Removal of nitrophenols from water using cellulose derived nitrogen doped graphitic carbon material containing titanium dioxide

Nitrophenols (NPs) and their derivatives are highly toxic, mutagenic and bio-refractory pollutants commonly present in natural water resources and industrial wastewater. To remove NPs from water, N-doped graphitic carbon (NGC) and NGC adsorbent containing titanium dioxide (NGC–TiO₂) were synthesized by pyrolysis of microcrystalline cellulose and dopamine mixture, and the mixture along with TiO₂ at 500°C, respectively. NCG-TiO₂ was thoroughly characterized using various analytical techniques. NP adsorption on the NGC–TiO₂ adsorbent surface was studied by varying the pH, initial concentration of NP, and adsorbent dose. The results showed that the most efficient adsorption was achieved at pH 3. After 4?h sonication at pH 3, 80% 4-NP adsorption was achieved using NGC–TiO₂ compared to 74% with NGC adsorbent. The percentage removal of 4-NP was higher than 3-NP which was also higher than 2,4-DNP using NGC–TiO₂. 4-NP adsorption best fitted to the Langmuir isotherm plot with R² value of 0.9981 and adsorption capacity of 52.91?mg?g^?1. The adsorption process of NP was found to follow a pseudo-second-order kinetic model. The rate constant value for the adsorption of 10^?4?M 4-NP at pH 3 using 10?mg of NGC–TiO₂ adsorbent was found to be 3.76?×?10^?5?g.mg^?1.min^?1     

Dimensionality-dependent photocatalytic activity of TiO2-based nanostructures: nanosheets with a superior catalytic property

TiO₂-based nanostructures usually possess excellent photochemical properties. However, the relationship between their dimensionality and photocatalytic activity was rarely investigated. In this study, a series of TiO₂-based nanostructures in various dimensionalities (such as nanosheets, nanotubes) were obtained by hydrothermal treatment of P25, and the process of structural evolution was also systematically investigated by TEM, BET, Raman, and XRD analysis. Much higher rate constant (3.7 × 10^?2 min^?1) for the degradation of rhodamine B was found for nanosheets, comparing with those of three-dimensional P25 nanoparticles (0.59 × 10^?2 min^?1) and one-dimensional nanotubes (0.85 × 10^?2 min^?1). It is found that the hydrothermally prepared TiO₂-based nanosheets possess small thickness (ca. 5 nm) and plentiful surface hydroxyl groups, and the reason why TiO₂-based nanosheets possess superior photocatalytic activity is also discussed in detail from the microstructure and surface chemical states. In addition, TiO₂-based nanosheets exhibit good reusability in the cyclic experiments, implying a potential application for photocatalytic degradation of organic pollutants.     

Kinetics study of a palladium–nickel colloidal nanocatalyst synthesized by a wet-chemical method for reduction of nitrophenol,nitroaniline, and 4-nitrobenzo-15-crown compounds

A bimetallic, palladium–nickel (Pd–Ni) stable colloidal nanocatalyst was synthesized by a wet-chemical reduction technique using Aerosol OT (AOT) as the surfactant and hydrazine hydrate as a reducing agent. The particle size of a colloidal nanocatalyst was controlled by varying precursor concentration, reducing agent, and surfactant concentration. The particle size and morphology of the colloidal catalyst were investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM), respectively. TEM images show the actual particle size of Pd?Ni nanocatalysts to be in the range of 10?28 nm at 10 mM concentration of AOT and hydrazine hydrate. The activity of the colloidal catalyst (bimetallic) was evaluated for reduction of nitro aromatic compounds which includes 4-NP, 3-NP, 2-NP, 4-nitrobenzo-15-crown, and 4-NA. The rate constant of the Pd–Ni colloidal nanocatalyst indicates that the activity of bimetallic catalysts was higher than the monometallic catalyst for various nitro compounds. The rate constant of 4-nitrophenol was found to be ～61 × 10^?2 min^?1 at room temperature.     

