Metanilate-layered double hydroxide nanohybrid compound was synthesized for controlled release purposes through co-precipitation method of the metal cations and organic anion. The effect of various divalent metal cations (M2+), namely Zn2+, Mg2+ and Ca2+ on the formation of metanilate-LDH nanohybrids, in which metanilate anion was intercalated into three different layered double hydroxide (LDH) systems; Zn-Al, Mg-Al and Ca-Al were investigated. The syntheses were carried out with M2+ to Al3+ initial molar ratio, R of 4. The pH of the mother liquor was maintained at pH 7.5 and 10 during the synthesis, and the resulting mixture was aged at around 70 degrees C for about 18 h. The intercalation of metanilate anion into the host was found to be strongly influenced by the M2+ that formed the inorganic metal hydroxide layers. Under our experimental condition, the formation of the nanohybrid materials was found to be more feasible for the Zn-Al than for the other two systems, in which the former showed well-ordered layered organic-inorganic nanohybrid structure with good crystallinity. Intercalation is confirmed by the expansion of the interlayer spacing to about 15-17 A when metanilate was introduced into the interlamellae of Zn-Al LDHs. In addition, CHNS and FTIR analyses also support that metanilate anion has been successfully intercalated into the interlamellae of the inorganic LDH. Apart from M2+, this study also shows that the initial pH of the mother liquor plays an important role in determining the physicochemical properties of the resulting nanohybrids, especially the mole fraction of the Zn2+ substituted by the Al3+ ion in the LDH inorganic sheets which in turn controlled the loading percentage of the organic anion, surface properties and the true density. Preliminary study shows that LDH can be used to host beneficial guests, active agent with controlled release capability of the guests. Generally the overall process is governed by pseudo second order kinetic but for the first 180 min, the release process can be slightly better described by parabolic diffusion than the other models.
Layered organic-inorganic hybrid nanocomposite material was synthesised using 4-chlorophenoxyacetate (4CPA) as guest anion intercalated into the Zn-Al layered double hydroxide inorganic host by direct co-precipitation method at pH = 7.5 and Zn to Al molar ratio of 4. Both PXRD and FTIR results confirmed that the 4CPA was successfully intercalated into the Zn-AI-LDH interlayer. As a result, a well-ordered nanolayered organic-inorganic hybrid nanocomposite, with the expansion of the basal spacing from 8.9 angstroms in the layered double hydroxide to 20.1 angstroms in the resulting nanocomposite was observed. The FTIR spectrum of the nanocomposite (ZAC) showed that it composed spectral features of Zn-AI-LDH (ZAL) and 4CPA. The nanocomposites synthesized in this work are of mesoporous-type containing 39.8% (w/w) of 4CPA with mole fraction of Al3+ in the inorganic brucite-like layers (xAI) of 0.224. The release studies showed a rapid release of the 4CPA for the first 600 min, and more sustained thereafter. The total amount of 4CPA released from the nanocomposite interlayer into the aqueous solution were 21%, 66%, and 72% in 0.0001, 0.00025, and 0.0005 M sodium carbonate, respectively. In distilled water, about 75, 35, and 57% of 4CPA could be released in 1000 min, when the pH of the release media was set at 3, 6.25, and 12, respectively. In comparison with a structurally similar organic moiety with one more chlorine atom at the 2-position of the aromatic ring, namely 2,4-dichlorophenoxyacetate (24D), the 4CPA showed a slower release rate. The slightly bulkier organic moiety of 24D together with the presence of chlorine atom at the 2-position presumably had contributed to its higher release rate, and it seems that these factors may be exploited for tuning the release rate of intercalated guest anions with similar properties. This study suggests that layered double hydroxide can be used as a carrier for an active agent and the chemical structure of the intercalated moiety can be used to tune the desired release kinetics of the beneficial agent.
