Nanoscale iron (oxyhydr)oxide-modified carbon nanotube filter for rapid and effective Sb(iii) removal

Herein, nanoscale iron (oxyhydr)oxide-coated carbon nanotube (CNT) filters were rationally designed for rapid and effective removal of Sb(iii) from water. These iron (oxyhydr)oxide particles (<5 nm) were uniformly coated onto the CNT sidewalls. The as-fabricated hybrid filter demonstrated improved sorption kinetics and capacity compared with the conventional batch system. At a flow rate of 6 mL min⁻¹, a Sb(iii) pseudo-first-order adsorption rate constant of 0.051 and a removal efficiency of >99% was obtained when operated in the recirculation mode. The improved Sb(iii) sorption performance can be ascribed to the synergistic effects of convection-enhanced mass transport, limited pore size, and more exposed active sorption sites of the filters. The presence of 1–10 mmol L⁻¹ of carbonate, sulfate, and chloride inhibits Sb(iii) removal negligibly. Exhausted hybrid filters can be effectively regenerated by an electrical field-assisted chemical washing method. STEM characterization confirmed that Sb was mainly sequestered by iron (oxyhydr)oxides. XPS, AFS and XAFS results suggest that a certain amount of Sb(iii) was converted to Sb(v) during filtration. DFT calculations further indicate that the bonding energy for Sb(iii) onto the iron (oxyhydr)oxides was 2.27–2.30 eV, and the adsorbed Sb(iii) tends to be oxidized.

Herein, nanoscale iron (oxyhydr)oxide-coated carbon nanotube (CNT) filters were rationally designed for rapid and effective removal of Sb(iii) from water.     

Arsenic(iii) removal from aqueous solution using TiO2-loaded biochar prepared by waste Chinese traditional medicine dregs

Oxidation of As(iii) to As(v) is an effective way to improve the performance of most arsenic removal technologies. In this study, a new alternative biosorbent, TiO₂-loaded biochar prepared by waste Chinese traditional medicine dregs (TBC) was applied in remediation for As(iii) from aqueous solution. Compared with unmodified biochar, the specific surface areas and total pore volumes of TBC increased while the average aperture decreased due to the loading of nano-TiO₂. The X-ray diffraction (XRD) of TBC confirmed that the precipitated titanium oxide was primarily anatase. pH did not have a significant effect on the adsorption capacity at 10 mg L⁻¹ As(iii) in suspension with a pH ranging from 2 to 10. Adsorption kinetics data were best fitted by the pseudo-second-order model (R² > 0.999). The Sips maximum adsorption capacity was 58.456 mg g⁻¹ at 25 °C, which is comparable with other adsorbents reported in previous literature. The Gibbs free energy (ΔG) of As(iii) adsorption was negative, indicating the spontaneous nature of adsorption. The results of free radical scavenging and N₂ purging experiments indicated that O₂ acted as an electron accepter and O₂˙⁻ dominated the oxidation of As(iii). The oxidation of As(iii) obviously affected the adsorption capacity for As(iii) by TBC. X-ray photoelectron spectroscopy (XPS) studies showed that As(iii) and As(v) existed on the surface of TBC, suggesting that the oxidation of As(iii) occurred. TBC played multiple roles for As(iii), including direct adsorption and photocatalytic oxidation adsorption. Regeneration and stability experiments showed that TBC was an environment-friendly and efficient adsorbent for As(iii) removal.

TiO₂-loaded biochar prepared by waste Chinese traditional medicine dregs (TBC) was applied in remediation for As(iii) from aqueous solution.     

