Yolk-shell smart polymer microgels and their hybrids: fundamentals and applications.

Yolk-shell microgels and their hybrids have attained great importance in modern-day research owing to their captivating features and potential uses. This manuscript provides the strategies for preparation, classification, properties and current applications of yolk-shell microgels and their hybrids. Some of the yolk-shell microgels and their hybrids are identified as smart polymer yolk-shell microgels and smart hybrid microgels, respectively, as they react to changes in particular environmental stimuli such as pH, temperature and ionic strength of the medium. This unique behavior makes them a perfect candidate for utilization in drug delivery, selective catalysis, adsorption of metal ions, nanoreactors and many other fields. This review demonstrates the contemporary progress along with suggestions and future perspectives for further research in this specific field.

Tungsten oxide encapsulated phosphate-rich porous alginate composites for efficient U(VI) capture: Insights into synthesis, adsorption kinetics and thermodynamics.

In this work, novel monoclinic tungsten oxide (WO3)-encapsulated phosphate-rich porous sodium alginate (PASA) microspherical hydrogel beads were prepared for efficient U(VI) capture. These macroporous and hollow beads were systematically characterized through XRD, FTIR, EDX-mapping, and SEM-EDS techniques. The O and P atoms in the PO and monoclinic WO3 offered inner-spherical complexation with U(VI). The in situ growth of WO3 played a significant role inside the phosphate-rich biopolymeric network to improve its chemical stability, specific surface area, adsorption capacity, and sorption rate. The phytic acid (PA) served for heteroatom doping and crosslinking. The encapsulated WO3 mass ratio was optimized in different composites, and WO3/PASA3 (the microspherical beads with a mass ratio of 30.0 % w/w) exhibited remarkable maximum sorption capacity qm (336.42 mg/g) computed through the best-fit Langmuir model (R2 ≈ 0.99) and rapid sorption equilibrium, teq (150 min). The isothermal sorption studies were conducted at different temperatures (298, 303, and 308 K) and thermodynamic parameters concluded that the process of U(VI) sorption using WO3/PASA3 is endothermic and feasible having ΔHo (8.19 kJ/mol), ΔGo (-20.75, -21.38, and - 21.86 kJ/mol) and proceeds with a minute increase in randomness ΔSo (0.09 kJ/mol.K). Tungsten oxide (WO3)-encapsulated phosphate-rich porous microspherical beads could be promising material for uranium removal.

Recent developments in chitosan based microgels and their hybrids.

Chitosan based microgels have gained great attention because of their chemical stability, biocompatibility, easy functionalization and potential uses in numerous fields. Production, properties, characterization and applications of chitosan based microgels have been systematically reviewed in this article. Some of these systems exhibit responsive behavior towards external stimuli like pH, light, temperature, glucose, etc. in terms of swelling/deswelling in an aqueous medium depending upon the functionalities present in the network which makes them a potential candidate for various applications in the fields of biomedicine, agriculture, catalysis, sensing and nanotechnology. Current research development and critical overview in this field accompanying by future possibilities is presented. The discussion is concluded with recommended possible future works for further progress in this field.

Microfluidic Fabrication of Monodisperse and Recyclable TiO2-Poly(ethylene glycol) Diacrylate Hybrid Microgels for Removal of Methylene Blue from Aqueous Medium.

