Aromatic Ring Opening Research Articles

Atomically dispersed Fe boosting elimination performance of g-C3N4 towards refractory sulfonic azo compounds via catalyst-contaminant interaction

Herein, an oxygen-doped porous g-C3N4 photocatalyst modified with atomically dispersed Fe (Fe1/OPCN) is successfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants from water via catalyst-contaminant interaction. The elimination performance of Fe1/OPCN towards acid red 9, acid red 13 and amaranth containing similar azonaphthalene structure and increasing sulfonic acid groups increases gradually. The amaranth degradation rate of Fe1/OPCN is 17.7 and 6.1 times as that of homogeneous Fenton and OPCN, respectively. In addition, Fe1/OPCN also has more outstanding removal activities towards other contaminants with sulfonic acid and azo groups alone. The considerable enhancement for removing sulfonic azo contaminants of Fe1/OPCN is mainly ascribed to the following aspects: (1) The modified Fe could enhance the adsorption towards sulfonic azo compounds to accelerate the mass transfer, act as e- acceptor to promote interfacial charge separation, and trigger the self-Fenton reaction to convert in-situ generated H2O2 into •OH. (2) Fe(Ⅲ) could coordinate with —N=N— to form d-π conjugation, which could attract e- transfer to attack —N=N— bond. Meanwhile, the inhibited charge recombination could release more free h+ to oxidize sulfonic acid groups into SO4-•. (3) Under the cooperation of abundant multiple active species (•O2-, h+, e-, •OH, SO4-•) formed during the degradation reaction, sulfonic azo compounds could be completely mineralized into harmless small molecules (CO2, H2O, etc.) by means of —N=N— cleavage, hydroxyl substitution, and aromatic ring opening. This work offers a novel approach for effectively eliminating refractory sulfonic azo compounds from wastewater.

Simultaneous degradation of pharmaceuticals and personal care products in hospital wastewater using ozone under ultraviolet irradiation

The discharge of Pharmaceuticals and personal care products (PPCPs) from industries and hospitals are responsible for the contamination of water body with slow or non-degradable toxic compounds. The removal of these contaminants required advanced treatment process because of unable to treat by conventional wastewater treatment process. In this study, the degradation of PPCP compounds, including caffeine (CAF), atenolol (ATL), carbamazepine (CBZ), sulfamethoxazole (SMX), trimethoprim (TMP), and acetaminophen (ACT) was evaluated under exposure to 1.0 and 1.5 mg/L dissolved ozone (O3), both with and without ultraviolet (UV) irradiation (254 nm). Using liquid chromatography with tandem mass spectrometry, we determined that the removal efficiency for the targeted contaminants exceeded 95 % within just 20 min of exposure to both 1.0 and 1.5 mg/L O3. However, when treated with UV light alone, the removal efficiency was limited at 3 %–11 %. A combination treatment involving dissolved 1.5 mg/L O3 and UV light led to over 97 % removal within 7 min. This outcome was attributed to hydroxylation reactions, aromatic ring opening, oxidation, and mineralization facilitated by the HO and peroxide generated through the photolysis of O3. The degradation rate of PPCP compounds followed pseudo-first-order kinetics and showed a decrease in the presence of humic acid and hospital wastewater further decreased it. Moreover, O3/UV treatment generated lower-weight degradation products. The toxicity analysis revealed that these transformation products exhibited environmental benignity and minimal health risks which O3/UV treatment potentially minimizes the presence of harmful byproducts. These findings provide a foundation for developing combined hybrid systems for PPCP containing wastewater, containing membrane filtration with ozonation system.

Effective abatement of naphthalene from flue gas by V-W/Ti catalyst: Study of vanadium species and reaction mechanism

