MOF-Templated Synthesis of 3D Bi2O3 Supracrystals with Bcc Packing

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.