Novel magnetically separable anhydride-functionalized Fe3O4@SiO2@PEI-NTDA nanoparticles as effective adsorbents: synthesis,stability and recyclable adsorption performance for heavy metal ions

In this paper, a novel adsorbent, Fe₃O₄@SiO₂@PEI-NTDA, was first prepared by the immobilization of an amine and anhydride onto magnetic Fe₃O₄@SiO₂ nanoparticles with polyethylenimine (PEI) and 1,4,5,8-naphthalenetetracarboxylic-dianhydride (NTDA) for the removal of heavy metal ions from aqueous solutions. The structure of Fe₃O₄@SiO₂@PEI-NTDA was systematically investigated; the results confirmed that amine and anhydride groups were successfully covalently grafted onto the surface of Fe₃O₄@SiO₂, which showed a homogenous core–shell structure with three layers of about 300 nm diameter (Fe₃O₄ core: 200 nm, nSiO₂ layer: 20 nm, and PEI-NTDA layer: 20 nm). The adsorption performance of Fe₃O₄@SiO₂@PEI-NTDA NPs was evaluated for single Pb²⁺ and coexisting Cd²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ ions in an aqueous solution in a batch system. The amine and anhydride groups may have a synergistic effect on Pb²⁺ removal through electrostatic interactions and chelation; Fe₃O₄@SiO₂@PEI-NTDA NPs exhibited preferable removal of Pb²⁺ with maximum adsorption capacity of 285.3 mg g⁻¹ for Pb²⁺ at a solution pH of 6.0, adsorbent dosage of 0.5 g L⁻¹, initial Pb²⁺ concentration of 200 mg L⁻¹ and contact time of 3 h. The adsorption mechanism conformed well to the Langmuir isotherm model, and the adsorption kinetic data were found to fit the pseudo-second order model. Fe₃O₄@SiO₂@PEI-NTDA NPs could be recovered easily from their dispersion by an external magnetic field and demonstrated good recyclability and reusability for at least 6 cycles with a high adsorption capacity above 204.5 mg g⁻¹. The magnetic adsorbents showed high stability with a weight loss below 0.65% in the acid leaching treatment by 2 M HCl solution for 144 h. This study indicates that Fe₃O₄@SiO₂@PEI-NTDA NPs are new promising adsorbents for the effective removal of Pb²⁺ in wastewater treatment.

A magnetically separable adsorbent, anhydride-functionalized Fe₃O₄@SiO₂@PEI-NTDA, was successfully constructed for removal of heavy metal ions from aqueous solution.     

Zn2+ removal from the aqueous environment using a polydopamine/hydroxyapatite/Fe3O4 magnetic composite under ultrasonic waves

In this study, an easily magnetically recoverable polydopamine (PDA)-modified hydroxyapatite (HAp)/Fe₃O₄ magnetic composite (HAp/Fe₃O₄/PDA) was suitably synthesized to exploit its adsorption capacity to remove Zn²⁺ from aqueous solution, and its structural properties were thoroughly examined using different analytical techniques. The effect of multiple parameters like pH, ultrasonic power, ultrasonic time, adsorbent dose, and initial Zn²⁺ concentration on the adsorption efficiency was assessed using RSM-CCD. According to the acquired results, by increasing the adsorbent quantity, ultrasonic power, ultrasonic time, and pH, the Zn²⁺ adsorption efficiency increased and the interaction between the variables of ultrasonic power/Zn²⁺ concentration, pH/Zn²⁺ concentration, pH/absorbent dose, and ultrasonic time/adsorbent dose has a vital role in the Zn²⁺ adsorption. The uptake process of Zn²⁺ onto PDA/HAp/Fe₃O₄ followed Freundlich and pseudo-second order kinetic models. The maximum capacity of Zn²⁺ adsorption (q_m) obtained by PDA/HAp/Fe₃O₄, HAp/Fe₃O₄, and HAp was determined as 46.37 mg g⁻¹, 40.07 mg g⁻¹, and 37.57 mg g⁻¹, respectively. Due to its good performance and recoverability (ten times), the HAp/Fe₃O₄/PDA magnetic composite can be proposed as a good candidate to eliminate Zn²⁺ ions from a water solution.

A magnetically recoverable polydopamine (PDA)-modified hydroxyapatite (HAp)/Fe₃O₄ magnetic composite (HAp/Fe₃O₄/PDA) was synthesized to exploit its adsorption capacity to remove Zn²⁺ from aqueous solution and the structural properties were examined.     