Optimization of the adsorption and removal of Sb(iii) by MIL-53(Fe)/GO using response surface methodology

In this study, a graphene oxide metal–organic framework (MIL-53(Fe)/GO) composite adsorbent was successfully synthesized using a simple method at room temperature. The specific surface area of the synthesized MIL-53(Fe)/GO nanoparticles was 268.43 m² g⁻¹, with an average pore size of 2.52 nm. The Box–Behnken response surface method was applied to optimize the adsorption time, dosage, pH, temperature, and initial concentration of Sb(iii) in the MIL-53(Fe)/GO adsorption treatment employed for synthetic wastewater containing Sb(iii). We determined the optimal adsorption conditions and explored the isotherm model, adsorption kinetic model, and adsorption mechanism during the adsorption process. For an optimal adsorption of Sb(iii) by MIL-53(Fe)/GO, the adsorption time, dosage, pH, temperature, and initial Sb(iii) concentration should be set to 4.86 h, 85.79 mg L⁻¹, 10.00, 39.29 °C, and 10.09 mg L⁻¹, respectively. Under these optimal conditions, the removal rate of Sb(iii) will be as high as 97.97%. The adsorption of Sb(iii) by MIL-53(Fe)/GO conformed to the Freundlich isotherm adsorption model, and its maximum adsorption capacity was 69.014 mg g⁻¹. The adsorption kinetics process, which is a nonhomogeneous reaction, could be fitted using a quasi-first-order kinetic model. A Fourier transform infrared spectroscopy analysis showed that MIL-53(Fe)/GO hydroxyl and amine groups play a vital role in the adsorption process. MIL-53(Fe)/GO did not exhibit any changes in its adsorption efficiency in the presence of its anion and showed high specificity to Sb(iii). XPS characterization showed that Sb successfully adsorbed onto the adsorbent and that no oxidation–reduction reaction occurred during the adsorption process. The adsorption efficiency remained high even after four cycles of use. MIL-53(Fe)/GO is highly recyclable with significant application potential for treating wastewater containing Sb(iii).

In this study, a graphene oxide metal–organic framework (MIL-53(Fe)/GO) composite adsorbent was successfully synthesized using a simple method at room temperature.     

Simultaneous removal of Sb(iii) and Cd(ii) in water by adsorption onto a MnFe2O4–biochar nanocomposite

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption. The MnFe₂O₄–BC nanocomposite was prepared via a co-precipitation method and analyzed using various techniques. The results confirm the successful decoration of the biochar surface with MnFe₂O₄ nanoparticles. The maximum Sb(iii) removal efficiency was found to be higher from bi-solute solutions containing Cd(ii) than from single-solute systems, suggesting that the presence of Cd(ii) enhances the removal of Sb(iii). The Langmuir isotherm model describes well Sb(iii) and Cd(ii) removal via adsorption onto the MnFe₂O₄–BC nanocomposite. The maximum adsorption capacities are 237.53 and 181.49 mg g⁻¹ for Sb(iii) and Cd(ii), respectively, in a bi-solute system. Thus, the prepared MnFe₂O₄–BC nanocomposite is demonstrated to be a potential adsorbent for simultaneously removing Sb(iii) and Cd(ii) ions from aqueous solutions.

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption.     

Synthesis of nano-zirconium-iron oxide supported by activated carbon composite for the removal of Sb(v) in aqueous solution

In this study, nano zirconium iron oxide based on activated carbon (ZIC) was successfully prepared by using the coprecipitation method. Compared with unmodified activated carbon, ZIC increases the number of active sites by adding metal oxides and hydroxyl groups and greatly improves the adsorption capacity of Sb(v). The synthesized nanocomposites were characterized and analysed by XRD, SEM, FT-IR, VSM and other techniques. The results showed that the zirconium iron oxide particles were successfully loaded and uniformly distributed on the surface of the activated carbon, and the agglomeration phenomenon was reduced. The saturation magnetization of ZIC was 1.89 emu g⁻¹, which easily achieved solid–liquid separation under the action of an external magnetic field. In batch experiments, when the initial concentration was 1 mg L⁻¹, the dosage of ZIC was 600 mg L⁻¹, the pH value was 5.0, the contact time was 180 min, and the removal rate of Sb(v) reached 97.82%. The maximum adsorption capacity of ZIC for Sb(v) was 11.80 mg g⁻¹. Under the interference of various inorganic ions and dissolved organics, the excellent adsorption capacity was still due to ZIC. The adsorption form was multimolecular-layer adsorption, the adsorption process was an endothermic reaction, and chemical adsorption was dominant as the adsorption mechanism. ZIC has good removal efficiency and is reusable, which indicates that ZIC has prospects for practical wastewater treatment.