Nearly monodisperse titanium oxide-polyethylene glycol diacrylate [TiO2-P(EGDA)] hybrid microbeads containing 0.5 wt % TiO2 nanoparticles entrapped within a P(EGDA) cross-linked polymeric network were synthesized using a modular Lego-inspired glass capillary microfluidic device. TiO2-P(EGDA) hybrid microgels were characterized by optical microscopy, scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, and thermogravimetric analysis. The fabricated TiO2-P(EGDA) hybrid microgel system showed 100% removal efficiency of methylene blue (MB) from its 1-3 ppm aqueous solutions after 4 h of UV light irradiation at 0.2 mW/cm2 at the loading of 25 g/L photocatalyst beads in the reaction mixture, corresponding to the loading of naked TiO2 of just 0.025 g/L. No decrease in photocatalytic efficiency was observed in 10 repeated runs with recycled photocatalyst using a fresh 1 ppm MB solution in each cycle. The rate of photocatalytic degradation was controlled by the UV light irradiance, catalyst loading, and the initial dye concentration. Physical adsorption of MB onto the surface of composite microgel was also observed. The adsorption data was best fitted with the Langmuir adsorption isotherm and the Elovich kinetic model. TiO2-P(EGDA) microgel beads are biocompatible, can be prepared with a tunable size in the microfluidic device, and can easily be separated from the reaction mixture by gravity settling. The TiO2-P(EGDA) system can be used for the removal of other toxic dyes and micropollutants from industrial wastewater.

An innovative approach to synthesize graft copolymerized acetylacetone chitosan/surface functionalized alginate/rutile for efficient Ni(II) uptake from aqueous medium.

In this study, an innovative approach is followed to synthesize graft copolymerized chitosan with acetylacetone (AA-g-CS) through free-radical induced grafting. Afterwards, AA-g-CS and rutile have been intercalated uniformly into amino carbamate alginate matrix to prepare its biocomposite hydrogel beads of improved mechanical strength having different mass ratio i.e., 5.0 %, 10.0 % 15.0 % and 20.0 % w/w. Biocomposites have been thoroughly characterized through FTIR, SEM and EDX analysis. Isothermal sorption data showed good fit with Freundlich model as conferred from regression coefficient (R2 ≈ 0.99). Kinetic parameters were evaluated through non-linear (NL) fitting of different kinetic models. Experimental kinetic data exhibited close agreement to quasi-second order kinetic model (R2 ≈ 0.99) which reveals that chelation between heterogeneous grafted ligands and Ni(II) is occurring through complexation. Thermodynamic parameters were evaluated at different temperatures to observe the sorption mechanism. The negative values of ΔG° (-22.94, -23.56, -24.35 and - 24.94 kJ/mol), positive ΔH° (11.87 kJ/mol) and ΔS° (0.12 kJ/molK-1) values indicated that the removal process is spontaneous and endothermic. The maximum monolayer sorption capacity (qm) was figured as 246.41 mg/g at 298 K and pH = 6.0. Hence, 3AA-g-CS/TiO2 could be better candidate for economic recovery of Ni(II) ions from waste effluents.

Fabrication of silver nanoparticles within chitosan based microgels for catalysis.

Chitosan based monodisperse poly[chitosan-N-isopropylmethacrylamide-acrylic acid] [P(CNA)] microgels were produced via precipitation polymerization. Resulting crosslinked P(CNA) micro particles were used as micro-reactors to prepare silver nanoparticles within the polymeric network by chemical reduction of Ag+ ions with sodium borohydride. Various techniques including transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and ultraviolet-visible (UV-vis) spectroscopy were used to analyze P(CNA) microgels and Ag-P(CNA) hybrid microgels. Catalytic potential of Ag-P(CNA) hybrid system towards individual and simultaneous reduction of various nitroarenes like p-nitrophenol (pNP), o-nitrophenol (oNP), p-nitroaniline (pNA) and o-nitroaniline (oNA) into corresponding aminoarenes using sodium borohydride as a reductant in aqueous medium was evaluated. The catalytic activity of Ag-P(CNA) system towards both the individual and simultaneous reduction of nitroarenes was examined at various concentrations of catalyst. The values of pseudo first order rate constant (k1) for reduction of individual nitroarene and multiple nitroarenes were determined for comparison. The Ag-P(CNA) hybrid microgel system was found to be stable, economical and efficient catalyst for rapid individual and simultaneous reduction of nitroarenes.

Microfluidic Fabrication and Applications of Microgels and Hybrid Microgels.

