A novel graphene-chitosan-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposite modified sensor for sensitive and selective electrochemical determination of a monoamine neurotransmitter epinephrine

A novel sensitive electrochemical sensor has been developed by modification of glassy carbon electrode (GCE) with graphene (GRP), chitosan (CHIT), and bismuth oxide (Bi₂O₃) nanoparticles. The morphological characteristics of nanocomposite (GRP-CHIT-Bi₂O₃ or GCB) were studied by scanning electron microscope and atomic force microscopy. The electrochemical behavior of epinephrine at nanocomposite modified GCE (GCB/GCE) was investigated in pH 7.4 phosphate buffer solution using cyclic voltammetry and square wave voltammetry. GCB/GCE showed an enhancement in the current response as compared to bare GCE. Electrochemical impedance spectra showed a reduction of charge transfer resistance and higher electrocatalytic behavior of the sensor. The electrooxidation process of epinephrine at the modified sensor was found to be diffusion controlled. GCB/GCE showed a linear response to epinephrine in the range 100 to 500 nM. The limit of detection and limit of quantification were found to be 3.56 and 11.85 nM, respectively, which is lower than many other sensors reported for epinephrine in literature. The modified sensor showed high sensitivity (1.3 nA/nM) and selectivity for epinephrine. The method was employed for quantification of epinephrine in pharmaceutical formulation and human blood serum samples.     

Photocatalytic degradation of azo dyes using Zn-doped and undoped TiO2 nanoparticles

Undoped and Zn-doped TiO₂ nanoparticles were synthesized by the sol gel method. The dopant (Zn) was taken at 0.1, 0.2, 0.5, 0.7, and 1.0 mol%. The initial precursors were titanium tetraisopropoxide and zinc acetate. The samples were characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and UV–vis diffuse reflectance. The photocatalytic activity of the prepared nanoparticles was studied by observing their role in degradation of two azo dyes, i.e., Eriochrome Black T and Methyl Red under UV–visible light. The results revealed that Zn-doped TiO₂ nanoparticles exhibited better degradation as compared to undoped TiO₂ nanoparticles. In this study, 0.7 mol% Zn-doped TiO₂ showed highest photocatalytic activity. Doping of Zn allowed better separation of electron–hole pairs which results in increased oxidation and reduction reactions.     

Photocurrent enhancement of heat treated CdSe-sensitized titania nanotube photoelectrode

The self-organized titania nanotube arrays (NTAs) fabricated by anodisation has gained enormous interest due to its high spatial orientation, excellent charge transfer structure, and large internal surface area; all are crucial properties influencing the absorption and propagation of light. In this study, a composite material, CdSe nanoparticle/TiO₂ nanotube arrays (CdSe/TiO₂ NTAs) were assembled through the insertion of CdSe nanoparticles onto the anodized TiO₂ nanotube arrays via electrochemical deposition. The annealing temperature of CdSe/TiO₂ NTAs was varied from 200 to 350 °C and was found to play an important role in controlling the formation of CdSe nanoparticles on TiO₂ NTAs. Characterizations of the films were performed by using field emission scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, high resolution transmission electron microscopes, X-ray diffractometry and UV–visible diffuse reflectance spectroscopy. The transient photocurrent was examined in a three-electrode system under halogen illumination by using the prepared film as the photoanode. It was found that the CdSe nanoparticles were susceptible to spread through electrochemical deposition and formed on the nanotubes by annealing in nitrogen atmosphere. The increment in annealing temperature has resulted in greater amount of CdSe loaded onto TiO₂ nanotube arrays. Therefore, a suitable annealing temperature can enhance the particle interaction, leading to considerable improvement in PEC performance. The sensitized CdSe/TiO₂ NTAs annealed at 250 °C displayed 84 folds improvement in photoconversion efficiency than that of bare TiO₂ NTAs counterparts.     

