Removal Of Cr Research Articles

Synthesis and characterisation of superior AC/ZnO NPs biocomposite for hexavalent chromium Cr(VI) adsorption

This study aims to synthesize biocomposite by combining banana stem activated carbon (AC) and ZnO Nanoparticles (NPs) to evaluate their adsorption potential towards hexavalent chromium (Cr (VI)) (20 mg/L). The AC used was successfully synthesized by an impregnation method using phosphoric acid (H3PO4) for 24 h, followed by a carbonization method. ZnO NPs were synthesized using the direct precipitation method using zinc acetate dihydrate (0.2 M) and KOH (0.4 M) as precursors. The AC/ZnO NPs biocomposite was fabricated using the mechanical alloying method at a frequency of 10 Hz for 30 min. The FTIR results show that both adsorbents, namely pure AC and AC/ZnO NPs have abundant functional groups. XRD results show the adsorbent is amorphous with pure AC at 89.95% and AC/ZnO NPs biocomosite at 56.49%. SEM results showed that the morphology of AC resembled crushed bovine bone marrow, and the morphology of ZnO NPs showed a marshmallow-like shape. The UV–vis spectrometer test results show that at the absorption peak of 350 nm the Cr (VI) removal efficiency slowly decreases and disappears at a dose variation of 1.5 g pure AC, 2 g biocomposite AC/ZnO NPs, and 2 g pure AC with Cr (VI) removal efficiency of 99.61%, 99.64%, and 99.83% respectively. Finally, we can report that the high degradation ability for Cr (VI) can be related to thesharp peak of –C=O group, reduced ΔLO−TO, and smaller average crystallite size in AC/ZnO NPs biocomposite.

Effect of straw decomposition on hexavalent chromium removal by straw: Significant roles of surface potential and dissolved organic matter

Mobility and bioavailability of hexavalent chromium (Cr(VI)) in agricultural soils are affected by interactions between Cr(VI) and returned crop straws. However, the effect of straw decomposition on Cr(VI) removal and underlying mechanisms remain unclear. In this study, Cr(VI) removal by pristine and decomposed rice/rape straws was investigated by batch experiments and a series of spectroscopies. The results showed that straw decomposition inhibited Cr(VI) removal, regardless of straw types. However, the potential mechanisms of the inhibition were distinct for the two straws. For the rice straw, a lower zeta potential after decomposition suppressed Cr(VI) sorption and subsequent reduction. In addition, less Cr(VI) was reduced by the decomposed rice straw-derived dissolved organic matter (DOM) than the pristine one. In contrast, for the rape straw, due to the increased zeta potential after decomposition, the decreased Cr(VI) removal was mainly ascribed to less Cr(VI) reduction by the rape straw-derived DOM. These results emphasized the significant roles of straw surface potential and DOM in Cr(VI) removal, depending on straw types and decomposition, which facilitate the fundamental understanding of Cr(VI) removal by straws and are helpful for predicting the environmental risk of Cr and rational straw return in Cr(VI)-contaminated fields.

Reduction Removal of Cr(VI) Using Oxalic Acid With MOF‐525(Fe) as Catalyst: Performance and Mechanism