Smart microgels have gained much attention because of their wide range of applications in the field of biomedical, environmental, nanotechnological and catalysis sciences. Most of the applications of microgels are strongly affected by their morphology, size and size distribution. Various methodologies have been adopted to obtain polymer microgel particles. Droplet microfluidic techniques have been widely reported for the fabrication of highly monodisperse microgel particles to be used for various applications. Monodisperse microgel particles of required size and morphology can be achieved via droplet microfluidic techniques by simple polymerization of monomers in the presence of suitable crosslinker or by gelation of high molecular weight polymers. This report gives recent research progress in fabrication, characterization, properties and applications of microgel particles synthesized by microfluidic methods.

Polymer hydrogels for stabilization of inorganic nanoparticles and their application in catalysis for degradation of toxic chemicals.

Poly(styrene-N-isopropylmethacrylamide-methacrylic acid) core-shell [P(SNM)CS] microgel particles were synthesised by seed-mediated emulsion polymerisation method. Silver nanoparticles were loaded into shell of P(SNM)CS microgels by in situ reduction of Ag+ ions. Synthesised core-shell microgels and hybrid core-shell microgels were characterised by using Fourier transformed infrared spectroscopy (FTIR), Transmission electron microscopy (TEM), UV-Visible spectroscopy and Dynamic light scattering (DLS). Stability of Ag nanoparticles within P(SNM)CS system was also investigated over the time using UV-Visible spectroscopy. Catalytic properties of silver nanoparticles loaded microgel system [Ag-P(SNM)CS] were studied by reducing Eosin-Y and Methylene blue with NaBH4 in water. The values of observed rate constant (kobs) were determined under different reaction conditions. The hybrid system was capable to degrade both dyes and may be used for degradation of several other toxic chemicals efficiently.

Preparation of stimuli responsive microgel with silver nanoparticles for biosensing and catalytic reduction of water pollutants.

Herein, we report poly(N-isopropylacrylamide/2-acrylamido-2-methylpropane sulfonic acid) microgel fabricated with silver nanoparticles. The identification of copolymerization and functional groups in the bare microgel and those fabricated with silver nanoparticles was examined by Fourier transform infrared spectroscopy. The pH and temperature sensitivity of microgels was studied using dynamic light scattering. Thermogravimetric analysis was carried out to study the thermal stability. X-Ray diffraction patterns indicated the amorphous nature of bare microgel and crystalline nature of those containing silver nanoparticles. A bathochromic shift was found in the surface plasmon resonance of silver nanoparticles present in microgel with increase in pH of the medium. Moreover, the microgel containing silver nanoparticles served as an effective catalyst for reducing the toxic nitroaromatic pollutants and carcinogenic dyes. The microgel containing silver nanoparticles also showed good capability to serve as biosensor for the detection of hydrogen peroxide.

Effective biosorption of Cu(II) using hybrid biocomposite based on N-maleated chitosan/calcium alginate/titania: Equilibrium sorption, kinetic and thermodynamic studies.

In this research work, a hybrid biocomposite based on N-maleated chitosan, amino-thiocarbamate functionalised calcium alginate and anhydrous Titania nanoparticles (NMC-MCA-TiO2) was fabricated. The study involves the one pot facile synthesis of N-maleated chitosan and amino-thiocarbamate functionalised alginate under moderate conditions. Sorbent was conditioned in the form of hydrogel beads and characterized through FT-IR and SEM analysis. Newly grafted functional groups could act as potential chelating sites for enhanced Cu(II) sorption. Modified biopolymers were organo-functionalised which provided excellent support for immobilization of Titania nanoparticles (TiO2) as inorganic filler. Kinetic data illustrated the manifestation of intrinsic chemisorption instead of simple bulk/film diffusion. Equilibrium sorption data fitted well with Freundlich adsorption model (R2 ≈ 0.99) which designated the heterogeneous nature of sorbent. Maximum sorption capacity of biosorbent was found 192 mg/g at 298 K and pH = 6.0. Standard Gibbs free energy change ∆Go (-21.53, -21.97, and - 22.42 kJ/mol), standard enthalpy change ∆Ho (5.12 kJ/mol) and standard entropy change ∆So (0.09 kJ/mol K-1) values suggested that the sorption process to be spontaneous and endothermic. The sorbent 3NMC-MCA-TiO2 could be competitive candidate for economical and rapid adsorptive removal of Cu(II) from dilute contaminated liquids.

