Unveiling the Mechanism and Kinetics of Pollutant Attenuation by Free Radicals Triggered from Goethite in Water Distribution Systems.

Investigating the fate of persistent organic pollutants in water distribution systems (WDSs) is of great significance for preventing human health risks. The role of iron corrosion scales in the migration and transformation of organics in such systems remains unclear. Herein, we determined that hydroxyl (•OH), chlorine, and chlorine oxide radicals are generated by Fenton-like reactions due to the coexistence of oxygen vacancy-related Fe(II) on goethite (a major constituent of iron corrosion scales) and hypochlorous acid (HClO, the main reactive chlorine species of residual chlorine at pH ∼ 7.0). •OH contributed mostly to the decomposition of atrazine (ATZ, model compound) more than other radicals, producing a series of relatively low-toxicity small molecular intermediates. A simplified kinetic model consisting of mass transfer of ATZ and HClO, •OH generation, and ATZ oxidation by •OH on the goethite surface was developed to simulate iron corrosion scale-triggered residual chlorine oxidation of organic compounds in a WDS. The model was validated by comparing the fitting results to the experimental data. Moreover, the model was comprehensively applicable to cases in which various inorganic ions (Ca2+, Na+, HCO3-, and SO42-) and natural organic matter were present. With further optimization, the model may be employed to predict the migration and accumulation of persistent organic pollutants under real environmental conditions in the WDSs.

Transforming Plain LaMnO3 Perovskite into a Powerful Ozonation Catalyst: Elucidating the Mechanisms of Simultaneous A and B Sites Modulation for Enhanced Toluene Degradation.

Herein, we propose preferential dissolution paired with Cu-doping as an effective method for synergistically modulating the A- and B-sites of LaMnO3 perovskite. Through Cu-doping into the B-sites of LaMnO3, specifically modifying the B-sites, the double perovskite La2CuMnO6 was created. Subsequently, partial La from the A-sites of La2CuMnO6 was etched using HNO3, forming novel La2CuMnO6/MnO2 (LCMO/MnO2) catalysts. The optimized catalyst, featuring an ideal Mn:Cu ratio of 4.5:1 (LCMO/MnO2-4.5), exhibited exceptional catalytic ozonation performance. It achieved approximately 90% toluene degradation with 56% selectivity toward CO2, even under ambient temperature (35 °C) and a relatively humid environment (45%). Modulation of A-sites induced the elongation of Mn-O bonds and decrease in the coordination number of Mn-O (from 6 to 4.3) in LCMO/MnO2-4.5, resulting in the creation of abundant multivalent Mn and oxygen vacancies. Doping Cu into B-sites led to the preferential chemisorption of toluene on multivalent Cu (Cu(I)/Cu(II)), consistent with theoretical predictions. Effective electronic supplementary interactions enabled the cycling of multiple oxidation states of Mn for ozone decomposition, facilitating the production of reactive oxygen species and the regeneration of oxygen vacancies. This study establishes high-performance perovskites for the synergistic regulation of O3 and toluene, contributing to cleaner and safer industrial activities.

Determination of hexachlorobutadiene, pentachlorobenzene, and hexachlorobenzene in waste incineration fly ash using ultrasonic extraction followed by column cleanup and GC-MS analysis.

Hexachlorobutadiene (HCBD) was listed as a new controlling persistent organic pollutant in the Stockholm Convention because of its wide industrial applications and potential genotoxicity and carcinogenicity. However, only limited information exists on the release of HCBD from unintentional sources, such as waste incineration. Identification and quantification of HCBD in fly ash, one of the major outputs of waste incineration, is imperative. This work presents a simple method for determining HCBD in waste incineration fly ash based on ultrasonic extraction coupled with a silica gel-Florisil column cleanup followed by gas chromatography-mass spectrometry detection. Two typical persistent organic pollutants, pentachlorobenzene (PeCB) and hexachlorobenzene (HCB), were measured simultaneously. The parameters that influence the extraction efficiency and the quality of instrument detection were studied. Under the optimum experimental conditions, high sensitivity (detection limit 0.25-0.53 ng g-1), acceptable recoveries (64.0-71.4%) at spiking levels of 5-500 ng g-1, and good repeatability [relative standard deviation (n = 3) of 14% or less] were achieved for all target analytes. The validation of this method was performed by analysis of six real fly ash samples from different waste incinerators in eastern China. The concentrations of HCBD detected in these samples (1.39-97.6 ng g-1) were comparable to those of PeCB (1.22-150 ng g-1) and HCB (0.82-120 ng g-1), indicating that the residual HCBD as well as PeCB and HCB in waste incineration fly ash should not be ignored. The results confirm for the first time that waste incineration is an unintentional source of HCBD in China. Graphical abstract An analytical method for hexachlorobutadiene, pentachlorobenzene, and hexachlorobenzene in fly ash from waste incineration. GC-MS gas chromatography-mass spectrometry, Ph-d10 phenanthrene-d10.

