Branched poly(ethylene imine) support for resins with retention properties for heavy metal ions

A crosslinked poly(ethylene imine), using epichlorohydrin as crosslinker, was prepared and subsequently modified in order to obtain the corresponding N-methylated, N-carboxymethylated and N-phosphonomethylated derivatives. The sorption characteristics of these functionalized resins were studied by a batch equilibration technique, for uptake of Cu(II), Fe(II), Fe(III) and uranyl ions from aqueous solution. Resins with tertiary amine or ammonium groups show negligible sorption for Fe(II), Fe(III) and Cu(II) at pH 1, in contrast with high sorption for U(VI), which is readily eluted with sodium carbonate.     

Construction of defect-containing UiO-66/MoSe2 heterojunctions with superior photocatalytic performance for wastewater treatment and mechanism insight

Metal–organic frameworks are recognized as promising multifunctional materials, especially metal–organic framework-based photocatalysts, which are considered to be ideal photocatalytic materials. Herein, a new type of UiO-66/MoSe₂ composite was prepared using the solvothermal method. The optimum composite was selected by adjusting the mass ratio of UiO-66 and MoSe₂. X-ray diffraction analysis showed that the mass ratio influenced the crystal plane exposure rate of the composite, which may have affected its photocatalytic performance. The composite is composed of ultra-thin flower-like MoSe₂ that wrapped around cubic UiO-66, a structure that increases the abundance of active sites for reactions and is more conducive to the separation of carriers. The photocatalytic properties of the composite were evaluated by measuring the degradation rate of Rhodamine B and the catalyst’s ability to reduce Cr(VI)-containing wastewater under visible light irradiation. Rhodamine B was decolorized completely in 120 min, and most of the Cr(VI) was reduced within 150 min. The photochemical mechanism of the complex was studied in detail. The existence of Mo⁶⁺ and oxygen vacancies, in addition to the Z-type heterojunction promote the separation of electrons and holes, which enhances the photocatalytic effect.     

Simultaneous degradation of RhB and reduction of Cr(VI) by MIL-53(Fe)/Polyaniline (PANI) with the mediation of organic acid

MIL-53(Fe)/polyaniline (PANI) composite was prepared by in situ depositing PANI on the surface of MIL-53(Fe) and their catalytic performances on the simultaneous removal of RhB and Cr(VI) were investigated. The elimination efficiency of both RhB and Cr(VI) reached more than 98% under pH=2 where hydrochloric acid and citric acid were used to adjust the pH. The results indicated that MIL-53(Fe)/PANI revealed an obvious pH response to the degradation of RhB, while citric acid promoted the Cr(VI) photoreduction. UV-Vis spectra, EIS, and photocurrent response experiments showed that MIL-53(Fe)/PANI had a better light response and carrier migration ability than MIL-53(Fe). The transient absorption spectra also exhibited that the lifetimes of photo-generated carriers were prolonged after the conductive polymer deposition on the MIL-53(Fe) surface. Scavenger experiments demonstrated that the main active species were ·O₂^- and OH. Combined with activity evaluation results, and the possible photocatalytic mechanism of MIL-53(Fe)/PANI on RhB oxidation and Cr(VI) reduction was proposed. The addition of conductive polymer can effectively improve the light response of the catalyst under acidic conditions, and meanwhile citric acid also provided a new mediation for the synergistic degradation of multiple pollutants. Good activity and stability of the catalysts made the scale-up purification of acid water feasible under UV-Vis light.     

Removal of Cr(VI) from water using Fe(II)-modified natural zeolite

In this study, natural zeolite aggregates with the particle size of 1.4–2.4 mm were modified by Fe(II). The unmodified zeolite and Fe(II)-modified zeolite (Fe-eZ) were subjected to batch and column tests to study the Cr(VI) sorption, transport, and retardation. Modification of the natural zeolite with Fe(II) resulted in an increase in Cr(VI) sorption to 6 mmol/kg. The Cr(VI) sorption followed a pseudo-second-order kinetics with a rate of 17 mmol/g h and a rate constant of 0.7 g/mmol h. Cr(VI) removal from solution increased with an increase in ionic strength, but decreased as the solution pH increased. At a Cr(VI) input concentration of 100 mg/L, unmodified zeolite did not show any Cr(VI) retardation at all. In contrast, the observed retardation factor of Fe-eZ for Cr(VI) increased by a factor of 6. The hydraulic conductivity of the zeolite showed little change before and after Fe(II) modification and before and after Cr(VI) sorption, suggesting its good mechanical stability to be used as packing materials for permeable reactive barriers in groundwater remediation.     