Photodegradation Study of Sodium Usnate Solution: Influence of pH

Photodegradation of 2.6 × 10^?5 M aqueous solutions of sodium usnate at various pH was studied. Photodegradation appeared to follow first-order kinetics and was found to be pH dependent. The degradation rate constant was calculated to be 9.20 × 10^?4 min^?1, 5.93 × 10^?4 min^?1, 9.69 × 10^?4 min^?1, and 9.88 × 10^?4 min^?1 at pH 6, pH 7, pH 8, and pH 9, respectively.     

Ion irradiation-induced modifications of diamond nanorods synthesised by microwave plasma chemical vapour deposition

Diamond nanorods (DNRs) synthesised by the high methane content in argon rich microwave plasma chemical vapour deposition (MPCVD) have been implanted with nitrogen ions. The nanorods were characterised by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The DNRs consist of single-crystalline diamond cores of 3–5?nm in diameter and several tens of nanometres in length. For purification from non-diamond contents, hydrogen plasma etching of DNRs was performed. Structural modifications of etched DNRs were studied after irradiating with 50?keV nitrogen ions under the fluence of 5?×?10¹⁴, 1?×?10¹⁵, 5?×?10¹⁵ and 1?×?10¹⁶?ions?cm^?2. Nitrogen-ion implantation changes the carbon–carbon bonding and structural state of the nanocrystalline diamond (NCD). Raman spectroscopy was used to study the structure before and after ion irradiation, indicating the coexistence of diamond and graphite in the samples. The results indicated the increase in graphitic and sp²-related content, at the expense of decrease in diamond crystallinity, for ion implantation dose of 5?×?10^15?cm^?2 and higher. The method proves valuable for the formation of hybrid nanostructures with controlled fractions of sp³–sp² bonding.     

Effect of acetic acid and water content in the spray solution on structural,morphological, optical and electrical properties of Al and In co-doped zinc oxide thin films

Aluminium and indium co-doped zinc oxide (AIZO) thin films were deposited using ultrasonic spray pyrolysis. Depositions were performed by varying the acetic acid and water content in the spraying solution which resulted in the formation of different nanostructures like hexagons, flowers, chisels, curved nanostructures, hexagonal pyramids, super grown hexagons, and inter-connected nanostructures. Further, the physical properties such as structural, optical, electrical, and surface texture parameters were examined. The structural studies showed that films were of crystalline nature, with different crystallite sizes and grown with a preferential orientation along (002) plane. The optical transmittance assessments proved that films were highly transparent (>?80%) in the visible region. The electrical sheet resistance was found to be in the range 29–1K Ω/□. Surface parameters like average roughness, root mean square roughness, and peak-valley height values helped to understand the homogeneity of the thin films. Finally, the suitability of AIZO films for transparent conductive oxide applications were tested by estimating the figure of merit (FOM). Among the different solution conditions, films fabricated using a starting solution containing 25 ml of acetic acid and 25 ml of water exhibited the lowest resistivity (2.47?±?0.03?×?10^?3 Ω-cm) along with the highest FOM (5.83?±?0.42?×?10^?3/Ω).     

The superplasticity and microstructure evolution of coarse-grained Ti40 alloy

The superplastic deformation characteristics of coarse-grained Ti40 alloy have been studied in the temperature and strain rate range of 760–880°C and 5?×?10^?4 to 1?×?10^?2?s^?1, respectively. The alloy exhibited good superplasticity in all test conditions except at 760°C and strain rate higher than 5?×?10^?3?s^?1, with the maximum elongation of 436% at 840°C, 1?×?10^?3?s^?1. The activation energy value was found to be close to the self-diffusion activation energy of Ti40 alloy, suggesting that the rate controlling mechanism was lattice diffusion. The coarse grain was elongated and refined which can be attributed to the occurrence of dynamic recovery and continuous dynamic recrystallisation. These processes were promoted by the subgrain formation and evolution, resulting in the good superplasticity of Ti40 alloy with coarse grains.     

