Electron delocalization triggers nonradical Fenton-like catalysis over spinel oxides.

Nonradical Fenton-like catalysis offers opportunities to overcome the low efficiency and secondary pollution limitations of existing advanced oxidation decontamination technologies, but realizing this on transition metal spinel oxide catalysts remains challenging due to insufficient understanding of their catalytic mechanisms. Here, we explore the origins of catalytic selectivity of Fe-Mn spinel oxide and identify electron delocalization of the surface metal active site as the key driver of its nonradical catalysis. Through fine-tuning the crystal geometry to trigger Fe-Mn superexchange interaction at the spinel octahedra, ZnFeMnO4 with high-degree electron delocalization of the Mn-O unit was created to enable near 100% nonradical activation of peroxymonosulfate (PMS) at unprecedented utilization efficiency. The resulting surface-bound PMS* complex can efficiently oxidize electron-rich pollutants with extraordinary degradation activity, selectivity, and good environmental robustness to favor water decontamination applications. Our work provides a molecule-level understanding of the catalytic selectivity and bimetallic interactions of Fe-Mn spinel oxides, which may guide the design of low-cost spinel oxides for more selective and efficient decontamination applications.

Peroxymonosulfate activation by walnut shell activated carbon supported nano zero-valent iron for the degradation of tetracycline: Performance, degradation pathway and mechanism.

In this study, activated carbon (WS-AC) was prepared from walnut shell. Nano-zero-valent iron (nZVI) was loaded on walnut shell activated carbon by liquid phase reduction method and used as catalyst (WS-AC/nZVI) to activate peroxymonosulfate (PMS) to efficiently degrade tetracycline (TC) in solution. The composite material with a mass ratio of WS-AC to nZVI of 1:1 has the highest catalytic performance for activating PMS to degrade TC. The results showed that under the conditions of TC concentration of 100 ppm, PMS dosage of 0.2 mM and WS-AC/nZVI dosage of 0.1 g/L, the removal efficiency of TC could reach 81%. Based on quenching experiments and electron spin resonance (EPR), it was verified that •OH, SO4•- and 1O2 bound on the catalyst surface were the main reactive oxygen species during the reaction. The intermediate products of TC were identified by liquid chromatography-mass spectrometry (HPLC-MS) and DFT calculation, and the possible degradation pathway of TC was proposed. The catalyst still maintained high removal efficiency of TC after four cycles of experiments, and the minimal iron loss on the surface of the catalyst indicated that it had good stability. The efficient and stable WS-AC/nZVI activated PMS showed great potential in the degradation of antibiotics.

Peroxymonosulfate-Based Electrochemical Advanced Oxidation: Complication by Oxygen Reduction Reaction.

Peroxymonosulfate (PMS)-based electrochemical advanced oxidation processes (EAOPs) have received widespread attention in recent years, but the precise nature of PMS activation and its impact on the overall process performance remain poorly understood. This study presents the first demonstration of the critical role played by the oxygen reduction reaction in the effective utilization of PMS and the subsequent enhancement of overall pollutant remediation. We observed the concurrent generation of H2O2 via oxygen reduction during the cathodic PMS activation by a model nitrogen-doped carbon nanotube catalyst. A complex interplay between H2O2 generation and PMS activation, as well as a locally increased pH near the electrode due to the oxygen reduction reaction, resulted in a SO4•-/•OH-mixed oxidation environment that facilitated pollutant degradation. The findings of this study highlight a unique dependency between PMS-driven and H2O2-driven EAOPs and a new perspective on a previously unexplored route for further enhancing PMS-based treatment processes.

UV absorbance and electron donating capacity as surrogate parameters to indicate the abatement of micropollutants during the oxidation of Fe(II)/PMS and Mn(II)/NTA/PMS.

