The present work reports microwave-assisted synthesis of SnO₂ nanoparticles via green route using Psidium Guajava extract. For the enhancement of catalytic activity, nanohybrids of SnO₂ were formulated using different ratios of polyaniline (PANI) via ultrasound-assisted chemical polymerization. Formation of nanohybrids was confirmed via IR and XPS studies. The UV–vis DRS spectra of PANI/SnO₂ revealed significant reduction in the optical band gap upon nanohybrid formation. Microwave-assisted catalytic efficiency of pure SnO₂, PANI, PANI/SnO₂ nanohybrids was investigated using DDT as a model persistent organic pollutant. The degradation efficiency of PANI/SnO₂ was found to increase with the increase in the loading of PANI. Around 87% of DDT degradation was achieved within a very short period of 12 min under microwave irradiation using PANI/SnO₂-50/50 as catalyst. The effect of DDT concentration was explored and the degradation efficiency of PANI/SnO₂-50/50 catalyst was noticed to be as high as 82% in presence of 100 mg/L of DDT. The effect of microwave power on the degradation efficiency revealed 79% degradation using the same nanohybrid when exposed to microwave irradiation for 5 min under 1110 W microwave power. Scavenging studies confirmed the generation of OH, O₂⁻ radicals. The fragments with m/z values as low as 86 and 70 were confirmed by LCMS analysis. Recyclability tests showed that PANI/SnO₂-50/50 nanohybrid exhibited 81% degradation of DDT (500 mg/L) even after the third cycle, which reflected high catalytic efficiency as well as remarkable stability of the catalyst. This green nanohybrid could therefore be effectively utilized for the rapid degradation of persistent organic pollutants.

Herein, a new peroxymonosulfate (PMS) activation system was established using a biochar (BC)-supported Co₃O₄ composite (Co₃O₄-BC) as a catalyst to enhance chloramphenicols degradation. The effects of the amount of Co₃O₄ load on the BC, Co₃O₄-BC amount, PMS dose and solution pH on the degradation of chloramphenicol (CAP) were investigated. The results showed that the BC support could well disperse Co₃O₄ particles. The degradation of CAP (30 mg/L) was enhanced in the Co₃O₄-BC/PMS system with the apparent degradation rate constant increased to 5.1, 19.4 and 7.2 times of that in the Co₃O₄/PMS, BC/PMS and PMS-alone control systems, respectively. Nearly complete removal of CAP was achieved in the Co₃O₄-BC/PMS system under the optimum conditions of 10 wt% Co₃O₄ loading on BC, 0.2 g/L Co₃O₄-BC, 10 mM PMS and pH 7 within 10 min. The Co₃O₄/BC composites had a synergistic effect on the catalytic activity possibly because the conducting BC promoted electron transfer between the Co species and HSO₅⁻ and thus accelerated the Co³⁺/Co²⁺redox cycle. Additionally, over 85.0 ± 1.5% of CAP was still removed in the 10th run. Although both SO₄⁻ and OH were identified as the main active species, SO₄⁻ played a dominant role in CAP degradation. In addition, two other chloramphenicols, i.e., florfenicol (FF) and thiamphenicol (TAP), were also effectively degraded with percentages of 86.4 ± 1.3% and 71.8 ± 1.0%, respectively. This study provides a promising catalyst Co₃O₄-BC to activate PMS for efficient and persistent antibiotics degradation.

Achieving large pore size, high catalytic performance with stable structure is critical for metal–organic frameworks (MOFs) to have more hopeful prospects in catalytic applications. Herein, we had reported a method to synthesize highly reactive yet stable defective iron-based Metal organic frameworks by using different monocarboxylic acids with varying lengths as a modulator. The physical−chemical characterization illustrating that modulators could improve the crystallinity, enlarge pore size and enhance catalytic performance and octanoic acid (OA) was screened to be the suitable choice. The catalytic performance of catalysts was detected through persulfate (PS) activation for degrading Tetrabromobisphenol A (TBBPA). The study demonstrated that the highest degradation efficiency for 0.018 mmol L−1 TBBPA was that 97.79% in the conditions of the 1.0 g L−1 Fe(BDC)(DMF,F)-OA-30 dosage and TBBPA:PS = 200:1. In addition, there was observed that no obvious change of the crystal structure, little the leachable iron concentration in the solutions and no significant loss of catalytic activities of Fe(BDC)(DMF,F)-OA-30 after 5th cycles. The iron valence state of Fe(BDC)(DMF,F)-OA-30 before and after degradation and electrochemical properties reveal that the partial substitution of organic ligands by octanoic acid, when removing OA and forming defects by heat and vacuum treatment to generate coordinatively unsaturated metal sites and accelerate the original transmission of electronic, leading to enhance the activity of persulfate activation for efficient removal TBBPA.