The removal of naphthalene is important but deficient, so that the available V-W/Ti catalysts (1.0 wt% V2O5/TiO2) were prepared for its efficient abatement in this work. Especially, influences of different existence status of vanadium species on naphthalene elimination were investigated via changing the pH value of precursor solution. With the increase of precursor solution acidity, more highly polymeric vanadium species were formed on the catalyst surface. The redox capability was enhanced markedly as a consequence of the stronger electron transfer between V/W and Ti that induced more surface active oxygen and V5+, whereas the catalytic activity was obviously boosted and almost 90 % conversion of naphthalene was achieved at 293 °C. Moreover, the weaker chemisorption between naphthalene and V-W/Ti catalyst allowed the deeper conversion to COx. GC–MS manifested that naphthalene seemed to be an organic component that was difficult to be totally degraded. Naphthalene oxidation was in the following pathway of naphthalene → 1,4-naphthoquinone → phthalic anhydride → phthalates → benzene → benzoquinone → maleic anhydride → COx/H2O. The opening of aromatic ring in phthalic anhydride and benzene ring in benzene were proven to be the rate-controlling step based on in-situ DRIFTS results. The key of naphthalene oxidation was the complete degradation of various intermediates.

From aromatic rings to aliphatic compounds - degradation of duloxetine with the use of visible light driven Z-scheme photocatalyst

The growing consumption of antidepressants, associated with their high chemical stability and low biodegradability, become a serious problem for aquatic environment. Many of their components are resistant to conventional water treatment technologies. The photocatalytic processes with the use of semiconductors becoming attractive methods of drugs degradation because the highly reactive species: electrons, holes, hydroxyl radicals (⦁OH) and superoxide anion radicals (O2⦁−) generated under illumination may be involved directly or indirectly in decomposition of complicated organic molecules.In this work we have shown for the first time that Z-scheme photocatalyst, consisted of bismuth vanadate (BiVO4), graphitic-like carbon nitride (g-C3N4) and Au nanoparticles (Au NPs) as a charge transfer mediator, is very efficient in degradation of duloxetine (DLX). We performed the comprehensive evaluation focused not only on degradation rate, mechanism of photocatalytic process, but also identification of decomposition products and the pathways of DLX degradation. Due to application of the elaborated Z-scheme photocatalyst, the degradation rate constant was more than 2-3 times higher than that obtained for photolysis, but more important, the final compounds were mainly aliphatic products, formed by opening of aromatic rings. The chemical structure of the degradation products were determined with the use of HPLC and LC-MS. The toxicity of photoproducts with respect to water organisms was tested by means of Spirotox and Microtox assays. The Microtox test indicated that toxicity of the products after 6h of the solution irradiation in the presence of Z-scheme photocatalyst is about 4 times lower than that after photolysis.

Molecular weight fraction-specific transformation of natural organic matter during hydroxyl radical and sulfate radical oxidation

Aquatic natural organic matter (NOM) is one of the main scavengers of reactive species (e.g., •OH and SO4•−) during oxidation processes and undergoes complex transformations. Here, the organic content, optical properties, and redox state in various MW fractions and bulk Suwannee River NOM (SRNOM) were simultaneously evaluated during •OH and SO4•− oxidation processes for the first time. The SRNOM transformation pathways were specific to radical species and MW fractions, which was evidenced by a proportional decrease in electron-donating moieties and chromophores during •OH oxidation but a higher decrease in electron-donating moieties than chromophores during SO4•− oxidation, particularly in lower MW fractions (<3 kDa). The •OH decomposed reactive moieties mainly via aromatic ring opening or depolymerization in all MW fractions. SO4•− oxidation followed a similar pathway in higher MW fractions (>3 kDa) but mainly formed compounds with UV-absorbing properties (e.g., quinones) in lower MW fractions (<3 kDa). With competitive kinetics and depolymerization model, •OH was quantified as approximately 10 times more reactive towards MW fractions than SO4•−. However, the SO4•− concentrations were approximately 10 times those of •OH, resulting in comparable performance to •OH oxidation. SRNOM depolymerization by •OH and SO4•− resulted in formation of more precursors of disinfection byproducts than the parent constituents, especially for •OH. This work improves our understanding of the transformation of specific SRNOM fractions during radical oxidation processes.