Cold deformation of dezincification resistant yellow brass for plumbing applications

In the present work, the room temperature deformation behavior of dezincification-resistant (DZR) brass was performed by varying strain rates (1?×?10^?4?s^?1, 0.55?×?10^?3?s^?1, 1?×?10^?3?s^?1, 0.55?×?10^?2?s^?1, 1?×?10^?2?s^?1) and percent cold works (15 to 65% with step of 10%). These parameters are important to plumbing parts of its forming. Room temperature deformation workability map was developed that provides the selection of safe deformation parameters without cracking. The as-received and deformed DZR brass samples were carefully characterized by various microscopes. The results revealed that more dislocations lines and twinning were observed through transmission electron microscope images as the strain rate (SR) increases which led to early failure of the sample before reaching the set height reduction. It was determined that more amount of strain hardening with designed height reduction was achieved at lower SR whereas less amount of strain hardening was achieved at higher SR due to strain mismatching phenomenon and various deformation mechanisms.     

Equilibria,kinetics and mechanism for the degradation of the cytotoxic compound L-NG-nitroarginine

L-N^G-nitroarginine (LNNA), an analog of L-arginine, is a competitive inhibitor of nitric oxide synthase which causes the selective reduction of blood flow to tumor cells. Despite the potential of LNNA to function as an adjuvant in cancer therapies, its poor solubility and stability have hindered the development of an injectable formulation of LNNA that is suitable for human administration. This work, for the first time, details a systematic study on the determination of equilibrium K_a constants and the rate law of LNNA degradation. The four K_a values of LNNA were determined to be 1.03, 1.10?×?10^?2, 2.51?×?10^?10, and 1.33?×?10^?13 M. From the kinetic and equilibrium studies, we have shown that the deprotonated form of LNNA is the main form of LNNA that undergoes degradation in aqueous media at room temperature. The rate law of LNNA degradation was found to be first order with respect to OH^? concentration and first order with respect to LNNA^? concentration. The rate constant at 25?°C and 1?atm was determined to be 0.04453 M^?1min^?1. A base catalyzed mechanism of LNNA degradation was proposed based on the kinetic study. The mechanism was found to be very useful in explaining the discrepancies and changes of the rate law at different pH values. It is thus recommended that LNNA should be formulated as a concentrated solution in acidic conditions for maximum chemical stability during storage and be diluted with a basic solution to near physiological pH just before administration.     

The usefulness of diffusion-weighted imaging for differentiating portal vein thrombus from tumour embolus

To investigate the usefulness of diffusion-weighted imaging (DWI) for differentiating bland portal vein thrombus from tumour thrombus. Fifteen patients with clinical comprehensive diagnoses of portal vein thrombus were analysed retrospectively. The thrombus signal intensity on 21 DWI slices and apparent diffusion coefficient (ADC) values were analysed quantitatively. The portal vein thrombus was divided into four types (low/low, high/low, low/high, and high/high) based on the DWI/ADC ratios between the thrombus and liver parenchyma (rDWI and rADC, respectively). Twenty patients with portal vein tumour thrombi were used for comparison as controls. The average ADC value for the bland thrombus was 1.84?±?0.70?×?10^?3?mm²?s^?1 (range: 0.46–2.77?×?10^?3?mm²?s^?1), and was 2.18?±?0.51?×?10^?3?mm²?s^?1 (range: 1.39–2.82?×?10^?3?mm²?s^?1) for the liver parenchyma; the rADC was therefore 0.90?±?0.45 (range: 0.26–1.86). The tumour thrombi were high/low and high/high type. The average ADC for the tumour thrombus was 1.25?±?0.26?×?10^?3?mm²?s^?1 (range: 0.68–1.67?×?10^?3?mm²?s^?1), and 1.56?±?0.33?×?10^?3?mm²?s^?1 (range: 1.11–2.34?×?10^?3?mm²?s^?1) for the liver parenchyma; the rADC was therefore 0.82?±?0.16 (range: 0.39–1.08). There was no statistical difference in rADC values and rDWI/rADC classification performance between the bland and tumour thrombi. The ADC difference between portal vein bland and tumour thrombi was statistically significant, but the ADC values of bland thrombi have a wider range, which contains the ADC values of tumour thrombi with a narrower range. The elevated ADC values of the liver parenchyma adjacent to portal vein emboli may be helpful for the diagnosis of bland thrombi.     

