Degradation Rate Constants Research Articles

Radiolytic degradation of 4-hydroxybenzoate in aerated and deoxygenated aqueous solutions.

The radiolytic degradation of 4-hydroxybenzoate (4-HBA-) in aerated, oxygen-free and N2O-saturated aqueous solutions at concentrations of 0.10 and 0.25 mmol/dm3 were gamma irradiated at different doses in a source of Co-60. The results show that ·OH adds predominantly to the 3 position of the aromatic ring, and elimination of the acid group leads to the degradation of 4-HBA-. With an N2O-saturated 0.10 mmol/dm3 4-HBA- solution, total degradation occurred at 1.6 kGy, and with a 0.25 mmol/dm3 solution, total degradation occurred at 3.5 kGy. In the aerated and oxygen-free 0.25 mmol/dm3 4-HBA- solutions, the behavior was similar, degradation occurring at a dose of 13.1 kGy. At the concentration of 0.10 mmol/dm3, total degradation occurred at 7.0 kGy, with small amounts of radiolytic products and byproducts. We propose a mechanism for the degradation of 4-HBA- caused by water radicals produced in the three environments, leading to formation of the identified stable products. Oxidation was followed by chemical oxygen demand (COD), which decreased as the 4-HBA- concentration increased. The kinetics showed a pseudo-first-order behavior. The rate constant of degradation was similar for the solutions with and without oxygen.

Visible light driven mesoporous ag/Ag2CrO4/g-C3N4 degrades multiple organic pollutants efficiently: Synthesis, mechanism, and degradation pathway

With the development of economy, overuse of antibiotics has been seen as a huge threat to human health. Photocatalytic degradation is an effective method for resolving this problem at present. The method of combining plasmon resonance effect and Z-scheme heterojunction can effectively improve the separation efficiency of photogenerated carrier, which is of great significance for the treatment of antibiotic wastewater. Herein, the Ag/Ag2CrO4/g-C3N4 catalyst was prepared by in-situ loading and photo-reduction method for the degradation of antibiotic wastewater containing tetracycline and quinolone antibiotics. The research results showed that mesoporous graphitized carbon nitride (denoted as g-C3N4) provided good support for Ag and Ag2CrO4 nanoparticles, and mesoporous composite Ag/Ag2CrO4/g-C3N4 (denoted as ACO/CN) provided more reaction sites for organic pollutants degradation. Under visible light irradiation, 5%ACO/CN catalyst showed the best degradation activity and stability for tetracycline (TC), levofloxacin (LVFX), oxytetracycline hydrochloride (OTC) and norfloxacin (NFLX), and their degradation rate constants were respectively 5.66, 8.26, 11.72 and 15.97 times of Ag2CrO4 which indicated it had good potential application value in the treatment of wastewater containing various organic pollutants. This benefits from the plasmon resonance effect of silver effectively improves the utilization efficiency of visible light and the Z-scheme heterojunction between Ag2CrO4 and g-C3N4 promotes the rapid transmission of photogenerated carriers. Based on the experimental results, the possible TC degradation pathway and photocatalytic mechanism were proposed. This study provides a simple way for the successful design and preparation of plasmon resonance effect synergistic Z-scheme heterojunction with promising applications in the treatment of antibiotic wastewater.

LCQDs modified Bi2MoO6 hydrangea composite photocatalyst for tetracycline degradation from wastewater: Performance, efficiency, and adsorption synergistic photocatalytic mechanism

This study used alkaline lignin as the carbon source for preparing alkaline lignin carbon quantum dots (LCQDs) based on the solvothermal method. To achieve efficient photocatalytic degradation of tetracyclic hydrochloride antibiotics (TCH), hydrangea-shaped LCQDs/Bi2MoO6 composites were prepared in situ by the solvothermal method exploiting the optical properties of LCQDs. The composite material was systematically characterized using XRD, FTIR, XPS, SEM, TEM, EIS, nitrogen adsorption-desorption testing, and UV–vis DRS to determine its crystal structure, microstructure, and optoelectronic properties. The results show that the sample has high purity and good crystallinity. The experiment on photocatalytic degradation further demonstrated that the LCQDs/Bi2MoO6 composite material modified with LCQDs exhibited superior photocatalytic activity compared to a single Bi2MoO6. Among them, BMO/LCQDs-7 showed the best effect. After 120 min of illumination, the rate of TCH removal through photocatalysis was 98.76%, with a degradation rate constant: K= 0.026 min−1. After five cycles, the removal rate of TCH can still be maintained at 79.35%. The photocatalytic degradation of TCH has been demonstrated through EPR and LC-MS experiments primarily caused by h+ and ·O2-.

