Green synthesis, characterization and antimicrobial activity of silver nanoparticles using methanolic root extracts of Diospyros sylvatica

The current research study focuses to formulate the biosynthesized silver nanoparticles for the first time from silver acetate using methanolic root extracts of Diospyros sylvatica, a member of family Ebenaceae. TEM analysis revealed the average diameter of Ag NPs around 8 nm which is in good agreement with the average crystallite size (10 nm) calculated from X-ray Diffraction (XRD) analysis. Further the study has been extended to the antimicrobial activity against test pathogenic Gram (+) ve, Gram (−) ve bacterial and fungal strains. The bioinspired Ag-NP showed promising activity against all the tested bacterial strains and the activity was enhanced with increased dosage levels.     

Biosynthesis of gold nanoparticles by Trichoderma sp. WL-Go for azo dyes decolorization

Developing an eco-friendly approach for metallic nanoparticles synthesis is important in current nanotechnology research. In this study, green synthesis of gold nanoparticles(AuNPs) was carried out by a newly isolated strain Trichoderma sp. WL-Go. UV–vis spectra of Au NPs showed a surface plasmon resonance peak at 550 nm, and transmission electron microscopy images revealed that the Au NPs were of varied shape with well dispersibility.The optimal conditions for Au NPs synthesis were HAuCl_4 1.0 mmol/L, biomass 0.5 g and pH 7–11. Moreover, the bio-Au NPs could efficiently catalyze the decolorization of various azo dyes. This research provided a new microbial resource candidate for green synthesis of Au NPs and demonstrated the potential application of bio-Au NPs for azo dye decolorization.     

Synthesis, characterization and application of ZnO-Ag as a nanophotocatalyst for organic compounds degradation, mechanism and economic study

The current work deals with ZnO-Ag nanocomposites (in the wide range of x in the Zn_1 − xO-Ag_x chemical composition) synthesized using microwave assisted solution combustion method. The structural, morphological and optical properties of the samples were characterized by XRD (X-ray diffraction), FTIR (Fourier transform infrared spectrometry), SEM (scanning electron microscopy technique), EDX (energy dispersive X-ray spectrum), ICP (inductively coupled plasma technique), TEM (transmission electron microscopy), BET (Brunauer–Emmett–Teller method), UV–Vis (ultraviolet–visible spectrophotometer) and photoluminescence spectrophotometer. The photocatalytic activity of the ZnO-Ag was investigated by photo-degradation of Acid Blue 113 (AB 113) under UV illumination in a semi-batch reactor. This experiment showed that ZnO-Ag has much more excellent photocatalytic properties than ZnO synthesized by the same method. The enhanced photocatalytic activity was due to the decrease in recombination of photogenerated electron-holes. The results showed the improvement of ZnO photocatalytic activity and there is an optimum amount of Ag (3.5 mol%) that needs to be doped with ZnO. The effect of operating parameters such as pH, catalyst dose and dye concentration were investigated. The reaction byproducts were identified by LC/MS (liquid chromatography/mass spectrometry) analysis and a pathway was proposed as well. Kinetic studies indicated that the decolorization process follows the first order kinetics. Also, the degradation percentage of AB 113 was determined using a total organic carbon (TOC) analyzer. Additionally, cost analysis of the process, the mechanism and the role of Ag were discussed.     

Hydrothermal fabrication of selectively doped organic assisted advanced ZnO nanomaterial for solar driven photocatalysis

Hydrothermal fabrication of selectively doped (Ag⁺ + Pd^3 +) advanced ZnO nanomaterial has been carried out under mild pressure temperature conditions (autogeneous; 150°C). Gluconic acid has been used as a surface modifier to effectively control the particle size and morphology of these ZnO nanoparticles. The experimental parameters were tuned to achieve optimum conditions for the synthesis of selectively doped ZnO nanomaterials with an experimental duration of 4 hr. These selectively doped ZnO nanoparticles were characterized using powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UV–Vis spectroscopy and scanning electron microscopy (SEM). The solar driven photocatalytic studies have been carried out for organic dyes, i.e., Procion MX-5B dye, Cibacron Brilliant Yellow dye, Indigo Carmine dye, separately and all three mixed, by using gluconic acid modified selectively doped advanced ZnO nanomaterial. The influence of catalyst, its concentration and initial dye concentration resulted in the photocatalytic efficiency of 89% under daylight.     