Graphene–Ruthenium Complex Hybrid Photodetectors with Ultrahigh Photoresponsivity

The maximum responsivity of a pure monolayer graphene‐based photodetector is currently less than 10 mA W^?1 because of small optical absorption and short recombination lifetime. Here, a graphene hybrid photodetector functionalized with a photoactive ruthenium complex that shows an ultrahigh responsivity of ≈1 × 10⁵ A W^?1 and a photoconductive gain of ≈3 × 10⁶ under incident optical intensity of the order of sub‐milliwatts is reported. This responsivity is two orders of magnitude higher than the precedent best performance of graphene‐based photodetectors under a similar incident light intensity. Upon functionalization with a 4‐nm‐thick ruthenium complex, monolayer graphene‐based photodetectors exhibit pronounced n‐type doping effect due to electron transfer via the metal?ligand charge transfer (MLCT) from the ruthenium complex to graphene. The ultrahigh responsivity is attributed to the long lifetime and high mobility of the photoexcited charge carriers. This approach is highly promising for improving the responsivity of graphene‐based photodetectors.     

Argon ion irradiation effect on Zn nanotubes

The use of ionizing radiation is an effective tool for stimulating a controlled modification of structural and conductive properties of nanomaterials. The paper presents the results of studies of the influence of Ar⁸⁺ ions irradiation with an energy of 1.75 MeV/nucleon with a fluence from 1?×?10⁹ to 5?×?10¹¹ ion/cm² on structural and conductive properties of Zn nanotubes. It was established by scanning electron microscopy, X-ray diffraction and electron diffraction analysis methods that irradiation with Ar⁸⁺ ions makes it possible to modify the crystal structure of nanotubes, increasing their conductivity and decreasing the resistance of nanostructures, without destroying the structure. Zn nanotubes with a diameter of 380 nm were synthesized using the electrochemical synthesis method. An analysis of dislocations density change and stresses in irradiated nanostructures indicates that a deformation in structure and subsequent relaxation of internal stresses are observed. Also, it is shown that as the irradiation fluence increases, an insignificant increase in the parameters of the unit cell is observed, which may be due to an increase in the contribution of thermal vibrations.     

Structural,optical, and electrical properties of ZnTe:Cu thin films by PLD

In this work, ZnTe and ZnTe:Cu films were obtained by pulsed laser deposition using the co-deposition method. ZnTe and Cu₂Te were used as targets and the shots ratio were varied to obtain 0.61, 1.47, 1.72, and 3.46% Cu concentration. Doping of ZnTe films with Cu was performed with the purpose of increasing the p-type carrier concentration and establishing the effect of concentration of Cu on structural, optical, and electrical properties of ZnTe thin films to consider their potential application in electronic devices. According to X-ray diffraction, X-ray photoelectron spectroscopy, UV–visible spectroscopy, and Hall effect results, ZnTe and ZnTe:Cu films correspond to polycrystalline zinc–blende phase with preferential orientation in (111) plane. Optical characterization results indicate that as-deposited films (band gap?=?2.16 eV) exhibit a band gap decrease as function of the increase of Cu concentration (2.09–1.64 eV), while, annealed films exhibit a decrease from 1.75 to 1.46 eV, as the Cu concentration increases. Lastly, Hall effect results show that ZnTe films correspond to a p-type semiconductor with a carrier concentration of 3?×?10¹³ cm^?3 and a resistivity of 1.64?×?10⁵ Ω?cm. ZnTe:Cu films remain like a p-type material and present an increasing carrier concentration (from 3.8?×?10¹⁵ to 1.26?×?10¹⁹ cm^?3) as function of Cu concentration and a decreasing resistivity (from 7.01?×?103 to 2.6?×?10^?1 Ω cm). ZnTe and ZnTe:Cu thin films, with the aforementioned characteristics, can find potential application in electronic devices, such as, solar cells and photodetectors.     

