Large-Scale Synthesis of Hierarchical Porous MOF Particles via a Gelation Process for High Areal Capacitance Supercapacitors

Abstract

Metal–organic frameworks (MOFs) with hierarchical porous structures have been attracting intense interest currently due to their promising applications in catalysis, energy storage, drug delivery, and photocatalysis. Current fabrication methods usually employ template-assisted synthesis or thermal annealing at high temperatures. However, large-scale production of hierarchical porous metal–organic framework (MOF) particles with a simple procedure and mild condition is still a challenge, which hampers their application. To address this issue, we proposed a gelation-based production method and achieved hierarchical porous zeolitic imidazolate framework-67 (called HP-ZIF67-G thereafter) particles conveniently. This method is based on a metal–organic gelation process through a mechanically stimulated wet chemical reaction of metal ions and ligands. The interior of the gel system is composed of small nano and submicron ZIF-67 particles as well as the employed solvent. The relatively large pore size of the graded pore channels spontaneously formed during the growth process is conducive to the increased transfer rate of substances within the particles. It is proposed that the Brownian motion amplitude of the solute is greatly reduced in the gel state, which leads to porous defects inside the nanoparticles. Furthermore, HP-ZIF67-G nanoparticles interwoven with polyaniline (PANI) exhibited an exceptional electrochemical charge storage performance with an areal capacitance of 2500 mF cm−2, surpassing those of many MOF materials. This stimulates new studies on MOF-based gel systems to obtain hierarchical porous metal–organic frameworks which should benefit further applications in a wide spectrum of fields ranging from fundamental research to industrial applications.