The recent developments of nanostructured WO3 thin films synthesized through the electrochemical route of electrochemical anodization and cathodic electrodeposition for the application in photoelectrochemical (PEC) water splitting are reviewed. The key fundamental reaction mechanisms of electrochemical anodization and cathodic electrodeposition methods for synthesizing nanostructured WO3 thin films are explained. In addition, the effects of metal oxide precursors, electrode substrates, applied potentials and current densities, and annealing temperatures on size, composition, and thickness of the electrochemically synthesized nanostructured WO3 thin films are elucidated in detail. Finally, a summary is given for the general evaluation practices used to calculate the energy conversion efficiency of nanostructured WO3 thin films and a recommendation is provided to standardize the presentation of research results in the field to allow for easy comparison of reported PEC efficiencies in the near future.
Electrospinning of hydroxyapatite (HA)/polyvinyl butyral solution resulted in the formation of fibers with average diameter of 937-1440 nm. These fibers were converted into HA nanoparticles with size <100 nm after undergoing calcination treatment at 600°C. The diameter of the fiber was found to be influenced by applied voltage and spinning distance. The injection flowrate did not affect the diameter significantly. The electrospinning method successfully reduced the commercial HA particle size in the range of 400-1100 nm into <100 nm. The dispersion of the finally calcined HA nanoparticles was improved significantly after anionic sodium dodecyl sulfate surfactant was introduced. The experimental data of HA growth kinetics were subjected to the integral method of analysis, and the rate law of the reaction was found to follow the first order reaction.
Mixed dye consists of six commercial dyes and textile effluents from cotton dyeing process were treated by electrochemical-assisted photodegradation under halogen lamp illumination. Two types of effluents were collected which are samples before and after undergone pre-treatment at the factory wastewater treatment plant. The photodegradation process was studied by evaluating the changes in concentration employing UV-vis spectrophotometer (UV-vis) and total organic carbon (TOC) analysis. The photoelectrochemical degradation of mixed dye was found to follow the Langmuir Hinshelwood pseudo-first order kinetic while pseudo-second order kinetic model for effluents by using TOC analyses. The chemical oxygen demand (COD) and biochemical oxygen demand (BOD) values of mixed dye and raw effluents were reported. Photoelectrochemical characteristic of pollutants was studied using the cyclic voltammetry technique. Raw effluent was found to exhibit stronger reduction behaviour at cathodic bias potential but slightly less photoresponse at anodic bias than mixed dye.
Electrochemical-assisted photodegradation of methyl orange has been investigated using TiO2 thin films. The films were prepared by sol-gel dip-coating method. Several operational parameters to achieve optimum efficiency of this electrochemical-assisted photodegradation system have been tested. Photoelectrochemical degradation was studied using different light sources and light intensity. The light sources chosen ranged from ultraviolet to visible light. The effect of agitation of the solution at different speeds has also been studied. Slight improvement of photodegradation rate was observed by applying higher agitation speed. Investigation on the electrode after repeated usages show the electrode can be reused up to 20 times with percentage of deficiency less than 15%. The study on the effect of solution temperature indicated that the activation energy of the methyl orange degradation is 18.63 kJ mol(-1).
A novel label-free electrochemical DNA biosensor was constructed for the determination of Escherichia coli bacteria in environmental water samples. The aminated DNA probe was immobilized onto hollow silica microspheres (HSMs) functionalized with 3-aminopropyltriethoxysilane and deposited onto a screen-printed electrode (SPE) carbon paste with supported gold nanoparticles (AuNPs). The biosensor was optimized for higher specificity and sensitivity. The label-free E. coli DNA biosensor exhibited a dynamic linear response range of 1 × 10-10 µM to 1 × 10-5 µM (R2 = 0.982), with a limit of detection at 1.95 × 10-15 µM, without a redox mediator. The sensitivity of the developed DNA biosensor was comparable to the non-complementary and single-base mismatched DNA. The DNA biosensor demonstrated a stable response up to 21 days of storage at 4 ℃ and pH 7. The DNA biosensor response was regenerable over three successive regeneration and rehybridization cycles.
That water may not be an inert medium was indicated by the presence at water's interfaces a negatively charged solute free zone of several hundred microns in thickness called the exclusion zone (EZ). Further evidence was demonstrated by Ovchinnikova's experiments (2009) showing that water can store and release substantial amount of charge. We demonstrate that the charge storage capacity of water arises from highly stable large-scale ionic structures with measurable charge imbalances and discrete levels of charge density. We also show evidence that the charge zones formation requires ionic solutes, and their formation correlate to large change in conductivity, by as much as 250%. Our experiments indicate that large-scale structuring plays a pivotal role in electrolysis and conductivity in ionic solution. We propose that water is an electrochemically active medium and present a new model of electrolysis and conductivity in ionic solution.