Hot ductility of high Al TWIP steels containing Nb and Nb-V

The hot ductility of B-Ti-Nb-high Al (1.5%Al) containing TWIP steels having Ti/N ratios mainly in excess of 3.4/1 was obtained. After soaking at 1250°C, the tensile specimens were cooled at 12 or 60°C?min^?1 to the test temperature and then strained to failure at 3?×?10^?3?s^?1. Ductility was always good (reduction of area >40%), independent of Ti/N ratio or cooling rate. The good ductility is due to B segregation strengthening the grain boundaries and the low S level (0.005%S) limiting the volume fraction of MnS inclusions and restricting AlN precipitation to the matrix. Increasing the cooling rate, higher N levels and Nb resulted in a small improvement in ductility. An addition of V to the Nb-containing steels caused a slight deterioration in the hot ductility.     

Stability of Mixtoxantrone Hydrochloride in Solution

Abstract

A stability-indicating reversed-phase high performance liquid chromatographic method was developed for the detection of mitoxantrone HC1 and its degradation products under accelerated degradation conditions. The degradation kinetics of mitoxantrone HC1 in aqueous solution over a pH range of 1.18 to 7.20 and its stability in propylene glycol-or polyethylene glycol 400-based solutions were investigated. The observed rate constants were shown to follow apparent first-order kinetics in all cases. The pH-rate profile shows that maximum stability of mitoxantrone HC1 was obtained at pH 4.01. No general acid or base catalysis from acetate or phosphate buffer species was observed. The catalysis rate constants on the protonated mitoxantrone imposed by hydrogen ion water and hydroxy ion were determined to be 3.72 × 10 min^?1 5.64 × 10-min^?1 and 1.108 × 10^?2min^?1, respectively. The degradation rate constants of mitoxantrone affected by different ionic strength systems. Irradiation with 254 nm UV light at 25±0.5°C was found when canpared with the light-protected controls. Incorporation of nonaqueous propylene glycol or polyethylene glycol in the pH 4.01 mitoxantrone solution shows an increase in its stability at 502±0.5°C.     

Application of functionalized ZnS nanoparticles to determinate uracil and thymine as a fluorescence probe

ZnS nanoparticles were prepared by hydrothermal method and modified with mercaptoacetic acid in this paper. The functionalized nanoparticles were characterized using transmission electron microscopy (TEM), X-ray diffractometer (XRD) and photoluminescence spectroscopy. They were used as fluorescence probes in the determination of uracil and thymine. Under the optimum conditions, the fluorescence of functionalized ZnS nanoparticles was quenched by uracil and thymine, respectively. The responses are linearly proportional to the concentrations of uracil and thymine both between 0.8 × 10^?5 and 9.6 × 10^?5 mol L^?1and the limits of detection are 0.9 × 10^?6 and 0.4 × 10^?5 mol L^?1 for uracil and thymine, respectively.     

Modeling breakage and motion of black pepper seeds in cryogenic mill

The present investigation aims to represent three-dimensional motion and breakage phenomena of black pepper seeds in the cryogenic mill (hammer mill) using discrete element method (DEM). In DEM modeling, bonded particle model was coupled with Hertz-Mindlin contact model. Calibration method was used to select appropriate model (bond) parameters. The calibrated set of bond parameters includes 3.12?×?10¹¹?Pa?m^?1 normal stiffness; 1.56?×?10¹¹?Pa?m^?1 shear stiffness; 3.88?×?10⁸?Pa critical normal stiffness; 1.94?×?10⁸?Pa critical shear stiffness. Besides, the validity of calibrated parameters was tested in the hammer mill. The observed qualitative and quantitative results (breakage and flow pattern) of numerical and experimental approaches were in good agreement. Based on these results, a few prefatory suggestions were provided to improve the design aspects of the mill. Overall, DEM modeling offered a better understanding of particle breakage and flow pattern in the mill.     