Dissolved Organic Matter-Mediated Photosensitized Activation of Monochloramine for Micropollutant Abatement in Wastewater Effluent.

Utilizing solar light and water matrix components in situ to reduce the chemical and energy demands would make treatment technologies more sustainable for micropollutant abatement in wastewater effluents. We herein propose a new strategy for micropollutant abatement through dissolved organic matter (DOM)-mediated photosensitized activation of monochloramine (NH2Cl). Exposing the chlorinated wastewater effluent with residual NH2Cl to solar irradiation (solar/DOM/NH2Cl process) degrades six structurally diverse micropollutants at rate constants 1.26-34.2 times of those by the solar photolysis of the dechlorinated effluent (solar/DOM process). Notably, among the six micropollutants, the degradation rate constants of estradiol, acetaminophen, bisphenol A, and atenolol by the solar/DOM/NH2Cl process are 1.13-4.32 times the summation of those by the solar/DOM and solar/NH2Cl processes. The synergism in micropollutant degradation is attributed to the generation of reactive nitrogen species (RNS) and hydroxyl radicals (HO·) from the photosensitized activation of NH2Cl. Triplet state-excited DOM (3DOM*) dominates the activation of NH2Cl, leading to the generation of RNS, while HO· is produced from the interactions between RNS and other photochemically produced reactive intermediates (e.g., O2·- and DOM·+/·-). The findings advance the knowledge of DOM-mediated photosensitization and offer a sustainable method for micropollutant abatement in wastewater effluents containing residual NH2Cl.

Enhancing starch functionality through synergistic modification via sequential treatments with cold plasma and electron beam irradiation

The impact of dual sequential modifications using radio-frequency (RF) plasma and electron beam irradiation (EBI) on starch properties was investigated and compared with single treatments within an irradiation dose range of 5–20 kGy. Regardless of sequence, dual treatments synergistically affected starch properties, increasing acidity, solubility, and paste clarity, while decreasing rheological features with increasing irradiation dose. The molecular weight distribution was also synergistically influenced. Amylopectin distribution broadened particularly below 10 kGy. Amylose narrowed its distribution across all irradiation doses. This was due to dominating EBI-induced degradation and molecular rearrangements from RF plasma. With the highest average radiation-chemical yield (G) and degradation rate constant (k) of (2.12 ± 0.14) × 10−6 mol·J−1 and (3.43 ± 0.23) × 10−4 kGy−1, respectively, upon RF plasma pre-treatment, amylose underwent random chain scission. In comparison to single treatments, dual modification caused minor alterations in spectral characteristics and crystal short-range order structure, along with increased granule aggregation and surface irregularities. The synergistic effect was dose-dependent, significant up to 10 kGy, irrespective of treatment sequence. The highest synergistic ratio was observed when RF plasma preceded irradiation, demonstrating the superior efficiency of plasma pre-treatment in combination with EBI. This synergy has the potential to lower costs and extend starch's technological uses by enhancing radiation sensitivity and reducing the irradiation dose.

Integration of hydrogen evolution and dye removal in flexocatalysis by centrosymmetric semiconductor nanorods

In this work, coupling of the hydrogen (H2) production and dye degradation was first realized in a single flexocatalytic process using cerium oxide nanorods (CeO2 NRs). The flexoelectric polarization in a bending nanorod created an internal electric field, which promoted the separation of the thermal-excited electrons and holes. As a consequence, the H2 evolution rate of the flexocatalysis in dark was twice higher than that of the photocatalysis by the same CeO2 NRs. Moreover, simultaneous dye degradation was realized without reducing the H2 evolution rate, with the degradation constant rate of 0.065 min−1, dye removal efficiency of 89.3%, and H2 generation at 486.4 μmol g−1 h−1. The dual-functional catalytic performance of the CeO2 NRs was benefited from the unique periodic flexoelectric field induced by the ultrasound vibration, which could not be achieved by photocatalysis. This work revealed the important role of flexoelectric effect in overcoming the limitation in photocatalysis, which could be extended to a wide range of semiconductor nanomaterials for designing novel kinds of advanced flexocatalysts.