ABSTRACTHexavalent chromium (Cr(VI)) has attracted great considerations due to their high toxicity, teratogenicity, and carcinogenicity. In this study, four Zr‐MOFs were synthesized and used to comparative study their catalytic performances of oxalic acid (OA) for Cr(VI) removal. Results showed that the removal efficiency for Cr(VI) was reached 65.91%, 78.64%, 53.58%, and 96.32% by MOF‐525, MOF‐525(Co), MOF‐525(Zn), and MOF‐525(Fe) in the presence of OA when the initial Cr(VI) concentration was 100 mg·L−1, respectively. The single‐factor experiments for further improving the Cr(VI) removal by MOF‐525(Fe)/OA demonstrated that the optimal conditions were OA dosage of 790 mg·L−1, and MOF‐525(Fe) dosage of 500 mg·L−1 and pH of 2.0, and the MOF‐525(Fe)/OA system could be used to treat Cr(VI)‐containing wastewater at concentrations below 50 mg·L−1. Ionic strength studies indicated that Na+, K+, Mg2+, Cl−, and SO42− had little effect on the catalytic reduction of Cr(VI), while high concentrations of Ca2+ (0.10 and 0.25 mol·L−1), NO3− (0.25 mol·L−1), and PO43− (0.25 mol·L−1) had significant inhibition effects. The reusability experiments showed that the stability of MOF‐525(Fe) was excellent, and it could be used for potential applications. Based on the results of Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), and Electron Paramagnetic Resonance spectrometer (EPR), the possible reduction mechanism of Cr(VI) by MOF‐525(Fe)/OA system was proposed as follows: The complexation of OA with Fe3+ was first complexed to produce Fe2+ and CO2•−, then Cr(VI) was combined with Zr–O and Fe–O clusters in MOF‐525(Fe) to obtain activation energy, and the reduction ability was enhanced at the same time; finally, Cr(VI) obtained electrons from CO2•− and was sequentially reduced as Cr(V) and Cr(III).

One-pot amination and carboxylation functionalization of lignin for efficient adsorption of Cr(VI) and Cd(II): Influence of functional groups on adsorption equilibrium and mechanism

The removal of multiple heavy metal pollutants remains a challenge. Amination and carboxylation modified lignins (NCLs) prepared by one-pot hydrothermal method were used as adsorbents for Cr(VI) and Cd(II) removal. The oxygenous groups content in adsorbents was quantitatively analyzed by Boehm titration in which NCL10 (the mass ratio of citric acid: triethylene diamine = 10) possessed a maximum carboxyl group content of 1.22 mmol/g. The Langmuir adsorption isotherm model was the most suitable, with the highest theoretical adsorption capacity of Cr(VI) and Cd(II) of 1298.6 and 103.1 mg/g, respectively. Meanwhile, FT-IR and XPS exhibited that NCL5 surface contained many functional groups beneficial to the removal of Cr(VI) and Cd(II). The contribution of carboxyl and hydroxyl groups to the removal of Cr(VI) and Cd(II) was quantitatively analyzed. After the blocking of carboxyl and hydroxyl groups, the adsorption rate of Cr(VI) and Cd(II) decreased by 26.4 %, 67.7 % and 7.2 %, 43.3 %, respectively. This study provides effective strategies to overcome the limitations of lignin adsorbents for wastewaters containing a wide range of heavy metal pollutants.

Magnetic iron-based waterworks sludge modified by chitosan and FeS for aqueous Cr(vi) adsorption and reduction.

Heavy metals have been considered an evolving environmental concern due to their harmful and long-lasting impacts. We synthesized a composite of FeS/CS@MIBWS for aqueous Cr(vi) adsorption and reduction utilizing the iron-based waterworks sludge modified by chitosan and FeS. After determining the optimal conditions for the FeS/CS@MIBWS preparation, its Cr(vi) removal capability was evaluated using material characterisation and static Cr(vi) adsorption assays. Cr(vi) elimination by the composite was a pH-dependent process, with pH 2 being the optimum in the range of 2-10. The adsorption process was befitted a pseudo-second-order model, and the equilibrium results agreed well with the Langmuir model. The thermodynamics investigation showed that Cr(vi) removal by the composite has both spontaneous and endothermic nature. Considering the ionic effects, Cl-, SO4 2- and PO4 3- decreased Cr(vi) elimination in the sequence of Cl- < SO4 2- < PO4 3-. The key mechanisms for Cr(vi) elimination were physical and chemical adsorption, chelation, and Cr(vi) reduction into Cr(iii). Furthermore, FeS/CS@MIBWS demonstrated steady reusability (removal effectiveness of 70% after 5 cycles). FeS/CS@MIBWS's rapid, high-performance, reusable, and easily separable adsorption properties make it a promising choice for heavy metal environmental cleaning.