Facile preparation of amidoxime-functionalized Fe3O4@SiO2-g-PAMAM-AO magnetic composites for enhanced adsorption of Pb(ii) and Ni(ii) from aqueous solution

In this paper, using amidoxime as a functional monomer, different generations of polyamidoxime dendrimer magnetic microspheres (Fe₃O₄@SiO₂-g-PAMAM-AO) were fabricated to adsorb Pb²⁺ and Ni²⁺ in aqueous solution. The magnetic adsorbents were characterized by FTIR, XRD, SEM, XPS, TEM, EDS, TGA and BET. The effects of different factors (such as solution pH, adsorption time, adsorption temperature, adsorbent dosage etc.) on adsorption were evaluated. Fe₃O₄@SiO₂-g-PAMAM-AO has a maximum Pb(ii) adsorption of 157.25 mg g⁻¹ (100 mg L⁻¹) at pH 5.5. Furthermore, Fe₃O₄@SiO₂-g-PAMAM-AO showed an excellent adsorption performance for the removal of Ni(ii) with a maximum adsorption capacity of 191.78 mg g⁻¹ (100 mg L⁻¹) at pH 8.0. The sorption isotherm data fitted the Freundlich isotherm model well. Adsorption kinetics analysis showed that it was best described by the pseudo-second-order rate model. Desorption experiment results showed that the adsorbent can be reused in the adsorption–desorption cycles.

In this paper, using amidoxime as a functional monomer, different generations of polyamidoxime dendrimer magnetic microspheres (Fe₃O₄@SiO₂-g-PAMAM-AO) were fabricated to adsorb Pb²⁺ and Ni²⁺ in aqueous solution.     

Chitin/egg shell membrane@Fe3O4 nanocomposite hydrogel for efficient removal of Pb2+ from aqueous solution

The development of adsorbents by using the byproducts or waste from large-scale industrial and agricultural production is of great significance, and is considered to be an economic and efficient strategy to remove the heavy metals from polluted water. In this work, a novel chitin/EM@Fe₃O₄ nanocomposite hydrogel was obtained from a NaOH/urea aqueous system, where the proteins of egg shell membrane and Fe₃O₄ nanoparticles were chemically bonded to chitin polymer chains with the help of epichlorohydrin. Due to the existence of a large number of –NH₂, –OH, –CONH–, –COOH and hemiacetal groups, the adsorption efficiency for Pb²⁺ into the absorbent was dramatically enhanced. The experimental results revealed that the adsorption behavior strongly depends on various factors, such as initial pH, initial Pb²⁺ concentration, incubation temperature and contact time. The kinetic experiments indicated that the adsorption process for Pb²⁺ in water solution agreed with the pseudo-second-order kinetic equation. The film diffusion or chemical reaction is the rate limiting process in the initial adsorption stage, and the adsorption of Pb²⁺ into the nanocomposite hydrogel can well fit the Langmuir isotherm. Thermodynamic analysis demonstrated that such adsorption behaviors were dominated by an endothermic (ΔH° > 0) and spontaneous (ΔG° < 0) process.

A novel kind of chitin/EM@Fe₃O₄ nanocomposite hydrogel derived from the biowastes of egg shell membrane and chitin was successfully prepared for efficient removal of Pb²⁺ from wastewater solution.     

Adsorption behavior of magnetic bentonite for removing Hg(ii) from aqueous solutions

Bentonite is a porous clay material that shows good performance for adsorbing heavy metals and other pollutants for wastewater remediation. However, it is very difficult to separate the bentonite from water after adsorption as it forms a stable suspension. In this paper, we prepared magnetic bentonite (M-B) by loading Fe₃O₄ particles onto aluminum-pillared bentonite (Al-B) in order to facilitate its removal from water. The functional groups, skeleton structure, surface morphology and electrical changes of the prepared material were investigated by FT-IR, XRD, BET, SEM, VSM and zeta potential measurements. It was used as an adsorbent for Hg(ii) removal from aqueous solutions and the influence of various parameters on the adsorption performance was investigated. The adsorption kinetics were best fitted by the pseudo-second-order model, and also followed the intra-particle diffusion model up to 18 min. Moreover, adsorption data were successfully reproduced by the Langmuir isotherm, and the Hg(ii) adsorption saturation capacity was determined as 26.18 mg g⁻¹. The average adsorption free energy change calculated by the D-R adsorption isotherm model was 11.89 kJ mol⁻¹, which indicated the occurrence of ionic exchange. The adsorption thermodynamic parameter ΔH was calculated as 42.92 kJ mol⁻¹, which indicated chemical adsorption. Overall, the thermodynamic parameters implied that Hg(ii) adsorption was endothermic and spontaneous.

Bentonite is a porous clay material that shows good performance for adsorbing heavy metals in wastewater remediation. Magnetic bentonite (M-B) was prepared and it was successfully used as an adsorbent to remove Hg(ii) from aqueous solutions in this paper.     