Catalytic performance of MIL-100 (Fe,Cr) and MIL-101 (Fe,Cr) in the isomerization of endo- to exo-dicyclopentadiene

MIL-100 (Fe, Cr) and MIL-101 (Fe, Cr), metal-organic frameworks (MOFs), have been assessed in solvent-free isomerization of dicyclopentadiene (DCPD) from the endo- to exo-form. In the isomerization reaction, the conversion of endo-DCPD and selectivity for the exo-dimer strongly depend on the nature of the active metal center. The MIL-100 (Fe) catalyst possessing more acid sites shows the highest catalytic activity among the MILs and it was readily recoverable and reusable in subsequent reaction cycles for the isomerization. The effects of reaction parameters such as temperature, reaction time, and catalyst loading on the reactivity were also investigated.     

Effect of ortho- and pyrophosphates on dissolution of Fe,Al, Si,Ca, and organic C in three soils

Phosphate application changes chemical properties of surface soils, consequently influencing crop nutrient availability and pedological process. Sodium ortho- (OP) or pyrophosphate (PP) was equilibrated with three Quebec soils: an Uplands sand (Orthic-Podzol), a St. Bernard loam (Eutric-Cambisol), and a Dalhousie clay (Humic Gleysol) in 0.03 M KClO₄ solution at an initial pH 6.0. Both autoclaved and nonautoclaved soils were used, and dissolution of Fe, Al, Si, Ca and organic C was studied.Concentrations of Fe and Al in OP equilibrated solutions were not detectable. Ca solubility was reduced while dissolution of Si and organic C was increased in the presence of OP. These changes were possibly due to P—Ca precipitates or increased Ca sorption by P, and competition between OP and Si or organic materials for sorption sites. PP enhanced dissolution of Fe, Al, Si and organic C but reduced solubility of Ca. Comparisons showed that PP added to autoclaved soils had greater effects on increasing dissolutions of Fe, Al, Si and organic C and on reducing Ca solubility than OP in both autoclaved and nonautoclaved soils. Autoclaving resulted in greater dissolution of organic C. Dissolved Si with added OP was greater with nonautoclaved soils probably due to more P sorption in the nonautoclaved system, compared with autoclaved soil. Added PP dissolved Fe and Al ions which may ultimately enhance P precipitation by forming less soluble compounds upon hydrolysis of PP to OP.     

Coals as sorbents for the removal and reduction of hexavalent chromium from aqueous waste streams

The aim of this study is to demonstrate the potential of coals as a low-cost reactive barrier material for environmental protection applications, with the ability to prevent leaching of toxic Cr(VI) and other transition metals. Depending upon the type of ion and the surface functionalities, the uptake can involve ion sorption, ion exchange, chelation and redox mechanisms with the surface functionalities being considered as partners in electron transfer processes. The capacity for Cr(VI) uptake of low rank coals and oxidized bituminous coals has been found to lie within the range 0.2-0.6 mM g⁻¹. Air oxidation of bituminous coals can increase their Cr(VI) removal capacities. The effect of air oxidation of coals on uptake capacity was more pronounced for Cr(VI) than Cr(III), but less than for Hg(II) and the other ions (Ca²⁺, Ba²⁺, Zn²⁺, Cd²) investigated. As previously found for Hg(II), redox mechanisms play an important role in Cr(VI) uptake, with sorption of the resultant Cr(III) being aided by the functionalities arising from oxidation of the coal surface. In acidic media, much of the resultant Cr(III) is exchanged back into solution by hydrogen ions, but some of the sorbed chromium is irreversibly bound to the coal. The reduction of Cr(VI) alone is often considered a satisfactory solution in view of Cr(III) being essentially non-toxic.     

Au基MOFs双功能催化剂的制备及其催化CO2与苯胺/H2反应性能

以UiO-66(Zr)、MIL-100(Fe)、MIL-100(Cr)、MIL-101(Cr)、NH 2-MIL-101(Al)为载体,Au为活性组分,制备Au/UiO-66(Zr)、Au/MIL-100(Fe)、Au/MIL-100(Cr)、Au/MIL-101(Cr)、Au/NH 2-MIL-101(Al)双功能催化剂。采用XRD、BET、NH 3-TPD、HRTEM等表征催化剂的结构,在釜式反应器中评价催化剂对CO 2与苯胺/H 2反应生成N-甲基苯胺与N,N-二甲基苯胺的N-甲基化反应性能,考察反应条件对催化剂催化性能的影响。结果表明,催化剂的XRD特征衍射峰与相应MOFs的模拟特征峰基本一致;负载Au后催化剂仍具有高的比表面积和大的孔容、孔径;不同MOFs负载Au的催化剂具有不同的酸强度和酸量;Au纳米粒子的分散性很好,粒径为(3~7)nm。制备的催化剂均具有催化CO2与苯胺/H2的N-甲基化反应性能,其中质量分数2%Au/MIL-101(Cr)催化剂催化性能最好,苯胺转化率为45.26%,N-甲基苯胺和N,N-二甲基苯胺选择性分别为73.50%和26.50%,重复使用性能优异。     