Enhanced hydroxyl radical generation by zero-valent iron/ethylenediamine tetramethylene phosphonic acid for Cr(VI) reduction and 2,4-dichlorophenol degradation

Zero-valent iron (ZVI) has emerged as a promising material for water remediation in recent years. However, the formation of a passivation layer on the surface of ZVI significantly reduces its reactivity. Ethylenediamine tetramethylene phosphonic acid (EDTMPA), a chelating agent, aids in the prevention and passivation of ZVI. This chelating agent has been used in combination with ZVI to remove 2,4-dichlorophenol (2,4-DCP) and hexavalent chromium (Cr(VI)) simultaneously. In this study, the addition of EDTMPA significantly enhanced the removal efficiencies of Cr(VI) and 2,4-DCP by 7.7–10 times compared to ZVI, reaching complete removal of Cr(VI) and 80 % removal of 2,4-DCP within 120 min. Quenching and probing experiments have shown that hydroxyl radicals (•OH) serve as the predominant reactive species responsible for the degradation of 2,4-DCP. Meanwhile, pristine ZVI effectively reduced Cr(VI) to the less hazardous Cr(III) and reacted with oxygen in water to generate Fe(II) and hydrogen peroxide (H2O2), both critical for initiating the subsequent Fenton reaction. The addition of EDTMPA effectively mitigated the formation of the passivation layer on the surface of the ZVI, maintaining its reactivity. The ZVI/EDTMPA system offers an effective method for simultaneous remediation of Cr(VI) and 2,4-DCP by optimizing the application of ZVI.

New insights into the mechanism for Fe coordination promoting photocatalytic reduction of Cr(VI) by graphitic carbon nitride: The boosted transformation of Cr(V) to Cr(III)

Fe coordination is effective to promote photocatalytic Cr(VI) reduction by graphitic carbon nitride (g-C3N4) from wastewater; however, the role of Fe coordination in the Cr intermediate transformation is still unknown. Herein, a Cr intermediate, Cr(V), is detected by electron paramagnetic resonance and its generation and consumption kinetics are constructed for studying the visible-light photocatalytic processes of g-C3N4 and Fe anchored g-C3N4. The inclusion of Fe increased the photocatalytic Cr(VI) removal from 26.8 % to 51.3–85.6 %. The results reveal that Fe coordination of trivalent state can greatly enhance photocatalytic Cr(VI) reduction performance mainly through promoting interfacial electron transfer from g-C3N4 to Cr(V). Compared with pure g-C3N4, increasing Fe(III)/Fe(II) ratio of coordinated Fe species results in 8–11 times of enhancement of photocatalytic Cr(VI) reduction performance, 1–2 times of enhancement of photocatalytic Cr(V) generation, and 8–9 times of enhancement of photocatalytic Cr(V) consumption. This suggests the rate-limiting step for Cr(VI) reduction by g-C3N4-based photocatalysts is the transformation process of Cr(V) to Cr(III) and also illustrates the important role of the coordinated Fe(III) species in the photocatalytic transformation of Cr intermediates. This study deepens the understanding of Fe-coordination-promoted photocatalytic Cr(VI) reduction process and sheds light on developing high-performance g-C3N4-based photocatalysts for Cr(VI) removal from wastewater.

Cost-effective walnut shell biosorbent for efficient Cr(VI) removal from water: Batch adsorption and optimization using RSM-BBD

The conversion or recycling of waste materials into usable products is a sustainable and ecologically benign strategy, aligning with sustainable development and circular economy principles. This study presents a straightforward and cost-effective method for transforming walnut shells, commonly found in agricultural waste, into a biosorbent material highly effective in eliminating hexavalent chromium (Cr(VI)) from water. The prepared material underwent several analyses to determine its physical characteristics and surface chemistry, revealing an amorphous structure similar to lignocellulosic materials. Using Response Surface Methodology (RSM-BBD), we accurately forecasted and optimized the Cr(VI) adsorption process, evaluating and enhancing factors such as pH, biosorbent dosage, pollutant concentration, and adsorption time. Significant enhancement in the removal percentage (%R) was achieved, reaching 100 % after optimization. The RSM-BBD model provided high-quality prediction for data fitting (R² = 0.999). Various kinetic models, including PFO, PSO, and IPD models, were employed, with the PSO model providing the best depiction of adsorption. Equilibrium data analysis using the Langmuir, Freundlich, Redlich-Peterson and Temkin models revealed that the Freundlich model and R-P better fit the adsorption isotherm of Cr(VI) on treated walnut shell (WST). Furthermore, examination of Gibbs free energy and enthalpy indicated that the adsorption of Cr(VI) onto walnut shells is a spontaneous and exothermic reaction, resulting in the release of thermal energy.

