Biosorption of Cr(vi) from aqueous solution using dormant spores of Aspergillus niger

Spores of Aspergillus niger (denoted as A. niger) were used as a novel biosorbent to remove hexavalent chromium from aqueous solution. The effects of biosorbent dosage, pH, contact time, temperature and initial concentration of Cr(vi) on its adsorption removal were examined in batch mode. The Cr(vi) uptake capacity increased with an increase in Cr(vi) concentration until saturation, which was found to be about 97.1 mg g⁻¹ at pH 2.0, temperature of 40 °C, adsorbent dose of 2.0 g L⁻¹ and initial concentration of 300 mg L⁻¹. Scanning electron microscopy, energy dispersive X-ray spectroscopy, field-emission transmission electron microscopy (FETEM), XPS and Fourier-transform infrared spectroscopy were applied to study the microstructure, composition and chemical bonding states of the biomass adsorbent before and after spore adsorption. The mechanisms of chromate anion removal from aqueous solution by the spores of A. niger were proposed, which included adsorption of Cr(vi) onto the spores followed by its reduction to Cr(iii). The reduced Cr(iii) was rebound to the biomass mainly through complexation mechanisms, redox reaction and electrostatic attraction. The removal of Cr(vi) by spores of A. niger followed pseudo-second-order adsorption kinetics. Monolayer adsorption of Cr(vi) was revealed by the better fitting of the Langmuir model isotherm rather than multilayer adsorption for the Freundlich model. The results indicated that A. niger spores can be used as a highly efficient biosorbent to remove Cr(vi) from contaminated water.

Spores of Aspergillus niger (denoted as A. niger) were used as a novel biosorbent to remove hexavalent chromium from aqueous solution.     

Surfactant-assisted hydrothermal synthesis of rGO/SnIn4S8 nanosheets and their application in complete removal of Cr(vi)

To solve the problem of contamination of hexavalent chromium (Cr(vi)), visible-light-driven graphene-based ternary metal chalcogenide nanosheets (rGO/SnIn₄S₈) were synthesized via a one-pot surfactant-assisted hydrothermal method for the photoreduction of Cr(vi). Characterizations demonstrated that SnIn₄S₈ nanosheets were uniformly distributed on the surface of rGO and the as-synthesized nanosheets exhibited excellent photocatalytic activity under visible light. In addition, the effects of pH, concentration of critic acid, holes and electron scavengers on the reduction of Cr(vi) were systematically investigated. It was found that 50 mg L⁻¹ of Cr(vi) could be completely removed within 30 min at pH 2 when citric acid served as a hole scavenger. Kinetic studies showed that the photocatalytic reduction of Cr(vi) processes obeyed the pseudo first order model. Further study indicated that the Cr(iii) species was immediately adsorbed onto the surface of the rGO/SnIn₄S₈ nanosheets after photocatalytic reduction of Cr(vi). Additionally, recycling results suggested that rGO/SnIn₄S₈ nanosheets possessed high recycle ability and stability after repeated use (5 times). This effective and promising work might provide a new strategy for the photoreduction of Cr(vi) and complete removal of chromium from effluent through the novel photocatalyst rGO/SnIn₄S₈.

Fabrication of visible-light-responsive photocatalyst (rGO/SnIn₄S₈) for photoreduction of Cr(vi) and adsorption of Cr(iii).     

Mechanism and modeling of hexavalent chromium interaction with a typical black soil: the importance of the relationship between adsorption and reduction

