Karlsruhe Institute of Technology, Institute of Functional Interfaces (IFG), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
Nanoscale. 2018 Sep 20;10(36):17099-17104. doi: 10.1039/c8nr04204g.
We describe a non-conventional, MOF-based approach with modified linkers to fabricate 3D Bi2O3 supracrystals. The nanoparticle (NP) assembly exhibits bcc-packing, which is difficult to achieve with other methods. The NPs possess a very narrow size distribution. The individual NPs were synthesized inside the pores of a surface-mounted metal-organic framework (SURMOF) template via a photo-decomposition procedure. The supracrystals were thoroughly characterized using X-ray diffraction (XRD), infrared (IR) and Raman spectroscopy as well as high-resolution transmission electron microscopy (HR-TEM) and SAED (Selected Area Electron Diffraction). In order to achieve sharp size distributions of the NPs, the pores within the SURMOF were functionalized with amino (-NH2) functional groups acting as nucleation centers. MOFs lacking such additional functionalities, Cu3(BTC)2, yielded much broader size distributions. These findings provide a unique molecular design tool for creating nanometer-sized reaction compartments for the synthesis of supracrystals with packing types not accessible via self-assembly.
我们描述了一种基于 MOF 的非常规方法，通过修饰连接物来制造 3D Bi2O3 超晶体。该纳米粒子（NP）组装体表现出体心立方（bcc）堆积，这很难通过其他方法实现。NP 具有非常窄的尺寸分布。通过光分解程序，在表面安装的金属有机骨架（SURMOF）模板的孔内合成了单个 NPs。通过 X 射线衍射（XRD）、红外（IR）和拉曼光谱以及高分辨率透射电子显微镜（HR-TEM）和选区电子衍射（SAED）对超晶体进行了彻底的表征。为了实现 NP 尺寸分布的锐化，用氨基（-NH2）官能团对 SURMOF 内的孔进行功能化，作为成核中心。缺乏这种附加功能的 MOF，Cu3（BTC）2，产生了更宽的尺寸分布。这些发现为创建纳米级反应隔室提供了独特的分子设计工具，用于合成通过自组装无法获得的具有包装类型的超晶体。