The selective catalytic reduction of NO over Ce0.3TiOx-supported metal oxide catalysts

A Ce_(0.3)TiO_xoxide carrier was synthesized via a sol–gel process,and Ce_(0.3)TiO_xsupported metal(M=Cd,Mn,Fe,W,Mo)oxide catalysts were prepared by the method of incipient-wetness impregnation.The catalysts were characterized by means of X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET)analysis,scanning electron microscopy(SEM),transmission electron microscopy(TEM),Fourier transform infrared(FT–IR)spectroscopy,UV–Visdiffusereflectancespectroscopy(UV–VisDRS),and Temperature-programmed reduction with H_2(H_2-TPR).The catalytic activities for de-NO_(x )were evaluated by the NH_3-SCR reaction.Among all the catalysts tested,the 2 wt.%Cd/Ce_(0.3)TiO_xcatalyst exhibited the best NH_3-SCR performance,with a wide temperature window of 250–450°C for NO conversion above 90%.Moreover,the catalyst showed N_2 selectivity greater than 99%from 200 to 450°C.     

Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV–visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV–visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca^2 + and Mg^2 +) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments.     

Newly developed Fe3O4–Cr2O3 magnetic nanocomposite for photocatalytic decomposition of 4-chlorophenol in water

Chlorophenols, typically 4-chlorophenols are highly toxic and non-biodegradable organic contaminants which pose serious threat to the environment, particularly when released into aqueous medium. The removal of these pollutants by efficient method has received worldwide concern in recent past. A new Fe_3O_4–Cr_2O_3 magnetic nanocomposite was synthesized by wet chemical method under ultrasonic irradiation. Microstructure and morphology of the nanocomposite were characterized by powder X-ray diffraction(XRD),Fourier transform infrared(FT-IR), and a transmission electron microscope(TEM). Magnetic and optical properties were studied by a vibrating sample magnetometer(VSM) and an ultraviolet–visible(UV–Vis) spectrophotometer respectively. The magnetic nanocomposite(MNC) was used as photocatalyst for effective decomposition of 4-chlorophenol in water under ultraviolet(UV) irradiation.     

Synthesis,crystal structure,photodegradation kinetics and photocatalytic activity of novel photocatalyst ZnBiYO4

ZnBiYO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiYO₄ were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–Vis diffuse reflectance. ZnBiYO₄ crystallized with a tetragonal spinel structure with space group I41/A. The lattice parameters for ZnBiYO₄ were a = b = 11.176479 Å and c = 10.014323 Å. The band gap of ZnBiYO₄ was estimated to be 1.58 eV. The photocatalytic activity of ZnBiYO₄ was assessed by photodegradation of methyl orange under visible light irradiation. The results showed that ZnBiYO₄ had higher catalytic activity compared with N-doped TiO₂ under the same experimental conditions using visible light irradiation. The photocatalytic degradation of methyl orange with ZnBiYO₄ or N-doped TiO₂ as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01575 and 0.00416 min^− 1 for ZnBiYO₄ and N-doped TiO₂, respectively. After visible light irradiation for 220 min with ZnBiYO₄ as catalyst, complete removal and mineralization of methyl orange were observed. The reduction of total organic carbon, formation of inorganic products, SO₄^2 − and NO₃⁻, and evolution of CO₂ revealed the continuous mineralization of methyl orange during the photocatalytic process. The intermediate products were identified using liquid chromatography–mass spectrometry. The ZnBiYO₄/(visible light) photocatalysis system was found to be suitable for textile industry wastewater treatment and could be used to solve other environmental chemical pollution problems.     