In this study, the relative residual UV absorbance (UV254) and/or electron donating capacity (EDC) was investigated as a surrogate parameter to evaluate the abatement of micropollutants during the Fe(II)/PMS and Mn(II)/NTA/PMS processes. In the Fe(II)/PMS process, due to the generation of SO4•- and •OH at acidic pH, UV254 and EDC abatement was greater at pH 5. In the Mn(II)/NTA/PMS process, UV254 abatement was greater at pH 7 and 9, while EDC abatement was greater at pH 5 and 7. This was attributed to the fact that MnO2 was formed at alkaline pH to remove UV254 by coagulation, and manganese intermediates (Mn(V)) were formed at acidic pH to remove EDC via electron transfer. Due to the strong oxidation capacity of SO4•-, •OH and Mn(V), the abatement of micropollutants increased with increasing dosages of oxidant in different waters in both processes. In the Fe(II)/PMS and Mn(II)/NTA/PMS processes, except for nitrobenzene (∼23% and 40%, respectively), the removal of other micropollutants was greater than 70% when the oxidant dosages were greater in different waters. The linear relationship between the relative residual UV254, EDC and the removal of micropollutants was established in different waters, showing a one-phase or two-phase linear relationship. The differences of the slopes for one-phase linear correlation in the Fe(II)/PMS process (micropollutant-UV254: 0.36-2.89, micropollutant-EDC: 0.26-1.75) were less than that in the Mn(II)/NTA/PMS process (micropollutant-UV254: 0.40-13.16, micropollutant-EDC: 0.51-8.39). Overall, these results suggest that the relative residual UV254 and EDC could truly reflect the removal of micropollutants during the Fe(II)/PMS and Mn(II)/NTA/PMS processes.

A novel strategy and mechanism for high-quality volatile fatty acids production from primary sludge: Peroxymonosulfate pretreatment combined with alkaline fermentation.

To obtain high-quality VFAs production from primary sludge, a novel strategy that combined peroxymonosulfate (PMS) pretreatment and alkaline fermentation (i.e., PMS & pH9) was proposed in the study. The results showed that PMS & pH9 was efficient in sludge solubilization and hydrolysis, resulting in a maximal VFAs yield of 401.2 mg COD/g VSS, which was 7.3-, 2.1-, and 8.8-fold higher than the sole PMS, sole pH9, and control, respectively. Acetate comprised 87.6% of VFAs in this integration system. Mechanism investigations revealed that sulfate and free radicals produced by PMS play roles in improving VFAs yield under alkaline conditions. Besides, sulfate also aided in C3∼C5 VFAs converting to acetate under alkaline conditions depending on the increase of incomplete-oxidative sulfate-reducing bacteria (iso-SRB) (i.e., Desulfobulbus and Desulfobotulus). Moreover, the relative abundances of acid-forming characteristic genera (i.e., Proteiniborus, Proteinilcasticum, and Acetoanaerobium) were higher in PMS & pH9.

Cuprous-mediated peroxymonosulfate activation for Fenton-like removal of micropollutants: The function of co-catalyst and the accelerated degradation mechanism.

Introducing co-catalysts to enhance the activation of cuprous-mediated peroxymonosulfate (PMS) and induce the continuous generation of highly reactive oxygen species is promising. The function, effectiveness, and acceleration mechanism of co-catalysts in the cuprous-mediated PMS activation process were fully explored in this work, which focused on rhodamine B as the target contaminants. The results demonstrated that molybdenum (Mo) powder was a superb co-catalyst, and that the reaction of cuprous-mediated PMS system was carried out by surface Mo species as opposed to Mo ions in the solution. The Cu (II)/Cu(I) cycle was primarily encouraged by the Mo0, which also caused abundant ·HO and 1O2 and minimal SO4·- and ·O2- to be produced from PMS. The Mo/Cu2+/PMS system exhibited high removal efficiency towards typical pollutants, especially ciprofloxacin, methyl orange, malachite green, and crystal violet, with removal rates up to 93%, 99%, 97%, and 92%, respectively. Additionally, this system showed excellent adaptability to complex water environments. After four cycles, the Mo powder retained its properties and morphology, and the target pollutants could still maintain an 82% degradation efficiency. This study provides a basis for enhancing cuprous-mediated PMS activation for wastewater treatment.

Peroxymonosulfate activation by nitrogen-doped herb residue biochar for the degradation of tetracycline.

