A novel efficient bioflocculant QZ-7 for the removal of heavy metals from industrial wastewater

In this study, a novel bioflocculant QZ-7 was produced from Bacillus salmalaya 139SI for industrial wastewater treatment. Biochemical analysis, FTIR, scanning electron microscopy-energy dispersive X-ray spectroscopy, and thermogravimetric analysis were performed. A synthetic wastewater sample was used to validate the performance of the prepared OZ-7 for the adsorption efficiency of As, Zn²⁺ Pb²⁺, Cu²⁺, and Cd²⁺ under optimal experimental conditions such as initial metal concentrations, pH, contact time (h) and QZ-7 adsorbent dosage (mg mL⁻¹). The maximum removal efficiency for Zn²⁺ (81.3%), As (78.6%), Pb²⁺ (77.9%), Cu²⁺ (76.1%), and Cd²⁺ (68.7%) was achieved using an optimal bioflocculant dosage of 60 mg L⁻¹ at 2 h shaking time, 100 rpm and pH 7. Furthermore, the obtained optimum experimental conditions were validated using real industrial wastewater and the removal efficiencies of 89.8%, 77.4% and 58.4% were obtained for As, Zn²⁺ and Cu²⁺, respectively. The results revealed that the prepared bioflocculant QZ-7 has the capability to be used for the removal of heavy metals from industrial wastewater.

In this study, a novel bioflocculant was produced using Bacillus salmalaya 139SI for industrial waste water treatment.     

Acetylacetone functionalized magnetic carbon microspheres for the highly-efficient adsorption of heavy metal ions from aqueous solutions

Herein, Acac-C@Fe₃O₄, a magnetic carbon (C@Fe₃O₄) modified with acetylacetone (Acac), was first prepared and used as a solid-phase adsorbent for adsorbing some heavy metal ions from aqueous solution. The adsorbent was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM) and BET studies. Some parameters affecting the adsorption and desorption processes were studied in Pb²⁺ solution, including sample pH, contact time, initial concentration, type and connection of the desorption solution. Absorption results showed that removal of Pb²⁺ was 100% under optimal conditions at an initial concentration of 10.0 mg L⁻¹. The adsorption mechanism conformed well to a pseudo-second order kinetic model. The adsorption capacity of the sorbent also showed promising results with Hg²⁺, Cr³⁺, Fe²⁺, Cd²⁺, Mn²⁺, Zn²⁺, Cu²⁺ and Pb²⁺, where maximum adsorption capacities reached 98.0, 151.2, 188.9, 202.2, 286.3, 297.2, 305.1 and 345.3 mg g⁻¹, respectively. The Acac-C@Fe₃O₄ microsphere material was successfully applied to the adsorption of heavy metal ions in aqueous solution.

Herein, Acac-C@Fe₃O₄, a magnetic carbon (C@Fe₃O₄) modified with acetylacetone (Acac), was first prepared and used as a solid-phase adsorbent for adsorbing some heavy metal ions from aqueous solution.     

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.     

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.     

Sensitive electrochemical sensor based on poly(l-glutamic acid)/graphene oxide composite material for simultaneous detection of heavy metal ions

Heavy metal pollution can be toxic to humans and wildlife, thus it is of great significance to develop rapid and sensitive methods to detect heavy metal ions. Here, a novel type of electrochemical sensor for the simultaneous detection of heavy metal ions has been prepared by using poly(l-glutamic acid) (PGA) and graphene oxide (GO) composite materials to modify the glassy carbon electrode (GCE). Due to the good binding properties of poly(l-glutamic acid) (PGA) for the heavy metal ions (such as Cu²⁺, Cd²⁺, and Hg²⁺) as well as good electron conductivity of graphene oxide (GO), the heavy metal ions, Cu²⁺, Cd²⁺, and Hg²⁺ in aqueous solution can be accurately detected by using differential pulse anodic stripping voltammetry method (DPASV). Under the optimized experiment conditions, the modified GCE shows excellent electrochemical performance toward Cu²⁺, Cd²⁺, and Hg²⁺, and the linear range of PG/GCE for Cu²⁺, Cd²⁺, and Hg²⁺ is 0.25–5.5 μM, and the limits of detection (LODs, S/N ≥ 3) Cu²⁺, Cd²⁺, and Hg²⁺ are estimated to be 0.024 μM, 0.015 μM and 0.032 μM, respectively. Moreover, the modified GCE is successfully applied to the determination of Cu²⁺, Cd²⁺, and Hg²⁺ in real samples. All obtained results show that the modified electrode not only has the advantages of simple preparation, high sensitivity, and good stability, but also can be applied in the field of heavy metal ion detection.