Precise Modulation of the Coordination Environment of Single Cu Site Catalysts to Regulate the Peroxymonosulfate Activation Pathway for Water Remediation.

Single atom site catalysts (SACs) with atomically dispersed active sites can be expected to be potential ideal catalysts for accurately modulating the persulfate activation pathway during the water remediation process because of their well-defined structure and the maximum metallic atom utilization. In this paper, a series of Cu SACs with different coordination environments were synthesized to elaborately regulate the peroxymonosulfate activation pathway in AOPs to clarify active species generation and transformation in water remediation. The degradation rate constants (kobs) of Cu-N2, Cu-N3, and Cu-N4 were 0.028, 0.021, and 0.015 min-1, respectively. Cu-N2 SACs exhibited a noticeable enhanced performance for bisphenol A (BPA) removal from water compared to that of the Cu-Nx SACs (x = 3, 4), accompanied by peroxymonosulfate (PMS) activation pathway variation. As shown by experimental and theoretical results, the PMS activation pathway was transformed from ROS to electron transfer with nitrogen coordination numbers decreasing from 4 to 2, which can be ascribed to the uneven charge distribution of Cu sites as well as upshifts in the d-band center, and thereby optimized electron transfer for PMS activation. Furthermore, the increasing nitrogen vacancies of single Cu site catalysts can also result in more unoccupied 3d orbitals of Cu atoms in SACs, thereby improving the intermediates' (PMS and BPA) adsorption-desorption process and BPA removal performance. These findings provided a beneficial approach for the coordination number regulation of SACs in water remediation.

Continuously Adjustable Thickness of Bi2MoO6 Nanosheets Enhances Photocatalytic Oxidation.

In this study, two-dimensional (2D) nanosheet photocatalysts of Bi2MoO6 with varying thicknesses were synthesized by adjusting the temperature during the hydrothermal reaction. The thinnest Bi2MoO6 nanosheet reached an approximate thickness of ∼4 nm, while the thickest nanosheet measured only ∼16 nm. The photocatalytic performance for Rhodamine B (RhB) degradation was found to be the most effective for the thinnest Bi2MoO6 nanosheet, displaying a degradation rate constant of 0.11 min-1. This rate was 2.5 times higher than that observed for the ∼16 nm thick Bi2MoO6 photocatalyst. The enhanced performance of the thinner two-dimensional nanostructure can be attributed to improved separation and migration of photogenerated charges. Additionally, the study identified hydroxyl radicals (•OH) and superoxide radicals (•O2-) as crucial oxidative species, contributing to the efficient mineralization of RhB dye. This work highlights the controllable synthesis of 2D materials with varying thicknesses and their specific applications in photocatalytic oxidation.

Biochar-Supported FeCo-MOF derivative catalyzes PDS-Mediated degradation of tetracycline

Bimetallic metal–organic framework (MOF) has gained wide attention in the field of advanced oxidative processes (AOPs), however, the agglomeration problem severely limits its active sites and its activation mechanism still needs to be further explored. This study developed the BC@CoFe composite material, utilizing biochar (BC) to support FeCo-MOF derivatives, effectively alleviating their agglomeration and structural collapse. The results of the BC@CoFe activated peroxydisulfate (PDS) system for the degradation of tetracycline (TC) revealed an excellent degradation efficiency up to 97.7 % in 2 h for TC solution (20 mg/L, degradation rate constants k = 7.066 mM-1min−1). Furthermore, the BC@CoFe/PDS system exhibits exceptionally high cyclic stability (73.23 % degradation efficiency after 12 h continuous degradation), a wide range of pH (3–11) and temperature tolerance (20-60℃), resistance to background ion interference (SO42-, H2PO4-, NO3– and HA), and reduced toxicity of the degradation products. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) analyses show that the exceptional catalytic performance of BC@CoFe primarily stems from the synergistic effect between Fe(II)/Co(III) and Fe(III)/Co(II). Regarding the reactive active species involved in TC degradation, the contribution rates of 1O2, SO4•- and ·OH were measured and calculated to be 73.6 %, 14.9 %, and 11.5 %, respectively. Thus, the BC@CoFe/PDS system exhibits outstanding catalytic activity and has broad practical applications in water treatment.

