Removal Of Dichromate Research Articles

A water-stable photochromic MOF with controllable iodine sorption and efficient removal of dichromate

A photochromic cationic MOF with one-dimensional channels was prepared based on a π-conjugated electron-deficient viologen, which exhibits high uptake capacity for Cr2O72− through ion-exchange and controllable iodine adsorption behavior.

3D Metallo-organic coordination assembly-based anion-enriched supramolecular material for fast and efficient removal of Cr2O72−

Chromium(VI), especially dichromate (Cr2O72−) contamination in wastewater due to rapid industrialization with uncontrolled effluent management is still a serious concern which needs focused attention. Multiprong approaches are practiced such as chemical precipitation, reverse osmosis, ion-exchange, adsorption by granular activated carbon etc. to capture and separate this “Group A” human carcinogenic effluent from water. However, low capture capacity, non-reusability, poor selectivity, pH-limited performance are some major limitations of these techniques. Recently, metal organic frameworks (MOFs), metal organic cages (MOCs), porous organic polymers (POPs) or covalent organic frameworks (COFs), covalent organic networks (CONs) etc. emerged as new-generation materials to overcome such limitations. However, the development is still in initial stage and issues related to structural stability and integrity of many MOFs in water and in wide pH range, as well as reusability need to be addressed. At this juncture, herein we report a novel [Zn(terpyridine)2]2+-templated trisimidazolium-based highly cationic three-dimensional metal-organic coordination assembly (3D MOCA), serving as a new class of efficient, fast, robust and recyclable dichromate-removal material. Not only the highly cationic assembly is enriched with a high density of Br− anions, but its three-dimensional propagation and flexibility also exposes the exchangeable Br− ions for facile anion-metathesis with Cr2O72−. By virtue of the benefits of these attributes, the presented supramolecular material exhibits a high capture capacity (469 mg g−1), fast exchange kinetics (0.028 g mg−1 min−1), wide working pH range (pH 2–12) and reusability up to a minimum of 10 cycles without much loss of efficiency. Key mechanistic examinations highlight the evidences in favor of ion-exchange-based chemistry to be responsible for dichromate removal with the present material.

Evaluation of Chitosan Modified by Sodium Dodecyl Sulfate for Removing Hexavalent Chromium from Aqueous Solutions

Hexavalent chromium (Cr(VI)) has the characteristic of forming anionic species, which are very toxic, very soluble in water and difficult to be removed. In this study, dichromate removal from aqueous solutions by chitosan and chitosan modified by sodium dodecyl sulfate (SDS) was addressed. The effect of various experimental parameters, such as pH (1-9), initial concentration (10-100 mg L-1), adsorbent dose (0.005-0.350 g) and contact time (5-60 min) was investigated. All experiments were conducted in batch mode at room temperature (~21 oC). The obtained equilibrium adsorption isotherms were analyzed using the Langmuir and Freundlich models. Furthermore, the kinetics of dichromate removal was analyzed by pseudo-first order, pseudo-second order and the Elovich models. Optimum conditions for obtaining high removal (~97%) within a relatively short time (60 min) are: 5.0 pH, 0.100 g SDS-chitosan dosage and an initial Cr2O72- concentration of 10 mg L-1. The dichromate adsorption capacity of chitosan is 8.3 mg L-1, while that of SDS-chitosan is 9.7 mg L-1. In addition, the adsorption of dichromate by chitosan and SDS-chitosan is well-fitted by the Langmuir and Freundlich models while the adsorption kinetics is best fitted by the pseudo-second-order kinetic model.

Novel synthesis of Ni/Fe layered double hydroxides using urea and glycerol and their enhanced adsorption behavior for Cr(VI) removal