A novel electrochemical sensor with high stability and good reproducibility for the simultaneous detection of heavy metal ions was prepared by using PGA/GO to modify the GCE, showing high sensitivity of superior to most of the reported values.     

Electrochemical heavy metal removal from water using PVC waste-derived N,S co-doped carbon materials

The removal of heavy metal contaminants has aroused global attention due to water shortage and the lax control on the discharge of heavy metal pollutants. Capacitive deionization (CDI) has emerged as a robust, energy-/cost-efficient technique for water treatment. Herein, we reported the simple synthesis of N, S-co-doped carbon materials (NS-C) derived from PVC plastic wastes as CDI electrode materials for the efficient removal of heavy metal ions (HMIs). The NS-C exhibited a large specific surface area (∼1230 m² g⁻¹) and contained heavy heteroatom doping (∼4.55 at% N and ∼13.30 at% S). The CDI electrode fabricated using NS-C showed high removal efficiency (94–99%), high capacity (36–62 mg g⁻¹), and good regeneration capability for the adsorption of various kinds of low-concentration heavy metal ions (including Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Pb²⁺, and Cd²⁺). Moreover, PVC plastic wastes that are heavily accumulated in the environment and extremely hard to be decomposed and recycled were applied as the carbon source in this study for the fabrication of NS-C, which further rendered the importance of our study in practically treating hazardous waste (HMIs) with waste (PVC plastic wastes) in a clean and efficient way.

N, S-codoped carbon materials derived from PVC plastic wastes were used for electrochemically removing heavy metal pollutants from water.     

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.     

Microwave-assisted synthesis of glutathione-coated hollow zinc oxide for the removal of heavy metal ions from aqueous systems

Glutathione has tremendous binding potential with metal ions present in water. However, the solubility of glutathione in water limits its productivity in the removal of these toxic ions from aqueous systems. The removability of heavy ions with glutathione and the associated adsorption capability are enhanced; for this purpose, glutathione is coated over hollow zinc oxide particles. Glutathione-coated hollow zinc oxide (Glu@h-ZnO) was successfully synthesized under microwave (MW) conditions using polystyrene (PS) as the template. The as-synthesized material was characterized by Fourier transform infrared (FTIR) spectroscopy, and the results were supported by X-ray diffraction crystallography (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), differential thermal analysis (DTA), dynamic light scattering (DLS), Brunauer–Emmett–Teller (BET) studies and zeta potential (ζ) analysis. The sorption performance of Glu@h-ZnO towards the uptake of Hg²⁺, Cd²⁺ and Pb²⁺ ions from an aqueous medium under non-competitive batch conditions was investigated and the material was found to have the maximum affinity for Hg²⁺ ions with a maximum adsorption (q_m) capacity of 233 mg g⁻¹. The adsorption kinetics for Hg²⁺ ions and the effects of pH and ζ on the adsorption properties were also studied in detail. Finally, the experimental data were correlated with theoretical data obtained from density functional theory (DFT) studies and good agreement between the two was obtained.

Environmentally benign Glu@h-ZnO possesses good affinity for heavy metal ions, with enhanced adsorption capacity due to its high specific surface area.     

Nanochannel-based sensor for the detection of lead ions in traditional Chinese medicine

