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

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.

Enhancing catalytic activity of CuCoFe-layered double oxide towards peroxymonosulfate activation by coupling with biochar derived from durian peel for antibiotic degradation: The role of C=O in biochar and underlying mechanism of built-in electric field.

CuCoFe-LDO/BCD was successfully synthesized from CuCoFe-LDH and biochar derived from durian shell (BCD). Ciprofloxacin (CFX) degraded more than 95% mainly by O2•- and 1O2 in CuCoFe-LDO/BCD(2/1)/PMS system within 10 min with a rate constant of 0.255 min-1, which was 14.35 and 2.66 times higher than those in BCD/PMS and CuCoFe-LDO/PMS systems, respectively. The catalytic system exhibited good performance over a wide pH range (3-9) and high degradation efficiency of other antibiotics. Built-in electric field (BIEF) driven by large difference in the work function/Fermi level ratio between CuCoFe-LDO and BCD accelerated continuous electron transfer from CuCoFe-LDO to BCD to result in two different microenvironments with opposite charges at the interface, which enhanced PMS adsorption and activation via different directions. As a non-radical, 1O2 was mainly generated via PMS activation by C=O in BCD. The presence of C=O in BCD resulted in an increase in atomic charge of C in C=O and redistributed the charge density of other C atoms. As a result, strong adsorption of PMS at C atom in C=O and other C with a high positive charge was favorable for 1O2 generation, whereas an enhanced adsorption of PMS at negatively charged C accounted for the generation of •OH and SO4•-. After adsorption, electrons in C of BCD became deficient and were fulfilled with those transferred from CuCoFe-LDO driven by BIEF, which ensured the high catalytic activity of CuCoFe-LDO/BCD. O2•-, on the other hand, was generated via several pathways that involved in the transformation of •OH and SO4•- originated from PMS activation by the transition of metal species in CuCoFe-LDO and negatively charged C in BCD. This study proposed a new idea of fabricating a low-cost metal-LDH and biomass-derived catalyst with a strong synergistic effect induced by BIEF for enhancing PMS activation and antibiotic degradation.

Templating agent-mediated Cobalt oxide encapsulated in Mesoporous silica as an efficient oxone activator for elimination of toxic anionic azo dye in water: Mechanistic and DFT-assisted investigations.

While Azorubin S (AZRS) is extensively used as a reddish anionic azo dye for textiles and an alimentary colorant in food, AZRS is mutagenic/carcinogenic, and it shall be removed from dye-containing wastewaters. In view of advantages of SO4•--related chemical oxidation technology, oxone (KHSO5) would an ideal source of SO4•- for degrading AZRS, and heterogeneous Co3O4-based catalysts is required and shall be developed for activating oxone. Herein, a facile protocol is proposed for fabricating mesoporous silica (MS)-confined Co3O4 by a templating agent-mediated dry-grinding procedure. As the templating agent retained inside the ordered pores of MS (before calcination) would facilitate insertion and dispersion of Co ions into pores, the resulting Co3O4 nanoparticles (NPs) would be grown and confined within the pores of MS after calcination, affording Co@MS. On the contrary, another analogue, Co/MS, is also prepared using the similar protocol without the templating agent-mediated introduction of Co, but Co3O4 NPs seriously aggregate as clusters on MS. Therefore, Co@MS outperforms Co/MS for activating oxone to eliminate AZRS. Co@MS shows a noticeably lower activation energy of AZRS elimination than the existing catalysts, revealing its advantage over the reported catalysts. Moreover, the mechanistic investigation of AZRS elimination by Co@MS-activated oxone has been also elucidated for identifying the presence of SO4•‒, •OH, and 1O2 in AZRS degradation using scavengers, electron paramagnetic resonance spectroscopy, and semi-quantification. The AZRS decomposition pathway is also investigated and unveiled in details via the DFT calculation. These results validate that Co@MS appears as a superior catalyst of oxone activation for AZRS degradation.

Boosting elimination of sunscreen, Tetrahydroxybenzophenone (BP-2), from water using monopersulfate activated by thorny NanoBox of Co@C prepared via the engineered etching strategy: A comparative and mechanistic investigation.