Multiple effects of iron oxides on the adsorption and oxidation of dissolved organic matter by manganese oxides

Adsorptive fractionation and oxidation of dissolved organic matter (DOM) on manganese (Mn) oxide surfaces alter the molecular composition and stability of DOM, but the impact of iron (Fe) oxides on the coupled adsorption-oxidation processes of DOM by Mn oxides is largely unknown. In this study, the underlying mechanisms of molecular transformation of DOM on birnessite (Bir) in the presence of ferrihydrite (Fh), with varying Fh/Bir mass ratios, were investigated at both molecular levels and microscopic scales with a suite of characterization techniques, including Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and spherical aberration corrected scanning transmission electron microscopy (Cs-STEM). We found that higher Fh/Bir mass ratio impeded the adsorption of DOM by birnessite and the reductive dissolution of birnessite to release dissolved Mn, and the impediment on the reductive dissolution of birnessite was proportional to Fh/Bir mass ratio. Overall, during the interactions of DOM with ferrihydrite and birnessite, phenolic compounds were preferentially adsorbed by Fe and Mn minerals, and compounds with higher oxygen contents and polymeric substances were formed. FT-ICR-MS analysis further suggested that higher Fh/Bir mass ratio inhibited the occurrence of aromatic ring-opening and carboxylation of substituted groups on aromatic rings, but promoted polymerization of phenolic compounds. Cs-STEM analysis revealed that DOM distributions on ferrihydrite, birnessite, and their mixtures were regulated by their microscopic structures and reactivity. Compared with aromatic carbon (C), carboxylic and phenolic C were more likely to associate with birnessite. Our results highlighted the significance of organo-mineral associations with the mixed minerals in regulating the distribution and reactivity of organic C. This study has provided molecular evidences for molecular transformation of DOM mediated by both Mn and Fe oxides, which contributed to advancing our understanding on coupled reactions of organic C at the mineral–water interfaces in the environment.

Influence mechanisms of torrefaction on syngas production from bio-waste molten salt thermal treatment

The production of high-value syngas from bio-wastes through thermal conversion is a promising way to achieve carbon neutrality. In order to reduce the cost of the process, molten salt thermal treatment has been used for bio-wastes syngas production. Moreover, the removal of oxygen and water induced by torrefaction can effectively enhance the energy density of biomass, and the effect of these changes on the quality of syngas was widely investigated. This study proposed to torrefy bio-wastes and then produce syngas in molten NaNO3-NaNO2-KNO3 at 300 ℃. Results showed that the evaluation indices of syngas were improved, while the cold gas efficiency reached 44.02 % for beech wood torrefied at 280 ℃, and the syngas quality is equivalent to the products obtained by gasification of bio-wastes. The gas yield of the torrefied bio-wastes was increased by 8.08–45.23 % compared to the raw bio-wastes. Na+ and K+ in the molten salt catalyzed the cracking of propyl chains and ring opening of aromatic rings in lignin, resulting in a prominent enhancement in CO yield. Meanwhile, torrefaction could change the solid structure, leading to a delay in gas production, and torrefaction could also increase graphitization degree of char (C–C/C = C up to 50.72 % for SB-280), thus preventing the reaction proceeding. This study provided a new approach to enhance the content and quality of syngas from bio-wastes at low temperatures.

Aerobic Microbial Transformation of Fluorinated Liquid Crystal Monomer: New Pathways and Mechanism.

Fluorinated liquid crystal monomers (FLCMs) have been suggested as emerging contaminants, raising global concern due to their frequent occurrence, potential toxic effects, and endurance capacity in the environment. However, the environmental fate of the FLCMs remains unknown. To fill this knowledge gap, we investigated the aerobic microbial transformation mechanisms of an important FLCM, 4-[difluoro(3,4,5-trifluorophenoxy)methyl]-3, 5-difluoro-4'-propylbiphenyl (DTMDPB), using an enrichment culture termed as BG1. Our findings revealed that 67.5 ± 2.1% of the initially added DTMDPB was transformed in 10 days under optimal conditions. A total of 14 microbial transformation products obtained due to a series of reactions (e.g., reductive defluorination, ether bond cleavage, demethylation, oxidative hydroxylation and aromatic ring opening, sulfonation, glucuronidation, O-methylation, and thiolation) were identified. Consortium BG1 harbored essential genes that could transform DTMDPB, such as dehalogenation-related genes [e.g., glutathione S-transferase gene (GST), 2-haloacid dehalogenase gene (2-HAD), nrdB, nuoC, and nuoD]; hydroxylating-related genes hcaC, ubiH, and COQ7; aromatic ring opening-related genes ligB and catE; and methyltransferase genes ubiE and ubiG. Two DTMDPB-degrading strains were isolated, which are affiliated with the genus Sphingopyxis and Agromyces. This study provides a novel insight into the microbial transformation of FLCMs. The findings of this study have important implications for the development of bioremediation strategies aimed at addressing sites contaminated with FLCMs.