Novel modified Ni/Fe layered double hydroxides with different morphology of spherical – like shape were fabricated via using urea as a ligand and glycerol (Ni/Fe LDH/GL) with Ni:Fe molar ratios of 2:1 by the simplest co -precipitation method. Also, for comparison purposes, Ni/Fe LDH was synthesized to be used as a control one. A suggested interpretation for the morphology change was also given. The materials were characterized by X-ray diffraction (XRD), The Fourier transform infrared (FT - IR) spectroscopy, field emission scanning electron microscopy (FESEM), EDX for elemental analysis, high resolution transmission electron microscopy (HRTEM), Brunauer, Emmett, and Teller (BET) equation, particle size distributions and Zeta potential measurements. In addition, the synthesized materials were used as adsorbents for removal of potassium dichromate from aqueous solutions under various experimental conditions. The adsorption of Cr (VI) was strongly pH dependant and the pHPZC was studied. Kinetic studies were evaluated through different models including, pseudo first and second orders, mixed 1, 2 orders, intra particle diffusion and Avrami models. For adsorption isotherms, two-parameter models (Langmuir, Freundlich and Temkin) and three parameter models (Sips, Langmuir-Freundlich and Tooth) were investigated showing maximum adsorption capacity of 50.43 mg/g and 136.05 mg/g for Ni/Fe LDH and Ni/Fe LDH/GL, respectively. Also, the effect of temperature was investigated at (23, 35, 45, 55 °C) and the thermodynamic parameters (∆H°, ∆S° and ∆G°) were calculated showing exothermic and spontaneous adsorption process. The effect of coexisting anions (Cl−, SO42− and HPO42−) and humic acid at different concentrations on the removal efficiency of dichromate ions was investigated. Chemical stability and recyclability of these adsorbents were also studied. The intermolecular hydrogen bonds formation between dichromate ion, urea, glycerol, LDH was explored by Monte Carlo simulation This study suggested that the modified Ni/Fe LDH/GL materials were promising nanoadsorbents for efficient potassium dichromate removal.

Dual-Functionalized Fluorescent Cationic Organic Network: Highly Efficient Detection and Removal of Dichromate from Water.

Dichromate is a widespread contaminant in wastewater, threatening the health of humans and other organisms. Therefore, effective detection and removal of dichromate from water is of great significance. Herein, a tetraphenylethylene functionalized cationic organic network (CON-LDU2) was constructed via a facile quaternization reaction. CON-LDU2 was successfully integrated with both detection and removal functionalities toward dichromate. On the one hand, benefiting from the strong fluorescence, CON-LDU2 was employed as a chemosensor, it could efficiently and selectively probe Cr2O72- in water with "turn-off" fluorescent response. On the other hand, the cationic skeleton and free anions inside framework make CON-LDU2 an excellent adsorbent for Cr2O72-, it could capture Cr2O72- from water with rapid kinetics and high capacity. The kinetic constant for adsorption of Cr2O72- can reach up to 1.784 g mg-1 min-1, while the capacity is determined as 325 mg g-1. Furthermore, CON-LDU2 displayed good recyclability and can be reused for at least 5 cycles. Therefore, CON-LDU2 can serve as an ideal candidate not only in detection but also in removal of Cr2O72- in water medium.

Selective removal of anionic dyes with exceptionally high adsorption capacity and removal of dichromate (Cr2O72-) anion using Ni-Co-S/CTAB nanocomposites and its adsorption mechanism

An adsorbent Ni-Co-S/CTAB nanocomposites have been synthesized at low temperature in aqueous medium using nickel acetate, cobalt acetate, thioacetamide and hexadecyltrimethyl ammonium bromide (CTAB) as reagents. The nanocomposites exhibited exceptionally high adsorption capacity towards anionic adsorbates with high selectivity. The maximum adsorption capacity of nanocomposites were 1995.02 mg g−1 for Congo red (CR), 2223.15 mg g−1 for Methyl orange (MO) anionic dyes and 790.69 mg g−1 for Cr2O72- metal anion. They exhibit negligible adsorption ability towards cationic dyes 2.33 mg g−1 for MB and 42.05 mg g−1 for RhB. The nanocomposite is able to adsorb anionic dyes from a binary mixture of cationic and anionic dyes with high separation factor. It also shows good results with synthetic effluents. The removal of adsorbates followed modified Zhu and Gu isotherm model. FTIR and Zeta-potential measurement confirmed that electrostatic interactions are predominating factor for the adsorption of anionic adsorbates followed by hydrophobic interactions between adsorbates. Moreover, ethanol is used to regenerate the adsorbent and reused up to five times with good adsorption capacities. Thus, the nanocomposite can be used as an efficient adsorbent for the removal and seperation of anionic adsorbates from binary mixtures as well as synthetic effluents.

