Intermolecular interactions in mixed dye systems and the effects on dye wastewater treatment processes.

Dye wastewater discharge is a critical concern across textiles, paper, cosmetics, and other industries. This study explores the impact of dye-dye interactions on chemical coagulation and ultrafiltration process. Using basic and reactive dyes, representing cationic and anionic compounds, the intricate interplay between these dyes was examined through spectroscopic analysis. Remarkably, interactions between dyes of opposite charges exhibited significant effects on both techniques. Electrostatic attractions played a key role. Positive coagulant hydrolysates selectively attracted negative dyes, while negatively charged membranes effectively captured positive dyes. Combining dyes with opposite charges resulted in enhanced removal efficiency, addressing challenging dyes collectively. This discovery offers a novel approach to improving dye removal, utilizing opposite-charged dye mixtures can tackle stubborn dyes unmanageable by conventional methods.

Boosting Charge Transport and Catalytic Performance in MoS2 by Zn2+ Intercalation Engineering for Lithium-Sulfur Batteries.

Transition metal dichalcogenides (TMDs) have been widely studied as catalysts for lithium-sulfur batteries due to their good catalytic properties. However, their poor electronic conductivity leads to slow sulfur reduction reactions. Herein, a simple Zn2+ intercalation strategy was proposed to promote the phase transition from semiconducting 2H-phase to metallic 1T-phase of MoS2. Furthermore, the Zn2+ between layers can expand the interlayer spacing of MoS2 and serve as a charge transfer bridge to promote longitudinal transport along the c-axis of electrons. DFT calculations further prove that Zn-MoS2 possesses better charge transfer ability and stronger adsorption capacity. At the same time, Zn-MoS2 exhibits excellent redox electrocatalytic performance for the conversion and decomposition of polysulfides. As expected, the lithium-sulfur battery using Zn0.12MoS2-carbon nanofibers (CNFs) as the cathode has high specific capacity (1325 mAh g-1 at 0.1 C), excellent rate performance (698 mAh g-1 at 3 C), and outstanding cycle performance (it remains 604 mAh g-1 after 700 cycles with a decay rate of 0.045% per cycle). This study provides valuable insights for improving electrocatalytic performance of lithium-sulfur batteries.

Comparative Investigation of the Microstructure of MgCl2 Aqueous Solutions Using Different X-ray Scattering Sources, Raman Spectroscopy, and Atomistic Simulations.

Aqueous solutions of magnesium chloride (MgCl2(aq)) are often used to test advances in the theory of electrolyte solutions because they are considered an ideal strong 2:1 electrolyte. However, there is evidence that some ion association occurs in these solutions, even at low concentrations. Even a small ion-pairing constant can have a significant impact on the chemical speciation of ions, so it is important to determine whether ion pairing actually occurs. In this study, MgCl2(aq) with concentrations ranging from 1 to 35% was studied using three methods: X-ray scattering (XRS) with the Shanghai Synchrotron Radiation Facility (SSRF) and silver-anode laboratory sources, Raman spectroscopy, and molecular dynamics (MD) simulations with the COMPASS-II and Madrid force fields. XRS results were analyzed in the framework of PDF theory to obtain the reduced structure function F(Q) and the reduced pair distribution function G(r). The F(Q) values from synchrotron radiation and laboratory sources both showed that the tetrahedral hydrogen bonds in bulk water were destroyed with the increased MgCl2 concentration. The results of G(r) indicated that the main peaks centered at 2.05 and 2.80 Å can be ascribed to the interactions of Mg-O and O-O, respectively. The peak at 3.10 Å is attributed to the combined effect of O-O and Cl-O. By comparing the structural information on MgCl2 solution obtained from the two light sources, it was found that both SSRF and silver-anode laboratory sources can reflect the above-mentioned structural information on MgCl2 solution. The radial distribution function (RDF) obtained from MD simulations of MgCl2 solutions assigned the peaks at 2.0, 2.8, and 3.2 Å to the Mg-O, O-O, and Cl-O interatomic pairs, respectively. The decrease in the O-O coordination number confirms that the hydrogen-bonding network of water is disrupted by increasing MgCl2 observed by X-ray scattering. The proportion of Mg-Cl contact ion pairs gradually increases with MgCl2 concentration as does the coordination number. Raman spectroscopy results show that the bond type changes from double donor double acceptor (DDAA) to single donor-single acceptor (DA) with increasing concentration, providing explicit details of the hydrogen-bond evolution in the aqueous solution.