Nanocrystalline CuO thin films: synthesis, microstructural and optoelectronic properties

Nanocrystalline copper oxide (CuO) thin films have been synthesized by a sol–gel method using cupric acetate Cu (CH₃COO) as a precursor. The as prepared powder was sintered at various temperatures in the range of (300–700?°C) and has been deposited onto a glass substrates using spin coating technique. The structural, compositional, morphological, electrical optical and gas sensing properties of CuO thin films have been studied by X-ray diffraction, Scanning Electron Microscopy (SEM), Four Probe Resistivity measurement and UV–visible spectrophotometer. The variation in annealing temperature affected the film morphology and optoelectronic properties. X-ray diffraction patterns of CuO films show that all the films are nanocrystallized in the monoclinic structure and present a random orientation. The crystallite size increases with increasing annealing temperature (40–45?nm).The room temperature dc electrical conductivity was increased from 10^?6 to 10^?5 (Ω?cm)^?1, after annealing due to the removal of H₂O vapor which may resist conduction between CuO grain. The thermopower measurement shows that CuO films were found of n-type, apparently suggesting the existence of oxygen vacancies in the structure. The electron carrier concentration (n) and mobility (μ) of CuO films annealed at 400–700?°C were estimated to be of the order of 4.6–7.2?×?10¹⁹?cm^?3 and 3.7–5.4?×?10^?5?cm²?V^?1?s^?1?respectively. It is observed that CuO thin film annealing at 700?°C after deposition provide a smooth and flat texture suited for optoelectronic applications. The optical band gap energy decreases (1.64–1.46?eV) with increasing annealing temperature. It was observed that the crystallite size increases with increasing annealing temperature. These modifications influence the morphology, electrical and optical properties.     

Carrier properties of B atomic-layer-doped Si films grown by ECR Ar plasma-enhanced CVD without substrate heating

Abstract

The atomic-layer (AL) doping technique in epitaxy has attracted attention as a low-resistive ultrathin semiconductor film as well as a two-dimensional (2-D) carrier transport system. In this paper, we report carrier properties for B AL-doped Si films with suppressed thermal diffusion. B AL-doped Si films were formed on Si(100) by B AL formation followed by Si cap layer deposition in low-energy Ar plasma-enhanced chemical-vapor deposition without substrate heating. After fabrication of Hall-effect devices with the B AL-doped Si films on unstrained and 0.8%-tensile-strained Si(100)-on-insulator substrates (maximum process temperature 350°C), carrier properties were electrically measured at room temperature. Typically for the initial B amount of 2?×?10¹⁴ cm^?2 and 7?×?10¹⁴ cm^?2, B concentration depth profiles showed a clear decay slope as steep as 1.3 nm/decade. Dominant carrier was a hole and the maximum sheet carrier densities as high as 4?×?10¹³ cm^?2 and 2?×?10¹³ cm^?2 (electrical activity ratio of about 7% and 3.5%) were measured respectively for the unstrained and 0.8%-tensile-strained Si with Hall mobility around 10–13 cm² V^?1 s^?1. Moreover, mobility degradation was not observed even when sheet carrier density was increased by heat treatment at 500–700 °C. There is a possibility that the local carrier (ionized B atom) concentration around the B AL in Si reaches around 10²¹ cm^?3 and 2-D impurity-band formation with strong Coulomb interaction is expected. The behavior of carrier properties for heat treatment at 500–700 °C implies that thermal diffusion causes broadening of the B AL in Si and decrease of local B concentration.     

Enhancement of antibacterial properties of Ag nanorods by electric field

Abstract

The effect of an electric field on the antibacterial activity of columnar aligned silver nanorods was investigated. Silver nanorods with a polygonal cross section, a width of 20–60 nm and a length of 260–550 nm, were grown on a titanium interlayer by applying an electric field perpendicular to the surface of a Ag/Ti/Si(100) thin film during its heat treatment at 700 °C in an Ar+H₂ environment. The optical absorption spectrum of the silver nanorods exhibited two peaks at wavelengths of 350 and 395 nm corresponding to the main surface plasmon resonance bands of the one-dimensional silver nanostructures. It was found that the silver nanorods with an fcc structure were bounded mainly by {100} facets. The antibacterial activity of the silver nanorods against Escherichia coli bacteria was evaluated at various electric fields applied in the direction of the nanorods without any electrical connection between the nanorods and the capacitor plates producing the electric field. Increasing the electric field from 0 to 50 V cm^?1 resulted in an exponential increase in the relative rate of reduction of the bacteria from 3.9×10^?2 to 10.5×10^?2 min^?1. This indicates that the antibacterial activity of silver nanorods can be enhanced by applying an electric field, for application in medical and food-preserving fields.