TiO2-modified g-C3N4 nanocomposite for photocatalytic degradation of organic dyes in aqueous solution.

In the current study, a direct S-scheme titanium dioxide/graphitic carbon nitride (TiO2/g-C3N4) heterojunction structure was fabricated via simultaneous calcination of TiO2 precursors and g-C3N4. Guava leaf extract was utilized as a reductant for TiO2 production through a green synthetic method, and g-C3N4 was prepared by thermal decomposition of melamine. The pristine and nanocomposite photocatalysts were characterized by XRD, FTIR, BET, TGA, HRTEM, UV-vis DRS, and PL to elucidate their physicochemical properties. The photocatalytic activity of synthesized photocatalysts was examined through the degradation of rhodamine B (RhB) and methylene blue (MB) dyes under simulated solar light irradiation. The nanocomposite exhibited commendable photocatalytic performances with 96% degradation efficiency of RhB attained in 120 min and 95% degradation efficiency of MB achieved in 150 min. The enhanced photocatalytic activities were attributable to visible light-harvesting characteristics and the formation of an S-scheme heterojunction system between two catalysts which promotes interfacial charge separation efficiency and longer charge carrier lifespan. After 4 consecutive cycles, the degradation efficiencies of both RhB and MB remained above 85%. According to the trapping experiments, OH• and O2 •- radicals were critical in the degradation of RhB, while h+ and O2 •- radicals were dominant in the degradation of MB. The nanocomposite was also tested for elution of actual water pollutants by combining two dyes, and above 90% degradation efficiencies were achieved for both dyes after 240 min.

Nanocellulose-based composites for the removal of contaminants from wastewater.

Polymers derived from plant and animal sources are of great interest in wastewater remediation due to their cost-effectiveness and renewable adsorption capabilities, one such polymer is nanocellulose (NC). NC has gained a lot of attention in various research fields due to its abundance in nature, nano-dimension, high surface area, stability and bio-compatibility. As a result, NC has emerged as a great potential adsorbent for the removal of contaminants such as heavy metals, organic dyes, oils, pharmaceutical and etc. in the environmental remediation. This review focuses on the description of the building blocks, structure, properties, isolation and also discusses the potential of nanocellulose based composites materials with reinforcements such as activated carbon, carbon nanotube, graphene oxides, metals, non-metals and ceramics that were effectively used as an adsorbents for diverse organic and inorganic contaminants in water.

Mechanistic pathways for the degradation of SMX drug and floatation of degraded products using F-Pt co-doped TiO2 photocatalysts.

This work presents smart pathways to enhance the photocatalytic activity of TiO2 via co-doping with fluorine (F) and platinum (Pt) to form F-Pt co-doped TiO2 photocatalysts and investigates the unique and unusual fluorination of the floated products. Our investigations indicate that the crystalline structure of the photocatalysts was a mixture of anatase and brookite phases and that the nanoparticles of the synthesized nanocomposites had nanometric sizes (4-25 nm). The F-Pt co-doped TiO2 nano-photocatalysts demonstrated degradation of sulfamethoxazole (SMX) drug of >93% within 90 min under direct solar light and 58% degradation within 360 min under a solar simulator. Thus, co-doping TiO2 with F and Pt atoms to form F-Pt co-doped TiO2 nanocomposite is an efficient pathway to achieve high photocatalytic performance escorted with the formation of floating metal-fluoropolymer, unlike pristine TiO2 which has less photocatalytic degradation and no generation of a floating polymer. Our photocatalytic protocol demonstrates that the degradation of SMX started with redox reactions of oxygen and water absorbed on the surface of the prepared nanocomposites to form superoxide anions (O2˙-) and hydroxy radicals (˙OH) which have oxidation superpower. The resultant products were subsequently fluorinated by fluoride radical ions and floated as metal-fluoropolymer.

Impact of Fluorination on Microstructures and Surface Properties of SiC Nanocomposites with Si x C y F z Composition.

Silicon carbide (SiC) is an effective catalyst for generating fuel from organics through gasification. SiC has shown promising results as a catalyst due to its extraordinary thermal and oxidation resistance abilities. Researchers are yet to identify an efficient silicon carbide composite material that enhances the desired quality of fuel/liquid production. The present study deals with in situ synthesis of fluorine-doped silicon carbide using agriculture waste. Biochar, a waste by-product from the gasification process, proved to be a potential carbon source for fabrication of silicon carbide nanowires (SiCNWs). Pristine SiCNWs exhibited nanospheres and freestanding nanowire (coiled, rods, bamboolike, or hexagonal prism) structures with transversal optical mode indexed to the ß-phase (ß-SiC). Fabrication of fluorine (F)-doped SiC from a silica-carbon-fluorine (SiO x /C y /F z ) precursor resulted in uneven flat-surfaced silicon carbide materials accompanied by progressive pore blockage with increasing F-content. Pore blockage was confirmed by declining the surface area from 60.70 m2 g-1 of the lowest dopant to 17.33 m2 g-1 of the maximum dopant, compared to neat SiC (63.20 m2 g-1). Introduction of fluorine led to decreased silicon contents and collapsed nanowire while the carbon and oxygen contents increased.