Biochar is an environmentally friendly material with potential applications in water purification. In this study, herb residue nitrogen-doped biochar (N-BC) was fabricated and used to activate peroxymonosulfate (PMS). Characterization and density-functional theory (DFT) studies were conducted to explore the influence of nitrogen doping. Radical scavenging activity and electron paramagnetic resonance (EPR) spectroscopy revealed that non-radical singlet oxygen (1O2) is the main reactive oxidative species. Additionally, pyridinic-N was shown to play a pivotal role in the 1O2-dominated pathway. Three possible degradation pathways were proposed based on the identified degradation intermediates. Batch experiments confirmed that N-BC showed excellent catalytic performance and reusability. The best condition for tetracycline (TC) degradation efficiency (>99%) in 60 min was obtained when the dosage of N-BC was 1 g/L and the concentration of PMS was 5 mM. Furthermore, N-BC showed approximately 65.5% degradation efficiency within 4 cycles. Furthermore, the toxicity of degradation intermediates was examined using ECOSAR and T.E.S.T procedures. This study brings forth a feasible strategy to synthesize biochar. Furthermore, the proposed approach will facilitate the use of biochar in water purification.

Controlling methane emissions from Integrated Vertical-Flow Constructed Wetlands by using potassium peroxymonosulfate as oxidant.

It is very important to control methane emissions to reduce global warming. In this study, a new attempt of one oxidant (potassium peroxymonosulfate (PMS)) was made to adjust the oxidation-reduction potential (Eh) by adding different mass of (0 g, 31.25 g, 62.5 g, 125 g, 250 g and 500 g) for the reduction of methane emissions from integrated vertical-flow constructed wetland (IVCW), where the IVCW system has been divided into the root-water system and the stem-leaf system of methane emissions. Results show that the reduced CH4 emission from IVCW was the highest with decreased by 43.5% compared to blank group (PMS = 0), when adding 125 g PMS. Importantly, the reduced CH4 from the root-water system of IVCW was higher than that of the stem-leaf system of IVCW, when adding PMS. It's found that Eh not only has a significant correlation with CH4 flux, but also has a significant relationship between PMS quality, DO, water temperature and sampling time (yEh = -0.44XPMS + 6.82XDO + 0.38t - 264.1, R2 = 0.99). It concludes that PMS, as an oxidant, is a very feasible method for controlling methane emissions from IVCW. It's concluded from this study that it is a feasible engineering method by using PMS as an oxidant for reducing methane emissions from IVCWs when treating artificial domestic sewage. Further research may combine other methods together such as microbiology, physical control and hydrology control for mitigating the CH4 emissions from constructed wetlands for more types of wastewater.

Peroxymonosulfate activation using a composite of copper and nickel oxide coated on SBA-15 for the removal of sulfonamide antibiotics.

The sluggish Ni(II)/Ni(III) redox cycle does not benefit perxymonosulfate (PMS) activation for recalcitrant pollutant degradation. To solve this problem, a heterogeneous catalyst, Cu0.2Ni0.8O/SBA-15 (CNS), was constructed to activate PMS for decomposing two sulfonamide antibiotics, sulfachlorpyridazine (SACP) and sulfapyridine (SAP). SACP and SAP were completely degraded over Cu0.2Ni0.8O/SBA-15/PMS (CNSP) after 90 min. O2.- was the dominant active species involved in the degradation of SACP and SAP. Structural analysis and elemental valence state observations indicated that Cu(Ⅰ) provided electrons through Cu-O-Ni bonds to realize the charge compensation for Ni(Ⅲ) in the CNSP system. Thus, the in situ Cu(I)/Cu(II) promoting the Ni(II)/Ni(III) cycle could accelerate the PMS activation. This work provides new insights into the electron transfer between transition metals and the charge compensation mechanism for PMS activation. The degradation mechanism was proposed based on the XPS results before and after the reaction, a radical quenching test, and an EPR test. Combined with the SACP and SAP degradation intermediates identified by LC-MS, we suggest that the choice of treatment process depends on the occurrence of a steric hindrance effect between the molecular structure of the degradation target and free radicals.

