Degradation Of Organic Contaminants Research Articles

Carbazolyl-Decorated Metal-Organic Framework with a High Fluorescent Quantum Yield for Detection and Photocatalytic Degradation of Organic Contaminants.

A carbazolyl-based fluorescent metal-organic framework with deep-blue light emission and a high quantum yield (88%) has been screened out by changing the ratio of mixed ligands, named Cz-MOF-2, which was constructed by ZrO4(OH)4 clusters, 3-(9-ethyl-9H-carbazol-3-yl)-4-methylthieno[2,3-b]thiophene-2,5-dicarboxylate (H2ECMTDC) and 3,4-dimethyl-dihydrothieno[2,3-b]thiophene-2,5-dicarboxylate (H2DMTDC). Cz-MOF-2 has excellent sensitivity in fluorescent sensing of 2,6-dichloro-4-nitroaniline (DCN), nitrofurazone (NZF), and nitrofurantoin (NFT) with detection limits of 3.37 × 10-7, 1.64 × 10-5, and 1.76 × 10-5 M, respectively. The quenching mechanisms involving electron transfer and competitive absorption were comprehensively elucidated through DFT calculations and UV absorption experiments. Cz-MOF-2 has been fabricated into a rapidly regenerated composite membrane with PVDF as a visualized fluorescent sensor for DCN. Furthermore, the carbazolyl groups covalently modified in the framework endowed Cz-MOF-2 with a suitable band gap (2.58 eV) for photocatalytic degradation of organic contaminants. It demonstrated superior photocatalytic efficiency compared to UiO-66 and NH2-UiO-66 in the degradation of tetracycline (TC), and the removal efficiency was up to 85% (20 mg of catalyst, 50 mL, 20 mg/L TC solution and 180 min) under simulated sunlight irradiation using a 300 W Xe lamp. Photoelectrochemical tests demonstrate that Cz-MOF-2 exhibits high photocurrent density and low charge transfer resistance, which provide evidence for the efficient charge separation capability. Radical trapping experiments and ESR detection have substantiated that ·O2- and h+ are the primary active species involved in this photocatalytic reaction. This work highlights the potential of MOFs in the targeted design and development of fluorescent sensors and photocatalysts for environmental detection and remediation.

Cellulose acetate membrane doped with silver-reduced graphene oxide nanocomposites to enhance the visible-light photocatalytic degradation of organic contaminants

Cellulose acetate membrane doped with silver-reduced graphene oxide nanocomposites to enhance the visible-light photocatalytic degradation of organic contaminants

High-Valent Iron–Oxo species in heterogeneous Catalysis: Formation, Mechanism, and reactivity for the degradation of various emerging organic contaminants

High-valent iron–oxo species (FeⅣ/Ⅴ=O), generated via peroxide activation with Fe-based catalysts, have shown potential in the selective and efficient degradation of organic contaminants. However, a comprehensive understanding of the oxidative degradation mechanism induced by FeⅣ/Ⅴ=O is still pending. In this research, to unravel this oxidation mechanism, an Fe-single atom catalyst (FeN4-C) was synthesized, and FeⅤ=O was formed as the predominant reactive species upon peroxymonosulfate (PMS) activation. The FeN4-C/PMS system was experimentally studied on its catalytic oxidation behavior for the degradation of 34 typical emerging organic contaminants (EOCs) in water, exhibiting a significant variation in the pseudo first-order kinetic rate constants (kobs) among the EOCs. A quantitative structure–activity relationship (QSAR) model was established based on the molecular structure feature and measured kobs of the EOCs. The model infers that EOCs with higher electron donating ability (EHOMO) are more susceptible towards FeN4-C/PMS oxidation, implying an electrophilic reaction following the single electron transfer (SET) mechanism. Further exploration of the degradation pathways for seven representative EOCs revealed that the oxidation occurs through the abstraction of either a hydrogen atom or a nonbonded (or π) electron by FeⅤ=O, enabling processes such as C-, N-, and S-oxidation, along with N- and O-dealkylation and deamination, to effectively degrade EOCs. These research findings provide a robust theoretical framework for understanding the reaction mechanisms and predicting the degradability and removal of various EOCs by FeⅣ/Ⅴ=O for water purification.