C vacancy and F decorated g-C3N4 for boosting photocatalytic ozonation of sodium p-perfluorinated nonoxybenzenesulfonate

Photocatalytic ozonation (PCO) was a novel water treatment method, but the low photo-generated electron (e-) utilization and ambiguous ROS formation mechanism restrained its performance. Herein, C vacancy and F co-decorated g-C3N4 (FCN_Cv) was designed to accelerate the PCO performance with sodium p-perfluorinated nonoxybenzenesulfonate (OBS) acting as model pollutant. Comparative characterizations revealed that FCN_Cv remained the inherent structure of g-C3N4 (BCN), and had an enhanced conduction band potential, narrower band gap and longer e- lifetime. FCN_Cv exhibited the greater activity over BCN, with 99.3 % OBS removal in 30 min but only 78.3 % for BCN during PCO process. •OH was the main ROS for degrading OBS. The greater •OH yield was obtained by FCN_Cv PCO process because of the increase of e- utilization. On one hand, the two electrons reduction of O2 into H2O2 on FCN_Cv was accelerated, which triggered the peroxone reaction between photogenerated-H2O2 and O3. On the other hand, the direct one electron reduction of O3 by e- also accounted for •OH generation. 17 kinds of intermediates were detected and the OBS degradation routes were inferred, which was involved with hydroxylation, C-O cleavage and aromatic ring opening reactions. Overall, this study demonstrated the feasibility of decorating F element and C vacancy on g-C3N4 in enhancing e- utilization and •OH generation during PCO process as well as deepened the understanding of fate of OBS in PCO process.

The mechanism of H2O in the superheated steam affecting pyrolysis of the kaolinite-associated kerogen

In this work, ReaxFF molecular dynamics (MD) simulation was adopted to investigate the effect of superheated steam on the conversion of the kaolinite-associated Barkol kerogen (BLK) and reveal the corresponding mechanism. The ReaxFF simulated weight loss rate (DTG) and release tendency of H2O, H2 and CO2 for BLK and the kaolinite-associated BLK agreed well with the results of Py-MS experiments. H-rich rate, double bond equivalents (DBEs), and hydrocarbon content were adopted to assess the quality of C5-C40, and configurations of C40+ were extracted to investigate the characteristics of residues. And the H2Osteam- and kaolinite-involved (steam refers to the superheated steam) reactions were analyzed. The results indicate that B- and L-acid sites of kaolinite co-catalyzed decomposition of BLK into heavy oil and shale gas in the kaolinite-pyrolysis system, and in steam/kaolinite-pyrolysis system, H2Osteam further promoted decomposition of BLK into higher quality shale oil, especially for C5-C13 components, remaining higher aromatic and porous residues. And this enhanced effect of H2Osteam is attributed to kaolinite and the induced decomposition of H2Osteam molecules and their participation as reactants in reactions in two aspects: i) interaction between kaolinite and H2Osteam, on one hand, inhibited formation of L-acids and facilitated generation of B-acids to catalyze carbocation ion reactions process, further weakened dehydrogenation of organics catalyzed by L-acid sites, and enhanced cracking of residues catalyzed by B-acaid sites, on the other hand, promoted decomposition of H2Osteam molecules to form H-rich environment and further weakened dehydrogenation of organics; ii) attacking Car directly, H2Osteam promoted shedding of alkyl side chains and ring-opening of aromatics to increase the –CH2– content in shale oil. This paper provides theoretical guidance for further understanding mechanism of H2Osteam on pyrolysis of kaolinite-associated kerogen and corresponding catalyst development and preparation.

