1. Enzyme-immobilized hierarchically porous covalent organic framework biocomposite for catalytic degradation of broad-range emerging pollutants in waterNada Elmerhi, Khadega Al-Maqdi, Khawlah Athamneh, Abdul Khayum Mohammed, Tina Škorjanc, Felipe Gándara, Jesus Raya, Pascal Simon, Olivier Siri, Ali Trabolsi, 2023, original scientific article Abstract: Efficient enzyme immobilization is crucial for the successful commercialization of large-scale enzymatic water treatment.
However, issues such as lack of high enzyme loading coupled with enzyme leaching present challenges for the widespread adoption
of immobilized enzyme systems. The present study describes the development and bioremediation application of an enzyme
biocomposite employing a cationic macrocycle-based covalent organic framework (COF) with hierarchical porosity for the
immobilization of horseradish peroxidase (HRP). The intrinsic hierarchical porous features of the azacalix[4]arene-based COF
(ACA-COF) allowed for a maximum HRP loading capacity of 0.76 mg/mg COF with low enzyme leaching (<5.0%). The
biocomposite, HRP@ACA-COF, exhibited exceptional thermal stability (~200% higher relative activity than the free enzyme),
and maintained ~60% enzyme activity after five cycles. LCMSMS analyses confirmed that the HRP@ACA-COF system was able
to achieve >99% degradation of seven diverse types of emerging pollutants (2-mercaptobenzothiazole, paracetamol, caffeic acid,
methylparaben, furosemide, sulfamethoxazole, and salicylic acid)in under an hour. The described enzyme-COF system offers
promise for efficient wastewater bioremediation applications.
Keywords: covalent organic frameworks, enzymes, emerging pollutants, water purification, biocomposite
Published in RUNG: 11.08.2023; Views: 2825; Downloads: 11
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2. Defective ▫$TiO_2$▫ nanotube arrays for efficient photoelectrochemical degradation of organic pollutantsManel Machreki, Takwa Chouki, Georgi Tyuliev, Dušan Žigon, Bunsho Ohtani, Alexandre Loukanov, Plamen Stefanov, Saim Emin, 2023, original scientific article Abstract: Oxygen vacancies (OVs) are one of the most critical factors that enhance the electrical and catalytic characteristics of metal oxide-based photo-electrodes. In this work, a simple procedure was applied to prepare reduced TiO 2 nanotube arrays (NTAs) (TiO 2−x) via a one-step reduction method using NaBH 4. A series of characterization techniques were used to study the structural, optical, and electronic properties of TiO 2−x NTAs. X-ray photoelectron spectroscopy confirmed the presence of defects in TiO 2−x NTAs. Photoacoustic measurements were used to estimate the electron-trap density in the NTAs. Photoelectrochemical studies show that the photocurrent density of TiO 2−x NTAs was nearly 3 times higher than that of pristine TiO 2. It was found that increasing OVs in TiO 2 affects the surface recombination centers, enhances electrical conductivity, and improves charge transport. For the first time, a TiO 2−x photoanode was used in the photo-electrochemical (PEC) degradation of a textile dye (basic blue 41, B41) and ibuprofen (IBF) pharmaceutical using in situ generated reactive chlorine species (RCS). Liquid chromatography coupled with mass spectrometry was used to study the mechanisms for the degradation of B41 and IBF. Phytotoxicity tests of B41 and IBF solutions were performed using Lepidium sativum L. to evaluate the potential acute toxicity before and after the PEC treatment. The present work provides efficient PEC degradation of the B41 dye and IBF in the presence of RCS without generating harmful products.
