D. Harikishore Kumar Reddy

Application of magnetic chitosan composites for the removal of toxic metal and dyes from aqueous solutions.

Magnetic chitosan composites (MCCs) are a novel material that exhibits good sorption behavior toward various toxic pollutants in aqueous solution. These magnetic composites have a fast adsorption rate and high adsorption efficiency, efficient to remove various pollutants and they are easy to recover and reuse. These features highlight the suitability of MCCs for the treatment of water polluted with metal and organic materials. This review outlines the preparation of MCCs as well as methods to characterize these materials using FTIR, XRD, TGA and other microscopy-based techniques. Additionally, an overview of recent developments and applications of MCCs for metal and organic pollutant removal is discussed in detail. Based on current research and existing materials, some new and futuristic approaches in this fascinating area are also discussed. The main objective of this review is to provide up-to-date information about the most important features of MCCs and to show their advantages as adsorbents in the treatment of polluted aqueous solutions.

Biosorption of Pb2+ from aqueous solutions by Moringa oleifera bark: Equilibrium and kinetic studies

Biosorption of Pb(2+) from aqueous solution by biomass prepared from Moringa oleifera bark (MOB), an agricultural solid waste has been studied. Parameters that influence the biosorption such as pH, biosorbent dose, contact time and concentration of metal ion were investigated. The experimental equilibrium adsorption data were tested by four widely used two-parameter equations, the Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherms. Results indicated that the data of Pb(2+) adsorption onto MOB were best fit by the Freundlich model. The adsorption capacity (Q(m)) calculated from the Langmuir isotherm was 34.6mgPb(2+)g(-1) at an initial pH of 5.0. Adsorption kinetics data were analyzed using the pseudo-first-, pseudo-second-order equations and intraparticle diffusion models. The results indicated that the adsorption kinetic data were best described by pseudo-second-order model. Infrared (IR) spectral analysis revealed that the lead ions were chelated to hydroxyl and/or carboxyl functional groups present on the surface of MOB. Biosorbent was effective in removing lead in the presence of common metal ions like Na(+), K(+), Ca(2+) and Mg(2+) present in water. Desorption studies were carried out with dilute hydrochloric acid for quantitative recovery of the metal ion as well as to regenerate the adsorbent. Based on the results obtained such as good uptake capacity, rapid kinetics, and its low cost, M. oleifera bark appears to be a promising biosorbent material for the removal of heavy metal ions from wastewater/effluents.

Removal of microelemental Cr(III) and Cu(II) by using soybean meal waste – Unusual isotherms and insights of binding mechanism

In the present study soybean meal (SBM) waste has been used for the removal Cr(III) and Cu(II) from aqueous solutions. Effect of variable parameters including pH, contact time, biomass dose and initial concentration of metal ions were studied. Biosorption kinetics was very fast and the kinetics data were successfully modeled using nonlinear pseudo-second-order model. A series of isotherm experiments revealed that pH 5 favored Cr(III) and Cu(II) biosorption and the affinity order of SBM was Cu(II) > Cr(III). Biosorption mechanism was confirmed by the functional group blocking, FTIR and scanning electron microscopy/energy-dispersive X-ray results. The biosorption mechanism was due to (i) ion-exchange, (ii) chelation by carboxyl and hydroxyl groups present on the SBM surface, (iii) further precipitation of metal ions on the surface of biomass. Our results revealed that SBM could be employed as an effective and low-cost biosorbent for removal of Cr(III) and Cu(II) from contaminated effluents.

Synthesis, spectral characterization and antioxidant activity studies of a bidentate Schiff base, 5-methyl thiophene-2-carboxaldehyde-carbohydrazone and its Cd(II), Cu(II), Ni(II) and Zn(II) complexes.

A new Schiff base bidentate ligand (L), 5-methyl thiophene-2-carboxaldehyde-carbohydrazone and its metal (Cu(II), Cd(II), Ni(II) and Zn(II)) complexes with general stoichiometry [M(L)2X2] (where X=Cl) were synthesized. The ligand and its metal complexes were characterized by elemental analyses, IR, 1H NMR, ESR spectral analyses, and molar conductance studies. The molar conductance data revealed that all the metal chelates are non-electrolytes. IR spectra showed that ligand (L) is coordinated to the metal ions in a bidentate manner with N and O donor sites of the azomethine-N, and carbonyl-O. ESR and UV-Vis spectral data showed that the geometrical structure of the complexes are Orthorhombic. Furthermore, the antioxidant activity of the ligand and its complexes was determined by hydroxyl radical scavenging, DPPH, NO, reducing power methods in vitro. The obtained IC50 value of the DPPH activity for the copper complex (IC50=66.4 μm) was higher than other compounds. Microbial assay of the above complexes against Staphylococcus aureus, Escherichia coli, Rhizocotonia bataticola and Alternaria alternata showed that copper complex exhibited higher activity than the other complexes.