Chitosan-lignin-titania nanocomposites for the removal of brilliant black dye from aqueous solution.

A nanoadsorbent was synthesized from kraft lignin derived from paper and pulp black liquor, chitosan, and titania (TiO2) and used to remove Brilliant Black dye (BB) from aqueous solution. Transmission electron microscopy measurements confirmed the material was nanoscale and BET studies showed a pore width of 11.36 nm with a BET surface area (SBET) of 10.75 m2/g. The presence of NH, O and TiO functional groups was confirmed by ATR-FTIR, and thermogravimetric analysis indicated the nanoadsorbent was thermally stable up to 300 °C. Scanning electron microscopy showed that lignin had larger particles with well-defined edges, while the surface morphology of chitosan showed non-uniform, short fibrous microstructures. The diffraction patterns of the nanocomposite showed a polycrystalline anatase phase and selected area electron diffraction analysis showed the nanocomposite has small spots making up a ring, indicating the nanoparticles has a crystalline structure. The effects of contact time, solution pH, adsorbent dosage, and initial dye concentration on the adsorption of BB were investigated. The batch adsorption data obeyed the Freundlich isotherm (r2 = 0.91), and the monolayer adsorption capacities calculated using the linear Langmuir isotherm was 15.8 mg/g at 25 °C. The adsorption kinetic data were described by the pseudo-second order kinetic model (r2 = 0.93).

Conversion of post consumer waste polystyrene into a high value adsorbent and its sorptive properties for Congo Red removal from aqueous solution.

Using post-consumer waste polystyrene (WPS), a conjugated microporous polymer (CMP) was synthesised and activated into a sulphonic-group carrying resin (SCMP). The surface chemistry of the materials showed a decline in both the aromatic CH and aliphatic CH2 stretching vibrations confirming successful crosslinking. The synthesised polymers were thermally stable with decomposition temperatures above 300 °C, had surface heterogeneity, and BET surface areas of 752 and 510 m2/g, respectively. A distribution of pores ranging from meso- to micro-pores was comparable to other CMPs. The materials had maximum adsorption capacities of 500 and 357 mg/g for Congo Red (CR) on CMP and SCMP, respectively. Converting waste polystyrene to an adsorbent is a cost effective way of handling waste and simultaneously providing material for wastewater remediation.

Catalytic reduction of p-nitrophenol by using platinum nanoparticles stabilised by guar gum.

We report a facile and green method to synthesise highly stable dispersions of platinum nanoparticles (PtNPs) with an average particle size of ∼ 6 nm. Natural, nontoxic, eco-friendly biopolymer guar gum was utilised as both the reducing and capping agent precursor in aqueous medium. The PtNPs that had been stabilised by guar gum (GG-s-PtNPs) were characterised by UV-vis spectroscopy, XRD, TEM and XPS. GG-s-PtNPs performed better in terms of catalytic activity for the liquid phase reduction of p-nitrophenol (p-NP) compared to p-aminophenol (p-AP). The efficiency of the catalytic reduction of p-NP over GG-s-PtNPs was found to be 97% in a total time of 320 s at room temperature. The mechanisms of the synthesis and catalytic reduction of p-NP are also discussed. The synthesis approach presented here does not require stringent conditions or toxic agents and thus is a straightforward, rapid, efficient, and green approach to the fabrication of highly active catalysts.

Effect of functionalization on the adsorption capacity of cellulose for the removal of methyl violet.

In this research paper a comparative study has been carried out for the removal of methyl violet dye using unfunctionalized and functionalized cellulose. The functionalization was achieved through esterification of cellulose with furan-2,5-dione. The functionalization of the cellulose was evidenced using BET, FT-IR, SEM and TGA. The adsorption isotherm data was fitted using different isotherm models like Langmuir, Freundlich, Temkin, Flory-Huggins and Dubinin-Kaganer-Radushkevich models and found to follow Langmuir and Temkin isotherm models with high value of correlation coefficients. Functionalized cellulose (106.38 mg g(-1)) showed higher dye removal capability than unfunctionalized cellulose (43.668 mg g(-1)). The kinetics of adsorption was investigated using pseudo first order, second order, Elovich, liquid film diffusion and intra-particle diffusion models. The mechanism of adsorption was found to follow pseudo second order rate equation. Thermodynamic studies showed that the adsorption process was endothermic and spontaneous.

