Apparent Reaction Rate Constant Research Articles

Modeling and experimental verification for photodegradation in a spinning disk reactor

The spinning disk reactor has been regarded as a process intensification device in photochemical processes, which decreases the light path length by the thin film formation created by centrifugal force. A reliable reactor model was indispensable for the practical application of photoreactors. Our previous studies proposed a spinning disk reactor with elliptic-cylindrical and cylindrical spoilers for photochemical process intensification, and then hydrodynamic parameters of liquid film thickness, photon absorption rate, and residence time distribution were obtained. Based on the obtained parameters, herein, a reactor model was further established for the description of photodegradation reaction in the innovative spinning disk reactor. Different non-ideal flow models were employed during the model development, including the tanks-in-series model and axial dispersion model. The apparent reaction rate constant of a spinning disk reactor with spoilers was determined by the photon absorption rate, which was in the range of 0.088–0.268 s−1. The reactor model was verified by the experiments on photodegradation of Methylene Blue under different disk configurations and operating conditions. The degradation efficiency of Methylene Blue could reach up to 89.8 % in 25 min at N = 200 r/min, Q = 60 L/h, and I0 = 8 mW/cm2. The deviation between predicted and experimental Methylene Blue degradation efficiencies was within ± 20 %, confirming the rationality of the reactor model. The developed model lays the foundation for the scaling-up and commercial applications of the novel spinning disk reactors.

An intermediary route to CdS/Bi2S3 architectures with high-activity and stability in photocatalytic water splitting and dye degradation

The binary CdS/Bi2S3 heterostructures were fabricated by employing ZnO/Bi2S3 as active intermediates for the first time, which consisted of 0D CdS nanoparticles with sizes of 10–20 nm decorated on 3D Bi2S3 mircoflowers assembled by 1D nanorods. The whole formation mechanism of CdS/Bi2S3 heterostructure was systematically investigated. Specifically, the optimal CdS/Bi2S3 sample (CB-3) achieved the highest photocatalytic hydrogen evolution reaction rate of 3.85 mmol·g−1·h−1, about 16.74 and 25.67 times greater than that of single Bi2S3 and CdS. Besides, the apparent reaction rate constant of CB-3 for photodegradation of Congo red reached up to 0.0412 min−1, being 41.2 and 4.08 folds higher than that of solo Bi2S3 and CdS. The recycled tests over CB-3 were ready to take on the superb photostability. Furthermore, the S-scheme mechanism of photoinduced charges was rationally proposed. This work provides a new insight for the construction of composite photocatalysts for boosted solar-light-driven photocatalytic performance.

Gas-liquid-soild triphasic continuous flow microreactor for improving homogeneous distribution of solid composites in heterogeneous photocatalytic degradation progress

The homogeneous distribution of solid composites in continuous flow photocatalytic progress is difficult due to the settle and clog in capillary. To overcome this challenge, a gas–liquid-soild triphasic continuous flow photoreactor was designed and used for heterogeneous photocatalytic degradation of antibiotics wastewater. In this work, take Bi2WO6 as photocatalyst, photocatalytic degradation of ofloxacin wastewater was studied systematically under different operational parameters and flow characteristics. The photocatalytic degradation performance of flow photoreactor was superior to batch counterpart, especially in later stage of reaction. The apparent reaction rate constants (k) of flow photoreactor was about 1.6 times that of batch counterpart. The gas–liquid mass transfer coefficient of flow photoreactor was more than 25 times that of batch photoreactor. Moreover, the influence mechanism of gas fraction, flow rate and tube diameter on photocatalytic degradation performance was investigated under various continuous flow conditions. Higher gas fraction, faster flow rate and smaller tube diameter were beneficial to improve photocatalytic degradation performance due to the enhancement of irradiation transmission and intensification of mass transfer. Therefore, the results of this work provided a guideline for the application of gas–liquid-soild triphasic continuous flow photocatalytic degradation technology in the future.