Black soils have a significant retention effect on the migration of Cr(vi) towards groundwater, and Cr(vi) adsorption and reduction are both involved in this process. However, the adsorption and reduction of Cr(vi) were always investigated separately in previous studies resulting in an unclear relationship between them. In this study, the adsorption and reduction kinetic processes of Cr(vi) by a typical black soil were separately investigated under different initial Cr(vi) concentrations (40–400 mg L⁻¹) and pH conditions (3.5–7.0) by the means of desorption treatment, and the equilibrium relationship between aqueous and adsorbed Cr(vi) was innovatively established based on the kinetic data. It was found that under pH 5.7 the adsorbed Cr(vi) content on soil particles was linearly correlated with the remaining Cr(vi) concentration in solution with time (R² = 0.98), and the reduction rate of Cr(vi) in the reaction system was linearly correlated with the adsorbed Cr(vi) content on soil particles with time (R² = 0.99). With pH decreasing from 7.0 to 3.5, the partition of Cr(vi) between solid and aqueous phases turned out to be of a non-linear nature, which can be fitted better by the Freundlich model. The retention of Cr(vi) by black soil was determined to follow the “adsorption–reduction” mechanism, where the Cr(vi) was first rapidly adsorbed onto the soil particles by a reversible adsorption reaction, and then the adsorbed Cr(vi) was gradually reduced into Cr(iii). A two-step kinetic model was developed accordingly, and the experimental data were fitted much better by the two-step adsorption–reduction kinetic model (R² = 0.89 on average) compared with the traditional first-order and second-order kinetic models (R² = 0.66 and 0.76 on average respectively). This paper highlights the novel two step kinetic model developed based on the proposed “adsorption–reduction” mechanism of Cr(vi) retention by a typical black soil.

A novel two-step kinetic model was developed based on the proposed “adsorption–reduction” mechanism of Cr(vi) retention by a typical black soil.     

Removal of Pb(ii) and Cr(vi) from aqueous solutions using the prepared porous adsorbent-supported Fe/Ni nanoparticles

In this study, Fe/Ni nanoparticles supported by a novel fly ash-based porous adsorbent (FBA-Fe/Ni) for Cr(vi) and Pb(ii) removal were investigated. In order to enhance the reactivity of zero-valent iron (ZVI), ZVI particles were deposited on the surface or in the inner pores of FBA as a support material and Ni nanoparticles were introduced. FBA was prepared with the solid waste such as Enteromorpha prolifera, bentonite and fly ash. FBA-Fe/Ni was characterized via Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction and the Brunauer–Emmett–Teller model and energy-dispersive spectrometry. The effects of various parameters on Cr(vi) and Pb(ii) removal by FBA-Fe/Ni, such as FBA-Fe/Ni dosage, pH of the solution, reaction temperature, Cr(vi) and Pb(ii) concentrations, co-existing ions and ionic strength were discussed. The possible removal mechanisms were proposed and the results indicated that there was a three-step reaction including the adsorption of Cr(vi) and Pb(ii) on the surface of FBA-Fe/Ni, the subsequent reduction and precipitation. The removal capacity of Cr(vi) and Pb(ii) by FBA-Fe/Ni was 25.07 mg g⁻¹ and 164.19 mg g⁻¹ at 303 K with an initial concentration of 1000 mg L⁻¹ and FBA-Fe/Ni dosage of 0.20 g. In conclusion, this work demonstrated that FBA-Fe/Ni was a promising alternative material for Cr(vi) and Pb(ii) removal.

In this study, Fe/Ni nanoparticles supported by a novel fly ash-based porous adsorbent (FBA-Fe/Ni) for Cr(vi) and Pb(ii) removal were investigated.     

Recyclable functionalized polymer films for the efficient removal of hexavalent chromium from aqueous solutions

In this study, polyethylenimine-functionalized poly(vinyl alcohol) (PEI-PVA) films were prepared for the first time to remove aqueous Cr(vi). The results indicate that our PEI-PVA films have an excellent potential for Cr(vi) removal and their maximum removal capacity was 396.83 mg g⁻¹. The optimized pH value was 2, the adsorption of Cr(vi) was fitted to the Langmuir model, and the kinetics of uptake could be described well by a pseudo-second-order rate model. Taking into account the simplified separation method of adsorbents and solutions, we used a PVA film as a carrier in which PEI-PVA microspheres were filled to obtain a PEI-PVA functionalized film (PPF). The PPF shows a great efficiency in the removal of Cr(vi) ions in solution, which can absorb and reduce the Cr(vi) ion concentration in the solution in 90 min. PPF has excellent selectivity and the removal efficiency of Cr(vi) ions in the presence of co-existing ions is not reduced. It also has good recycling properties; the removal efficiency remains at 77% over four cycles. The removal mechanism of Cr(vi) ions by PEI-PVA microspheres involves the reduction of the adsorbed Cr(vi) ions to Cr(iii) ions, which are less toxic.