Preparation of terpyridine-functionalized paramagnetic nickel–zinc ferrite microspheres for adsorbing Pb(ii), Hg(ii), and Cd(ii) from water

A paramagnetic microsphere combining special functional groups may be one kind of the most promising methods for heavy metal adsorption, due to their specific separation capacity, selectivity and reusability. In this study, a novel terpyridine-based magnetic solid-phase adsorbent (TPY-M) is successfully constructed. The paramagnetic Ni_0.25Zn_0.75Fe₂O₄ microsphere (M) is synthesized and applied as a magnetic core, and is functionalized by terpyridine (TPY) groups. The naked magnetic core and TPY-M are characterized by vibration sample magnetism (VSM), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and Fourier-transform infrared spectroscopy (FT-IR) techniques. Some parameters of the TPY-M samples are evaluated as potential adsorbents for heavy metal ions in various aqueous solutions. The adsorption capacities of TPY-M for Pb(ii), Hg(ii) and Cd(ii) were 64.75 mg g⁻¹, 33.94 mg g⁻¹ and 24.64 mg g⁻¹ under given conditions, respectively. In the case of Pb(ii), some influencing factors on the TPY-M adsorbent are investigated, including the pH, adsorption time, and ion concentrations. The adsorbent can be easily regenerated by HCl solution after use. The adsorbent revealed good adsorption performance in some real water samples.

A paramagnetic microsphere combining special functional groups may be one kind of the most promising methods for heavy metal adsorption, due to their specific separation capacity, selectivity and reusability.     

Preparation,characterization and application of CS@PDA@Fe3O4 nanocomposite as a new magnetic nano-adsorber for the removal of metals and dyes in wastewater

This study aimed to develop a novel magnetic chitosan/dopamine/Fe₃O₄ nano-adsorber (CS@PDA@Fe₃O₄) for the removal of heavy metal ions and organic dye molecules from aqueous solution. CS@PDA@Fe₃O₄ was prepared by surface modification of PDA/Fe₃O₄ nanoparticles with chitosan using IPTES as the cross-linker. The surface structure, composition, and properties of the CS@PDA@Fe₃O₄ nano-adsorber were characterized by elemental (EDS), spectroscopic (XRD, XPS, and FT-IR), magnetic intensity (VSM), surface and morphological (TEM and SEM) analyses. In order to study its adsorption behavior, equilibrium and kinetics studies were carried out through batch experiments. Additionally, the influences of the pH value, initial concentration, adsorbent dose, and contact time were also evaluated. The CS@PDA@Fe₃O₄ nano-adsorber exhibited high adsorption capacity especially for Cu(ii), with a maximum adsorption capacity of 419.6 mg g⁻¹. The experimental data were well described by the Langmuir isotherm kinetic models.

Synthesis of CS@PDA@Fe₃O₄ nanocomposite and heavy metal ion adsorption.     

MoS42− intercalated NiFeTi LDH as an efficient and selective adsorbent for elimination of heavy metals

The enormous increase of heavy metal pollution has led to a rise in demand for synthesizing efficient and stable adsorbents for its treatment. Therefore, we have designed a novel adsorbent by introducing (MoS₄)²⁻ moieties within the layers of NiFeTi LDH-NO₃, via an ion exchange mechanism, as a stable and efficient adsorbent to deal with the increasing water pollution due to heavy metals. Characterization techniques such as XRD, FTIR, TGA, SEM, TEM, and Raman spectroscopy were used to confirm the formation of (MoS₄)²⁻ intercalated NiFeTi LDH and structural changes after the adsorption process. The efficiency of the material was tested with six heavy metal ions, among which it was found to be effective for toxic Pb²⁺ and Ag⁺ ions. When selectivity was studied with all six of the metal ions copresent in one solution, the material showed greater selectivity for Pb²⁺ and Ag⁺ ions with the selectivity order of Ni²⁺ < Cu²⁺ < Zn²⁺ < Fe³⁺ < Pb²⁺ < Ag⁺, with great adsorption capacities of 653 mg g⁻¹ for Pb²⁺ and 856 mg g⁻¹ for Ag⁺ metal ions. Further, the kinetics adsorption study for both the metal ions had a great correlation with the pseudo-second-order model and supported the chemisorption process via the formation of M–S bonding. The adsorption process obeyed the Langmuir model. Therefore, the MoS₄-LDH material could be a promising adsorbent for the removal of heavy metals.

Elimination of the heavy metals by using the MoS₄-LDH adsorbent.     