Cobalt and sulfur co-doped nano-size TiO2 for photodegradation of various dyes and phenol

Various compositions of cobalt and sulfur co-doped titania nano-photocatalyst are synthesized via sol–gel method. A number of techniques including X-ray diffraction(XRD), ultraviolet–visible(UV–Vis), Rutherford backscattering spectrometry(RBS), thermal gravimetric analysis(TGA)Raman, N2 sorption, electron microscopy are used to examine composition, crystalline phase, morphology, distribution of dopants, surface area and optical properties o synthesized materials. The synthesized materials consisted of quasispherical nanoparticles of anatase phase exhibiting a high surface area and homogeneous distribution o dopants. Cobalt and sulfur co-doped titania demonstrated remarkable structural and optical properties leading to an efficient photocatalytic activity for degradation of dyes and phenol under visible light irradiations. Moreover, the effect of dye concentration catalyst dose and p H on photodegradation behavior of environmental pollutants and recyclability of the catalyst is also examined to optimize the activity of nano-photocatalys and gain a better understanding of the process.     

Physico-chemical characterization and source tracking of black carbon at a suburban site in Beijing

Particles from ambient air and combustion sources including vehicle emission, coal combustion and biomass burning were collected and chemically pretreated with the purpose of obtaining isolated BC (black carbon) samples. TEM (transmission electron microscopy) results indicate that BC from combustion sources shows various patterns, and airborne BC appears spherical and about 50 nm in diameter with a homogeneous surface and turbostratic structure. The BET (Barrett–Emmett–Teller) results suggest that the surface areas of these BC particles fall in the range of 3–23 m²/g, with a total pore volume of 0.03–0.05 cm³/g and a mean pore diameter of 7–53 nm. The nitrogen adsorption–desorption isotherms are indicative of the accumulation mode and uniform pore size. O₂-TPO (temperature programmed oxidation) profiles suggest that the airborne BC oxidation could be classified as the oxidation of amorphous carbon, which falls in the range of 406–490°C with peaks at 418, 423 and 475°C, respectively. Generally, the BC characteristics and source analysis suggest that airborne BC most likely comes from diesel vehicle emission at this site.     

Photocatalytic reduction of organic pollutant under visible light by green route synthesized gold nanoparticles

We report a rapid method of green chemistry approach for synthesis of gold nanoparticles(AuNPs)using Lagerstroemia speciosa leaf extract(LSE). L. speciosa plant extract is known for its effective treatment of diabetes and kidney related problems. The green synthesis of Au NPs was complete within 30 min at 25°C. The same could also be achieved within 2 min at a higher reaction temperature(80°C). Both UV–visible spectroscopy and transmission electron microscopy results suggest that the morphology and size distribution of Au NPs are dependent on the pH of gold solution,gold concentration,volume of LSE,and reaction time and temperature. Comparison between Fourier transform infrared spectroscopy(FT-IR)spectra of LSE and the synthesized Au NPs indicate an active role of polyphenolic functional groups(from gallotannins,lagerstroemin,and corosolic acid)in the green synthesis and capping of Au NPs. The green route synthesized Au NPs show strong photocatalytic activity in the reduction of dyes viz.,methylene blue,methyl orange,bromophenol blue and bromocresol green,and 4-nitrophenol under visible light in the presence of Na BH_4. The non-toxic and cost effective LSE mediated Au NPs synthesis proposed in this study is extremely rapid compared to the other reported methods that require hours to days for complete synthesis of Au NPs using various plant extracts. Strong and stable photocatalytic behavior makes Au NPs attractive in environmental applications,particularly in the reduction of organic pollutants in wastewater.     

