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.     

Efficient recovery of Cr(vi) from electroplating wastewater by iron-modified sludge-based hollow-structured porous carbon: coexistence effects and competition for adsorption

In the present work, porous carbon was made from sewage sludge and hybrid liriodendron leaves, and modified with iron ions (Fe@LS-BC) carried out on Cr(vi) in aqueous solution from a single-component system and in competitive biosorption with methyl orange (MO) from a binary-component system. The iron ion-modified porous carbon (Fe@LS-BC) showed higher efficiency in the removal of Cr(vi) compared to porous carbon prepared by the co-pyrolysis of sludge and hybrid liriodendron leaves. The incorporation of the Fe element improved the ability of the material to redox Cr(vi), while imparting magnetic characteristics to the porous carbon and improving the reusability of the porous carbon. On the other hand, Fe@LS-BC exhibited a better pore volume, facilitating the contact of the material with Cr(vi) ions. The highest adsorption capacity was 0.33 mmol g⁻¹, and the adsorption experimental results for the single-component and binary-component systems of Cr(vi) matched well with the Langmuir–Freundlich models. When the concentration of MO was 0.2 and 0.8 mmol L⁻¹, respectively, the highest adsorption capacity of Cr(vi) was 0.35 and 0.46 mmol g⁻¹ in the binary system. The positively charged N–CH₃⁺ on the MO molecule promoted the electrostatic adsorption between HCrO₄⁻, CrO₄²⁻, and Fe@LS-BC, and increased the adsorption potential of Cr(vi).

Mechanism for the adsorption of hexavalent chromium and methyl orange in a binary system.     

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.     

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.     

Lead and uranium sorptive removal from aqueous solution using magnetic and nonmagnetic fast pyrolysis rice husk biochars

This paper discusses the sorption characteristics of Pb(ii) and U(vi) on magnetic and nonmagnetic rice husk biochars. The porosity, specific surface area, hydrophobility, and reusability of biochar were effectively improved (1–2 times) after magnetic modification. The optimum adsorption conditions were as follows: biochar loading was 0.4 g L⁻¹, pH value was 7.0, and anion strength of NO₃⁻ and PO₄³⁻ were 0.01 mol L⁻¹ for Pb(ii) and 0.04 mol L⁻¹ for U(vi) respectively. Compared with U(vi), Pb(ii) had the faster adsorption rate and higher adsorption capacity on magnetic biochar (MBC). The adsorption experimental data were well fitted by pseudo-second-order kinetic and Langmuir isotherm models. The maximum adsorption capacity of Pb(ii) and U(vi) on MBC was 129 and 118 mg g⁻¹ at 328 K respectively, which was significantly higher than that of other sources biochars. Pb(ii) was mainly bonded to biochar by physisorption but the adsorption of U(vi) on biochar was mostly chemisorption. Fe oxides in MBC noticeably improved the ion exchange and complexation action between biochar and metal ion especially for U(vi). The experimental results confirmed MBC material can be used as a cost-effective adsorbent for the removal of Pb(ii) and U(vi) and can be separated easily from aqueous solution when application.

This paper discusses the sorption characteristics of Pb(ii) and U(vi) on magnetic and nonmagnetic rice husk biochars.     

Synthesis and characterization of activated carbon from sugar beet residue for the adsorption of hexavalent chromium in aqueous solutions

A series of micro–mesoporous activated carbons (ACs) were prepared from sugar beet residue by a two-step method including KOH chemical activation and were used for Cr(vi) removal from aqueous solutions. Several characterization techniques, including SEM, TEM, N₂ adsorption, XRD, FTIR, and Raman spectroscopy, were used to determine the chemical and physical characteristics of the ACs, and the adsorption properties of the ACs were tested. The results indicated that the high specific surface area of the ACs reached 2002.9 m² g⁻¹, and the micropore surface area accounts for 85% of the total area. The optimal conditions for achieving the maximum Cr(vi) adsorption capacity of 163.7 mg g⁻¹ by the ACs were activation with a KOH/carbon ratio of 3.0, an initial Cr(vi) concentration of 400 mg L⁻¹, an adsorbent dose of 2.0 g L⁻¹ and pH of 4.5. Therefore, the ACs exhibit excellent adsorption performance for removing Cr(vi) from aqueous solutions. According to an investigation of the adsorption process, the adsorption isotherm is most consistent with the Langmuir isotherm model, and the adsorption kinetics were well described by the pseudo-second-order model.