A PEI-PVA functionalized composite film has been developed to remove hexavalent chromium ion Cr(vi) from water by an adsorption–reduction mechanism.     

Adsorption and reduction of hexavalent chromium on magnetic greigite (Fe3S4)-CTAB: leading role of Fe(ii) and S(−ii)

In this study, a facile one-step route was used to synthesize a novel magnetic mesoporous greigite (Fe₃S₄)-CTAB composite, which was utilized to remove hexavalent chromium (Cr(vi)). The optimized Fe₃S₄-CTAB_0.75 composite with a CTAB dosage of 0.75 g possessed the maximum specific surface, showing the highest Cr(vi) adsorption capacity of 330.03 mg g⁻¹. The mechanism analysis revealed that Fe(ii) and S(−ii) were critical for the reduction of Cr(vi). CTAB can promote the removal of Cr(vi) by Fe₃S₄-CTAB composites, possibly due to increased S(−ii) concentration, better dispersion of nanoparticles, and greater zeta potential. Besides, there is mild effect of Fe⁰ on Cr(vi) removal, which is confirmed by the disappearance of the Fe⁰ peak from the XPS analysis. The pseudo-second-order kinetic model could explain the Cr(vi) removal processes well. The adsorption of Cr(vi) at different initial concentrations was more consistent with a Langmuir isotherm. The existence of H⁺ was beneficial for Cr(vi) removal by Fe₃S₄-CTAB_0.75. Our work confirmed that the obtained Fe₃S₄-CTAB_0.75 composites exhibit considerable potential for Cr(vi) removal from aqueous solution.

The presence of CTAB can promote the removal of hexavalent chromium from the Fe₃S₄-CTAB surface.     

Characterization of CMC–LDH beads and their application in the removal of Cr(vi) from aqueous solution

In this study, CMC–LDH beads were prepared and characterized using SEM, FTIR and TG analysis. The beads were applied for the removal of Cr(vi) from aqueous solution. The effects of adsorbent dosage, initial pH and initial concentration of Cr(vi) solution on Cr(vi) uptake were investigated in detail. Moreover, adsorption isotherms and adsorption kinetic models were employed to analyze the adsorption process, and a preliminary study of the reusability of the adsorbent was performed. The experimental results showed that the CMC–LDH beads could remove Cr(vi) from aqueous solution efficiently. When the initial concentration of the Cr(vi) solution was 100 mg L⁻¹ and the adsorbent dosage was 12 g L⁻¹, the removal efficiency of Cr(vi) reached 96.2%. After the CMC–LDH beads were reused 10 times, the removal efficiency of Cr(vi) still remained at 89.6%.

CMC–LDH beads were prepared, characterized and applied for the removal of heavy metal ions in this study.     

The development of a ternary nanocomposite for the removal of Cr(vi) ions from aqueous solutions

The aim of this study is to develop a ternary nanocomposite (NC) of polyaniline (PANI)/2-acrylamido-2-methylpropanesulfonic acid (AMPSA)-capped silver nanoparticles (NPs)/graphene oxide quantum dots (PANI/Ag (AMPSA)/GO QDs) as an efficient adsorbent for the removal of the highly toxic hexavalent chromium (Cr(vi)) from polluted water. PANI/Ag (AMPSA)/GO QDs NC was synthesized via in situ oxidative polymerization. The effects of pH, adsorbent dose, initial concentration, temperature, contact time, ionic strength and co-existing ions on the removal of Cr(vi) by PANI/Ag (AMPSA)/GO QDs were investigated. The PANI/Ag (AMPSA)/GO QDs NC (25.0 mg) removed 99.9% of Cr(vi) from an aqueous solution containing 60 mg L⁻¹ Cr(vi) ions at pH 2. Energy dispersive X-ray (EDX) and inductively coupled plasma spectrometry (ICP) studies confirmed the adsorption of Cr(vi) and that some of the adsorbed Cr(vi) was reduced to Cr(iii). Cr(vi) removal by the PANI/Ag (AMPSA)/GO QDs NC followed the pseudo-second order kinetic model, and the removal was highly selective for Cr(vi) in the presence of other co-existing ions. In summary, the PANI/Ag (AMPSA)/GO QDs NC has potential as a novel adsorbent for Cr(vi).