Hydrotalcite-like inorganic layers of Zn-Al, a host containing an organic moiety, 2,4-dichlorophenoxy-acetate, as a guest, was prepared by the spontaneous self-assembly method from an aqueous solution for the formation of a new layered organic-inorganic hybrid nanocomposite material. In this synthesis, the host- and guest-forming species were simultaneously included in the mother liquor, aged, and separated. Various Zn/Al ratios (R = 2, 3, and 4), concentrations of 2,4-dichlorophenoxyacetic acid (0.03-0.1 M), and pH (7 and 10) were studied to optimize the formation of the layered nancomposite. It was found that the optimum conditions for the formation of the nanocomposite were R = 4, pH 7, and concentration of 2,4-dichlorophenoxyacetic acid = 0.08 M. X-ray diffraction shows that this sample affords a nanolayered structure with a basal spacing of 24.6 A.
This paper reports the performance of two different artificial neural networks (ANN), Multi Layer Perceptron (MLP) and Radial Basis Function (RBF) compared to conventional software for prediction of the pore size of the asymmetric polyethersulfone (PES) ultrafiltration membranes. ANN has advantages such as incredible approximation, generalization and good learning ability. The MLP are well suited for multiple inputs and multiple outputs while RBF are powerful techniques for interpolation in multidimensional space. Three experimental data sets were used to train the ANN using polyethylene glycol (PEG) of different molecular weights as additives namely as PEG 200, PEG 400 and PEG 600. The values of the pore size can be determined manually from the graph and solve it using mathematical equation. However, the mathematical solution used to determine the pore size and pore size distribution involve complicated equations and tedious. Thus, in this study, MLP and RBF are applied as an alternative method to estimate the pore size of polyethersulfone (PES) ultrafiltration membranes. The raw data needed for the training are solute separation and solute diameter. Values of solute separation were obtained from the ultrafiltration experiments and solute diameters ware calculated using mathematical equation. With the development of this ANN model, the process to estimate membrane pore size could be made easier and faster compared to mathematical solutions.
Silver-reduced graphene oxide (Ag-rGO) nanohybrid was synthesized by applying a slight modification to the Turkevich method using trisodium citrate as a reducing and stabilizing agent to catalyze the non-enzymatic electrochemical detection of hydrogen peroxide (H₂O₂). Spherical silver nanoparticles (AgNPs) with an average particle size of 2.2 nm surfaced on reduced graphene oxide (rGO) sheets. Cyclic voltammograms (CV) obtained from glassy carbon (GC) electrode coated with Ag-rGO nanohybrid (4 mM) exhibited a peak at an overpotential of -0.52 V, with a larger faradaic current for the reduction of H₂O₂. Using the modified electrode for the linear sweep voltammetry (LSV) detection of H₂O₂, the detection limit and sensitivity were determined to be 4.8 μM (S/N ═ 3) and 0.0262 μA μM-1, respectively. The sensor appeared selective and stable towards H₂O₂ in the presence of possible interference, and it also demonstrated good recoveries of H₂O₂ concentration in real water samples.
Ga₂O₃/ITO/glass photoelectrodes prepared by the CVD method has rarely been tested in the electrochemical cell for water splitting. In this study, we investigate the photoelectrolytic performance of Ga₂O₃/ITO-glass photocatalysts produced by the high-temperature CVD route. The changing of N₂ carrier gas flow rate from 0 to 1800 seem induces change in the materials properties. XRD signal strength of the produced bi-phase Ga₂O₃ is observed to deteriorate, while diffraction line width broadens with increasing N₂ supply. Films show a combination of nanoclumps and nanostrips morphology. Ga/O ratio decreases, while the optical bandgap gradually increases from 4.37 to 4.42 eV with increasing O content and crystallite size. Photoluminescence measurements show UV, blue, green and red emissions, respectively. Linear sweep voltammetry of the electrodes in 0.1 M KOH electrolyte shows improvement in photocurrent density from 160 to 257 μA/cm² versus Ag/AgCl at 1 V bias, and a maximum photon-to-current conversion efficiency 0.06%.
The fabrication of a network of glucose oxidase-horseradish peroxidase/tin oxide (GOx-HRP/SnO₂), immobilized onto a glassy carbon electrode (GCE) and its utilization as a biosensor for glucose detection is reported. The network established with GOx-HRP/SnO₂ possess high sensitivity and stability by performing the electrocatalytic features in the sensing of glucose. The turbidity of fabrication had been scanned and analyzed using UV-vis spectroscopy. The morphology and composition of the fabricated GOx-HRP/SnO₂ networks were characterized by scanning electron microscopy (SEM). Cyclic voltammetry and amperometry were employed to study the electrochemical properties of the proposed biosensor. The effect of applied electrode potential and pH were systemically investigated. The biosensor responds to glucose at work potential values between -400 mV, and exhibited a lower detection limit (0.025 mM) and long linear range (0.25 to 7.0 mM), and was resistant to common interferences.
