Highly Selective Anion Recognition, Extraction and Deep Removal Using a Superphane

Highly selective anion recognition and extraction are critical and challenging to deep removal of pollutants from the environment and effective recovery of valuable chemicals from low–content (at sub–ppm or ppb level) sources. Herein, we detail the gram–scale synthesis of a superphane 2, a new supramolecular host that was found capable of encapsulating ReO4– with high selectivity, as suggested by the single–crystal structures, NMR spectroscopy and theoretical calculations. Under solid–liquid extraction condidtions, 2 proved able to extract perrhenate from the solid mixture containing trace ReO4– (as low as 200 ppb) with near 100% selectivity over other 7 competing anions. Under liquid–liquid extraction conditions, using 2 as the supramolecular extractant, over 99.99% of ReO4– could be separated from the complex simulated aqueous waste streams containing ppm–level perrhenate and large excess of competing ions. Notably, after extraction, 2 could be recycled and reused by simple treatment with NaHCO3. This study opens up the door to development of superphane–based advanced materials for deep elimination of pollutants from the envirenment and purification of chemicals of interest with high efficiency and selectivity.

Pure and Sb-doped ZrO2 for removal of IO3− from radioactive waste solutions

Radioactive 129I with a long half-life (1.57 × 107 y) and high mobility is a serious radiohazard and one of the top risk radionuclides associated with its accidental and planned releases to nature. The complex speciation chemistry of iodine makes its removal a complicated task, and usually a single method is not able to remove all iodine species. Especially its oxidized form iodate (IO3−) lacks a selective and effective removal method. Here, the granular aggregates of hydrous zirconium oxides with and without antimony doping were tested for IO3− removal and the effects of contact time, competing anions in different concentrations and pH were examined. The materials showed high selectivity for IO3− (Kd over up to 50,000 ml/g) in the presence of competing ions and relatively fast uptake kinetics (eq. < 1 h). However, B(OH)4− and SO42−, as competing ions, lowered the iodate uptake significantly in basic and acidic solution, respectively. The suitability of the materials for practical applications was tested in a series of column experiments where the materials showed remarkably high apparent capacity for the IO3− uptake (3.2–3.5 mmol/g). Graphic abstract

Magnetically attracted iron scrap anode based electrocoagulation for phosphate removal

This study shows the effectiveness of a novel electrocoagulation process using magnetically attracted iron scrap anodes for phosphate removal from aqueous solution. The effect of contact time, reaction temperature, dose of iron scrap, initial phosphate concentration, applied voltage, pH, magnetic force, and the species of competing anions on the efficiency of phosphate removal and the reaction products has been investigated. The techniques of XRD, XPS, and VSM were used to characterize the elemental composition and the types of the reaction products in order to clarify the interaction between novel anode and phosphate ions. The removal of phosphate was fitted by a pseudo first-order reaction kinetic model. The results showed that magnetically attracted iron scrap anodes was electrodissoluted under an applied potential and reacted with phosphate into Fe-hydroxo-phosphate complexes. The work suggested that electrocoagulation using magnetically attracted iron scrap anodes had the potential to become a promising technique for phosphate precipitation.

Applicability of ferric(III) hydroxide as a phosphate selective adsorbent for sewage treatment

This research was undertaken to evaluate the usability of ferric(III) hydroxide for phosphate removal from sewage. A batch adsorption experiments, partly a fixed bed column experiments, were conducted to study the influence of various factors, competing anions and contact time on the adsorption of phosphate on ferric(III) hydroxide. Processing ferric iron in the form of akaganeite (β-FeOOH) greatly increased the adsorption capacity for phosphate. The optimum phosphate removal was observed in the pHeq ≤ 6.0. All results from this study demonstrate the potential usability of β-FeOOH as a good phosphate selective adsorbent for the phosphate removal system of sewage treatment plant.