Valorisation of post-sorption materials: Opportunities, strategies, and challenges

Adsorption is a facile, economic, eco-friendly and low-energy requiring technology that aims to separate diverse compounds (ions and molecules) from one phase to another using a wide variety of adsorbent materials. To date, this technology has been used most often for removal/recovery of pollutants from aqueous solutions; however, emerging post-sorption technologies are now enabling the manufacture of value-added key adsorption products that can subsequently be used for (i) fertilizers, (ii) catalysis, (iii) carbonaceous metal nanoparticle synthesis, (iv) feed additives, and (v) biologically active compounds. These new strategies ensure the sustainable valorisation of post-sorption materials as an economically viable alternative to the engineering of other green chemical products because of the ecological affability, biocompatibility, and widespread accessibility of post-sorption materials. Fertilizers and feed additives manufactured using sorption technology contain elements such as N, P, Cu, Mn, and Zn, which improve soil fertility and provide essential nutrients to animals and humans. This green and effective approach to managing post-sorption materials is an important step in reaching the global goals of sustainability and healthy human nutrition. Post-sorbents have also been utilized for the harvesting of metal nanoparticles via modern catalytic pyrolysis techniques. The resulting materials exhibited a high surface area (>1000m2/g) and are further used as catalysts and adsorbents. Together with the above possibilities, energy production from post-sorbents is under exploration. Many of the vital 3E (energy, environment, and economy) problems can be addressed using post-sorption materials. In this review, we summarize a new generation of applications of post-adsorbents as value-added green chemical products. At the end of each section, scientific challenges, further opportunities, and issues related to toxicity are discussed. We believe this critical evaluation not only delivers essential contextual information to researchers in the field but also stimulates new ideas and applications to further advance post-sorbent applications.

Adsorption of Pb(II) from Aqueous Solutions by Chemically Modified Zeolite supported Carbon Nanotubes: Equilibrium, Kinetic, and Thermodynamic Studies

Zeolite supported carbon nanotubes (ZCNTs) were synthesized by the catalytic chemical vapor deposition (CCVD) method. The physical and chemical properties such as surface area, pore diameter, surface functional groups, and total acidic and basic sites of the ZCNTs were studied. They were employed as adsorbent to study the adsorption characteristics of Pb(II) in aqueous solution. The adsorption of Pb(II) increase with an increase of contact time and temperature and reaches equilibrium within 80 min. The maximum removal of Pb (II) was found at pH 5.0. The kinetic data are analyzed using the pseudo-first, second-order kinetics, and intra particle diffusion. The equilibrium data are analyzed through Langmuir, Freundlich, and Dubinin–Radushkevich isotherm models. The results have shown that the pseudo-second-order model fits the experimental data very well. The Langmuir model provides a best correlation with an adsorption capacity of 55.74 mg/g at 313 K. The thermodynamic properties ΔGo, ΔHo, and ΔSo showed that adsorption of Pb (II) onto ZCNTs was found to be spontaneous, endothermic and feasible in the temperature range of 293–313 K. The ZCNTs possess higher Pb(II) sorption capacities, hence are a more promising Pb(II) adsorbent in water and useful in wastewater treatment.

Poly(styrenesulfonic acid)-impregnated alginate capsule for the selective sorption of Pd(II) from a Pt(IV)-Pd(II) binary solution

Poly(styrenesulfonic acid)-impregnated alginate capsule (PSSA-AC) was prepared using a simple fabrication process, and used for selective separation of Pd(II) and Pt(IV) from their mixture. Evaluation of the pH effect revealed that PSSA-AC had good Pd(II) selectivity especially when the pH was between 3 and 5 at which neutral species Pd(OH)2 are present. Experiments on metal penetration through the Ca(2+)-alginate film showed that anionic species hardly penetrate through the alginate film (acting as an ionic barrier). The selective sorption mechanism is proposed as the following steps: (1) selective penetration of the neutral Pd(OH)2 through the ionic barrier (Ca(2+)-alginate shell) and then (2) chelation reaction of the neutral Pd(OH)2 with the SO3(-) groups of PSSA in the core. The maximum Pd(II) uptake was 291.19±17.48mg/g, which was about 32 times higher than that of Pt(IV). The results of the sorption/desorption test indicated that the PSSA-AC has good reusability potential. Even through one cycle of sorption/desorption, Pd(II) and Pt(IV) were successfully separated from their mixture with significantly high purities of 98.65% Pd(II) and 98.71% Pt(IV). This study reports for the first time the feasibility and potential of ionic barrier-based sorbents as selective separation of precious metals which have different speciations.

