Expanded Properties and Applications of Porous Flame-Retardant Polymers Containing Graphene and Its Derivatives.

With the integration and miniaturization of modern equipment and devices, porous polymers, containing graphene and its derivatives, with flame-retardancy have become a research hotspot. In this paper, the expanded properties and high-end applications of flame-retardant porous materials containing graphene and its derivatives were discussed. The research progress regarding graphene-based porous materials with multiple energy conversion, thermal insulation, an electromagnetic shielding property, and a high adsorption capacity were elucidated in detail. The potential applications of materials with the above-mentioned properties in firefighter clothing, fire alarm sensors, flexible electronic skin, solar energy storage, energy-saving buildings, stealth materials, and separation were summarized. The construction strategies, preparation methods, comprehensive properties, and functionalization mechanisms of these materials were analyzed. The main challenges and prospects of flame-retardant porous materials containing graphene and its derivatives with expanded properties were also proposed.

Weak static magnetic fields facilitated highly efficient 2,4,6-trichlorophenol removal by sulfurized nanoscale zero-valent iron supported on biochar (BC-SNZVI) at neutral pH.

Sulfurized nanoscale zero-valent iron supported on biochar (BC-SNZVI) has been successfully synthesized for 2,4,6-trichlorophenol (2,4,6-TCP) removal, while was only effectively under acidic conditions. To obtain highly efficient removal of 2,4,6-TCP within a broader pH range, weak static magnetic fields (WMF) was applied in BC-SNZVI/2,4,6-TCP aqueous systems. Results showed 30 mT WMF supported the most extensive 2,4,6-TCP removal, and 87.4% of 2,4,6-TCP (initial concentration of 30 mg/L) was removed by 0.5 g/L BC-SNZVI at neutral pH (pH = 6.8) within 180 min, which was increased by 54.4% compared to that without WMF. The observed rate constant (Kobs) under 30 mT WMF was 2.1-fold greater than that without WMF. Although three typical anions (NO3- (0.5-10.0 mM), H2PO4- (0.05-0.5 mM), and HCO3- (0.5-5.0 mM)) still inhibited 2,4,6-TCP removal, WMF could efficiently alleviate the inhibitory effects. Moreover, 73.1% of 2,4,6-TCP was successfully removed by BC-SNZVI under WMF in natural water. WMF remarkably boosted the dechlorination of 2,4,6-TCP, increasing the 2,4,6-TCP dechlorination efficiency from 45.2% (in the absence of WMF) to 83.8% (in the presence of WMF) by the end of 300 min. And the complete dechlorination product phenol appeared within 10 min. Force analysis confirmed the magnetic field gradient force (FB) moved paramagnetic Fe2+ at the SNZVI surface along the direction perpendicular to the external applied field, promoting the mass-transfer controlled SNZVI corrosion. Corrosion resistance analysis revealed WMF promoted the electron-transfer controlled SNZVI corrosion by decreasing its self-corrosion potential (Ecorr). With the introduction of sulfur, the magnitude of FB doubled and the Ecorr decreased comparing with NZVI. Our findings provide a facile and viable strategy for treating chlorinated phenols at neutral pH.

Efficient biostimulation of microbial dechlorination of polychlorinated biphenyls by acetate and lactate under nitrate reducing conditions: Insights into dechlorination pathways and functional genes.