Size-controlled growth of gold nanoparticle-doped carbon foams as sensitive electrochemical sensors for the determination of Pb(II)

A sensitive and selective electrochemical Pb²⁺ sensor consisting of a gold-carbon foam/chitosan/gold (Au-CFs/Chit/Au)-modified electrode was prepared. The electrode was synthesized via an oil-in-water emulsion polymerization and carbonization approach. Phenolic resins were used as a carbon source. HAuCl₄ was used as a gold source and as an acidic catalyst. Melamine was used as a coordination and coupling agent to control the size of the Au nanoparticles (AuNPs). The morphologies and microstructures of the Au-CFs were characterized using scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The results revealed that the carbon foams contained interconnected macropores with diameters of nearly 5.0 μm and AuNPs with mean diameters of approximately 20.0, 9.0, and 7.0 nm. Brunauer–Emmett–Teller analysis revealed that the biggest surface area is 653.82 m²/g for Au/CFs-7. The electrochemical properties of modified electrodes and their responses to Pb²⁺ were characterized using cyclic voltammetry and differential pulse anodic stripping voltammetry. The influence of the test conditions were studied to optimize operational parameters such as the choice of supporting electrolyte, pH, deposition potential, and deposition time. Under optimal conditions, typical Au/CFs-7-modified gold electrodes exhibited an excellent electrochemical response for Pb²⁺ with a wide linear response range from 0.01 to 1.2 μM, a correlation coefficient of 0.995, and a lower limit of detection of 0.63 nM with deposition time of 180 s (S/N?=?3).     

Anatase TiO<Subscript>2</Subscript> nanoparticles for lithium-ion batteries

Anatase TiO₂ nanoparticles were prepared by a simple sol-gel method at moderate temperature. X-ray powder diffraction (XRD) and Raman spectroscopy revealed the exclusive presence of anatase TiO₂ without impurities such as rutile or brookite TiO₂. Thermogravimetric analysis confirmed the formation of TiO₂ at about 400 °C. Particle size of about 20 nm observed by transmission electron microscopy matches well with the dimension of crystallites calculated from XRD. The electrochemical tests of the sol-gel-prepared anatase TiO₂ show promising results as electrode for lithium-ion batteries with a stable specific capacity of 174 mAh g^?1 after 30 cycles at C/10 rate. The results show that improvement of the electrochemical properties of TiO₂ to reach the performance required for use as an electrode for lithium-ion batteries requires not only nanosized porous particles but also a morphology that prevents the self-aggregation of the particles during cycling.     

Curcumin-sensitized TiO2 for enhanced photodegradation of dyes under visible light

Curcumin was coated on P25 TiO₂ by using impregnation method from freshly prepared curcumin solution. The resulting products (Cur–TiO₂–P25) was studied by several techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier-transformed infrared spectroscopy, specific surface area by the Brunauer–Emmett–Teller method, and UV–Vis diffused reflectance spectroscopy. Experimental results revealed that impregnation of curcumin at 0.5, 3, 5, and 7 wt% did not affect the native phase of anatase and rutile in P25 significantly, however, it caused red shift of absorption onset in all curcumin-coated samples. The Cur–TiO₂–P25 showed enhanced adsorption efficiency and increased photocatalytic activity under visible light with optimal result at 5 wt% curcumin content. Commercial anatase and rutile coated with curcumin (Cur–TiO₂–an and Cur–TiO₂–ru) were also prepared by the same method for the use in comparative studies of photodegradation of dyes. Cur–TiO₂–an and Cur–TiO₂–ru were also characterized with some selected equipment above but not as extensively as the Cur–TiO₂–P25. Curcumin coating helped improve photocatalytic efficiencies of P25 and anatase but not for rutile. The mechanism of photocatalytic reaction was proposed that under visible light irradiation, curcumin molecule could act as dye sensitizing agent that injected electron into the conduction band of TiO₂ leading to photodegradation of dyes.     