Synthesis, characterization of hydroxyapatite from pomegranate fruit peel for Cr (VI) adsorption: Process modelling, kinetic and isotherm studies

The present work focuses on preparation of hydroxyapatite from pomegranate peels by precipitation method. The hydroxyapatite derived from pomegranate fruit peels (HA-PP) was characterized by XRD, FT-IR, SEM-EDS and BET techniques. The HA-PP has mesoporous in structure and had an area of 99.021 m2/g. Further HA-PP was used as adsorbent for the removal of Cr (VI) ion particles from K2Cr2O7. The adsorption trials were executed and found the optimized solution using response surface methodology (RSM). The experiments included parameters like pH 2, initial chromium concentration 200 mg/L, adsorbent loading 0.8 g, and contact time 60 min, respectively. Cr (VI) removal was 89.4 % at the optimum combination of these process parameters. A mathematical and statistical optimizing technique response surface methodology (RSM) was applied to verify the interactive effects of various parameters on the adsorption capacity. The analysis of variance (ANOVA) was used to predict the adequacy of the model (F 82.16) shows developed model is valid with R2 value 0.987, and p-value (>0.1). In this the Langmuir adsorption isotherm and the pseudo-second-order kinetic model are well explained for Cr (VI) adsorption onto HA-PP. This reaction is spontaneous and endothermic, as indicated by the negative change in the standard free energy (ΔG0 = −0.1732) and ΔH0 (+4.71) value at the selected temperature. The ΔS0 (+15.89) further confirms that the randomness increased at the solid-solution interface during adsorption.

Utilization of Base and Acid Modified Rice Husk-Corncobs Composite for Removal of Chromium (VI) Ion in Simulated Tannery Wastewater

In the ever-increasing blind race of industrialization and urbanization environmental contamination by toxic heavy metal ions is becoming a serious issue for both scientists and masses. Hence, the objective of this paper was to evaluate the utilization of base (BMOD) and acid (AMOD) modified rice husk-corncobs composite for the removal of chromium (VI) Ion in simulated tannery wastewater using appropriate standard techniques. SEM-EDX, XRD and FTIR characterizations revealed the elemental composition, crystallographic structures and the chemical bonds respectively. The results of the sorption kinetic study showed that the data fitted well with the pseudo-second order model for both acid modified (AMOD) and base modified (BMOD) biosorbent with a maximum adsorption of 28.46 mg/g and 39.66 mg/g respectively. The results of the sorption isotherm study showed that they both fitted Freundlich isotherm model. From the results obtained, rice husk and corn cob were effective biosorbent for the removal of Cr (VI) ion from tannery effluent.

Efficient co-removal of aqueous Cr(VI) and ciprofloxacin by alkali lignin-derived carbon supported nanoscale zero-valent iron via adsorption and redox synergistic mechanisms

