This paper presents the application of zinc/aluminium-layered double hydroxide-quinclorac (Zn/Al-LDH-QC) as a modifier of multiwalled carbon nanotubes (MWCNT) paste electrode for the determination of bisphenol A (BPA). The Zn/Al-LDH-QC/MWCNT morphology was examined by a transmission electron microscope and a scanning electron microscope. Electrochemical impedance spectroscopy was utilized to investigate the electrode interfacial properties. The electrochemical responses of the modified electrode towards BPA were thoroughly evaluated by using square-wave voltammetry technique. The electrode demonstrated three linear plots of BPA concentrations from 3.0 × 10-8⁻7.0 × 10-7 M (R² = 0.9876), 1.0 × 10-6⁻1.0 × 10-5 M (R² = 0.9836) and 3.0 × 10-5⁻3.0 × 10-4 M (R² = 0.9827) with a limit of detection of 4.4 × 10-9 M. The electrode also demonstrated good reproducibility and stability up to one month. The presence of several metal ions and organic did not affect the electrochemical response of BPA. The electrode is also applicable for BPA determination in baby bottle and mineral water samples with a range of recovery between 98.22% and 101.02%.
This paper presents novel research on the development of a generic intelligent oil fraction sensor based on Electrical Capacitance Tomography (ECT) data. An artificial Neural Network (ANN) has been employed as the intelligent system to sense and estimate oil fractions from the cross-sections of two-component flows comprising oil and gas in a pipeline. Previous works only focused on estimating the oil fraction in the pipeline based on fixed ECT sensor parameters. With fixed ECT design sensors, an oil fraction neural sensor can be trained to deal with ECT data based on the particular sensor parameters, hence the neural sensor is not generic. This work focuses on development of a generic neural oil fraction sensor based on training a Multi-Layer Perceptron (MLP) ANN with various ECT sensor parameters. On average, the proposed oil fraction neural sensor has shown to be able to give a mean absolute error of 3.05% for various ECT sensor sizes.
This paper presents the fabrication of a highly sensitive and selective glucose sensor based on cuprous oxide/graphene nanocomposites-modified glassy carbon electrode (Cu2O/graphene/GCE). The Cu2O/graphene nanocomposites were synthesized based on a simple and straightforward chemical reduction process in alkaline aqueous solution using sodium carbonate as reductant. The size and shape of Cu2O nanoparticles on graphene sheets can be controlled by changing the amount of graphene oxide added during reaction. The electrochemical properties of Cu2O/graphene/GCE in 0.1M phosphate buffer solution were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. It was found that the pH, concentration of supporting electrolyte, and scan rate had very crucial effect on the sensitivity of prepared sensor towards glucose oxidation. At an applied potential of +0.50V, the Cu2O/graphene/GCE presented a high sensitivity of 1330.05μAmM(-1)cm(-2) and fast response (within 3s). The amperometric non-enzymatic glucose sensor developed had a linear relationship from 0.01mM to 3.0mM glucose and detection limit of 0.36μM. In the presence of ascorbic acid, uric acid, dopamine, chloride and citrate ion and other carbohydrates, the interferences were negligible. The proposed sensor was successfully applied for the determination of glucose concentration in real human blood samples.