Lead ions (Pb²⁺) are used in the quality control of traditional Chinese medicine (TCM) preparations because they are highly toxic to human health. At present, sophisticated analytical instrumentation and complicated procedures for sample analysis are needed for the determination of Pb²⁺. Herein, a simple, fast, and sensitive peptide-modified nanochannel sensor to detect Pb²⁺ in TCM is reported, which is based on a Pb²⁺-specific peptide modified porous anodized aluminum membrane (PAAM). This peptide-based nanochannel clearly has the highest selectivity for Pb²⁺ when compared to other heavy metal ions, including As²⁺, Cd³⁺, Co²⁺, Cr²⁺, Cu²⁺, Fe³⁺, Hg²⁺, Mg²⁺, Mn²⁺, Ni²⁺, and Zn²⁺. Based on linear ranges from 0.01 to 0.16 μM and 10 to 100 μM, the detection limit was calculated to be 0.005 μM. Moreover, this peptide-based nanochannel sensor was successfully used to detect Pb²⁺ in complex TCM samples. In addition, when compared with the gold standard atomic absorption spectrophotometry (AAS) method, the recovery of the peptide-modified nanochannel sensor was between 87.7% and 116.8%. The experimental results prove that this new sensor is able to achieve accurate detection of Pb²⁺ in TCM samples. Thus, this sensor system could provide a simple assay for sensitive and selective detection of Pb²⁺ in TCM, thereby showing great potential in the practical application for the quality control of heavy metals in TCM.

The nanochannel-based sensor is able to achieve detection of Pb²⁺ in TCM samples.     

Adsorption of Cd2+ by an ion-imprinted thiol-functionalized polymer in competition with heavy metal ions and organic acids

The simultaneous presence of heavy metals and organic acids in nature and wastewaters and their competition for adsorption sites determine the migration, transformation and fate of pollutants in the environment. A Cd²⁺-ion-imprinted polymer (Cd²⁺-IIP) with a thiol-functional group was hydrothermally synthesized by a surface imprinting technique combined with ultrasonic heating for selective adsorption of Cd²⁺ from wastewaters. The adsorbent was characterized by SEM, EDS, XPS, BET and FT-IR measurements. The experimental results concerning Cd²⁺ adsorption from single-, binary-, ternary- and quaternary-metal aqueous solutions containing Cu²⁺, Ni²⁺ and Zn²⁺ revealed high selectivity. In binary-metal solutions, relative selectivity coefficients for Cd²⁺ in respect to Cd²⁺/Cu²⁺, Cd²⁺/Ni²⁺, and Cd²⁺/Zn²⁺ were as high as 3.74, 5.73 and 4.15, respectively. In multi-metal solutions, competing heavy metal ions had little effect on the adsorption of Cd²⁺ attributed to the high selectivity of Cd²⁺-IIP towards Cd²⁺ determined by its coordination geometry. The effect of low-molecular weight organic acids on the Cd²⁺ adsorption was also studied and the results showed that the presence of tartaric, citric and oxalic acids as admixtures in Cd²⁺ aqueous solutions noticeably reduced the cation adsorption in a wide range of concentrations with the minor exception of low contents of citric and tartaric acids slightly improving adsorption.

A Cd²⁺-imprinted thiol-functionalized polymer in competition with heavy metal ions and low molecular weight organic acids was investigated.     

A rapid on-site analysis method for the simultaneous extraction and determination of Pb2+ and Cd2+ in cereals

In order to achieve rapid on-site screening and solve the problem of rapid pretreatment for the determination of lead (Pb²⁺) and cadmium (Cd²⁺) in cereals by a portable electrochemical analyzer with disposable screen-printed electrodes (SPEs), a new reliable and simple extraction method for Pb²⁺ and Cd²⁺ in cereals was developed. The Pb²⁺ and Cd²⁺ in cereals were purified by a mixed solution of 1 mol L⁻¹ potassium iodide (KI)/5% vitamin C (VC)/ethyl acetate after being extracted by 10% HNO₃, which transfers the Pb²⁺ and Cd²⁺ into ethyl acetate after a reaction with KI–VC. Then, the Pb²⁺ and Cd²⁺ were eluted from ethyl acetate with 5% HNO₃ and were determined by an electrochemical analyzer with screen printed electrodes. Under the optimized conditions, the matrix calibration curves of Pb²⁺ and Cd²⁺ in rice and wheat showed good linear relationships with R² > 0.996. The method shows a detection limit (LOD) for Cd²⁺ in rice and wheat of 6.7 μg kg⁻¹ and 11.5 μg kg⁻¹, and the corresponding values for Pb²⁺ were 34.9 and 31.1 μg kg⁻¹, respectively. The relative standard deviation (RSD) was less than 8.7% for Cd²⁺ and Pb²⁺. In addition, the recoveries of the tested reference materials using this method were between 80% and 120%. From sample pretreatment to testing results, the whole process took no more than 25 min, and the operation was simple for operators, green to the environment, cheap in terms of instruments, and above all suitable for on-site detection. The results implied that this portable electrochemical method with new pretreatment may be a good choice for screening Pb²⁺ and Cd²⁺ in cereal samples on-site.