A series of micro–mesoporous activated carbons (ACs) were prepared from sugar beet residue by a two-step method including KOH chemical activation and were used for Cr(vi) removal 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.     

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.     

Degradation of tetrabromobisphenol A by a ferrate(vi)–ozone combination process: advantages,optimization, and mechanistic analysis

This study systematically investigated the ferrate(vi)–ozone combination process for TBBPA degradation. Firstly, the advantages of a ferrate(vi)–ozone combination process were assessed as compared with a sole ozone and ferrate(vi) oxidation process. Then, the performance of the ferrate(vi)–ozone combination process was investigated under different experimental conditions, including the dosing orders of oxidants, dosing concentrations of oxidants, and the initial solution pH. At the same time, toxicity control (including the acute and chronic toxicity) and mineralization were analyzed after optimization. Finally, a mechanism was proposed about the synergetic effects of the ferrate(vi)–ozone combination process for decontamination. The ferrate(vi)–ozone combination process proved to be an efficient and promising technology for removing TBBPA from water. After being pre-oxidized by ferrate(vi) for 3 min and then co-oxidized by the two oxidants, TBBPA of 1.84 μmol L⁻¹ could be completely degraded by dosing only 0.51 μmol L⁻¹ of ferrate(vi) and 10.42 μmol L⁻¹ of ozone within 10 min in wide ranges of pH (5.0–11.0). Up to 91.3% of debromination rate and 80.5% of mineralization rate were obtained, respectively. In addition, no bromate was detected and the acute and chronic toxicity were effectively controlled. The analysis of the proposed mechanism showed that there might exist a superposition effect of the oxidation pathways. In addition, the interactions between the two oxidants were beneficial for the oxidation efficiency of ferrate(vi) and ozone, including the catalytic effect of ferrate(vi) intermediates on ozone and the oxidation of low-valent iron compounds by ozone and the generated ·OH radical.

This study systematically investigated the ferrate(vi)–ozone combination process for TBBPA degradation.     

Hexavalent chromium ion and methyl orange dye uptake via a silk protein sericin–chitosan conjugate

Sericin, a protein waste product of the silk industry, was crosslinked with chitosan, and a chitosan–sericin conjugate (CS) was prepared, characterized and used to remove hexavalent chromium (Cr(vi)) ions and methyl orange (MO) dye from aqueous solutions. The CS was shown to effectively remove Cr(vi) ions and MO dye at maximum adsorption capacities (Langmuir) of 139 mg g⁻¹ for Cr(vi) ions and 385 mg g⁻¹ for MO dye. Moreover, the adsorption of both Cr(vi) ions and MO dye was highly pH dependent and varied under different experimental conditions. Cr(vi) ion and MO dye uptake by the CS was confirmed by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS) and energy dispersive spectrometry analysis. Additionally, XPS analysis of the Cr(vi)-loaded CS revealed that Cr(vi) was reduced to the less toxic Cr(iii). The CS was shown not only to be highly amenable to regeneration, but also to be able to effectively remove MO dye and Cr(vi) ions from a binary mixture.

Sericin, a protein waste product of the silk industry, was crosslinked with chitosan, and a chitosan–sericin conjugate (CS) was prepared, characterized and used to remove hexavalent chromium (Cr(vi)) ions and methyl orange dye from aqueous solutions.     

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.     