Gum ghatti and Fe3O4 magnetic nanoparticles based nanocomposites for the effective adsorption of rhodamine B.

This article reports the development of a new nanocomposite using gum ghatti crosslinked with poly(acrylic acid-co-acrylamide) reinforced with iron oxide magnetic nanoparticles. The nanocomposite was characterized through BET, FT-IR, XRD, SEM-EDX, TGA and TEM and applied for the removal of RhB. Different optimized adsorption parameters were adsorbent dose (0.8 g/L) and pH (7.0). The adsorption isotherm data was used to study Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich isotherm models. The value of correlation coefficient confirmed the applicability of Langmuir isotherm model with maximum adsorption efficiency of 654.87 mg/g. The adsorption kinetics data showed pseudo second order reaction. Thermodynamic studies showed that the adsorption process was endothermic and spontaneous. Moreover, the adsorbent was successfully utilized for successive three cycles for the adsorption-desorption of RhB.

Biosorption potential of Gum ghatti-g-poly(acrylic acid) and susceptibility to biodegradation by B. subtilis.

This article reports the biosorption potential of Gum ghatti (Gg)-grafted-acrylic acid (AA) polymer and its susceptibility to biodegradation by Bacillus subtilis (BS) in two different liquid media, i.e. phosphate buffered saline (PBS) and mineral salt medium (MSM). The progress of biodegradation was monitored after every 15 days using FT-IR and SEM techniques. The degradation of the polymer was further evidenced by a loss of weight of 23.2% and 27% in BS-MSM and BS-PBS, respectively, after 60 days. The AA-grafted polymer was then utilized for the removal of Pb(II) and Cu(II) from aqueous solution. The adsorption isotherm data were studied using Langmuir, Freundlich, Temkin, Flory-Huggins and Dubinin-Kaganer-Radushkevich isothermal models. High values of correlation coefficients confirmed the applicability of Langmuir isotherm model used to determine the adsorption capacity of the AA-grafted polymer. The maximum adsorption capacity was found to be 84.74 mg/g for Cu(II) and 310.55 mg/g for Pb(II). Kinetic data were evaluated using pseudo first order, pseudo second order, Elovich, intraparticle diffusion and liquid film diffusion models. The experimental kinetic data fitted well with the pseudo second order rate model.

Metal doped nanosized titania used for the photocatalytic degradation of rhodamine B dye under visible-light.

Metal-doped anatase nanosized titania photocatalysts were successfully synthesized using a sol-gel process. Different amounts of the dopants (0.2, 0.4, 0.6, 0.8 and 1.0%) of the metals (Ag, Ni, Co and Pd) were utilized. The UV-Vis spectra (solid state diffuse reflectance spectra) of the doped nanoparticles exhibited a red shift in the absorption edge as a result of metal doping. The metal-doped nanoparticles were investigated for their photocatalytic activity under visible-light irradiation using Rhodamine B (Rh B) as a control pollutant. The results obtained indicate that the metal-doped titania had the highest activity at 0.4% metal loading. The kinetic models revealed that the photodegradation of Rh B followed a pseudo first order reaction. From ion chromatography (IC) analysis the degradation by-products Rhodamine B fragments were found to be acetate, chloride, nitrite, carbonate and nitrate ions.

Preparation of poly(acrylamide-co-acrylic acid)-grafted gum and its flocculation and biodegradation studies.

Biodegradation studies of Gum ghatti (Gg) and acrylamide-co-acrylic acid based flocculants [Gg-cl-poly(AAm-co-AA)] have been reported using the soil composting method. Gg-cl-poly(AAm-co-AA) was found to degrade 89.76% within 60 days. The progress of biodegradation at each stage was monitored through FT-IR and SEM. Polymer was synthesized under pressure using potassium persulphate-ascorbic acid as a redox initiator and N,N'-methylene-bis-acrylamide as a crosslinker. Synthesized polymer was found to show pH, temperature and ionic strength of the cations dependent swelling behavior. Gg-cl-poly(AAm-co-AA) was utilized for the selective absorption of saline from different petroleum fraction-saline emulsions. The flocculation efficiency of the polymer was studied as a function of polymer dose, temperature and pH of the solution. Gg-cl-poly(AAm-co-AA) showed maximum flocculation efficiency with 20 mol L(-1) polymer dose in acidic medium at 50 °C.