The adsorbent was highly effective in the removal of Sb(v). The adsorbent easily achieved solid–liquid separation under the action of an external magnetic field.     

An efficient mercapto-functionalized organic–inorganic hybrid sorbent for selective separation and preconcentration of antimony(iii) in water samples

This work reported on the application of mercapto-functionalized silica-supported organic–inorganic hybrid sorbent as a solid phase extraction (SPE) extractant for effective separation and preconcentration of Sb(iii) species in real water samples. The influences of pH, sorbent amounts, flow rates and the concentration of eluent on the adsorption and desorption of Sb(iii) species had been evaluated. The recovery of Sb(iii) species at pH 5 with 100 mg mercapto-functionalized hybrid sorbent at the flow rate of 5.0 mL min⁻¹ was greater than 95% without interference from all of metal ions tested. The trapped Sb(iii) species by extractant was then eluted with 5% HCl solution at the flow rate of 5.0 mL min⁻¹. The proposed procedure permitted large enrichment factors of about 200 and higher for 10 μg L⁻¹ of Sb(iii) species. The merits of analytical figures for the determination of Sb(iii) species were as follows: detection limit (3σ, n = 11), 2 ng L⁻¹; precision, 1.6% (n = 11) for 10 μg L⁻¹ of Sb(iii) species; the linear calibration curve presented in the concentration range of 1.0–200.0 μg L⁻¹. The validity of the proposed procedure was checked by the analysis of standard reference materials. Excellent agreement between the analytical results and the certified values (t-test at 95% confidence level) was found. The mercapto-functionalized hybrid sorbent as a SPE extractant was applied to the determination of Sb(iii) species in various water samples with satisfactory results.

This work reported on the application of mercapto-functionalized silica-supported organic–inorganic hybrid sorbent as a solid phase extraction (SPE) extractant for effective separation and preconcentration of Sb(iii) species in real water samples.     

Facile transmetallation of [SbIII(DOTA)]− renders it unsuitable for medical applications

The antimony(iii) complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA) has been prepared and its exceptionally low stability observed. The Sb(iii) ion in Na[Sb(DOTA)]·4H₂O shows an approximately square antiprismatic coordination geometry that is close to superimposable to the Bi(iii) geometry in [Bi(DOTA)]⁻ in two phases containing this anion, Na[Bi(DOTA)]·4H₂O, [H₃O][Bi(DOTA)]·H₂O for which structures are also described. Interestingly, DOTA itself in [(H₆DOTA)]Cl₂·4H₂O·DMSO shows the same orientation of the N₄O₄ metal binding cavity reflecting the limited flexibility of DOTA in an octadentate coordination mode. In 8-coordinate complexes it can however accommodate M(iii) ions with r_ion spanning a relatively wide range from 87 pm (Sc(iii)) to 117 pm (Bi(iii)). The larger Bi³⁺ ion appears to be the best metal–ligand size match since [Bi(DOTA)]⁻ is associated with greater complex stability. In the solution state, [Sb(DOTA)]⁻ is extremely susceptible to transmetallation by trivalent ions (Sc(iii), Y(iii), Bi(iii)) and, significantly, even by biologically important divalent metal ions (Mg(ii), Ca(ii), Zn(ii)). In all cases just one equivalent is enough to displace most of the Sb(iii). [Sb(DOTA)]⁻ is resistant to hydrolysis; however, since biologically more abundant metal ions easily substitute the antimony, DOTA complexes will not be suitable for deployment for the delivery of the, so far unexploited, theranostic isotope pair ¹¹⁹Sb and ¹¹⁷Sb.

