Magnetic raspberry-like CuCo nanoalloy-embedded carbon as an enhanced activator of Oxone to degrade azo contaminant: Cu-induced hollowed structure and boosted activities.

Azo compounds, particularly azo dyes, are widely used but pose significant environmental risks due to their persistence and potential to form carcinogenic by-products. Advanced oxidation processes (AOPs) are effective in degrading these stubborn compounds, with Oxone activation being a particularly promising method. In this study, a unique nanohybrid material, raspberry-like CuCo alloy embedded carbon (RCCC), is facilely fabricated using CuCo-glycerate (Gly) as a template. With the incorporation of Cu into Co, RCCC is essentially different from its analogue derived from Co-Gly in the absence of Cu, affording a popcorn-like Co embedded on carbon (PCoC). RCCC exhibits a unique morphology, featuring a hollow spherical layer covered by nanoscale beads composed of CuCo alloy distributed over carbon. Therefore, RCCC significantly outperforms PCoC and Co3O4 for activating Oxone to degrade the toxic azo contaminant, Azorubin S (AS), in terms of efficiency and kinetics. Furthermore, RCCC remains highly effective in environments with high NaCl concentrations and can be efficiently reused across multiple cycles. Besides, RCCC also leads to the considerably lower Ea of AS degradation than the reported Ea values by other catalysts. More importantly, the contribution of incorporating Cu with Co as CuCo alloy in RCCC is also elucidated using the Density-Function-Theory (DFT) calculation and synergetic effect of Cu and Co in CuCo contributes to enhance Oxone activation, and boosts generation of SO4•-and •OH. The decomposition pathway of AS by RCCC + Oxone is also comprehensively investigated by studying the Fukui indices of AS and a series of its degradation by-products using the DFT calculation. In accordance to the toxicity assessment, RCCC + Oxone also considerably reduces acute and chronic toxicities to lower potential environmental impact. These results ensure that RCCC would be an advantageous catalyst for Oxone activation to degrade AS in water.

Enhancing catalytic activity of CuCoFe-layered double oxide towards peroxymonosulfate activation by coupling with biochar derived from durian peel for antibiotic degradation: The role of C=O in biochar and underlying mechanism of built-in electric field.

CuCoFe-LDO/BCD was successfully synthesized from CuCoFe-LDH and biochar derived from durian shell (BCD). Ciprofloxacin (CFX) degraded more than 95% mainly by O2•- and 1O2 in CuCoFe-LDO/BCD(2/1)/PMS system within 10 min with a rate constant of 0.255 min-1, which was 14.35 and 2.66 times higher than those in BCD/PMS and CuCoFe-LDO/PMS systems, respectively. The catalytic system exhibited good performance over a wide pH range (3-9) and high degradation efficiency of other antibiotics. Built-in electric field (BIEF) driven by large difference in the work function/Fermi level ratio between CuCoFe-LDO and BCD accelerated continuous electron transfer from CuCoFe-LDO to BCD to result in two different microenvironments with opposite charges at the interface, which enhanced PMS adsorption and activation via different directions. As a non-radical, 1O2 was mainly generated via PMS activation by C=O in BCD. The presence of C=O in BCD resulted in an increase in atomic charge of C in C=O and redistributed the charge density of other C atoms. As a result, strong adsorption of PMS at C atom in C=O and other C with a high positive charge was favorable for 1O2 generation, whereas an enhanced adsorption of PMS at negatively charged C accounted for the generation of •OH and SO4•-. After adsorption, electrons in C of BCD became deficient and were fulfilled with those transferred from CuCoFe-LDO driven by BIEF, which ensured the high catalytic activity of CuCoFe-LDO/BCD. O2•-, on the other hand, was generated via several pathways that involved in the transformation of •OH and SO4•- originated from PMS activation by the transition of metal species in CuCoFe-LDO and negatively charged C in BCD. This study proposed a new idea of fabricating a low-cost metal-LDH and biomass-derived catalyst with a strong synergistic effect induced by BIEF for enhancing PMS activation and antibiotic degradation.

Effective activation of peroxymonosulfate by CoCr-LDH for removing organic contaminants in water: from lab-scale to practical applications.

