Pressure-induced amorphization is one of the processes inhibiting functional properties of metal-organic frameworks (MOFs). Such amorphization often occurs when MOFs are being shaped for practical applications, as well as during certain exploitations. Typically, the porosity of MOFs, which is crucial for sorption, separation, and catalysis, suffers under external pressure. We report a new experimental approach for efficient monitoring of pressure-induced processes in MOFs that employs trace amounts of spin probes (stable nitroxide radicals) embedded in the pores of MOF and detection by electron paramagnetic resonance (EPR). EPR spectra of spin probes in MOF ZIF-8 demonstrate significant changes upon pressure-induced amorphization, whose extent can be quantitatively determined from the spectral shapes. Moreover, stabilization of ZIF-8 against amorphization via reversible adsorption of various guests was studied using this approach. Mitigation effect depends on diffusion parameters and localization of guest molecules in the cavity, and maintaining of the structure and permeability up to 80% was achieved even at 1.15 GPa applied. Therefore, the proposed methodology allows significant mitigation of MOF amorphization under external pressure and conveys further perspectives of the controlled adjustment of stabilizing agents for various MOFs and their applications.
Keywords: EPR spectroscopy; MOF; ZIF-8; amorphization; pressure; shaping; spin probe.