Sorption of Uranium and other Metal Ions on Amine-Functionalized Silica Materials

Sorption of U(VI) and other metal ions on amine-functionalized silica was studied, including aminopropylsilica (APS), 3-(ethylenediamino)propyl silica (ENPS), and 3-[2-(2-aminoethylamino)ethylamino]propyl silica (DIENPS). DIENPS showed the strongest and fastest sorption for U(VI) that can be described by Langmuir isotherm, suggesting U(VI) was sorbed at well-defined and energetically identical sites independent from each other. The sorption efficiency of DIENPS follows the order: U(VI) > Fe(III) > Cu(II) > Pb(II) > Ni(II) > Mg(II) > Sr(II). Results demonstrate that the amine-functionalized silica materials could be used as efficient sorbents to remove uranium and hazardous metal ions in environmental remediation.     

Extraction Chromatography of Actinides Using Cyanex‐923 as Stationary Phase

Abstract

Cyanex‐923 has been used as the stationary phase in the extraction chromatographic separation of actinide ions from simulated high‐level waste (SHLW). Chromosorb‐W was used as the solid inert support. The uptake behaviour of U(VI), Pu(IV), and Am(III) was studied by batch studies. Breakthrough capacity of the column for Am(III) in the presence of macro amount of Eu(III) has been determined in three successive cycles of loading and elution. The influence of interfering ions like Fe(III), Cr(VI), Al(III), and Ni(II), etc. has been investigated. Effect of column parameters like diameter and height on Am(III) elution profile has also been studied.     

Iron incorporated rice husk silica as a sorbent for hexavalent chromium attenuation in aqueous system

An environmentally benign metal oxide, Fe, was incorporated into silica derived from rice husk via the sol gel route and the physiognomies of both the modified (IRS) and raw rice husk derived silica (RHS) were studied via FTIR and XRD analysis and pH_PZC and surface area determinations. The stability of the Fe incorporated into the silica matrix, determined via the toxicity characteristic leaching procedure, showed that the integrity of the sorbent was intact only in basic medium but got vitiated in acidic medium. The sorption process conformed to the pseudo second order model than reversible first order and pseudo first order kinetic models and the rate of sorption of Cr(VI) onto either sorbents was determined by film diffusion. Process variables optimization showed that the amount of Cr(VI) removed per gram of sorbent reduced with increase in initial solution pH and the negative impact of the anionic interference was more in the presence of SO₃²⁻ than NO₃²⁻ and Cl⁻. The predicted Langmuir monolayer sorption capacity (mg/g) of the IRS (63.69) was higher than that of the RHS (61.35). The value of the mean free energy (kJ/mol) of sorption, obtained for IRS (267.26) and RHS (100.00), and the significant changes in the peak positions of specific functional groups on the Cr(VI) laden sorbents showed that chemisorption was the dominant mechanism of Cr(VI) uptake.     

Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction: a density functional theory study

Recently, metal–organic frameworks are one of the potential catalytic materials for electrocatalytic applications. The oxygen reduction reaction and oxygen evolution reaction catalytic activities of heterometallic cluster-based organic frameworks are investigated using density functional theory. Firstly, the catalytic activities of heterometallic clusters are investigated. Among all heterometallic clusters, Fe₂Mn–Mn has a minimum overpotential of 0.35 V for oxygen reduction reaction, and Fe₂Co–Co possesses the smallest overpotential of 0.32 V for oxygen evolution reaction, respectively 100 and 50 mV lower than those of Pt(111) and RuO₂(110) catalysts. The analysis of the potential gap of Fe₂M clusters indicates that Fe₂Mn, Fe₂Co, and Fe₂Ni clusters possess good bifunctional catalytic activity. Additionally, the catalytic activity of Fe₂Mn and Fe₂Co connected through 3,3′,5,5′-azobenzenetetracarboxylate linker to form Fe₂M–PCN–Fe₂M is explored. Compared with Fe₂Mn–PCN–Fe₂Mn, Fe₂Co–PCN–Fe₂Co, and isolated Fe₂M clusters, the mixed-metal Fe₂Co–PCN–Fe₂Mn possesses excellent bifunctional catalytic activity, and the values of potential gap on the Mn and Co sites of Fe₂Co–PCN–Fe₂Mn are 0.69 and 0.70 V, respectively. Furthermore, the analysis of the electron structure indicates that constructing a mixed-metal cluster can efficiently enhance the electronic properties of the catalyst. In conclusion, the mixed-metal cluster strategy provides a new approach to further design and synthesize high-efficiency bifunctional electrocatalysts.     