Degradation and mineralization of anti-cancer drugs Capecitabine, Bicalutamide and Irinotecan by UV-irradiation and ozone

The degradation of three anti-cancer drugs (ADs), Capecitabine (CAP), Bicalutamide (BIC) and Irinotecan (IRI), in ultrapure water by ozonation and UV-irradiation was tested in a bench-scale reactor and AD concentrations were measured through ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). A low-pressure mercury UV (LP-UV) lamp was used and degradation by UV (λ = 254 nm) followed pseudo-first order kinetics. Incident radiation in the reactor was measured via chemical actinometry using uridine. The quantum yields (φ) for the degradation of CAP, BIC and IRI were 0.012, 0.0020 and 0.0045 mol Einstein−1, respectively. Ozone experiments with CAP and IRI were conducted by adding ozone stock solution to the reactor either with or without addition of tert-butanol (t-BuOH) as radical quencher. Using this experimental arrangement, no degradation of BIC was observed, so a semi-batch setup was employed for the ozone degradation experiments of BIC. Without t-BuOH, apparent second order reaction rate constants for the reaction of the ADs with molecular ozone were determined to be 3.5 ± 0.8 ∙ 103 L mol−1 s−1 (CAP), 7.9 ± 2.1 ∙ 10−1 L mol−1 s−1 (BIC) and 1.0 ± 0.3 ∙ 103 L mol−1 s−1 (IRI). When OH-radicals (∙OH) were quenched, rate constants were virtually the same for CAP and IRI. For BIC, a significantly lower constant of 1.0 ± 0.5 ∙ 10−1 L mol−1 s−1 was determined. Of the tested substances, BIC was the most recalcitrant, with the slowest degradation during both ozonation and UV-irradiation. The extent of mineralization was also determined for both processes. UV irradiation was able to fully degrade up to 80% of DOC, ozonation up to 30%. Toxicity tests with Daphnia magna (D. magna) did not find toxicity for fully degraded solutions of the three ADs at environmentally relevant concentrations.

Synthesis of 1D magnetic Fe3O4@SiO2/TiO2 nanostir bar photocatalyst for the degradation of MB under UV light

Here, a novel one-dimensional (1D) magnetic Fe3O4@SiO2/TiO2 nanostir bar both with high-efficient adsorption and photocatalysis of Methylene blue (MB) has been explored. Firstly, silicon and titanium precursor were loaded on the surface of Fe3O4 through the static magnetic induced self-assembly. Then the TiO2/SiO2 hybrid shell were formed by the hydrothermal treatment process to achieve the 1D magnetic nanostir bar. The 1D magnetic Fe3O4@SiO2/TiO2 photocatalyst exhibited good adsorption capacity and degradation activity of MB. The adsorption capacity of MB by Fe3O4@SiO2/TiO2(60 %) was 40 mg g−1. The apparent reaction rate constant of Fe3O4@SiO2/TiO2 (60 %) was 0.129 min−1. This work will provide a general strategy to explore other useful 1D magnetic nanomaterials for micro-reaction system.

Integrated model of ozone mass transfer and oxidation kinetic: Construction, solving and analysis

Ozone-based advanced oxidation process (O3-AOPs) is rapidly evolving, but the surge of emerging pollutants brings new challenges for ozone oxidation research. Herein, we proposed a state-of-the-art model for simultaneously analyzing both ozone mass transfer and oxidation kinetics during ozone oxidation of emerging organic contaminants. The numerical solution and graphical representations of the integrated model were utilized to analyze the dynamics of ozone and pollutant concentration. An in-depth analysis of the integrated model revealed that the reaction rate constants in this present study were higher than previously reported apparent reaction rate constants, and catalysts were not always necessary. Finally, we developed an installable mobile application (APP) that allowed the simulation of the dynamic process for ozone oxidizing organic pollutants in the laboratory, which offered theoretical support for the selection of experimental conditions. The results of model simulation not only provide scientific explanations for counter-intuitive experimental phenomena, but also optimized experimental conditions to enhance ozone utilization.

