Magnetic raspberry-like CuCo nanoalloy-embedded carbon as an enhanced activator of Oxone to degrade azo contaminant: Cu-induced hollowed structure and boosted activities.

ABSTRACT

Azo compounds, particularly azo dyes, are widely used but pose significant environmental risks due to their persistence and potential to form carcinogenic by-products. Advanced oxidation processes (AOPs) are effective in degrading these stubborn compounds, with Oxone activation being a particularly promising method. In this study, a unique nanohybrid material, raspberry-like CuCo alloy embedded carbon (RCCC), is facilely fabricated using CuCo-glycerate (Gly) as a template. With the incorporation of Cu into Co, RCCC is essentially different from its analogue derived from Co-Gly in the absence of Cu, affording a popcorn-like Co embedded on carbon (PCoC). RCCC exhibits a unique morphology, featuring a hollow spherical layer covered by nanoscale beads composed of CuCo alloy distributed over carbon. Therefore, RCCC significantly outperforms PCoC and Co3O4 for activating Oxone to degrade the toxic azo contaminant, Azorubin S (AS), in terms of efficiency and kinetics. Furthermore, RCCC remains highly effective in environments with high NaCl concentrations and can be efficiently reused across multiple cycles. Besides, RCCC also leads to the considerably lower Ea of AS degradation than the reported Ea values by other catalysts. More importantly, the contribution of incorporating Cu with Co as CuCo alloy in RCCC is also elucidated using the Density-Function-Theory (DFT) calculation and synergetic effect of Cu and Co in CuCo contributes to enhance Oxone activation, and boosts generation of SO4•-and •OH. The decomposition pathway of AS by RCCC + Oxone is also comprehensively investigated by studying the Fukui indices of AS and a series of its degradation by-products using the DFT calculation. In accordance to the toxicity assessment, RCCC + Oxone also considerably reduces acute and chronic toxicities to lower potential environmental impact. These results ensure that RCCC would be an advantageous catalyst for Oxone activation to degrade AS in water.