Microbial-catalyzed reductive dechlorination of polychlorinated biphenyls (PCBs) is largely affected by the indigenous sediment geochemical properties. In this study, the effects of nitrate on PCB dechlorination and microbial community structures were first investigated in Taihu Lake sediment microcosms. And biostimulation study was attempted supplementing acetate/lactate. PCB dechlorination was apparently inhibited under nitrate-reducing conditions. Lower PCB dechlorination rate and less PCB dechlorination extent were observed in nitrate amended sediment microcosms (T-N) than those in non-nitrate amended microcosms (T-1) during 66 weeks of incubation. The total PCB mass reduction in T-N was 17.6% lower than that in T-1. The flanked-para dechlorination was completely inhibited, while the ortho-flanked meta dechlorination was only partially inhibited in T-N. The 7.5 mM of acetate/lactate supplementation recovered PCB dechlorination by resuming ortho-flanked meta dechlorination. Repeated additions of lactate showed more effective biostimulation than acetate. Phylum Chloroflexi, containing most known PCB dechlorinators, was found to play a vital role on stability of the network structures. In T-N, putative dechlorinating Chloroflexi, Dehalococcoides and RDase genes rdh12, pcbA4, pcbA5 all declined. With acetate/lactate supplementation, Dehalococcoides grew by 1-2 orders of magnitude and rdh12, pcbA4, pcbA5 increased by 1-3 orders of magnitude. At Week 66, parent PCBs declined by 86.4% and 80.9% respectively in T-N-LA and T-N-AC compared to 69.9% in T-N. These findings provide insights into acetate/lactate biostimulation as a cost-effective approach for treating PCB contaminated sediments undergoing nitrate inhibition.

Short-chain fatty acids facilitated long-term dechlorination of PCBs in Taihu Lake sediment microcosms: Evidence from PCB congener and microbial community analyses.

Microbial reductive dechlorination hosts great promise as an in situ bioremediation strategy for polychlorinated biphenyls (PCBs) contamination. However, the slow dechlorination in sediments limits natural attenuation. Short-chain fatty acids, as preferred carbon sources and electron donors for dechlorinating microorganisms, might stimulate PCB dechlorination. Herein, two sets of short-chain fatty acids, sole acetate and a fatty acid mixture (acetate, propionate, and butyrate), were amended periodically into Taihu Lake (China) sediment microcosms containing nine PCB congeners (PCB5, 12, 64, 71, 105, 114, 149, 153, and 170) after 24 weeks of incubation. Short-chain fatty acids facilitated the long-term PCB dechlorination and the promoting effect of the fatty acid mixture compared favorably with that of sole acetate. By the end of 108 weeks, the total PCB mass concentrations in acetate amended and fatty acid mixture amended microcosms significantly declined by 7.6% and 10.3% compared with non-amended microcosms (P < 0.05), respectively. Short-chain fatty acids selectively favored the removal of flanked meta and single-flanked para chlorines. Notably, a rare ortho dechlorination pathway, PCB25 (24-3-CB) to PCB13 (3-4-CB), was enhanced. Supplementary fatty acids significantly increased reductive dehalogenases (RDase) gene pcbA5 instead of improving the growth of Dehalococcoides. These findings highlight the merits of low cost short-chain fatty acids on in situ biostimulation in treating PCBs contamination.

Biochar-supported sulfurized nanoscale zero-valent iron facilitates extensive dechlorination and rapid removal of 2,4,6-trichlorophenol in aqueous solution.

Nanoscale zero-valent iron (NZVI) has been widely used in rapid remediation of contaminants. However, several obstacles such as aggregation and surface passivation hampered NZVI from further application. In this study, sulfurized nanoscale-zero valent iron supported by biochar (BC-SNZVI) was successfully synthesized and utilized for highly efficient 2,4,6-trichlorophenol (2,4,6-TCP) dechlorination in aqueous solution. SEM-EDS analysis revealed the even distribution of SNZVI on the surface of BC. FTIR, XRD, XPS and N2 Brunauer-Emmett-Teller (BET) adsorption analyses were carried out to characterize the materials. Results showed that BC-SNZVI with S/Fe molar ratio of 0.088, Na2S2O3 as sulfurization agent, and pre-sulfurization as the sulfurization strategy exhibited the superior performance for 2,4,6-TCP removal. The overall removal of 2,4,6-TCP was well described with the pseudo-first-order kinetics (R2 > 0.9), and the observed kinetics constant Kobs was 0.083 min-1 with BC-SNZVI, which was one order of magnitude higher than that of BC-NZVI (0.0092 min-1) and SNZVI (0.0042 min-1), and two orders of magnitude higher than that of NZVI (0.00092 min-1). Moreover, the removal efficiency of 2,4,6-TCP reached 99.5% by BC-SNZVI with dosage of 0.5 g L-1, initial 2,4,6-TCP concentration of 30 mg L-1 and initial solution pH of 3.0 within 180 min. The removal of 2,4,6-TCP by BC-SNZVI was acid-promoted and the removal efficiencies of 2,4,6-TCP decreased with the increase of initial 2,4,6-TCP concentrations. Furthermore, more extensive dechlorination of 2,4,6-TCP was achieved with BC-SNZVI and complete dechlorination product phenol became predominant. The facilitation of sulfur for Fe0 utilization and electron distribution in the presence of biochar remarkably enhanced the dechlorination performance of BC-SNZVI for 2,4,6-TCP. These findings provide insights into BC-SNZVI as an alternative engineering carbon based NZVI material for treating chlorinated phenols.