Cobalt incorporated sulfur-doped graphitic carbon nitride with bismuth oxychloride (Co/S-gC3N4/BiOCl) heterojunction is prepared by an ultrasonically assisted hydrothermal treatment. The heterojunction materials have employed in photoelectrochemical (PEC) water splitting. The PEC activity and stability of the materials are promoted by constructing an interface between the visible light active semiconductor photocatalyst and cocatalysts. The photocurrent density of Co-9% S-gC3N4/BiOCl has attained 393.0 μA cm-2 at 1.23 V vs. RHE, which is 7-fold larger than BiOCl and ~3-fold higher than 9% S-gC3N4/BiOCl. The enhanced PEC activity can be attributed to the improved electron-hole charge separation and the boosted charge transfer is confirmed by photoluminescence (PL) and electrochemical impedance spectroscopy (EIS) analysis. The fabricated Co/S-gC3N4/BiOCl nanohybrid material has exhibited high stability of up to 10,800 s (3 h) at 1.23 V vs. RHE during PEC water splitting reaction and the obtained photo-conversion efficiency is 3.7-fold greater than S-gC3N4/BiOCl and 17-fold higher than BiOCl. The FESEM and HRTEM images have revealed the formation of heterojunction interface between S-gC3N4 and BiOCl and the elemental mapping has confirmed the presence of cobalt over S-gC3N4/BiOCl. The heterojunction interface has facilitated the photo-excited charge separation and transport across the electrode/electrolyte interface and also the flat-band potential, which is confirmed by Mott-Schottky analysis.
Glycolipid, found commonly in membranes, is also a liquid crystal material which can self-assemble without the presence of a solvent. Here, the dielectric and conductivity properties of three synthetic glycolipid thin films in different thermotropic liquid crystal phases were investigated over a frequency and temperature range of (10(-2)-10(6) Hz) and (303-463 K), respectively. The observed relaxation processes distinguish between the different phases (smectic A, columnar/hexagonal, and bicontinuous cubic Q) and the glycolipid molecular structures. Large dielectric responses were observed in the columnar and bicontinuous cubic phases of the longer branched alkyl chain glycolipids. Glycolipids with the shortest branched alkyl chain experience the most restricted self-assembly dynamic process over the broad temperature range studied compared to the longer ones. A high frequency dielectric absorption (Process I) was observed in all samples. This is related to the dynamics of the hydrogen bond network from the sugar group. An additional low-frequency mechanism (Process II) with a large dielectric strength was observed due to the internal dynamics of the self-assembly organization. Phase sensitive domain heterogeneity in the bicontinuous cubic phase was related to the diffusion of charge carriers. The microscopic features of charge hopping were modelled using the random walk scheme, and two charge carrier hopping lengths were estimated for two glycolipid systems. For Process I, the hopping length is comparable to the hydrogen bond and is related to the dynamics of the hydrogen bond network. Additionally, that for Process II is comparable to the bilayer spacing, hence confirming that this low-frequency mechanism is associated with the internal dynamics within the phase.
The molecular dynamics of a synthetic branched chain glycolipid, 2-decyl-tetradecyl-β-d-maltoside (C14-10G2), in the dry assemblage of smectic and columnar liquid crystal phases has been studied by dielectric spectroscopy as a function of frequency and temperature during the cooling process. Strong relaxation modes were observed corresponding to the tilted smectic and columnar phases, respectively. At low frequency (∼900 Hz to 1 kHz) in the smectic phase, Process I* was observed due to the tilted sugar bilayer structure. The process continued in the columnar phase (Process I) with an abrupt dynamic change due to phase transition in the frequency range of ∼1.3 kHz to 22 kHz. An additional process (Process II) was observed in the columnar phase with a broader relaxation in the frequency range of ∼10 Hz to 1 kHz. A bias field dependence study was performed in the columnar phase and we found that the relaxation strength rapidly decreased with increased applied dc bias field. This relaxation originates from a collective motion of polar groups within the columns. The results of dielectric spectroscopy were supported by a molecular dynamics simulation study to identify the origin of the relaxation processes, which could be related to the chirality and hydrogen bonds of the sugar lipid.