The antimony(iii) complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA) has been prepared and its exceptionally low stability observed.     

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.     

Rational fabrication of a new ionic imprinted carboxymethyl chitosan-based sponge for efficient selective adsorption of Gd(iii)

The selective recovery of Gd(iii) from wastewater is very meaningful for the prospective development of economics and the environment. To overcome disadvantages of poor adsorption capacity, low selectivity and complex preparation process in conventional adsorbents, herein a new ionic imprinted carboxymethyl chitosan (CMC) sponge functionalized by hyperbranched polyethyleneimine (PEI) with a 3D network structure (PEI-CMC-IIS) was successfully prepared and applied in the selective adsorption of Gd(iii). The PEI-CMC-IIS is endowed with lots of amino groups due to the combination of biomass CMC with highly branched PEI, which is helpful for the adsorption of Gd(iii). The imprinting sites are located at the surface of channels in PEI-CMC-IIS, which can achieve the adsorption specificity to Gd(iii) and improve adsorption capacity. It is found that the maximum adsorption capacity of PEI-CMC-IIS is 38.64 mg g⁻¹ at pH = 7. Meanwhile, the selectivity tests suggest that the PEI-CMC-IIS presents preferential adsorption for Gd(iii) with a distribution coefficient of 437.5 mL g⁻¹. Furthermore, the PEI-CMC-IIS displays excellent reusing and regeneration ability. Our findings will bring about potential application in fabrication of other high-efficiency adsorbents for selective adsorption of Gd(iii).

In this work, a new PEI-CMC-IIS adsorbent with 3D network structure was fabricated for the selective adsorption of Gd(iii).     

Synchronous oxidation and sequestration for As(iii) from aqueous solution by modified CuFe2O4 coupled with peroxymonosulfate: a fast and stable heterogeneous process

Bifunctional heterogeneous catalytic processes for highly efficient removal of arsenic (As(iii)) are receiving increased attention. However, the agglomerated nature and stability of nanoparticles are major concerns. Herein, we report a new process regarding the anchoring of CuFe₂O₄ nanoparticles on a substrate material, a kind of Fe–Ni foam, to form porous CuFe₂O₄ foam (CuFe₂O₄-foam) by in situ synthesis. The prepared material was then applied to activate peroxymonosulfate (PMS) for fast and efficient removal of As(iii) from water. The results of removal experiments show that the complete removal of arsenic (<10 μg L⁻¹) from 1 mg L⁻¹ As(iii) aqueous solution can be achieved within shorter time (<10 min) using this adsorbent coupled with PMS. The maximum adsorption capability of As(iii) and As(v) on the prepared adsorbent is observed to be about 105.78 mg g⁻¹ and 120.32 mg g⁻¹, respectively. CuFe₂O₄-foam/PMS couple could work effectively in a wide pH range (3.0–9.0) and temperature range (10–60 °C), which is more beneficial to its application in actual water treatment engineering. The exhausted adsorbents can be refreshed for cyclic runs (at least 7 cycles) with insignificant capacity loss using alkaline solution as a regeneration strategy, suggesting this process has good stability. Investigation of the mechanism reveals that the route to the removal of As(iii) is synchronous oxidation and sequestration in the arsenic removal process. The large As(iii) removal capability and stability of CuFe₂O₄-foam/PMS show its potential as a promising candidate in real As(iii)-contaminated groundwater treatment.

Bifunctional heterogeneous catalytic processes for highly efficient removal of arsenic (As(iii)) are receiving increased attention.     