Long-term nitrogen and phosphorus removal, shifts of functional bacteria and fate of resistance genes in bioretention systems under sulfamethoxazole stress.

To understand the long-term performance of bioretention systems under sulfamethoxazole (SMX) stress, an unplanted bioretention system (BRS) and two modified BRSs with coconut-shell activated carbon (CAC) and CAC/zero-valent-iron (Fe0) granules (CAC-BRS and Fe/CAC-BRS) were established. Both CAC-BRS and Fe/CAC-BRS significantly outperformed BRS in removing total nitrogen (TN) (CAC-BRS: 82.48%; Fe/CAC-BRS: 78.08%; BRS: 47.51%), total phosphorous (TP) (CAC-BRS: 79.36%; Fe/CAC-BRS: 98.26%; BRS: 41.99%), and SMX (CAC-BRS: 99.74%, Fe/CAC-BRS: 99.80%; BRS: 23.05%) under the long-term SMX exposure (0.8 mg/L, 205 days). High-throughput sequencing revealed that the microbial community structures of the three BRSs shifted greatly in upper zones after SMX exposure. Key functional genera, dominantly Nitrospira, Rhodoplanes, Desulfomicrobium, Geobacter, were identified by combining the functional prediction by the FAPROTAX database with the dominant genera. The higher abundance of nitrogen functional genes (nirK, nirS and nosZ) in CAC-BRS and Fe/CAC-BRS might explain the more efficient TN removal in these two systems. Furthermore, the relative abundance of antibiotic-resistant genes (ARGs) sulI and sulII increased in all BRSs along with SMX exposure, suggesting the selection of bacteria containing sul genes. Substrates tended to become reservoirs of sul genes. Also, co-occurrence network analysis revealed distinct potential host genera of ARGs between upper and lower zones. Notably, Fe/CAC-BRS succeeded to reduce the effluent sul genes by 1-2 orders of magnitude, followed by CAC-BRS after 205-day exposure. This study demonstrated that substrate modification was crucial to maintain highly efficient nutrients and SMX removals, and ultimately extend the service life of BRSs in treating SMX wastewater.

Study on Microstructure of Fiber Laser Welding of CoCrCuFeNi High Entropy Alloy.

A CoCrCuFeNi high-entropy alloy was successfully welded in this study using fiber laser welding. The effects of the welding parameters on the microstructure and mechanical properties were studied. Three zones were formed: the fusion zone, partial melting zone, and base metal. The base metal exhibited a typical dendrite structure, and the Cu element segregated in the interdendrite. The fusion zone consisted of fine equiaxed crystals and columnar crystals with the same crystalline structure as the base metal. The fusion zone exhibited minimal compositional microsegregation after laser welding. Electron backscatter diffraction results showed that the low-angle grain boundary fraction in the fusion zone increased. Furthermore, some dislocations and dislocation pile-ups were present in the fusion zone, and the densities of the dislocations and dislocation pile-ups were higher than those of the base metal. The hardness of the fusion zone was considerably higher than that of the base metal, while the ultimate tensile strength and elongation values were lower than those of the base metal for all conditions. The ultimate tensile strength and the elongation increased gradually and then decreased with increasing laser power. The maximum ultimate tensile strength exceeded that of the base metal by 90%.