In this work, the direct electrochemistry of hemoglobin (Hb), which was immobilized on carbonyl functionalized single walled carbon nanotube (SWCNT) and deposited onto a gold (Au) electrode has been described. The synthesis of the network of crosslinked SWCNT/Hb was done with the help of crosslinking agent EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide). The UV-Vis and FTIR spectroscopy of SWCNT/Hb networks showed that Hb maintained its natural structure and kept good stability. In addition with this, scanning electron microscopy (SEM) illustrated that SWCNT/Hb networks had a featured layered structure and Hb being strongly liked with SWCNT surface. Cyclic voltammetry (CV) was used to study and to optimize the performance of the resulting modified electrode. The cyclic voltammetric (CV) responses of SWCNT/Hb networks in pH 7.0 exhibit prominent redox couple for the FeIII/II redox process with a midpoint potential of -0.46 V and -0.34, cathodic and anodic respectively. Furthermore, SWCNT/Hb networks are utilized for the detection of hydrogen peroxide (H2O2). Electrochemical measurements reveal that the resulting SWCNT/Hb electrodes display high electrocatalytic activity to H2O2 with high sensitivity, wide linear range, and low detection limit. Overall, the electrochemical results are due to excellent biocompatibility and excellent electron transport efficiency of CNT as well as high Hb loading and synergistic catalytic effect of the modified electrode toward H2O2.
A multiporous nanofiber (MPNFs) of SnO₂ and chitosan has been used for the immobilization of a redox protein, hemoglobin (Hb), onto the surface of glassy carbon electrode (GCE). The multiporous nanofiber of SnO₂ that has very high surface area is synthesized by using electrospinning technique through controlling the tin precursor concentration. Since the constructed MPNFs of SnO₂ exposes very high surface area, it increases the efficiency for biomolecule-loading. The morphology of fabricated electrodes is examined by SEM observation and the absorbance spectra of Hb/(MPNFs) of SnO₂ are studied by UV-Vis analysis. Cyclic Voltammetry and amperometry are employed to study and optimize the performance of the resulting fabricated electrode. After fabrication of the electrode with the Hb and MPNFs of SnO₂, a direct electron transfer between the protein's redox centre and the glassy carbon electrode was established. The modified electrode has showed a couple of redox peak located at -0.29 V and -0.18 V and found to be sensitive to H₂O₂. The fabricated electrode also exhibited an excellent electrocatalytic activity towards the reduction of H₂O₂. The catalysis currents increased linearly to the H₂O₂ concentration in a wide range of 5.0×10-6-1.5×10-4 M. Overall experimental results show that MPNFs of SnO₂ has a role towards the enhancement of the electroactivity of Hb at the electrode surface. Thus the MPNFs of SnO₂ is a very promising candidate for future biosensor applications.
Zinc oxide (ZnO) is an emerging optoelectronic material in large area electronic applications due to its various functional behaviors. We present the fabrication and the characterization of ZnO nanorods. The ZnO nanorods were synthesized using sol-gel hydrothermal technique on oxidized silicon substrates. Different post-annealing temperatures were explored in the sol-gel hydrothermal synthesis of the ZnO nanorods. The surface morphology of the ZnO nanorods were examined using scanning electron microscope (SEM). In order to investigate the structural properties, the ZnO nanorods were measured using X-ray diffractometer (XRD). The optical properties were measured using ultraviolet-visible (UV-Vis) spectroscopy. The influence of the post-annealing temperature on the realized ZnO nanorods will be revealed and discussed in this paper.