Boosting persulfate activation through efficient π → π* transition activated by Cu ion anchored porphyrin-based metal–organic framework

Photocatalytic persulfate activation provides a promising approach for the elimination of persistent organic pollutants from water. This has been exemplified in porphyrin-based metal organic frameworks (PMOFs), which however come with ineffective electron transition within the porphyrin ligand. Herein, we present a Cu ion modification strategy capable of boosting electron transition by inducing electron delocalization under visible light. The introduction of Cu ions increased the degradation rate constant of ciprofloxacin (CIP) by nearly 44 times, surpassing most state-of-the-art photocatalysts. The in-situ characterizations and theoretical calculations suggest that π-electron localization constitutes the origin of ineffective electron transition in PMOFs. The introduction of Cu ions induces π-electron delocalization to intensify the π → π* transition, forming electron-rich centers of Cu to lower the energy barrier for O-O bond cleavage. This work offers fundamental insights into the electron transition within PMOFs, upon which the universal strategy is proposed for improved water decontamination performance via persulfate activation.

Nano-architected titania/gold@GO nanosheets for sonocatalytic degradation of azo dyes in textile wastewater

Environmental pollution is creating serious risks to both human health and the atmosphere which has been a major threat on a global scale. Therefore, it is necessary to focus on the evolution of the environment and trace contaminants for effective and reliable detection and degradation methods. Photochemical methods such as Surface-Enhanced Raman Scattering (SERS) and sono-catalytic degradation can be used to accelerate the detection and degradation of toxic dyes. In the present work, a Gold/Titania/Graphene oxide nanocomposite (ATG) was investigated as a capable dual substrate for SERS sensing and sono-catalytic degradation of pollutants. The nanosize distribution (6–12 nm) of ATG was synthesized by a solvothermal route. X-ray diffraction pattern illustrates the anatase phase of the titanium dioxide. Sonocatalytic degradation was aided using Raman spectroscopy. The effectiveness of ATG as a sono-catalytic substrate and SERS sensor was first evaluated using commercial dyes, such as malachite green and Bismarck brown. Furthermore, research has been conducted on the harmful elements in textile effluents (TE). The NN and C-N bands found in the SERS spectra of TE indicates the presence of carcinogenic azo-dye impurities. The enhancement factor was observed to be 5.77×1012 with the limit of detection (LOD) as 6.0×10−12M. Additionally, the sono-catalysis of ATG was evaluated for the elimination of these dye pollutants in TE. Following sono-catalysis by ATG, a high degradation rate constant of approximately 8.44 ×10−3/min was noted in TE with 89 % of degradation efficiency. The enhanced SERS detection, sono-catalytic degradation of synthetic dyes and effluent stem from the combined action of’ plasmonic characteristics of Au NPs, anatase TiO2, and the π-π stacking characteristic of GO.

Enhanced PMS activation and NSAID degradation selectivity by hydrophobic microenvironment regulation on Fe3+@Cu-MOF

In this study, the activation of peroxymonosulfate (PMS) and selective degradation of nonsteroidal anti-inflammatory drugs were investigated using hydrophobically modified Fe3+@Cu-MOF. The Fe3+@Cu-MOF-CTAB/PMS system demonstrated high-efficiency, achieving near-complete degradation of diclofenac within 120 min. The degradation rate constants for diclofenac, ibuprofen, and naproxen were 0.0048, 0.00103, and 0.00046 min−1, respectively, positively correlated with their hydrophobicity. Longer hydrophobic surfactant chains in Fe3+@Cu-MOFs lead to greater initial adsorption of diclofenac, enhancing degradation efficiency upon the introduction of PMS. The Fe3+@Cu-MOF-CTAB/PMS system removes over 80 % of diclofenac in various water matrices, showing optimal efficiency in acidic environments but reduced effectiveness with competing anions. Post-degradation changes in the oxidation states of copper and iron in the MOF structure indicated a synergistic redox mechanism essential for PMS activation. The hydroxylation and C-N bond cleavage in diclofenac were key degradation pathways. This study highlights the potential of hydrophobically modified Fe3+@Cu-MOFs in water treatment, providing insights into the interplay between material design, hydrophobic interactions, and catalytic performance.