Natural sunlight driven degradation of tetracycline in wastewater by dual Z − scheme photocatalyst of hollow nanospherical β–In2S3 decorated g − C3N4/WO3: performance, mechanism and products toxicity

The dual Z–scheme photocatalysts of β–In2S3/g − C3N4/WO3 (ISCNWO) were synthesized with improved light adsorption, carrier separation and specific surface area for tetracycline (TC) degradation by sunlight irradiation. The ISCNWO2 exhibited superior solar photodegradation performance of TC, and the kinetic constant was 2.2, 5.6 and 2.3 times that of g–C3N4, WO3 and In2S3, respectively. According to response surface methodology, the optimum TC removal was 96.4 ± 0.37 % at pH = 3.4 for 140 min irradiation without electrolyte. Even in river, municipal, hospital, frog farming field and tail wastewater, TC degradation efficiencies under solar irradiation for 300 min were > 74 %. As the lower work function of WO3 than that of In2S3 and g–C3N4 calculated by density functional theory (DFT), the electrons migrated from WO3 to In2S3 and g–C3N4 driven by built–in electric field. Under destruction of O2− and OH radicals, TC progressively transformed into 22 intermediates by addition, aromatic ring opening, etc. The toxicity prediction and in vivo experiments towards D. magna, V. fisheri and E. coil suggested that some intermediate products had relative high acute and bioaccumulation toxicity, so it was necessary to control ecological risks. Besides, as the satisfactory reusability of ISCNWO2 with 82.9 % TC removal after 5 cycles, the ISCNWO might had great application prospects in the treatment and remediation of antibiotic contaminated wastewater/natural water.

Investigating pyrolysis characteristics of Shengdong coal through Py-GC/MS

Abstract Shengdong coal was single-step and multi-step pyrolyzed by pyrolysis-gas chromatography/mass spectrometry. In the single-step pyrolysis process, Mono-ring aromatics contents reach a maximum value at 800°C, while phenolic contents are significantly reduced, which might be attributed to the dehydroxylation of phenolics. Naphthalene content also reaches a maximum value at 800°C in the single-step pyrolysis process; however, naphthalene was not detected in the multi-step pyrolysis process. So naphthalene might come from the ring-opening of multi-ring aromatics or the cyclization of mono-ring aromatics in the single-step pyrolysis process. Only phenol and o-cresol were detected, but no p-cresol in the multi-step pyrolysis process; however, p-cresol content reaches a maximum value at 800°C, meanwhile, phenol content was decreased and o-cresol was disappeared in the single-step pyrolysis process, which suggests that p-cresol may be derived from isomerization of o-cresol or alkylation of phenol. It provides an idea for strengthening more basic research related to the rapid pyrolysis of coal.

Reaction Steps in Heterogeneous Photocatalytic Oxidation of Toluene in Gas Phase-A Review.

A review of the current literature shows there is no clear consensus regarding the reaction mechanisms of air-borne aromatic compounds such as toluene by photocatalytic oxidation. Potential oxidation reactions over TiO2 or TiO2-based catalysts under ultraviolet and visible (UV/VIS) illumination are most commonly considered for removal of these pollutants. Along the pathways from a model pollutant, toluene, to final mineralization products (CO2 and H2O), the formation of several intermediates via specific reactions include parallel oxidation reactions and formation of less-reactive intermediates on the TiO2 surface. The latter may occupy active adsorption sites and causes drastic catalyst deactivation in some cases. Major hazardous gas-phase intermediates are benzene and formaldehyde, classified by the International Agency for Research on Cancer (IARC) as Group 1 carcinogenic compounds. Adsorbed intermediates leading to catalyst deactivation are benzaldehyde, benzoic acid, and cresols. The three most typical pathways of toluene photocatalytic oxidation are reviewed: methyl group oxidation, aromatic ring oxidation, and aromatic ring opening.

Crystal structure of the monocupin ring-cleaving dioxygenase 5-nitrosalicylate 1,2-dioxygenase from Bradyrhizobium sp.