A general purpose enzyme-based amperometric electrochemical genosensor assay was developed wherein polymerase chain reaction (PCR) amplicons labeled with both biotin and fluorescein were detected with peroxidase-conjugated antifluorescein antibody on a screen-printed carbon electrode (SPCE). As a proof of principle, the response selectivity of the genosensor was evaluated using PCR amplicons derived from lolB gene of Vibrio cholerae. Factors affecting immobilization, hybridization, and nonspecific binding were optimized to maximize sensitivity and reduce assay time. On the basis of the background amperometry signals obtained from nonspecific organisms and positive signals obtained from known V. cholerae, a threshold point of 4.20 microA signal was determined as positive. Under the optimum conditions, the limit of detection (LOD) of the assay was 10 CFU/mL of V. cholerae. The overall precision of this assay was good, with the coefficient of variation (CV) being 3.7% using SPCE and intermittent pulse amperometry (IPA) as an electrochemical technique. The assay is sensitive, safe, and cost-effective when compared to conventional agarose gel electrophoresis, real-time PCR, and other enzyme-linked assays for the detection of PCR amplicons. Furthermore, the use of a hand-held portable reader makes it suitable for use in the field.
An electrogenerative flow-through reactor with an activated reticulated vitreous carbon cathode was developed. The influence of palladium-tin activation of the cathode towards gold deposition was studied by cyclic voltammetry. The reactor proved to be efficient in recovering more than 99% of gold within 4 h of operation. The performance of the reactor was evaluated with initial gold concentrations of 10, 100 and 500 mg L-1 and various electrolyte flow rates. Gold recovery was found to be strongly dependent on electrolyte flow rate and initial gold concentration in the cyanide solution under the experimental conditions used.
Traditional methods for the recovery of gold from electronic scrap by hydrometallurgy were cyanidation followed by adsorption on activated carbon or cementation onto zinc dust and by electrowinning. In our studies, a static batch electrochemical reactor operating in an electrogenerative mode was used in gold recovery from cyanide solutions. A spontaneous chemical reaction will take place in the reactor and generate an external flow of current. In this present work, a static batch cell with an improved design using three-dimensional cathodes namely porous graphite and reticulated vitreous carbon (RVC) and two-dimensional cathode materials, copper and stainless steel plates were coupled with a zinc anode. The electrogenerative system was demonstrated and the performance of the system using various cathode materials for gold recovery was evaluated. The system resulted in more than 90% gold being recovered within 3h of operation. Activated RVC serves as a superior cathode material having the highest recovery rate with more than 99% of gold being recovered in 1h of operation. The morphology of gold deposits on various cathode materials was also investigated.
Advanced oxidation processes (AOPs) such as Fenton, electro-Fenton and photo-Fenton have been applied effectively to remove refractory organics from landfill leachate. The Fenton reaction is based on the addition of hydrogen peroxide to the wastewater or leachate in the presence of ferrous salt as a catalyst. The use of this technique has proved to be one of the best compromises for landfill leachate treatment because of its environmental and economical advantages. Fenton process has been used successfully to mineralize wide range of organic constituents present in landfill leachate particularly those recalcitrant to biological degradation. The present study reviews the use of Fenton and related processes in terms of their increased application to landfill leachate. The effects of various operating parameters and their optimum ranges for maximum COD and color removal are reviewed with the conclusion that the Fenton and related processes are effective and competitive with other technologies for degradation of both raw and pre-treated landfill leachate.
A newly developed electrochemical sensor for chlorothalonil based on nylon 6,6 film deposited onto screen printed electrode (SPE) with electrochemical modulation of pH at the electrode/solution interface was studied for the first time. Differential pulse cathodic stripping voltammetry (DPCSV) was used to carry out the electrochemical and analytical studies. Experimental parameters such as accumulation potential, initial potential, accumulation time and pH of Britton-Robinson buffer have been optimized. Chlorothalonil gave optimum analytical signal in a medium of 0.04 M Britton-Robinson buffer at pH 6.0. A well-defined reduction peak was observed, at Ep= -0.851 and -0.938 V vs. Ag/AgCl (3.0 M KCl) for both bare SPE and modified SPE, respectively. The peak currents of modified SPE were significantly increased as compared to bare SPE. At the modified SPE, a linear relationship between the peak current and chlorothalonil concentration was obtained in the range from 0.1 to 2.8 × 10-6 M with a detection limit of 1.53 × 10-8 M (S/N= 3). The practical applicability of the newly developed method has been demonstrated on analyses of real water samples. The newly developed sensor shows good reproducibility with RSD of 3.92%. The nylon 6,6 modified SPE showed itself as promising sensor with good selectivity for chlorothalonil determination.
A method to fabricate a bioinspired nanobiosensor using electronic-based artificial taste receptors for glucose diagnosis is presented. Fabricated bioinspired glucose nanobiosensor designated based on an artificial taste bud including an amperometric glucose biosensor and taste bud-inspired circuits. In fact, the design of the taste bud-inspired circuits was inspired by the signal-processing mechanism of taste nerves which involves two layers. The first, known as a type II cell, detects the glucose by glucose oxidase and transduces the current signal obtained for the pulse pattern is conducted to the second layer, called type III cell, to induce synchronisation of the neural spiking activity. The oscillation results of fabricated bioinspired glucose nanobiosensor confirmed an increase in the frequency of the output pulse as a function of the glucose concentration. At high glucose concentrations, the bioinspired glucose nanobiosensor showed a pulse train of alternating short and long interpulse intervals. A computational analysis performed to validate the hypothesis, which was successfully reproduced the alternating behaviour of bioinspired glucose our nanobiosensor by increasing the output frequency and alternation of pulse intervals according to the reduction in the resistivity of the biosensor.
