The Defects, Physicochemical Properties, and Surface Charge of MIL-88A (Al) Crystal Were Regulated for Highly Efficient Removal of Anionic Dyes: Preparation, Characterization, and Adsorption Mechanism.

In this paper, the physicochemical properties, surface charge, and crystal defects of MIL-88A (Al) were controlled by adjusting the ratio of metal ligands and temperature in the synthetic system without the addition of surfactants. The adsorption properties of different crystals for Congo red (CR) were studied. Among them, MIL-88A (Al)-130 and MIL-88A (Al)-d have the best adsorption properties. The maximum adsorption capacities are 600.8 and 1167 mg · g-1, respectively. Compared with MIL-88A (Al)-130, the adsorption performance of MIL-88A (Al)-d was increased by 94.2%, and the adsorption rate was increased by about 4 times. It can be seen that increasing the proportion of metal ligands within a certain range will improve the adsorption capacity. The structure and morphology of the adsorbent were characterized by XRD, FTIR, SEM, EDS, TGA, BET, and zeta potential. The effects of time, temperature, pH, initial solution concentration, and dosage on CR adsorption properties were systematically discussed. The pseudo-second-order kinetic model and Langmuir isothermal model can well describe the adsorption process, which indicates that the adsorption process is a single-layer chemisorption occurring on a uniform surface. According to thermodynamics, this adsorption is an endothermic process. The mechanism of CR removal is proposed as the electrostatic attraction, hydrogen bond, metal coordination effect, π-π conjugation, crystal defect, and pore-filling effect. In addition, MIL-88A (Al)-d has good repeatability, indicating that it is a good material for treating anionic dye wastewater.

Polydopamine coating for enhanced electrostatic adsorption of methylene blue by multiwalled carbon nanotubes in alkaline environments.

The removal of dye molecules in alkaline environments is an issue that should receive increased attention. In this study, the interaction mechanism between polydopamine-modified multiwalled carbon nanotubes (P-MWCNTs) and multiwalled carbon nanotubes (MWCNTs) with the cationic dye methylene blue (MB) in alkaline environments was explained in depth by adsorption, spectroscopy, and density functional theory (DFT). The mechanism of action and dominant forces between the adsorbent and adsorbate were analyzed graphically by introducing energy decomposition analysis (EDA) and an independent gradient model (IGM) into the DFT calculations. In addition, the force distribution was investigated through an isosurface. Moreover, batch adsorption studies were conducted to evaluate the performance of MWCNTs and P-MWCNTs for MB removal in alkaline environments. The maximum MB adsorption capacities of the MWCNTs and P-MWCNTs in solution were 113.3 mg‧g-1 and 230.4 mg‧g-1, respectively, at pH 9. The IGM and EDA showed that the better adsorption capacity of the P-MWCNTs originated from the enhancement of the electrostatic effect by the proton dissociation of polydopamine. Moreover, the adsorption of MB by MWCNTs and P-MWCNTs in alkaline environments was governed by dispersion and electrostatic effects, respectively. Through this study, it is hoped that progress will be made in the use of DFT to explore the mechanism of adsorbent-adsorbate interactions.

High-efficient removal of anionic dye from aqueous solution using metal-organic frameworks@chitosan aerogel rich in benzene structure.

With the exponentially increase of dye pollutants, the purification of dye wastewater has been an urgent ecological problem. As a novel type of porous adsorbent, metal-organic frameworks still face challenges in recyclability, agglomeration, and environmentally unfriendly synthesis. Herein, MOF-525 was in-situ growth onto the surface of the chitosan (CS) beads to fabricate MOF-525@CS aerogel. CS was utilized as substrate to uniformly disperse MOF-525, thereby significantly mitigating agglomeration and improving recyclability of MOF-525. The characterization results shown that MOF-525@CS aerogel had a high specific surface area of 103.0 m2·g-1, and MOF-525 was uniformly distributed in the 3D porous structure of CS, and the presence of benzoic acid was detected. The MOF-525@CS aerogel had a remarkable adsorption capacity of 1947 mg·g-1 for Congo red, which is greater than the sum of its parts. MOF-525@CS aerogel also inherited the rapid adsorption ability of MOF-525, removing 80 % of Congo red within 600 min. Such excellent adsorption performance can be attributed to the benzoic acid trapped by CS via CN band to enhance the π-π stacking interactions. Additionally, the utilization of benzoic acid makes the synthesis process of MOF-525@CS aerogel more environmentally friendly. The high-efficient MOF-525@CS aerogel is a competitive candidate for dye pollution adsorption.