Properties and mechanism for selective adsorption of Au(iii) on an ionic liquid adsorbent by grafting N-methyl imidazole onto chloromethylated polystyrene beads

To recover Au(iii) from an acidic chloride-containing solution efficiently, an ionic liquid absorbent (CMPS-IL) was synthesized by grafting N-methyl imidazole onto chloromethylated polystyrene beads (CMPS). The adsorption capacity, selectivity, and reusability were systematically evaluated by a series of adsorption experiments. The maximum adsorption capacity reached up to 516.5 mg g⁻¹ at 318 K. The adsorbent can selectively recover Au(iii) from binary system solutions with a higher separation factor β_Au/M (10⁴–10⁶). Moreover, the adsorption–desorption cycles (7 cycles) showed that the CMPS-IL maintained a stable adsorption performance and high adsorption efficiency. Finally, the adsorption mechanism of CMPS-IL for Au(iii) was investigated by SEM, TEM, XPS, and FT-IR, then proposed with a combination of electrostatic interactions and d–π interaction between imidazolium and AuCl₄⁻. This study provides an easily-prepared and economical adsorbent for Au(iii) with high selectivity and large adsorption capacity to boost its practical applications.

The synthesis and adsorption properties for Au(iii) of CMPS-IL synthesized by grafting N-methyl imidazole onto chloromethylated polystyrene beads (CMPS).     

Hydrothermal synthesis of a novel nanolayered tin phosphate for removing Cr(iii)

In this work, an outstanding nanolayered tin phosphate with 15.0 Å interlayer spacing, Sn (HPO₄)₂·3H₂O (SnP–H⁺), has been synthesized by conventional hydrothermal method and first used in the adsorptive removal of Cr(iii) from aqueous solution. A number of factors such as contact time, initial concentration of Cr(iii), temperature, pH, and ionic strength on adsorption were investigated by batch tests. Moreover, the isothermal adsorption characteristics and kinetic model of Cr(iii) onto SnP–H⁺ were studied. The results showed that the adsorption of Cr(iii) by SnP–H⁺ was in accordance with the Langmuir adsorption isotherm model and the pseudo-second-order kinetic model. The adsorption capacity of Cr(iii) onto SnP–H⁺ at temperature 40.0 °C and pH 3.0 could reach 81.1 mg g⁻¹. And the distribution coefficient K_d was 23.0 g L⁻¹. Overall, experiments certified that SnP–H⁺ was an excellent adsorbent that can effectively remove Cr(iii) from aqueous solution.

In this work, an outstanding nanolayered tin phosphate with 15.0 Å interlayer spacing, Sn (HPO₄)₂·3H₂O (SnP–H⁺), has been synthesized by conventional hydrothermal method and first used in the adsorptive removal of Cr(iii) from aqueous solution.     

Synthesis of alginate–polycation capsules of different composition: characterization and their adsorption for [As(iii)] and [As(v)] from aqueous solutions

The uptake of arsenite [As(iii)] and arsenate [As(v)] by functionalized calcium alginate (Ca-Alg) beads from aqueous solutions was investigated. Ca-Alg beads were protonated with poly-l-lysine (PLL) or polyethyleneimine (PEI) using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide/N-hydroxysuccinimide (EDC/NHS) or glutaraldehyde (GA) as crosslinking agents. Four types of protonated beads were prepared: Ca-Alg-EDC/NHS (PLL or PEI) and Ca-Alg-GA (PLL or PEI). Fourier transform infrared spectroscopy in total attenuated reflection mode (FTIR-ATR), analysis showed presence and increased intensity of bands corresponding to OH, NH, CH₂ and CH₃ groups in modifications with both polycations. In addition, thermogravimetric analysis and atomic force microscopy of all modified capsules showed an increase in thermal stability and uniformity of the capsules, respectively. Ca-Alg-EDC/NHS-PLL beads had the maximum adsorption capacity of [As(v)] (312.9 ± 4.7 μg g⁻¹ of the alginate) at pH 7.0 and 15 minute exposure, while Ca-Alg-EDC/NHS-PEI beads had the maximum adsorption capacity of [As(iii)] (1052.1 ± 4.6 μg g⁻¹ of alginate). However, all these EDC containing beads were degraded in the presence of citrate. Ca-Alg-GA-PEI beads removed 252.8 ± 9.7 μg of [As(v)] μg g⁻¹ of alginate and 524.7 ± 5.3 de [As(iii)] μg g⁻¹ of alginate, resulting the most stable capsules and suitable for As removal.