Distinguishable photorecycling of PVDF nanocomposites membrane for reactive yellow 145 dye and real industrial wastewater treatment by different photocatalytic processes

This paper investigates the photocatalytic performance and recyclability of PVDF-MWCNTs-TiO2 nanocomposite membranes for the treatment of textile wastewater under sunlight irradiation. The nanocomposites were fabricated by incorporating varying weight ratios of MWCNTs-TiO2 (1 %, 3 %, 6 %, and 9 %) into PVDF matrices using a solvent casting method. Optimal loading of MWCNTs-TiO2 at 9 wt% resulted in nanocomposites with enhanced surface area (94.15 m2/g), reduced band gap (2.38 eV), uniform dispersion of nanoparticles, and abundant surface hydroxyl groups. Under Xenon lamp irradiation, the optimized PVDF-9 %(MWCNTs-9 %TiO2) nanocomposite achieved a high apparent reaction rate constant (kapp) of 9.92 × 10−3 s−1 for photocatalytic degradation of the model dye Reactive Yellow 145. Significantly, when tested on-site at a Saudi Arabian textile facility over 6 months, this nanocomposite effectively reduced the chemical oxygen demand (COD) of real wastewater samples to regulatory limits of 1000 ppm under natural sunlight irradiation. The COD values were lowered from an initial 5050–6200 ppm to a final range of 785–945 ppm using the PVDF-9 %(MWCNTs-9 %TiO2) membrane. Furthermore, the optimized nanocomposite exhibited good recyclability, retaining around 87 % of its initial activity after 8 reuse cycles for industrial wastewater treatment. The excellent photocatalytic efficiency and reusability of the MWCNTs-TiO2 modified PVDF nanocomposite under solar irradiation highlight its promise as a sustainable membrane technology for environmental remediation.

Exfoliated MXene-AuNPs hybrid in sensing and multiple catalytic hydrogenation reactions.

The increasing use of nanomaterials in consumer products is expected to lead to environmental contamination sometime soon. As water pollution is a pressing issue that threatens human survival and impedes the promotion of human health, the search for adsorbents for removing newly identified contaminants from water has become a topic of intensive research. The challenges in the recyclability of contaminated water continue to campaign the development of highly reusable catalysts. Although exfoliated 2D MXene sheets have demonstrated the capability towards water purification, a significant challenge for removing some toxic organic molecules remains a challenge due to a need for metal-based catalytic properties owing to their rapid response. In the present study, we demonstrate the formation of hybrid structure AuNPs@MXene (Mo2CTx) during the sensitive detection of Au nanoparticle through MXene sheets without any surface modification, and subsequently its applications as an efficient catalyst for the degradation of 4-nitrophenol (4-NP), methyl orange (MO), and methylene blue (MB). The hybrid structure (AuNPs@MXene) reveals remarkable reusability for up to eight consecutive cycles, with minimal reduction in catalytic efficiency and comparable apparent reaction rate constant (Kapp) values for 4-NP, MB, and MO, compared to other catalysts reported in the literature.

Applying microelectrodes to investigate aged ductile iron and copper coupon reactivity during free chlorine application

In drinking water distribution systems, including premise plumbing, dissolved oxygen (DO) and free chlorine (FC) are common oxidants and ductile iron (DI) and copper (Cu) are commonly used pipe materials. Microelectrodes as a tool have been applied in previous corrosion research and were used in this study to collect quantifiable data and understand DO and FC reactivity and pH changes at the water-metal interface. Using microelectrodes, pH, DO, and FC profiles from the bulk water to near and at the surface of aged DI (154–190 d) and Cu (2 d and 86–156 d) coupons were investigated during periods of flow and stagnation (30 min). Using the measured microelectrode profiles, oxidant fluxes and apparent surface reaction rate constants were calculated to elucidate differences between DO and FC reactivity with the coupons. Microelectrodes were successfully applied to measure pH, DO, and FC profiles from the bulk water to near aged DI and Cu coupon surfaces; Cu coupons aged quickly and exhibited less reactivity at 2 d with DO and FC than aged DI coupons did after 154–190 d; and for the aged DI coupon experiments, orthophosphate presence stabilized pH profiles where without orthophosphate pH fluctuations of greater than 2 pH units occurred from the bulk water to the DI coupon surface.