The aim is to develop a ternary nanocomposite of polyaniline/2-acrylamido-2-methylpropanesulfonic acid-capped silver nanoparticles/graphene oxide quantum dots as an efficient adsorbent for the removal of the highly toxic hexavalent chromium (Cr(vi)) from polluted water.     

Positive effects of concomitant heavy metals and their reduzates on hexavalent chromium removal in microbial fuel cells

Cr(vi) laden wastewaters generally comprise a range of multiple heavy metals such as Au(iii) and Cu(ii) with great toxicity. In the present study, cooperative cathode modification by biogenic Au nanoparticles (BioAu) reduced from aqueous Au(iii) and in situ Cu(ii) co-reduction were investigated for the first time to enhance Cr(vi) removal in microbial fuel cells (MFCs). With the co-existence of Cu(ii) in the catholyte, the MFC with carbon cloth modified with nanocomposites of multi-walled carbon nanotubes blended with BioAu (BioAu/MWCNT) obtained the highest Cr(vi) removal rate (4.07 ± 0.01 mg L⁻¹ h⁻¹) and power density (309.34 ± 17.65 mW m⁻²), which were 2.73 and 3.30 times as high as those for the control, respectively. The enhancements were caused by BioAu/MWCNT composites and deposited reduzates of Cu(ii) on the cathode surface, which increased the adsorption capacity, electronic conductivity and electrocatalytic activity of the cathode. This study provides an alternative approach for efficiently remediating co-contamination of multiple heavy metals and simultaneous bioenergy recovery.

The cooperative cathode modification by BioAu from Au(iii) and in situ Cu(ii) co-reduction enhanced Cr(vi) removal and bioelectricity generation in MFCs.     

Self-assembly preparation of lignin–graphene oxide composite nanospheres for highly efficient Cr(vi) removal

Recently, research interest in the application of lignin is growing, especially as adsorbent material. However, single lignin shows unsatisfactory adsorption performance, and thus, construction of lignin-based nanocomposites is worth considering. Herein, we introduced graphene oxide (GO) into lignin to form lignin/GO (LGNs) composite nanospheres by a self-assembly method. FTIR and ¹H NMR spectroscopy illustrated that lignin and GO are tightly connected by hydrogen bonds. The LGNs as an environmental friendly material, also exhibit excellent performance for Cr(vi) removal. The maximum sorption capacity of LGNs is 368.78 mg g⁻¹, and the sorption efficiency is 1.5 times than that of lignin nanospheres (LNs). The removal process of Cr(vi) via LGNs mainly relies on electrostatic interaction, and it also involves the reduction of Cr(vi) to Cr(iii). Moreover, LGNs still have high adsorption performance after repeating five times with the sorption capacity of 150.4 mg g⁻¹ in 200 mg g⁻¹ Cr(vi) solution. Therefore, the prepared lignin–GO composite nanospheres have enormous potential as a low-cost, high-absorbent and recyclable adsorbent, and can be used in wastewater treatment.

Lignin/GO (LGNs) composite nanospheres were prepared by self-assembly method, which showed excellent adsorption performance for Cr(vi) removal.     

Freezing/thawing pretreatment of dormant Aspergillus niger spores to increase the Cr(vi) adsorption capacity: process and mechanism

Hexavalent chromium is a widespread pollutant that threatens ecological and human health. However, its removal from the environment is limited by the high cost and energy consumption rate of current technologies. In this study, the Cr(vi) biosorption mechanism of Aspergillus niger spores pretreated by freezing/thawing was studied by batch experiments and surface chemistry analyses. The results indicated that pretreatment enhanced the spores'' Cr(vi) removal efficiency. The cell surface, internal functional groups, and morphology of the freezing/thawing-pretreated spores (FTPS) before and after Cr(vi) loading were characterized by advanced spectroscopy techniques such as SEM-EDAX, XPS, FTIR, and FETEM analyses. The SEM and BET data showed that the surface of FTPS was rougher than that of untreated spores. The XPS data showed that FTPS bio-transformed Cr(vi) into Cr(iii). The intracellular localization of chromium was visualized by FETEM, and both surface and intracellular structures removed Cr(vi) following pseudo-second-order biosorption kinetics. The biosorption dynamics of Cr(vi) fit the Langmuir isotherm model describing a monolayer. These results suggest that freezing/thawing pretreatment of A. niger spores could lead to the development of a novel, efficient biomaterial for the removal of Cr(vi).