Microenvironment modulation of Fe single atoms in porous g-C3N4 by introducing −SOx groups for enhanced photo-Fenton reactions

Heterogeneous photo-Fenton reactions based on hydrogen peroxide (H2O2) activation exhibit great potential in the treatment of organic wastewater. For developing efficient photo-Fenton catalysts, a fundamental investigation into the specific catalytic sites and the reaction mechanism is highly desired. Herein, a novel photo-Fenton catalyst (Fe1/CN-SOx) was constructed by synchronously anchoring Fe single atoms (SAs) and oxidized sulfur (−SOx) groups into porous graphitic carbon nitride (g-C3N4). The presence of trace −SOx groups altered the local configuration of g-C3N4 and optimized the coordination microenvironment of Fe SAs, thereby modulating the electronic structures of catalytic sites in favor of H2O2 activation. The cooperation between Fe SAs and the neighboring C atoms bonded with −SOx (C-SOx) enhanced the adsorption and cleavage of H2O2. The photoinduced charge carriers further accelerated Fe2+/Fe3+ redox cycles and hydroxyl radical (•OH) production, achieving an efficient photo-Fenton synergistic catalysis for continuous degradation of organic contaminants. The Fe1/CN-SOx catalyst also exhibited excellent anti-interference performance in diverse aquatic systems and good long-term stability, indicating its great potential for applications in water treatment. This study provides an in-depth insight into the optimal fabrication of single-atom active sites by modulating the local structures of support materials, aiming to enhance photo-Fenton reactions.

Effective photocatalytic hydrogen generation and degradation for single cobalt and tungsten metal atom oxide anchored on titanium dioxide-bismuth molybdate-reduced graphene oxide

A simple hydrothermal method was used to prepare the single-metal atom oxide (SMAO) catalyst. The prepared dual Cobalt and tungsten (CoW) single metal atom oxide anchored on the TiO2-Bi2MoO6-reduced graphene oxide (rGO), an interstitial atomic line of tungsten and cobalt. The prepared photocatalyst showed good photocatalytic hydrogen (H2) evolution and organic contaminant degradation. As co-catalysts, surface-dispersed CoW sites were created using a Co mono-substituted hetero-polyacid (HPA-Co). A larger quantity of single atoms were uniformly decorated on the TiO2-Bi2MoO6-Ethylenediamine (ED)-rGO catalyst. The presence of the CoW species was verified employing extended X-ray absorption near edge structure (XANES), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and extended X-ray absorption fine structure (EXAFS) analyses after a TiO2-Bi2MoO6-CoW-ED-rGO composite synthesized. The findings demonstrate that TiO2-Bi2MoO6-CoW-ED-rGO catalysts were more capable of producing hydrogen and degrading Ciprofloxacin (CIP) (21.46 mmol/g/h, 97.2%) than other bare and binary catalysts. Furthermore, it showed remarkable stability and reusability after five consecutive CIP photodegradation and H2 production cycles. Gas chromatography/mass spectroscopy (GC/MS) techniques were used to identify the intermediates in the photodegradation process. The prepared photocatalyst was significantly increased, and the separation of charge carriers was further boosted, thanks to the CoW material and the synergistic effect. A possible Z-scheme mechanism was proposed for the photocatalytic H2 production activity. More electrons can contribute to the reduction of H2 evolution because of the processability of the Z-scheme. This work created a recyclable, inexpensive, highly effective, and non-toxic catalytic material for H2 generation and CIP degradation.

Harnessing the interfacial charge transfer in Mn-doped γ-Fe2O3@ZnO heterojunction for broad spectrum photocatalytic degradation of organic dyes

Developing affordable, sustainable, and environmentally friendly water remediation strategies is inevitable to achieve water security worldwide. To align with these challenges, this investigation successfully synthesized low-cost Mn-doped iron oxide and its heterojunction with Zinc Oxide (ZnO) as an efficient recovery mechanism for deteriorated water. Comprehensive characterization of Mn-doped γ-Fe2O3@ZnO heterojunction was performed using X-ray diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy, Energy dispersive X-ray, and Photoluminescence analysis. The electrical behaviors of all samples were characterized using Electrochemical impedance spectroscopy and Mott-Schottky analysis. This heterojunction showed distinct structural features along with a bandgap energy of 2.61 eV, confirming the formation of a heterojunction. The effectiveness of this heterojunction was assessed using Congo red (CR) and Crystal violet as model pollutants. The photodegradation capability using a small amount of as-synthesized photocatalyst (10 mg) reached 90.8 % for CR and 90.5 % for CV under natural sunlight for a duration of 105 min. The key findings of this report clearly demonstrated the effectiveness of the interfacial charge transfer mechanism of Mn-γ-Fe2O3@ZnO heterojunction towards the degradation of organic water contaminants.