Photothermal-assisted S-scheme PDIs/C, N, S-CeO2 derived from MOF-808 (Ce) heterojunction for photocatalytic removal of antibiotics

In this research, an organic supermolecule self-assembly perylene diimides (PDIs) semiconductor was wrapped around the surface of three-dimensional metal oxides frame (C, N, S-CeO2) by oil bath heating method. The photocatalytic ability was determined by the degradation of organic pollutants under visible light. The photodegradation rate of tetracycline (TC) was nearly 80.1% within 30 min, and the apparent reaction rate constant (k) was 15.83 times higher than that of C, N, S-CeO2. Free radical capture experiments and electron spin resonance analysis showed that •O2-, •OH and 1O2 were the main active species. The structure of PDIs/C, N, S-CeO2 maintained stable after four cycles, meanwhile, anti-ion interference experiment illustrated that degradation efficiency was not affected by neutral ionic intensity. Further, the formation pathways of main degradation intermediates during the degradation process and the toxicity prediction of degradation intermediates were proposed. In addition, 10% PDIs/C, N, S-CeO2 could also efficiently degrade other organic pollutants (chlorotetracycline (CTC), ciprofloxacin (CIP), rhodamine B (RhB), methylene blue (MB)). The excellent photocatalytic activity of 10% PDIs/C, N, S-CeO2 was attributed to the matched energy band structure, establishment of multi-dimensional channels, more significant visible light assimilation performance and enhanced photothermal ability. This work provides a new perspective on the construction of n-n S-scheme heterojunction photocatalysts between self-assembled organic supramolecular materials and MOF-derived metal oxides.

Magnetic recoverable Ag3PO4/Fe3O4/γ-Fe2O3 nanocomposite

The use of nanomaterials in water treatment is an alternative for the development of new systems to optimize the purification process. Heterogeneous photocatalysis is used for the treatment of wastewaters contaminated with recalcitrant pollutants that cannot be removed with conventional wastewater treatment techniques. Silver phosphate (Ag3PO4) can be used in visible-light driven photocatalysis. An important challenge of heterogeneous photocatalysis is to find a proper support for the photocatalysts to reduce the expense associated with the separation and reuse of these materials. However, the immobilization of the catalyst leads to lower reaction rates because the exposed surface area decreases and the material used as support can also interfere. In the last years, the use of magnetic materials to support photocatalysts has attracted special attention because it allows high surface areas to be exposed. Only few authors have reported the use of Ag3PO4/magnetic nanocomposites for photocatalysis and these need to be continued to improve their efficiency. In this work we synthesized Ag3PO4 and supported it on ferromagnetite (Fe3O4). In this study, Fe3O4 was synthesis following the Massart’s method. Ag3PO4 was synthesised over Fe3O4 from the reaction between silver nitrate (AgNO3) and disodium hydrogen phosphate (Na2HPO4). For characterization, DRS, SEM, XRD and magnetization studies were carried out. Ag3PO4 was synthesised and satisfactorily supported over magnetite (Fe3O423). The photodegradation of 10 mg·L−1 of methylene blue was achieved, although the apparent reaction rate constant was slightly lower for the magnetic composite than for bare Ag3PO4. This is explained because the composite contained 48% of the active Ag3PO4 material, as depicted form XRD studies.

Investigation of α-Fe2O3 catalyst structure for efficient photocatalytic fenton oxidation removal of antibiotics: preparation, performance, and mechanism.

