Shaping Phenolic Resin-Coated ZIF-67 to Millimeter-Scale Co/N Carbon Beads for Efficient Peroxymonosulfate Activation

Catalytic performance decline is a general issue when shaping fine powder into macroscale catalysts (e.g., beads, fiber, pellets). To address this challenge, a phenolic resin-assisted strategy was proposed to prepare porous Co/N carbon beads (ZACBs) at millimeter scale via the phase inversion method followed by confined pyrolysis. Specially, p-aminophenol-formaldehyde (AF) resin-coated zeolitic imidazolate framework (ZIF-67) nanoparticles were introduced to polyacrylonitrile (PAN) solution before pyrolysis. The thermosetting of the coated AF improved the interface compatibility between the ZIF-67 and PAN matrix, inhibiting the shrinkage of ZIF-67 particles, thus significantly improving the void structure of ZIF-67 and the dispersion of active species. The obtained ZACBs exhibited a 99.9% removal rate of tetracycline (TC) within 120 min, with a rate constant of 0.069 min^-1 (2.3 times of ZIF-67/PAN carbon beads). The quenching experiments and electron paramagnetic resonance (EPR) tests showed that radicals dominated the reaction. This work provides new insight into the fabrication of high-performance MOF catalysts with outstanding recycling properties, which may promote the use of MOF powder in more practical applications.