To achieve rapid on-site screening rapid pretreatment for the determination of Pb²⁺ and Cd²⁺ in cereals by a portable electrochemical analyzer with disposable screen-printed electrodes, a new reliable and simple extraction method for Pb²⁺ and Cd²⁺ was developed.     

Correction: Nano zero valent iron (nZVI) particles for the removal of heavy metals (Cd2+, Cu2+ and Pb2+) from aqueous solutions

Correction for ‘Nano zero valent iron (nZVI) particles for the removal of heavy metals (Cd²⁺, Cu²⁺ and Pb²⁺) from aqueous solutions’ by Mekonnen Maschal Tarekegn et al., RSC Adv., 2021, 11, 18539–18551. DOI: 10.1039/D1RA01427G.

The authors regret that reference 48 was incorrect. The correct reference is given below as reference 1.¹The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.     

Assembly with copper(ii) ions and D–π–A molecules on a graphene surface for ultra-fast acetic acid sensing at room temperature

In this study, a graphene-based composite 4HQ-rGO/Cu²⁺ was prepared via the supramolecular assembly of graphene nanosheets with 4-hydroxyquinoline (4HQ) and copper(ii) ions. The as-prepared supramolecular assembly exhibited an excellent and enhanced sensing performance towards acetic acid at room-temperature, which was due to the fact that the D–π–A molecules, i.e. 4HQ, were able to accelerate the charge transfer between the graphene nanosheets and 4HQ molecules when acetic acid was attached. In addition, at room temperature, the copper(ii) ions also played a critical role as the main active site for gas adsorption, and thus the as-fabricated sensor exhibited a high response, outstanding selectivity, and ultra-fast response/recovery time. To examine the selectivity of the Cu²⁺ ions for the supramolecular assembly, various other transition metal ions such as Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, and Cd²⁺ were attached to the 4HQ-rGO assembly, and their acetic sensing performance was determined. Interestingly, the supramolecular assembly with the Cu²⁺ ions (4HQ-rGO/Cu²⁺) exhibited the best sensing performance compared to other metal ion-based 4HQ-rGO materials. Compared with the typical acetic acid gas sensors reported in the literature, it is noteworthy to mention that the as-prepared 4HQ-rGO/Cu²⁺ supramolecular assembly exhibited the shortest gas response time (within 5 s) at room temperature. The presented study demonstrates that the as-prepared supramolecular assembly is a promising material as a room temperature acetic acid gas sensor in practical applications.

The as-prepared 4HQ-rGO/Cu²⁺ sensor possessed a high response, outstanding selectivity and fast response-recovery characteristic, which was mainly attributed to the supramolecularly assemble of 4-hydroxyquinoline, and Cu²⁺ with graphene nanosheets.     

Triazole-based novel bis Schiff base colorimetric and fluorescent turn-on dual chemosensor for Cu2+ and Pb2+: application to living cell imaging and molecular logic gates

A triazole-based novel bis Schiff base colorimetric and fluorescent chemosensor (L) has been designed, synthesized and characterized by elemental analysis, ¹H-NMR, ESI-MS, FTIR spectra and DFT studies. The receptor L showed selective and sensitive colorimetric sensing ability for Cu²⁺ and Pb²⁺ ions by changing color from colorless to yellow and light yellow respectively in CH₃OH–tris-buffer (1 : 1, v/v). However, it displayed strong fluorescence enhancement upon the addition of both Cu²⁺ and Pb²⁺ ions, attributed to the blocking of PET. The fluorometric detection limits for Cu²⁺ and Pb²⁺ were found to be 12 × 10⁻⁷ M and 9 × 10⁻⁷ M and the colorimetric detection limits were 3.7 × 10⁻⁶ M and 1.2 × 10⁻⁶ M respectively; which are far below the permissible concentration in drinking water determined by WHO. Moreover, it was found that chemosensor L worked as a reversible fluorescence probe towards Cu²⁺ and Pb²⁺ ions by the accumulation of S²⁻ and EDTA respectively. Based on the physicochemical and analytical methods like ESI-mass spectrometry, Job plot, FT-IR, ¹H-NMR spectra and DFT studies the detection mechanism may be explained as metal coordination, photoinduced electron transfer (PET) as well as an internal charge transfer (ICT) process. The sensor could work in a pH span of 4.0–12.0. The chemosensor L shows its application potential in the detection of Cu²⁺ and Pb²⁺ in real samples, living cells and building of molecular logic gate.