Developing an efficient co-removal strategy is crucial for the treatment of combined contaminants with heavy metals and antibiotics due to their great threat to sustainable advancement and ecological preservation. Herein, the efficient co-removal of aqueous hexavalent chromium (Cr(VI)) and ciprofloxacin (CIP) is achieved via a newly developed composite of nanoscale zero-valent iron particles embedded into alkali lignin-derived carbon (nZVI/ALC) without external assistance (such as light, advanced oxidants). nZVl/ALC demonstrates superior co-removal efficiencies of Cr(VI) (99.9 %) and CIP (89.9 %) with high removal kinetic rate constants of 1.595 and 0.779 min−1, respectively. The underlying mechanisms involving the co-removal of Cr(VI) and CIP verify that Cr(VI) ions are adsorbed onto the skeleton of nZVI/ALC originating from the electrostatic interaction, and CIP molecules adsorbed on nZVl/ALC act as a bridge, complexing with the Cr(VI) ions to promote Cr(VI) removal. Meanwhile, the CIP adsorption by nZVI/ALC involves hydrogen bonding, π-π interaction, and complexation. The coexisting Cr(VI) ions are transformed into Cr(III) components with abundant electron transfer, leading to the generation of more •O2– radicals, thus the self-generating reactive oxygen species (•OH, •O2– and 1O2) in ambient-air condition promote CIP degradation in the binary system. The CIP molecules’ degradation pathways mainly include piperazine ring cracking, piperazine epoxidation, quinolone ring opening and defluorination according to the analysis of HPLC-MS and FuKui function, along with the gradual reduction in toxicity throughout the degradation process of CIP molecules. This study offers a new insight on the co-removal of Cr(VI) and CIP, which would provide promising guidance for the remediation of compound wastewater with heavy metals and antibiotics.

Sulfidized nanoiron-loaded carbon for efficient removal of Cr(VI) from wastewater

With the advancement of industrial development, the threat of chromium (Cr) pollution in the aquatic environment has escalated significantly. So, it is essential to develop economically and environmentally friendly means to remove Cr(VI). In this experiment, a novel material, activated carbon loaded sulfidized nanoscale zero-valent iron (S-nZVI@AC) was prepared by sulfide modification and activated carbon (AC) loading modification. According to the data, the most effective material was found to have a S/Fe molar ratio of 0.07 and an S-nZVI@AC mass ratio of 3:1, with a removal rate (RR%) was as high as 99.9% at 60 min. The RR% of the dosage of 0.8 g/L was 99.9% and demonstrated good economic efficiency. The RR% of S-nZVI@AC for Cr(VI) was higher at pH = 3 or 7, reaching 99.8% and 99.6%, respectively. The presence of coexisting ions significantly impacted the RR%, with SO42−, K+, and high concentration of Na+ promoting removal, while PO43−, CO32− and Ca2+ had an inhibitory effect. Of these, PO43− could even reduce the RR% to about 10%, whereas a low concentration of Na+ had minimal impact. S-nZVI@AC also exhibited good resistance to aging, maintaining approximately 80% removal after being soaked in water for 10 days. Furthermore, using kinetic and thermodynamic studies, the pseudo-first-order kinetic model, Freundilch, and Elovich models were found to suit the experimental data better. Cr(VI) was eliminated by S-nZVI@AC via a combination of adsorption, reduction, co-precipitation. In summary, it is concluded that S-nZVI@AC was a new material that showed promise in the treatment of Cr(VI) effluent.

Preparation of MoS2/V2O5 nanocomposites for ciprofloxacin degradation and Cr (VI) reduction

In this study, MoS2/V2O5 nanocomposites are obtained by hydrothermal process, and used for photocatalytic system of Ciprofloxacin (CIP) degradation and Cr (VI) reduction. Owing to its novel characteristics, MoS2/V2O5 heterojunctions are revealed as potential semiconductors in this region. V2O5 photocatalyst acts as a charge acceptor, meantime MoS2 acts as an electron donor, therefore promoting charge carrier separation and enhancing photocatalytic efficiency. The MoS2/V2O5 nanocomposites displayed enhanced photocatalytic CIP (98.7 %) and Cr (VI) reduction (98.8 %) after 120 min and 100 min of visible light activity. In contrast, in the first cycle, the photocatalysis capability of the photocatalyst performed in six cycles is 93.8 %. The Kapp values of MoS2/ V2O5 nanocomposites displayed about 11.2 and 19.5-times improvement of photocatalytic of CIP degradation and Cr (VI) reduction, respectively. The MoS2/V2O5 nanocomposites exhibited an enhanced photocurrent density of 0.082 μA/cm−2 compared to a pristine MoS2 sample of 0.045 μA/cm−2. The distinguished heterojunction photocatalysis performance is due to the significant migration of interfacial charges and the inhibited recombination rate of electron-hole pairs. CIP Pollutants eventually decay into H2O, CO2, and small molecule intermediates by generating •O2-, •OH, and h+. The influences of reactive radicals follow the order of •O2- radicals > h+ radicals > •OH radicals. Then, the probable structures of intermediates and achievable photodegradation pathways were discussed for the removal of CIP and Cr (VI) reduction using nanocomposite with visible light response.