Trimetallic MOF–derived Fe–Mn–Sn oxide heterostructure enabling exceptional catalytic degradation of organic pollutants

Developing efficient and environmentally benign heterogeneous catalysts that activate peroxymonosulfate (PMS) for the degradation of persistent organic contaminants remains a challenge. Metal–organic frameworks (MOFs)–derived metal oxide catalysts in advanced oxidation processes (AOPs) have received considerable attention research fraternity. Herein, we report an innovative magnetic trimetallic MOF-derived Fe-Mn-Sn oxide heterostructure (FeMnO@Sn) with adjustable morphology, size and Sn content, prepared through an impregnation–calcination strategy. The formation of a novel magnetic Fe2O3/Fe3O4/Mn3O4 heterostructure induces the generation of abundant Fe2+ and Mn2+ sites on the FeMnO@Sn surface. Meanwhile, the introduction of SnO2 into the Fe2O3/Fe3O4/Mn3O4 heterostructure facilitates the cleavage of the OO bond in adsorbed PMS. The synergy among the different functionalities of each metal oxide plays a vital role in the swift and effective degradation of pollutants. In addition, the uniquely designed catalyst exhibits magnetic properties that facilitate easy recycling and repeated use, thereby meeting environmental protection requirements. Overall, this research highlights the design of heterogeneous catalysts for the effective activation of PMS and provides valuable insights for the advancement of future environmental catalysts.

Regulating the Electronic Structure of Cu Single-Atom Catalysts toward Enhanced Electro-Fenton Degradation of Organic Contaminants via 1O2 and •OH.

Heterogeneous electro-Fenton degradation with 1O2 and •OH generated from O2 reduction is cost-effective for the removal of refractory organic pollutants from wastewater. As 1O2 is more tolerant to background constituents such as salt ions and a high pH value than •OH, tuning the production of 1O2 and •OH is important for efficient electro-Fenton degradation. However, it remains a great challenge to selectively produce 1O2 and improve the species yield. Herein, the electronic structure of atomically dispersed Cu-N4 sites was regulated by doping electron-deficient B into porous hollow carbon microspheres (CuBN-HCMs), which improved *O2 adsorption and significantly enhanced 1O2 selectivity in electro-Fenton degradation. Its 1O2 yield was 2.3 times higher than that of a Cu single-atom catalyst without B doping. Meanwhile, •OH was simultaneously generated as a minor species. The CuBN-HCMs were efficient for the electro-Fenton degradation of phenol, sulfamethoxazole, and bisphenol A with a high mineralization efficiency. Its kinetic constants showed insignificant changes under various anions and a wide pH range of 1-9. More importantly, it was energy-efficient for treating actual coking wastewater with a low energy consumption of 19.0 kWh kgCOD-1. The superior performance of the CuBN-HCMs was contributed from 1O2 and •OH and its high 1O2 selectivity.

Structural and morphological studies of g-C3N4-functionalized MWCNTs nanocomposite for sunlight-responsive photocatalytic activity