Efficient adsorption of radioactive iodine by covalent organic framework/chitosan aerogel.

Radioactive iodine is considered one of the most dangerous radioactive elements in nuclear waste. Therefore, effective capture of radioactive iodine is essential for developing and using nuclear energy to solve the energy crisis. Some materials that have been developed for removing radioactive iodine still suffer from complex synthesis, low removal capacity, and non-reusability. Herein, covalent organic framework (COF)/chitosan (CS) aerogels were prepared using vacuum freeze-drying, and the COF nanoparticles were tightly attached on the green biomass material CS networks. Due to the synergistic effect of both COF and CS, the composite aerogel shows a three-dimensional porous and stable structure in the recycle usage. The COF/CS aerogel exhibits excellent iodine adsorption capacity of 2211.58 mg g-1 and 5.62 g g-1 for static iodine solution and iodine vapor, respectively, better than some common adsorbents. Furthermore, COF/CS aerogel demonstrated good recyclability performance with 87 % of the initial adsorption capacity after 5 cycles. In addition, the interaction between iodine and imine groups, amino groups, and benzene rings of aerogel are the possible adsorption mechanisms. COF/CS aerogel has excellent adsorption properties, good chemical stability, and reusable performance, which is a potential and efficient adsorbent for industrial radioactive iodine adsorption from nuclear waste.

Porous metal-organic framework-acrylamide-chitosan composite aerogels: Preparation, characterization and adsorption mechanism of azo anionic dyes adsorbed from water.

Micro- and nano-metal-organic frameworks with different adsorption properties were prepared by a time-modulation hydrothermal method. By comparing the adsorption properties, the most effective MIL-68(Fe)-12 was selected to be mixed with chitosan (CS), and porous metal-organic framework-acrylamide-chitosan composite aerogel (PMACA) was prepared by introducing acrylamide prior to glutaraldehyde crosslinking. The adsorption capacity of PMACA doped with acrylamide was as high as 2086.44 mg·g-1. The adsorption performance of PMACA was 1.48 times higher compared to the porous metal-organic framework-chitosan composite aerogel (PMCA) undoped with acrylamide. With the introduction of acrylamide, the stability of PMACA was improved, making it less prone to dispersion and decomposition. Structural characterization and adsorption properties were analyzed using methods such as XRD, FTIR, TGA, SEM, BET, and Zeta potential. The adsorption performance of PMACA was investigated further through batch tests with variables such as adsorbent dosage, pH, contact time, initial CR solution concentration, and temperature. The model fitting of PMACA was consistent with the pseudo-second-order model and the Sips model. The adsorption thermodynamics showed that high temperature promoted spontaneous adsorption behavior. PMACA showed a recovery rate of approximately 86 % after six cyclic adsorption tests. PMACA maintained a recovery rate of roughly 86 % after six cyclic adsorption tests. The combined effects of electrostatic attraction, hydrogen bonding, and π-π conjugation resulted in excellent adsorption performance, while pore filling also contributed to the efficient adsorption of Congo red (CR).

Green preparation of magnetic ferroferric oxide-polyvinyl alcohol-alginate coated UiO-67 nanospheres: Characterization, adsorption properties and adsorption mechanism of methylene blue.