Super rapid removal of copper,cadmium and lead ions from water by NTA-silica gel

Copper (Cu²⁺), cadmium (Cd²⁺) and lead ions (Pb²⁺) are toxic to human beings and other organisms. In this study, a silica gel material modified with nitrilotriacetic acid (NTA-silica gel) was sensibly designed and prepared via a simple amidation procedure for the removal of Cu²⁺, Cd²⁺ and Pb²⁺ from water. The NTA-silica gels showed rapid removal performances for the three metal ions (Pb²⁺ (<2 min), Cu²⁺ and Cd²⁺ (<20 min)) with relatively high adsorption capacities (63.5, 53.14 and 76.22 mg g⁻¹ for Cu²⁺, Cd²⁺ and Pb²⁺, respectively). At the same concentration of 20 mg L⁻¹, the removal efficiencies of the three metals by the adsorbent ranged from 96% to 99%. The Freundlich and Langmuir models were utilized to fit the adsorption isotherms. The adsorption kinetics for the three metal ions was pseudo-second-order kinetics. The removal performance of the NTA-silica gels increased in a wide pH range (2–9) and maintained in the presence of competitive metal ions (Na⁺, Mg²⁺, Ca²⁺ and Al³⁺) with different concentrations. In addition, the NTA-silica gels were easily regenerated (washed with 1% HNO₃) and reused for 5 cycles with high adsorption capacity. This study indicates that the NTA-silica gel is a reusable adsorbent for the rapid, convenient, and efficient removal of Cu²⁺, Cd²⁺, and Pb²⁺ from contaminated aquatic environments.

A silica gel material modified with nitrilotriacetic acid (NTA-silica gel) was sensibly designed and prepared via a simple method for the super rapid removal of Cu²⁺, Cd²⁺ and Pb²⁺ from water.     

Selective aptamer conjugation to silver-coated magnetite nanoparticles for magnetic solid-phase extraction of trace amounts of Pb2+ ions

Herein, a novel aptamer-functionalized magnetic adsorbent was developed and combined with magnetic solid-phase extraction (MSPE) for the specific enrichment of Pb²⁺ ions prior to flame atomic absorption spectrometric detection. First, silver-coated magnetite core–shell nanoparticles (Fe₃O₄@Ag MNPs) were synthesized by the chemical reduction of silver ions on the surface of magnetite nanoparticles. After that, the selective DNA aptamer against Pb²⁺ was conjugated on the surface of the synthesized nanoparticles to form aptamer-modified magnetic nanoparticles (Fe₃O₄@Ag-APT). The characterization of the prepared adsorbent was performed through SEM imaging, XRD, FT-IR, EDX, and DRS instruments. The influence of the various experimental parameters on the adsorption and desorption steps in MSPE was investigated via Taguchi experimental design to optimize different parameters. Under the optimized conditions, the Pb²⁺ calibration graph was linear in the range of 33–1000 μg L⁻¹. The relative standard deviation (RSD%) of the method for six replicates containing 100 μg L⁻¹ of Pb²⁺ ions was 0.34%. Furthermore, the limit of detection (LOD) and the limit of quantification (LOQ) were 10 μg L⁻¹ and 33.3 μg L⁻¹, respectively. Finally, the applicability of the proposed method was successfully confirmed by preconcentration and determination of trace amounts of Pb²⁺ ions in tap and seawater samples. We showed a proof of concept for Fe₃O₄@Ag-APT as an efficient bio-adsorbent, offering a promising strategy for the specific binding/removal of toxic heavy metal ions.

Herein, a novel aptamer-functionalized magnetic adsorbent was developed and combined with magnetic solid-phase extraction (MSPE) for the specific enrichment of Pb²⁺ ions prior to flame atomic absorption spectrometric detection.     

Synthesis of Fe3O4@PVBC–TMT nanoparticles for the efficient removal of heavy metals ions

Core–shell magnetic Fe₃O₄@PVBC–TMT (Fe₃O₄@polyvinylbenzyl chloride–trithiocyanuric acid) nanoparticles containing trithiocyanuric acid groups were fabricated and employed for the fast removal of heavy metals from an aquatic environment. The morphology, structure and properties of Fe₃O₄@PVBC–TMT nanoparticles were characterized by a series of modern analytical tools. The adsorption behavior of the Fe₃O₄@PVBC–TMT nanoparticles for heavy metals ions in aqueous solutions was investigated by batch experiments. The maximum removal capacities of the Fe₃O₄@PVBC–TMT nanoparticles toward Mn²⁺, Ni²⁺, Cu²⁺, Cd²⁺ and Pb²⁺ ions were 127.4, 146.6, 180.5, 311.5, and 528.8 mg g⁻¹, respectively. Importantly, it is found that Pb²⁺ ions can be completely and quickly removed by the Fe₃O₄@PVBC–TMT nanoparticles. The equilibrium was established within 6 min, and the removal efficiencies were found to be 99.9%, 99.8% and 99.5% for Pb²⁺ ions at the initial concentrations of 100 mg L⁻¹, 200 mg L⁻¹ and 300 mg L⁻¹, respectively. It is hoped that the core–shell magnetic Fe₃O₄@PVBC–TMT nanoparticles may find application in wastewater treatment.