Synthesis of hybrid biosorbent based on 1,2-cyclohexylenedinitrilotetraacetic acid modified crosslinked chitosan and organo-functionalized calcium alginate for adsorptive removal of Cu(II).

The present study is based on the synthesis of a novel hybrid biosorbent using 1,2-cyclohexylenedinitrilotetraacetic acid modified crosslinked chitosan and amino-thiocarbamate moiety functionalized sodium alginate (CDTA-CS/TSC-CA). The fabricated sorbent was employed to investigate the efficient recovery of Cu(II) from aqueous media. CDTA-CS/TSC-CA was characterized using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). Analysis confirmed the successful modification of both biopolymers and subsequent loading of Cu(II) ions. CDTA-CS/TSC-CA was casted in the form of hydrogel beads having different CDTA-CS to TSC-CA mass ratios i.e., 10.0-40.0% by mass. The hydrogel beads 4CDTA-CS/TSC-CA with CDTA-CS/TSC-CA mass ratio of 40.0% was found most effective for copper sorption. Equilibrium sorption results showed that initial concentration of copper, medium pH, contact time, sorbent dosage and temperature influenced the sorption capacity (qe). Rate of sorption data was interpreted using different kinetic models and found best fitted with pseudo second order rate expression (R2 ≈ 0.99), illustrating that the rate determining step includes the electron density transfer from sorbent coordination sites to central copper ions. Crank's RIDE equation and Elovich chemisorption model (ECM) revealed the presence of two sorption phases, initially rapid sorption followed by comparatively a slow uptake. Equilibrium sorption data was well depicted by Langmuir model and maximum monolayer adsorption capacity (qm) was computed as 276.53 mg·g-1 at 298 K. Standard Gibbs free energy change, ∆G° (-19.99, -20.18 and -20.36 kJ/ mol), standard enthalpy change, ∆H° (-8.95 kJmol) and standard entropy change, ∆S° (0.04 kJ/mol K-1) values suggested that the adsorption process is spontaneous and exothermic. Hence, 4CDTA-CS/TSC-CA was found efficient biosorbent for copper removal from its dilute effluents.

Polymer microgels for the stabilization of gold nanoparticles and their application in the catalytic reduction of nitroarenes in aqueous media.

Polymer microgels containing a polystyrene core and poly(N-isopropylmethacrylamide) shell were synthesized in aqueous media following a free radical precipitation polymerization. Au nanoparticles were fabricated into the shell region of the core-shell microgels denoted as P(STY@NIPM) by the in situ reduction of chloroauric acid with sodium borohydride. Various characterization techniques such as transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-visible) and Fourier transform infrared spectroscopy (FTIR) were used for the characterization of Au-P(STY@NIPM). The catalytic potential of Au-P(STY@NIPM) toward the reductive reaction of 4-nitrophenol (4NP) under various reaction conditions was evaluated. The Arrhenius and Eyring parameters for the catalytic reduction of 4NP were determined to explore the process of catalysis. A variety of nitroarenes were converted successfully into their corresponding aminoarenes with good to excellent yields in the presence of the Au-P(STY@NIPM) system using NaBH4 as a reductant. The Au-P(STY@NIPM) system was found to be an efficient and recyclable catalyst with no significant loss in its catalytic efficiency.

Modified alginate-chitosan-TiO2 composites for adsorptive removal of Ni(II) ions from aqueous medium.