The synthesis of a BiOClxBr1−x nanostructure photocatalyst with high surface area for the enhanced visible-light photocatalytic reduction of Cr(vi)

The photocatalytic reduction of poisonous Cr(vi) to environmentally friendly Cr(iii) driven by visible-light is highly foreseen. The construction of heterojunctions is a promising and solid strategy to tune the photocatalytic performance of BiOCl in the visible region. Herein, for the first time, we report Cr(vi) reduction by a BiOCl_0.8Br_0.2 composite produced via a facile in situ synthetic process at room temperature while making use of PVP (MW = 10 000). In this study, a series of BiOCl_xBr_1−x nanocomposites with different concentrations of chlorine and bromine have been prepared. The results show that BiOCl_0.8Br_0.2 has crystalline lattice, a large surface area (147 m² g⁻¹), a microporous structure (0.377 cm³ g⁻¹), and very high chemical stability. It is revealed that the BiOCl_0.8Br_0.2 composite is much more active than those synthesized using different molar concentrations of chlorine and bromine. The DRS analysis and high photocurrent suggested that BiOCl_0.8Br_0.2 possessed absorption properties under visible light, which is beneficial for the efficient generation and separation of electron–hole pairs. In addition, we evaluated the photocatalytic activity of BiOCl_0.8Br_0.2 on the reduction of Cr(vi) under visible light irradiation and found that the obtained composite material exhibited a higher photocatalytic activity than single BiOCl or BiOBr without any decline in the activity after five cycles and is the best performing photocatalyst among those tested.

Cr(vi) reduction is performed by BiOCl_0.8Br_0.2 composite produced via a facile in situ synthetic process at room temperature while making use of PVP (M_w = 10 000).     

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.     

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).     

NH2-MIL-88B (FeαIn1−α) mixed-MOFs designed for enhancing photocatalytic Cr(vi) reduction and tetracycline elimination

Aiming at solving the issue of wastewater purification, this work synthesized NH₂-MIL-88B (Fe_αIn_1−α) photocatalysts by a simple one-pot method, which was employed for photocatalytic reduction of Cr(vi) and oxidation of TC-HCl. Compared with traditional NH₂-MIL-88B (Fe) photocatalysts, NH₂-MIL-88B (Fe_0.6In_0.4) displayed excellent photocatalytic performance; the photocatalytic redox rate for Cr(vi) and TC-HCl reached 86.83% and 72.05%, respectively. The good photocatalytic performance might be attributed to the metal-to-metal charge transition (MMCT) between Fe–O clusters and In–O clusters formed by doping In(iii) into NH₂-MIL-88B (Fe), which provides effective active sites for the photocatalytic reduction and oxidation routes. Besides, the synergistic effect of the ligand-to-metal charge transition (LMCT) and MMCT expands the separation and transfer of photogenerated carriers and inhibits the recombination of electron–hole pairs, thus effectively improving the photocatalytic performance. Therefore, this work could provide a new method for the construction of mixed metal MOFs for the photocatalytic degradation of pollutants.

Aiming at solving the issue of wastewater purification, this work synthesized NH₂-MIL-88B (Fe_αIn_1−α) photocatalysts by a simple one-pot method, which was employed for photocatalytic reduction of Cr(vi) and oxidation of TC-HCl.     

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.     

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.     

Removal of Cr(vi) from wastewater by a two-step method of oxalic acid reduction-modified fly ash adsorption

Excessive Cr(vi) emissions have been and continue to be a major contributor to heavy-metal pollution; recently, the development of a low-cost, safe and efficient method for the removal of Cr has attracted significant attention. In the present study, a two-step method involving oxalic acid reduction and modified fly ash adsorption was developed. The experimental results showed that this methodology exhibited high Cr(vi) removal efficiency under the following conditions: 1.5 g L⁻¹ of oxalic acid, modification of fly ash (FA) by 20 wt% KOH, a contact time of 2 h and a mass of 0.3 g of modified fly ash (MFA) at room temperature (15–25 °C). The influencing factors of the adsorbent were discussed by characterized for their elemental composition, functional groups, surface area and surface morphology. According to the characteristic parameters and q_e, the isothermal adsorption process could be well-described by the Langmuir model. The adsorption process resembles more closely to the pseudo-second-order kinetic model. In conclusion, this two-step method of oxalic acid reduction-modified fly ash adsorption is promising for Cr(vi) removal.

Removal of Cr(vi) from wastewater using a two-step method.