Humin and biochar accelerated microbial reductive dechlorination of 2,4,6-trichlorophenol under weak electrical stimulation.

The extracellular electron transfer (EET) is regarded as one of the crucial factors that limit the application of the bioelectrochemical system (BES). In this study, two different solid-phase redox mediators (RMs), biochar (1.2 g/L, T-B) and humin (1.2 g/L, T-H) were used for boosting the microorganisms accessing the electrons required for 2,4,6-TCP dechlorination under weak electrical stimulation (-0.278 V vs. Standard hydrogen electrode). BES with dissolved RM anthraquinone-2,6-disulfonate (AQDS 0.5 mmol/L, T-A) was used as a comparison. The results showed that dechlorination of 2,4,6-TCP could be greatly accelerated by biochar (1.78 d-1) and humin (1.50 d-1) than AQDS (0.24 d-1) and no RM control (T-M, 0.27 d-1). Moreover, phenol became the predominant dechlorination product in T-H (78.5 %) and T-B (63.0 %) instead of 4-CP in T-M (67.1 %) and T-A (89.8 %). Pseudomonas, Sulfurospirillum, Desulfuromonas, Dehalobacter, Anaeromyxobacter, and Dechloromonas belonging to Proteobacteria or Firmicutes rather than Chloroflexi might be responsible for the dechlorination activity. Notably, different RMs tended to stimulate distinct electroactive bacteria. Pseudomonas was the most abundant microorganism in T-M (41.92 %) and T-A (17.24 %), while Rhodobacter was most prevalent in T-H (20.04 %) and Azonexus was predominant in T-B (48.48 %). This study is essential in advancing the understanding of EET in BES for microbial degradation of organohalide contaminants under weak electrical stimulation.

Efficient activation of peroxymonosulfate by nanotubular Co3O4 for degradation of Acid Orange 7: performance and mechanism.

Morphology optimization of catalysts has been considered as a viable strategy to improve the catalytic efficiency for peroxymonosulfate (PMS) activation by providing high surface area and abundant active sites. In this study, nanotubular Co3O4 (NT-Co3O4) was successfully synthesized as a PMS activator for the rapid removal of acid orange 7 (AO7) in aqueous solutions. Characterization results showed that NT-Co3O4 presented as aggregated nanotubes, with an average pore diameter of 10 nm. The specific surface area of NT-Co3O4 was as high as 41.8 m2 g-1. Catalytic experiments demonstrated that the degradation rate of AO7 in the NT-Co3O4/PMS system was 15 times greater than that in commercially available Co3O4/PMS system. The effects of various experimental parameters, including catalyst dose, PMS dose, pH, and temperature, were comprehensively investigated. The reactive species in the NT-Co3O4/PMS system were identified as sulfate radical (SO4•-) through both quenching tests and electron paramagnetic resonance (EPR) technology, and ≡CoOH+ played an important role in PMS activation. N atoms in the AO7 molecule were found to be preferentially attacked by SO4•-. Moreover, the good stability and reusability of NT-Co3O4 were confirmed by a five-cycle AO7 removal experiment. This study provides a broader view of the potential applications of nanotubular materials to achieve highly efficient PMS activation in treating dyes in wastewater.

Long-Term Dechlorination of Polychlorinated Biphenyls (PCBs) in Taihu Lake Sediment Microcosms: Identification of New Pathways, PCB-Driven Shifts of Microbial Communities, and Insights into Dechlorination Potential.