Emissions of major reactive nitrogen compounds, including nitric oxide (NO), nitrogen dioxide (NO₂) and ammonia (NH₃), from heavy-duty diesel vehicles (HDDVs) place substantial pressure on air quality for many large cities in China. To control nitrogen oxide (NOX) emissions from HDDVs, selective catalytic reduction (SCR) systems have been widely used since the China IV standards. To investigate the impacts of aftertreatment technologies and driving conditions on real-world emissions of reactive nitrogen compounds, a portable emissions measurement system was employed to test eighteen heavy-duty diesel trucks in China. The results showed that the China IV and China V HDDVs with appropriate SCR functionality could reduce NOX emissions by 36% and 53%, respectively, compared to the China III results, although their real-world emissions were still higher than the corresponding emission limits for regulatory engine tests. For these HDDVs, five samples were tested with NH₃ emissions, ranging from 1.67 ppm to 51.49 ppm. The NH₃ emission rates tended to significantly increase under high-speed driving conditions. The results indicate that the current SCR technology may have certain risks in exceeding the future China VI NH₃ limit. However, five China IV/V HDDVs were found to have SCR temperature sensors that were intentionally tampered with, resulting in comparable or even higher NOX emissions and zero NH₃ emissions. Increased NO₂ emissions due to the adoption of diesel oxidation catalysts and diesel particulate filters were also found from our experiments. This study highlights the importance of enhancing in-use compliance requirements and eliminating aftertreatment tampering for China IV and China V HDDVs.

The N, S, and Fe-tridoped carbon catalysts (NSFe-Cs), Fe/ACNS1 and Fe/ACNS2, were synthesized by wet impregnation with different concentration of ammonium ferrous sulfate solution. The prepared catalysts have a similar textural structure. The N species, S species, Feᴵᴵ and Feᴵᴵᴵ were simultaneously introduced onto the surface of catalysts. Comparison with the only Fe doped catalyst, NSFe-Cs showed greater stability and higher phenol removal in catalytic wet peroxide oxidation at different reaction condition. The main intermediates including p-hydroxybenzoic acid, formic acid, and maleic acid were determined in the treated wastewater. The high catalytic activity for NSFe-C was related to the ability of H₂O₂ decomposition. NSFe-Cs have more amount of Feᴵᴵ partially due to the formation of FeS₂, which promoted the decomposition of H₂O₂ on Fe/ACNS1 and Fe/ACNS2 surface. The generation of ·OH and ·HO₂/·O₂⁻ radicals in the bulk solution was crucial to phenol degradation, and the decomposition of H₂O₂ complied with the pseudo-first-order kinetics. The highly linear relationship between decomposition kinetic constant for H₂O₂ and the amount of surface groups suggested, including Feᴵᴵ species, pyridinic N/Fe-bonded N, pyrrolic N as well as graphitic N were responsible to the high activity of NSFe-Cs.

Platinum-Group Elements (PGEs, i.e. platinum; Pt, palladium; Pd and rhodium; Rh) are extensively employed in the production of automotive catalytic converters to catalyze and control harmful emissions from exhaust fumes. But catalytic converters wear out over time and the emission of PGEs along with the exhaust fumes are nowadays known to be the main reason of the presence of PGEs in urban environments. PGEs contents were studied on three gasoline 3-way catalytic convertors with low, medium and high kilometers. PGEs emission factors via exhaust gases from Euro 3, 4, 5 and 6 gasoline and diesel vehicles, were monitored using catalytic converters. Results show variable content for PGEs for the three converters, in the ranges of 6–511, 0.5–2507 and 0.1–312 mg kg⁻¹ for Pt, Pd and Rh respectively. PGEs contents in different catalyst supports show the replacement of Pt by Pd in more recent converters. Analysis of the exhaust gas shows that catalytic converters expel up to 36.5 ± 3.8 ng km⁻¹ of Pt, 8.9 ± 1.1 ng km⁻¹ of Pd and 14.1 ± 1.5 ng km⁻¹ of Rh. Higher emissions of PGEs have been observed by gasoline Euro 3 vehicle, possibly due to the older technology of motorization and of the catalytic converter in this vehicle. Euro 3 and 4 diesel vehicles seem to emit more PGEs during urban cycles. Emission of PGEs has been also observed during the cold start of the majority of vehicles which seems to be the result of incomplete combustion during the rise of temperature in the engine. Higher PGEs emissions were also observed during motorway cycles in newer (Euro 4 and 5) petrol and diesel vehicles, conceivably due to the greater combustion as the engine speeds up during this cycle.

Advanced oxidation processes based on carbon catalysis is a promising strategy possessing great potential for environmental pollution degradation. Herein, nitrogen-doped biochar nanosheets (NCS-x) were synthesized using a nitrogen-rich biomass (Candida utilis) as sole precursor. The involvement of environmental-friendly molten salt (NaCl and KCl) in pyrolysis process not only facilitated the exfoliation of biochar, but also favored the retention of N element in biochar. When applying as catalyst for peroxymonosulfate activation, the as-obtained NCS-6 exhibited outstanding performance in catalytic degradation of bisphenol A (BPA). A 100% removal efficiency was observed in 6 min with fast reaction kinetic (k = 1.36 min⁻¹). Based on quenching test and in-situ electron paramagnetic resonance analysis, both radical pathway and non-radical pathway were suggested to be involved in BPA degradation, while singlet oxygen was identified as the dominant reactive oxygen species. Furthermore, the ecotoxicity evaluation using Chlorella vulgaris as ecological indicator indicated that BPA solution after degradation was less toxic than the original solution. It is expected that this green and facile strategy holds great promise for value-added conversion of nitrogen-rich biomass to highly efficient biochar nanosheets for environment remediation.