Selective removal of nitrate using a novel asymmetric amine based strongly basic anion exchange resin

In this study, a novel asymmetric amine-based strongly basic anion exchange resin SE-1 was synthesized successfully via the reaction of chloromethylated styrene–divinylbenzene copolymer with N, N-dimethyloctylamine. The sorption performance of SE-1 for selective removal of nitrate in aqueous solution was compared to a commercially available nitrate specialty resin, namely Purolite A 520E (A 520E). It was found that the kinetic data could be described better by the pseudo-second-order model, and SE-1 indicated a faster sorption kinetics than A 520E resin. The Langmiur model was more appropriate for explicating the sorption isotherm. Importantly, SE-1 exhibited a greater sorption capacity for nitrate regardless of the absence or presence of competing anions in solutions. The result of column tests reinforced the feasibility of SE-1 for practical application in groundwater treatment.

A Comparison among Synthetic Layered Double Hydroxides (LDHs) as Effective Adsorbents of Inorganic Arsenic from Contaminated Soil–Water Systems

The need for cost-effective adsorbents of inorganic arsenic (As(III) and As(V)) stimulates the academia to synthesize and test novel materials that can be profitably applied at large-scale in most affected areas worldwide. In this study, four different layered double hydroxides (Cu-Al-, Mg-Al-, Mg-Fe- and Zn-Al-LDH), previously synthesized and studied for As(III) removal capacity, were evaluated as potential adsorbents of As(V) from contaminated systems, in absence or presence of common inorganic anions (Cl−, F−, SO42−, HCO3− and H2PO4−). The As(V) desorption by H2PO4− was also assessed. Lastly, the As(V) adsorption capacities of the four layered double hydroxides (LDHs) were compared with those observed with As(III) in a complementary paper. All the LDHs adsorbed higher amounts of As(V) than As(III). Fe-Mg-LDH and Cu-Al-LDH showed higher adsorption capacities in comparison to Mg-Al-LDH and Zn-Al-LDH. The presence of competing anions inhibited the adsorption of two toxic anions according to the sequence: Cl− < F− < SO42− < HCO3− < < H2PO4−, in particular on Mg-Al-LDH and Zn-Al-LDH. The kinetics of As(V) desorption by H2PO4− indicated a higher occurrence of more easily desorbable As(V) on Zn-Al-LDH vs. Cu-Al-LDH. In conclusion, synthetic Cu- and Fe-based LDHs can be good candidates for an efficient removal of inorganic As, however, further studies are necessary to prove their real feasibility and safety.

Extraction and transport of sulfate using macrocyclic squaramide receptors

Lipophilic macrocycles efficiently extract sulfate ions from water into chloroform and transport this ion across a bulk liquid membrane in the presence of competing anions (chloride, nitrate and dihydrogenphosphate).

Enhanced adsorption of nitrate from water by modified wheat straw: equilibrium, kinetic and thermodynamic studies

This study represents the first attempt to chemically modify wheat straw (WS) using 3-chloropropyltrimethoxysilane (CPTMS) and (1,4-diazabicyclo[2.2.2]octane) (DABCO). Field emission scanning electron micrographs (FESEM), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectra confirmed the successful morphological and structural modification of WS and the thermal stability of the modified WS (MWS). The MWS was used to remove nitrate from water. The optimum conditions of nitrate adsorption onto MWS were examined by conducting batch experiments. The results indicated that 85% of nitrate was removed under the conditions of initial nitrate concentration = 20 mg L−1, initial solution pH = 7, contact time = 10 min, MWS dosage = 2 g L−1 and temperature ≈ 25 °C. The kinetic adsorption data were best fitted to the general order model and the adsorption process occurred in three distinct stages. The equilibrium adsorption data were well described by the Langmuir isotherm. Additionally, separation factor values were smaller than 1, implying that the adsorption process was favorable. The presence of competing anions impeded the nitrate adsorption in the order of sulfate &gt; chloride &gt; bicarbonate&gt; phosphate. Thermodynamic parameters suggested that the adsorption process was exothermic, feasible and spontaneous in nature. Overall, the MWS could achieve efficient removal of nitrate under the simplest operating conditions.

Selective sensing of ATP by hydroxide-bridged dizinc(ii) complexes offering a hydrogen bonding cavity

Hydroxide-bridged dizinc(ii) complexes, offering a hydrogen bonding based cavity, illustrate highly selective turn-on sensing of ATP in the presence of other competing anions, such as AMP, ADP, PPi and other phosphates.