Photocatalytic degradation of organic contaminants has been proven to be one of the greatest economical and efficient techniques to address environmental pollution problems. Multi-walled carbon nanotubes (MWCNTs)/g-C3N4 (GCN) nanocomposites (NCs) were synthesized by a hydrothermal process aided by ultrasound to produce active photocatalysts. The effective synthesis of GCN, MWCNTs, and MWCNTs/GCN NCs was confirmed by X-ray diffraction (XRD) patterns. The fabrication of GCN nanosheets (NSs), the nanotubular structure of MWCNTs, and a network of neuron-like structures for MWCNTs/GCN NCs were all revealed by structural and morphological characterization. The elemental mapping of NCs containing the suitable quantity of MWCNTs revealed a uniform distribution of the sample's component elements. When the optical properties of the fabricated nanomaterials were examined by employing UV–visible spectroscopy, the results revealed a blue shift (a shift of maximum absorption to the UV region), which suggests that the addition of MWCNTs increased the band-gap energy. The behaviour of e––h+ pair recombination was revealed by measuring the charge carrier movement and trapping efficiency using photoluminescence (PL) spectroscopy. Crystal violet (CV) dye was photocatalytically degraded using prepared NCs in the presence of sunlight, and the synergistic effects of GCN and MWCNTs were examined. With a degradation efficiency of 99.32 %, MWCNTs/GCN NCs demonstrated the best sunlight-irradiated photocatalytic activity for CV degradation. The degradation of CV was discovered to follow pseudo-first-order kinetics. Throughout five consecutive studies, the NCs demonstrated the highest levels of catalytic efficiency and recyclability, with 5 % reduced degrading activities. The trapping tests showed that the primary reactive species involved in the breakdown of CV were the •O2– and •OH radicals.

Photoelectrocatalytic degradation of organic contaminants by spray coated Z-scheme TiO2/Bi2WO6 heterostructure electrode under solar light

This study demonstrates that spray deposited layered TiO2/Bi2WO6 heterostructure photoelectrodes exhibit strong interfacial interactions, leading to significant enhancements in photoelectrochemical performance. Time-resolved photoluminescence (TRPL) spectra indicated a prolonged lifetime of photoinduced carriers. The red shift in the absorption edge of TiO2/Bi2WO6 improved the visible light harvesting capability of Bi2WO6. Nyquist plots showed effective charge separation, and the TiO2 layer at the bottom significantly influenced the flat band potential compared to pristine Bi2WO6, as evidenced by Mott-Schottky analysis. This configuration improved the separation of photogenerated charge carriers via a Z-scheme charge transfer mechanism. The TiO2/Bi2WO6 electrode demonstrated a higher efficiency of 94% for methylene blue degradation within 160 min, compared to pure Bi2WO6. Quenching experiments confirmed the Z-scheme charge transfer mechanism in the coupled TiO2/Bi2WO6 heterojunction during degradation reactions. This study highlights the benefits of semiconductor coupling with different band potentials, promoting large-scale applications of solar-driven TiO2/Bi2WO6 photoelectrodes for environmental remediation.

Nanostructured NiCo2S4 immobilized on nickel foam as recyclable catalyst for activating peroxymonosulfate toward doxycycline degradation: Performance and mechanism

The existing powder catalysts used in sulfate radical-based advanced oxidation processes (SR-AOPs) commonly suffer from severe limitation due to the difficulty of recycling and inadequate exposure of the active site. In this work, spinel sulfide (NiCo2S4) was uniformly grown on 3D nickel foam (NF) through a one-step hydrothermal route for the activation of peroxymonosulfate (PMS) toward highly efficient degradation of doxycycline (DOX). Due to the synergistic effect of Ni and Co in the NiCo2S4, the NiCo2S4/NF (0.6 g/L) combined with PMS (3.0 mmol L-1) can promote a nearly complete degradation (98.2 %) toward 0.3 mmol/L DOX within 6 min. Density functional theory (DFT) calculations illustrated that the NiCo2S4/NF can adsorb PMS through a unique Ni-S-Co structure and “conducting bridge” mode of NF, accelerating the electron transfer from NiCo2S4/NF to PMS and the subsequent O-O bond cleavage. Especially, the Co/Ni dual-site enhanced the adsorption of PMS and promotes electron transfer to form surface-activated PMS complex (catalyst-PMS*), leading to the generation of surface-bound reactive oxygen species (ROS) on the NiCo2S4 surface. Quenching experiments and ESR tests demonstrated that radicals such as SO4•-, 1O2, •OH and surface-bound ROS play a vital role in DOX degradation. Moreover, the potential mechanism and pathway of DOX degradation are reasonably deduced by investigating and analyzing the intermediates with liquid chromatography-mass spectromsetry (LC-MS). Consequently, this study provides a deep insight on the systhsis of spinel sulfide and its intrinsic mechanism of PMS activation toward organic contaminant degradation.