Currently, the surface structure modification of photocatalysts is one of the effective means of enhancing their photocatalytic efficiency. Therefore, it is critically important to gain a deeper understanding of how the surface of α-Fe2O3 photocatalysts influences catalytic activity at the nanoscale. In this work, α-Fe2O3 catalysts were prepared using the solvothermal method, and four distinct morphologies were investigated: hexagonal bipyramid (THB), cube (CB), hexagonal plate (HS), and spherical (RC). The results indicate that the hexagonal bipyramid (THB) exhibits the highest degradation activity towards tetracycline (TC), with a reaction rate constant of k = 0.0969 min-1. The apparent reaction rate constants for the cube (CB), hexagonal plate (HS), and spherical (RC) morphologies are 0.0824, 0.0726, and 0.0585 min-1, respectively. In addition, it has been observed that the enhancement of photocatalytic activity is closely related to the increase in surface area, which provides more opportunities for interactions between Fe2+ and holes. The quenching experiments and electron paramagnetic resonance (EPR) results indicate that the ˙O2, ˙OH and h+ contribute mainly to the degradation of TC in the system. This research contributes to a more comprehensive understanding of catalyst surface alterations and their impact on catalytic performance.

Exploring the Remarkably High Photocatalytic Efficiency of Ultra-Thin Porous Graphitic Carbon Nitride Nanosheets.

Graphitic carbon nitride (g-C3N4) is a metal-free photocatalyst used for visible-driven hydrogen production, CO2 reduction, and organic pollutant degradation. In addition to the most attractive feature of visible photoactivity, its other benefits include thermal and photochemical stability, cost-effectiveness, and simple and easy-scale-up synthesis. However, its performance is still limited due to its low absorption at longer wavelengths in the visible range, and high charge recombination. In addition, the exfoliated nanosheets easily aggregate, causing the reduction in specific surface area, and thus its photoactivity. Herein, we propose the use of ultra-thin porous g-C3N4 nanosheets to overcome these limitations and improve its photocatalytic performance. Through the optimization of a novel multi-step synthetic protocol, based on an initial thermal treatment, the use of nitric acid (HNO3), and an ultrasonication step, we were able to obtain very thin and well-tuned material that yielded exceptional photodegradation performance of methyl orange (MO) under visible light irradiation, without the need for any co-catalyst. About 96% of MO was degraded in as short as 30 min, achieving a normalized apparent reaction rate constant (k) of 1.1 × 10-2 min-1mg-1. This represents the highest k value ever reported using C3N4-based photocatalysts for MO degradation, based on our thorough literature search. Ultrasonication in acid not only prevents agglomeration of g-C3N4 nanosheets but also tunes pore size distribution and plays a key role in this achievement. We also studied their performance in a photocatalytic hydrogen evolution reaction (HER), achieving a production of 1842 µmol h-1 g-1. Through a profound analysis of all the samples' structure, morphology, and optical properties, we provide physical insight into the improved performance of our optimized porous g-C3N4 sample for both photocatalytic reactions. This research may serve as a guide for improving the photocatalytic activity of porous two-dimensional (2D) semiconductors under visible light irradiation.

Sulfur-Doped g-C3N4 Heterojunctions for Efficient Visible Light Degradation of Methylene Blue.

The discharge of synthetic dyes from different industrial sources has become a global issue of concern. Enormous amounts are released into wastewater each year, causing concerns due to the high toxic consequences. Photocatalytic semiconductors appear as a green and sustainable form of remediation. Among them, graphitic carbon nitride (g-C3N4) has been widely studied due to its low cost and ease of fabrication. In this work, the synthesis, characterization, and photocatalytic study over methylene blue of undoped, B/S-doped, and exfoliated heterojunctions of g-C3N4 are presented. The evaluation of the photocatalytic performance showed that exfoliated undoped/S-doped heterojunctions with 25, 50, and 75 mass % of S-doped (g-C3N4) present enhanced activity with an apparent reaction rate constant (kapp) of 1.92 × 10-2 min-1 for the 75% sample. These results are supported by photoluminescence (PL) experiments showing that this heterojunction presents the less probable electron-hole recombination. UV-vis diffuse reflectance and valence band-X-ray photoelectron spectroscopy (VB-XPS) allowed the calculation of the band-gap and the valence band positions, suggesting a band structure diagram describing a type I heterojunction. The photocatalytic activities calculated demonstrate that this property is related to the surface area and porosity of the samples, the semiconductor nature of the g-C3N4 structure, and, in this case, the heterojunction that modifies the band structure. These results are of great importance considering that scarce reports are found concerning exfoliated B/S-doped heterojunctions.