In this paper, a kind of magnetic ferric oxide/polyvinyl alcohol/calcium alginate/UiO-67 (Fe3O4/PVA/CA/UiO-67) nanospheres with homogeneous surface interconnecting structures was prepared by using macromolecular polymer polyvinyl alcohol and sodium alginate as carriers and zirconium organic skeleton as nanocrystals. The properties of magnetic nanospheres were studied by SEM, FT-IR, TGA, XRD, BET, VSM and Zeta potential. The impression of diverse temperatures, MB concentrations, interaction time, pH, and magnetic aerogel sphere dose on MB removal was studied. The optimum adsorption temperature and pH of magnetic nanospheres for MB were 298 K, and 10, respectively. Langmuir simulated that the maximum removal of MB by magnetic nanospheres at room temperature (298 K) was 1371.8 mg/g. The removal of MB by magnetic nanospheres complied with the pseudo-first-order kinetic model. The isotherm simulation can infer that the Langmuir model was more comply with MB adsorption on magnetic aerogel spheres. Thermodynamic studies have confirmed that the removal of MB by magnetic nanospheres was exothermic and spontaneous. The interaction mechanism of MB on magnetic nanospheres can be deduced by FT-IR and BET, including hydrogen bond, π-π bond, electrostatic interaction, and mesoporous pore flow. The removal rate of nanospheres for MB still reached 70.06 % after six cycles.

Efficient adsorption of methylene blue in water by nitro-functionalized metal-organic skeleton­calcium alginate composite aerogel.

This paper presents the first investigation of the adsorption performance of methylene blue by the nitro-functionalized metal-organic framework (MIL-88B-NO2). MIL-88B-NO2 has a specific surface area of 836.0 m2/g, which is 109.8 % higher than MIL-88B. The maximum adsorption capacity of methylene blue is 383.6 mg/g, which is 68.2 % higher than that of MIL-88B. This phenomenon can be attributed to the great increase in specific surface area and the introduction of nitro-functional groups. However, its microcrystalline nature makes it difficult to remove in practical applications and quickly causes secondary pollution. Therefore, the composite of MIL-88B-NO2 and calcium alginate (CA) to form aerogel maintains the inherent properties of the two materials and makes it easy to recycle. The utmost adsorption capability of MIL-88B-NO2/CA-2 aerogel is 721.0 mg/g. Compared with MIL-88B-NO2, the adsorption performance of MIL-88B-NO2/CA-2 aerogel is further improved by 88.0 %. The higher adsorption capacity of the adsorbent may be due to the synergistic interplay of electrostatic attraction, π-π conjugation, hydrogen bonding, metal coordination effect, and physicochemical properties. Also, MIL-88B-NO2/CA-2 aerogel has good recyclability, indicating that it has broad application prospects in the removal of positive dyes in contaminated water.

Removal of Methylene Blue Dye from Aqueous Solutions by Pullulan Polysaccharide/Polyacrylamide/Activated Carbon Complex Hydrogel Adsorption.

In this study, composite hydrogels were prepared using a simple synthetic technique to adsorb methylene blue (MB) from water. The hydrogel comprised potassium persulfate (KPS) as the initiator, N,N'-methylene bisacrylamide as the crosslinking agent, and sodium hydroxide (NaOH) as the activator. It was employed to adsorb MB at different concentrations from water. The morphology and properties of PUL/PAM/GO composites were characterized through thermogravimetric analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. Moreover, the adsorption properties, adsorption isotherms, adsorption kinetics, adsorption thermodynamics, and swelling properties of the hydrogel for MB were investigated. The optimal ratio of PUL to AC was obtained as 6:1 by fixing the amount of PUL and loading AC of different masses. The maximum adsorption capacity was obtained as 591.4 mg/g. It also exhibited certain mechanical strength. The adsorption of MB conforms to pseudo-first-order kinetics and Langmuir isotherms. In this study, an environment-friendly, cheap, simple, and efficient way was presented for the composite hydrogel in the direction of water treatment.

Enhanced methylene blue adsorption using zirconate alginate/graphene oxide/UiO-67 aerogel spheres: Synthesis, characterization, kinetic studies, and adsorption mechanisms.