Statistical analysis and optimization of mechanical-chemical electro-Fenton for organic contaminant degradation in refinery wastewater

Refinery wastewater (RWW) poses significant environmental challenges due to its high concentration of organic contaminants, necessitating effective treatment solutions. This study employs the mechanical design of the Electro-Fenton (EF) technique as a feasible alternative for treating RWW. The anode and cathode electrodes, made of stainless steel and iron, respectively, were utilized to conduct organic removal (OR) from RWW. To maximize performance, two metric optimization design techniques were examined: Box Behnken Design (BBD) and response surface methodology. The analysis of variance revealed a high coefficient of determination value (R2 = 0.9685), indicating a second-order provable relationship between the response and self-governing variables. Additional statistical analysis was performed to assess the validity and reliability of the suggested approach. A predictive regression model was developed based on unresolved values, demonstrating a high level of agreement with experimental values. This model identified the optimal equation for the empirical model to predict OR based on predetermined parameters. Based on the BBD, the percentage of OR reached 93.45 % at pH 3, temperature, and electrolysis time of 60 °C, and 30 minutes, respectively. The implications of this study suggest that the optimized Electro-Fenton technique could serve as a robust solution for addressing the environmental impact of RWW, contributing to sustainable wastewater management practices.

One-step hydrothermal synthesis of ternary heterostructure stannic sulfide - bismuth sulfide - bismuth oxychloride (SnS2-Bi2S3-BiOCl) composite loaded on carbon felt for highly efficient piezocatalytic degradation of organic dyes and antibiotics

The piezoelectric catalysis technique harnesses naturally occurring vibrational energy to remove organic pollutants from water in an environmentally friendly manner. In this study, a ternary heterostructure SnS2-Bi2S3-BiOCl (S-B-B) composite was successfully synthesized via a one-step hydrothermal method and simultaneously deposited on the surface of carbon felt. The S-B-B heterojunction exhibits significantly enhanced piezoelectric catalytic activity compared to SnS2, Bi2S3, and BiOCl, achieving a k value of 2.26 × 10⁻² min⁻¹ and a degradation efficiency of 89.9 % towards methyl orange (MO) dye after 100 min of ultrasonic degradation. This performance is markedly superior to the individual components, with k values of 3.80 × 10⁻⁴ min⁻¹ for SnS2, 1.16 × 10⁻² min⁻¹ for BiOCl, and 1.31 × 10⁻² min⁻¹ for Bi2S3. Moreover, in addition to levofloxacin (LV), it demonstrates high removal efficiency for Congo red (CR), methylene blue (MB), tetracycline hydrochloride (TC-HCl), and sulfanilamide (SN). Furthermore, it can be loaded onto carbon felt for use in piezoelectric catalytic degradation of dyeing wastewater, highlighting its potential for practical applications. Trapping experiments suggest that singlet oxygen non-radicals and hydroxyl radicals play a critical role in the piezocatalytic degradation of organic contaminants. Based on LC-MS results, a possible degradation pathway for MO dye is proposed. Furthermore, DFT calculations confirm electron transfer from Bi2S3 to SnS2 and BiOCl at the interfaces between SnS2/Bi2S3 and BiOCl/Bi2S3. The piezoelectric mechanism of the S-B-B composite is also elucidated, highlighting the interaction and electron dynamics within the heterostructure.

Porous aromatic framework with active carbonyl sites as a metal-free peroxymonosulfate activator for organic contaminants degradation: Free radical and non-radical pathway mechanisms

Transition metal-based catalysts used in advanced oxidation processes may encounter problems of metal ion leaching. Therefore, advanced oxidation processes initiated by metal-free carbon catalysts are regarded as competitive solutions for environmental remediation. In light of this, we have prepared PAF-145, a porous aromatic framework containing carbonyl groups (C = O) that serves as a stable and eco-friendly metal-free carbon catalyst for activating peroxymonosulfate. The stable structure and abundant C = O groups of PAF-145 endow it with excellent degradation performance, good reusability and adaptability to a wide pH range and environments with various coexisting anions. PAF-145 degraded 98.7 % of Rhodamine B within 20 min, achieving a reaction rate constant that was 48.5 times higher than that of PAF without carbonyl groups. PMS is oxidized to 1O2 and O2•− on the electron-deficient carbon atoms within the carbonyl groups. Using quenching experiments, electron paramagnetic resonance analysis, and electrochemical tests, it was determined that the degradation of Rhodamine B is primarily governed by both a non-radical pathway that includes 1O2 and the electron transfer mechanism, as well as a radical pathway that involves O2•− in the PAF-145/PMS system.