Efficiently Removing Heavy Metals from High-Salinity Wastewater via Ionic Liquid-Based Aqueous Biphasic Systems.

For the separation of metal ions, ionic liquid-based aqueous biphasic systems (IL-ABSs) offer a promising alternative to solvent extraction. However, the incorporation of an extensive quantity of inorganic salts restricts their practical application. Because heavy metal wastewater often contains high concentrations of inorganic salts, it offers good prospects for the application of IL-ABSs in the separation of heavy metals. In this work, an IL-ABS was formed by tributyltetradecylphosphonium chloride ([P44414]Cl), and simulated high-salinity wastewater (NaCl and Na2SO4 as the main inorganic salts) was used for the separation of heavy metals. The phase diagram results indicated that the formation of a two-phase system required a relatively high salt concentration. The extraction process followed the mechanism of anion exchange; thus, heavy metals such as zinc and cadmium that formed complexes with chloride ions could be effectively extracted (extraction rate >99.5%) with a very fast rate (extraction time <1 min) at a wide pH range (pH = 2-7). After extraction, the metals could be stripped well (stripping rate >99.5%) after contact with the NaOH solution. This research provided a new approach for treating heavy metals in high-salinity effluents, which has the advantages of IL-ABS and avoids the disadvantages of adding large amounts of inorganic salts at the same time.

Application of bipolar membrane electrodialysis for simultaneous recovery of high-value acid/alkali from saline wastewater: An in-depth review.

With the development of comprehensive utilization of high-salinity wastewater, salt resources regeneration has been considered as the fundamental requirement for process sustainability and economic benefits. As one of the potential candidates, bipolar membrane electrodialysis (BMED) was rapidly developed in recent years for the treatment of saline wastewater. Different from other methods directly obtaining salts or condensed wastewater, BMED could utilize and convert the dissolved waste salt into higher-value acid and alkali simultaneously, which has various advantages including outstanding environmental effects and economic benefits. In this review, the recent applications of BMED for waste salt recovery and high-value acid/alkali generation from saline wastewater were systematically outlined. Based on the summary above, the economy analysis of BMED was further reviewed from the roles of desalination and resources recovery. In addition, the BMED-based processes integrated with in-situ utilization of the generated acid/alkali resources were discussed. Furthermore, the influence of operating factors on BMED performance were outlined. Finally, the strategies for improving BMED performance were concluded. Furthermore, the future application and prospects of BMED was presented. This work would provide guidance for the applications of bipolar membrane electrodialysis in saline wastewater treatment and the high-value conversion of salt resources into acids and alkalis.

Study on the Structure of a Mixed KCl and K2SO4 Aqueous Solution Using a Modified X-ray Scattering Device, Raman Spectroscopy, and Molecular Dynamics Simulation.

The microstructure of a mixed KCl and K2SO4 aqueous solution was studied using X-ray scattering (XRS), Raman spectroscopy, and molecular dynamics simulation (MD). Reduced structure functions [F(Q)], reduced pair distribution functions [G(r)], Raman spectrum, and pair distribution functions (PDF) were obtained. The XRS results show that the main peak (r = 2.81 Å) of G(r) shifted to the right of the axis (r = 3.15 Å) with increased KCl and decreased K2SO4. The main peak was at r = 3.15 Å when the KCl concentration was 26.00% and the K2SO4 concentration was 0.00%. It is speculated that this phenomenon was caused by the main interaction changing, from K-OW (r = 2.80 Å) and OW-OW (r = 2.80 Å), to Cl−-OW (r = 3.14 Å) and K+-Cl− (r = 3.15 Å). According to the trend of the hydrogen bond structure in the Raman spectrum, when the concentration of KCl was high and K2SO4 was low, the destruction of the tetrahedral hydrogen bond network in the solution was more serious. This shows that the destruction strength of the anion to the hydrogen bond network structure in solution was Cl− > SO42−. In the MD simulations, the coordination number of OW-OW decreased with increasing KCl concentration, indicating that the tetrahedral hydrogen bond network was severely disrupted, which confirmed the results of the Raman spectroscopy. The hydration radius and coordination number of SO42− in the mixed solution were larger than Cl−, thus revealing the reason why the solubility of KCl in water was greater than that of K2SO4 at room temperature.

Carbon dioxide capture coupled with magnesium utilization from seawater by bipolar membrane electrodialysis.

