced Fluorine-Containing Materials, Zhejiang Normal University, Jinhua 321004, China.
J Environ Sci (China). 2023 Oct;132:22-30. doi: 10.1016/j.jes.2022.10.037. Epub 2022 Oct 31.
The reduction of CO into high value-added chemicals and fuels by a photocatalytic technology can relieve energy shortages and the environmental problems caused by greenhouse effects. In the current work, an amino-functionalized zirconium metal organic framework (Zr-MOF) was covalently modified with different functional groups via the condensation of Zr-MOF with 2-pyridinecarboxaldehyde (PA), salicylaldehyde (SA), benzaldehyde (BA), and trifluoroacetic acid (TA), named Zr-MOF-X (X = PA, SA, BA, and TA), respectively, through the post-synthesis modification. Compared with Zr-MOF and Zr-MOF-TA, the introduction of PA, SA, or BA into the framework of Zr-MOF can not only enhance the visible-light harvesting and CO capture, but also accelerate the photogenerated charge separation and transfer, thereby improving the photocatalytic ability of Zr-MOF for CO reduction. These results indicate that the modification of Zr-MOF with electron-donating groups can promote the photocatalytic CO reduction. Therefore, the current work provides an instructive approach to improve the photocatalytic efficiency of CO reduction through the covalent modification of MOFs.
通过光催化技术将 CO 转化为高附加值的化学品和燃料,可以缓解能源短缺和温室效应引起的环境问题。在本工作中,通过 Zr-MOF 与 2-吡啶甲醛(PA)、水杨醛(SA)、苯甲醛(BA)和三氟乙酸(TA)的缩合,将氨基功能化的锆金属有机骨架(Zr-MOF)用不同的官能团共价修饰,分别命名为 Zr-MOF-X(X=PA、SA、BA 和 TA)。与 Zr-MOF 和 Zr-MOF-TA 相比,将 PA、SA 或 BA 引入 Zr-MOF 的骨架中不仅可以增强可见光捕获和 CO 捕获,还可以加速光生载流子的分离和转移,从而提高 Zr-MOF 对 CO 还原的光催化能力。这些结果表明,用给电子基团修饰 Zr-MOF 可以促进光催化 CO 还原。因此,本工作通过 MOFs 的共价修饰为提高 CO 还原的光催化效率提供了一种有指导意义的方法。