In this study, CoCr layered double hydroxide material (CoCr-LDH) was prepared and used as an effective catalyst for peroxymonosulfate (PMS) activation to degrade organics in water. The prepared CoCr-LDH material had a crystalline structure and relatively porous structure, as determined by various surface analyses. In Rhodamine B (RhB) removal, the most outstanding PMS activation ability belongs to the material with a Co:Cr molar ratio of 2:1. The removal of RhB follows pseudo-first-order kinetics (R2 > 0.99) with an activation energy of 38.23 kJ/mol and efficiency of 98% after 7 min of treatment, and the total organic carbon of the solution reduced 47.2% after 10 min. The activation and oxidation mechanisms were proposed and the RhB degradation pathways were suggested with the key contribution of O2•- and 1O2. Notably, CoCr-LDH can activate PMS over a wide pH range of 4 - 9, and apply to a wide range of organic pollutants and aqueous environments. The material has high stability and good recovery, which can be reused for 5 cycles with a stable efficiency of above 88%, suggesting a high potential for practical recalcitrant water treatment via PMS activation by heterogeneous catalysts.

Synthesis of Inexpensive Ternary Metal Oxides by a Co-Precipitation Method for Catalytic Oxidation of Carbon Monoxide.

By using a simple co-precipitation method, new Fe2 O3 -based nanocatalysts (samples) were synthesized. The samples were composites of two or three transition metal oxides, MOx (M=Fe, Mn, Co, Ni, and Cu). The average size of CuO crystallites in the composites composed of two oxide components (CuO-Fe2 O3 ) was about 14.3 nm, while in those composed of three (CuO-MnOx -Fe2 O3 ), the composite's phase compositions were almost in the amorphous form when annealing the sample at 300 °C. The latter sample had a specific surface area higher than that of the former, 207.9 and 142.1 g/m2 , respectively, explaining its higher catalytic CO oxidation. The CO conversion over the CuO-MnOx -Fe2 O3 -300 catalyst (1 g of catalyst, 2600 ppm of CO concentration in air, and 1.0 L/min of gas flow rate) begins at about 40 °C; the temperature for 50 % CO conversion (t50 ) is near 82 °C; and CO removal is almost complete at t99 ≈110 °C. The activity of the optimal sample was tested in different catalytic conditions, thereby observing a high durability of 99-100 % CO conversion at 130 °C. The obtained results were derived from XRD, FTIR, BET, SEM, elemental analysis and mapping, as well as catalytic experiments.

Hollow-Architected Heteroatom-Doped Carbon-Supported Nanoscale Cu/Co as an Enhanced Magnetic Activator for Oxone to Degrade Toxicants in Water.

Even though transition metals can activate Oxone to degrade toxic contaminants, bimetallic materials possess higher catalytic activities because of synergistic effects, making them more attractive for Oxone activation. Herein, nanoscale CuCo-bearing N-doped carbon (CuCoNC) can be designed to afford a hollow structure as well as CuCo species by adopting cobaltic metal organic frameworks as a template. In contrast to Co-bearing N-doped carbon (CoNC), which lacks the Cu dopant, CuCo alloy nanoparticles (NPs) are contained by the Cu dopant within the carbonaceous matrix, giving CuCoNC more prominent electrochemical properties and larger porous structures and highly nitrogen moieties. CuCoNC, as a result, has a significantly higher capability compared to CoNC and Co3O4 NPs, for Oxone activation to degrade a toxic contaminant, Rhodamine B (RDMB). Furthermore, CuCoNC+Oxone has a smaller activation energy for RDMB elimination and maintains its superior effectiveness for removing RDMB in various water conditions. The computational chemistry insights have revealed the RDMB degradation mechanism. This study reveals that CuCoNC is a useful activator for Oxone to eliminate RDMB.

Fe(II) and Pyridinic N complex sites synergy to activate PMS for specific generation of 1O2 to degrade antibiotics with high efficiency.