Photocatalytic activity of TiO2 containing anatase nanoparticles and rutile nanoflower structure consisting of nanorods.

A series of TiO2 with different crystal phases and morphologies was synthesized via a facile hydrothermal process using titanium n-butoxide and concentrated hydrochloric acid as raw materials. The photocatalytic activity of the samples was evaluated by degradation of Methyl Orange in aqueous solution under UV-Visible light irradiation. On the basis of detailed analysis of the characterizing results of high-resolution transmission electron microscopy, X-ray powder diffraction measurements, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller measurement, it was concluded that the photo-activity of the catalyst is related directly to the 3D morphology and the crystal phase composition. An excellent catalyst should have both a rutile 3D flower-like structure and anatase granulous particles. The 3D flower-like structure could enhance light harvesting, as well as the transfer of reactant molecules from bulk solution to the reactive sites on TiO2. In addition, the optimum anatase/rutile phase ratio was found to be 80:20, which is beneficial to the effective separation of the photogenerated electron-hole pairs.

Covalent Triazine Frameworks Decorated with Pyridine-Type Carbonitride Moieties: Enhanced Photocatalytic Hydrogen Evolution by Improved Charge Separation.

A simple procedure of calcination under an Ar atmosphere has been successfully applied to create a covalent triazine framework bearing pyridine-type carbonitride moieties (PCN@CTF). The appending of PCN on the CTF led to visible light absorption at up to 600 nm in the UV/Vis diffuse-reflectance spectra. Photoluminescence and electrochemical impedance spectroscopy have been applied to clarify how modification of the CTF with PCN enhanced the separation efficiency of photoexcited charge carriers. An optimized 1%PCN@CTF sample showed the highest photocatalytic hydrogen evolution reaction (HER) rate of 170.2 ± 2.3 µmol g-1·h-1, 3.9 times faster than that over the pristine CTF. The apparent quantum efficiency of the HER peaked at (7.57 ± 0.10)% at 490 nm. This representative 1% PCN@CTF sample maintained continuous function for at least 15 h. This work provides new guidance for modification with PCN materials as a means of obtaining high photocatalytic efficiency and sheds light on the effect of appended pyridine rings on a CTF.

Electron transfer enhancing the Mn(II)/Mn(III) cycle in MnO/CN towards catalytic ozonation of atrazine via a synergistic effect between MnO and CN.

In this study, manganese oxide (MnO) dispersed on CN (Mn-nCN) was fabricated as a catalyst in heterogeneous catalytic ozonation (HCO), achieving excellent catalytic performance on refractory organic pollutant degradation via the synergistic effects between MnO and CN. The study demonstrated that the C-N-Mn and C-O-Mn bonds constructed in the catalyst linking MnO and CN created the synergistic effects which could overcome typical problems, such as metal leaching etc. The C-N-Mn and C-O-Mn bonds could promote electron transfer from cation-π reactions to form electron-rich Mn(II) sites and electron-poor CN sites. The electron-rich Mn(II) sites as active sites supplied electrons to ozone which then further evolved into reactive oxygen species (ROS). The electron-poor CN sites captured electrons from the pollutant intermediate radicals to electron-rich Mn(II) sites via cation-π reactions with the help of C-N-Mn and C-O-Mn bonds, which promote the redox reactions of Mn. The surface hydroxyl groups also participated in ozone decomposition and ROS production. Additionally, •OH was the dominant ROS of the Mn-nCN HCO processes. This study presents the excellent HCO performance of Mn-nCN, as well as provides views on the electron transfer route between the catalyst, pollutant and ozone, which is crucial for the design of the catalyst.