A synchronous defluorination-oxidation process for efficient mineralization of fluoroarenes with photoelectrocatalysis

Fluoroarene (FA) derivatives are persistent, toxic, and bioaccumulative pollutants, which pose severe risks to ecosystems and human health. Efficient cleavage of C–F bonds and complete mineralization of defluorinated intermediates are the keys for the deep treatment of FAs due to the high dissociation energy of C–F bonds and the high stability of aromatic rings. Herein, we report a synchronous defluorination-oxidation process using a photoelectrocatalytic device with a TiO2 photoanode, in which FAs are selectively cleavage of C–F bonds by photolysis and subsequently efficient oxidized by on-site generated •OH radical. Complete defluorination and mineralization (both over 99.9%) of 4-fluorophenol are achieved under irradiation at 1.0 VRHE in 120 min, the apparent reaction rate constant is 14.4 g h−1 m−2. This synchronous defluorination-oxidation process provides an efficient and practical technique for the mineralization of FAs in wastewater under mild conditions.

Br-Doped BiOCl Nanosheet Exposed (001) Facet: Surface Oxygen Vacancy and Directed Electron Flow Boosting the Photocatalytic Performance.

The defective BiOCl nanosheet exposed (001) facet with favorable photocatalytic performance was designed. The surface microstructure analysis and theoretical calculation certified the dominant exposed (001) facet and rich surface oxygen defects of Br--doped BiOCl (B-6) nanosheets. The energy level structure analysis indicates that the band gap can be narrowed and the light absorption range can be widened by introducing Br- to BiOCl, and the presence of defective energy levels increases the photogenerated carrier transfer efficiency. Moreover, the doping of Br- in BiOCl promotes the directional flow of electrons to the surface of B-6, which improves the photocatalytic performance of the sample. Thus, the Br--doped BiOCl can degrade 96.5% RhB within 6 min under visible-light irradiation with high apparent reaction rate constants of 0.51 min-1, exhibiting the strongest photocatalytic degradation performance. This work provides guidance for the preparation of Bi-based photocatalysts with excellent performance.

Roles of temperature and ventilation in oxygen consumption: A chemical kinetics view from the van't Hoff-based formulation

In this study, we successfully estimated the apparent activation energy of a microbially driven oxygen-consuming reaction (microbial-driven) based on tracer data. The concept of the apparent chemical reaction rate constant was employed to estimate various thermodynamic parameters associated with the oxygen consumption rate in conjunction with Arrhenius/Eyring equations. Normal Ea values of 80–90 kJ mol−1 were found in the upper layers of the South China Sea and Sulu Sea, while higher Ea values (300–1000 kJ mol−1) were observed in the rapidly ventilated Mediterranean Sea, the Sea of Japan, and the Bering Sea with lower temperatures. We classified the characteristics of typical sea basins into four categories. The temperature-dependent oxygen consumption rate relationship in each marine region was systematically calculated to derive the respective thermodynamic characteristic values. This allowed us to parameterize the rate-temperature relationship into thermodynamic quantities, enabling more effective integration of distinct basin characteristics within different sea areas into the marine biochemical model. Parameterization facilitates relatively accurate prediction of changes such as temperature, oxygen consumption rate.