Keywords: TiO2, nanotube arrays, photoelectrochemical degradation, organic pollutants
Published in RUNG: 12.06.2023; Views: 2568; Downloads: 12
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3. Effects of Different Copper Loadings on the Photocatalytic Activity of TiO2-SiO2 Prepared at a Low Temperature for the Oxidation of Organic Pollutants in WaterT. Čižmar, Iztok Arčon, Mattia Fanetti, Urška Lavrenčič Štangar, 2018, original scientific article Abstract: The objective of this research is to examine how Cu modification can improve the photocatalytic activity of TiO2-SiO2, to explainthe correlation between the Cu concentration and the chemical state of Cu cations in the TiO2-SiO2 matrix, and the photocatalytic activity under UV/solar irradiation. The Cu-modified TiO2-SiO2 photocatalysts were prepared by a low-temperature sol–gel method from organic Cu, Si and Ti precursors with various Cu concentrations (0.05–3 mol %). The sol–gels were dried at 150 8C to obtain the photocatalysts in a powder form. The photocatalytic activity was determined by using a fluorescence- based method of terephthalic acid decomposition. An up to three times increase in photocatalytic activity is obtained if the TiO2-SiO2 matrix is modified with Cu in a narrow concentration
range from 0.05 to 0.1 mol%. At higher Cu loadings,
the photocatalytic activity of the Cu-modified photocatalysts is lower than that of the un-modified reference TiO2-SiO2 photocatalyst. XRD was used to show that all Cu-modified TiO2-SiO2 composites with different Cu concentrations have the same crystalline structure as un-modified TiO2-SiO2 composites. The addition of Cu does not change the relative ratio between the anatase and brookite phases or unit cell parameters of the two TiO2 crystalline structures. We used Cu K-edge X-ray absorption near edge structure and extended X-ray absorption fine structure analyses to determine the valence state and local structure of Cu cations in the Cu-modified TiO2-SiO2 photocatalysts. The results elucidate the mechanism responsible for the improved photocatalytic activity. In samples with a low Cu content,
which exhibit the highest activity, Cu@O@Ti connections
are formed, which suggests that the activity enhancement is
caused by the attachment of CuII cations on the surface of the photocatalytically active TiO2 nanoparticles, so CuII cations may act as free-electron traps, which reduce the intensity of recombination between electrons and holes at the TiO2 photocatalyst surface. At higher Cu loadings no additional Cu@O@Ti connections are formed, instead only Cu@O@Cu connections are established. This indicates the formation of amorphous or nanocrystalline
copper oxide, which hinders the photocatalytic activity
of TiO2.
Keywords: Cu modified TiO2-SiO2 photocatalyst
Cu EXAFS, XANES, Organic pollutants
Published in RUNG: 30.08.2018; Views: 5247; Downloads: 0
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4. Extraction of Organochlorine Pesticides from Plastic Pellets and Plastic Type AnalysisMaryline Pflieger, Petra Makorič, Manca Kovač Viršek, Špela Koren, 2017, review article Abstract: Plastic resin pellets, categorized as microplastics (≤5 mm in diameter), are small granules that can be unintentionally released to the
environment during manufacturing and transport. Because of their environmental persistence, they are widely distributed in the oceans and
on beaches all over the world. They can act as a vector of potentially toxic organic compounds (e.g., polychlorinated biphenyls) and might
consequently negatively affect marine organisms. Their possible impacts along the food chain are not yet well understood. In order to assess the
hazards associated with the occurrence of plastic pellets in the marine environment, it is necessary to develop methodologies that allow for rapid
determination of associated organic contaminant levels. The present protocol describes the different steps required for sampling resin pellets,
analyzing adsorbed organochlorine pesticides (OCPs) and identifying the plastic type. The focus is on the extraction of OCPs from plastic pellets
by means of a pressurized fluid extractor (PFE) and on the polymer chemical analysis applying Fourier Transform-InfraRed (FT-IR) spectroscopy.
The developed methodology focuses on 11 OCPs and related compounds, including dichlorodiphenyltrichloroethane (DDT) and its two main
metabolites, lindane and two production isomers, as well as the two biologically active isomers of technical endosulfan. This protocol constitutes
a simple and rapid alternative to existing methodology for evaluating the concentration of organic contaminants adsorbed on plastic pieces.
Keywords: Environmental Sciences, Issue 125, Microplastics, resin pellets, pesticides, persistent organic pollutants, organochlorine pesticides, dichlorodiphenyltrichloroethane, endosulfan, hexachlorocyclohexane, lindane, Fourier transform infrared spectroscopy, pressurized fluid extractor
Published in RUNG: 10.07.2017; Views: 6150; Downloads: 0 |