Mechanism-Property Correlation in Coordination Polymer Crystals toward Design of a Superior Sorbent.

A methodology was developed to design superior sorbents of oxoanions. To integrate the high efficiency of chemisorption, selectivity, and recyclability into one sorbent, understanding the nature of oxoanions-sorbent interactions and the structural evolution of the sorbents is essential. Three cationic Ag(I) coordination polymers (CPs) are synthesized for dichromate (Cr2O72-) removal, and three distinct oxoanion-exchange mechanisms are identified, namely, the replacement, breath, and reconstruction processes, depending on the degree of framework distortion induced by the dichromate-CP interactions. The single crystal to single crystal transformation during the oxoanion exchange has been investigated by using single-crystal X-ray diffraction and energy-dispersive X-ray microanalysis. The replacement process, due to a weak chemisorption, shows excellent recyclability at the cost of reduction of efficiency and selectivity of adsorption. The reconstruction process may achieve a high efficiency and selectivity, but it loses recyclability. Due to the formation of a Ag-O(dichromate) bond and the breathing effect of the framework, the sorbent with the breath mechanism shows both superior efficiency and high recyclability in dichromate removal. The study of perrhenate (ReO4-) removal using the same CPs demonstrates that one CP performing the reconstruction process during dichromate removal turns to the breath process in removal of perrhenate anions. These results of mechanism-property correlation provide an insight into improvement of the methodology to fabricate a superior CP sorbent for oxoanion removal.

A mesoporous cationic metal-organic framework with a high density of positive charge for enhanced removal of dichromate from water.

An imidazolium-functionalized mesoporous cationic Cr-based metal-organic framework (MOF) with high densities of positive charges was synthesized for the first time via a mixed-solvent strategy. The cationic mesoporous Cr-based MOF showed excellent adsorption performances in the removal of dichromate Cr2O72- from water with a large uptake of 321 mg g-1 and good regeneration ability.

Bioremediation of chromium contaminated water by diatoms with concomitant lipid accumulation for biofuel production

Hexavalent chromium compounds such as chromate and dichromate, commonly designated as Cr (VI) compounds, are widely used heavy metals in different industries and are considered highly toxic to most life forms. Unfortunately, they have become a major pollutant of groundwater and rivers around dichromate using industries. Bioremediation is widely used to decrease the amount of dichromate in wastewater but requires large amounts of precious fresh water. Here we tested two marine micro-algal species, Phaeodactylum tricornutum strain CCY0033 and Navicula pelliculosa strain CCMP543, for their ability of dichromate bioremediation and concomitantly producing lipids that can serve as biofuel. Dichromate tolerance of the strains was investigated under different growth conditions in order to obtain high biomass yields, high lipid accumulation and high dichromate removal from the medium. Both algal strains grew well and produced high biomass in media containing up to 1 mg of dichromate per liter. Variations in growth conditions revealed that dichromate removal from the medium correlated positively with biomass yield. Dichromate removal using living cells was in the same order of magnitude as with autoclaved dead cells or when using extracted extracellular polymeric substances (EPS). This suggests biosorption of dichromate to cell-associated polymeric substances as the major mechanism of the bioremediation process. For both strains, optimal dichromate removal and lipid production were achieved at a light intensity of 55 μmol m−2s−1 and at a sodium nitrate concentration of 3 mM. The optimal temperature for dichromate removal and lipid production was 23 °C for P. tricornutum and 27 °C for N. pelliculosa. Compared to P. tricornutum strain CCY0033, N. pelliculosa strain CCMP543 produced an overall higher lipid yield under these conditions.

Removal of arsenate and dichromate ions from different aqueous media by amine based p(TAEA-co-GDE) microgels

