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Biopolymer adsorbents are versatile in their application for removal of heavy metals. The present work is focused towards the preliminary study of the interaction of diphenylthiocarbazone (DTZ) complex of chromium(VI) in acidic medium with cellulose biopolymer. Chromium-DTZ complex could be quantitatively adsorbed on a cellulose column in the pH range 1.0-2.5 and the effect of various experimental parameters such as stability of the column and the complex, column breakthrough volume, and interfering ions have been studied in detail. The probable mechanism of adsorption of complex on the cellulose biopolymer was corroborated using Fourier transform infra-red spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and solid state 13C nuclear magnetic resonance techniques (CP-MAS). The pores formed due to the hydrogen bond between the cellulose layers and then the ensuing occupation of the complex between these layers and on the surface of the biopolymer layer through electrostatic attractive force and Π interaction of aromatic ring with cellulose are expected to play a vital role in the interaction. The cellulose column could be regenerated using environmentally benign polyethylene glycol-400 (PEG-400) in acidic medium. The cellulose biosorbent has been successfully tested to study the removal of chromium as its dithizone complex from synthetic and real waste water samples., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Abstract: Biopolymers such as chitosan possess excellent properties suited for varied applications. In this work, we describe a novel microwave assisted method for the preparation of n-butylacrylate grafted chitosan adsorbent and its utility for the adsorption of chromium(VI). A 3min irradiation time was enough to prepare the adsorbent, and techniques such as FT-IR, powder XRD, SEM and EDS were used for comprehensive characterization. The adsorption was effective at pH 3.5 with 25mL of 20ppm Cr(VI) solution. Langmuir, Freundlich, Dubinin–Radushkevich, Temkin, Elovich and Redlich isotherms were studied in detail. The ΔG, ΔH and ΔS parameters were evaluated to understand the adsorption thermodynamics. The adsorption involves the interaction of Cr(VI) with the hydroxyl and amino groups in chitosan. [Copyright &y& Elsevier]

Inthis work, we present an interesting method for the adsorption ofHg(II) involving its interaction with cellulose and mercaptobenzothiazole(MBT). This affinity could be realized with cellulose and MBT actingas host and guest in the first instance followed by the subsequentcomplexation of Hg(II) with MBT. The soft–soft interactionbetween Hg(II) and sulfur enhances the effective complexation withMBT. The favorable experimental conditions, isotherm models, mechanismof interaction, and thermodynamics are discussed. The negative valuesof free energy obtained at various temperatures and the endothermicadsorption process affirms the spontaneity of adsorption. FT-IR, SEM,EDS, and XRD techniques were utilized to characterize the MBT impregnatedcellulose as well as the Hg(II)-loaded adsorbent. With a high adsorptioncapacity of 204.08 mg g–1a sample volume of 500mL could be quantitatively treated by column method. Potassium thiocyanatefunctions as a valuable reagent for the desorption of Hg(II). Thepractical application was tested for the adsorption of mercury vaporemanating from a used Compact Fluorescent Lamp (CFL). [ABSTRACT FROM AUTHOR]

Abstract: The molecular interaction of biopolymers with an array of substrates offers interesting insight into the adsorption phenomenon. The present work proposes the preparation and characterization of cellulose–methyltrioctylammonium chloride (MeTOACl)–a room temperature ionic liquid (IL) blend polymeric sorbent and its application for the adsorption of carcinogenic chromium(VI). The blend adsorbent material was synthesized in a relatively green solvent (methylisobutylketone) medium by ultrasonication. The mechanism of interaction of biopolymer with the ionic liquid could be conceptualized as electrostatic attraction, hydrogen bonding, and Van der Waals force of attraction with the hydroxyl groups of cellulose as a bilayer assembly. The composition, crystallinity, and the surface area of the prepared material were comprehensively characterized using FT-IR, solid-state 13C NMR, TGA, XRD, SEM, EDX, XPS, and BET isotherm study. The adsorption capacity of chromium(VI) calculated from Langmuir isotherm model was found to be 38.94mgg−1 with adherence to the second-order kinetics. The study of thermodynamic parameters that affect the sorption process indicated the spontaneity and exothermic nature of adsorption. The green aspect in the methodology is brought out in the regeneration of the adsorbent, where Cr(VI) could be effectively reduced to the less toxic Cr(III) using ascorbic acid. [Copyright &y& Elsevier]

Abstract: A simple, economical and green methodology has been developed for the adsorption of malachite green using cellulose powder as the adsorbent. Batch experimental procedures were conducted to investigate the adsorption ability of this bio-polymer to remove malachite green from aqueous medium. The adsorbed dye on cellulose was characterized by Fourier transform-infrared spectroscopy (FT-IR). The various analytical parameters such as the effect of contact time, pH, temperature, etc. were optimized. The adsorption was efficient at a neutral pH (7.2) and both Langmuir and Freundlich isotherm models showed good fit into the experimental data. The adsorption kinetics indicated that the adsorption proceeds according to pseudo-second-order model. The adsorption of malachite green was found to be exothermic and it was accompanied by decrease in the entropy. Column studies were performed and the regeneration of the adsorbent was done easily using environmentally benign polyethylene glycol-400. [Copyright &y& Elsevier]

Abstract: Biopolymers as well as ionic liquids are known for their potential applications. In this work, we report the utility of chitosan as an excellent platform for impregnating the ionic liquid, tetraoctylammonium bromide by ultrasonication and its subsequent adsorption for chromium(VI). The effective mass transfer due to sonication coupled with the hydrogen bonding interaction between chitosan-ionic liquid and the electrostatic interaction involving the amino groups in chitosan and hexavalent chromium governs this three center (3c) co-operative mechanism. The adsorption followed a pseudo second order kinetics with a Langmuir adsorption capacity of 63.69mgg−1. Various isotherm models were used to correlate the experimental data and the adsorption process is exothermic with a decreased randomness at the solid–solution interface. The thermodynamics of the spontaneous adsorption process could be explained through a positive co-operative effect between the host (chitosan) and the guest (ionic liquid). The adsorbed chromium(VI) could be converted to ammonium chromate using ammonium hydroxide, thereby regenerating the adsorbent. The method could be translated into action in the form of practical application to a real sample containing chromium. [Copyright &y& Elsevier]