In this study, organo-funtionalization of sodium-alginate has been carried out using phenylsemicarbazide as modifier to graft N, O-donor atoms containing functional groups (amino-carbamate moieties) to offer novel support for TiO2 immobilization. Hybrid composite made of aminocarbamated alginate, carboxymethyl chitosan (CMC) and titanium oxide TiO2 (MCA-TiO2) was prepared for the promising adsorptive remediation of Ni(II). FT-IR, SEM-EDX were employed to characterize MCA-TiO2. The optimization of TiO2 to modified alginate mass ratio was carried out and hydrogel beads with TiO2/MCA mass ratio of 10.0% (2MCA-TiO2) revealed highest sorption efficiency. The produced sorbents were adapted in the form of hydrogel beads for operation. Organic functionalization based on aminocarbamate (OCONHNH2) moieties on linear chains of alginate embedded additional chelating functional sites which enhanced sorption and selectivity. Batch mode experiments were conducted for optimization of pH and sorbent dose. Equilibrium sorption, kinetic and thermodynamic studies were performed to pattern the nature of sorption. Kinetic data was found in close agreement with pseudo-second order rate expression (PSORE). Isothermal equilibrium sorption data was well fitted with Langmuir adsorption model. Maximum sorption capacity was evaluated as 229 mg/g at 298 K and pH = 6.0.

Lab-scale continuous flow studies for comparative biosorption of cadmium (II) on untreated and xanthated Ficus religiosa biomass.

The present studies report the use of an ecofriendly biomass Ficus religiosa in untreated (UFR) and xanthate treated (XFR) forms for the Cd (II) ions removal in a fixed bed column. FTIR, SEM-EDS, BET surface area, and elemental analysis (CHNS) techniques were used to characterize the biosorbents. The acquired data supported FTIR findings regarding the nature of functional groups present in the materials. Packed bed continuous flow studies explored the effects of various parameters such as Cd (II) ion concentration (100 mg/L-300 mg/L), bed heights (5 cm-30 cm), pH (3-5), at a constant linear flow rate (~1.13 cm/min). The obtained S-shaped breakthrough curves indicated the efficiency of the packed bed for the Cd (II) removal. Breakthrough time and exhaust times increased (67.5 min-390 min and 292.5 min-1852.5 min) (97.5 min-442.5 min and 345 min-1920 min) for unmodified and modified respectively with bed heights. The BDST, Thomas, and Yoon-Nelson models were used to evaluate the experimental results. The Yoon-Nelson model describes the breakthrough data more efficiently compared to other models. Under similar conditions, the modified material exhibited 400% increased capacity (55.20 mg/g) than that of unmodified material (13.33 mg/g). Thus, xanthate modification significantly enhanced the capacity for Cd (II) ions from aqueous solutions. PRACTITIONER POINTS: Xanthate modification of Ficus religiosa is an environmentally friendly process. Modified and unmodified materials were utilized for Cd (II) removal in fixed bed column process which is industrially viable process. Low inlet Cd (II) concentration at pH 5 and higher bed height favored the continuous flow process at fixed flow rate. Modification caused an increase of about 400% in the capacity of material.

Inorganic nanoparticles for reduction of hexavalent chromium: Physicochemical aspects.

Hexavalent Chromium [Cr(VI)] is a highly carcinogenic and toxic material. It is one of the major environmental contaminants in aquatic system. Its removal from aqueous medium is a subject of current research. Various technologies like adsorption, membrane filtration, solvent extraction, coagulation, biological treatment, ion exchange and chemical reduction for removal of Cr(VI) from waste water have been developed. But chemical reduction of Cr(VI) to Cr(III) has attracted a lot of interest in the past few years because, the reduction product [Cr(III)] is one of the essential nutrients for organisms. Various nanoparticles based systems have been designed for conversion of Cr(VI) into Cr(III) which have not been critically reviewed in literature. This review present recent research progress of classification, designing and characterization of various inorganic nanoparticles reported as catalysts/reductants for rapid conversion of Cr(VI) into Cr(III) in aqueous medium. Kinetics and mechanism of nanoparticles enhanced/catalyzed reduction of Cr(VI) and factors affecting the reduction process have been discussed critically. Personal future insights have been also predicted for further development in this area.