Photocatalytic decomposition of acrylonitrile with N–F codoped TiO2/SiO2 under simulant solar light irradiation

The solid acid catalyst, N–F codoped TiO₂/SiO₂ composite oxide was prepared by a sol–gel method using NH₄F as nitrogen and fluorine source. The prepared materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV–Visible diffuse reflectance spectroscopy (UV–Vis), ammonia adsorption and temperature-programmed desorption (NH₃-TPD), in situ Fourier transform infrared spectroscopy (FT-IR) and N₂ physical adsorption isotherm. The photocatalytic activity of the catalyst for acrylonitrile degradation was investigated under simulant solar irradiation. The results showed that strong Lewis and Brønsted acid sites appear on the surface of the sample after N–F doping. Systematic investigation showed that the highest photocatalytic activity for acrylonitrile degradation was obtained for samples calcined at 450°C with molar ratio (NH₄F to Ti) of 0.8. The degradation ratio of 71.5% was achieved with the prepared catalyst after 6-min irradiation, demonstrating the effectiveness of photocatalytic degradation of acrylonitrile with N–F codoped TiO₂/SiO₂ composite oxide. The photocatalyst is promising for application under solar light irradiation. Moreover, the intermediates generated after irradiation were verified by gas chromatography–mass spectrometry (GC–MS) analysis and UV–Vis spectroscopy to be simple organic acids with lower toxicity, and the degradation pathway was also proposed for acrylonitrile degradation with the prepared catalyst.     

MnFe2O4 nanoparticles as new catalyst for oxidative degradation of phenol by peroxydisulfate

Manganese ferrite nanopowder was prepared by thermal decomposition at 400°C of the gel synthesized from manganese and iron nitrates and polyvinyl alcohol. X-ray diffractometry evidenced that manganese ferrite was formed as single crystalline phase at this temperature. Scanning electron microscope images evidenced the formation of very fine spherical particles(d 11 nm) of manganese ferrite, with specific surface area of 147 m~2/g.The powder obtained at 400°C was used as a catalyst for the oxidative degradation of phenol in aqueous solutions, in the presence of potassium peroxydisulfate as oxidant. High phenol removal efficiencies above 90% were reached at: pH 3–3.5, phenol initial concentration around 50 mg/L, peroxydisulfate:phenol mass ratio 10:1, and catalyst dose 3 g/L. Total organic carbon measurements showed that the degradation of phenol goes, under these conditions, to mineralization in an extent of 60%.     

Modifying glass fiber surface with grafting acrylamide by UV-grafting copolymerization for preparation of glass fiber reinforced PVDF composite membrane

Experimental design and response surface methodology(RSM) were used to optimize the modification of conditions for glass surface grafting with acrylamide(AM) monomer for preparation of a glass fiber reinforced poly(vinylidene fluoride)(PVDF) composite membrane(GFRP-CM). The factors considered for experimental design were the UV(ultraviolet)-irradiation time, the concentrations of the initiator and solvent, and the kinds and concentrations of the silane coupling agent. The optimum operating conditions determined were UV-irradiation time of 25 min, an initiator concentration of 0–0.25 wt.%,solvent of N-Dimethylacetamide(DMAC), and silane coupling agent KH570 with a concentration of 7 wt.%. The obtained optimal parameters were located in the valid region and the experimental confirmation tests conducted showed good accordance between predicted and experimental values. Under these optimal conditions, the water absorption of the grafted modified glass fiber was improved from 13.6% to 23%; the tensile strength was enhanced and the peeling strength of the glass fiber reinforced PVDF composite membrane was improved by 23.7% and 32.6% with an AM concentration at 1 wt.% and 2 wt.%. The surface composition and microstructure of AM grafted glass fiber were studied via several techniques including Field Emission Scanning Electron Microscopy(FESEM), Fourier transform infrared spectroscopy-attenuated total reflectance(FTIR-ATR) and energy dispersive X-ray spectroscopy(EDX). The analysis of the EDX and FTIR-ATR results confirmed that the AM was grafted to the glass fiber successfully by detecting and proving the existence of nitrogen atoms in the GFRP-CM.     