Core–shell Fe₃O₄@PVBC–TMT nanoparticles were fabricated and served as a valid magnetic adsorbent for the removal of heavy metals ions.     

Single-component and competitive adsorption of tetracycline and Zn(ii) on an NH4Cl-induced magnetic ultra-fine buckwheat peel powder biochar from water: studies on the kinetics,isotherms, and mechanism

Single-component and competitive adsorption of tetracycline (TC) and Zn(ii) on an NH₄Cl-induced magnetic ultra-fine buckwheat peel powder biochar (NH₄Cl-BHP-char/Fe₃O₄) was investigated in batch experiments. NH₄Cl-BHP-char/Fe₃O₄ exhibited a large surface area of 1119.097 m² g⁻¹ and a total pore volume of 0.139 cm³ g⁻¹ and was easily separated from aqueous solution using a magnet. Also, adsorption was endothermic, spontaneous, and highly pH-dependent. The optimum pH of the single-component adsorption of TC and Zn(ii) was 4.0 and 6.5, respectively, and the optimum pH of co-adsorption was 6.0. The kinetics studies showed the prepared biochar could be rapidly adsorbed within 60 min, and chemical adsorption was dominant. For single-component adsorption, the maximum adsorption capacities of TC and Zn(ii) were 106.38 and 151.52 mg g⁻¹, respectively, and they underwent monolayer adsorption on the biochar surface. Moreover, for competitive adsorption, maximum TC and Zn(ii) adsorption capacities of 126.58 and 357.14 mg g⁻¹ were achieved. Both film diffusion and intra-particle diffusion were found to be significant processes to facilitate adsorption. TC and Zn(ii) promoted the adsorption of each other. The proposed biochar could be used repeatedly for at least four cycles. All these results demonstrated that developed NH₄Cl-BHP-char/Fe₃O₄ was regarded as a low-cost alternative adsorbent to remove the heavy metal ions and antibiotic pollutants from water or wastewater.

Single-component and competitive adsorption of tetracycline (TC) and Zn(ii) on an NH₄Cl-induced magnetic ultra-fine buckwheat peel powder biochar (NH₄Cl-BHP-char/Fe₃O₄) was investigated in batch experiments.     

Preparation of activated carbon from Dipterocarpus alatus fruit and its application for methylene blue adsorption

Activated carbons were prepared from three parts of Dipterocarpus alatus fruit (wing, endocarp and pericarp), an abundant and renewable waste in Southeast Asia, by chemical activation using ZnCl₂, FeCl₃, H₃PO₄ and KOH and physical activation using CO₂ and steam. This study indicated that activated carbon prepared from Dipterocarpus alatus fruit could be employed as a promising adsorbent for the removal of methylene blue from aqueous solution. ZnCl₂ activation led to an activated carbon with a surface area of 843 m² g⁻¹ and was able to remove methylene blue from aqueous solution. Adsorption studies were performed and analysed using Langmuir and Freundlich isotherm equations. Adsorption data demonstrated an excellent fit with the Langmuir isotherm model, with the maximum adsorption capacity of 269.3 mg g⁻¹ at equilibrium. Pseudo-first order and pseudo-second order kinetic models were used in this study to describe the adsorption mechanism. The results show that methylene blue adsorption is pseudo-second order, indicating that liquid film diffusion, intra-particle diffusion and surface adsorption coexisted during methylene blue adsorption on the activated carbon. The activated carbon prepared from Dipterocarpus alatus fruit is a low cost and effective adsorbent with a fast rate for the removal of methylene blue from aqueous solutions when compared with a number of activated carbons studied in the literature.

Activated carbons were prepared from Dipterocarpus alatus fruit by chemical and physical activation and used for the removal of methylene blue from aqueous solution.     

K6P2W18O62 encapsulated into magnetic Fe3O4/MIL-101 (Cr) metal–organic framework: a novel magnetically recoverable nanoporous adsorbent for ultrafast treatment of aqueous organic pollutants solutions