In this work, microgels based on tris(2-aminoethyl) amine (TAEA) and glycerol diglycidyl ether (GDE) via simple microemulsion polymerization was prepared as p(TAEA-co-GDE) microgels were used as adsorbent for removal of dichromate (Cr (VI)) and arsenate (As (V)) ions from different aqueous environments. The p(TAEA-co-GDE) microgels were demonstrated very efficient adsorption capacity for Cr (VI), and As (V) that are 164.98 mg/g, and 123.64 mg/g from distilled (DI) water, respectively. The effect of the medium pH on the adsorption capacity of p(TAEA-co-GDE) microgels for Cr (VI) and As (V) ions were investigated. The maximum adsorption capacity was obtained at pH 4.0 for both ions with maximum adsorbed amounts of 160.62, and 98.72 mg/g, respectively. In addition, the microgels were also shown moderate adsorption capacity for Cr (VI) and As (V) from other water sources; tap water with 115.18 mg/g and 82.86 mg/g, sea water with 64.24 mg/g and 46.88 mg/g and creek water with 73.52 mg/g and 59.33 mg/g, respectively. Moreover, the increase in adsorbent dose from 0.025 to 0.125 g enhanced % adsorption of Cr (VI) from 54.13 to 98.03, and As (V) from % 26.72–98.70, respectively. For the adsorption process Langmuir and Freundlich adsorption isotherms were applied and found that Langmuir adsorption isotherm with R2 value of 0.99 for both the metal ions are suitable. Moreover, the experimental adsorption capacities of Cr (VI) and As (V) were found very close to the theoretical values calculated from Langmuir adsorption isotherm. More importantly, the microgels were made magnetic responsive to recover them easily from adsorption medium for reuse studies by applying external magnetic field with little decrease in adsorption capacity. Additionally, reusability of p(TAEA-co-GDE) microgels was also evaluated for adsorption of Cr (VI) and As (V) from DI water.

A microporous cationic metal–organic framework for the efficient removal of dichromate and the selective adsorption of dyes from water

A microporous anionic metal–organic framework has been synthesized, which can be used as the effective adsorbent to methyl orange and Cr2O72− from aqueous solutions.

Enhanced removal of soluble Cr(VI) by using zero-valent iron composite supported by surfactant-modified zeolites.

Zero-valent iron (ZVI) was immobilized onto surfactant-modified zeolites (SMZ) using calcium alginate. Scanning electron microscopy showed that ZVI powder was uniformly immobilized on the surface of the SMZ. The added ZVI powder resulted in enhanced dichromate removal efficiency and the heterogeneous surface of the composite. The adsorption of dichromate onto the ZVI-SMZ composites fitted well to a pseudo-second-order model and the Langmuir adsorption isotherm. The maximum dichromate adsorption capacity of the composite was 2.49 mg/g at the temperature of 293 K. Higher removal efficiency was obtained at pH lower than 7. X-ray photoelectron spectrometry revealed that the composites combined the strong reductive quality of ZVI and superior adsorption of SMZ.

Arsenate and Dichromate Removal Efficiency of a New Calix[4]arene Impregnated Resin

This article highlights a newly synthesized 5,11,17,23-tetra-tert.butyl-25,26,27,28-tetrakis(hydrazidecarbonylmethoxy)-calix[4]arene (3) impregnated resin 4 and it's sorption ability for the removal of selected oxoanions, i.e., (arsenate and dichromate) from aqueous environment. Resin 4 was characterized by using FT-IR spectroscopy, scanning electron microscope (SEM), elemental, and thermogravimetic (TGA) analyses techniques. Sorption study was carried out through static and dynamic methods with continuous flow operation to evaluate the potency of resin 4 under various conditions. Several parameters, such as effect of sorbent dosage, contact time, pH, and initial concentration were optimized through batch experiments. Results justify that % sorption of these oxoanions is highly dependent on pH of the solution. Equilibrium was achieved in 45 min, while sorption efficiency of resin 4 can be better explained by Langmuir and Temkin isotherm models. Furthermore, kinetically both oxoanions follow pseudo second order model. Additionally, sorption of arsenate more appropriately could be explained by Moris-Weber diffusion kinetic model. For the dynamic method, Thomas model was used to calculate the kinetic coefficient (kTH) and maximum sorption capacity (qo) of resin 4 which are 3.84 and 5.94 ml mg−1 min−1 and 0.185, 0.160 mg g−1 for As (V) and Cr (VI) respectively. Furthermore, resin 4 has been found as potential sorbent for removal of these oxoanions from contaminated surface water samples.