In this study, specific generation of 1O2 was achieved by activation of peroxymonosulfate (PMS) using N-doped porous carbon with Fe nanoparticles (NPC-Fe), synthesized by carbonizing MIL-88B(Fe) metal-organic frameworks modified with ionic liquid. Fe(II) in the catalyst was found to react with PMS to form •O2-, and Pyridinic N promoted the conversion of •O2- to 1O2. Consequently, the NPC-Fe/PMS reaction system could generate a large amount of 1O2 by the synergistic effect of Fe(II) and Pyridinic N. The system demonstrated excellent performance in a wide pH range for the degradation of contaminants represented by antibiotics. Additionally, the catalyst NPC-Fe had good stability and recyclability. This work provides novel insights for generating 1O2 by activation of PMS for environmental remediation.

Green and Facile Synthesis of Porous SiO2@C Adsorbents from Rice Husk: Preparation, Characterization, and Their Application in Removal of Reactive Red 120 in Aqueous Solution.

In this work, a green, novel, fast, and facile approach for synthesizing a SiO2/C nanocomposite series from rice husk (RH) through quenching and grinding techniques has been reported along with its application for the adsorptive removal of Reactive Red 120 (RR120) dye from an aqueous solution. The effect of carbonization temperature on the textural and interfacial features of RH was confirmed by scanning electron microscopy (SEM), while the structure and elemental composition of the as-synthesized RH were investigated via XRD, Brunauer-Emmett-Teller (BET), FT-IR, Raman, and X-ray photoelectron spectroscopy (XPS). The RH had a high surface area (521.35 m2 g-1), large micropores, mesopores, and total pore volumes of 0.5059, 3.9931, and 5.2196 cm3 g-1, while SiO2 and C were the two major components. In the batch adsorption test, the effects of pH, contact time, adsorbent mass, temperature, and initial RR120 concentration were investigated. The maximum adsorption capacity was fitted by Langmuir, Freundlich, Temkin, Dubinin-Radushkevich (D-R), Hasley, Harkins-Jura, and BET isotherm models, and Langmuir was the best-fitted model. In addition, the pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich chemisorption models were used to explain the adsorption kinetics. Additionally, the values of Gibbs free energy, enthalpy, and entropy thermodynamics suggested that the RR120 adsorption phenomenon by RH8-3 was endothermic and spontaneous. The adsorption process was controlled by a physical mechanism, and the maximum adsorption capacity was found to be 151.52 mg g-1 at pH 2, with a contact time of 90 min, adsorbent amount of 0.03 g, and temperature of 313 K. The adopted technique may open up a new alternative route for the mass utilization of RH for the removal of dyes in water and wastewater and also for various practical applications.

Boosting elimination of sunscreen, Tetrahydroxybenzophenone (BP-2), from water using monopersulfate activated by thorny NanoBox of Co@C prepared via the engineered etching strategy: A comparative and mechanistic investigation.

As sunscreens, benzophenones (BPs), are regarded as emerging contaminants, most of studies are focused on removal of 2-hydroxy-4-methoxybenzophenone (BP-3), which, however, has been employed for protecting skin. Another major class of BPs, which is used to prevent UV-induce degradation in various products, is completely neglected. Thus, this present study aims to develop a useful advanced oxidation process (AOP) for the first time to eliminate such a class of BP sunscreens from contaminated water. Specifically, 2,2',4,4'-Tetrahydroxybenzophenone (BP-2) would be focused here as BP-2 is intensively used in perfumes, lipsticks, and plastics for preventing the UV-induced degradation. As monopersulfate (MPS)-based AOP is practical for degrading emerging contaminants, a facile nanostructured cobalt-based material is then developed for maximizing catalytic activities of MPS activation by immobilizing Co nanoparticles onto carbon substrates. In particular, ZIF-67 is employed as a template, followed by the etching and carbonization treatments to afford the thorny nanobox of Co@C (TNBCC) with the hollow-nanostructure. In comparison to the solid (non-hollow) nanocube of Co@C (NCCC) from the direct carbonization of ZIF-67, TNBCC possesses not only the excellent textural features, but also superior electrochemical properties and highly reactive surfaces, making TNBCC exhibit the significantly higher catalytic activity than NCCC as well as Co3O4 in activating MPS to degrade BP-2. Mechanisms of BP-2 degradation are also elucidated and ascribed to both radical and non-radical routes. These advantageous features make TNBCC a useful catalyst of activating MPS in BP-2 degradation.