5-Nitrosalicylate 1,2-dioxygenase (5NSDO) is an iron(II)-dependent dioxygenase involved in the aerobic degradation of 5-nitroanthranilic acid by the bacterium Bradyrhizobium sp. It catalyzes the opening of the 5-nitrosalicylate aromatic ring, a key step in the degradation pathway. Besides 5-nitrosalicylate, the enzyme is also active towards 5-chlorosalicylate. The X-ray crystallographic structure of the enzyme was solved at 2.1 Å resolution by molecular replacement using a model from the AI program AlphaFold. The enzyme crystallized in the monoclinic space group P21, with unit-cell parameters a=50.42, b = 143.17, c = 60.07 Å, β = 107.3°. 5NSDO belongs to the third class of ring-cleaving dioxygenases. Members of this family convert para-diols or hydroxylated aromatic carboxylic acids and belong to the cupin superfamily, which is one of the most functionally diverse protein classes and is named on the basis of a conserved β-barrel fold. 5NSDO is a tetramer composed of four identical subunits, each folded as a monocupin domain. The iron(II) ion in the enzyme active site is coordinated by His96, His98 and His136 and three water molecules with a distorted octahedral geometry. The residues in the active site are poorly conserved compared with other dioxygenases of the third class, such as gentisate 1,2-dioxygenase and salicylate 1,2-dioxygenase. Comparison with these other representatives of the same class and docking of the substrate into the active site of 5NSDO allowed the identification of residues which are crucial for the catalytic mechanism and enzyme selectivity.

Chemically Recyclable Polymer System Based on Nucleophilic Aromatic Ring-Opening Polymerization.

The development of chemically recyclable polymers with desirable properties is a long-standing but challenging goal in polymer science. Central to this challenge is the need for reversible chemical reactions that can equilibrate at rapid rates and provide efficient polymerization and depolymerization cycles. Based on the dynamic chemistry of nucleophilic aromatic substitution (SNAr), we report a chemically recyclable polythioether system derived from readily accessible benzothiocane (BT) monomers. This system represents the first example of a well-defined monomer platform capable of chain-growth ring-opening polymerization through an SNAr manifold. The polymerizations reach completion in minutes, and the pendant functionalities are easily customized to tune material properties or render the polymers amenable to further functionalization. The resulting polythioether materials exhibit comparable performance to commercial thermoplastics and can be depolymerized to the original monomers in high yields.

Probing the Actual Role and Activity of Oxygen Vacancies in Toluene Catalytic Oxidation: Evidence from In Situ XPS/NEXAFS and DFT +UCalculation

Metal oxide catalysts like CeO2 exhibit promising prospects to replace the currently used noble metal catalysts in the catalytic oxidation of volatile organic compounds (VOCs). Although the oxygen vacancy is regarded as an active site of these novel catalysts in VOC elimination (e.g., toluene), its actual function and activity remain unclear due to the limitation in following its dynamic evolution during reactions. Meanwhile, because the oxygen vacancy involves the generation–consumption cycle of reactive oxygen species rather than being constant, this barrier causes a deficient understanding of oxygen species backfilling in rate-determining steps. Hence, CeO2-based catalysts with varying oxygen vacancy concentrations were synthesized for toluene oxidation through the tensile-strained lattice and electron deficit induced by cobalt doping. The evolutions of oxygen vacancies and oxygen species were directly followed by means of in situ X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure. Evidence was captured that oxygen vacancies directly participate in the subsurface storage and diffusion of reactive oxygen species besides their surface regeneration. This mechanism reflects the fundamentals of oxygen storage capacity in CeO2 by providing additional oxygen species as a supplement when needed. Additionally, part of the oxygen vacancies was discerned to be not active enough in oxygen species backfilling, leaving this process as a crucial rate-determining step besides aromatic ring opening. The toluene degradation mechanism, including electrophilic adsorption sites, and how cobalt regulates oxygen vacancy activity were also revealed via in situ spectroscopy and density functional theory + U calculation.

Design and synthesis of TiO2/Ti3C2 composites for highly efficient photocatalytic removal of acetaminophen: The relationships between synthesis parameters, physicochemical properties, and photocatalytic activity

In this study, we report the potential of TiO2/Ti3C2 composite fabricated by oxidation of MXene for degradation of persistent organic pollutants. The effect of the synthesis conditions (time, temperature, and reaction environment) on the morphology, physicochemical properties, and photocatalytic activity was investigated. It was found that acetaminophen degradation was positively correlated with TiO2 content in the composite structure. Furthermore, the findings confirmed that the synthesis reaction environment strongly influenced the obtained materials photocatalytic activity. The TiO2/Ti3C2 composite obtained by solvothermal route in the presence of hydrochloric acid and ammonium fluoride exhibited the highest efficiency towards acetaminophen degradation than other composite materials, for which ACT removal reached 92 % within 60 min of irradiation under simulated solar light. The improved photocatalytic performance can be attributed to the presence of anatase-rutile polymorphs exposing highly active { 0 0 1} and { 1 0 1} facets coupled with MXene. Superoxide anion radicals and hydroxyl radicals played a major role in ACT degradation. Moreover, 3-hydroxyacetaminophen was detected as the first intermediate of ACT degradation, leading quickly to aromatic ring opening and production of aliphatic acids. Overall, this work provides an effective strategy for designing novel and efficient MXene-based photocatalysts for the degradation of emerging contaminants in water systems.