As sunscreens, benzophenones (BPs), are regarded as emerging contaminants, most of studies are focused on removal of 2-hydroxy-4-methoxybenzophenone (BP-3), which, however, has been employed for protecting skin. Another major class of BPs, which is used to prevent UV-induce degradation in various products, is completely neglected. Thus, this present study aims to develop a useful advanced oxidation process (AOP) for the first time to eliminate such a class of BP sunscreens from contaminated water. Specifically, 2,2',4,4'-Tetrahydroxybenzophenone (BP-2) would be focused here as BP-2 is intensively used in perfumes, lipsticks, and plastics for preventing the UV-induced degradation. As monopersulfate (MPS)-based AOP is practical for degrading emerging contaminants, a facile nanostructured cobalt-based material is then developed for maximizing catalytic activities of MPS activation by immobilizing Co nanoparticles onto carbon substrates. In particular, ZIF-67 is employed as a template, followed by the etching and carbonization treatments to afford the thorny nanobox of Co@C (TNBCC) with the hollow-nanostructure. In comparison to the solid (non-hollow) nanocube of Co@C (NCCC) from the direct carbonization of ZIF-67, TNBCC possesses not only the excellent textural features, but also superior electrochemical properties and highly reactive surfaces, making TNBCC exhibit the significantly higher catalytic activity than NCCC as well as Co3O4 in activating MPS to degrade BP-2. Mechanisms of BP-2 degradation are also elucidated and ascribed to both radical and non-radical routes. These advantageous features make TNBCC a useful catalyst of activating MPS in BP-2 degradation.

Ultrasound process-enhanced removal of the toxic disinfection by-product bromate from water by aluminum: A comparative study.

As bromate removal and reduction can be also achieved using metals, aluminum (Al) appears as the most promising one for reduction of bromate because Al is abundant element and exhibits a high reduction power. Reactions between bromate and Al shall be even enhanced through ultrasound (US) process because US can facilitate mass transfer on liquid/solid interfaces and clean surfaces via generating microscale turbulence to facilitate reactions. Therefore, the aim of this study is for the first time to investigate the effect of US on bromate removal by Al metal. Specifically, Al particle would be treated by HCl to afford HCl-treated Al (HCTAL), which is capable of removing bromate and even reducing it to bromide. Such a mechanism is also validated by density function theory calculation through determining adsorption energy as -152.8 kJ/mole, and oxygen atoms of bromate would be extracted and reacted with Al atoms, releasing bromide ion. US not only facilitated bromate removal by further increasing removal capacity under the acidic condition but also suppressed the inhibitive effect from basicity at relatively high pH. The spent HCTAL could still remove bromate and convert it to bromide after regeneration. These features indicate that US considerably enhances bromate removal by Al. PRACTITIONER POINTS: Bromate removed by Al is elucidated by DFT calculation with Eabsorption = -152.8 kJ/mole. Oxygen atoms of bromate are extracted and reacted with Al atoms, releasing bromide ion. A higher power of ultrasound would substantially enhance bromate removal efficiency. Ultrasound also suppresses the inhibitive effect from basicity at relatively high pH. With ultrasound, the interference of co-existing anions on bromate removal is lessened.

Enhanced degradation of ultra-violet stabilizer Bis(4-hydroxy)benzophenone using oxone catalyzed by hexagonal nanoplate-assembled CoS 3-dimensional cluster.

As UV-light stabilizers, Bis(4-hydroxy)benzophenone (BBP), are extensively consumed to quench radicals from photooxidation, continuous release of BPs into the environment poses serious threats to the ecology in view of their xenohormone toxicities, and BBP shall be eliminated from water to avoid its adverse effect. Since sulfate radical (SR)-based chemical oxidation techniques have been proven as effective procedures for eliminating organic emerging contaminants, this study aims to develop useful SR-based procedures through activating Oxone for degrading BBP in water. In contrast to the conventional Co3O4, cobalt sulfide (CoS) is particularly proposed as an alternative heterogeneous catalyst for activating Oxone to degrade BBP because CoS exhibits more reactive redox characteristics. As structures of catalysts predominantly control their catalytic activities, in this study, a unique nanoplate-assembled CoS (NPCS) 3D cluster is fabricated via a convenient one-step process to serve as a promising heterogeneous catalyst for activating Oxone to degrade BBP. With NPCS = 100 mg/L and Oxone = 200 mg/L, 5 mg/L of BBP can be completely eliminated in 60 min. The catalytic activity of NPCS towards Oxone activation also significantly surpasses the reference material, Co3O4, to enhance degradation of BBP. Ea of BBP degradation by NPCS-activated Oxone is also determined as a relatively low value of 42.7 kJ/mol. The activation mechanism as well as degradation pathway of BBP degradation by NPCS-activated Oxone was investigated and validated through experimental evidences and density functional theory (DFT) calculation to offer valuable insights into degradation behaviors for developing SR-based processes of BBP degradation using CoS catalysts.