Silver nanoparticles stabilized in polymer hydrogels for catalytic degradation of azo dyes.

Fabrication of poly-(N-isopropylmethacrylamide-co-methacrylic acid) [p(NMA)] microgels to be utilized as microreactors to synthesize stable Ag nanoparticles for catalytic reductive degradation of dyes has been addressed in this work. Both p(NMA) microgel and Ag-p(NMA) hybrid microgel systems have been analyzed by Fourier transform infra-red and Dynamic light scattering, Ultraviolet-Visible spectroscopy, X-ray diffraction and Transmission electron microscopy. Catalytic activity of Ag-p(NMA) towards reductive degradation of Congo Red (CR), Methyl Orange (MO) and Alizarin Yellow (AY) was investigated under different operating conditions. Spectrophotometry was employed to check the progress of reaction while the rate constant (kapp) value of degradation reaction was determined under various conditions to optimize reaction parameters for rapid and economical degradation of these dyes. An increase in kapp value was observed by increasing feed content of dye up to a certain value that decreases again by further increment in dye concentration which reflects that catalysis follows Langmuir-Hinshelwood mechanism. A gradual increase in the kapp value was also observed with increasing quantity of hybrid microgel used as a catalyst. By comparing kapp values of degradation of aforementioned dyes, it was found that Ag-p(NMA) hybrid microgel gives better activity for MO dye degradation in comparison to catalytic degradation of CR and AY.

Synthesis and characterization of poly(N-isopropylmethacrylamide-acrylic acid) smart polymer microgels for adsorptive extraction of copper(II) and cobalt(II) from aqueous medium: kinetic and thermodynamic aspects.

Extraction of toxic heavy metal ions from aqueous medium using poly(N-isopropylmethacrylamide-acrylic acid) (P(NiPmA-Ac)) microgels as adsorbent has been investigated in present study. P(NiPmA-Ac) microgel particles were prepared by free radical precipitation polymerization in aqueous medium. Morphology and size of the prepared microgel particles was investigated by transmission electron microscopy (TEM). The Fourier transform infrared (FT-IR) analysis of pure and metal ion-loaded microgel particles was performed to confirm the presence of various functionalities of microgel particles and their interaction with metal ions extracted from aqueous medium. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used to investigate the thermal stability and thermal behavior of pure and metal ion-loaded microgel particles. Contents of metal ions loaded into microgel particles were determined by TGA analysis. It was observed that P(NiPmA-Ac) particles have a potential to extract Cu2+ and Co2+ ions from aqueous medium. The Freundlich adsorption isotherm model best interprets the adsorption process as compared with the Langmuir model. Value of R2 according to the Freundlich adsorption isotherm was found to be 0.994 and 0.993 for Cu2+ and Co2+ ions, respectively. Adsorption process was followed by pseudo second order kinetics for Cu2+ and Co2+ ions with R2 values of 0.999 for both metal ions. Thermodynamic study showed that adsorption process was spontaneous, feasible, and endothermic in nature. Entropy was decreased at adsorbate-adsorbent interface during adsorption process. Adsorbent was recycled and reused for removal of Cu2+ ions, and adsorption efficiency was found to be maintained up to three cycles. Microgel particles also have ability to extract Cu2+ ions efficiently from electroplating wastewater. Graphical abstract.

Environmentally benign extraction of cellulose from dunchi fiber for nanocellulose fabrication.