A facial strategy to efficiently improve catalytic performance of CoFe2O4 to peroxymonosulfate.

Cobalt iron spinel (CoFe2O4) has been considered as a good heterogeneous catalysis to peroxymonosulfate (PMS) in the degradation of persistent organic pollutants due to its magnetic properties and good chemical stability. However, its catalytic activity needs to be further improved. Here, a facial strategy, "in-situ substitution", was adopted to modify CoFe2O4 to improve its catalytic performance just by suitably increasing the Co/Fe ratio in synthesis process. Compared with CoFe2O4, the newly synthesized Co1.5Fe1.5O4, could not only significantly improve the degradation efficiency of phenol, from 50.69 to 93.6%, but also exhibited more effective mineralization ability and higher PMS utilization. The activation energy advantage for phenol degradation using Co1.5Fe1.5O4 was only 44.2 kJ/mol, much lower than that with CoFe2O4 (127.3 kJ/mol). A series of related representations of CoFe2O4 and Co1.5Fe1.5O4 were compared to explore the possible reasons for the outstanding catalytic activity of Co1.5Fe1.5O4. Results showed that Co1.5Fe1.5O4 as well represented spinel crystal as CoFe2O4 and the excess cobalt just partially replaced the position of iron without changing the original structure. Co1.5Fe1.5O4 had smaller particle size (8.7 nm), larger specific surface area (126.3 m2/g), which was more favorable for exposure of active sites. Apart from the superior physical properties, more importantly, more reactive centers Co (Ⅱ) and surface hydroxyl compounds generated on Co1.5Fe1.5O4, which might be the major reason. Furthermore, Co1.5Fe1.5O4 behaved good paramagnetism, wide range of pH suitability and strong resistance to salt interference, making it a new prospect in environmental application.

Biogeochemical Alteration of an Aquifer Soil during In Situ Chemical Oxidation by Hydrogen Peroxide and Peroxymonosulfate.

In this study, the effects of in situ chemical oxidation (ISCO) on the biogeochemical properties of an aquifer soil were evaluated. Microcosms packed with an aquifer soil were investigated for 4 months in two phases including oxidant exposure (phase I) and biostimulation involving acetate addition (phase II). The geochemical and microbial alterations from different concentrations (0.2 and 50 mM) of hydrogen peroxide (HP) and peroxymonosulfate (PMS) were assessed. The 50 mM PMS-treated sample exhibited the most significant geochemical changes, characterized by the decrease in pH and the presence of more crystalline phases. Microbial activity decreased for all ISCO-treated microcosms compared to the controls; particularly, the activity was severely inhibited at high PMS concentration exposure. The soil microbial community structures were shifted after the ISCO treatment, with the high PMS causing the most distinct changes. Microbes such as the Azotobacter chroococcum and Gerobacter spp. increased during phase II of the ISCO treatment, indicating these bacterial communities can promote organic degradation despite the oxidants exposure. The HP (low and high concentrations) and low concentration PMS exposure temporarily impacted the microbial activity, with recovery after some duration, whereas the microbial activity was less recovered after the high concentration PMS exposure. These results suggest that the use of HP and low concentration PMS are suitable ISCO strategies for aquifer soil bioattenuation.

Enhanced peroxymonosulfate activation over heterogeneous catalyst Cu0.76Co2.24O4/SBA-15 for efficient degradation of sulfapyridine antibiotic.