Edge functionalized with benzenesulfonyl groups of g-C3N4 nanosheets as a highly efficient photocatalyst for water purification

Photocatalytic water purification is a promising method for environmental remediation, but it is greatly hindered by the rapid charge carrier recombination behavior of the photocatalysts. Herein, a simple wet-chemical method is developed for grafting electron-withdrawing benzenesulfonyl groups at the edges of g-C3N4 nanosheets. These exhibited a superior and versatile photocatalytic performance on the degradation of organic contaminant, as well as disinfected Escherichia coli (E. coli) bacteria under visible light illumination. Systematic studies reveal that the grafting of benzenesulfonyl groups led to the synergic effect in ultrathin g-C3N4 nanosheets of enhancing the photogenerated charge carrier separation on surface, improving light absorption, changing electronic band structure, and causing surface charge redistribution, all of which are beneficial for enhancing the photocatalytic performance. Notably, these edge-activated g-C3N4 photocatalysts also demonstrate remarkable photocatalytic activity in the real tap water and urban wastewater, indicating their promising potential for application in real wastewater treatment.

Sonocatalytic degradation of tetracycline hydrochloride using SnO2 hollow-nanofiber decorated with UiO-66-NH2

In this study, a porous hollow nanofiber SnO2 was decorated with UiO-66-NH2 nanoparticles with straightforward solvothermal method and utilized for sonocatalytic degradation of tetracycline (TC) by ultrasonic irradiation (USI). The prepared materials were characterized using different techniques such as SEM, EDS, FTIR, XRD, BET, XPS, UV-DRS, EIS, and zeta potential. SnO2 PHNF/UiO-66-NH2 nanocomposite offered the highest apparent rate constant of 0.0397 min−1 which was 6.3 and 3.1 times higher than those obtained for SnO2 PHNF and UiO-66-NH2, respectively. The integration of nanocomposite components revealed the synergy factor of 1.58, which can be due to the created heterojunctions resulted in efficiently charge carriers separation and retaining high redox ability. The effects of different affecting parameters such as TC initial concentration, pH of the solution, catalyst dosage, trapping agents, and coexisting anions on the catalytic performance were examined. The inhibitory effects of anions were confirmed to be decreased in the sequence of Cl− > NO3− > SO42−, while the sonocatalytic efficiency of the nanocomposite improved considerably in the presence of humic acid and bicarbonate. Also, the excellent performance of the catalyst was preserved during six successive cycles, suggesting the high stability of the prepared catalyst. In addition, based on the scavenger analysis, the created O2·−, OH·, and holes were contributed to the TC degradation. In conclusion, the creation heterojunction is an impressive methodology for improving the sonocatalytic activity of a catalyst, and SnO2 PHNF/UiO-66-NH2 nanocomposite was introduced as a satisfactory catalyst in sonocatalytic degradation of organic contaminants.

Photoactivation of sulfite by FeTiO3 for organic pollutant degradation: Performance and mechanism

In recent years, the exploration of sulfite (S(IV))-based advanced oxidation processes has attracted increasing attention due to its high performance in the degradation of aqueous organic contaminants. In this study, we investigated the activation of S(IV) by ilmenite (FeTiO3) under photo irradiation using phenol as a substrate. The FeTiO3/S(IV)/photo system demonstrated a remarkable phenol removal rate, achieving 81.4 % degradation within 30 min under optimal conditions. The photocatalytic mechanism involves the generation of electron-hole pairs in FeTiO3, with photogenerated holes activating the adsorbed S(IV) on the catalyst’s surface to produce various free radicals, among which SO4− is identified as the primary active species. Density functional theory calculations further suggest that electron transfer between ilmenite and S(IV) may occur via a Fe-O-S bridge. Additionally, the approach demonstrates satisfactory reusability of the photocatalyst and consistent effectiveness in real-water matrices. This study contributes to the development of more efficient, cost-effective, and environmentally friendly water treatment strategies by providing a deeper understanding of the proposed FeTiO3/S(IV)/photo system.