Freezing/thawing pretreatment of A. niger spores could lead to the development of a novel, efficient biomaterial for the removal of Cr(vi).     

High dispersions of nano zero valent iron supported on biochar by one-step carbothermal synthesis and its application in chromate removal

A one-step carbothermal synthesis and characterization of biochar-supported nanoscale zero-valent iron (nZVI/BC) was performed for the removal of hexavalent chromium (Cr(vi)) from aqueous solution. High dispersions of nanoscale zero-valent iron supported on biochar were successfully synthesized by the pyrolysis of an iron-impregnated biomass (corn stover) as the carbon and iron source under nitrogen atmosphere. The effects of the pyrolytic temperature on the Fe mineralogies formed on the biochar are discussed. In general, the effects of the treatment time, initial solution pH, and nZVI/BC dosage on the Cr(vi) removal are presented. The results showed high crystallinity and purity, and nZVI/BC was obtained at a pyrolytic temperature of 800 °C. The batch experimental results determined that the adsorption capacity of Cr(vi) decreases with the increase in the initial pH value from 4.0 to 10.0. The Cr(vi) adsorption kinetics data effectively followed a pseudo-second-order kinetics with a calculated rate constant of 0.0.3396 g mg⁻¹ min⁻¹. The calculated thermodynamic parameters, such as ΔG°, ΔH°, and ΔS°, were evaluated, and the results indicated that the Cr(vi) reduction on nZVI/BC was a spontaneous and endothermic process. The adsorption mechanism of Cr(vi) was investigated by XRD and XPS analyses and the results demonstrated that Cr(vi) was reduced to Cr(iii) and the oxidation of nZVI occurred during the reaction process. These results prove that nZVI/BC synthesized by a one-step carbothermal method can be considered as a potential candidate for the removal of Cr(vi) from aqueous solutions.

A one-step carbothermal synthesis and characterization of biochar-supported nanoscale zero-valent iron (nZVI/BC) was performed for the removal of hexavalent chromium (Cr(vi)) from aqueous solution.     

Reduced graphene oxide supported ZnO quantum dots for visible light-induced simultaneous removal of tetracycline and hexavalent chromium

Semiconducting nanomaterials play an important role in the photocatalytic removal of aqueous pollutants like heavy metals, organic compounds, pathogens and antibiotics. In this study, we prepared ZnO quantum dots (QD) by the precipitation method and ZnO/rGO materials with varying percentages (0.5–2 wt%) of ZnO were prepared by the hydrothermal method. The synthesized catalysts were characterized by various physicochemical techniques, such as powder X-ray diffraction (XRD), Raman spectroscopy, ultraviolet-visible-diffuse reflectance spectroscopy (UV-VIS-DRS), Transmission Electron Microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR) and Brunauer–Emmett–Teller (BET) analysis to determine the structural as well as textural and surface properties. The photocatalytic activity of the prepared catalysts was analyzed during the individual and simultaneous removal of tetracycline (TC) and hexavalent chromium [Cr(vi)] in aqueous medium. Among all the catalysts, 1.5 wt% ZnO/rGO showed the highest visible light activity, where 68% tetracycline and 84% Cr(vi) abatement was observed after 120 min irradiation time. Moreover, tetracycline showed 70% mineralization. The photocatalytic activity is explained based on the photo-generated electron transfer from the conduction band (CB) of ZnO to the surface of rGO which prevents the recombination of excitons and produces OH˙ and O₂⁻˙; these radicals play an important role in degrading the TC and Cr(vi). The mechanism suggested that the co-existence of oxidizable and reducible species such as TC and Cr(vi) ensured the effective use of the photo-generated electrons and holes that leads to the efficient oxidation of TC and Cr(vi) reduction.

The photocatalytic mechanism explains that electrons and hydroxyl radicals were responsible for reduction of Cr(vi) and oxidation of tetracycline.     