The largest source of resistant bacteria or viruses is the overuse and misuse of antibiotics in humans and animals. These resistant bacteria or viruses may evolve into superbacteria or superviruses, which causes global plague. Therefore, it is significant to find a highly efficiency and low-cost method to eliminate antibiotics in water environment from inappropriate discharge. Here, a highly active and highly stable heterogeneous catalyst, Cu0.76Co2.24O4/SBA-15 (CCS) was prepared for peroxymonosulfate (PMS) activation in aim of decomposing persistent sulfapyridine (SPD). The reaction mechanism was thoroughly investigated via in situ quenching test and in situ electron paramagnetic resonance. Four reactive species, SO4·-, O2·-, 1O2 and ·OH were generated in Cu0.76Co2.24O4/SBA-15/PMS (CCSP) system. The SO4·- and O2·- were dominant active species responsible for SPD degradation. Co(Ⅱ)↔Co(Ⅲ)↔Co(Ⅱ) redox reaction cycle was constructed due to the different redox potential of Co(Ⅱ)/Co(Ⅲ), HSO5-/SO4∙-, and HSO5-/SO5∙-. Interestingly, Cu(Ⅰ) could urge the redox reaction cycle for PMS activation to be more thermodynamically feasible. Therefore, CCS possessed a highly catalytic activity and excellent stability. Meanwhile, the anions interference test indicated Cl-, NO3-, HCO3-, and H2PO4- had almost no inhibitory effect on SPD degradation over this catalytic system. We sincerely expected that this catalyst system would be applied extensively into antibiotics degradation in real water bodies.

Mn-O Covalency Governs the Intrinsic Activity of Co-Mn Spinel Oxides for Boosted Peroxymonosulfate Activation.

Transition metal (TM)-based bimetallic spinel oxides can efficiently activate peroxymonosulfate (PMS) presumably attributed to enhanced electron transfer between TMs, but the existing model cannot fully explain the efficient TM redox cycling. Here, we discover a critical role of TM-O covalency in governing the intrinsic catalytic activity of Co3-x Mnx O4 spinel oxides. Experimental and theoretical analysis reveals that the Co sites significantly raises the Mn valence and enlarges Mn-O covalency in octahedral configuration, thereby lowering the charge transfer energy to favor MnOh -PMS interaction. With appropriate MnIV /MnIII ratio to balance PMS adsorption and MnIV reduction, the Co1.1 Mn1.9 O4 exhibits remarkable catalytic activities for PMS activation and pollutant degradation, outperforming all the reported TM spinel oxides. The improved understandings on the origins of spinel oxides activity for PMS activation may inspire the development of more active and robust metal oxide catalysts.

CuCo2O4 supported on activated carbon as a novel heterogeneous catalyst with enhanced peroxymonosulfate activity for efficient removal of organic pollutants.

CuCo2O4 was synthesized via a relatively simple method, and innovatively supported onto the activated carbon (AC) by calcination to obtain a novel heterogeneous catalyst (AC-CuCo2O4). Brilliant red 3BF (3BF) was selected as the probe compound to investigate the catalytic activity of AC-CuCo2O4 in the presence of peroxymonosulfate (PMS). The results showed that 98% removal rate could be achieved and the reaction rate constant (0.476 min-1) was 5.2 times greater than that of CuCo2O4 alone (0.091min-1), suggesting that the introduction of AC could greatly enhance the catalytic activity of pure CuCo2O4. Typically, the 3BF removal was as high as 96% after five cycles, showing the good stability of catalyst reuse. Additionally, the effects of the initial pH, catalyst dosage, PMS concentration and reaction temperature on the 3BF removal were investigated, demonstrating that AC-CuCo2O4 effectively remove 3BF over a wide pH range (5.0-10.0) and possessed temperature-tolerant performance. To further explore the 3BF removal mechanism, electron paramagnetic resonance technology combining with trapping agents was employed to confirm the involvement of reactive oxygen species including SO4•-, •OH, O2•- and 1O2, which distinctly differed from the reported CuCo2O4 for PMS activation. These findings provided an addition promising strategy in environmental remediation.

Carbamazepine degradation by heterogeneous activation of peroxymonosulfate with lanthanum cobaltite perovskite: Performance, mechanism and toxicity.

The widely used carbamazepine (CBZ) is one of the most persistent pharmaceuticals and suffers insufficient removal efficiency by conventional wastewater treatment. A synthesized Co-based perovskite (LaCoO3) was used to activate peroxymonosulfate (PMS) in order to degrade CBZ. Results showed that LaCoO3 exhibited an excellent performance in PMS activation and CBZ degradation at neutral pH, with low cobalt leaching. The results of FT-IR and XPS verified the high structurally and chemically stability of LaCoO3 in PMS activation. Electron spin resonance (ESR) analysis suggested the generation of radical species, such as sulfate radicals (SO4-) and hydroxyl radicals (OH). Radical quenching experiments further revealed the responsibility of SO4- as the dominant oxidant for CBZ oxidation. Ten products were detected via the oxidation of CBZ, with the olefinic double bond attacked by SO4- as the initial step. Hydroxylation, hydrolysis, cyclization and dehydration were involved along the transformation of CBZ. The toxicity of CBZ solution was significantly reduced after treating by PMS/LaCoO3.