Microbial reductive dechlorination of polychlorinated biphenyls (PCBs) is regarded as an alternative approach for in situ remediation and detoxification in the environment. To better understand the process of PCB dechlorination in freshwater lake sediment, a long-term (108 weeks) dechlorination study was performed in Taihu Lake sediment microcosms with nine parent PCB congeners (PCB5, 12, 64, 71, 105, 114, 149, 153, and 170). Within 108 weeks, the total PCBs declined by 32.8%, while parent PCBs declined by 84.8%. PCB dechlorinators preferred to attack meta- and para-chlorines, principally para-flanked meta and single-flanked para chlorines. A total of 58 dechlorination pathways were observed, and 20 of them were not in 8 processes, suggesting the broad spectrum of PCB dechlorination in the environment. Rare ortho dechlorination was confirmed to target the unflanked ortho chlorine, indicating a potential for complete dechlorination. PCBs drove the shifts of the microbial community structures, and putative dechlorinating bacteria were growth-linked to PCB dechlorination. The distinct jump of RDase genes ardA, rdh12, pcbA4, and pcbA5 was found to be consistent with the commencement of dechlorination. The maintained high level of putative dechlorinating phylum Chloroflexi (including Dehalococcoides and o-17/DF-1), genus Dehalococcoides, and four RDase genes at the end of incubation revealed the long-term dechlorination potential. This work provided insights into dechlorination potential for long-term remediation strategies at PCB-contaminated sites.

Facile synthesis of high iron content activated carbon-supported nanoscale zero-valent iron for enhanced Cr(VI) removal in aqueous solution.

Nanoscale zero-valent iron (nZVI) based materials are considered as one of the most promising in situ remediation materials in the remediation of groundwater contaminated by a variety of pollutants. Supporting nZVI on activated carbon (AC) could reduce the aggregation of nZVI and lead to better utilization during application. The most used method for synthesizing nZVI/AC is liquid-phase reduction synthesis. However, the problem of nZVI shedding during the synthesis remains unsolved. In this study, an improved liquid-phase reduction synthesis method of nZVI/AC was developed. Compared to the conventional method, the improved method could significantly increase the Fe content of the obtain nZVI/AC (from 3.8% to 5.9%) and the utilization of reactant FeSO4·7H2O (from 49% to 77%) easily by changing the addition order and form of reactants, while using the same reaction precursors. The improved method reduced the shedding of nZVI from AC by taking advantage of the different solubility of FeSO4 in ethanol and water, and the different reactivity of NaBH4 in ethanol and water. The characterization results demonstrated that more nZVI was supported to the pores and outer surface of AC. The removal experiments of Cr(VI) (5.0 mg/L) from water showed that the nZVI/AC synthesized using the improved method exhibited better removal efficiency (85.6%) than that of the nZVI/AC synthesized using the conventional method (67.4%). These results suggested that selecting the appropriate solvent and optimizing the synthesis process may greatly improve the performance of nZVI-based materials.

Effects of iron-carbon materials on microbial-catalyzed reductive dechlorination of polychlorinated biphenyls in Taihu Lake sediment microcosms: Enhanced chlorine removal, detoxification and shifts of microbial community.

Nano zero-valent iron particles (nZVI, 0.09 wt%), micro zero-valent iron particles (mZVI, 0.09 wt%), granular activated carbon (GAC, 3.03 wt%), GAC supported nZVI (nZVI/GAC, 3.12 wt%) and nZVI&GAC (nZVI 0.09 wt%, GAC 3.03 wt%) were evaluated for their effects on polychlorinated biphenyls (PCBs) anaerobic reductive dechlorination, detoxification, as well as microbial community structure in Taihu Lake (China) sediment microcosms. The results showed that all of these five materials could stimulate PCBs reductive dechlorination, especially for dioxin-like PCB congeners, and nZVI&GAC had the best removal effect on PCBs. The reduction of total PCBs increased from 13.5% to 33.2%. H2 generated by zero-valent iron corrosion was utilized by organohalide-respiring bacteria (OHRB) to enhance the dechlorination of PCBs predominantly via meta chlorine removal in the short term. The addition of ZVI had little impact on the total bacterial abundance and the microbial community structure. The adsorption of GAC and potential bioremediation properties of attached biofilm could promote the long-term removal of PCBs. GAC, nZVI/GAC, nZVI&GAC had different influences on the microbial structure. These findings provide insights into the biostimulation technique for in situ remediations of PCBs contaminated sediments.