Insights into conduction band flexibility induced by spin polarization in titanium-based metal-organic frameworks for photocatalytic water splitting and pollutants degradation.

Solar energy is becoming the most promising option to mitigate the energy crisis in the future and can be applied in renewable and economical technologies such as water splitting and pollutants degradation. The promotion of the electronic energetic level is considered an efficient method to enhance the photocatalytic performance of semiconductor materials for solar energy conversion. The highly energetic electrons exhibit a remarkable reduction ability by virtue of the electronic spin polarization, which is associated with the conduction band (CB) position. Thus, the regulation of the CB position due to the redistribution of electrons by means of defect engineering presents potential. Here, a series of titanium-based metal-organic frameworks (Ti-based MOFs) named MIL-125-m% containing different extents of defects are reported to enable photocatalytic activity under simulated sunlight and visible light illumination for remarkably enhanced photocatalytic hydrogen evolution and pollutant degradation. The experimental results illustrated that MIL-125-5 % exhibited a superior photocatalytic hydrogen evolution rate (16507.27 µmol·g-1·h-1), much higher than that of MIL-125-0 % (1.444 µmol·g-1·h-1). The excellent photocatalytic performance was attributed to upshift of d-band center, which strengthened the adsorption of H*, facilitating the H2 evolution reaction. In addition, the degradation rate of MIL-125-5 % was up to twice the original rate, for the highly energetic electrons induced by the CB flexibility alleviated the photoinduced electron recombination in defective MIL-125. The strategy of defect engineering provides a new path to control the flexibility of the CB position by electronic spin polarization on adjustable metal-organic frameworks (MOFs), and the photocatalytic effect is changed accordingly.

Constructed electron-dense Mn sites in nitrogen-doped Mn3O4 for efficient catalytic ozonation of pyrazines: Degradation and odor elimination.

In this study, N-doped Mn3O4 catalysts (Mn-nN) with electron-dense Mn sites were synthesized and employed in heterogeneous catalytic ozonation (HCO). These catalysts demonstrated excellent performance in pyrazines degradation and odor elimination. The synthesis of Mn-nN was achieved through a facile urea-assisted heat treatment method. Experimental characterization and theoretical analyses revealed that the MnN structures in Mn-nN, played a crucial role in facilitating the formation of electron-dense Mn sites that served as the primary active sites for ozone activation. In particular, Mn-1N exhibited excellent performance in the HCO system, demonstrating the highest 2,5-dimethylpyrazine (2,5-DMP) degradation efficiency. •OH was confirmed as the primary reactive oxygen species involved in the HCO process. The second-order rate constants for 2,5-DMP degradation with O3 and •OH, were determined to be (3.75 ± 0.018) × 10-1 and (6.29 ± 0.844) × 109 M-1 s-1, respectively. Seventeen intermediates were identified through GC-MS analysis during the degradation of 2,5-DMP via HCO process with Mn-1N. The degradation pathways were subsequently proposed by considering these identified intermediates. This study introduces a novel approach to synthesize N-doped Mn3O4 catalysts and demonstrates their efficacy in HCO for the degradation of pyrazines and the elimination of associated odors. The results show that the catalysts are promising for addressing odor-related environmental issues and provide valuable insights about the broader significance of catalytic ozonation processes.

Boosting photocatalytic H2 evolution on UIO-66-NH2/covalent triazine-based frameworks composites by constructing a covalent heterojunction.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been proved as efficient catalysts for photocatalytic hydrogen (H2) evolution, thanks to their tunable functionalities, permanent porosity, excellent visible light response, and physicochemical stability. Herein, a series of photocatalysts (termed NUBC) was fabricated by loading different amounts of Zr-UiO-66-NH2 (NU) onto a benzoic acid-modified covalent triazine-based framework (BC) based on post-synthetic covalent modification. The resulting NUBC catalysts exhibited a type-II Z-scheme heterojunction structure formed via the amide covalent bonds between the amine groups on NU and carboxyl groups on BC. The optimal loading of NU on BC is 30 wt.% (30NUBC) and the corresponding photocatalytic H2 evolution rate was 378 µmol h-1 g-1, almost 445 and 2 times than that of NU and BC, respectively. The synergistic effect between the type-II Z-scheme heterojunctions and amide bonds was conducive to boosting visible light harvesting and facilitating charge transportation and separation. Furthermore, the prepared NUBC catalysts show great reusability and stability. Overall, this work sheds light on the design of novel MOF/COF hybrid materials and provides a systematic exploration of their photocatalytic H2 evolution properties.