Development of 2D/2D h-MoO3/Ag/g-C3N4 heterojunction photocatalyst with enhanced photocatalytic performance for the detoxification of methylene blue and tetracycline under solar light illumination

In this study, direct thermal polycondensation, hydrothermal, and ultrasonic techniques were used to fabricate photocatalysts consisting of bare g-C3N4 (GCN), h-MoO3 (MoO3), MoO3/g-C3N4 (MGCN), and MoO3/Ag/g-C3N4 (MAGCN) composites. These methods were used to improve the photocatalytic effect, especially for environmental applications. The surface and chemical properties of the fabricated samples were investigated by XRD, FT-IR, FE-SEM, HR-TEM, UV-DRS, XPS, and PL analysis. Bare and composite photocatalysts were tested for photodegradation of the methylene blue (MB) dye and tetracycline (TC) antibiotic under solar irradiation. The MAGCN composite material exhibits remarkable efficiency in degrading 99% of MB dye and 90% of TC antibiotic within a time frame of 60 min when exposed to sunlight irradiation. The degradation rate constants (k) of MB and TC in the most active MAGCN photocatalyst were 11.02 and 7.03 times higher than those of pristine GCN, respectively. The scavenger reaction shows that the most important reactive species in the photocatalytic process are superoxide and photogenerated holes. The outstanding photocatalytic efficiency of the MAGCN catalyst was demonstrated by the fact that Ag nanoparticles act as mediators of fast charge transfer, resulting in higher absorption of sunlight, enhanced charge separation/transfer, and regeneration by MoO3 and GCN. The MAGCN photocatalyst exhibits remarkable activity, maintains its performance over six consecutive reaction cycles, and exhibits excellent stability and reusability. Intermediates were analyzed by GC-MS, and suitable degradation pathways were proposed. These results enable the development of an effective Z-scheme heterojunction photocatalyst and facilitate its wide application in the degradation of organic pollutants in wastewater.

The experimental study of the kinetics and modes of polymethyl methacrylate thermal degradation in argon flows

The experimental study of the kinetics and modes of the thermal degradation of polymethyl methacrylate (PMMA) in an argon flow was carried out. During thermogravimetric analysis the sample heating rates were 2, 5, 8, 20 and 35 K/min. Based on the integral isoconversional method the values of the kinetic rate constants of the PMMA thermal degradation were determined. When modeling the decomposition process of PMMA for low conversion degrees, it is advisable to use the reaction rate constant obtained for the conversion degree equal to 20 %, and for modeling the whole process – 50 %. Therefore, for evaluation calculations, it is possible to describe the process of PMMA decomposition with one gross reaction. Also, the investigation of the thermal degradation of PMMA particles under conductive heating conditions (680, 700, 720 K) in an argon and air was carried out. Based on the analysis of the data obtained, a scheme for the decomposition of PMMA, consisting of four stages, was established.

A novel bifunctional particle electrode with abundant Fe/Fe3C and Fe-N-C sites to enhance the performance of electro-Fenton in degrading organic pollutant

Electro-Fenton (EF) technology emerges as a promising approach to address the treatment of persistent organic pollutants. Nevertheless, its practical implementation often comes with certain drawbacks, like the low H2O2 activation efficiency, poor pH adaptability, and difficult recycling of the catalysts. To this end, we introduced highly active Fe-N-C sites onto the surface of nitrogen-doped graphene, improved the chemical environment of its central Fe atoms with Fe/Fe3C nanoparticles, effectively regulated the multi-electron oxygen reduction process of the catalyst in the electrochemical reaction, and realized the efficient production and activation of H2O2 in the electro-Fenton process. The synthesized Fe/Fe3C@FeNG-1000 achieved efficient removal of refractory organic pollutants in neutral conditions. The rate constant of degradation for tetracycline hydrochloride (TC) in the electro-Fenton reaction system at pH 7 was recorded as 0.1011 min−1. Additionally, a removal rate of 67.4% for total organic carbon (TOC) was achieved in just 120 min. The treatment of actual wastewater also showed excellent performance, with an average specific energy consumption of 6.16 kWh kg−1 COD−1. Fe/Fe3C@FeNG-1000 can still achieve more than 90% degradation efficiency after 5 consecutive cycles of the experiment, showing excellent stability, and the catalyst can be conveniently retrieved via magnetic methods following the reaction. The results show that the Fe/Fe3C@FeNG-1000-EF system has a wide range of pH applicability, long-term stability and good recyclability, has a good application value in practical wastewater treatment.