Zinc oxide (ZnO) is an emerging material in large area electronic applications such as thin-film solar cells and transistors. We report on the fabrication and characterization of ZnO microstructures and nanostructures. The ZnO microstructures and nanostructures have been synthesized using sol-gel immerse technique on oxidized silicon substrates. Different precursor's concentrations ranging from 0.0001 M to 0.01 M (M=molarity) using zinc nitrate hexahydrate [Zn(NO3)2. 6H2O] and hexamethylenetetramine [C6H12N4] were employed in the synthesis of the ZnO structures. The surface morphologies were examined using scanning electron microscope (SEM) and atomic force microscope (AFM). In order to investigate the structural properties, the ZnO microstructures and nanostructures were measured using X-ray diffractometer (XRD). The optical properties of the ZnO structures were measured using photoluminescence (PL) and ultraviolet-visible (UV-Vis) spectroscopies.
Herein, we report the facile synthesis, characterization and visible-light-driven photocatalytic degradation of perforated curly Zn0.1Ni0.9O nanosheets synthesized by hydrothermal process. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies confirmed the cubic phase crystalline structure and growth of high density perforated curly Zn0.1Ni0.9O nanosheets, respectively. As a photocatalyst, using methylene blue (MB) as model pollutant, the synthesized nanosheets demonstrated a high degradation efficiency of ~76% in 60 min under visible light irradiation. The observed results suggest that the synthesized Zn0.1Ni0.9O nanosheets are attractive photocatalysts for the degradation of toxic organic waste in the water under visible light.
Solid polymer electrolytes (SPEs) were prepared using rice starch as the polymer, sodium iodide (NaI) as the salt and 1-hexyl-3-methylimidazolium iodide (HMII) as the ionic liquid (IL). The solution casting technique was used for preparation of the PEs. The ionic conductivity and temperaturedependent properties of the PEs were measured and all the SPEs were found to follow the Arrhenius thermal activated model. Ionic conductivity increased as the percentage of ILs increased. The SPE containing 20% (wt) of HMII IL showed the highest ionic conductivity of 1.83×10-3 S/cm. Spectral and structural characterization of the PEs were performed by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD), respectively. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicate that the decomposition temperature (Tdc), glass transition temperatures (Tg) and melting points (Tm) shifted when complexation with HMII occurred. The PEs were used to fabricate dye-sensitized solar cells (DSSCs) and the DSSCs were analyzed under a 1-sun simulator. The SPE with the highest ionic conductivity displayed a short circuit current density (Jsc) of 9.07 (mA cm-2), open circuit voltage (Voc) of 0.58 (V), a fill factor (FF) of 0.65 and had the highest energy conversion efficiency of 3.42%.
The utilization of carbon dioxide for the production of valuable chemicals via catalysts is one of the efficient ways to mitigate the greenhouse gases in the atmosphere. It is known that the carbon dioxide conversion and product yields are still low even if the reaction is operated at high pressure and temperature. The carbon dioxide utilization and conversion provides many challenges in exploring new concepts and opportunities for development of unique catalysts for the purpose of activating the carbon dioxide molecules. In this paper, the role of carbon-based nanocatalysts in the hydrogenation of carbon dioxide and direct synthesis of dimethyl carbonate from carbon dioxide and methanol are reviewed. The current catalytic results obtained with different carbon-based nanocatalysts systems are presented and how these materials contribute to the carbon dioxide conversion is explained. In addition, different strategies and preparation methods of nanometallic catalysts on various carbon supports are described to optimize the dispersion of metal nanoparticles and catalytic activity.
Using solar-powered water electrolysis systems for hydrogen generation is a key decision for the development of a sustainable hydrogen economy. A facile approach is presented in the present investigation to improve the solar-powered photoelectrochemical performance of water electrolysis systems by synthesising well-aligned and highly ordered TiO₂ nanotube films without bundling through the electrochemical anodisation technique. Herein, geometrical calculations were conducted for all synthesised TiO₂ nanotubes, and determination of the aspect ratio (AR) and geometric surface area factor (G) was achieved. On the basis of the collected data, well-aligned TiO₂ nanotubes with an AR of approximately 60 and G of approximately 400 m² ·g-1 were successfully formed in an electrolyte mixture of ethylene glycol with 0.3 wt% NH4F and 5 wt% H₂O₂ at 40 V for 60 min. The nanotubes were subsequently annealed at 400 °C to form anatase-phase TiO₂ nanotube films. The resultant well-aligned and highly ordered TiO₂ nanotube films exhibited a photocurrent density of 1.5 mA · cm-2 due to a large number of photo-induced electrons moving along the tube axis and perpendicular to the Ti substrate, which greatly reduces interfacial recombination losses.