Chloride-mediated transformation of sulfate radicals to hydroxyl radicals for enhanced contaminant degradation in high-temperature wastewater

Using the excess heat in high-temperature industrial wastewater to activate oxidant precursors for organic contaminant degradation would make advanced oxidation processes more sustainable in the context of carbon neutrality, while the salt-mediated radical transformation chemistry in such wastewater is poorly understood. We herein demonstrate that chloride (Cl–) in the range of 0.28–56.34 mM accelerates the degradation of organic contaminants in the heat activated persulfate process in both synthetic and authentic wastewater. We use laser flash photolysis technique together with kinetic modeling to directly determine the bimolecular rate constants of radical–radical (e.g., kSO4·--SO4·- = 2.50 × 109 M−1 s−1), Cl–-radical (e.g., kSO4·--Cl- = 3.75 × 108 M−1 s−1), and radical-contaminant (e.g., kHO·-BA = 1.02 × 1010 M−1 s−1) reactions at 55 °C, which are substantially higher than those at ambient water temperature (25 °C). We also combine experimental and modelling results to calculate the contribution of different radicals to contaminant removal at 55 °C. The results clearly demonstrate that Cl– in the range of 0.28–56.34 mM promotes the transformation of SO4– to HO at 55 °C, with reactive chlorine species involved as the intermediates. The findings improve fundamental understanding of Cl–-mediated radical chemistry in high-temperature water and provide an engineering strategy to recycle the heat in wastewater to enhance contaminant remediation.

Upcycling polystyrene microplastics to Fe/Mo-doped sponge-carbon: Mo5+ enhanced electron transfer for boosting Fenton-like performance

The rate-limiting steps of promoting the conversion of Fe3+ to Fe2+ in Fenton-like systems are crucial for achieving efficient degradation of organic contaminants in aquatic environments. Herein, a novel magnetic Fe/Mo bimetallic doped sponge carbon (Fe/Mo-N-C) derived from polystyrene microplastics was successfully synthesized and the presence of metastable Mo5+ remarkably synergized the electron transfer of Fe2+ in internal microenvironment. In the Fe/Mo-N-C activating peroxymonosulfate (PMS) system, Mo5+ boosted the oxidation of Fe2+, and the conversion of Mo4+/Mo6+ accelerated the restoration of Fe2+ from Fe3+, resulting in nearly 100 % of 17α-ethinylestradiol (EE2) degradation with the kinetic rate constant of 0.343 min−1, which was 8.1 times faster than that of Fe-N-C. Moreover, Fe/Mo-N-C possessed excellent resistance to interference from various coexisting anions (especially chloride, sulfate, and nitrate ions up to 500 mM), natural organic matter, nano-plastics, and different water matrices. Density functional theory analysis demonstrated that Mo centers regulated the electron rearrangement of the Fe 3d orbital, enhancing the activation performance of Fe/Mo-N-C towards PMS. This study lays the groundwork for understanding the mechanism of metastable Mo, which holds significant importance for the up-recycling of polyethylene plastics and environmental remediation.

The surface functional groups-driven fast and catalytic degradation of naproxen on sludge biochar enhanced by citric acid

In this work, a sludge biochar (CA-SBC-300) with efficient activation of peroxymonosulfate (PMS) was prepared by citric acid modification. CA-SBC-300 achieved efficient degradation of naproxen (NPX) (95.5%) within 10 min by activating PMS. This system was highly resilient to common disruptive factors such as inorganic anions, humic acid (HA) and solution pH. The results of XPS and Raman showed that the content of oxygenated functional groups (OFGs) and the degree of defects on the sludge biochar increased after citric acid modification, which may be an important reason for the enhanced catalytic performance of SBC. In the CA-SBC-300/PMS system, 1O2 and O2•− made the main contributions to the degradation of NPX. XPS analysis and DFT calculations demonstrated that C=O/C−O and pyridine N on CA-SBC-300 were the crucial active sites for PMS activation. According to the results of UPLC-MS analysis, three possible pathways for NPX degradation were inferred. This study provided a feasible strategy for sludge resource utilization combined with efficient catalytic degradation of toxic organic contaminants in wastewater.