A new supramolecular electrochemical sensor for highly sensitive detection of dopamine (DA) was fabricated based on supramolecular assemblies of mixed two surfactants, tetra-butylammonium bromide (TBABr) and sodium dodecyl sulphate (SDS), on the electrodeposition of gold nanoparticles on graphene oxide modified on glassy carbon electrode (AuNPs/GO/GCE). Self-assembled mixed surfactants (TBABr/SDS) were added into the solution to increase the sensitivity for the detection of DA. All electrodes were characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The supramolecular electrochemical sensor (TBABr/SDS⋅⋅⋅AuNPs/GO/GCE) showed excellent electrocatalytic activity toward the oxidation of DA. Under the optimum conditions, the concentration of DA was obtained in the range from 0.02 µM to 1.00 µM, with a detection limit of 0.01 µM (3s/b). The results displayed that TBABr/SDS⋅⋅⋅AuNPs/GO/GCE exhibited excellent performance, good sensitivity, and reproducibility. In addition, the proposed supramolecular electrochemical sensor was successfully applied to determine DA in human serum samples with satisfactory recoveries (97.26% to 104.21%).
In this work, 10 mol% yttrium-doped ceria powders, Ce0.9Y0.1O1.95, were synthesised using a new mechanical technique, mechanochemical reaction, in which both impact action and shearing forces were applied for efficient fine grinding, subsequently leading to higher homogeneity of the resultant powders. Ce0.9Y0.1O1.95 prepared using this new technique was systematically compared with a sample of the same prepared using conventional solid-state methodology. X-ray diffraction analysis showed all prepared samples were single phase with a cubic fluorite structure. Generally, Y2O3-doped CeO2 electrolytes prepared by mechanochemical reactions were stable at a lower temperature (1100 °C) compared with a sample of the same synthesised using the conventional solid-state method. Characterisations using differential thermal analysis (DTA) and thermogravimetric analysis (TGA) showed no thermal changes and phase transitions, indicating all materials were thermally stable. The electrical properties of the samples investigated by AC impedance spectroscopy in the temperature range 200–800 ˚C are presented and discussed. Scanning electron microscopy (SEM) was used to study the morphology of the materials. Fine-grained powders with uniform grain-size distribution were obtained from the mechanochemical reaction.
A label-free chemical bonding strategy mediated by reduced graphene oxide (rGO) basal plane functional groups has been developed for cardiac Troponin I (cTnI) detection. Four different chemical strategies on respective electrode sensing surface were precedingly examined using electrochemical impedance spectroscopy. The impedimetric assessment was carried out by sweeping frequency at the range 0.1-500 kHz perturbated at a small amplitude of AC voltage (25 mV). The chemical strategy-4 denoted as S-4 shows a significant analytical performance on cTnI detection in spiked buffer and human serum, whereby the pre-mixture of rGO and (3-Aminopropyl)triethoxysilane (APTES) creates a large number of amine sites (-NH2), which significantly enhanced the antibody immobilization without excessive functionalization. The as-fabricated immunosensor exhibited an ultra-low limit of detection of 6.3 ag mL-1 and the lowest antigen concentration measured was at 10 ag mL-1. The immunosensor showed a linear and wide range of cTnI detection (10 ag mL-1-100 ng mL-1) in human serum with a regression coefficient of 0.9716, rapid detection (5 min of binding time), and stable and highly reproducible bioelectrode response with RSD
Bismuth chromium solid solutions, with a general formula Bi6-xCr2Oδ, where -1 ≤ x ≤ 2, were successfully synthesized via the conventional solid state method. The phases of the synthesized samples were determined by X-ray diffraction (XRD) analysis. The properties of single-phase compounds were characterized by using differential thermal analysis (DTA), thermal gravimetric analysis (TGA), AC impedance spectroscopy, and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The occurrence of phase transitions was confirmed by DTA and TGA, where a thermal event was observed by DTA at around 800oC. In addition, TGA studies also showed that there was a weight loss at around 800oC. Elemental analysis of Bi6Cr2O15 and its solid solutions by ICP-AES showed a good agreement between the expected value and the experimental value on the compositions, with no evidence of any systematic deviation from stoichiometric. Electrical properties of Bi6Cr2O15 and its solid solutions were investigated by using AC impedance spectroscopy from 300oC to 650oC. Ionic conductivity increased with the increasing temperature and bismuth content, and the best ionic conductivity was observed for Bi7Cr2O16.5. The activation energy (Ea) of Bi6Cr2O15 and its solid solutions were in the range of 1.22-1.32 eV.