One-pot,large-scale synthesis silica-encapsulated NIR alloy quantum dots CdSeTe within short time

Hydrothermal process has been employed to synthesize titanium oxide (TiO₂) bottle brush. The nanostructured bottle brushes with tetragonal nanorods of ~75 nm diameter have been synthesized by changing the nature of the precursors and hydrothermal processing parameters. The morphological features and structural properties of TiO₂ films were investigated by field emission scanning electron microscopy, X-ray diffraction, high-resolution transmission electron spectroscopy, Fourier transform Raman spectroscopy, and X-ray photoelectron spectroscopy. The influence of such nanostructures on the performance of dye-sensitized solar cells (DSSCs) is investigated in detail. The interface and transient properties of these nanorods and bottle brush-based photoanodes in DSSCs were analyzed by electrochemical impedance spectroscopic measurements in order to understand the critical factors contributing to such high power conversion efficiency. Surface area of sample was recorded using Brunauer–Emmett–Teller measurements. It is found that bottle brush provides effective large surface area 89.34 m² g^?1 which is much higher than TiO₂ nanorods 63.7 m² g^?1. Such effective surface area can facilitate the effective light harvesting, and hence improves the dye adsorption and the photovoltaic performance of DSSCs, typically in short-circuit photocurrent and power conversion efficiency. A best power conversion efficiency of 6.63 % has been achieved. We believe that the present device performance would have wide interests in dye-sensitized solar cell research.     

Preparation and electrochemical performances of nanoporous/cracked cobalt oxide layer for supercapacitors

Nanoporous/cracked structures of cobalt oxide (Co₃O₄) electrodes were successfully fabricated by electroplating of zinc–cobalt onto previously formed TiO₂ nanotubes by anodizing of titanium, leaching of zinc in a concentrated alkaline solution and followed by drying and annealing at 400 °C. The structure and morphology of the obtained Co₃O₄ electrodes were characterized by X-ray diffraction, EDX analysis and scanning electron microscopy. The results showed that the obtained Co₃O₄ electrodes were composed of the nanoporous/cracked structures with an average pore size of about 100 nm. The electrochemical capacitive behaviors of the nanoporous Co₃O₄ electrodes were investigated by cyclic voltammetry, galvanostatic charge–discharge studies and electrochemical impedance spectroscopy in 1 M NaOH solution. The electrochemical data demonstrated that the electrodes display good capacitive behavior with a specific capacitance of 430 F g^?1 at a current density of 1.0 A g^?1 and specific capacitance retention of ca. 80 % after 10 days of being used in electrochemical experiments, indicating to be promising electroactive materials for supercapacitors. Furthermore, in comparison with electrodes prepared by simple cathodic deposition of cobalt onto TiO₂ nanotubes(without dealloying procedure), the impedance studies showed improved performances likely due to nanoporous/cracked structures of electrodes fabricated by dealloying of zinc, which provide fast ion and electron transfer routes and large reaction surface area with the ensued fast reaction kinetics.     

Synthesis and structure refinement studies of LiNiVO4 electrode material for lithium rechargeable batteries

The lithium nickel vanadate (LiNiVO₄) cathode material has been synthesized by using sol-gel method. The thermal behavior of the material has been examined by thermogravimetric and differential thermal analysis (TG/DTA). The structure of LiNiVO₄ compound has been studied by the Rietveld refined x-ray diffraction (XRD) technique. The Brunauer–Emmett–Teller (BET) surface area of 0.79 m² g^?1 was estimated with N₂ absorption characteristics. The synthesized powder morphology was observed by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) studies of synthesized LiNiVO₄ powder indicate that the oxidation states of nickel and vanadate are +2 and +5, respectively. The electrochemical properties were monitored using 2032 coin cells by cyclic voltammetry and EIS, which showed that the microscopic structural features were deeply related with the electrochemical performance.     

The role of W doping in response of hydrogen sensors based on MAO titania films

Anatase TiO₂ and W doped TiO₂ films were fabricated by micro-arc oxidation (MAO) on titanium substrates and their hydrogen sensing properties were investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the oxide films and electrochemical impedance spectroscopy (EIS) was applied to investigate the gas sensing mechanism. It is found that the conductivity of TiO₂ films varies with the introduction of W dopant. EIS analysis reveals that the grains and especially the grain boundaries are mainly contributed to the hydrogen response and their equivalent circuits could be represented electrochemically by parallel resistor and constant phase element (CPE). The enhanced sensor signal at higher measuring temperature (300 °C) is observed with an optimal doping concentration of W ions (1.81 at.%).     

