Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry , Chinese Academy of Sciences , Beijing 100190 , P. R. China.
School of Chemistry and Chemical Engineering , University of Chinese Academy of Sciences , Beijing 100049 , P. R. China.
ACS Appl Mater Interfaces. 2018 May 16;10(19):16418-16423. doi: 10.1021/acsami.8b01462. Epub 2018 May 2.
Metal-organic frameworks (MOFs) have proven to be an interesting class of sacrificial precursors of functional inorganic materials for catalysis, energy storage, and conversion applications. However, the controlled synthesis of MOF-derived materials with desirable compositions, structures, and properties still remains a big challenge. Herein, we propose a post-solvothermal route for the outer-to-inner loss of organic linkers from MOF, which is simple, rapid, and controllable and can be operated at temperature much lower than that of the commonly adopted pyrolysis method. By such a strategy, the MIL-125-NH particles coated by TiO nanosheets were produced, and the thickness of TiO shell can be easily tuned. The MIL-125-NH@TiO core-shell particles combine the advantages of highly active TiO nanosheets, MIL-125-NH photosensitizer, plenty of linker defects and oxygen vacancies, and mesoporous structure, which allows them to be utilized as photocatalysts for the visible-light-driven hydrogen production reaction. It is remarkable that the hydrogen evolution rate by MIL-125-NH@TiO can be enhanced 70 times compared with the pristine MIL-125-NH. Such a route can be easily applied to the synthesis of different kinds of MOF-derived functional materials.
金属-有机骨架（MOFs）已被证明是一类很有前途的牺牲前驱体，可用于催化、储能和转化等应用领域的功能无机材料。然而，如何可控地合成具有理想组成、结构和性能的 MOF 衍生材料仍然是一个巨大的挑战。在此，我们提出了一种 MOF 中有机配体的从外向内的后溶剂热损失方法，该方法简单、快速且可控，操作温度远低于常用的热解法。通过这种策略，制备了 TiO 纳米片包覆的 MIL-125-NH 颗粒，且 TiO 壳层的厚度可以很容易地进行调控。MIL-125-NH@TiO 核壳颗粒结合了高活性 TiO 纳米片、MIL-125-NH 敏化剂、丰富的配体缺陷和氧空位以及介孔结构的优点，可作为可见光驱动制氢反应的光催化剂。值得注意的是，与原始的 MIL-125-NH 相比，MIL-125-NH@TiO 的制氢速率提高了 70 倍。这种方法可以很容易地应用于不同种类的 MOF 衍生功能材料的合成。