Barium strontium titanate (Ba0.7Sr0.3TiO3) powder was processed at temperature 80 o C by reacting titania sol in aqueous solutions that contained BaCl2, SrCl2 and NaOH at atmospheric pressure.
The structural characteristic of the powder and sintered pellet were studied using Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD) whereas the electrical characteristic was determined via Impedance Spectroscopy (IS) and LCR meter. The synthesized powder was found to have a tetragonal phase after heating at 1300 o C. XRD pattern also showed the presence of secondary phase BaTi2O5 (BT2). The SEM results shows the fine grain size was in the range of 0.2 Pm to 0.4 Pm whereas the large ones are approximately 0.8 Pm to 1.2 Pm The ac response of sample sintered at 1300 o C indicated that three electrically different regions. Element 1 can be assigned as a ferroelectric grain boundary region and it is actually BT2, element 2 as a ferroelectric bulk region and the third element is a conductive core which has a low resistance (200 :) and capacitance value.
This paper is focussed on conductivity and dielectric properties of Poly (vinyl) chloride (Pvc)- ammonium triflate (NH4CF3SO3) - butyltrimethyl ammonium bis (trifluoromethyl sulfonyl) imide (Bu3MeNTf2N) ionic liquid, electrolyte system. The electrolyte is prepared by solution cast technique. In this work, the sample containing 30 wt. % NH4CF3SO3 exhibits the highest room temperature conductivity of 2.50 x 10-7 S cm' . Ionic liquid is added in various quantities to the 70 wt. % Pvc-30 wt. % NH4CF3SO3 composition in order to enhance the conductivity of the sample. The highest conductivity at room temperature is obtained for the sample containing 15 wt. % Bu3MeNTf2N with a value of 1.56 x 10 -4 S cm' . The effects of ionic liquid addition on the frequency dependent dielectric properties of PVC based electrolytes is investigated by electrochemical impedance spectroscopy (Eis) at room temperature. The values of dielectric constant were found to increase with increasing conductivity of the samples. Analysis of the ac conductivity data showed the electrolytes to be of the non-Debye type.
This article reports a degradation study that was done on stent prototypes made of biodegradable Fe35Mn alloy in a simulated human coronary arterial condition. The stent degradation was observed for a short-term period from 0.5 to 168 h, which simulates the early period of stenting procedure. Potentiodynamic polarization and electrochemical impedance spectroscopy were used to quantify degradation rate and surface property of the stents. Results showed that signs of degradation were visible on both crimped and expanded stents after 1 h of test, mostly located on the stent's curvatures. The degradation rate of stent was higher compared to that of the original alloy, indicating the surface altering effect of stent fabrication processing to degradation. A single oxide layer was formed and detected as a porous structure with capacitive behavior. Expanded stents exhibited lower polarization resistance compared to the nonexpanded ones, indicating the cold work effect of expansion procedure to degradation.