Microscopic and macroscopic analysis of hexavalent chromium adsorption on polypyrrole-polyaniline@rice husk ash adsorbent using statistical physics modeling

This paper contributed with new findings to understand and characterize a heavy metal adsorption on a composite adsorbent. The synthesized polypyrrole–polyaniline@rice husk ash (PPY–PANI@RHA) was prepared and used as an adsorbent for the removal of hexavalent chromium Cr(VI). The adsorption isotherms of Cr(VI) ions on PPY–PANI@RHA were experimentally determined at pH 2, and at different adsorption temperatures (293, 303, and 313 K). Multi-layer model developed using statistical physics formalism was applied to theoretically analyze and characterize the different interactions and ion exchanges during the adsorption process for the elimination of this toxic metal from aqueous solutions, and to attribute new physicochemical interpretation of the process of adsorption. The physicochemical structures and properties of the synthesized PPY–PANI@RHA were characterized via Fourier transform infrared spectroscopy (FTIR). Fitting findings showed that the mechanism of adsorption of Cr(VI) on PPY–PANI@RHA was a multi-ionic mechanism, where one binding site may be occupied by one and two ions. It may also be noticed that the temperature augmentation generated the activation of more functional groups of the composite adsorbent, facilitating the interactions of metal ions with the binding sites and the access to smaller pore. The energetic characterization suggested that the mechanism of adsorption of the investigated systems was exothermic and Cr(VI) ions were physisorbed on PPY-PANI@RHA surface via electrostatic interaction, reduction of Cr(VI) to Cr(III), hydrogen bonding, and ion exchange. Overall, the utilization of the theory of statistical physics provided fruitful and profounder analysis of the adsorption mechanism. The estimation of the pore size distribution (PSD) of the polypyrrole-polyaniline@rice husk ash using the statistical physics approach was considered stereographic characterization of the adsorbent (here PPY–PANI@RHA was globally a meso-porous adsorbent). Lastly, the mechanism of Cr(VI) removal from wastewater using PPY-PANI@RHA as adsorbent was macroscopically investigated via the estimation of three thermodynamic functions.

Designing Bi2O3-Sn3O4 Z-scheme heterojunction on TiO2 NTs for improving photocatalytic performance

The design of semiconductor heterostructures as the effective strategy are recognized to enhance the photocatalytic capacity of photocatalysts for the settlement of energy shortage and pollutant treatment. To efficiently utilize solar energy, the Bi2O3-Sn3O4 nanoparticles with the Z-scheme energy band structure were synthesized on TiO2 nanotube arrays (TiO2 NTs) by the solvothermal deposition method. The TiO2 NTs/Bi2O3-Sn3O4 exhibited the outstanding photocatalytic dye degradation and Cr(VI) removal, which was much higher than those of single Bi2O3 or Sn3O4 sensitized samples. The H2 evolution test indicated that the Bi2O3-Sn3O4 cosensitization dramatically enhanced the photocatalytic H2 generation ability of TiO2 NTs with the rate of 58.75 μmol·h−1·cm−2. The high photoelectric conversion was also confirmed, and the outstanding photocatalytic performance was further revealed by the contrast experiment. The plausible photocatalytic mechanism based on the ESR and capturing experiments indicated that the Z-scheme energy band structure induced the photoelectron separation and the generation of O2 and OH radicals, which was the decisive role for the improved photocatalytic performance.