Carbon dioxide (CO2) capture coupled with further mineralization in high value-added form is a great challenge for carbon capture utilization and storage (CCUS) processes. In this work, a bipolar membrane electrodialysis (BMED) technique integrated with crystallization chamber was proposed to utilize CO2-derived carbonates and the residual magnesium resource from seawater to produce functional nesquehonite. To ensure the stable CO2 storage and magnesium extraction by BMED process, the metastable zone during nesquehonite crystallizing was first measured to modulate crystallization rate, obtain high-quality crystal products and inhibit membrane fouling states. Subsequently, the effects of current density, temperature, and CO2 flow rate during the whole BMED-crystallization process were further investigated. The increase in current density and temperature was conducive for the extraction of magnesium while the enlarged gas flow rate induced higher absorption of CO2. Under the current density at 22 A/m2, CO2 flow rate at 50 mL/min and temperature at 30 °C, the optimal carbon absorption ratio and the magnesium extraction ratio reached 50.85% and 56.71%, respectively. Under this condition, the explosion nucleation of the nesquehonite was effectively avoided to inhibit membrane fouling and the generation of magnesium hydroxide was depressed to obtain the target product nesquehonite. This study on simultaneous carbon capture and magnesium utilization provides theoretical guidance for the industrial green storage of CO2 and development of valuable magnesium products.

Response of salinity gradient power generation to inflow mode and temperature difference by reverse electrodialysis.

Sustainable utilization has been becoming the core idea of concentrated seawater disposal, which makes the harvest of salinity gradient power based on reverse electrodialysis (RED) become one of the important ways. As the important factors affecting RED performance, different flow orientations along the membrane and solution temperature have been studied in the previous researches. However, there are still some details that need to be clarified. In this study, the inflow mode was further detailed investigated. The results showed that after eliminating the interference of bubbles in the counter-current, the co-current was still better than the counter-current; when the solution of HCC (high concentration compartment) and LCC (low concentration compartment) was circulated for 3 h, the concentration of concentrated seawater discharge liquid was reduced by 6.93%, which was conducive to reducing the negative impact on the marine ecological environment. Meanwhile, the response of salinity gradient power generation to temperature difference was that high temperature had a positive effect on power density, and the order was both the HCC and LCC (0.44 W m-2) > LCC (0.42 W m-2) > HCC (0.39 W m-2). Although the RED performance was more sensitive to the temperature rise of LCC, the positive temperature difference between HCC and LCC is a more practical advantage because the temperature of concentrated seawater in HCC is usually high. These new observations could provide supports for the industrial development of RED in generating electricity economically and reducing the negative environmental impact of concentrated seawater.

ZnO/Cu2O/g-C3N4 heterojunctions with enhanced photocatalytic activity for removal of hazardous antibiotics.

In view of the environmental pollution caused by antibiotics, the creation of an efficient photocatalytic material is an effectual way to carry out water remediation. Herein, we developed a smart strategy to synthesize ZnO/Cu2O/g-C3N4 heterojunction photocatalysts for the photodegradation of hazardous antibiotics by one-pot synthesis method. In this system, the Cu2O nanoparticles with electrons reducing capacity were coupled with g-C3N4 composites. The photocarriers were generated from the electric field of type Ⅰ heterojunction between ZnO and g-C3N4 and type Ⅱ heterojunction between Cu2O and g-C3N4. ZnO as a co-catalyst was doped to Cu2O/g-C3N4 catalyst system for removal of broad-spectrum antibiotics with the condition of visible light to protect Cu2O from photocorrosion, which thereby accelerated photocatalytic reactivity. Benefiting by new p-n-n heterojunction, the resulting ZnO/Cu2O/g-C3N4 composites had an excellent degradation performance of broad-spectrum antibiotics such as tetracycline (TC), chlortetracycline (CTC), oxytetracycline (OTC) and ciprofloxacin (CIP), the degradation of which were 98.79%, 99.5%, 95.35% and 73.53%. In particular, ZnO/Cu2O/g-C3N4 photocatalysts showed a very high degradation rate of 98.79% for TC in first 30 min under visible light, which was 1.35 and 10.62 times higher than that of Cu2O/g-C3N4 and g-C3N4, respectively. This work gives a fresh visual aspect for simultaneously solving the instability deficiencies of traditional photocatalysts and improving photocatalytic performance.

A comparative dynamic study of seawater pretreatment using experimental and pilot bubble tower.

