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1.
J Colloid Interface Sci ; 675: 275-292, 2024 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-38970913

RESUMO

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.

2.
Nanomaterials (Basel) ; 13(18)2023 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-37764595

RESUMO

Even though transition metals can activate Oxone to degrade toxic contaminants, bimetallic materials possess higher catalytic activities because of synergistic effects, making them more attractive for Oxone activation. Herein, nanoscale CuCo-bearing N-doped carbon (CuCoNC) can be designed to afford a hollow structure as well as CuCo species by adopting cobaltic metal organic frameworks as a template. In contrast to Co-bearing N-doped carbon (CoNC), which lacks the Cu dopant, CuCo alloy nanoparticles (NPs) are contained by the Cu dopant within the carbonaceous matrix, giving CuCoNC more prominent electrochemical properties and larger porous structures and highly nitrogen moieties. CuCoNC, as a result, has a significantly higher capability compared to CoNC and Co3O4 NPs, for Oxone activation to degrade a toxic contaminant, Rhodamine B (RDMB). Furthermore, CuCoNC+Oxone has a smaller activation energy for RDMB elimination and maintains its superior effectiveness for removing RDMB in various water conditions. The computational chemistry insights have revealed the RDMB degradation mechanism. This study reveals that CuCoNC is a useful activator for Oxone to eliminate RDMB.

3.
Chemosphere ; 327: 138469, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36963579

RESUMO

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.


Assuntos
Protetores Solares , Água , Água/química , Carbono/química , Cobalto/química , Plásticos
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