In this work, we report on the synthesis and characterization of nanoporous bimetallic metal-organic frameworks (FeCo-BDC). Effects of synthesis time and temperature on the structures, morphology, and catalytic performance of FeCo-BDC were investigated. Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) were used to reveal the morphological and textural characteristics. The crystal structure and chemical composition of FeCo-BDC were determined by means of X-ray powder diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Photoelectron Spectroscopy (XPS), and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) measurements. Interestingly, FeCo-BDC grew into the same crystal structure with different morphology in the temperature of 110–150 °C with 12–48 h. The heterogeneous catalytic activity of FeCo-BDC was tested to activate peroxydisulfate (PDS) and peroxymonosulfate (PMS) for removal of methylene blue (MB). The results found that FeCo-BDC synthesized at 150 °C with 24 h exhibited the best catalytic performance for PMS and obtained 100% of MB removal within 15 min. The abundant unsaturated metal active sites of Fe(II) and Co(II) in the skeleton of FeCo-BDC made a great contribution to the generation of sulfate (▪) and hydroxyl radicals (OH), which resulted in the excellent performance for MB degradation.

The cobalt ferrite-reduced oxidized graphene (CoFe2O4/rGO) catalyst was synthesized by hydrothermal method and characterized by Powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning electron microscope (SEM), Brunauere Emmette Teller (BET) and Hysteresis loop. For developing a new method of removing elemental mercury (Hg0) from flue gas, the effects of catalyst dosage, PMS concentration, solution pH and reaction temperature on the removal efficiency were investigated experimentally by using peroxymonosulfate (PMS) catalyzed by CoFe2O4/rGO at a self-made bubbling reactor. The average removal efficiency of Hg0 in a 30-min period reached 95.56%, when CoFe2O4/rGO dosage was 0.288 g/L, PMS concentration was 3.5 mmol/L, solution pH was 5.5 and reaction temperature was 55 °C. Meanwhile, based on the free radical quenching experiments, in which, ethyl alcohol and tert butyl alcohol were used as quenchers to prove indirectly the presence of •OH and SO4•−, the characterizations of catalysts and reaction products, and the existing results from other scholars. The reaction mechanism was proposed.

CuFeO₂/CeO₂ as a novel catalyst was synthesized and its catalytic performance was evaluated for electro-Fenton degradation of acid orange 7 (AO7). It was demonstrated from the characterization results that the rhombohedral structure of CuFeO₂ and face-centered cubic fluorite structure of CeO₂ remained stable after nanocomposite construction. The impact of such operating parameters as pH, current intensity and, catalyst amount was investigated and the optimum conditions (100 mgL⁻¹ AO7, pH 3, 150 mgL⁻¹ CuFeO₂/CeO₂, I: 150 mA) determination led to 99.3% AO7 removal and 79.1% COD removal in 60 min. The introduction of CeO₂ as non-inert support had a significant impact on H₂O₂ electro-generation as an important step in AO7 removal. CuFeO₂/CeO₂ presented negligible metal leaching (iron 4.13%, copper 2.4%, and cerium 0.33%) which could be due to the strong interaction between active species and support. The nanocomposite performed efficiently in salty systems and two samples of real wastewaters due to Brønsted acidity character of ceria, which makes it a potential choice in industrial applications. The good performance of nanocomposite could be the result of the synergistic effect between Fe, Cu, and Ce. Regarding scavenging measurements results, the electro-Fenton process followed the Haber-Weiss mechanism. The by-products detection was performed using GC-MS analysis to propose an acceptable pathway for EF degradation of AO7. The BMG kinetics model (1/b = 0.969 (min) and 1/m = 0.269 (min⁻¹)) was matched with the experimental data and described the kinetics of reaction very well. The catalytic activity of CuFeO₂/CeO₂ almost remained after six cycles. Based on the obtained results, CuFeO₂/CeO₂ using the benefit of the synergistic effect of Ce³⁺ with Fe²⁺ and Cu⁺can be introduced as a promising novel catalyst for the electro-Fenton reaction in wastewater treatment.