In the previous study, greenhouse gas CO2 was successfully used as the precipitator to realize its carbonation by calcium ions in seawater with the help of magnesium oxide. In this study, the reaction process was firstly analyzed by a proposed reaction mechanism, and then the dynamic simulation of the gas-liquid-solid system was carried out via kinetic Monte Carlo simulation. Based on the reaction mechanism, the continuous experimental study was realized in a bubble column. The effects of air flow rate, carbon dioxide flow rate and temperature on the effectiveness evaluation indexes of decalcification efficiency, total mass transfer coefficient and carbon sequestration rate were studied. Finally, a bonnet tower with a diameter of 1 m and a height of 8 m was built to carry out the pilot test. In the laboratory experiments, the calcium removal rate reached 94%, the carbon sequestration rate reached 63.6%, and pure micron calcium carbonate products were obtained. The decalcification rate reached 95% in the pilot test, which is consistent with the results of the laboratory experiment.

Effective treatment of levofloxacin wastewater by an electro-Fenton process with hydrothermal-activated graphite felt as cathode.

The performance of the cathode significantly affects the ability of the electro-Fenton (EF) process to degrade chemicals. In this study, a simple method to modify the graphite felt (GF) cathode was proposed, i.e. oxidizing GF by hydrothermal treatment in nitric acid. The surface physical and electrochemical properties of modified graphite felt were characterized by several techniques: scanning electron microscope (SEM), water contact angle, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and linear scanning voltammetry (LSV). Compared with an unmodified GF (GF-0), the oxygen reduction reaction (ORR) activity of a modified GF was significantly improved due to the introduction of more oxygen-containing functional groups (OGs). Furthermore, the results showed that GF was optimally modified after 9 h (GF-9) of treatment. As an example, the H2O2 generation by GF-9 was 2.26 times higher than that of GF-0. After optimizing the process parameters, which include the initial Fe2+ concentration and current density, the apparent degradation rate constant of levofloxacin (LEV) could reach as high as 0.40 min-1. Moreover, the total organic carbon (TOC) removal rate and mineralization current efficiency (MCE) of the modified cathode were much higher than that of the GF-0. Conclusively, GF-9 is a promising cathode for the future development in organic pollutant removal via EF.

The Influence of Materials, Heterostructure, and Orientation for Nanohybrids on Photocatalytic Activity.

In this work, different structures based on electrodeposited n-type ZnO nanorods and p-type Cu2O, CuSCN, and NiO nanostructures are fabricated for the degradation of methyl orange (MO). The influence of materials, heterostructure, and orientation for nanohybrids on photocatalytic activity is discussed for the first time. The heterojunction structures show remarkable enhancement compared to the bare semiconductor. The morphology of nanostructure has mainly an influence on the photocatalytic activity. NiO has the highest catalytic activity among the four pristine semiconductor nanostructures of ZnO, Cu2O, CuSCN, and NiO. The greatest enhancement of the photocatalytic activity is obtained using a ZnO/NiO (1 min) heterostructure attributed to the heterojunction structure and extremely higher specific surface area, which can degrade MO (20 mg/L) into colorless within 20 min with the fastest photocatalytic speed among homogeneous heterojunction structures. Meanwhile, the methodology and data analysis described herein will serve as an effective approach for the design of hybrid nanostructures for solar energy application, and the appropriate nanohybrids will have significant potential to solve the environment and energy issues.

Local structures and the dissolving behavior of aqueous ammonia and its KCl and NH4Cl solutions: A Raman spectroscopy and X-ray scattering study.

The aqueous ammonia (5%-15%) and its KCl and NH4Cl solutions have been studied by Raman spectroscopy and X-ray scattering. The microscopic structures in these solutions were proposed. The addition of KCl reinforced the hydrogen bond between NH3 and H2O. On contrary, NH4Cl destroyed this interaction by forming hydrogen bond NH4(+)-NH3. This study gave an interpretation of the different dissolving behavior of KCl and NH4Cl in aqueous ammonia, which may have important implications in the separation of potassium and ammonium salt during the industrial production.

Removal of ammonium from wastewater using calcium form clinoptilolite.

The paper concerns the removal of ammonium ions from aqueous solution using a modified clinoptilolite-Ca(2+)-formed clinoptilolite (CaY) prepared from natural clinoptilolite. The batch study results show that the pH has an effect on ammonium adsorption capacity as it can influence both the character of the exchanging ions and the clinoptilolite itself; the CaY has a high selectivity to NH(4)(+) and the exchange decreases with increasing temperature; ammonium ion uptake onto CaY was suitably described by the Langmuir model. The column results indicated that the effluent of simulated wastewater treated with CaY could meet the integrated wastewater discharge standard of China, and CaY can be circulated through regenerating by Ca(OH)(2).