Flocculation characteristics and biodegradation studies of Gum ghatti based hydrogels.

Biodegradable flocculants of Gum ghatti (Gg) with acrylamide (AAm) were prepared through graft co-polymerization technique using potassium persulphate (KPS)-ascorbic acid (ABC) redox pair as initiator and N,N'-methylene-bis-acrylamide (MBA) as a crosslinker. Gg-cl-poly(AAm) was found to exhibit pH and temperature responsive swelling behavior. Maximum flocculation efficiency of Gg-cl-poly(AAm) was observed with 15 mg L(-1) polymer dose in acidic medium at 50°C. Biodegradation studies of Gg and Gg-cl-poly(AAm) were done using composting method. Gg was found to degrade within 20 days, whereas, Gg-cl-poly(AAm) was found to degrade 88.18% within 60 days. Different stages of bio-degradation were characterized through FT-IR and SEM techniques.

Stabilisation of silver and copper nanoparticles in a chemically modified chitosan matrix.

This work describes the stabilisation of silver and copper nanoparticles in chemically modified chitosan colloidal solution. Chitosan-N-2-methylidene-hydroxy-pyridine-6-methylidene hydroxy thiocarbohydrazide (CSPTH) was used as a stabilising and reducing agent for silver and copper nanoparticles. The modified chitosan derivatives and the synthesised nanoparticles were characterised by Fourier transform infrared (FT-IR) spectroscopy, Ultraviolet-visible (UV-Vis) spectroscopy and X-ray diffraction (XRD). Particle size, morphology and segregation of the nanoparticles were determined by transmission electron microscopy (TEM). The size of the nanoparticles was found to be less than 20 nm and 50 nm for silver and copper nanoparticles, respectively. These nanoparticles were stabilised in a chemically modified chitosan solution and their properties were studied using fluorescence spectroscopy, photoluminescence spectroscopy and surface-enhanced Raman scattering (SERS). The optical properties of silver nanoparticles in surface plasmon band (SPB) were enhanced at 407 nm compared to those of copper nanoparticles. Fluorescence (400 nm and 756 nm), photoluminescence (450 and 504 nm) and Raman scattering (1382 and 1581 cm(-1)) properties for the copper nanoparticles were superior to those of the silver nanoparticles.

Chromatographic resolution of racemic α-amino acids: chiral stationary phase derived from modified xanthan gum.

Enantiomeric resolution of α-amino acids into L-amino acid and D-amino acid via column chromatography using chiral stationary phase was performed. For this purpose, a dynamic chiral stationary phase prepared by grafting of methylmethacrylate onto xanthan gum (XG) was successfully employed in resolving various α-amino acids racemates. The peculiarities of the chromatographic behaviour of xanthan gum-graft-poly(methylmethacrylate)-amino acid interaction and the mechanism of their retention in column are discussed. The enantioselective properties of the xanthan gum-graft-poly(methylmethacrylate) in the separation of enantiomers of α-amino acids were studied using acidic solution of alanine, leucine, valine and tryptophan. The procedure is characterized by simplicity, efficiency and relatively low cost to analyze enantiomers of some amino acids.

Microwave synthesized xanthan gum-g-poly(ethylacrylate): an efficient Pb2+ ion binder.

Microwave induced emulsion copolymerization of ethylacrylate and xanthan gum resulted in copolymer samples of different % grafting (%G). The synthesis was done in the presence of catalytic amount of KPS as an initiator and the adsorption behavior of the copolymer (360%G) was investigated by performing both the kinetics and equilibrium studies in batch conditions. The copolymer was characterized by different techniques. Several experimental parameters were varied to optimize the adsorption conditions. The most favorable pH for the adsorption was pH 5, and at this pH the adsorption data were modeled using Langmuir and Freundlich isotherms. On the basis of the Langmuir model, Q0 was calculated to be 142.86 mg g(-1) for microwave synthesized copolymer (mwXG-g-PEA). The sorption by mwXG-g-PEA followed pseudo second-order kinetics where a linear plot of t/(qt) versus t was obtained, the correlation coefficient (R(2)) and rate constant at 100 mg L(-1) Pb(II) being 0.994 and 3.013×10(-4)g/(mg min), respectively.

Graft copolymerization of ethylacrylate onto xanthan gum, using potassium peroxydisulfate as an initiator.