In this study, a Wells–Dawson type K₆P₂W₁₈O₆₂ polyoxometalate was encapsulated into the magnetic Fe₃O₄/MIL-101 (Cr) metal–organic framework and applied as a new magnetically recoverable ternary adsorbent to remove organic dyes from aqueous solutions. The as-prepared ternary magnetically recyclable hybrid (denoted as P₂W₁₈O₆₂@Fe₃O₄/MIL-101 (Cr)) was characterized by FT-IR spectroscopy, powder X-ray diffraction (XRD), Raman spectroscopy, EDX, SEM, BET surface area, and magnetic measurements. The results showed the successful encapsulation of K₆P₂W₁₈O₆₂ (∼26.5 wt%) into the magnetic Fe₃O₄/MIL-101 (Cr) framework. The magnetic hybrid had a high specific surface area of 934.89 m² g⁻¹. The adsorption efficiency of this nanohybrid for the removal of methylene blue (MB), rhodamine B (RhB), and methyl orange (MO) from aqueous solutions was evaluated. The magnetic nanohybrid demonstrated the fast and selective adsorption of cationic dyes from mixed dye solutions. The adsorption rate and capacity of P₂W₁₈O₆₂@Fe₃O₄/MIL-101 (Cr) were increased as compared with MIL-101 (Cr), P₂W₁₈O₆₂, and Fe₃O₄/MIL-101 samples due to the increased electrostatic attraction. The effects of parameters such as the adsorbent dosage, temperature, dye concentration, and pH were investigated on the adsorption process. The adsorption kinetics was analyzed by the Freundlich, Langmuir, and Temkin isotherm models and pseudo-second-order and pseudo-first-order kinetics models, with the Langmuir isotherm and pseudo-second-order kinetic model found to be suitable to describe the equilibrium data. Also, the thermodynamic results of the nanohybrid indicated that the adsorption was an endothermic and spontaneous process. After the adsorption reaction, the magnetic nanohybrid could be easily separated and reused without any change in structure. Based on the results of this study, the nanohybrid was an efficient adsorbent for eliminating cationic dyes.

A Wells–Dawson-type K₆P₂W₁₈O₆₂ polyoxometalate was encapsulated into the magnetic Fe₃O₄/MIL-101 (Cr) metal–organic framework and applied as a new magnetically recoverable ternary adsorbent to remove organic dyes from aqueous solutions.     

Hydrothermal synthesis and adsorption behavior of H4Ti5O12 nanorods along [100] as lithium ion-sieves

The adsorption method is a promising route to recover Li⁺ from waste lithium batteries and lithium-containing brines. To achieve this goal, it is vital to synthesize a stable and high adsorption capacity adsorbent. In this work, Li₄Ti₅O₁₂ nanorods are prepared by two hydrothermal processes followed by a calcination process. Then the prepared Li₄Ti₅O₁₂ nanorods are treated with different HCl concentrations to obtain a H₄Ti₅O₁₂ adsorbent with 5 μm length along the [100] direction. The maximum amount of extracted lithium can reach 90% and the extracted titanium only 2.5%. The batch adsorption experiments indicate that the H₄Ti₅O₁₂ nanorod maximum adsorption capacity can reach 23.20 mg g⁻¹ in 24 mM LiCl solution. The adsorption isotherms and kinetics fit a Langmuir model and pseudo-second-order model, respectively. Meanwhile, the real adsorption selectivity experiments show that the maximum Li⁺ adsorption capacity reaches 1.99 mmol g⁻¹, which is far higher than Mg²⁺ (0.03 mmol g⁻¹) and Ca²⁺ (0.02 mmol g⁻¹), implying these nanorods have higher adsorption selectivity for Li⁺ from Lagoco Salt Lake brine. The adsorption capacity for Li⁺ remains 91% after five cycles. With the help of XPS analyses, the adsorption mechanism of Li⁺ on the H₄Ti₅O₁₂ nanorods is an ion exchange reaction. Therefore, this nanorod adsorbent has a potential application for Li⁺ recovery from aqueous lithium resources.

H₄Ti₅O₁₂ nanorods were successfully prepared by hydrothermal methods followed by a calcination process. Batch experiments indicate that the nanorod adsorbent is a promising adsorbent to recover lithium from liquid lithium resources.     

In situ fabrication of hierarchical biomass carbon-supported Cu@CuO–Al2O3 composite materials: synthesis,properties and adsorption applications

Hierarchical Cu–Al₂O₃/biomass-activated carbon composites were successfully prepared by entrapping a biomass-activated carbon powder derived from green algae in the Cu–Al₂O₃ frame (H–Cu–Al/BC) for the removal of ammonium nitrogen (NH₄⁺-N) from aqueous solutions. The as-synthesized samples were characterized via XRD, SEM, BET and FTIR spectroscopy. The BET specific surface area of the synthesized H–Cu–Al/BC increased from 175.4 m² g⁻¹ to 302.3 m² g⁻¹ upon the incorporation of the Cu–Al oxide nanoparticles in the BC surface channels. The experimental data indicated that the adsorption isotherms were well described by the Langmuir equilibrium isotherm equation and the adsorption kinetics of NH₄⁺-N obeyed the pseudo-second-order kinetic model. The static maximum adsorption capacity of NH₄⁺-N on H–Cu–Al/BC was 81.54 mg g⁻¹, which was significantly higher than those of raw BC and H–Al/BC. In addition, the presence of K⁺, Na⁺, Ca²⁺, and Mg²⁺ ions had no significant impact on the NH₄⁺-N adsorption, but the presence of Al³⁺ and humic acid (NOM) obviously affected and inhibited the NH₄⁺-N adsorption. The thermodynamic analyses indicated that the adsorption process was endothermic and spontaneous in nature. H–Cu–Al/BC exhibited removal efficiency of more than 80% even after five consecutive cycles according to the recycle studies. These findings suggest that H–Cu–Al/BC can serve as a promising adsorbent for the removal of NH₄⁺-N from aqueous solutions.

