Monodispersed ZIF-67 in situ nucleated on CoAl-LDH nanosheets for efficient carbamazepine degradation via activation of peroxymonosulfate

Abstract

Abundant exposed ligand-unsaturated sites of Co have been found to enhance the catalytic oxidation property of ZIF-67 material for peroxymonosulfate (PMS) catalysis. Nevertheless, serious stacking of ZIF-67 still poses a challenge to its application. Herein, we employed a specific in situ growth strategy to establish an LDHNS@ZIF-67 composite based on morphology modulation and performance optimization for carbamazepine (CBZ) degradation. ZIF-67 crystals were successfully grown in situ via nucleating on the CoAl-LDH nanosheets (LDHNSs) substrate surface, which facilitated the crystals’ dispersion. LDHNS@ZIF-67 (0.1 M) was optimized to display outstanding PMS catalytic activity for CBZ degradation, with almost 100% degradation in 5 min (PMS dose, 0.2 mM, catalyst dose, 25 mg/L, and CBZ concentration, 5 ppm). Quenching and electron paramagnetic resonance (EPR) tests confirmed that both radical substances (SO4•-) and nonradical substances (1O2) dominated the reaction system. As the active site, Co(II) ions on the LDHNS@ZIF-67 (0.1 M) surface effectively promoted active substance formation. The intermediate degradation products and pathways for CBZ were investigated. Toxicity assessment for CBZ and its intermediates was conducted. This work will broaden the application of ZIF-67 materials in advanced oxidation process design based on persulfate.