Enhanced removal of sulfamethoxazole and tetracycline in bioretention cells amended with activated carbon and zero-valent iron: System performance and microbial community.

Antibiotics, heavily used as medicine, enter the environment inevitably and raise concerns of the risk to the ecosystems. In this study, we explored the removal efficiency and mechanism of sulfamethoxazole (SMX) and tetracycline (TC) in activated carbon (AC) and AC-zero-valent iron amended bioretention cells (AC-BRC and AC-Fe-BRC) compared with a conventional bioretention cell (BRC). Moreover, the system performance of BRCs, the shifts of the microbial community, as well as the fate of corresponding antibiotic resistance genes (ARGs) were comprehensively investigated. The results showed that, exposed to antibiotics notwithstanding, AC-BRC and AC-Fe-BRC significantly outperformed BRC on total nitrogen (TN) removal (BRC: 70.36 ± 13.61%; AC-BRC: 91.43 ± 6.41%; AC-Fe-BRC: 83.44 ± 12.13%). Greater than 97% of the total phosphorous (TP) was removed in AC-Fe-BRC, remaining unimpacted despite of the selective pressure from SMX/TC. Excellent removals of antibiotics (above 99%) were achieved in AC-BRC and AC-Fe-BRC regardless of the types and initial concentrations (0.8 mg/L, 1.2 mg/L and 1.6 mg/L) of antibiotics, dwarfing the removal performance of BRC (12.2 ± 4.4%-64.2 ± 5.5%). The illumina high throughput sequencing analysis demonstrated the concomitant variations of microbial communities as SMX/TC was loaded. AC layers tended to alleviate the adverse effect of SMX/TC on microbial biodiversity. Proteobacteria (34.55-68.47%), Chloroflexi (7.13-33.54%), and Bacteroidetes (6.20-21.03%) were the top three dominant phyla in the anaerobic zone of the BRCs. The abundance of antibiotic resistance genes (ARGs) sulI, sulII and tetA genes were dramatically higher in AC-BRC and AC-Fe-BRC when exposed to 0.8 mg/L SMX/TC, which indicated that relatively low concentrations of SMX/TC induced the production of these three ARGs in the presence of AC. Although the amendment of AC led to highly efficient SMX/TC removals, further investigation is still required to improve the retention of ARGs in BRCs.

Facile synthesis of oxygen vacancies enriched α-Fe2O3 for peroxymonosulfate activation: A non-radical process for sulfamethoxazole degradation.

Hematite (α-Fe2O3) has been commonly used as an eco-friendly catalyst for peroxymonosulfate (PMS) to generate free radicals (SO4•- and/or •OH). However, the activation efficiency of PMS relies heavily on the conversion of Fe(III) to Fe(II) that is slow and rate-limiting. In this study, oxygen vacancies enriched α-Fe2O3 was prepared from thermally treated goethite (α-FeOOH) and employed as a PMS activator. Systematic characterization demonstrated that α-Fe2O3 with most abundant oxygen vacancies could be obtained by heating α-FeOOH at 300 °C. The as-prepared α-Fe2O3 exhibited excellent catalytic activity in activation of PMS for oxidation of sulfamethoxazole (SMX, k = 0.04 min-1). The SMX degradation rate was found to be positively correlated with the concentration of oxygen vacancies. Quenching experiments, EPR, LC/MS and XPS analysis revealed that singlet oxygen (1O2) was the predominant reactive oxygen species. The effects of pH, PMS dosage, catalyst loading, temperature, and anions on SMX degradation were comprehensively investigated. Moreover, the plausible degradation pathways of SMX in the α-Fe2O3/PMS system were proposed. This work not only provides a valuable insight into the mechanism of PMS activation by α-Fe2O3 but also establishes a new strategy for the design of more efficient and practical iron-based catalyst for PMS activation.