Highly selective electrocatalytic reduction of CO2 to HCOOH over an in situ derived hydrocerussite thin film on a Pb substrate.

A metal oxide electrode has been developed for the electrochemical CO2 reduction reaction (eCO2RR). It exhibits superior activity and product selectivity towards eCO2RR by circumventing the previously encountered problem of self-reduction with high-valence metals. Specifically, a hydrocerussite [Pb3(CO3)2(OH)2] thin film has been synthesized in situ on a Pb substrate (denoted as ER-HC) by an electroreduction method using a lead-based metal-organic framework (Pb-MOF) as a precursor. The ER-HC electrode exhibits a high selectivity of 96.8% towards HCOOH production with a partial current density of 1.9 mA cm-2 at -0.88 V vs. the reversible hydrogen electrode (RHE). A higher HCOOH partial current density of 7.3 mA cm-2 has been achieved at -0.98 V vs. RHE. Physicochemical and electrochemical characterization results demonstrate that the defective hydrocerussite surface exhibits appropriate adsorption free energy of formate (HCOO-) and a lower reaction free energy for HCOOH production from CO2, which greatly boosts the eCO2RR activity and HCOOH production selectivity. The structure and eCO2RR performance of the hydrocerussite thin film remain stable in 0.1 M KHCO3 as electrolyte, ensuring its durability. Overall, this work not only provides a metal oxide electrode (metal hydroxide, to be more precise) with excellent eCO2RR performance, but also expands the in situ electrochemical derivatization strategy for the fabrication of metal oxide electrodes.

Chlorophene degradation by combined ultraviolet irradiation and ozonation.

Ozonation combined with UV irradiation (UV/O(3)) is an advanced oxidation technique that is very promising for the destruction of organic compounds in aqueous solution. In this study, chlorophene was chosen as a model substrate to investigate the effects of pH, initial substrate concentration, ozone dose, and UV light intensity in degradation experiments. The pseudo-first-order rate constant for total organic carbon (TOC) removal was 2.4 × 10(-2), 9.8 × 10(-4), and 6.4 × 10(-2) min(-1) for O(3), UV, and UV/O(3) treatment, respectively. Clearly, UV-enhanced ozonation leads to a synergetic increase in the overall degradation efficiency. Comparative experiments were performed to investigate the effect of the matrix (distilled water or sewage) on chlorophene removal. The organic compounds in sewage retarded the rate of chlorophene removal by 38%, probably by competitively reacting with the oxidizing agent and screening light. The compound 2-benzoylbenzo-1,4-quinone, benzo-1,4-quinone, hydroquinone and maleic acid were identified as primary intermediates by gas chromatography-mass spectrometry. The concentrations of acetic, formic and oxalic anions were detected by ion chromatography. A possible degradation pathway is proposed on the basis of the reaction products identified.

A visible light-responsive iodine-doped titanium dioxide nanosphere.

I-doped titanium dioxide nanospheres (I-TNSs) were synthesized via a two-step hydrothermal synthesis route, their potential for the efficient utilization of visible light was evaluated. The prepared anatase-phase I-TNSs had a bimodal porous size distribution with a Brunauer-Emmett-Teller surface area of 76 m2/g, a crystallite size of approximately 14 nm calculated from X-ray diffraction data, and a remarkable absorption in the visible light region at wavelengths > 400 nm. The photocatalytic activity of the samples was evaluated by decoloration of Methyl Orange in aqueous solution under visible light irradiation in comparison to the iodine-doped TiO2 (I-TiO2). The I-TNSs showed higher photocatalytic efficiency compared with I-TiO2 after irradiation for 180 min even though the latter had a much greater surface area (115 m2/g). It was concluded that the surface area was not the predominant factor determining photocatalytic activity, and that the good crystallization and bimodal porous nanosphere structure were favourable for photocatalysis.