Small concentrations, big results: µM addition of photoactive iron oxides with PMS, PDS, or H2O2, leads to enhanced removal of viruses at near-neutral pH.

The photo-Fenton process is effective for pathogen removal, and its low-cost versions can be applied in resource-poor contexts. Herein, a photo-Fenton-like system was proposed using low concentrations of iron oxides (hematite and magnetite) and persulfates (peroxymonosulfate - PMS, and peroxydisulfate - PDS), which exhibited excellent inactivation performance towards MS2 bacteriophages. In the presence of bacteria, MS2 inactivation was inhibited in H2O2 and PDS systems but promoted in PMS-involved systems. The inactivation efficacy of all the proposed systems for mixed bacteria and viruses was greater than that of the sole bacteria, showing potential practical applications. The inactivation performance of humic acid-incorporated iron oxides mediating photo-Fenton-like processes was also studied; except for the PMS-involved system, the inactivation efficacy of the H2O2- and PDS-involved systems was inhibited, but the PDS-involved system was still acceptable (< 2 h). Reactive species exploration experiments indicated that ·OH was the main radical in the H2O2 and PDS systems, whereas 1O2 played a key role in the PMS-involved system. In summary, hematite- and magnetite-mediated persulfate-assisted photo-Fenton-like systems at low concentrations can be used as alternatives to the photo-Fenton process for virus inactivation in sunny areas, providing more possibilities for point-of-use drinking water treatment in developing countries.

Nucleophilic hydrolysis of dichloroacetonitrile and trichloroacetonitrile disinfection byproducts by peroxymonosulfate: Kinetics and mechanisms.

In this work, it was found that peroxymonosulfate (PMS) could appreciably accelerate the transformation rates of dichloroacetonitrile (DCAN) and trichloracetonitrile (TCAN) in aqueous solutions, especially under alkaline pHs. The impact of reactive oxygen species scavengers (methyl alcohol for sulfate radical, tert-butyl alcohol for hydroxyl radical, and azide for singlet oxygen) and water matrices (chloride (Cl-), bicarbonate (HCO3-), and natural organic matter (NOM)) on DCAN and TCAN transformation by PMS is evaluated, revealing negligible effects. A nucleophilic hydrolysis pathway, as opposed to an oxidation process, was proposed for the transformation of DCAN and TCAN by PMS, supported by the hydrolyzable characteristics of these compounds and validated through density functional theory calculations. Kinetic analysis indicated that the transformation of DCAN and TCAN by PMS adhered to a second-order kinetic law, with higher reaction rates observed at elevated pH levels within the range of 7.0-10.0. Kinetic modeling incorporating the hydrolytic contributions of water, hydroxyl ion, and protonated and deprotonated PMS (i.e., HSO5- and SO52-) effectively fitted the experimental data. Species-specific second-order rate constants reveal that SO52- exhibited significantly higher reactivity towards DCAN ((1.69 ± 0.22) × 104 M-1h-1) and TCAN ((6.06 ± 0.18) × 104 M-1h-1) compared to HSO5- ((2.14 ± 0.12) × 102 M-1h-1) for DCAN; and (1.378 ± 0.11) × 103 M-1h-1 for TCAN). Comparative analysis of DCAN and TCAN transformation efficiencies by four different oxidants indicated that PMS rivaled chlorine but falls short of hydrogen peroxide, with peroxydisulfate displaying negligible reactivity. Overall, this study uncovers the nucleophilic hydrolysis characteristics of PMS, supplementing its recognized role as an oxidant precursor or mild oxidant, and underscores its significant implications for environmental remediation.

Reactive layered hydroxide membrane for advanced water treatment: Micropollutant degradation and antifouling potential.