Nanomolar detection limit for determination of norepinephrine in the presence of acetaminophen and tryptophan using carbon nanotube-based electrochemical sensor

A carbon paste electrode modified by carbon nanotubes and a synthesized hydroquinone derivative (abbreviated as DHB) was fabricated. It was used as an electrochemical sensor for simultaneous determination of norepinephrine (NE), acetaminophen (AC), and tryptophan (Trp). Oxidation potential of NE decreased about 220 mV at the modified electrode in comparison with unmodified electrode because of electrocatalysis of oxidation of NE via E? mechanism at the modified electrode. Differential pulse voltammetry was used for obtaining the calibration plot of NE and two linear range of 0.2–20.0 μM and 20.0–1,500.0 μM and an interesting detection limit (3σ) of 40.0 nM were obtained for NE. Also, simultaneous determination of NE, AC, and Trp was described by the proposed sensor and linear range of 20.0–800.0 μM was found for AC and Trp. Finally, the electrochemical sensor was used for the determination of NE, AC, and Trp in mixture.     

The effect of different concentrations of Na2SnO3 on the electrochemical behaviors of the Mg-8Li electrode

In this research, the effect of the different concentrations of NaSnO₃ as the electrolyte additive in 0.7 mol L^?1 NaCl solution on the electrochemical performances of the magnesium-8lithium (Mg-8Li) electrode are investigated by methods of potentiodynamic polarization, potentiostatic current-time, electrochemical impedance technique, and scanning electron microscopy (SEM). The corrosion resistance of the Mg-8Li electrode is improved when Na₂SnO₃ is added into the electrolyte solution. The potentiostatic current-time curves show that the electrochemical behaviors of the Mg-8Li electrode in the electrolyte solution containing 0.20 mmol L^?1 Na₂SnO₃ is the best. The electrochemical impedance spectroscopy results indicate that the polarization resistance of the Mg-8Li electrode decreases in the following order with the concentrations of Na₂SnO₃: 0.05 mmol L^?1?>?0.00 mmol L^?1?>?0.30 mmol L^?1?>?0.10 mmol L^?1?>?0.20 mmol L^?1. The scanning electron microscopy studies indicate that the electrolyte additive prevents the formation of the dense oxide film on the alloy surface and facilitates the peeling off of the oxidation products.     

Analysis of fiber optic SPR sensor utilizing platinum based nanocomposites

SPR based fiber optic sensor using nanocomposite is presented. Nanocomposites comprising of Pt nanoparticles with various volume fractions embedded in dielectric matrices of TiO₂ and SnO₂ are considered. Sensitivity enhances with increase in thickness of nanocomposite and volume fraction of nanoparticles for both nanocomposites. Optimized thicknesses are obtained to be 40 and 50 nm for Pt–TiO₂ and Pt–SnO₂ nanocomposites respectively while optimized volume fraction is found to be 0.85 for both nanocomposites. 40 nm thick Pt–TiO₂ nanocomposite based sensor with 0.85 volume fraction possesses utmost sensitivity.     

Titanium-modified Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> with a synergistic effect of surface modifying,bulk doping,and size reducing

In this work, a one-step solid-phase sintering process via TiO₂ and Li₂CO₃ under an argon atmosphere, with ultra-fine titanium powder as the modifying agent, was used to prepare a nano-sized Li₄Ti₅O₁₂/Ti composite (denoted as LTO–Ti) at 800 °C. The introduction of ultra-fine metal titanium powder played an important role. First, X-ray photoelectron spectroscopy demonstrates that Ti⁴⁺ was partially changed into Ti³⁺, through the reduction of the ultra-fine metal titanium powder. Second, X-ray diffraction revealed that the ultra-fine metal titanium powder did not react with the bulk structure of Li₄Ti₅O₁₂, while some pure titanium peaks could be seen. Additionally, the size of LTO–Ti particles could be significantly reduced from micro-scale to nano-scale. The structure and morphology of LTO–Ti were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. Electrochemical tests showed a charge/discharge current of 0.5, 1, 5, and 10 C; the discharge capacity of the LTO–Ti electrode was 170, 161, 140, and 111 mAh g^?1. It is believed that the designed LTO–Ti composite makes full use of both components, thus offering a large contact area between the electrolyte and electrode, high electrical conductivity, and lithium-ion diffusion coefficient during electrochemical processes. Furthermore, ultra-fine titanium powder, as the modifying agent, is amenable to large-scale production.     