Facile treatment tuning the morphology of Pb with state-of-the-art selectivity in CO2 electroreduction to formate.

This study presents a facile treatment to modify the commercial irregular shaped polycrystalline Pb into well-defined octahedral Pb with unique Pb(111) facets. Efficient, selective, and stable electrochemical reduction of CO2 toward formate has been achieved on the treated Pb electrode. The faradaic efficiency of formate production from the CO2RR is 98.03%, which is the highest reported to date. The results from the combination of theoretical calculations and experimental tests demonstrate that the enhanced catalytic performance on the treated Pb electrode stems from the electrode morphology characterized by a unique Pb(111) surface with lower Gibbs free energies (ΔG) for the formation of intermediate OCHO*.

In situ chloride-mediated synthesis of TiO2 thin film photoanode with enhanced photoelectrochemical activity for carbamazepine oxidation coupled with simultaneous cathodic H2 production and CO2 conversion to fuels.

This study investigated the simultaneous photoelectrochemical (PEC) degradation of carbamazepine (CBZ), reduction of CO2 and production of H2 using a TiO2 thin film as photoanode and Ag plate as cathode. The photoanode was fabricated using sequential hydrothermal and calcination processes. The use of chloride during the hydrothermal process enhanced formation of oxygen vacancies and defects on the TiO2 surface. Calcination not only further strengthened those features but also enhanced the crystallinity and anatase/rutile ratio, endowing the TiO2 photoanode with superior PEC capacity. Characterization of physicochemical and PEC properties revealed that photogenerated electrons-holes were rapidly generated and efficiently separated on the TiO2 surface during the PEC process. Hydroxyl radicals were the main active species responsible for anodic oxidation of carbamazepine, while hydrogen radicals and carbon dioxide radical anions mediated CO2 reduction and H2 production in the cathodic process. This work confirms the suitability of the prepared TiO2 photoanode for PEC degradation of organic pollutants coupled with CO2 reduction and H2 production.

In situ formation of nitrogen-doped carbon-wrapped Co3O4 enabling highly efficient and stable catalytic reduction of p-nitrophenol.

This study presents a novel nitrogen-doped carbon-wrapped Co3O4 prepared by a facile impregnation-carbonization process using low-cost raw materials. The optimized catalyst exhibits the highest activity reported to date for Co-based catalysts used in the reduction of p-nitrophenol to p-aminophenol with NaBH4 and remains highly stable over seven continuous runs.

Enhanced electrocatalytic hydrodechlorination of 2,4-dichlorophenoxyacetic acid by a Pd-Co3O4/Ni foam electrode.

A new Pd-Co3O4/Ni foam electrode was synthesized by a facile two-step method comprising co-electrodeposition and calcination. Compared with Ni foam-supported Pd electrodes obtained by electrodeposition or chemical deposition, the new Pd-Co3O4/Ni foam electrode exhibited greatly enhanced catalytic hydrodechlorination activity. The introduction of Co3O4 reduced the amount of Pd required. For the same degree of dechlorination of 2,4-D, only 25% of the Pd was required in the Pd-Co3O4/Ni foam electrode compared with the Ni foam electrode prepared by chemical deposition. Various characterizations indicated that Co3O4 on the surface of the Ni foam enhanced catalytic performance through accelerated generation of atomic H*. In addition, the good distribution of macropores, providing a larger specific surface area and lower electron transfer impedance, enabled more adsorption of atomic .

A review of sources, environmental occurrences and human exposure risks of hexachlorobutadiene and its association with some other chlorinated organics.