Facile preparation of hybrid porous polyanilines for highly efficient Cr(vi) removal

In the present work, leucoemeraldine-based hybrid porous polyanilines (LHPPs) have been synthesized by the Friedel–Crafts reaction of leucoemeraldine and octavinylsilsesquioxane (OVS) for Cr(vi) removal. The resulting LHPPs were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and N₂ adsorption–desorption. The findings indiated that the LHPPs were amorphous, with apparent surface areas (S_BET) in the range of 147 to 388 m² g⁻¹ and total volumes in the range of 0.13 to 0.44 cm³ g⁻¹. Cr(vi) removal experiments displayed that the LHPPs exhibited highly efficient Cr(vi) removal performance. The maximum Cr(vi) removal capacity of LHPP-1 was 990.1 mg g⁻¹ at 308 K and pH 1, which is higher than those of other reported polyaniline-based adsorbents. The adsorption process was a spontaneous, endothermic and chemical adsorption process. The adsorption behavior agreed well with Langmuir models and pseudo second-order equations. X-ray photoelectron spectroscopy and Fourier transformed infrared (FTIR) spectroscopy analysis revealed that the highly efficient Cr(vi) removal performance can be mainly attributed to the existence of numerous amine and imine groups on the surface of the LHPPs; these can function as adsorption active sites for Cr(vi) removal through electrostatic adsorption and reduction to Cr(iii) under acidic conditions. Moreover, the LHPPs exhibited excellent adsorption selectivity for Cr(vi) despite the presence of other metal ions (K⁺, Cu²⁺, Mn²⁺) and anions (NO₃⁻, SO₄²⁻). Therefore, the LHPPs have potential applications for Cr(vi) removal in industrial wastewater.

In the present work, leucoemeraldine-based hybrid porous polyanilines (LHPPs) have been synthesized by the Friedel–Crafts reaction of leucoemeraldine and octavinylsilsesquioxane (OVS) for Cr(vi) removal.     

Efficient removal of chromate ions from aqueous solution using a highly cost-effective ferric coordinated [3-(2-aminoethylamino)propyl]trimethoxysilane–MCM-41 adsorbent

The present investigation involves synthesis and characterization of MCM-41–AEAPTMS–Fe(iii)Cl using coordinated Fe(iii) on MCM-41–AEAPTMS for efficient removal of hazardous Cr(vi) ions from aqueous solution. The adsorbent MCM-41–AEAPTMS–Fe(iii)Cl was characterized using small-angle X-ray diffraction (SAX), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Fourier-transform infrared (FT-IR) and Brunauer–Emmett–Teller (BET) surface analyzer techniques. The BET surface area was found to be 87.598 m² g⁻¹. The MCM-41–AEAPTMS–Fe(iii)Cl effectively adsorbs Cr(vi) with an adsorption capacity acquiring the maximum value of 84.9 mg g⁻¹ at pH 3 at 298 K. The data followed pseudo-second-order kinetics and obeyed the Langmuir isotherm model. The thermodynamic data proved the exothermic and spontaneous nature of Cr(vi) ion adsorption on MCM-41–AEAPTMS–Fe(iii). Further, the higher value of ΔH° (−64.339 kJ mol⁻¹) indicated that the adsorption was chemisorption in nature.

The present investigation involves synthesis and characterization of MCM-41–AEAPTMS–Fe(iii)Cl using coordinated Fe(iii) on MCM-41–AEAPTMS for efficient removal of hazardous Cr(vi) ions from aqueous solution.     

Synthesis and evaluation of ion-imprinted composite membranes of Cr(vi) based on β-diketone functional monomers