A novel triazole-based bis Schiff base colorimetric and fluorescent chemosensor (L) has been designed, synthesized and characterized. The chemo-sensor L shows its application potential in the detection of Cu²⁺ and Pb²⁺ in living cells and building molecular logic gate.     

A bifunctional sensor based on diarylethene for the colorimetric recognition of Cu2+ and fluorescence detection of Cd2+

A novel bifunctional sensor based on diarylethene with a benzyl carbazate unit was synthesized successfully. It not only served as a colorimetric sensor for the recognition of Cu²⁺ by showing changes in absorption spectra and solution color, but also acted as a fluorescent sensor for the detection of Cd²⁺ through obvious emission intensity enhancement and fluorescence color change. The sensor exhibited excellent selectivity and sensitivity towards Cu²⁺ and Cd²⁺, and the limits of detection for Cu²⁺ and Cd²⁺ were 8.36 × 10⁻⁸ mol L⁻¹ and 1.71 × 10⁻⁷ mol L⁻¹, respectively, which were much lower than those reported by the WHO and EPA in drinking water. Furthermore, its application in practical samples demonstrated that the sensor can be effectively applied for the detection of Cu²⁺ and Cd²⁺ in practical water samples.

A bifunctional sensor for colorimetric recognition of Cu²⁺ and fluorescent detection of Cd²⁺ was synthesized. It not only showed high selectivity and sensitivity to Cu²⁺ and Cd²⁺, but also could be used in practical water samples with high accuracy.     

Simple,selective detection and efficient removal of toxic lead and silver metal ions using Acid Red 94

Toward the goal of detecting toxic elements and removing them from drinking water, we report herein the utilization of Acid Red 94 (AR94) in sensing the hazardous metal ions in water. Among the various examined metal ions (Ag⁺, Pb²⁺, K⁺, Mn²⁺, Zn²⁺, La³⁺, Hg²⁺, Ca²⁺, Cd²⁺, Co²⁺, and Ni²⁺), the UV-visible absorption spectra showed high selectivity and sensitivity for toxic silver and lead metal ions in an aqueous solution. The observed absorption spectral changes and the rapid color changes confirm complex formation between AR94 and both Ag⁺ and Pb²⁺ metal ions. The emission measurements showed the significant fluorescence quenching of the singlet excited state of AR94 in the presence of Ag⁺ and Pb²⁺ metal ions suggesting the formation of an irradiative dye–metal complex under the prevailing experimental conditions. In order to remove the accumulated complexes of AR94 with silver metal ions, safe and harmless mesoporous titanium dioxide was utilized efficiently in removing the complexes with adsorption capacities of 91% at 30 minutes. These findings suggest a simple, fast and efficient method for both detecting silver in water, and removing the formed AR94–metal complexes in water. In addition, AR94 is shown to be a good sensor for the presence of Ag and Pb nanoparticles, NPs, in aqueous solution. The absorption and emission spectra of AR94 showed significant changes that may be rationalized by the strong electromagnetic coupling induced by NPs plasmonic effects. These findings render AR94 a sensitive and selective sensor and a visual indicator for the qualitative and quantitative detection of silver ions, lead ions and their nanoparticles.

Toward the goal of detecting toxic elements and removing them from drinking water, we report herein the utilization of Acid Red 94 (AR94) in sensing the hazardous metal ions in water.     