Uniformly sized TiO2 nanotubes with high aspect ratios were synthesised on a large substrate (100 mm x 100 mm) via the bubbling system through anodisation of Ti in ethylene glycol containing 5 wt% NH4F and 5 wt% H2O2. The benefits of bubbling system in producing uniformly sized TiO2 nanotubes throughout the Ti foil are illustrated. Moreover, the effects of applied voltage and fluoride content on the resulting nanotubes were also considered. Such uniform sized TiO2 nanotubes are a key to produce hydrogen efficiently using PEC cell. The results show higher photocurrent responses for the high aspect ratio, uniform TiO2 nanotubes because of excellent interfacial electron transfer.
Well aligned TiO2 nanotubes were successfully synthesized by anodization of Ti foil at 60 V in a fluorinated bath comprised of ethylene glycol with 5 wt% of NH4F and 5 wt% of H2O2. In order to enhance the visible light absorption and photoelectrochemical response of pure TiO2 nanotube arrays, a mixed oxide system (W-TiO2) was investigated. W-TiO2 nanotube arrays were prepared using radio-frequency (RF) sputtering to incorporate the W into the lattice of TiO2 nanotube arrays. The W atoms occupy the substitutional position within the vacancies of TiO2 nanotube arrays. The as-anodized TiO2 is amorphous in nature while the annealed TiO2 is anatase phase. The mixed oxide (W-TiO2) system in suitable TiO2 phase plays important roles in efficient electron transfers due to the reduction in electron-hole recombination. In this article, the effect of the sputtered W into the as-anodized/annealed TiO2 nanotube arrays on the photoelectrochemical response was presented.
In this study, performances of mesoporous Mo/Al2O3 catalysts prepared by sol-gel and post-hydrolysis methods in hydrocracking of atmospheric residual oil were compared. In addition, different methods: (i) the single step and (ii) conventional impregnation method to incorporate active metal over the mesoporous support were also investigated. For single step method, Mo/Al2O3 catalysts were synthesized directly by sol-gel and post-hydrolysis method. On the other hand, the impregnation method was a two step procedure which involved the production of alumina via sol-gel or post-hydrolysis method and followed by respective Mo impregnation. In general, mesoporous Mo/Al2O3 catalysts prepared by sol-gel method resulted in relatively higher surface area (> 400 m2/g) and large pore volume (- 0.8 cm3/g). Mo/Al2O3 catalysts prepared by sol-gel method exhibited higher hydrocracking activity as well. The Mo crystal size was found to relate directly with the hydrocracking result.
The substrate effects on surface morphologies, crystal structures, and magnetic properties of the sputter-deposited FePt thin films on Corning 1737, normal glass, and Si wafer substrates, respectively, were investigated. High in-plane coercivities of 10 kOe were obtained for the air-annealed films on Corning 1737 and Si wafer, where both films similarly have granular-like morphologies. Besides, increasing grain size and surface roughness of all the FePt films with the post-anneal temperature were observed. Moreover, partially separated grains were seen in the film on Si wafer, where the formation of Fe silicides during post-anneal is suspected, in which has enhanced the magnetic ordering.
This study presents the preparation of regenerated cellulose (RC)/graphene nanoplatelets (GNPs) nanocomposites via room temperature ionic liquid, 1-ethyl-3-methylimidazolium acetate (EMIMAc) using solution casting method. The thermal stability, gas permeability, water absorption and mechanical properties of the films were studied. The synthesized nanocomposite films were characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The T20 decomposition temperature of regenerated cellulose improved with the addition of graphene nanoplatelets up to 5 wt%. The tensile strength and Young's modulus of RC films improved by 34 and 56%, respectively with the addition of 3 wt% GNPs. The nanocomposite films exhibited improved oxygen and carbon dioxide gas barrier properties and water absorption resistance compared to RC. XRD and SEM results showed good interaction between RC and GNPs and well dispersion of graphene nanoplatelets in regenerated cellulose. The FTIR spectra showed that the addition of GNPs in RC did not result in any noticeable change in its chemical structure.