Hierarchical Cu–Al₂O₃/biomass-activated carbon composites were successfully prepared by entrapping a biomass-activated carbon powder derived from green algae in the Cu–Al₂O₃ frame (H–Cu–Al/BC) for the removal of ammonium nitrogen (NH₄⁺-N) from aqueous solutions.     

H2O2-independent chemodynamic therapy initiated from magnetic iron carbide nanoparticle-assisted artemisinin synergy

Chemodynamic therapy (CDT) is a booming technology that utilizes Fenton reagents to kill tumor cells by transforming intracellular H₂O₂ into reactive oxygen species (ROS), but insufficient endogenous H₂O₂ makes it difficult to attain satisfactory antitumor results. In this article, a H₂O₂-free CDT technique with tumor-specificity is developed by using pH-sensitive magnetic iron carbide nanoparticles (PEG/Fe₂C@Fe₃O₄ NPs) to trigger artemisinin (ART) to in situ form ROS. ART-loaded PEG/Fe₂C@Fe₃O₄ NPs are fabricated for the enormous release of Fe²⁺ ions induced by the acidic conditions of the tumor microenvironment after magnetic-assisted tumor enrichment, which results in the rapid degradation of the PEG/Fe₂C@Fe₃O₄ NPs and release of ART once endocytosed into tumor cells. In situ catalysis reaction between the co-released Fe²⁺ ions and ART generates toxic ROS and then induces apoptosis of tumor cells. Both in vitro and in vivo experiments demonstrate that the efficient Fe-enhanced and tumor-specific CDT efficacy for effective tumor inhibition based on ROS generation. This work provides a new direction to improve CDT efficacy based on H₂O₂-independent ROS generation.

Chemodynamic therapy (CDT) is a booming technology that utilizes Fenton reagents to kill tumor cells by transforming intracellular H₂O₂ into reactive oxygen species (ROS), but insufficient endogenous H₂O₂ makes it difficult to attain satisfactory antitumor results.     

Novel magnetic nickel ferrite nanoparticles modified with poly(aniline-co-o-toluidine) for the removal of hazardous 2,4-dichlorophenol pollutant from aqueous solutions

Chlorinated organic and phenolic compounds are still purely studied by many researchers because of their severe damage to the aquatic environment and their carcinogenic effect on many living organisms. Therefore, there is a great interest in removing these environmental pollutants from aqueous mediums by easy and inexpensive methods. Herein, novel nickel ferrite (NiFe₂O₄) nano composite modified with poly(aniline-co-o-toluidine) (PAOT) is prepared, characterized, and used for the removal of 2,4-dichlorophenol (2,4-DCP) as an organic chlorinated environmental pollutant. The morphological properties of the composite are characterized by Fourier transform infrared spectrometry (FTIR), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), and Brunauer–Emmett–Teller (BET) methods. The prepared composite is tested for the removal of the hazardous dichlorophenol pollutant from aqueous solutions. Under optimized conditions and with effective control of parameters including, contact time, pH of the test solution, adsorbent dose, and temperature, over 83% of the pollutant is adsorbed and removed. The adsorption capacity is 162 mg g⁻¹. Adsorption kinetics, adsorption isotherm and some physicochemical parameters of the reaction are evaluated. The Redlich–Peterson isothermal model is the appropriate model for describing the adsorption process. These results indicate that NiFe₂O₄/PAOT nanocomposites are promising adsorbents for the removal of persistent organic pollutants (e.g., DCP) from aqueous solutions. The results also reveal that modification of NiFe₂O₄ particles with poly(aniline-co-o-toluidine) (PAOT) significantly enhances the adsorption capacity of the adsorbent. This is probably due to the electrostatic attraction and non-covalent interactions (e.g. π–π) between the aromatic rings in both dichlorophenol and poly(aniline-co-o-toluidine) copolymer. Advantages offered by using NiFe₂O₄/PAOT nanocomposites are the high stability, reasonable efficiency, reusability for at least five adsorption–desorption cycles and the ability to remove the adsorbent from aqueous solutions for reuse using an external magnetic field.