Visible light driven Z-scheme α-MnO2 (1D)/Bi7O9I3 (2D) heterojunction photocatalyst for efficient degradation of bisphenol A in water

Z-scheme heterojunctions are gaining attention for their outstanding photocatalytic performance in degrading organic pollutants due to improved charge separation efficiency. In view of this, the present study is focused on the synthesis of novel 3D α-MnO2/Bi7O9I3 (MB) nanocomposites heterojunctions of varying α-MnO2 contents via facile in-situ chemical precipitation method at room temperature. Under optimum conditions, MB4 (comprising 485 mg of α-MnO2) exhibited exceptional performance, achieving about 97.5% of bisphenol A (BPA) degradation in 80 mins with a degradation rate constant of 0.08354 min−1. Such superior performance is attributed to efficient interfacial integration and charge separation, validated through various characterization techniques. Further, MB4 heterojunction facilitated Z-scheme electron-hole pair transfer and exhibited an augmented specific surface area. The active species involved in the degradation of BPA were identified as •O2– and •OH in scavenging experiments and supported by findings based on EPR. Additionally, degradation pathways and plausible BPA intermediates have been proposed based on LC-MS/MS studies. Furthermore, with an impressive mineralization rate (89.5%), the toxicity study unveiled less harmful intermediates than the parent compound BPA. MB4 photocatalyst also exhibited commendable stability, as evidenced by its studies based on five reuse cycles with 92.9% efficiency. In essence, visible-light-driven Z-scheme α-MnO2/Bi7O9I3 heterojunction photocatalyst offered a simple and sustainable approach for producing environmentally friendly materials, underscoring its potential in the removal of BPA in water and wastewater treatment.

Synthesis of a novel biomass waste-based photocatalyst for degradation of high concentration organic pollutants under visible light: Optimization of synthesis condition and operational parameters via RSM-CCD

Reducing electron-hole pair recombination rate under visible light and preventing α-Fe2O3/WO3 nanoparticle aggregation enhances the photocatalytic efficiency. Herein, a novel heterojunction-activated carbon-based photocatalyst (α-Fe2O3/WO3/AC) was successfully synthesized from Rosa Canina seeds and characterized by PL, EIS, Photocurrent, ESR, XPS, LC-MS, FTIR, XRD, SEM, EDS-map, TEM, and BET analyses. Investigating the influence of significant parameters, including impregnation ratio (1–5), activation temperature (400–600 °C), and α-Fe2O3/WO3 loading (10–90 wt.%) by RSM method resulted in optimal photocatalyst synthesis (50 wt.%: FeW/AC3–500) evidenced by its capability for doxycycline degradation. The maximum doxycycline degradation (98.01 %) was achieved under optimal conditions with a degradation rate constant of 0.03 min−1. Trapping experiments revealed that •OH and •O2− played crucial roles in photocatalysis. The possible doxycycline degradation pathway of (50 wt.%: FeW/AC3–500) photocatalyst is proposed. Based on the transient photocurrent measurements and EIS results, the 50 wt.% FeW/AC3–500 composite exhibited a significant enhancement in photocatalytic activity, which can be attributed to the efficient speed of electron-hole separation. Overall, an innovative approach was introduced to design an efficient AC-based photocatalytic process, which enhances the performance of wastewater treatment and environmental remediation.

Fabricated layered g-C3N4 nanosheets for high efficiency photocatalytic degradation of atrazine：Insight into terminal-NHx in-situ activation of H2O2

It is well known that graphite-like carbon nitride (g-C3N4) is a good photocatalyst for in-situ the production of H2O2. However, how to activate H2O2 generating the strong oxidizing ·OH is the key factor to affect the degradation of pollutants. In this paper, the layered g-C3N4 nanosheets were prepared by using urea and H2O with different mass ratios and calcined in Muffle furnace by one-step synthesis method. The morphology, composition and structure of photocatalysts were analyzed, indicating that the as-prepared L-g-C3N4-7 had abundant edge regions in comparison with L-g-C3N4 made by solid urea. The photocatalytic performance of g-C3N4 nanosheets was investigated with atrazine (ATZ) as the target pollutant in water. The results revealed that the prepared L-g-C3N4-7 exhibited the best photocatalytic activity in visible light (λ ≥ 420 nm). The degradation of 1.0 mg/L ATZ reached over 96% after 3 hours and the photocatalytic degradation rate constant (k) was 6.8 times than that of L-g-C3N4 photocatalyst. In addition, under the same conditions, the H2O2 production of L-g-C3N4-7 was 4.5 times than that of L-g-C3N4 photocatalyst. Based on the capture experiments of free radicals, it was found that the contribution rate of ·OH in L-g-C3N4-7 photocatalytic increased to 17 % compared to 4 % of L-g-C3N4 photocatalyst during the degradation of ATZ. The ·OH quantitative experiment indicated that the L-g-C3N4-7 photocatalyst could obviously activate H2O2 to generate ·OH and the amount of ·OH was 2.5 times than that of the L-g-C3N4 photocatalyst. More importantly, a large amount of terminal-NHx (14.6 %) in L-g-C3N4-7 was measured by the XPS, FT-IR and zeta potential. The additive H2O2 adsorption experiment in the dark was used to confirm terminal-NHx sites of L-g-C3N4-7 photocatalyst, which was beneficial to adsorb and activate H2O2. The results illustrated that the L-g-C3N4-7 photocatalyst with rich edge regions and terminal-NHx had the characteristics of in-situ the activation of H2O2 to generate ·OH. The findings suggest that designing and developing efficient g-C3N4 photocatalysts pave a new avenue for activating in situ self-synthesizing H2O2 and the removal of atrazine in water.