A nanofilter composed of carbon nanotube-silver composites for virus removal and antibacterial activity improvement

We have developed a new nanofilter using a carbon nanotube-silver composite material that is capable of efficiently removing waterborne viruses and bacteria.The nanofilter was subjected to plasma surface treatment to enhance its flow rate,which was improved by approximately 62%.Nanoscale pores were obtained by fabricating a carbon nanotube network and using nanoparticle fixation technology for the removal of viruses.The pore size of the nanofilter was approximately 38 nm and the measured flow rate ranged from 21.0 to 97.2 L/(min·m~2)under a pressure of 1–6 kgf/cm~2 when the amount of loaded carbon nanotube-silver composite was 1.0 mg/cm~2.The nanofilter was tested against Polio-,Noro-,and Coxsackie viruses using a sensitive real-time polymerase chain reaction assay to detect the presence of viral particles within the outflow.No trace of viruses was found to flow through the nanofilter with carbon nanotube-silver composite loaded above 0.8 mg/cm~2.Moreover,the surface of the filter has antibacterial properties to prevent bacterial clogging due to the presence of 20-nm silver nanoparticles,which were synthesized on the carbon nanotube surface.     

Shellac-coated iron oxide nanoparticles for removal of cadmium(II) ions from aqueous solution

This study describes a new effective adsorbent for cadmium removal from aqueous solution synthesized by coating a shellac layer, a natural biodegradable and renewable resin with abundant hydroxyl and carboxylic groups, on the surface of iron oxide magnetic nanoparticles. Transmission Electron Microscopy (TEM) imaging showed shellac-coated magnetic nanoparticle (SCMN) adsorbents had a core-shell structure with a core of 20 nm and shell of 5 nm. Fourier Transform Infrared Spectroscopic analysis suggested the occurrence of reaction between carboxyl groups on the SCMN adsorbent surface and cadmium ions in aqueous solution. Kinetic data were well described by pseudo second-order model and adsorption isotherms were fitted with both Langmuir and Freundlich models with maximum adsorption capacity of 18.80 mg/g. SCMN adsorbents provided a favorable adsorption capacity under high salinity conditions, and cadmium could easily be desorbed using mild organic acid solutions at low concentration.     

Comparative cytotoxicity of nanoparticles and ions to Escherichia coli in binary mixtures

The objective of this study was to understand toxicity of mixture of nanoparticles (NPs) (ZnO and TiO₂) and their ions to Escherichia coli. Results indicated the decrease in percentage growth of E. coli with the increase in concentration of NPs both in single and mixture setups. Even a small concentration of 1 mg/L was observed to be significantly toxic to E. coli in binary mixture setup (exposure concentration: 1 mg/L ZnO and 1 mg/L TiO₂; 21.15% decrease in plate count concentration with respect to control). Exposure of E. coli to mixture of NPs at 1000 mg/L (i.e., 1000 mg/L ZnO and 1000 mg/L TiO₂) resulted in 99.63% decrease in plate count concentration with respect to control. Toxic effects of ions to E. coli were found to be lesser than their corresponding NPs. The percentage growth reduction was found to be 36% for binary mixture of zinc and titanium ions at the highest concentration (i.e., 803.0 mg/L Zn and 593.3 mg/L Ti where ion concentrations are equal to the Zn ions present in 1000 mg/L ZnO NP solution and Ti^+ 4 ions present in 1000 mg/L TiO₂ NP solution). Nature of mixture toxicity of the two NPs to E. coli was found to be antagonistic. The alkaline phosphatase (Alp) assay indicated that the maximum damage was observed when E. coli was exposed to 1000 mg/L of mixture of NPs. This study tries to fill the knowledge gap on information of toxicity of mixture of NPs to bacteria which has not been reported earlier.     