Efficient chromium(VI) removal using trioctylmethylammonium salicylate as the carrier in polymer inclusion membranes.

In this study, the ionic liquid (IL) trioctylmethylammonium salicylate (TOMAS) was prepared and incorporated into a polymer inclusion membrane (PIM) based on cellulose triacetate (CTA) as the polymer for the removal of Cr(VI). Various parameters including the effect of membrane composition (plasticizer and carrier concentration) as well as variables affecting both the feed phase and receiving solution have been investigated. Optimal results were achieved with a PIM made of 50% CTA and 50% TOMAS (% in mass) without the addition of any plasticizer. Using this PIM, Cr(VI) was effectively transported from a feed solution consisting of 10mg L-1 Cr(VI) in 0.01mol L-1 NaNO3 at pH = 2, to a receiving solution containing 0.1mol L-1 NaOH. The transport of Cr(VI) was not affected by the presence of other metals, such as Cr(III), Cd(II), Zn(II), Cu(II), and Ni(II), and a selective recovery rate of 93.61% for both single-ion and mixed-ion solutions after 24h of processing was obtained. Finally, the stability of the membrane was also investigated, with a slight decrease in efficiency observed after 5days of reuse.

Construction of Pillared-Layer Metal-Organic Frameworks as an All-Visible-Light Switchable Photocatalyst for Aqueous Cr(VI) Reduction.

Recently, two-dimensional metal-organic frameworks that are photoactive have shown great potential for efficiently converting solar energy into chemical energy. In this work, we successfully synthesized and designed two M2-MOFs ([Cu(L1)((CH3)2NH)]n (Cu-MOF) and [Zn(L1)(CH3)2NH)]n (Zn-MOF), H2L1 = 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid). Structural analysis suggests that the five-coordinated M(II) ion is surrounded by four oxygen ions from two ligands and one nitrogen atom from one dimethylamine molecule. The ligand spacer acts as a bridge between two SBUs and forms a 2D layer with rhomboid windows. These moieties are arranged in a staggered ABAB pattern, which likely aids in exfoliation. The UV-vis diffuse reflectance spectra (DRS) test shows that when the metal center in the MOF framework is replaced with Cu(II) ions, the light absorption range covers 200-1100 nm, which is much larger than the light absorption range of Zn-MOF. Moreover, the photoelectric current, electrochemical impedance spectra (EIS), and Mott-Schottky tests all indicate that Cu-MOF has better photoelectric properties. When applied to the photocatalytic reduction of Cr(VI), Cu-MOF and Zn-MOF can completely reduce Cr(VI) within 100 min under 450 nm LED light irradiation. Under sunlight irradiation, Cu-MOF can completely reduce Cr(VI) within 40 min, achieving the removal of Cr(VI) ions, which is much faster than the rate of Cr(VI) removal by Zn-MOF.

Visible-NIR responsive Ag2O couple with MIL-53(Fe) on CS as S-scheme photocatalyst for efficient simultaneous removal of Cr(VI) and norfloxacin

This study addresses the urgent need to develop easily recoverable and efficient photocatalysts for the treatment of compound polluted wastewater. Herein, S-scheme MIL-53(Fe)/Ag2O heterojunctions on a charcoal sponge (CS) were constructed by solvothermal-chemical precipitation method, exhibiting high separation efficiency of photoinduced carriers and reduction–oxidation (REDOX) capacity. The synthesized CS/MIL-53(Fe)/Ag2O was characterized by SEM, TEM, XRD, and XPS, confirming the successful deposition and uniform distribution of MIL-53(Fe) and Ag2O nanoparticles on CS. Moreover, CS/MIL-53(Fe)/Ag2O exhibits an extensive light absorption range from visible to near-infrared (NIR) light, thereby significantly enhancing its photocatalytic activity. In present of H2O2, CS/MIL-53(Fe)/Ag2O demonstrated outstanding removal efficacy of norfloxacin (NFX, 96 %, pH=7) or Cr(VI) (100 %, pH=3) through the photocatalytic-Fenton reaction, which was notably superior to that of CS/MIL-53(Fe) (50.4 % NFX, 56.8 % Cr(VI)) and CS/Ag2O (44.3 % NFX, 38 % Cr(VI)). Importantly, when CS/MIL-53(Fe)/Ag2O was used to treat combined polluted wastewater containing both Cr(VI) and NFX, the removal efficiency of Cr(VI) and NFX showed a significant synergistic effect. Additionally, inhibition zone tests demonstrated that the toxicity of NFX intermediates to E. coli gradually decreased as the degradation of NFX progressed. Furthermore, density functional theory (DFT) calculation and relevant characterization were conducted to elucidate the reaction mechanism of S-scheme heterojunctions, highlighting the enhanced separation rate of photo-induced carriers and REDOX capability. This work not only offers a promising approach for construction of MOF-based S-scheme semiconductor heterojunctions, but also presents promising prospects for the purification of compound polluted wastewater containing norfloxacin and Cr(VI).