An efficient photo-Fenton In2O3@FeIn2S4 composite catalyst for tetracycline degradation

Photo-Fenton technology has been widely used as an efficient and environmentally friendly method for pollutant degradation. Herein, novel In2O3@FeIn2S4 microflowers are prepared by a two-step hydrothermal method and used as the photo-Fenton catalyst for tetracycline (TC) degradation. Under illumination (λ > 420 nm), the In2O3@FeIn2S4-0.5 (molar mass ratio of FeIn2S4 to In2O3 is 0.5) shows a higher removal efficiency of TC (98.3 %) in 75 min, than pure In2O3 (60.8 %) and FeIn2S4 (65.8 %). The degradation rate constant of In2O3@FeIn2S4-0.5 for TC is about 5.1 and 3.2 times compared to that of In2O3 and FeIn2S4. In addition, the TC removal efficiency only dropped by 6.7 % after 5 cycles, indicating the superior stability of In2O3@FeIn2S4-0.5. Superoxide radical (∙O2–), hydroxide radical (∙OH), and singlet oxygen (1O2) play a crucial role in TC degradation process, while photogenerated holes (h+) only play a minor role. The improved performance of In2O3@FeIn2S4 photo-Fenton catalyst could be described as the following: the porous In2O3 microflower supporter extends the reactive interface of FeIn2S4; FeIn2S4 effectively enhances optical absorption ability in the visible range; 2D-2D tight interface formed between In2O3 and FeIn2S4 helps to accelerate the charge transfer; the formation of S-scheme heterostructures improves the parting ability of the photoproduced carriers.

Degradation mechanisms of antibiotics in UV222/H2O2 and UV222/persulfate systems: Dual roles of inorganic anions

Advanced oxidation processes based on KrCl* excimer lamps (UV222-AOPs) have recently received widespread attention in water treatment due to their high radical yields. In this investigation, the degradation of two typical antibiotics, florfenicol (FLO) and ciprofloxacin (CIP), by UV222 and its combination with hydrogen peroxide (H2O2) or persulfate (PDS) were studied, respectively. The dual effects of inorganic anions on the degradation performance of UV222/UV222-AOPs were determined. It was found that NO3– significantly enhanced the photolysis of CIP, and the degradation rate constants increased from 1.03 × 10-4 mJ−1 cm2 (without NO3–) to 2.56 × 10-4 mJ−1 cm2 (with 1 mM NO3–). However, NO3– markedly inhibited the photolysis of FLO, leading to a decrease in the degradation rate constants from 1.18 × 10-3 mJ−1 cm2 (without NO3–) to 5.27 × 10-4 mJ−1 cm2 (with 1 mM NO3–). HCO3– was found to have a certain promoting effect on the photolysis of FLO and CIP, and SO42- has a negligible effect on the photolysis of both antibiotics. The above three inorganic ions decelerated the degradation of CIP and FLO in UV222-AOP, where NO3– exerted the most inhibition. Through LC-MS analysis and ECOSAR model, the main transformation products were individually determined and evaluated for toxicity. In addition, the performance of UV222-AOPs and UV254-AOPs in reclaimed wastewater (RWW) treatment were compared, and the steady-state concentration of radicals was measured. This study provided novel insight into the application of UV222-AOPs in RWW treatment.