Adsorption of chlorophenols on polyethylene terephthalate microplastics from aqueous environments: Kinetics, mechanisms and influencing factors.

Microplastics have received growing attention as carriers of organic pollutants in the water environment. To better understand the contribution of hydrophobic interaction, hydrogen-bonding interaction, π-π interaction and electrostatic interaction on the adsorption of hydrophilic compounds on microplastics and their adsorption behavior in natural waters, polyethylene terephthalate (PET, <150 µm) was used as an adsorbent and 4-chlorophenol (MCP), 2,4-dichlorophenol (DCP) and 2,4,6-trichlorophenol (TCP) were used as adsorbates. The results of batch adsorption experiments showed that chlorophenols (CPs) reached adsorption sites of PET through film diffusion and intra-particle diffusion. pH greatly affected the adsorption capacity. Hydrophobic interaction was the main adsorption mechanism of undissociated CPs on PET. Hydrogen-bonding interaction was also an adsorption mechanism between undissociated CPs and PET, and the contribution of hydrogen-bonding interaction to adsorption decreased with the increase of chlorine content. Meanwhile, the increase of chlorine content was favorable to the hydrophobic interaction between undissociated CPs and PET. However, higher chlorine content CPs with lower pKa values tended to dissociate at neutral pH condition and resulted in stronger electrostatic repulsion with PET. The increase of solution ionic strength and fulvic acid content negatively affected the adsorption of DCP and TCP on PET, but did not show significant impacts on MCP adsorption. Similarly, the adsorption capacity obtained using Taihu lake water and Bohai seawater as matrices was much lower than that using laboratory water for both DCP and TCP, while the adsorption coefficient (Kd) of MCP remained at approximately 10.6 L/kg to 11.4 L/kg in the three different solution matrices. The Kd values exhibited using natural water matrices consistently followed the order of DCP > MCP > TCP. This study provides insights into the fate of CPs in the presence of microplastics and suggests that the potential risks posed by CPs and microplastics to aqueous ecosystems merit further investigation.

Formation of Cu2O Solid Solution via High-Frequency Electromagnetic Field-Assisted Ball Milling: The Reaction Mechanism.

The contamination of environmental water with organic pollutants poses significant challenges for society, and much effort has been directed toward the development of catalysts and methods that can decompose these pollutants. While effort has been directed toward the fabrication of Cu2O catalysts by ball milling, this technique can involve long preparation times and provide low yields. In this study, we synthesized a solid solution of Cu2O in 22 h by high-frequency electric-field-assisted ball milling below 40 °C in only one step under aqueous conditions. We investigated the catalytic activities of the produced Cu2O solid solution in the microwave-assisted degradation of dyes, namely rhodamine B, phenol red and methyl orange. The prepared Cu2O solid solution was very catalytically active and completely degraded the above-mentioned dyes within 2 min. The one-dimensional diffusion model and the phase boundary (planar) model were found to describe the kinetics well. Synergism between ball milling and the high-frequency electromagnetic field plays a key role in the preparation of Cu2O solid solution nanoparticles. Ball milling facilitates the relaxation of the Cu2O lattice and high-frequency electromagnetic radiation accelerates the diffusion of Fe atoms into the Cu2O crystal along the (111) crystal plane, quickly leading to the formation of a Cu2O solid solution.

Preparation of FeOOH/Cu with High Catalytic Activity for Degradation of Organic Dyes.

In this study, high-frequency electromagnetic-assisted ball-milling was used to prepare FeOOH/Cu catalyst. The combined effect of the high-frequency electromagnetic field and ball-milling resulted in the complete conversion of raw materials into FeOOH/Cu nanomagnetic hybrid at ~40 °C in only 30 h. Experiments showed that Rhodamine B was completely degraded within only 3 min, which was much faster than with previously reported catalysts. The combination effect of ball milling and microwave afforded excellent catalytic activity. Furthermore, the produced catalyst could be recovered easily using an external magnetic field for reuse. The influence of pH on the catalytic activity for degrading Rhodamine B, Phenol Red, Methyl Orange, and Methylene Blue were also investigated; Rhodamine B was completely degraded at pH 9 within only 2 min.