Using Cr(vi) as the imprinted ions and 2-allyl-1,3-diphenyl-1,3-propanedione (ADPD) (a compound synthesized by independent design) as the functional monomer, a series of chromium ion-imprinted composite membranes (Cr(vi)-IICMs) and corresponding non-imprinted composite membranes (NICMs) were synthesized and tested. The results showed that the Cr(vi)-IICM₁₀ membrane prepared under optimal experimental conditions exhibited a high adsorption capacity towards Cr(vi) (Q = 30.35 mg g⁻¹) and a high imprinting factor (α = 2.70). The structural characteristics of Cr(vi)-IICM₁₀ and NICM₁₀ were investigated using FE-SEM, ATR-FTIR, and BET techniques combined with UV-Vis photometry and inductively coupled plasma emission spectrometry (ICP-OES) to evaluate the adsorption performance and permeation selectivity, while the effect on adsorption permeance of varying the experimental conditions including the solvent type, pH, and temperature was also investigated. The results showed that Cr(vi)-IICM₁₀ is a mesoporous material with excellent permeation selectivity, reusability, and favorable pH response, and that its adsorption behavior is in accordance with the Langmuir model and pseudo-first-order kinetics. Thus, Cr(vi)-IICM₁₀ shows great potential towards utilization as a “smart membrane” to control the separation and removal of Cr(vi) in wastewater, and also proved a reasonable design of the new functional monomer ADPD.

Using Cr(vi) as the imprinted ions and 2-allyl-1,3-diphenyl-1,3-propanedione (a compound of independent design) as the functional monomer, a series of chromium ion-imprinted composite membranes and corresponding non-imprinted composite membranes were synthesized and tested.     

Post synthetically modified IRMOF-3 for efficient recovery and selective sensing of U(vi) from aqueous medium

A simple and efficient route to develop various novel functionalized MOF materials for rapid and excellent recovery of U(vi) from aqueous medium, along with selective sensing has been demonstrated in the present study. In this connection, a set of four distinct post synthetically modified (PSM) iso-reticular metal organic frameworks were synthesized from IRMOF-3 namely, IRMOF-PC (2-pyridine carboxaldehyde), IRMOF-GA (glutaric anhydride), IRMOF-SMA (sulfamic acid), and IRMOF-DPC (diphenylphosphonic chloride) for the recovery and sensing of U(vi) from aqueous medium. The MOFs were characterized by Fourier transform infrared spectroscopy (FTIR), powder XRD, BET surface area analysis, thermogravimetric analysis (TGA), NMR (¹³C, ¹H and ³¹P), Scanning Electron Microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). Among all MOFs, post synthetically modified IRMOF-SMA showed enhanced thermal stability of about 420 °C. The MOFs were investigated for U(vi) sorption studies using a batch technique. All the MOFs exhibit excellent sorption capacity towards U(vi) (>90%) and maximum uptake was observed at pH 6. Sorption capacity of MOFs have the following order; IRMOF-3-DPC (300 mg U g⁻¹) > IRMOF-SMA (292 mg U g⁻¹) > IRMOF-PC (289 mg U g⁻¹) > IRMOF-GA (280 mg U g⁻¹) > IRMOF-3 (273 mg U g⁻¹). IRMOF-DPC shows rapid sorption of uranium within 5 min with excellent uptake of U(vi) (>99%). The desorption of U(vi) was examined with different eluents and 0.01 M HNO₃ was found to be most effective. The fluorescence sensing studies of U(vi) via IRMOF-3 and its PSM MOFs revealed high sensitivity and selectivity towards U(vi) over other competing rare earth metal ions (La³⁺, Ce⁴⁺, Sm³⁺, Nd³⁺, Gd³⁺, and Eu³⁺), wherein IRMOF-GA displayed an impressive detection limit of 0.36 mg L⁻¹ for U(vi).

Four IRMOFs following PSM strategy were prepared. The MOFs were characterized by different techniques and were investigated for U(vi) sorption. PSM MOFs displayed impressive fluorescent sensing and selectivity of U(vi) over competing metal ions.     

Novel synthesis of a clay supported amorphous aluminum nanocomposite and its application in removal of hexavalent chromium from aqueous solutions

A bentonite supported amorphous aluminum (B–Al) nanocomposite was synthesized by the NaBH₄ reduction method in an ethanol–water interfacial solution and characterized with SEM, TEM, XRD, FT-IR and XRF. Surface morphology and line scans obtained from TEM imaging suggest the successful synthesis of the nanocomposite while XRF data shows a drastic change in Al concentration in the synthesized nanocomposite with respect to raw bentonite. This synthesized nanocomposite was further utilized for the removal of hexavalent chromium (Cr(vi)) from aqueous solutions. The very high removal efficiency of the composite for Cr(vi) (i.e. 49.5 mg g⁻¹) was revealed by the Langmuir sorption isotherm. More than 90% removal of Cr(vi) in just 5 minutes of interaction suggests very fast removal kinetics. Inner sphere complexation and coprecipitation of Cr(vi) can be concluded as major removal mechanisms. No influence of ionic strength suggests inner sphere complexation dominated in Cr(vi) uptake. pH of the solution didn''t influence the sorption much but comparatively the removal was higher under alkaline conditions (99.4%) than under acidic conditions (93.7%). The presence of humic acid and bicarbonate ions reduced the sorption significantly. The final product, Cr–Al(OH)₃ results in precipitation by forming alum which indicates that clay supported amorphous aluminum nanocomposites can be considered as potential sorbents for toxic metal ions in the environment.