Orange G degradation by heterogeneous peroxymonosulfate activation based on magnetic MnFe2O4/α-MnO2 hybrid.

Wastewater containing an azo dye Orange G (OG) causes massive environmental pollution, thus it is critical to develop a highly effective, environmental-friendly, and reusable catalyst in peroxymonosulfate (PMS) activation for OG degradation. In this work, we successfully applied a magnetic MnFe2O4/α-MnO2 hybrid fabricated by a simple hydrothermal method for OG removal in water. The characteristics of the hybrid were investigated by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller method, vibrating sample magnetometry, electron paramagnetic resonance, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The effects of operational parameters (i.e., catalytic system, catalytic dose, solution pH, and temperature) were investigated. The results exhibited that 96.8% of OG degradation was obtained with MnFe2O4/α-MnO2(1:9)/PMS system in 30 min regardless of solution pH changes. Furthermore, the possible reaction mechanism of the coupling system was proposed, and the degradation intermediates of OG were identified by mass spectroscopy. The radical quenching experiments and EPR tests demonstrated that SO4•̶, O2•̶, and 1O2 were the primary reactive oxygen species responsible for the OG degradation. The hybrid also displayed unusual stability with less than 30% loss in the OG removal after four sequential cycles. Overall, magnetic MnFe2O4/α-MnO2 hybrid could be used as a high potential activator of PMS to remove orange G and maybe other dyes from wastewater.

An electrical- and chemical-free approach using microfilter and Ag-based catalysts for emergency drinking water treatment.

In emergency cases such as disasters, supplying enough safe drinking water is one of the most urgent needs for human life. This research aimed to develop a chemical- and electricity-free drinking water treatment system based on microfiltration and catalysts of Ag and Ag-TiO2-SiO2 coated on glass spheres in both dark and sunlight conditions. The system was applied to treat raw water samples taken from five rivers in Vietnam, simulated floodwater samples with high turbidity and E. coli concentration, and real flooding water samples. The results showed the filtration unit fed with simulated floodwater generated lower fluxes and shorter working durations before chemical cleaning than that fed with normal river water. However, filtrate quality was not significantly different for these five water samples with very low values of turbidity (0-0.66 NTU), total coliform (5-19 CFU (100 mL)-1), and E. coli (0-17 CFU (100 mL)-1). The catalyst units using glass spheres coated with either Ag in dark and sunlight or Ag-TiO2-SiO2 under sunlight can completely remove E. coli and coliform as well as additionally mitigate natural organic matters. This study hence suggests the combination of microfiltration and Ag-based catalytic treatment for safe drinking water supply in emergencies, especially for flooding conditions.

A Novel Conjugate Mechanism for Enhancing the Adsorption Capacity of Amine-Functionalized Activated Rice Husk Ash for Simultaneous Removal of Organics and Anions in Wastewater: Experimental and Theoretical Explanations.

In this study, amine-functionalized rice husk ash (TRI-ARHA) was prepared and successfully applied as a multipurpose adsorbent for simultaneous removal of organics (i.e., methyl orange, MO), nitrate, and phosphate in wastewater with adsorption capacities of around 16.6 mgMO/g, 32.9 mgNO3 --N/g, and 13.4 mgPO4 3--P/g. These capacities were superior to those of the other commercially available materials such as activated carbon and ion-exchange resins in both individual and multipollutant adsorption experiments. In addition, the simultaneous adsorption of three components gives a higher adsorption capacity than individual adsorption for each anion (e.g., 1.18 times for nitrate and 1.11 times for phosphate). A conjugated adsorption mechanism may occur on the surface of the TRI-ARHA material, which can be ascribed to the amine groups in the MO molecule that are further activated by H+ (released from the surface amine groups) or Na+ ions (present in the solution), to form new adsorption centers for nitrate and phosphate. The integration process of H+ and Na+ to the nitrogen positions of MO was also studied by computational chemistry with the basis set of B3LYP/6-32G* calculated by Gaussian 16 software. The application in the treatment of real wastewaters proved that the TRI-ARHA material was more advantageous for multipollutant removal than other materials, thanks to its conjugated adsorption mechanism.