The effective removal of micropollutants by water treatment technologies remains a significant challenge. Herein, we develop a CoFe layered double hydroxide (CoFeLDH) catalytic membrane for peroxymonosulfate (PMS) activation to achieve efficient micropollutant removal with improved mass transfer rate and reaction kinetics. This study found that the CoFeLDH membrane/PMS system achieved an impressive above 98% degradation of the probe chemical ranitidine at 0.1 mM of PMS including five more micropollutants (Sulfamethoxazole, Ciprofloxacin, Carbamazepine, Acetaminophen and Bisphenol A) at satisfactory level (above 80%). Moreover, significant improvements in water flux and antifouling properties were observed, marking the membrane as a specific advancement in the removal of membrane fouling in water purification technology. The membrane demonstrated consistent degradation efficiency for several micropollutants and across a range of pH (4-9) as well as different anionic environments, thereby showing it suitability for scale-up application. The key role of reactive species such as SO4•-, and O2• - radicals in the degradation process was elucidated. This is followed by the confirmation of the occurrence of redox cycling between Co and Fe, and the presence of CoOH+ that promotes PMS activation. Over the ten cycles, the membrane could be operated with a flux recovery of up to 99.8% and maintained efficient performance over 24 h continuous operation. Finally, the efficiency in degrading micropollutants, coupled with reduced metal leaching, makes the CoFeLDH membrane as a promising technology for application in water treatment.

Attuning doped ZnO-based composites for an effective light-driven mineralization of pharmaceuticals via PMS activation.

Water treatment technologies need to go beyond the current control of organic contaminants and ensure access to potable water. However, existing methods are still costly and often inadequate. In this context, novel catalysts that improve the mineralization degree of a wider range of pharmaceuticals through more benign and less consuming methodologies are highly sought after. ZnO, especially when doped, is a well-known semiconductor that also excels in the photocatalytic removal of persistent organic pollutants. In this study, we investigated the effect of doping ZnO nanoparticles with either copper, gallium or indium on the structure, morphology, photophysical properties and photocatalytic mineralization of pharmaceuticals. Their architecture was further improved through the fabrication of composites, pairing the best performing doped ZnO with either BaFe12O19 or nickel nanoparticles. Their suitability was tested on a complex 60-ppm multi-pollutant solution (tetracycline, levofloxacin and lansoprazole). The activation strategy combined photocatalysis with peroxymonosulfate (PMS) as an environmentally friendly source of highly oxidative sulfate radicals. The alliance of doped ZnO and BaFe12O19 was particularly successful, resulting in magnetic microcroquette-shaped composites with excellent inter-component synergy. In fact, indium outperformed the other proposed metal dopants, exceeding 97% mineralization after 1 h and achieving complete elimination after 3 h. All composites excelled in terms of reusability, with no catalytic loss after 10 consecutive cycles and minimal leakage of metal ions, highlighting their applicability in water remediation.

In situ N-doping engineered biochar catalysts for oxidation degradation of sulfadiazine via nonradical pathways: Singlet oxygen and electron transfer.

Understanding the structure of non-metallic heteroatom-doped carbon catalysts and the subsequent degradation of new pollutants is crucial for designing more efficient carbon catalysts. Environmentally friendly in situ N-doped biochar catalysts were prepared for peroxymonosulfate (PMS) activation and sulfadiazine (SDZ) degradation. The acid washing process and calcination temperature of catalyst increased π-π* shake up, graphitic N percentage, specific surface area and defects, promoting the transformation of pollutant degradation mechanism from radical pathway to non-radical pathway. 100 % of the SDZ with the initial concentration of 10 mg/L was quickly degraded within 60 min using 0.2 g/L catalysts and 0.5 mM PMS. Excellent catalytic performance was attributed to singlet oxygen and electron transfer-dominated non-radical pathways. The four potential degradation pathways of SDZ were proposed, and toxicity predication indicated that overall biotoxicity of the intermediates during SDZ degradation was decreased. This research deepens our understanding of the mechanisms of non-radical pathways and guides the synthesis of carbon-based catalysts.