Synthesis of polyaniline nanocomposite and its application for chromium removal from aqueous solution

The aim of this research was to investigate the sorption characteristics of polyaniline coated on sawdust (PAn/SD) for the removal of Cr(VI) ions from aqueous solutions. The sorption of Cr(VI) ions was carried out by the batch method. Characterization of PAn/SD was done by FTIR and SEM. The optimum conditions of sorption were found to be a PAn/SD dose of 0.6 g in 100 mL of Cr(VI) solution (50 mg/L), a contact time of 20 min, pH 2, and a temperature of 20°C, Increased temperature had a negative effect on the removal efficiency. Three equations, that is Morris–Weber, Lagergren, and pseudo‐second‐order, were tested to track the kinetics of the removal process. The kinetic data indicated that the adsorption process was described by the Morris–Weber equation. The Langmuir, Freundlich, and Dubinin–Radushkevick models were used with sorption data to estimate sorption capacity, intensity, and energy. The data were fitted with the Freundlich model. The thermodynamic parameters ΔH, ΔS, and ΔG were evaluated. They showed that the adsorption of Cr(VI) onto PAn/SD was feasible, spontaneous, and exothermic under the studied conditions. For desorption of Cr(VI) adsorbed onto PAn/SD, aqueous NaOH was used; with it, 85% of the adsorbed Cr(VI) could be desorbed. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

金属有机框架MIL-100(Cr)和MIL-101(Cr)负载磷钨酸催化合成双酚F

采用两种具有相同拓扑结构而孔道不同的金属有机框架MIL-100(Cr)和MIL-101(Cr)负载磷钨酸(PTA),通过XRD、BET、FT-IR、TEM和ICP的对比测试分析,对它们负载磷钨酸前后及其不同负载量情况下的各种物化性质进行表征,并用于催化苯酚、甲醛合成双酚F。实验结果表明,在相同的W/Cr投料摩尔比下,MIL-100(Cr)的磷钨酸负载量大于MIL-101(Cr)的磷钨酸负载量;当MIL-100(Cr) 负载磷钨酸的W/Cr摩尔比为0.40时(磷钨酸负载量16.47%),其催化活性最好,双酚F收率和选择性分别达93.18%和96.11%,反应0.5 h双酚F 4,4'-位异构体比例高达74.24%,催化剂重复使用6次仍保持较高催化活性。     

Investigations of chromium (VI) ion sorption and reduction on strongly basic anion exchanger

Removal of chromium(VI) ions and their reduction were studied on the anion exchanger Dowex PSR-2 in the pH range from 1.5 to 10. The parameters of Cr(VI) sorption process on the anion exchanger were calculated based on the most popular isotherm models such as: Freundlich, Langmuir, Temkin, and Dubinin–Radushkevich (D-R). The Langmuir isotherm was the most appropriate to describe Cr(VI) sorption. The Cr(VI) uptake by Dowex PSR-2 was found to follow the pseudo-second-order rate kinetics. Reduction of chromium(VI) in the pH range 1.5–10 was observed using the HPLC-ICP-MS (high-performance liquid chromatography–inductively coupled plasma-mass spectrometry) method. Oxidation of tri-n-butyl quaternary ammonium groups during the chromate (VI) removal process was observed.     

Adsorption performance of suitable nanostructured novel composite adsorbent of poly(N-methylaniline) for removal of heavy metal from aqueous solutions

Poly(N-methylaniline) (PNMA) composite composed of N-methylaniline and poly(ethanol) was prepared by in situ polymerization technique and characterized using FTIR, SEM-EDS and XRD instruments. Characterization of product revealed that this composite is crystalline in nature and the particles size is less than100 nm. The potential of this composite in removal of Cr(VI) ions from synthetic aqueous effluents was investigated by batch sorption system. The experimental results confirmed that this adsorbent has the potential application for removal of Cr(VI) ions from aqueous solution with the sorption capacity of 125 mg/g of Cr(VI)/0.1 g of adsorbent.     