High-efficiency nanophotocatalysts with large specific surface areas have a broad range of application prospects in the catalytic oxidation treatment of organic pollutants in wastewater. A chemical method was used to synthesize a TiO₂ nanophotocatalyst with a mesoporous structure upon which a rare earth metal (Nd) was deposited, namely Nd-TiO₂-SBA-15 (NTS). The prepared NTS was characterized using X-ray diffractometry, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectrometry. The photocatalytic mechanism was explored using scavenger experiments with photoinduced carriers combined with total organic carbon and UV–Vis measurements. At the same time, the kinetic properties of the NTS photocatalytic degradation of methyl orange (MO) were evaluated. The results showed that the deposition of TiO₂ nanoparticles on the surface of the SBA-15 molecular sieve did not change the mesoporous structure, and Nd was uniformly distributed on the surface of the nanophotocatalyst. The photogenerated holes of the NTS played an important role in the photocatalysis process. In addition, the synthesized NTS had good adaptability in the range of pH 2–10. At pH 4, the reaction rate constant (k) of the MO photocatalytic degradation by NTS was 0.011825 mg·(L·min)⁻¹, and the adsorption equilibrium constant (K) was 0.051359 L mg⁻¹. In addition, the photocatalytic degradation rate of MO by NTS remained above 70%, even when the NTS was recycled four times. The NTS showed a good performance after recycling. This work provides a good foundation for the large-scale application of NTS.

Herein, we demonstrate a nanocomposite material Eu/ZnO/pPy for enhanced performance in photoelectrocatalytic degradation of chemical warfare agent sulphur mustard (SM) at ambient conditions which is growing concern of the Scientific Community amidst the current climate of terrorism. Eu/ZnO/pPy was electrochemically prepared on Au electrode at ambient conditions and was used for electrocatalytic reductive elimination of chloride from SM and results indicated one electron involvement process for the cleavage of the carbon-chloride bond. Surface morphology of Eu/pPy, ZnO/pPy and Eu/ZnO/pPy composites were characterized by SEM and confirmed the formation of the nanoparticles and nanorods on the modified electrode which leads to provide more surface area for the reductive elimination reaction. The elemental composition, functional groups and phase of materials on the modified electrode were deduced using EDX, Raman spectroscopy and XRD, respectively. Eu/ZnO/pPy/Au electrode was utilized for the photoelectrocatalytic degradation of SM as it exhibit excellent electrocatalytic activity and degradation products were analyzed by GC-MS. In the reductive elimination of SM, the following parameters were deduced (i) heterogeneous rate constant (0.127 s⁻¹), (ii) transfer coefficient (0.32) and (iii) number of electron involved (1.0). The enhanced photoelectrocatalytic capability of this nanocomposite could serve as a novel and promising catalyst in defence and environmental applications.

Batch experiments, in conjunction with chromatographic and spectroscopic measurements, were performed to comparatively investigate the degradation of various chlorophenolic (CP) compounds (e.g., 2-CP, 4-CP, 2,3-DCP, 2,4-DCP, 2,4,6-TCP, 2,3,4,6-TeCP) by a modified Fenton process using pyrite as the catalyst. The batch results show that the CP removal by pyrite-Fenton process was highly dependent on chemical conditions (e.g., pH, CP and pyrite concentration), CP type, number and location of chlorine atoms on the aromatic ring. With the exception of 2,3,4,6-TeCP and 2,3-DCP, the CP removal decreased with increasing the number of chlorine constituents. While the main mechanism responsible for monochlorophenol removal (e.g., 2-CP and 4-CP) was the hydroxyl radical attack on aromatic rings, the CP removal for multichlorophenolic compounds (e.g., 2,3,4,6-TeCP) was driven by both: (1) hydroxyl radical attack on aromatic rings by both solution and surface-bound hydroxyl radicals and (2) adsorption onto pyrite surface sites. The adsorption affinity increased with increasing the number of Cl atoms on the aromatic ring due to enhanced hydrophobic effect. The TOC removal was not 100% complete for all CPs investigated due to formation of chemically less degradable chlorinated intermediate organic compounds as well as low molecular weight organic acids such as formic and acetic acid. Spectroscopic measurements with SEM-EDS, zeta potential and XPS provided evidence for the partial oxidation of pyrite surface Fe(II) and disulfide groups under acidic conditions.

Aiming at realizing heavy metal recycling and resource utilization, a carbon-based iron catalyst (Fe@C) was synthesized through a resin carbonization method, and adopted for peroxymonosulfate (PMS) activation to remove bisphenol S (BPS), an emerging aquatic contaminant. This study demonstrated that Fe@C exhibited excellent catalytic potential for BPS degradation with a relatively low activation energy (Ea = 29.90 kJ/mol). Kinetic factors affecting the activation performance were thoroughly investigated. The obtained results indicated that Fe@C composite exhibited the superior uniformity with carbon as the framework and granular iron oxide as the coverage. pH increase could cause the inhibitive effect on BPS degradation, while the increasing catalyst loading (0.05–0.5 g/L) was conducive for the catalytic performance of Fe@C, with an optimal PMS concentration at 1.0 mM. A negative influence on BPS degradation was obtained in the presence of SO42−, HCO3− and lower concentration of Cl− (0–20 mM), compared to the promotion at higher concentration of Cl− (>50 mM). Based on the electron spin resonance (ESR) monitoring and radical scavenging results, it is demonstrated that singlet oxygen, a non-radical species, emerged together with ·SO4− and ·OH for BPS degradation. A three-channel catalytic mechanism was verified through typical characterizations. Furthermore, the degradation pathway of BPS was proposed based on the identified intermediates. This novel carbon-based activator for PMS showed notable potential for the waste resin recycling and water decontamination.A novel Fe-based activator carbonized from a saturated resin exhibits excellent performance for Bisphenol S degradation with activated peroxymonosulfate.