Zirconium alginate/graphene oxide (ZA/GO) hydrogel spheres were prepared by crosslinking sodium alginate and GO with Zr4+. Then Zr4+ on the surface of the ZA/GO substrate acted as the metal nucleation site of the UiO-67 crystal and interacted with the organic ligand biphenyl 4-4'-dicarboxylic acid (BPDC) to make UiO-67 grow in situ on the surface of the ZA/GO hydrogel sphere by the hydrothermal method. The BET surface areas of ZA/GO, ZA/UiO-67, and ZA/GO/UiO-67 aerogel spheres were 1.29, 47.71, and 89.33 m2/g respectively. The maximum adsorption capacities of ZA/GO, ZA/UiO-67, and ZA/GO/UiO-67 aerogel spheres for methylene blue (MB) at room temperature (298 K) were 145.08, 307.49, and 1105.23 mg/g respectively. The kinetic analysis showed that the adsorption process of MB on the ZA/GO/UiO-67 aerogel sphere was consistent with the pseudo-first-order kinetic model. Isotherm analysis showed that MB was adsorbed on ZA/GO/UiO-67 aerogel spheres as a single layer. Thermodynamic analysis showed that the adsorption process of MB on the ZA/GO/UiO-67 aerogel sphere was exothermic and spontaneous. Adsorption of MB on ZA/GO/UiO-67 aerogel spheres is mainly dependent on π-π bond, electrostatic interaction, and hydrogen bond. After 8 cycles, ZA/GO/UiO-67 aerogel spheres still showed high adsorption performance and good reuse ability.

Efficient adsorption of Congo red by micro/nano MIL-88A (Fe, Al, Fe-Al)/chitosan composite sponge: Preparation, characterization, and adsorption mechanism.

MIL-88A crystals with three different metal ligands (Fe, Al, FeAl) were prepared by hydrothermal method for the first time. The three materials' crystal structure and surface morphology are different, leading to different adsorption properties of Congo red (CR). The maximum adsorption capacities of MIL-88A (Fe), MIL-88A (FeAl), and MIL-88A (Al) are 607.7 mg · g-1, 536.4 mg · g-1, and 512.1 mg · g-1 respectively. In addition, MIL-88A was combined with chitosan (CS) respectively, and MIL-88A/CS composite sponge was prepared by the freeze-drying method, which not only solved the defect that MIL-88A powder was difficult to recover but also further improved the removal ability of CR by the adsorbent. The maximum adsorption capacities of MIL-88A (FeAl)/CS, MIL-88A (Fe)/CS, MIL-88A (Al)/CS, and CS are 1312 mg · g-1, 1056 mg · g-1, 996.7 mg · g-1, and 769.6 mg · g-1, respectively. The structure and physicochemical properties of the materials were analyzed by SEM, FTIR, XRD, TGA, BET, and Zeta. The adsorption process of CR follows pseudo-second-order kinetics and Langmuir, Sips isotherm model. Combined with thermodynamic parameters, the adsorption behavior was described as endothermic monomolecular chemical adsorption. The removal of CR is attributed to electrostatic interactions, hydrogen bonding, metal coordination effects, and size-matching effects.

Simple synthesis of chitosan/alginate/graphene oxide/UiO-67 amphoteric aerogels: Characterization, adsorption mechanism and application for removal of cationic and anionic dyes from complex dye media.

A chitosan/alginate/graphene oxide/UiO-67 (CS/SA/GO/UiO-67) amphoteric aerogel was synthesized successfully. A series of characterization experiments of CS/SA/GO/UiO-67 amphoteric aerogel was performed by SEM, EDS, FT-IR, TGA, XRD, BET, and zeta potential. The competitive adsorption properties of different adsorbents for complex dyes wastewater (MB and CR) at room temperature (298 K) were compared. Langmuir isotherm model predicted that the maximum adsorption quantity of CS/SA/GO/UiO-67 for CR and MB was 1091.61 and 1313.95 mg/g, respectively. The optimum pH values of CS/SA/GO/UiO-67 for the adsorption of CR and MB were 5 and 10, respectively. The kinetic analysis showed that the adsorption of MB and CR on CS/SA/GO/UiO-67 was more suitable for the pseudo-second-order and pseudo-first-order kinetic model, respectively. The isotherm study revealed that the adsorption of MB and CR was consistent with the Langmuir isotherm model. The thermodynamic study demonstrated that the adsorption process of MB and CR was exothermic and spontaneous. FT-IR analysis and zeta potential characterization experiments revealed that the adsorption mechanism of MB and CR on CS/SA/GO/UiO-67 depended on π-π bond, hydrogen bond, and electrostatic attraction. Repeatable experiments showed that the removal rates of MB and CR of CS/SA/GO/UiO-67 after six cycles of adsorption were 67.19 and 60.82 %, respectively.

Efficient adsorption of azo anionic dye Congo Red by micro-nano metal-organic framework MIL-68(Fe) and MIL-68(Fe)/chitosan composite sponge: Preparation, characterization and adsorption performance.

