ABSTRACT
In this work, chemical modification of the chitosan with ethyl acetoacetate was performed through a base-catalyzed reaction in which epichlorohydrin facilitated the insertion as well as nucleophilic substitution reaction to graft the 1,3-dioxo moiety across the linear chains of the base biopolymer to establish specificity and selectivity for U(VI) removal. The modified chitosan (EAA-CS) was intercalated into phosphate rich alginate matrix (PASA). Later on, the WO3-doped composites with different WO3 to PASA mass ratio were prepared and characterized using FTIR, XPS, SEM-EDS, XRD, and elemental mapping analysis. WO3 significantly contributed to chemically stable inorganic-organic composites with improved porous texture. Among the prepared composites, MCPS-3 microspherical beads, having mass ratio of 30.0 % w/w, exhibited excellent sorption capacity for U(VI) at an optimal pH 4.5. The successful U(VI) sorption was validated by the existence of two U4f peaks at 392.25 and 381.36 eV due to U4f5/2 and U4f7/2 sub-peaks with an intensity ratio of 3:4, respectively. Batch mode sorption kinetics followed pseudo-second-order rate equation (R2 ≈ 0.99, qe,th ≈ 116.88 mg/g, k2 = 0.86 × 10-4 g/mg.min-1) and equilibrium sorption data aligns with Langmuir (R2 = 0.99, qm = 343.85 mg/g at 310 K and pH = 4.5, KL = 2.00 × 10-2 L/mg) and Temkin models (R2 ≈ 0.99). Thermodynamic parameters ΔHo (30.51 kJ/mol), ΔSo (0.19 kJ/mol.K) and ΔGo (-25.64, -26.89, and - 27.91 kJ/mol) at 298, 305, and 310 K, respectively, suggested that the uptake process is feasible, endothermic and spontaneous. Based on these findings, it is reasonable to conclude that MCPS-3 could be a better hydrogel-based biomaterial for appreciable uranium recovery.
Subject(s)
Alginates , Chitosan , Oxides , Phytic Acid , Tungsten , Uranium , Chitosan/chemistry , Alginates/chemistry , Adsorption , Tungsten/chemistry , Oxides/chemistry , Phytic Acid/chemistry , Uranium/chemistry , Kinetics , Hydrogen-Ion Concentration , Water Purification/methodsABSTRACT
In this study, AgNPs-loaded polyurethane-sodium alginate (PU-S/Alg) composite polymers were prepared by precipitation polymerization and in-situ reduction method. Their catalytic potential was evaluated for the reduction of methyl orange (MO), brilliant blue (BB), Rhodamine B (RhB), 4-nitroaniline (4-NA), and 4-nitrophenol (4-NP). Successful preparation of samples was confirmed by UV-Visible spectrophotometry (UV-Visible), Fourier transform infrared (FTIR), and Scanning electron microscopy (SEM) analysis. During the catalytic study, the value of kapp for the reduction of MO in the presence of NaBH4 and catalyst was found 0.488 min-1 while, in the presence of NaBH4 and catalyst alone, were found as 0.9 × 10-4 and 0.8 × 10-5 min-1, respectively which indicates the role of catalyst in making the reaction speedy. The value of kapp for the reduction of BB, RhB, 4-NA, and 4-NP was found as 0.764, 0.475, 0.212 and 0.757 min-1, respectively. Simultaneous reduction of dyes induced a decreased reaction completion time under the same reaction conditions. A slight increase in the value of kapp for the catalytic reduction of MO was also observed when reactions were performed in the presence of ionic media of different salts such as NaCl, KCl, CaCl2, and MnCl2. The rate of reduction of MO was increased with the increase in ionic strength of the medium. However, the presence of SDS (surfactant) in the reaction mixture induced the decreased activity of the catalyst and increased reaction completion time. The same value of kapp for the reduction of MO was observed in the case of freshly prepared and several days old nanocomposite catalyst. These results illustrate the stability and maintained catalytic potential of metal NPs for a prolonged time. Our reported catalyst also showed good potential for the treatment of dyes-polluted textile industry wastewater.
ABSTRACT
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.
ABSTRACT
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.
Subject(s)
Alginates , Oxides , Tungsten , Uranium , Alginates/chemistry , Adsorption , Phosphates , Porosity , Thermodynamics , Kinetics , Uranium/chemistry , Hydrogen-Ion ConcentrationABSTRACT
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.