A novel self-assembly method was developed to prepare a γ-Fe₂O₃/graphene oxide (GO) heterogeneous catalyst that showed excellent synergy between photocatalysis and Fenton-like reactions. The γ-Fe₂O₃/GO catalyst prepared on the iron plates demonstrated efficient and reproducible catalytic activities for water treatment. It takes only 80 min to degrade 50 mg L⁻¹ methylene (MB) completely, which is the main non-biodegradable dye in wastewater from the textile industry. The heterogeneous catalyst is stable over a wide range of pH (from 2.0 to 10.2) for MB degradation, and can be easily extracted from solution and repeatedly used with little loss of catalytic activity. The high activity and stability of the catalyst system can be attributed to charge separation between γ-Fe₂O₃ and GO, which could accelerate Fenton-like process and photocatalysis. In addition, the dominant reactive oxidant species responsible for the MB degradation, including the hydroxyl radicals (•OH) and holes (h⁺), were trapped on the surface of the γ-Fe₂O₃/GO composite, as proved by a free-radical quenching experiment. The γ-Fe₂O₃/GO heterogeneous catalyst could potentially provide a solution for removal of non-biodegradable dyes from wastewater in the textile industry.

Particulate matter (PM) oxidative potential (OP) is an emerging health metric, but studies examining the OP of indoor PM are rare. This paper focuses on the relationships between respiratory exposure to OP and PM water-soluble composition in indoor environments. Size-resolved PM samples were collected between November 2015 and June 2016 from an office, home (including bedroom, living room, and storeroom), and laboratory using a MOUDI sampler. Particles from each source were segregated into eleven size bins, and the water-soluble metal content and dithiothreitol (DTT) loss rate were measured in each PM extract. The water-soluble OP (OPwₛ) of indoor PM was highest in the office and lowest in the home, varying by factors of up to 1.2; these variations were attributed to differences in occupation density, occupant activity, and ventilation. In addition, the particulate Cu, Mn, and Fe concentrations were closely correlated with OPwₛ in indoor particles; the transition metals may have acted as catalysts during oxidation processes, inducing ·OH formation through the concomitant consumption of DTT. The OPwₛ particle size distributions featured single modes with peaks between 0.18 and 3.2 μm across all indoor sites, reflecting the dominant contribution of PM₃.₂ to total PM levels and the enhanced oxidative activity of the PM₃.₂ compared to PM>₃.₂. Lung-deposition model calculations indicated that PM₃.₂ dominated the pulmonary deposition of the OPwₛ (>75%) due to both the high levels of metals content and the high deposition efficiency in the alveolar region. Therefore, because OPwₛ has been directly linked to various health effects, special attention should be given to PM₃.₂.

During their lifecycle, many engineered nanoparticles (ENPs) undergo significant transformations that may modify their toxicity, behaviour, and fate in the environment. Therefore, understanding the possible environmentally relevant transformations that ENPs may undergo as a result of their surroundings is becoming increasingly important. This work considers industrially produced ceria (CeO2) and focuses on a particle library consisting of seven zirconium-doped variants (Ce1-xZrxO2) where the Zr doping range is x = 0–1. The study assesses their potential transformation in the presence of environmentally relevant concentrations of phosphate. These ENPs have an important role in the operation of automotive catalysts and therefore may end up in the environment where transformations can take place. Samples were exposed to pH adjusted (c. 5.5) solutions made up of either 1 mM or 5 mM each of KH2PO4, citric acid and ascorbic acid and the transformed particles were characterised by means of DLS – size and zeta potential, UV/VIS, TEM, FT-IR, EDX and XRD. Exposure to the phosphate solutions resulted in chemical and physical changes in all ceria-containing samples to cerium phosphate (with the monazite structure). The transformations were dependent on time, ceria concentration in the particles (Ce:Zr ratio) and phosphate to ceria ratio. The presence of Zr within the doped samples did not inhibit these transformations, yet the pure end member ZrO2 ENPs showed no conversion to phosphate. The quite dramatic changes in size, structure and composition observed raise important questions regarding the relevant form of the materials to investigate in ecotoxicity tests, and for regulations based on one or more dimensions in the nanoscale.