Chlorine dioxide bleaching wastewater degradation in intimately coupled photocatalysis and functional bacteria: The roles of adsorption, photocatalysis, and biotransformation

Chlorine dioxide (ClO2) bleaching wastewater from bagasse brings a threat to human health. The intimate coupling of photocatalysis and biodegradation (ICPB) as a prospective green technique can remove environmental pollutants. Therefore, this study innovatively integrates functional bacteria with the ICPB system (ICPFB) and discusses the degradation mechanism, pathway, kinetic model, and microbial response behavior of the system to wastewater. The results show that the ICPFB system can simultaneously remove 95% absorbable organic halogen (AOX), 91% COD and 85% dissolved organic carbon (DOC), outperforming single photocatalysis (AOX 72%, COD 80%, DOC 68%) and biodegradation (AOX 41.4%, COD 66%, DOC 45%). Meanwhile, the reaction kinetics model of the ICPFB system is dC/dt = -KC1.22. According to the GC-MS analysis of degradation products, the degradation of organic compounds in wastewater involves gradual dechlorination and aromatic ring opening. Lastly, the Biofilm analysis shows that the functional bacteria possess abilities of dechlorination, aromatic ring opening and carbon oxidation.

Preparation and Performance Characterization of Exploding Foil Initiator Based on ODPA-ODA Polyimide Flyer.

The exploding foil initiator (EFI) system has been extensively used in ignition and detonation sequences and proved to be of high safety and reliability. Polyimide is considered the ideal flyer material for EFI due to its excellent performance, including thermal stability, outstanding mechanical properties, high radiation resistance, and excellent dielectric properties. In this study, we prepared the EFI based on a polyimide (ODPA-ODA) flyer, which is spin-coated and solidified on patterned copper film in situ. The electric explosion test shows that the prepared EFI has good working performance, and the 4000 V working voltage drove the flyer to reach a maximum velocity of 5096 m/s. The polyimide morphology and chemical structure after the electric explosion was observed by microscope, SEM, XPS, and FTIR, which showed that the polyimide flyer underwent thermal deformation and complex chemical reactions during an electric explosion. A large number of polyimide bonds broke to form new carbonyl compounds, and the opening of aromatic rings was accompanied by the formation of aliphatic hydrocarbon chains. The morphology and chemical structure analysis after the electric explosion test will lay a foundation for us to further understand the working principle and evolution process of polyimide (ODPA-ODA) flyer.

Insights into the degradation of diphenhydramine – An emerging SARS-CoV-2 medicine by UV/Sulfite

As Diphenhydramine (DPH) has been considered as a drug to treat SARS-CoV-2, the degradation of DPH from water was investigated and evaluated in this study by adopting an advanced oxidation/advanced reduction process – the UV/sulfite process. The UV/sulfite system was able to eliminate DPH within 6 mins under UV254nm and 1.0 mM sulfite. It was observed that the presence of NO3-, NO2-, Cl-, HCO3-, and SO42- anions in water can affect the performance of UV/Sulfite degradation system. The mechanism of UV/sulfite/anions was evaluated which the presence of NO3- in UV/sulfite process has revealed faster initial decay rate but lower final DPH removal. It was observed that the UV/Sulfite process was extremely sensitive to pH as the dissociation of ion species varied among pH. The reaction became sluggish in acidic solution due to the dissociation of less reactive species such as HSO3-. In alkaline solution, SO32- was the dominant species, producing powerful SO3∙- and eaq- when activated by UV at 254 nm. By conducting LC/MS analysis, the degradation pathway was proposed and can be summarized into four main pathways: hydroxylation, side chain cleavage, losing aromatic ring or ring opening. Scavenging tests were also carried out and validated the presence of various radicals contributing to the reaction, including eaq-, Ḣ, OḢ, SO3̇-, O2•- and SO4̇-.