Interface Engineering of Co(OH)₂ Nanosheets Growing on the KNbO₃ Perovskite Based on Electronic Structure Modulation for Enhanced Peroxymonosulfate Activation

Abstract

Material-enhanced heterogonous peroxymonosulfate (PMS) activation on emerging organic pollutant degradation has attracted intensive attention, and a challenge is the electron transfer efficiency from material to PMS for radical production. Herein, an interface architecture of Co(OH) 2 nanosheets growing on the KNbO 3 perovskite [Co(OH) 2 /KNbO 3 ] was developed, which showed high catalytic activity in PMS activation. A high reaction rate constant ( k 1 ) of 0.631 min –1 and complete removal of pazufloxacin within 5 min were achieved. X-ray photoelectron spectroscopy, X-ray absorption near edge structure spectra, and density functional theory (DFT) calculations revealed the successful construction of the material interface and modulated electronic structure for Co(OH) 2 /KNbO 3, resulting in the hole accumulation on Co(OH) 2 and electron accumulation on KNbO 3 . Bader topological analysis on charge density distribution further indicates that the occupations of Co-3d and O-2p orbitals in Co(OH) 2 /KNbO 3 are pushed above the Fermi level to form antibonding states (σ*), leading to high chemisorption affinity to PMS. In addition, more reactive Co(II) with the closer d-band center to the Fermi level results in higher electron transfer efficiency and lower decomposition energy of PMS to SO 4 •– . Moreover, the reactive sites of pazufloxacin for SO 4 •– attack were precisely identified based on DFT calculation on the Fukui index. The pazufloxacin pathways proceeded as decarboxylation, nitroheterocyclic ring opening reaction, defluorination, and hydroxylation. This work can provide a potential route in developing advanced catalysts based on manipulation of the interface and electronic structure for enhanced Fenton-like reaction such as PMS activation.

Topics & Concepts