Ag@AgCl nanoparticles grafted on carbon nanofiber: an efficient visible light plasmonic photocatalyst via bandgap reduction.

A novel silver@silver chloride/carbon nanofiber (Ag@AgCl/CNF) hybrid was synthesized by electrospinning, heat treament, and subsequentin situchemical oxidation strategy. The synthesized materials were characterized using x-ray diffraction, Fourier-transform infrared, UV-Vis diffuse reflectance spectroscopy, scanning electron microscopy, and energy dispersive x-ray. The experimental results reveal that the electrospun AgNO3/PAN was carbonized and reduced to Ag/CNF, the Ag/CNF was then partly oxidized to form Ag@AgCl/CNF in which Ag@AgCl nanoparticles (ca. 10-20 nm in diameter) were uniformly bounded to CNFs (ca. 165 nm in diameter). The obtained Ag@AgCl/CNF was employed for Na2S2O8activation under visible light irradiation to treat Rhodamine B (RhB). A remarkable RhB removal of ca. 94.68% was achieved under optimal conditions, and the influence of various parameters on removal efficiency was studied. Quenching experiments revealed that HO•, SO4•-,1O2, and O2•-were major reactive oxygen species, in which O2•-played a pivotal role in RhB degradation. A possible mechanistic route for RhB degradation was proposed.

Field study of visitors' behavior in incense burning and its induced air pollution assessment and treatment.

This study conducted a field investigation in the behavior of visitors in the pagoda and burning incense as well as its air pollution situation in Vietnam, and revealed that 92% of people used stick form for offering incense and mainly burning either 1 or 3 sticks/time. Incense smoke exposure caused aroma, comfortable, eye irritation, or hard to breathe. There were 70% of people being aware of the hazard of incense smoke. VOCs, PM2.5, PM10, and CO2 concentrations from burning incense in the Great hall were 1.6-2.5 times higher than those in outside areas. Pollutants' concentrations on the first of the month, full moon day, and Lunar New Year were from 1.5 to 2.0 times higher than those of normal days. A model was designed to collect incense smoke emitted by burning 1 and 3 sticks of seven types of incense on an open area. Except for CO found at low concentrations, VOCs, HCHO, PM2.5, PM10, and CO2 appeared in the smoke with the maximum concentrations higher 2.5-13.5 times than their allowable values. A photocatalytic device using titania nanotubes (TNTs) impregnated with various metals (Cd, Zn, Al, Cu, and Fe) was installed for incense smoke treatment. Effect of type and amount of photocatalyst, as well as initial VOC concentration, were tested. The results show that using 2.0 g of Zn/TNT photocatalysts under UV irradiation provided the highest VOC removal efficiency of 73%, suggesting the potential of application for burning incense in open areas.

A comprehensive study on the heterogeneous electro-Fenton degradation of tartrazine in water using CoFe2O4/carbon felt cathode.

In this study, cobalt ferrite coated carbon felt (CoFe2O4/CF) was synthesized by solvothermal method and applied as cathode for electro-Fenton (EF) treatment of tartrazine (TTZ) in water. The materials were characterized by SEM, XRD, FTIR, CV, and EIS to explore their physical, chemical, and electrical properties. The effects of solvothermal temperature and metal content on the TTZ removal were examined, showing that 220 °C with 2 mM of Co and 4 mM of Fe precursors were the best synthesis condition. Various influencing factors such as applied current density, pH, TTZ concentration, and electrolytes were investigated, and the optimal condition was found at 8.33 mA cm-2, pH 3, 50 mgTTZ L-1, and 50 mM of Na2SO4, respectively. By radical quenching test, , 1O2, and HO were recognized as the key reactive oxygen species and the reaction mechanism was proposed for the EF decolorization of TTZ using CoFe2O4/CF cathode. The reusability and stability test showed that the highly efficient CoFe2O4/CF cathode is very promising for practical application in wastewater treatment, especially for dyes and other recalcitrant organic compounds to improve its biodegradability.

A simple and efficient ultrasonic-assisted electrochemical approach for scalable production of nitrogen-doped TiO2nanocrystals.