A simple protonation of alginate beads allows the absorption of arsenate and arsenite.     

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.     

Three-dimensional mesoporous calcium carbonate–silica frameworks thermally activated from porous fossil bryophyte: adsorption studies for heavy metal uptake

In this paper, three-dimensional mesoporous calcium carbonate–silica frameworks have been created from the straw tufa (ST) originating from porous fossil bryophyte by a thermal activation technique. A batch of adsorption kinetic and thermodynamic experiments were used to investigate the adsorption capacity of Cd(ii) onto the samples. The ST after thermal activation has shown a significant ability for the uptake of heavy metals. It exhibited maximum adsorption capacities of 12.76 mg g⁻¹, 14.09 mg g⁻¹, 17.00 mg g⁻¹, and 33.81 mg g⁻¹ for Cd(ii) at the activation temperature of 300, 450, 600 and 750 °C, respectively. Through competitive adsorption for Cd(ii)and Pb(ii), the ST thermally activated at 750 °C exhibited maximum equilibrium adsorption capacities of 24.65 mg g⁻¹, 25.91 mg g⁻¹, and 30.94 mg g⁻¹ for Cd(ii) uptake at 298.1 K, 308.1 K and 318.1 K, respectively, whereas it exhibited values of 91.59 mg g⁻¹, 101.32 mg g⁻¹, and 112.19 mg g⁻¹ for Pb(ii) removal. The adsorption capacities of Cd(ii) and Pb(ii) both decrease with the addition of the other heavy metal cations, indicating that the adsorption is hindered by the competitive adsorption and the adsorption active sites on the mineral surface are readily exchangeable. The adsorption of Cd(ii) and Pb(ii) followed the pseudo-second order kinetics model well. In addition, the Langmuir model could accurately describe the adsorption isotherms. Based on the results of characterization with TEM, XRD and XPS, the adsorption mechanisms could be primarily explained as formation of Cd(OH)₂ and CdCO₃ as well as Cd(HCO₃)₂ precipitation on the surface of ST. These characteristics of ion-exchange and the adsorptive property for ST modified allow it to be widely used in artificial wetland landfill and environmental protection.

Three-dimensional mesoporous calcium carbonate–silica frameworks have been created and have shown excellent adsorption capacities for Cd(ii) and Pb(ii).     

Submicron fibers as a morphological improvement of amorphous zirconium oxide particles and their utilization in antimonate (Sb(v)) removal

Mesoporous and large surface area zirconium oxide aggregate granules with good adsorption properties were synthesized using a simple precipitation method. Since utilization of these small and fragile particles is considered rather difficult in larger scale column operation, the product was formed into a fibrous form to improve its usability. The submicron fibers were obtained from an optimized electroblowing synthesis that resulted in elastic and uniform fibers with a tetragonal structure and high length-to-diameter ratio. In antimonate (Sb(v)) adsorption experiments, the higher calcination temperature (350 °C) of the fibers did not seem to decrease the Sb(v) adsorption capacity excessively since the high theoretical adsorption capacities were 113 mg g⁻¹ and 58 mg g⁻¹ for the aggregate and fibers, respectively. Both materials had fast kinetics, fibers being faster in the beginning of the reaction. Moreover, both materials offered efficient Sb(v) removal in the studied pH range from 1 to 11 by reaching over 99.9% adsorption in the optimal pH range. X-ray absorption near edge spectroscopy (XANES) revealed that Sb(v) stays as pentavalent antimony after being adsorbed by these materials and based on the isoelectric point shifts in the zeta potential measurement, adsorption occurs mainly by an inner-sphere complexation reaction. Finally, our study showed that pressure buildup in a flow-through column packed with zirconium oxide fibers was significantly lower than in a column packed with aggregates. Thus, zirconium oxide aggregates can be formed into submicron fibers with enhanced column operation properties without a too large compromise in the adsorption properties.