Sonochemical preparation of carbon nanosheets supporting cuprous oxide architecture for high‐performance and non-enzymatic electrochemical sensor in biological samples

Copper (Cu) based metal oxides have high electrocatalytic ability. In this work, we are synthesized stone-like cuprous oxide particles (Cu₂O SNPs) covered on acid functionalized graphene oxide (GOS) sheets using ultrasonic process (50 kHz and 100 W). Besides, the chemical structural and crystalline analyses of Cu₂O SNPs@GOS composites were characterized by transmission electron microscopy, X-ray crystallography and energy-dispersive X-ray spectroscopy. The Cu₂O SNPs@GOS nanomaterials were tested towards detection of 8-hydroxydeoxyguanosine (8-OHdG) in biological samples. As expected Cu₂O SNPs@GOS catalyst modified electrodes performed an outstanding catalytic ability on 8-hydroxydeoxyguanosine oxidation. 8-OHdG is oxidative stress biomarker. Further, it is noted that the detection performance of Cu₂O SNPs@GOS coated electrodes and it’s highly enhanced due to the synergistic effect of Cu₂O SNPs and GOS. Besides, the modified materials provide more electro-active faces and as well as rapid electron transport pathway and shorten diffusion. Moreover, oxidation of 8-OHdG sensor is exploring a long linear or working range of 0.02–1465 µM and high sensitivity (8.75 nM). The viability of the Cu₂O SNPs@GOS proposed electrochemical methods have tested, to find out 8-OHdG concentrations in biological fluids (blood serum and urine) with a satisfying recovery ranges.     

Influence of surface modification by vanadium oxide and carbon on the electrochemical performance of LiFePO4/C

Surface modification with metal oxides is an efficient method to improve the performance of LiFePO₄. Carbon and V₂O₃ co-coated LiFePO₄ is synthesized by carbothermal reduction method combined with star-balling technique, and vanadium oxide is produced in situ. The structure and pattern of LiFePO₄/C modified with different amounts of vanadium oxide (0–5 mol%) were studied by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and micro-Raman spectroscopy. The electrochemical performance of material electrodes was analyzed by constant current charge–discharge and electrochemical impedance spectra (EIS). Electrochemical test results show that sample B (1.0 mol%) exhibits the best electrochemical performance, whose discharge capacity is up to 160.1, 127.2, and 88.4 mAh?g^?1 at 1, 5, and 10 °C, respectively. It indicates that V₂O₃ modification efficiently improves specific capacity and rate capability. The EIS experiment demonstrates that catalytic activity and reversibility of the cathode electrode are obviously increased by the surface modification of vanadium oxide.     

Synthesis of Al2TiO5 and its effect on the properties of chitosan–NH4SCN polymer electrolytes

In this paper, Al₂TiO₅ ceramic material has been synthesised and used as filler in polymer electrolyte system to enhance the conductivity. The precursor sintered at 1,050 °C and contained 0.08 mole of aluminium nitrate gives the best and complete formation of Al₂TiO₅. Composite polymer electrolytes of chitosan–NH₄SCN containing different amount of home-made Al₂TiO₅ were prepared by solution casting. The addition of filler has enhanced the conductivity of polymer electrolyte. The sample 57 wt% chitosan–38 wt% NH₄SCN–5 wt% Al₂TiO₅ exhibited the highest electrical conductivity of 2.10?×?10^?4 S cm^?1 at room temperature. The presence of the Al₂TiO₅ creates favourable pathways for ionic conduction through Lewis acid–base type interactions between ionic species and O/OH surface groups on alumina filler grains. In addition, the space charge region created by the presence of Al³⁺ could attract SCN^?1 ions, thus immobilise it and increase the transport number of the cation. Degree of crystallinity is calculated from the deconvoluted X-ray diffraction patterns and it shows that the lowest degree of crystallinity is achieved when 5 wt% of filler is added. In Fourier transform infrared study, the carboxamide band of the polymer is observed to shift to higher wave number from 1,629 to 1,634 cm^?1, confirming the formation of chitosan–NH₄SCN–Al₂TiO₅ complexes. The morphology of composite polymer electrolyte has been studied using scanning electron microscopy at room temperature.     