Impacts of chloride ions on the electrochemical decomplexation and degradation of Cr(III)-EDTA: Reaction mechanisms of HO• and RCS

The removal of Cr(III)-organic complexes, encompassing both decomplexation and ligand degradation, presents significant challenges in industrial wastewater treatment. As one of the most common anions in wastewater, Cl− significantly improves the efficiency of electrochemically removing Cr(III)-organic complexes through generated reactive chlorine species (RCS). In the electrochemical chlorine (EC/Cl2) process, extensive experimentation revealed that ClO• plays a dominant role in the degradation of Cr(III)-EDTA, surpassing the effects of free chlorine, direct electrooxidation, HO•, and other RCS. Density functional theory calculations indicated that RCS, primarily Cl• and ClO•, preferentially oxidize the ligand in Cr(III)-EDTA via H-abstraction, whereas HO• trends to attack the Cr atom through electron transfer. The influential factors on the degradation efficiency of Cr(III)-EDTA, Cr(VI) yield, and total organic carbon removal in EC/Cl2 were also assessed, including Cl− concentration, current density, and pH. Real industrial wastewater was employed as a reaction matrix to evaluate the application of the EC/Cl2 process for treating Cr(III)-EDTA, accompanied by energy efficiency calculations. Additionally, a two-chamber reactor was established to simultaneously oxidize Cr(III)-EDTA at the anode and reduce Cr(VI) at the cathode. This study provided insight into developing RCS-dominated AOPs to effectively decomplex and decompose organic Cr(III)-complexes in Cl−-containing industrial wastewater.

Riboflavin derivatives as a novel electron transfer mediator for enhancing Cr(VI) removal by Shewanella oneidensis MR-1

Bioremediation has garnered considerable interest due to its advantages of economy and no secondary pollution. However, the direct electron transfer rate between microorganisms and Cr(VI) is low. The bioreduction of Cr(VI) by Shewanella oneidensis MR-1 (S. oneidensis) in the presence of formylmethylflavin (FMF) was conducted to understand how FMF mediated the extracellular electron transfer process to improve Cr(VI) removal. In this study, FMF was firstly synthesized by modifing RF to increase its solubility and redox activity. The findings indicate that S. oneidensis/FMF exhibited better Cr(VI) removal performance compared to that of S. oneidensis. Under optimum conditions, 40 mg/L Cr(VI) could be completely removed by S. oneidensis/FMF within 120 h, while only 48.6% of Cr(VI) was removed by S. oneidensis, and the first order rate constant (k) for the Cr(VI) elimination by S. oneidensis/FMF (0.033 h−1) was about 4.1-fold greater than that of S. oneidensis (0.008 h−1). Moreover, the removal of Cr(VI) by S. oneidensis/FMF were dominated by reduction, and supplemented by adsorption and complexation. FMF enhance the extracellular electron transfer rate (EETR) was confirmed by electrochemical cyclic voltammetry (CV) and linear scanning voltammetry (LSV) experiments. This study emphasizes the potential important role of FMF in environmental bioremediation.