Zirconium oxide was formed into submicron fibers to improve the Sb(v) separation performance compared to a conventional aggregate material.     

Mechanistic insights into dioxygen activation by a manganese corrole complex: a broken-symmetry DFT study

The Mn–oxygen species have been implicated as key intermediates in various Mn-mediated oxidation reactions. However, artificial oxidants were often used for the synthesis of the Mn–oxygen intermediates. Remarkably, the Mn(v)–oxo and Mn(iv)–peroxo species have been observed in the activation of O₂ by Mn(iii) corroles in the presence of base (OH⁻) and hydrogen donors. In this work, density functional theory methods were used to get insight into the mechanism of dioxygen activation and formation of Mn(v)–oxo. The results demonstrated that the dioxygen cannot bind to Mn without the axial OH⁻ ligand. Upon the addition of the axial OH⁻ ligand, the dioxygen can bind to Mn in an end-on fashion to give the Mn(iv)–superoxo species. The hydrogen atom transfer from the hydrogen donor (substrate) to the Mn(iv)–superoxo species is the rate-limiting step, having a high reaction barrier and a large endothermicity. Subsequently, the O–C bond formation is concerted with an electron transfer from the substrate radical to the Mn and a proton transfer from the hydroperoxo moiety to the nearby N atom of the corrole ring, generating an alkylperoxo Mn(iii) complex. The alkylperoxo O–O bond cleavage affords a Mn(v)–oxo complex and a hydroxylated substrate. This novel mechanism for the Mn(v)–oxo formation via an alkylperoxo Mn(iii) intermediate gives insight into the O–O bond activation by manganese complexes.

DFT calculations revealed a novel mechanism for the formation of Mn(v)–oxo in the dioxygen activation by a Mn(iii) corrole complex involving a Mn(iii)–alkylperoxo intermediate.     

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.     

Highly efficient and rapid removal of arsenic(iii) from aqueous solutions by nanoscale zero-valent iron supported on a zirconium 1,4-dicarboxybenzene metal–organic framework (UiO-66 MOF)

A zirconium 1,4-dicarboxybenzene metal–organic framework (UiO-66 MOF) was successfully used as a template to enhance the distribution and activity of nanoscale zero-valent iron (NZVI). MOF-NZVI showed good anti-interference ability to co-existing ions (Ca²⁺, Mn²⁺, Cu²⁺, H₂PO₄⁻ and SO₄²⁻) and organic acids (oxalic acid and citric acid). SEM and TEM analyses indicated that the MOF as a support efficiently prevent NZVI from aggregation for quick and effective removal of As(iii). Through the non-linear least-squares (NLLS) adjustment, As(iii) removal by MOF-NZVI could be well fitted by pseudo first and second order reaction kinetics, as well as the Freundlich isotherm. FTIR, XRD and XPS results verified that NZVI and iron oxyhydroxides (Fe₃O₄, γ-Fe₂O₃, γ-FeOOH and α-FeOOH) might be responsible for the effective removal of As(iii) and its oxidized product As(v) with an adsorption capacity of 360.6 mg As per g NZVI through chemical oxidation and physical adsorption. This work indicates that MOF-NZVI with good reusability and high efficiency is promising for application in As(iii)-polluted wastewater treatment.

A zirconium 1,4-dicarboxybenzene metal–organic framework (UiO-66 MOF) was successfully used as a template to enhance the distribution and activity of nanoscale zero-valent iron (NZVI).