Graft copolymer of xanthan gum (XG) and ethylacrylate (EA) has been synthesized by free radical polymerization using potassium peroxydisulfate (KPS) as an initiator in an air atmosphere. The grafting parameters, i.e. grafting ratio and efficiency decrease with increase in concentration of xanthan gum from 0.050 mg/25 mL to 0.350 mg/25 mL, but these grafting parameters increase with increase in concentration of ethylacrylate from 9×10(-2) to 17×10(-2) ML(-1), and KPS from 15×10(-3) to 35×10(-3) ML(-1). The graft copolymer has been characterized by FTIR, XRD, TGA and SEM analysis. The grafted copolymer was also evaluated as efficient Zn(2+) metal binder. The grafted copolymer shows improvement in the stability, solubility as well as their sorbing capacity. Thus graft copolymer formed could find applications in metal ion removal and in drug delivery.

Organic-inorganic hybrid of chitosan/organoclay bionanocomposites for hexavalent chromium uptake.

Organic-inorganic hybrid of chitosan and nanoclay (Cloisite 10A) was chosen to develop a nanomaterial with combine properties of hydrophilicity of an organic polycation and adsorption capacity of inorganic polyanion. The chitosan/clay nanocomposite (CCN) was prepared by solvent casting method. The material synthesis was found most efficient in adsorbent behavior was studied in detail taking Cr(VI) as representative ion. The chemical, structural and textural characteristics of the material were determined by FTIR, XRD, TEM, SEM and EDAX analysis. XRD and TEM results indicated that an exfoliated structure was formed with addition of small amounts of MMT-Na+(montmorillonite-Na(+)) to the chitosan matrix. These composite material were used for the removal of chromium(VI) from aqueous solution. The conditions for the adsorption by the composite have been optimized and kinetics and thermodynamic studies were performed. Though the adsorption takes place in wide pH range, pH 3 was found most suitable and at this pH the adsorption data were modeled using the Langmuir and Freundlich isotherms at 15 °C and 35 °C, where the data fitted satisfactorily to Langmuir isotherms, the R(2) values being 0.998 and 0.999 respectively indicating unilayer adsorption. Based on Langmuir model, Q(o) was calculated to be 357.14 mg/g. The adsorption showed pseudo second order kinetics with a rate constant of 8.0763 × 10(-4) g mg(-1) min(-1) at 100 ppm Cr(VI) concentration.

Experimental and theoretical assessment of the mechanism involved in the reaction of steroidal ketone semicarbazone with hydrogen peroxide.

3ß-Acetoxy-5α-cholestan-6-one semicarbazone 1 on reaction with hydrogen peroxide affords selectively 3ß-acetoxy-5α-cholestan-6-spiro-1',2',4'-triazolidine-3'-one 2. The structural assignment of the product was confirmed by spectral data and elemental analysis. A free radical mechanism of the present reaction was described successfully by calculating theoretical models of 1, A, B and 2, using DFT with B3LYP/6-31G* basis set. It was found that the reaction undergoes through the formation of two radical intermediates and the only one isomer of the product in which -NH-CO- group is cis with respect C5α-H, was selectively obtained. Frontier molecular orbital, spin electronic density, electrostatic potential and atomic charges were discussed.

Green synthesis and stabilization of gold nanoparticles in chemically modified chitosan matrices.

Chitosan-N-2-methylhydroxypyridine-6-methylcorboxylate (Ch-PDC) and chitosan-N-2-methylhydroxypyridine-6-methylhydroxy thiocarbohydrazide (Ch-PDC-Th) were synthesized for the first time using chitosan as precursor. Chitosan, Ch-PDC, Ch-PDC-Th were used in the synthesis of gold nanoparticles (AuNP) in aqueous medium. Chitosan and Ch-PDC-Th possess reducing properties which enabled the 'green' synthesis of AuNPs. The stabilization of the AuNPs was as a result of the thiocarbide (SC) and amine (NH(2)) groups in the chitosan matrix. The modified chitosan, its derivatives and the resulting AuNPs were characterized by Fourier transform infrared (FTIR) spectroscopy, Ultraviolet-visible (UV-vis) spectroscopy, Raman scattering measurements, powder X-ray diffraction (PXRD) and thermo gravimetric analysis (TGA). Particle size, morphology, segregation and individuality of the AuNPs were examined by transmission electron microscope (TEM) and energy dispersion spectroscopy (EDS). An average AuNPs size of 20 nm was observed for chitosan and Ch-PDC-Th while Ch-PDC was 50 nm. In comparison, AuNPs resulting from Ch-PDC-Th precursor has the most enhanced Raman and fluorescent intensities and was stable for over 2 months.