Development of polyethyleneimine-loaded core-shell chitosan hollow beads and their application for platinum recovery in sequential metal scavenging fill-and-draw process

Polyethyleneimine (PEI)-loaded chitosan hollow beads (CHBs) were fabricated through the ionotropic gelation process using sodium tripolyphosphate (TPP) as a counter polyanion. The CHBs were loaded with hydrophilic PEI in pre- and/or post-loading methods. Hence, the sorbent could possess a large number of amine groups which were able to function as the binding sites to recover platinum metal ions. The enhancement of the amine groups was confirmed by Fourier transform infrared spectroscopy (FTIR). Isotherm and kinetic studies were carried out to evaluate the sorption performance of the sorbents. The maximum Pt(IV) uptake by the PEI-loaded CHBs was estimated to be 815.2±72.6mg/g, which was much higher than that of a commercial ion exchange resin, Lewatit® MonoPlus TP214 (330.2±16.6mg/g). A sequential metal scavenging fill-and-draw process was operated using the PEI-loaded CHBs sorbents for ten cycles and the Pt(IV) recovery efficiency was kept above 97.4% even after the last cycle. These results indicated that the ionic polymer-loaded hydrogel hollow beads can be a novel platform to design high-performance sorbents able to recover and/or scavenge anionic precious metal ions even from trace metal solutions.

Fabrication of Stable and Regenerable Amine Functionalized Magnetic Nanoparticles as a Potential Material for Pt(IV) Recovery from Acidic Solutions

MnFe2O4@SiO2-NH2 magnetic nanocomposite (AFMNC) adsorbent with a particle size of ∼50 nm was successfully synthesized using a facile approach. The as-prepared composite particles showed a fast binding of Pt(IV) with easy magnetic solid-liquid separation. The kinetic data were fitted to both pseudo-first and second-order rate models, indicating that AFMNC exhibited a much higher rate of Pt(IV) binding (0.125 g mg-1 min-1) compared to that of commercial ion-exchange resin Amberjet 4200 (0.0002 g mg-1 min-1). The equilibrium adsorption data were fitted to the Langmuir isotherm model with a relatively high sorption capacity of 380 mg/g. Scanning transmission electron microscopy analysis demonstrated the presence of platinum chloride after sorption on AFMNC, suggesting an adsorbate-adsorbent anion-exchange interaction. In addition, due to its magnetic characteristics, AFMNC can be easily separated from the aqueous medium after the sorption process. The novel nanocomposite may facilitate recovery of Pt(IV) from waste solutions.

Effective adsorption of Pd(II), Pt(IV) and Au(III) by Zr(IV)-based metal–organic frameworks from strongly acidic solutions

Separation of precious metal ions from acidic solutions is of great importance due to their cumulative supply risk and environmental concern. However, their separation is still challenging as they are often present in extremely low pH solutions. Metal–organic frameworks (MOFs) have attracted extensive curiosity for adsorption owing to their fascinating physicochemical features including tunable pore sizes, active functional sites, and porosity. Here, two Zr-based MOFs of UiO-66 and UiO-66-NH2 with an 8-ligand-connected Zr6 node were fabricated and tested for adsorption of Pd(II), Pt(IV) and Au(III) anions (PdCl42−, PtCl62− and AuCl4−) in strongly acidic solutions. Both MOFs were tested for uptake time and adsorption capacities and showed rapid and high precious metal adsorption performances. Inner-sphere complexation between the precious metal anions and the incompletely coordinated Zr atoms in the MOFs was the key mechanism involved in the precious metal adsorption. In the case of UiO-66-NH2, additional electrostatic attraction was found between the protonated amine group (–NH3+) and the precious metal anions, as well as partial reduction of the bound precious metal ions. Moreover, the pathway of adsorption–reduction–crystallization–precipitation for the interaction of UiO-66-NH2 and AuCl4− resulted in extremely high recovery efficiency for gold.