Dye-Sensitized Solar Cells (DSSCs) have attracted great attention due to environmentally friendly low-cost processing, excellent working ability in diffuse light, and potential to meet the power demands of future buildings due the true class of building integrated photovoltaics (BIPV). Nevertheless, DSSCs have relatively low photoconversion efficiency (PCE) due to multiple issues. Several strategies have been employed to enhance its PCE. For instance, bi-layered structure of photoelectrode i.e., mesoporous TiO2 transparent layer with top scattering layer was introduced which scatter light inside on large angles improves the harvesting ability of photoelectrode thus enhanced PCE. However, scattering layer is composed of aggregated small particles which offer sluggish electron transport due to multiple grain boundaries, consequently, unwanted recombination reaction which leads to poor PCE. This issue has been addressed for transparent layer immensely but ignored for scattering layer. Mostly for scattering layer in previous studies novel structures have been proposed to enhance scattering properties and dye adsorption only. Therefore, in this study for the first time presenting dual functional graphene/TiO2 scattering layer in which solvent exfoliated graphene is incorporated in TiO2 submicron spheres which enhanced electron transport properties, while submicron spheres scatter light effectively. Scattering and electron transport characteristics of DSSCs are thoroughly investigated with the function of graphene loading. Electrochemical impedance spectroscopy (EIS) has revealed that diffusion coefficient length and coefficient and conductivity attained maximum value at 0.01 wt%. while other important parameters such as electron lifetime and electron density in conduction band have been improved till 0.020 wt% graphene loading. However, results indicated that with 0.01 w% graphene 33% higher PCE was achieved than without scattering layer and 13% higher than scattering layer without graphene. The depraving in PCE at >0.01 wt% graphene despite of excellent electron transport improvement is attributed to the loss of diffuse reflectance and higher optical absorption by graphene.
In the present work, polymer electrolytes of poly(vinylidene fluoride co-hexafluoroproplyne) (PVDF-HFP) and PVDF-HFP/poly(ethyl methacrylate) (PVDF-HFP/PEMA) blend complexed with different concentrations of ammonium triflate (NH4CF3SO3) were prepared and characterized. The structural and thermal properties of the electrolytes were studied by XRD and DSC while the electrical properties were investigated by impedance spectroscopy. Ionic transference number measurements were done by D.C polarization technique. The results of these study showed that the PVDF-HFP/PEMA based electrolytes exhibit higher ionic conductivity as compared to PVDF-HFP based electrolytes. This could be attributed to the higher degree of amorphicity in the PVDF-HFP/PEMA based electrolytes. The results of ionic transference number measurements showed that the charge transport in these electrolytes was mainly due to ions and only negligible contribution comes from electrons.
In this present study, a series of polymer electrolyte thin films were synthesized by incorporating different ratios of lithium triflate (LiCF3SO3) in a low molecular weight polyvinyl chloride (PVC) matrix by the solution casting technique. The incorporation of LiCF3SO3 suppressed the high degree of crystallinity in PVC enabling the system to possess an appreciable ionic conductivity. The ionic conductivity of the samples, with different LiCF3SO3 content, was determined by the aid of ac impedance spectroscopy. The highest ionic conductivity of 4.04 10–9 S cm–1 was identified for the composition of PVC: LiCF3SO3 (75:25). Further understanding of the ionic conductivity mechanism was based on temperature-dependent conductivity data which obeyed Arrhenius theory, indicating that the ionic conductivity enhancement was thermally assisted. The possible dipole-dipole interaction between the chemical constituents was confirmed with changes in cage peak, analysed using Fourier transform infrared spectroscopy.
For the past decade, much attention was focused on polysaccharide natural resources for various purposes. Throughout the works, several efforts were reported to prepare new function of chitosan by chemical modifications for renewable energy, such as fuel cell application. This paper focuses on synthesis of the chitosan derivative, namely, O-nitrochitosan which was synthesized at various compositions of sodium hydroxide and reacted with nitric acid fume. Its potential as biopolymer electrolytes was studied. The substitution of nitro group was analyzed by using Attenuated Total Reflectance Fourier Transform Infra-Red (ATR-FTIR) analysis, Nuclear Magnetic Resonance (NMR) and Elemental Analysis (CHNS). The structure was characterized by X-ray Diffraction (XRD) and its thermal properties were examined by using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Whereas, the ionic conductivity of the samples was analyzed by electrochemical impedance spectroscopy (EIS). From the IR spectrum results, the nitro group peaks of O-nitrochitosan, positioned at 1646 and 1355 cm-1, were clearly seen for all pH media. At pH 6, O-nitrochitosan exhibited the highest degree of substitution at 0.74 when analyzed by CHNS analysis and NMR further proved that C-6 of glucosamine ring was shifted to the higher field. However, the thermal stability and glass transition temperatures were decreased with acidic condition. The highest ionic conductivity of O-nitrochitosan was obtained at ~10-6 cm-1. Overall, the electrochemical property of new O-nitrochitosan showed a good improvement as compared to chitosan and other chitosan derivatives. Hence, O-nitrochitosan is a promising biopolymer electrolyte and has the potential to be applied in electrochemical devices.