Synthesis and application of bentonite supported amorphous aluminum nanocomposite as promising material for the removal of Cr(vi) from aqueous solutions.     

Treatment of electrochemical plating wastewater by heterogeneous photocatalysis: the simultaneous removal of 6:2 fluorotelomer sulfonate and hexavalent chromium

6:2 fluorotelomer sulfonate (6:2 FtS) is being widely used as a mist suppressant in the chromate (Cr(vi)) plating process. As a result, it is often present alongside Cr(vi) in the chromate plating wastewater (CPW). While the removal of Cr(vi) from CPW has been studied for decades, little attention has been paid to the treatment of 6:2 FtS. In this study, the removal of Cr(vi) and 6:2 FtS by Ga₂O₃, In₂O₃, and TiO₂ photocatalysts was investigated. In the Ga₂O₃/UVC system, over 95% of Cr(vi) was reduced into Cr(iii) after only 5 min. Simultaneously, 6:2 FtS was degraded into F⁻ and several perfluorocarboxylates. The predominant reactive species responsible for the degradation of 6:2 FtS in the Ga₂O₃ system were identified to be h_VB⁺ and O₂˙⁻. In addition, it was observed that the presence of Cr(vi) helped accelerate the degradation of 6:2 FtS. This synergy between Cr(vi) and 6:2 FtS was attributable to the scavenging of e_CB⁻ by Cr(vi), which retarded the recombination of e_CB⁻ and h_VB⁺. The In₂O₃/UVC system was also capable of removing Cr(vi) and 6:2 FtS, although at significantly slower rates. In contrast, poor removal of 6:2 FtS was achieved with the TiO₂/UVC system, because Cr(iii) adsorbed on TiO₂ and inhibited its reactivity. Based on the results of this study, it is proposed that CPW can be treated by a treatment train that consists of an oxidation–reduction step driven by Ga₂O₃/UVC, followed by a neutralization step that converts dissolved Cr(iii) into Cr(OH)_3(S).

6:2 fluorotelomer sulfonate (6:2 FtS) and chromate (Cr(vi)) in chromate plating wastewaters can be simultaneously removed by photocatalysis.     

Preparation and application synthesis of magnetic nanocomposite using waste toner for the removal of Cr(vi)

In this study, a novel magnetic nanocomposite was prepared using waste toner (WT) through high temperature decomposition, and calcination was conducted in different atmospheres (air, ammonia, and vacuum). WT calcined in ammonia (WT(NH₃)), and it was then utilized as an efficient absorbent for the reduction of Cr(vi) in aqueous solutions; a batch experiment with different conditions was performed to investigate its Cr(vi) removal ability. The effects of two pH-regulating acid (HCl and H₂SO₄) treatments were also studied. It was found that WT(NH₃) could remove about 99% Cr(vi) at pH 2 under H₂SO₄ treatment. The XRD and TEM results coupled with VSM results confirmed that WT(NH₃) is an Fe₃O₄/Fe₂N nanohybrid, which possesses excellent water-dispersibility and remarkable magnetic properties. XPS analysis showed the presence of Cr(vi) and Cr(iii) on the surface of WT(NH₃), which indicated that Cr(vi) was reduced to Cr(iii). Furthermore, H₂SO₄ regulation also promoted the reduction of Cr(vi) by WT(NH₃), and this reduction was higher than that obtained by HCl regulation.

A novel magnetic nanocomposite is prepared using waste toner via calcination in ammonia, which exhibits excellent magnetic properties and high efficiency for the removal of Cr(vi) via pH regulation using H₂SO₄.