Plasma treatment of sulfamethoxazole contaminated water: Intermediate products, toxicity assessment and potential agricultural reuse

The increasing global water demand has prompted the reuse of treated wastewater. However, the persistence of organic micropollutants in inefficiently treated effluents can have detrimental effects depending on the scope of the reclaimed water usage. One example is the presence of sulfamethoxazole, a widely used antibiotic whose interference with the folate synthesis pathway negatively affects plants and microorganisms. The goal of this study is to assess the suitability of a non-thermal plasma-ozonation technique for the removal of the organic pollutant and reduction of its herbicidal effect. Fast sulfamethoxazole degradation was achieved with apparent reaction rate constants in the range 0.21–0.49 min−1, depending on the initial concentration. The highest energy yield (64.5 g/kWh at 50 % removal) exceeds the values reported thus far in plasma degradation experiments. During treatment, 38 degradation intermediates were detected and identified, of which only 9 are still present after 60 min. The main reactive species that contribute to the degradation of sulfamethoxazole and its intermediate products were hydroxyl radicals and ozone, which led to the formation of several hydroxylated compounds, ring opening and fragmentation. The herbicidal effect of the target compound was eliminated with its removal, showing that the remanent intermediates do not retain phytotoxic properties.

Selective oxidation of histamine H2-Receptor antagonists by peracetic Acid: Kinetics and mechanism

Peracetic acid (PAA) is an emerging substitutive oxidant to chlorine disinfectants owing to the low generation of harmful by-products. Herein, we report PAA-induced oxidation of histamine H2-receptor antagonists (HRAs) via non-radical participation for the first time. Results showed that PAA can selectively oxidize HRAs with high reactivity to ranitidine (RNTD), nizatidine (NZTD), cimetidine (CMTD), and famotidine (FMTD), but low reactivity to roxatidine (RXTD). PAA-induced HRAs oxidation followed the second-order kinetic reaction, the apparent second-order reaction rate constants (k2, app) of RNTD, FMTD, CMTD and NZTD were 18.78 ± (2.4), 37.22 ± (6.1), 36.53 ± (7.8), 30.04 ± (2.4) M−1•s−1, respectively. The value of k2, app decreased as pH increased. Scavenging experiments indicated that PAA-induced HRAs oxidation proceeded via a non-radical process. The theoretical calculation and product analysis further reveal that the reaction involves the double-electron transfer from thioether sulfur in HRAs to peroxide bond. HRAs oxidation by PAA was not affected by water matrices (Cl-, HCO3–, HA), which has good applicability in surface water (SW) and wastewater (WW). Toxicity assessment indicated ecotoxicity of oxidation products was much lower than that of HRAs. This work provided a facile and emerging technology to eliminate the HRAs and their toxicity in the wastewater.

Oleyl Phosphate-Modified Crystalline-Amorphous TiO2/Ce2O3 heterojunction nanoparticles with significantly reduced photocatalytic activity as stable UV-Shielding fillers

As a stable and inexpensive UV-absorber, TiO2 is widely used in UV-shielding products. However, its poor compatibility with matrix polymers and photocatalytic degradation hazard still limit its performance. Herein, we construct the crystalline-amorphous TiO2/Ce2O3 heterojunctions with an average size of 15 nm via an in-situ solvothermal process, significantly reducing the photocatalytic activity through the carrier redistribution between TiO2 and Ce2O3. In the photocatalytic experiments for the degradation of three dyes (RhB, MB, and RR-120), the apparent reaction rate constants (k) of the optimal sample TiO2/Ce2O3-3 % are 33.92, 28.54, and 24.78 times lower than those of pure TiO2, respectively. The characterizations and theoretical calculations together reveal that the photogenerated carriers accumulate on the amorphous Ce2O3 with rich defects, promoting the recombination of electron-hole pairs and reducing the carriers’ redox potential. Additionally, oleyl phosphate (OP) is used for surface modification to achieve TiO2/Ce2O3 organic solvent-dispersible and improve its compatibility with matrix polymers, thus the UV-shielding OP-TiO2/Ce2O3/fluorocarbon hybrid coating is prepared with high transparency.