Structural and functional evolution of HKUST-1 nanoparticles induced by ball milling

In this study, the effect of post-synthetic ball milling on the structural and functional properties of as-synthesized nanoparticles of the copper-based metal-organic framework (MOF) HKUST-1 was investigated for the first time. Nanoparticles were synthesized using sodium formate as a capping agent. The crystalline particles were subjected to a controlled ball milling process, which induced significant structural changes. Powder X-ray diffraction (PXRD) revealed a reduction in crystallite size from 91 nm to 21 nm and the introduction of microstrain, partially disrupting the MOF's long-range crystalline order, as evidenced by peak broadening and the diminished intensity of high-angle reflections. Particle morphology pre- and post-milling was further studied with scanning electron microscopy (SEM) imaging, verifying a narrow particle size distribution of ± 22 nm after milling. Fourier-transform infrared spectroscopy (FTIR) indicated protonation of carboxylate groups in the larger pores of the framework, likely due to moisture incorporation during milling. Brunauer-Emmett-Teller (BET) surface area analysis showed a substantial decrease in specific surface area from 521 m²/g to 226 m²/g, suggesting a partial collapse of the porous framework. We discuss the applicability of ball milling as a versatile means of post-synthetic approach to reduce MOF particle sizes, a key element in the preparation of MOF-based thin films using inks or polymers.