Chlorinated organic and phenolic compounds are still purely studied by many researchers because of their severe damage to the aquatic environment and their carcinogenic effect on many living organisms.     

Simultaneous capture of methyl orange and chromium(vi) from complex wastewater using polyethylenimine cation decorated magnetic carbon nanotubes as a recyclable adsorbent

Most recently, the continuous deterioration of the aquatic environment triggered by both heavy metals and synthetic organic dyes has imparted serious threats to the ecosphere and drinking water safety. However, it is still extremely challenging to treat complex wastewater containing these two classes of pollutants via a one-step method owing to the significant differences in their physicochemical properties. In the current work, versatile magnetic MWCNTs decorated with PEI (denoted as MWCNTs@Fe₃O₄/PEI) was fabricated by a facile, rapid and reproducible strategy and applied to as a robust adsorbent for simultaneously removing methyl orange (MO) and Cr(vi) from aqueous solutions. The physicochemical properties of the as-designed nanohybrid were investigated using various analytical techniques, i.e. XRD, FT-IR, SEM, TEM, VSM, zeta potential, etc. It was found that the surface charge properties of the MWCNTs as well as its dispersion in aqueous solution were greatly changed after the introduction of PEI molecules. The resulting nanohybrid exhibited attractive adsorption capabilities toward anionic MO and Cr(vi). In the perspective of a mono-pollutant system, the time-dependent adsorption process matched well with a pseudo-second-order kinetics equation, the adsorption isotherm data at r.t. were well fitted by a Langmuir model with maximum monolayer uptake capacity of 1727.6 mg g⁻¹ for MO and 98.8 mg g⁻¹ for Cr(vi), and the removal process of both pollutants was thermodynamically spontaneous and exothermic. In the MO-Cr(vi) binary system, the uptake of Cr(vi) by the as-prepared adsorbent was evidently enhanced by the presence of MO, while the coexisting Cr(vi) exerted a small negative effect on the sorption of MO; which was attributed to the different adsorption mechanisms of both pollutants on the as-recommend adsorbent. The much better adsorbing performance of the resulting MWCNTs@Fe₃O₄/PEI for MO and Cr(vi) than that of the pristine MWCNTs or the MWCNTs/Fe₃O₄ composite was mainly ascribed to the high surface area of the MWCNTs, the high density of protonated N-rich groups of PEI as well as the excellent dispersion and solubility of the resulting nanocomposites. Moreover, the obtained nanohybrids can be easily recovered after being used by a permanent magnet and still retained high stability and excellent reusability after consecutive adsorption–desorption cycles, implying its great potential in practical applications. Therefore, the as-fabricated MWCNTs@Fe₃O₄/PEI composite could be recommended as a promising candidate adsorbent for the simultaneous capture of MO and Cr(vi) from complex wastewater via multiple uptake mechanisms (e.g. electrostatic attraction, π–π stacking and hydrogen bonding).

An MWCNTs@Fe₃O₄/PEI composite was facilely fabricated as a robust adsorbent for simultaneously capturing methyl orange (MO) and Cr(vi) from complex wastewater.     

Removal of arsenic(v) from aqueous solutions using sulfur-doped Fe3O4 nanoparticles

In this study, magnetic sulfur-doped Fe₃O₄ nanoparticles (Fe₃O₄:S NPs) were applied as adsorbents for the removal of As(v). Fe₃O₄:S NPs were fabricated by a two-step route, which included low-temperature mixing and high-temperature sintering. The as-prepared Fe₃O₄:S NPs could effectively remove As(v) under a wide pH range of 2–10 and presented a high As(v) adsorption capacity of 58.38 mg g⁻¹, which was much better than undoped Fe₃O₄ nanoparticles (20.24 mg g⁻¹). Adsorption experiments exhibited a pseudo-second-order model of adsorption kinetics and a Langmuir isotherm model of adsorption isotherms. Additionally, the coexisting ions such as NO₃⁻, SO₄²⁻, and CO₃²⁻ had no significant effect on As(v) adsorption and the adsorbent worked well in actual smelting wastewater. XPS and FTIR spectra of Fe₃O₄:S NPs before and after As(v) adsorption showed that Fe–OH groups played a significant role in the adsorption mechanisms. Moreover, the magnetic Fe₃O₄:S NPs adsorbents after adsorption could be rapidly separated from wastewater with an external magnetic field. Therefore, Fe₃O₄:S NPs could be an ideal candidate for the removal of As(v) from water.

Magnetic Fe₃O₄:S NPs presented a much better As(v) adsorption performance than undoped Fe₃O₄ NPs due to sulfur doping.