Research on hexachlorobutadiene (HCBD) has increased since its listing in the Stockholm Convention on Persistent Organic Pollutants in 2011. However, thorough reports on recent data regarding this topic are lacking. Moreover, potential associations between HCBD and some chlorinated organics have usually been ignored in previous research. In this review, possible formation pathways and sources, current environmental occurrences and human exposure risks of HCBD are discussed, as well as the association with several organochlorine compounds. The results reveal that unintentional production and emission from industrial activities and waste treatments are the main sources of HCBD. Similar precursors are found for HCBD and chlorobenzenes, indicating the presence of common sources. Although recent data indicates that levels of HCBD in the environment are generally low, risks from human exposure to HCBD, together with other pollutants, may be high. More attention in the future needs to be paid to the mixed contamination of HCBD and other pollutants from common sources.

Effect of operational parameters on the decolorization of C.I. Reactive Blue 19 in aqueous solution by ozone-enhanced electrocoagulation.

The aim of this paper was to investigate the efficiency of the ozone-enhanced electrocoagulation (EC) process in the decolorization of C.I. Reactive Blue 19 in water using iron electrodes. We determined the effects of various operating parameters such as initial pH, initial dye concentration, current density, salt concentration, temperature, ozone flow rate, and distance between electrodes on decolorization efficiency in a laboratory-scale reactor. Increasing the initial dye concentration decreased the decolorization efficiency, whereas increasing the distance between electrodes increased it. The other operating factors had both positive and negative effects. With an initial pH of 10.0, an initial dye concentration of 100mg/L, current density of 10mA/cm2, salt concentration of 3000mg/L, temperature of 30 degrees C, ozone flow rate of 20mL/min, and distance between electrodes of 3cm, over 96% of the color was removed after 10min. As a consequence, removal of total organic carbon (TOC) was over 80%.

Photocatalytic degradation of C.I. Direct Red 23 in aqueous solutions under UV irradiation using SrTiO3/CeO2 composite as the catalyst.

The photocatalytic degradation of C.I. Direct Red 23 (4BS) in aqueous solutions under UV irradiation was investigated with SrTiO3/CeO2 composite as the catalyst. The SrTiO3/CeO2 powders had more photocatalytic activity for decolorization of 4BS than that of pure SrTiO3 powder under UV irradiation. The effects of catalytic dose, pH value, initial concentration of dye, irradiation intensity as well as scavenger KI were ascertained, and the optimum conditions for maximum degradation were determined. Under the irradiation of a 250 W mercury lamp, the best catalytic dose was 1.5 g/L and the best pH was 12.0. Light intensity exhibited a significant positive effect on the efficiency of decolorization, whereas the initial dye concentration showed a significant negative effect. Under the conditions of a catalytic dose of 1.5 g/L, pH of 12.0, initial dye concentration of 100mg/L, light intensity of 250 W, and air flow rate of 0.15 m3/h, complete decolorization, as determined by UV-visible analysis, was achieved in 60 min, corresponding to a reduction in chemical oxygen demand (COD) of 69% after a 240 min reaction. A tentative degradation pathway based on the sensitization mechanism of photocatalysis is proposed.

Synergistically enhancing Fenton-like degradation of organics by in situ transformation from Fe3O4 microspheres to mesoporous Fe, N-dual doped carbon.

Nanocarbon materials are emerging as alternative activators of peroxymonosulfate (PMS) for organics decomposition. However, the relatively low activity and complex syntheses hindered their practical application and innovation with respect to rational design of carbocatalysts is highly desired. Herein, an in situ replication and transformation strategy was employed to facilely convert porous Fe3O4 microspheres into novel Fe/N codoped large-pore mesoporous carbon spheres (M­Fe/NC) as Fenton-like catalysts for PMS activation. Benefiting from the abundance of active sites induced by dual heteroatom doping, the enhanced active site exposure due to the unique mesoporous structure, and the high stability of carbon component, the derived M­Fe/NC was superior to the pristine Fe3O4 for PMS activation to degrade various organics and was efficient over a wide pH range (2-9). Compared with the proposed mechanisms of previous reports, both radical (surface-bound SO4- and OH) and nonradical (1O2 and direct oxidation) pathways are involved in the M­Fe/NC/PMS system. Furthermore, experimental observations in combination with DFT calculations reveal that graphitic N and FeN4 sites serve as dual reaction centers in the catalysis. This research opened an avenue for development of novel multi-doped carbocatalysts used to activate PMS for sustainable remediation.