In the current study, cellulose was extracted from the plant dunchi fiber by using an ecofriendly method followed by preparation of nanocellulose. The procedure involved an alkali treatment and chlorine-free bleaching for removal of lignin and hemicelluloses from material. Fourier transform infrared (FTIR) spectroscopy provided the evidence about removal of hemicellulose and lignin. The morphological changes in the surface of lignocellulosic fibers were studied through scanning electron microscopy (SEM). X-ray Diffraction (XRD) analysis measured the degree of crystallinity of extracted cellulosic material. By using Segal method, the degree of crystallinity was found 66.7%. Crystal thickness was determined by Scherrer equation and its value was found to be 40.07 Å. The values were closed to the values observed for commercial microcrystalline cellulose (MCC). The TGA curve showed the thermal degradation pattern of the cellulosic material and it was closed to the thermal behavior of pure cellulose. Finally, nanocellulose was produced by acid hydrolysis from the obtained cellulosic material. Transmission electron microscopy (TEM) showed the existence of nanocellulose with an average aspect ratio of 10.45 ± 3.44. In the future, dunchi fiber has a potential to be used as a renewable source to produce cellulose and subsequently its nanocellulose for a wide range of applications in composite materials.

Fabrication of a novel hybrid biocomposite based on amino-thiocarbamate derivative of alginate/carboxymethyl chitosan/TiO2 for Ni(II) recovery.

A novel hybrid biocomposite based on amino-thiocarbamate derivative of alginate, carboxymethyl chitosan and TiO2 (TiO2/TSC-CMC) was fabricated and characterized using Fourier transform Infrared spectroscopy (FTIR), Scanning electron microscopy (SEM) and Energy dispersive X-ray spectroscopy (EDX). The TiO2/TSC-CMC mass ratio (5.0-30.0%) was optimized and 3TiO2/TSC-CMC (hydrogel beads with TiO2/TSC-CMC mass ratio of 20.0%) was selected as the best sorbent for effective biosorption of Ni(II). Batch sorption experiments were conducted, instantaneous and equilibrium sorption capacities were investigated as function of pH, sorbent dose, initial metal concentration, contact time and temperature. Kinetic data could be well explained through pseudo second order rate equation (PSORE) depicting that the rate determining step involves the transfer of electron density from sorbent functional sites to central metal ion. Langmuir model fitted well with isothermal sorption data and maximum monolayer sorption capacity (qm) was computed as 172 mg/g at pH 6.0 and temperature 298 K. The values of thermodynamic parameters such as standard enthalpy change (16.94 kJ/mol) and standard Gibbs energy change (-18.67, -19.48, -20.57, and -21.38 kJ/mol) and standard entropy change (0.12 kJ/mol·K) concluded that sorption process is endothermic, spontaneous and resulted with increase in randomness. Hence, 3TiO2/TSC-CMC was found efficient and reusable sorbent.

Amino-carbamate moiety grafted calcium alginate hydrogel beads for effective biosorption of Ag(I) from aqueous solution: Economically-competitive recovery.

In present study, pure and amino-carbamate moiety grafted calcium alginate hydrogel beads (CA, PSC-CA) were prepared for their biosorption performance in the recovery of silver ions. The produced sorbents were characterized using FTIR, SEM, EDX and TGA. FTIR and SEM-EDX confirmed the successful modification and loading of silver ions onto hydrogel beads. When compared with CA, PSC-CA showed enhanced sorption but comparable kinetics. Equilibrium sorption studies showed that pH, sorbent dose, contact time and adsorbate concentration influenced the sorption capacity. The uptake kinetic data was well demonstrated by pseudo second order rate equation (PSORE). Elovich equation and the resistance to intra-particle diffusion model (RID) suggested that there were two phases of sorption, first one was rapid followed by relatively slow uptake step. Equilibrium isothermal sorption data was well fitted by Langmuir and Sips models. The separation factor RL was found as 0 < RL < 1 which indicated favourable sorption. The maximum monolayer sorption capacity was computed as 210 mg/g at 298 K. Thermodynamic studies revealed the sorption process to be spontaneous and exothermic. PSC-CA hydrogel beads were found as cost-effective and efficient sorbent for economically-competitive recovery of Ag(I).