In this study, we report a facile and effective approach for large-scale production of nitrogen-doped TiO2nanocrystals (UNTs) by a combination of ultrasonic irradiation and electrochemistry at room temperature using NH4NO3electrolyte as the nitrogen source. The as-prepared UNTs were then characterized by x-ray diffraction, Raman spectroscopy, x-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, and UV-visible diffuse reflectance spectroscopy. The results indicated that the nitrogen content of UNTs reached 9.3% and bandgap energy of 2.62 eV, thus gave the high photocatalytic degradation of methylene blue under visible light irradiation. The mechanism for the formation of UNTs by ultrasonic-assisted electrochemical approach was also proposed.

Gram-scale synthesis of electrochemically oxygenated graphene nanosheets for removal of methylene blue from aqueous solution.

In this study, oxygenated graphene nanosheets (OGNs) were successfully synthesized using a simple electrochemical exfoliation approach and applied to remove methylene blue (MB) in an aqueous solution. The surface morphology and structure of the OGNs were characterized by scanning electron microscopy, transmission electron microscopy, Raman, and x-ray photoelectron spectroscopy. The adsorption performance of OGNs towards aqueous MB was tested by batch experiments. Results showed that a large number of functional groups in OGNs enhanced the removal of MB from the aqueous solution due to the electrostatic interactions between the electrochemically oxygenated groups (e.g. C-OH, C-O, and C=O) and dye molecules. Using Langmuir adsorption isotherm, the maximum MB adsorption capacity (q max) was determined as high as 476.19 mg g-1. These results suggested that the as-prepared OGNs is an effective and promising adsorbent for removing MB, which could be studied extensively for color removal in wastewater treatment.

Preparation of Mn2O3/MIL-100(Fe) composite and its mechanism for enhancing the photocatalytic removal of rhodamine B in water.

In this study, Mn2O3/MIL-100(Fe) composite was successfully synthesized by the hydrothermal method and applied for photocatalytic removal of rhodamine B (RhB) in water. The physical and chemical properties of the synthesized materials were characterized by XRD, FTIR, SEM, UV-visible, and BET analyses. Experimental results showed a great enhancement in the photocatalytic ability of the Mn2O3/MIL-100(Fe) composite as compared to individual Mn2O3 or MIL-100(Fe) under visible light and persulfate activation. The affecting factors such as pH, photocatalyst dose, RhB concentration, and Na2S2O8 concentration were investigated to find out the best conditions for efficient photocatalysis. By conducting a radical quenching test, all radicals of HO˙, SO4˙-, 1O2, and O2˙- were found to be important in photocatalytic decomposition. The mechanism was proposed for the enhancement of photocatalytic RhB removal via band potential calculation, charge separation, surface redox reaction, and key reactive oxidation species. With its durability, reusability, and high efficiency, the Mn2O3/MIL-100(Fe) composite emerges as a potential photocatalyst working under visible light for application in wastewater treatment.

Metal organic framework-derived 3D nanostructured cobalt oxide as an effective catalyst for soot oxidation.

While Co3O4 represents one of the most promising catalysts for soot oxidation, conventional Co3O4 nanoparticles (NPs) tend to aggregate, losing their activities. Herein, an alternative approach is proposed for preparing three-dimensional nanostructured Co3O4 (NSCo) using the hierarchically-structured Co-based Metal Organic Frameworks as a precursor. Specifically, ZIF-67 is chosen as the precursor as ZIF-67 can be conveniently synthesized with high yields and it can be easily converted to NSCo via calcination. The resulting NSCo exhibits a unique morphology which enables NSCo to possess more porosities and surface areas than the typical Co3O4 NPs. Consequently, NSCo shows a much higher catalytic activity than the typical Co3O4 NPs for soot oxidation because of superior textural properties of NSCo. Besides, when the soot oxidation by the typical Co3O4 NPs produced a significant amount of unwanted CO, soot can be completely combusted into CO2 using NSCo. In comparison with other reported Co-related catalysts, NSCo also achieves a higher soot oxidation efficiency (100% conversion) at lower temperatures with Tig of 331 °C. NSCo can be reused over many continuous cycles and still retains its catalytic activities. These features validate that NSCo is an easy-to-prepare 3D nanostructured Co3O4 catalyst, which possesses advantageous capabilities for soot oxidation at lower temperatures.