Unraveling the size distributions of surface properties for purple soil and yellow soil

Soils contain diverse colloidal particles whose properties are pertinent to ecological and human health, whereas few investigations systematically analyze the surface properties of these particles. The objective of this study was to elucidate the surface properties of particles within targeted size ranges (i.e. > 10, 1–10, 0.5–1, 0.2–0.5 and < 0.2 μm) for a purple soil (Entisol) and a yellow soil (Ultisol) using the combined determination method. The mineralogy of corresponding particle-size fractions was determined by X-ray diffraction. We found that up to 80% of the specific surface area and 85% of the surface charge of the entire soil came from colloidal-sized particles (< 1 μm), and almost half of the specific surface area and surface charge came from the smallest particles (< 0.2 μm). Vermiculite, illite, montmorillonite and mica dominated in the colloidal-sized particles, of which the smallest particles had the highest proportion of vermiculite and montmorillonite. For a given size fraction, the purple soil had a larger specific surface area, stronger electrostatic field, and higher surface charge than the yellow soil due to differences in mineralogy. Likewise, the differences in surface properties among the various particle-size fractions can also be ascribed to mineralogy. Our results indicated that soil surface properties were essentially determined by the colloidal-sized particles, and the < 0.2 μm nanoparticles made the largest contribution to soil properties. The composition of clay minerals within the diverse particle-size fractions could fully explain the size distributions of surface properties.     

Synthesis, characterization, and photocatalytic activity of porous La–N–co-doped TiO2 nanotubes for gaseous chlorobenzene oxidation

The photocatalytic oxidation of gaseous chlorobenzene(CB) by the 365 nm-induced photocatalyst La/N–Ti O2, synthesized via a sol–gel and hydrothermal method, was evaluated. Response surface methodology(RSM) was used to model and optimize the conditions for synthesis of the photocatalyst. The optimal photocatalyst was 1.2La/0.5N–Ti O2(0.5) and the effects of La/N on crystalline structure, particle morphology, surface element content, and other structural characteristics were investigated by XRD(X-ray diffraction), TEM(Transmission Electron Microscopy), FTIR(Fourier transform infrared spectroscopy), UV–vis(Ultraviolet–visible spectroscopy), and BET(Brunauer Emmett Teller). Greater surface area and smaller particle size were produced with the co-doped Ti O2 nanotubes than with reference Ti O2. The removal of CB was effective when performed using the synthesized photocatalyst,though it was less efficient at higher initial CB concentrations. Various modified Langmuir-Hinshelwood kinetic models involving the adsorption of chlorobenzene and water on different active sites were evaluated. Fitting results suggested that competitive adsorption caused by water molecules could not be neglected, especially for environments with high relative humidity. The reaction intermediates found after GC–MS(Gas chromatography–mass spectrometry) analysis indicated that most were soluble, low-toxicity, or both. The results demonstrated that the prepared photocatalyst had high activity for VOC(volatile organic compounds) conversion and may be used as a pretreatment prior to biopurification.     

Photocatalytic parameters and kinetic study for degradation of dichlorophenol-indophenol (DCPIP) dye using highly active mesoporous TiO2 nanoparticles

Highly active mesoporous TiO_2 of about 6 nm crystal size and 280.7 m~2/g specific surface areas has been successfully synthesized via controlled hydrolysis of titanium butoxide at acidic medium. It was characterized by means of XRD(X-ray diffraction), SEM(scanning electron microscopy), TEM(transmission electron microscopy), FT-IR(Fourier transform infrared spectroscopy), TGA(thermogravimetric analysis), DSC(differential scanning calorimetry) and BET(Brunauer–Emmett–Teller) surface area. The degradation of dichlorophenol-indophenol(DCPIP) under ultraviolet(UV) light was studied to evaluate the photocatalytic activity of samples. The effects of different parameters and kinetics were investigated. Accordingly, a complete degradation of DCPIP dye was achieved by applying the optimal operational conditions of 1 g/L of catalyst, 10 mg/L of DCPIP, pH of 3 and the temperature at 25 ± 3°C after 3 min under UV irradiation. Meanwhile, the Langmuir–Hinshelwood kinetic model described the variations in pure photocatalytic branch in consistent with a first order power law model.The results proved that the prepared TiO_2 nanoparticle has a photocatalytic activity significantly better than Degussa P-25.