Micro-nano metal-organic framework (MIL-68(Fe)) for efficient adsorption of azo anionic dye Congo red (CR) was successfully prepared by one-step hydrothermal method under acidic environment. And a MIL-68(Fe)/chitosan composite sponge (MIL-68(Fe)/CS) was prepared under the coating of chitosan (CS). After comparing the performance of MIL-68(Fe) and MIL-68(Fe)/CS, we focus on exploring MIL-68(Fe)/CS. It ensured the CR removal efficiency while reaching the adsorption equilibrium faster than MIL-68(Fe), and solved the defect that the powder was difficult to be stripped by water after adsorption. The physicochemical properties and surface morphology of the adsorbent were characterized by SEM, FTIR, XRD, TGA, BET, and Zeta potential. The effects of pH, contact time, adsorbent dosage, initial solution concentration and temperature on the adsorption performance of the adsorbent were systematically analyzed. The pseudo-second-order model and the Sips model were most consistent for the adsorption process, indicating that the adsorption process of MIL-68(Fe)/chitosan composite sponge on CR is a complex physicochemical process. The removal rates of CR by MIL-68(Fe) and MIL-68(Fe)/chitosan composite sponge reached the maximum values of 99.55 % and 99.51 % at 318 K, respectively. And the maximum adsorption capacity of CR by MIL-68(Fe)/chitosan composite sponge at 318 K was 1184.16 mg·g-1. After six cycles of adsorption and desorption, the removal rate of CR was still higher than 80 %. The synergistic effects of π-π stacking, electrostatic interactions, hydrogen bonding and pore filling have important effects on CR removal.

Removal of Methylene Blue by Crosslinked Egg White Protein/Graphene Oxide Bionanocomposite Aerogels.

Egg white protein is a non-toxic and biodegradable biopolymer that forms a gel easily via simple thermal denaturation treatment. A novel aerogel on the basis of egg white protein crosslinked with graphene oxide was prepared via a facile freeze-drying method. The structure and physicochemical characteristics of the aerogels were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA) and Brunauer-Emmett-Teller (BET) analysis. The adsorption properties of the aerogels were investigated by studying the influencing factors such as the solution pH, dose, temperature and contact time. The adsorption capacity of methylene blue onto the aerogels was tested, whose maximum adsorption capacity, calculated by the Langmuir isotherm equation, reached 91.7 mg/g. Adsorption kinetics studies showed that the adsorption followed the pseudo-second-order kinetic model. Thermodynamic data implied that methylene blue adsorbed by the aerogels was an exothermic and spontaneous process.

Prevalence of Toxoplasma gondii antibodies and DNA in dogs in Shanghai, China.

The aim of this study was to estimate the prevalence of Toxoplasma gondii infection in dogs in Shanghai, China. A total of 1,736 sera (1,178 from the city center and 558 from the outskirts) was collected from healthy dogs and tested for T. gondii infection by indirect hemagglutination; 56 sera (3.2%) were considered positive, with titers > 1∶64. The seroprevalence in dogs from the outskirts of the city (town dogs, 6.0%; countryside dogs, 9.8%) was significantly higher (P > 0.05) than that in city center dogs (1.3%). The age of the dog has an apparent association with T. gondii infection; that is, the seroprevalence ranged from 1.9% (in dogs ≤ 1 year old) to 3.6% (in dogs > 5 years old). There was no significant difference in gender (P ≥ 0.05), that is, 1.4% versus 1.1% for male and female dogs in the city center, 6.2% versus 5.9% in town dogs, and 8.4% versus 11.5% in country dogs, respectively. These results suggest that T. gondii infections are common in dogs from the city center and outskirts of Shanghai, but the T. gondii seroprevalence in dogs is considerably lower than in other regions in PR China. The presence of T. gondii DNA was investigated by nested PCR on 110 blood samples from city center dogs, but no positive samples were found, which may suggest that there were no acute infections of T. gondii in the city center samples. Our results indicate that the control and treatment of toxoplasmosis in Shanghai has been effective. However, it is still essential to further implement integrated strategies to prevent and control T. gondii infection in dogs in both the city center and the outskirts.