Growth of undoped and Fe doped TiO2 nanostructures and their optical and photocatalytic properties

Undoped and Fe-doped TiO₂ nanostructures have been successfully grown on Pt-coated quartz and Si (100) substrates using vapor-liquid-solid (VLS) growth method. The scanning electron microscopy (SEM) image showed that TiO₂ grew in nanowires (NWs) with diameters of 200–400 nm and lengths greater than 12 μm. However, the morphology of Fe-doped TiO₂ consists of chunk shaped nanoparticles (NPs). The X-ray diffraction analysis for undoped TiO₂ NWs clearly showed the formation of tetragonal rutile TiO₂, whereas for the Fe-doped TiO₂ NPs it showed orthorhombic TiO₂ phase and there are no crystalline peaks for iron or iron oxide. The refractive index and extinction coefficient values of undoped and Fe-doped TiO₂ nanostructures were derived from the ellipsometric measurements. Enhanced photocatalytic activities were obtained for undoped and Fe-doped TiO₂ nanostructures. The obtained results may find potential applications in optical devices and degradation of organic wastes.     

Improving the electrochemistry and microstructure of nickel electrode by deposition on anodized titanium substrate for the electrocatalytic oxidation of methanol and ethanol

The electrodeposition process of nickel and the substrate used for the electrodeposition can be improved to obtain an effective catalyst for methanol oxidation. Thus, nanoparticles of nickel have been uniformly electrodeposited on the surface of previously anodized titanium at 5 V during 1 h. The optimized microstructure has been studied by using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The XPS and argon-ion etching experiments have revealed the composition profile of the titanium/titania/nickel thin film electrode. Metallic Ni is detected by XRD. The nickel particles dispersed in a porous TiO₂ substrate have great catalytic activity for methanol oxidation in basic solution and through the redox couple NiO(OH)/Ni(OH)₂. The optimized titania substrate yields to electrodes (crystalline titanium/amorphous titania/nanocrystalline nickel) with higher catalytic activity than non-anodized metallic titanium (titanium/nickel). However, further oxidation and thickening of the titania film drives to poorer electrochemical behavior. The SEM and EDS results show that the nickel particles exhibit certain tendency to agglomerate and to form spherical particles of around 2 μm. This electrode material also is active to oxidize ethanol, but this activity is poorer.     

Preparation and characterization of LiTi<Subscript>2</Subscript>O<Subscript>4</Subscript> anode material synthesized by one-step solid-state reaction

LiTi₂O₄ anode material for lithium-ion battery has been prepared by a novel one-step solid-state reaction method using Li₂CO₃, TiO₂, and carbon black as raw materials. X-ray diffraction, scanning electron microscopy, energy-dispersive spectrometry, and the determination of electrochemical properties show that the single phase of LiTi₂O₄ with spinel crystal structure is formed at 850?°C by this new method, and the lattice parameter is about 8.392?Å. The primary particle size of the LiTi₂O₄ powder is about 0.5–1.0 μm and its morphology is similar to a sphere. The lithium ion insertion voltage of LiTi₂O₄ anode material is about 1.50 V versus lithium metal, the initial discharge capacity is about 133.6 mAh g^-1, the charge–discharge voltage plateau is very flat, and no solid electrolyte interface film is formed when working potential is more than 1.0 V. The reaction reversibility and the cycling stability are excellent, and the high rate performance is good.