Microbial fuel cells (MFCs) have a high potential application for simultaneous wastewater treatment and electricity
generation. However, the choice of the electrode material and its design is critical and directly affect their performance.
As an electrode of MFCs, the anode material with surface modifications is an attractive strategy to improve the power
output. In this study, stainless steel (SS) and carbon steel (CS) was chosen as a metal anode, while graphite felt (GF)
was used as a common anode. Heat treatment was performed to convert SS, CS and GF into efficient anodes for MFCs.
The maximum current density and power density of the MFC-SS were achieved up till 762.14 mA/m2
and 827.25 mW/m2
,
respectively, which were higher than MFC-CS (641.95 mA/m2
and 260.14 mW/m2
) and MFC-GF (728.30 mA/m2
and 307.89
mW/m2
). Electrochemical impedance spectroscopy of MFC-SS showed better catalytic activity compared to MFC-CS and
MFC-GF anode, also supported by cyclic voltammetry test.
A unique nanocomposite was fabricated using negatively charged manganese dioxide nanoparticles, poly (3,4-ethylenedioxythiophene) and reduced graphene oxide (MnO2/PEDOT/rGO). The nanocomposite was deposited on a glassy carbon electrode (GCE) functionalized with amino groups. The modified GCE was used to electrochemically detect dopamine (DA). The surface morphology, charge effect and electrochemical behaviours of the modified GCE were characterized by scanning electron microscopy, energy dispersive X-ray analysis (EDX), cyclic voltammetry and electrochemical impedance spectroscopy, respectively. The MnO2/PEDOT/rGO/GCE exhibited excellent performance towards DA sensing with a linear range between 0.05 and 135 µM with a lowest detection limit of 30 nM (S/N = 3). Selectivity towards DA was high in the presence of high concentrations of the typical interferences ascorbic acid and uric acid. The stability and reproducibility of the electrode were good. The sensor accurately determined DA in human serum. The synergic effect of the multiple components of the fabricated nanocomposite were critical to the good DA sensing performance. rGO provided a conductive backbone, PEDOT directed the uniform growth of MnO2 and adsorbed DA via pi-pi and electrostatic interaction, while the negatively charged MnO2 provided adsorption and catalytic sites for protonated DA. This work produced a promising biosensor that sensitively and selectively detected DA.
In this study polymer electrolytes composed of poly(methyl methacrylate) (PMMA) as a host polymer and ethylene carbonate (EC) as a plasticizer complexed with different lithium salts, i.e. lithium tetrafluoroborate (LiBF4) and lithium triflate (LiCF3SO3) were prepared by the solution casting technique. The conductivities of the films were characterized by impedance spectroscopy. At room temperature, the highest conductivities were 4.07 × 10–7S cm–1 and 3.40 × 10–5 S cm–1 achieved, respectively from the films containing 30 wt% LiBF4 in the PMMA-EC-LiBF4 system and 35 wt% LiCF3SO3 in the PMMA-EC-LiCF3SO3 system. The conductivity-temperature dependence of the films seemed to obey the Arrhenius equation in which the ion transport in these materials was thermally assisted. Scanning electron microscopy analysis showed that the surface of PMMA-EC-LiCF3SO3 film was smooth and homogeneous, hence lithium ions could traverse through the PMMA-EC-LiCF3SO3 film more easily compared to the PMMA-EC-LiBF4 film. X-Ray diffraction studies revealed that complexation had occurred and the complexes formed were amorphous.