Mxene/alginate composites for lead and copper ion removal from aqueous solutions

Mxene has been widely used as a sorbent to remove heavy metal ions from sewage due to its unique two-dimensional layered structure and abundant oxygen-containing groups. However, Mxene has a relatively limited adsorption capacity for metal ions possibly due to the limited adsorption active sites. Herein, we reported novel Mxene/alginate composites for lead and copper ion removal from wastewater. The Mxene/alginate composites prepared in this study not only enhance the chelation ability of the lead and copper ions, but also accelerate the ion transport efficiency. The combined advantages of high adsorption capacity and short equilibrium time enable the Mxene/alginate composites to achieve the maximum adsorption capacity for Pb²⁺ and Cu²⁺ at 382.7 and 87.6 mg g⁻¹, respectively, and reach the adsorption equilibrium in 15 min. We believe that the composites developed in this study can open a new avenue for designing high adsorption capacity and high efficiency adsorbents.

Studies on Mxene/alginate composite adsorption have opened up a new avenue for designing adsorbents possessing high adsorption capacity and high efficiency.     

Selective determination of Ag+ in the presence of Cd2+, Hg2+ and Cu2+ based on their different interactions with gold nanoclusters

In this work, a fluorescence method was developed for selective detection of Ag⁺ in the presence of Cd²⁺, Hg²⁺, and Cu²⁺ based on gold nanoclusters (AuNCs). That is, bovine serum albumin (BSA) templated AuNCs with double emission peaks were synthesized using BSA as a protective agent. AuNCs with uniform distribution and average size between 2.0 and 2.2 nm were synthesized using a green and simple method, and showed bright orange-red fluorescence under ultraviolet light. AuNCs have two emission peaks at 450 nm and 630 nm with an excitation wavelength of 365 nm. Under alkaline conditions, Cd²⁺ can combine with the surface sulfhydryl groups of BSA–AuNCs to form Cd–S bonds, which cause AuNCs to aggregate, resulting in an increase in fluorescence intensity at 630 nm. Conversely, due to the d¹⁰–d¹⁰ metal affinity interaction, the addition of Hg²⁺ can reduce the fluorescence peak at 630 nm. Ag⁺ was reduced to Ag⁰ by gold nuclei in AuNCs, forming a stable hybrid Au@ AgNCs species with blue-shifted and enhanced fluorescence. Finally, the paramagnetic behavior of Cu²⁺ combined with BSA causes the excited electrons of the gold cluster to lose their energy via ISC, eventually leading to simultaneous quenching of the two emission peaks. The results show that the limit of detection (LOD) of Ag⁺, Hg²⁺, Cd²⁺ and Cu²⁺ is 1.19 μM, 3.39 μM, 1.83 μM and 5.95 μM, respectively.

A fluorescence method was developed for selective detection of Ag⁺ in the presence of Cd²⁺, Hg²⁺, and Cu²⁺ based on gold nanoclusters. The limit of detection for Ag⁺, Hg²⁺, Cd²⁺ and Cu²⁺ is 1.19 μM, 3.39 μM, 1.83 μM and 5.95 μM, respectively.     

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.     

Reusable bentonite clay: modelling and optimization of hazardous lead and p-nitrophenol adsorption using a response surface methodology approach

In this work, bentonite clay (BC) calcined at 500 °C was used as an adsorbent (BC-500) for the adsorption of Pb²⁺ and p-nitrophenol. The ability of BC-500 for the removal of Pb²⁺ and p-nitrophenol has been investigated. The adsorption studies tailored well the pseudo-first-order and the Langmuir model for Pb²⁺ and p-nitrophenol both. In addition, the optimal removal of Pb²⁺ and p-nitrophenol was found at pH 5 for Pb²⁺ and pH 6 for p-nitrophenol. However, the change of temperature (20–60 °C) was found to have a negative effect on the adsorption process on BC-500. Based on the Dubinin–Radushkevich model the adsorption occurs via a physical process. Accordingly, the adsorption mechanism was proposed using N₂-physisorption analysis before and after adsorption of Pb²⁺ and p-nitrophenol. The reusability of BC-500 was examined and the outcomes recommended that BC-500 had good potential as an economic and proficient adsorbent for Pb²⁺ or p-nitrophenol from contaminated water. Finally, the experimental Pb²⁺ and p-nitrophenol removal efficiency were found to be 90.93 ± 2.15% and 98.06 ± 1.87% while the predicted value by model equals 91.28 ± 1.68 and 97.24 ± 2.54, respectively, showing that the predicted model values are in good agreement with the experimental value.

In this work, bentonite clay (BC) calcined at 500 °C was used as an adsorbent (BC-500) for the adsorption of Pb²⁺ and p-nitrophenol.