Subject(s)
Chitosan , Microgels , Microgels/chemistry , Chitosan/chemistry , Gels/chemistry , Catalysis , NanotechnologyABSTRACT
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.
ABSTRACT
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.
Subject(s)
Chitosan , Water Pollutants, Chemical , Chitosan/chemistry , Alginates/chemistry , Adsorption , Thermodynamics , Kinetics , Water , Hydrogen-Ion ConcentrationABSTRACT
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.
Subject(s)
Chitosan , Metal Nanoparticles , Microgels , Metal Nanoparticles/chemistry , Chitosan/chemistry , Silver/chemistry , CatalysisABSTRACT
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.
ABSTRACT
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.
Subject(s)
Metal Nanoparticles , Microgels , Polymers/chemistry , Silver/chemistry , Metal Nanoparticles/chemistry , Hydrogels , CatalysisABSTRACT
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.
ABSTRACT
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.
Subject(s)
Chitosan , Water Pollutants, Chemical , Adsorption , Alginates/chemistry , Chitosan/chemistry , Hydrogen-Ion Concentration , Kinetics , Spectroscopy, Fourier Transform Infrared , Thermodynamics , TitaniumABSTRACT
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.
ABSTRACT
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.
Subject(s)
Chitosan , Water Pollutants, Chemical , Adsorption , Alginates/chemistry , Chitosan/chemistry , Copper/chemistry , Hydrogels/chemistry , Hydrogen-Ion Concentration , Ions , Kinetics , Spectroscopy, Fourier Transform InfraredABSTRACT
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.
Subject(s)
Alginates/chemistry , Chitosan/chemistry , Nanocomposites/chemistry , Nickel/chemistry , Titanium/chemistry , Adsorption , Hydrogen-Ion Concentration , Kinetics , Molecular Structure , Nanocomposites/ultrastructure , Spectroscopy, Fourier Transform InfraredABSTRACT
BACKGROUND: Sedation is a common and incapacitating clozapine adverse effect, but the factors associated with sedation and its pharmacological management remain poorly studied. METHODS: We conducted a retrospective cohort study based on deidentified electronic clinical records of clozapine-treated patients from the secondary mental health care provider for Cambridgeshire and Peterborough, United Kingdom. We first evaluated cross-sectionally the influence of clozapine dose, clozapine, and norclozapine plasma levels on self-reported hours slept, as a proxy for sedation, using bivariate correlation and then the longitudinal effect of changes in clozapine dose and other 23 medications using linear mixed effect models. We followed 241 clozapine-treated patients for 56 months on average, with 2237 face-to-face assessments in total. RESULTS: Patients slept for a mean of 9.35 h/d, with 46% reporting 10 h/d or more. Cross-sectionally, sleep duration did not correlate with clozapine dose (r = 0.14, P = 0.106), but with clozapine plasma levels (r = 0.38, P < 0.0001) and norclozapine plasma levels (r = 0.25, P = 0.005). Longitudinally, the final mixed-effects model revealed 4 pharmacological variables that had a significant impact on hours slept: clozapine, risperidone augmentation, and atenolol were associated with increased sleep, whereas aripiprazole augmentation was associated with decreased sleep. We found that 20 other psychotropic medications measured were not associated with changes in sleep when added to clozapine. Excess sleep is a clozapine level-dependent adverse effect. CONCLUSIONS: The impact of different augmentation strategies might help clinicians decide on the most adequate strategy, albeit further studies should confirm our results.
Subject(s)
Clozapine/adverse effects , Clozapine/pharmacology , Sleep/drug effects , Adult , Antipsychotic Agents/adverse effects , Antipsychotic Agents/pharmacology , Drug Interactions , Female , Humans , Male , Middle Aged , Retrospective Studies , Self Report , Time Factors , United KingdomABSTRACT
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.
Subject(s)
Ficus , Water Pollutants, Chemical , Water Purification , Adsorption , Biomass , Cadmium , Water Pollutants, Chemical/analysisABSTRACT
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.
ABSTRACT
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.
Subject(s)
Azo Compounds/chemistry , Metal Nanoparticles/chemistry , Silver/chemistry , Catalysis , Coloring Agents/chemistry , Congo Red/chemistry , Hydrogels/chemistry , Microscopy, Electron, Transmission , Polymers/chemistry , Spectrophotometry , X-Ray DiffractionABSTRACT
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.