Preparation and Application of Calix[4]arene Derivatives Bearing Pyridinium Units-Grafted Magnetite Nanoparticles for Removal of Dichromate and Arsenate Anions

Diamide derivatives of p-tert-butylcalix[4]arene (3a and 3b) have been immobilized onto [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilane-modified Fe3O4 magnetite nanoparticles to obtain D-Calix-GEPPTMS-MNs (4a and 4b) and investigate their sorption capability toward arsenate and dichromate anions at different pH. The novel calixarene derivatives were characterized by a combination of FTIR and H-NMR analyses. The morphology of the magnetic nanoparticles was examined by Transmission Electron Microscopy (TEM) and Thermogravimetric Analyses (TGA). In addition, a simple and versatile method has been used for the determination of arsenate in aqueous solution. In this method, the absorption of the excess dye gradually decreases because of its conversion to colorless carbinol species by combining with methyl violet cation (MV+) and forming stable blue micro particles of (MV+)-molybdoarsenate.

Synthesis of Calix[4]arene‐grafted Magnetite Nanoparticles and Evaluation of Their Arsenate as Well as Dichromate Removal Efficiency

AbstractIn this study, 5,17‐bis‐[(4‐benzylpiperidine)methyl]‐25,26,27,28‐tetrahydroxy‐calix[4]arene (3) has been prepared by the treatment of calix[4]arene with a secondary amine (4‐benzylpiperidine) and formaldehyde by means of Mannich reaction. The prepared Mannich base (3) has been grafted onto [3‐(2,3‐epoxypropoxy)‐propyl]‐trimethoxysilane‐modified Fe3O4 magnetite nanoparticles (EPPTMS‐MN) in order to obtain 5,17‐bis‐[(4‐benzylpiperidine)methyl]‐25,26,27,28‐tetrahydroxy calix[4]arene‐grafted EPPTMS‐MN (BP‐calix[4]arene‐grafted Fe3O4). All new compounds were characterized by a combination of FTIR and 1H‐NMR analyses. The morphology of the magnetic nanoparticles was examined by transmission electron microscopy. Moreover, the studies regarding the removal of arsenate and dichromate ions from the aqueous solutions were also carried out by using 5,17‐bis‐[(4‐benzylpiperidine)methyl]‐25,26,27,28‐tetrahydroxy‐calix[4]arene in liquid–liquid extraction and BP‐calix[4]arene‐grafted Fe3O4 (4) in solid–liquid extraction experiments. The extraction results indicated that 3 is protonated at proton‐switchable binding sites in acidic conditions. Hence, facilitating binding of arsenate and dichromate is resulted from both electrostatic interactions and hydrogen bonding. To understand the selectivity of 3, the retention of dichromate anions in the presence of Cl−, NO, and SO anions at pH 1.5 was also examined.

Synthesis and characterization of cellulose ion exchanger. II. Pilot scale and utilization in dye-heavy metal removal

Cotton fabric was converted into an ion exchanger by grafting it with (1) glycidyl methacrylate (GMA), followed by aminization with ethylene diamine; (2) dimethylaminoethyl methacrylate (DMAEMA), followed by quaternization; and (3) acrylic acid (AA). Grafting was carried out on a pilot scale using a thiocarbonate–H2O2 redox system. The so-obtained cotton graft copolymers were monitored for their ability to remove different dyes as well as heavy metals from aqueous solutions. It was found that the magnitude of dye exhaustion was as follows. For direct and reactive dyes the percentage of exhaustion follows the order of aminized GMA > quaternarized DMAEMA > DMAEMA, whereas for acid dye the percentage of exhaustion follows the order of quaternarized DMAEMA > DMAEMA > aminized GMA. On the other hand poly(AA)–cotton copolymer is very effective at removal of the basic dye. With respect to heavy metal ions removal, the copolymers show the following order: AA > aminized GMA > quaternarized DMAEMA > DMAEMA. While dichromate removal follows the order of quaternarized DMAEMA > DMAEMA > aminized GMA. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2151–2157, 1998

The Synthesis, Characterization, and Testing of a Reagent for the Selective Removal of Dichromate and Perchlorate from Aqueous Solution

Abstract N-4-Vinylbenzyl-N'-benzyl-1,4-diazabicyclo[2.2.2]octane was synthesized and tested to determine its ability to selectively precipitate anions. Fifty-one common anions were tested. The reagent reacted only with nine: dichromate, dithionate, ferricyanide, tetrafluoroborate, iodide, nitroferricyanide, perchlorate, persulfate, and picrate.