Enhanced heterogeneous Fenton-like degradation of methylene blue by reduced CuFe2O4.

To facilitate rapid dye removal in oxidation processes, copper ferrite (CuFe2O4) was isothermally reduced in a H2 flow and used as a magnetically separable catalyst for activation of hydrogen peroxide (H2O2). The physicochemical properties of the reduced CuFe2O4 were characterized with several techniques, including transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and magnetometry. In the catalytic experiments, reduced CuFe2O4 showed superior catalytic activity compared to raw CuFe2O4 for the removal of methylene blue (MB) due to its relatively high surface area and loading Fe0/Cu0 bimetallic particles. A limited amount of metal ions leached from the reduced CuFe2O4 and these leached ions could act as homogeneous Fenton catalysts in MB degradation. The effects of experimental parameters such as pH, catalyst dosage and H2O2 concentration were investigated. Free radical inhibition experiments and electron spin resonance (ESR) spectroscopy revealed that the main reactive species was hydroxyl radical (˙OH). Moreover, reduced CuFe2O4 could be easily separated by using an external magnet after the reaction and remained good activity after being recycled five times, demonstrating its promising long-term application in the treatment of dye wastewater.

Simultaneous removal of tetracycline and Cu(ii) by adsorption and coadsorption using oxidized activated carbon.

Co-contamination of antibiotics and heavy metals prevails in the environment. To overcome the obstacle of low metal uptake on activated carbon and to achieve simultaneous removal of tetracycline (TC) and Cu(ii) from water, coconut shell based granular activated carbon (GAC) treated with nitric acid was utilized. GAC property characterization showed that oxidation treatment distinctly decreased the surface area of GAC and significantly increased the content of oxygen containing functional groups. The oxidized GAC exhibited greater adsorption capacity for individual TC and Cu(ii). Kinetics studies demonstrated that although the overall removal rate of coexisting TC and Cu(ii) decreased, the ultimate removal efficiency was further enhanced in the binary system. The adsorption isotherms were well described by Langmuir and Freundlich models. Moreover, the maximum adsorption capacities of coexisting TC and Cu(ii) with oxidized GAC kept increasing within a pH range of 3.0-6.0, indicating an electrostatic repulsion mechanism as well as a competition for adsorption sites. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis revealed that the enhanced removal of TC and Cu(ii) was very likely as a result of coadsorption by forming TC-Cu(ii) complexes bridging between the adsorbate and the adsorbent.

Adsorption of anionic and cationic dyes on ferromagnetic ordered mesoporous carbon from aqueous solution: equilibrium, thermodynamic and kinetics.

Ordered mesoporous carbon (Fe-CMK-3) with iron magnetic nanoparticles was prepared by a casting process via SBA-15 silica as template and anthracene as carbon source, was used as a magnetic adsorbent for the removal of anionic dye Orange II (O II) and cationic dye methylene blue (MB) from aqueous solution. TEM and magnetometer images showed that the iron magnetic nanoparticles were successfully embedded in the interior of the mesoporous carbon. The effect of various process parameters such as temperature (25-45°C), initial concentration (100-500 mg L(-1)) and pH (2-12) were performed. Equilibrium adsorption isotherms and kinetics were also studied. The equilibrium experimental data were analyzed by the Langmuir, Freundlich, Temkin and Redlich-Peterson model. The equilibrium data for two dyes adsorption was fitted to the Langmuir, and the maximum monolayer adsorption capacity for O II and MB dyes were 269 and 316 mg g(-1), respectively. Pseudo-first-order and pseudo-second-order kinetic and intraparticle diffusion model were used to evaluate the adsorption kinetic data. The kinetic data of two dyes could be better described by the pseudo second-order model. Thermodynamic data of the adsorption process were also obtained. It was found that the adsorption process of the two dyes were spontaneous and exothermic.