F3-functionalized nanoscale metal–organic frameworks for tumor-targeting combined chemotherapy and chemodynamic therapy

Nanoscale metal–organic frameworks (nMOFs) have attracted much attention as emerging porous materials as drug delivery carriers. Appropriate surface modification of them can greatly improve stability and introduce biocompatibility and cancer targeting functionality into drug delivery systems. Herein, we prepared nano-sized MIL-101(Fe)-N₃ and loaded anticancer drug doxorubicin (DOX) into it. The synthetic polymer layer Alkyne-PLA-PEG was then attached to the F3 peptide (labeled as Alkyne-PLA-PEG-F3), and the surface of DOX/MIL-101(Fe)-N₃ was covalently modified with it to obtain DOX/MIL-101-PLA-PEG-F3. Nano-sized MIL-101(Fe)-N₃ has high drug loading capacity and the modification of MIL-101(Fe)-N₃ by polymer Alkyne-PLA-PEG not only improved the dispersion, but also avoided the sudden release of the drugs and increased the biocompatibility of nanocarriers. The F3 peptide introduced into the nanocarriers also enabled it to specifically target tumor tissues and achieved active targeted drug delivery. As a nucleolin-mediated endocytosis drug delivery system, DOX/MIL-101-PLA-PEG-F3 can not only deliver anticancer drugs to tumors accurately, but also participate in Fenton-like reaction to generate hydroxyl radicals (•OH) for chemodynamic therapy (CDT), thus enabling combination therapy. It holds great promise as drug candidates to reduce systemic toxicity and improve the efficacy of cancer treatment.     

Removal of Cr(VI) Oxy‐anions from Aqueous Solution by Sorption into Poly(Acrylamide‐Co‐Maleic Acid) Hydrogels

Abstract

The dynamic removal of hexavalent chromiuim by poly(acrylamide‐co‐maleic acid) hydrogels was studied by a batch equilibrium technique at 35°C. Various kinetic and adsorption parameters such as rate constant for sorption, intraparticle diffusion rate constant, Langmuir constant, and adsorption capacity have been evaluated. The sorption process follows the Langmuir‐type behavior and extent of sorption of Cr(VI) ions depends upon the composition of co‐polymeric gels, presence of other ions in the solution, and temperature of the system. Relatively higher temperature favors the sorption process. The activation energy was found to be ?20.369 kJ mol^?1. Finally, various thermodynamic parameters have also been calculated to elucidate the mechanism involved in the sorption process. The positive enthalpy change indicates the endothermic nature of the process. The presence of fluoride ions causes a decrease in the degree of sorption of Cr(VI). Finally, the sorption of Cr(VI) into the copolymeric sorbent has been explained on the basis of coordination between electron rich O and N atoms of sorbent molecules and the Cr(III) molecules. Moreover, H‐bonding interactions also seem to contribute to the sorption process.     

Adsorption behavior of metal ions by amidoxime chelating resin

The adsorption properties of poly(acrylamidoxime) chelating resin for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), Cr(III), and U(VI) are investigated by the batch technique. Based on the research results of the binding capacity effect of the pH value on sorption kinetic experiments, it is shown that this resin has higher binding capacity to uranyl ions, fast kinetics, and very good selectivity from binary metal ion mixtures with Cu(II) and Pb(II). The uranyl ion sorption strongly depends on the pH value of the solution. The highest value of 99% is at pH 5, but at pH 1 there is no retention. The adsorbed UO can be eluted by sulfuric acid and sodium carbonate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1994–1999, 2000     

ELECTRO-DEIONIZATION OF Cr (VI)-CONTAINING SOLUTION. PART I: CHROMIUM TRANSPORT THROUGH GRANULATED INORGANIC ION-EXCHANGER

Kinetics of Cr (VI) → OH^? exchange on both hydrogel and xerogel of hydrated zirconium dioxide was investigated. Self-diffusion coefficient of Cr (VI) species has been determined by analysis of kinetic curves. Transport of Cr (VI) anions through the inorganic ion exchangers under the influence of applied voltage was also researched. In the case of hydrogel, the ions are transported mainly through the solid phase. Diffusion coefficient of chromate anions through this material was estimated as 9.00 × 10^?12 m² s^?1. This is in agreement with self-diffusion coefficient of Cr (VI) obtained from kinetic measurements (1.60 × 10^?12–9.92 × 10^?12 m² s^?1). Owing to the rather high mobility of Cr (VI) through hydrogel of hydrated zirconium dioxide, this material was recommended for electro-deionization processes. On the other hand, the use of polymer anion-exchange membrane must be excluded to prevent poisoning of the inorganic ion exchanger with Cr (III) cations to be formed during chemical interaction of Cr (VI) with organic materials.