Estrogens, which are extensive in the eco-environments, are a category of high-toxic emerging contaminants that induce metabolic disorders and even carcinogenic risks in wildlife and humans. Here we investigate whether fungus-secreted laccase can be used as a green catalyst to eliminate a representative estrogen, 17β-estradiol (E2). A white-rot fungus Trametes hirsuta La-7 with high laccase-productivity, was isolated from pig manure-contaminated soil. Extracellular laccase activity expressed by strain La-7 was 65.4 U·mL⁻¹ for a 3 d inoculation under the optimal fermentation parameters. The concentrated-crude laccase from Trametes hirsuta La-7 (CC-ThLac) was capable of effectively metabolizing E2 at pH 4–6, and the apparent pseudo first-order reaction rate constant and half-life values were respectively 0.027–0.055 min⁻¹ and 25.86–12.67 min (R² > 0.98). The mass measurement of high-resolution mass spectrometry in combination with ¹³C-isotope labeling identified that the main by-products of E2 metabolism were dimers, trimers, and tetramers, which are consistent with radical-driven C–C and/or C–O–C covalent coupling pathway, involving the initial enzymatic production of phenoxy radical intermediates and then the successive oxidative-oligomerization of radical intermediates. The formation of oligomers dramatically reduced the estrogenic activity of E2. Additionally, CC-ThLac also exhibited high-efficiency metabolism capability toward E2 in the natural water and pig manure, with more than 94.4% and 91.0% of E2 having been metabolized, respectively. These findings provide a broad prospect for the clean biotechnological applications of Trametes hirsuta La-7 in estrogen-contaminated ecosystems.

This work reports the use of an iron ore tailings from waste dam as a catalyst and support for carbon nanotubes synthesis and their application in the adsorption of the 17α-ethinylestradiol hormone. The synthesis was carried out by Chemical Vapor Deposition (CVD) in a Fluidized Bed system using: ethylene at temperatures of 500, 600 and 700 °C, and acetonitrile at 500, 600, 700, 800 and 900 °C. The transmission electron microscopy (TEM) results showed that the two higher temperatures in each case favored the formation of nanostructures like carbon nanotubes (CNTs), with good yields. The ethylene source generated classic tubular structures of multiple walls. On the other hand, acetonitrile provided the formation of tubes with less organization, known as bamboo like. This morphology was caused by the insertion of nitrogen into the graphite structure (doping), which originates from the carbon source. The adsorptive capacity of the materials for 17α-Ethinylestradiol removal ranging from 9.2 mg g⁻¹ to 22.3 mg g⁻¹. The kinetic and adsorption isotherm studies were also performed for the systems. As for kinetics, all of them presented pseudo-second order behavior. In relation to the type of isotherm, the systems showed Freundlich behavior, that is, the adsorption occurs in multiple layers. Finally, it was concluded that the use of an iron ore tail as a catalyst in the production of CNTs by CVD is feasible. The materials synthesized still had good adsorptive capacity for an emerging contaminant, thus this study allowed the investigation of two environmental problems.

Imidacloprid (IMI) is one of the most extensively used chlorinated organic pesticides and its widespread occurrence makes it attract increased public concern and scientific interest. Peroxymonosulfate (PMS) activation has been widely studied for the elimination of organic pollutants from water. But few studies are focused on their heterogeneous catalytic performance towards imidacloprid especially with the presence of silver ferrite nanoparticles (nAgFeO₂)-based catalysts. Herein, the catalyst, nAgFeO₂, was prepared via a co-precipitation method, and further applied to activate PMS for the removal of imidacloprid (IMI). Our results demonstrated that the prepared nAgFeO₂ significantly promoted the activation of PMS for removing IMI, and the removal of IMI followed a pseudo first-order kinetics model with the corresponding nAgFeO₂ dosage. Electron paramagnetic resonance (EPR) and quenching tests revealed the singlet oxygen (¹O₂)-mediated nonradical pathway, instead of hydroxyl radical (•OH) or sulfate radical (SO4•−), played the dominant role in the degradation of IMI. Eight products were identified and the degradation pathways of IMI were proposed. It is postulated that the primary site at the C-1 position of IMI was more easily attacked by the •OH yielding (6-chloropyridin-3-yl) methanol). While the site at the amidine nitrogen (2) of IMI was more likely attacked by the ¹O₂, and then reacted with •OH to produce 5-hydroxy imidacloprid. Overall, this study provides insights into the mechanisms of nonradical oxidation processes based on PMS for the elimination of pesticides from water, broadening the application of silver ferrite nanoparticles in wastewater treatment.