The effect of scan rate on the accuracy of corrosion parameter in evaluating the efficiency of rice straw extract as corrosion inhibitor has been studied via potentiodynamic polarization measurement. Scan rate in the range of low (0.1- 0.25 mV s-1), medium (0.5-1.0 mV s-1) and high (1.5-2.0 mV s-1) scan were carried out on the carbon steel in 1 M HCl. The corrosion parameters such as corrosion rate, polarization resistance and corrosion current density have been analyzed through Tafel polarization curve. High scan rate gave poor accuracy of corrosion parameter compared to medium and low scan. Medium scan at 1.0 mV s-1 has been chosen as the optimum scan rate due to the approached steady-state and small disturbance of charged current. As a result, the addition of rice straw extract in 1 M HCl has reduced the values of corrosion current density in both cathodic and anodic reactions signified the corrosion has been inhibited. The efficiency of rice straw extracts as a corrosion inhibitor offer good result as much as 86%.
A new electrochemical biosensor is described for voltammetric detection of gene sequence related to Trichoderma harzianum. The sensor involves immobilization of a 20 base single-stranded probe (ssDNA), which is complementary to a specific gene sequence related to T. harzianum on a gold electrode through specific adsorption. The DNA probe was used to determine the amount of target gene in solution using methylene blue (MB) as the electrochemical indicator. The covalently immobilized probe could selectively hybridize with the target DNA to form a hybrid on the surface despite the bases being attached to the electrode. The changes in the peak currents of methylene blue (MB), an electroactive label, were observed upon hybridization of probe with the target. Peak currents were found to increase in the following order: hybrid-modified AuE and the probe-modified AuE which localized to the affinity of MB. Control experiments with the non-complementary oligonucleotides were performed to assess whether the DNA biosensor responds selectively, via hybridization, to the target. DNA biosensor also able to detect microorganism at the species levels without nucleic acid amplification. The redox current was linearly related to the concentration of target oligonucleotide DNA, ranged from 1-20 ppm. Numerous factors, affecting the probe immobilization, target hybridization and indicator binding reactions are optimized to maximize the sensitivity and reduce the assay time.
A gas sensor array was developed in a 10 × 10 mm(2) space using Screen Printing and Pulse Laser Ablation Deposition (PLAD) techniques. Heater, electrode, and an insulator interlayer were printed using the screen printing method on an alumina substrate, while tin oxide and platinum films, as sensing and catalyst layers, were deposited on the electrode at room temperature using the PLAD method, respectively. To ablate SnO(2) and Pt targets, depositions were achieved by using a 1,064 nm Nd-YAG laser, with a power of 0.7 J/s, at different deposition times of 2, 5 and 10 min, in an atmosphere containing 0.04 mbar (4 kPa) of O(2). A range of spectroscopic diffraction and real space imaging techniques, SEM, EDX, XRD, and AFM were used in order to characterize the surface morphology, structure, and composition of the films. Measurement on the array shows sensitivity to some solvent and wood smoke can be achieved with short response and recovery times.
A flow injection analysis (FIA) method for the determination of four residual chlorine species, namely combined available chlorine (CAC), free available chlorine (FAC), total available chlorine (TAC) and chlorite (ClO2-) was developed using a flow-through triiodide-selective electrode as a detector. An important strategy of speciation studies utilized the kinetic discrimination of reactions between the CAC and FAC with Fe2+, which was applied to the speciation of FAC, CAC and TAC. The speciation of available chlorine species and chlorite (an oxychlorine species) was achieved by using the same set-up, but using flow streams of different pH. The effects of the pH of the carrier stream, the flow rate and the sample volume were studied. The method exhibited linearity from 2.8 x 10(-6) to 2.8 x 10(-4) M active chlorine (expressed as OCl-) with a detection limit of 1.4 x 10(-6) M. The selectivity of the method was studied by examining the minimum pH for the oxidation of iodide by other oxidants, and also by assessing the potentiometric selectivity coefficients. The proposed method was successfully applied to the determination of chlorine species in tap water, and disinfecting formulations where good agreement occurred between the proposed and standard methods were found.
The response of trilayer graphene nanoribbon (TGN)-based ion-sensitive field-effect transistor (ISFET) to different pH solutions and adsorption effect on the sensing parameters are analytically studied in this research. The authors propose a TGN-based sensor to electrochemically detect pH. To this end, absorption effect on the sensing area in the form of carrier concentration, carrier velocity, and conductance variations are investigated. Also, the caused electrical response on TGN as a detection element is analytically proposed, in which significant current decrease of the sensor is observed after exposure to high pH values. In order to verify the accuracy of the model, it is compared with recent reports on pH sensors. The TGN-based pH sensor exposes higher current compared to that of carbon nanotube (CNT) counterpart for analogous ambient conditions. While, the comparative results demonstrate that the conductance of proposed model is lower than that of monolayer graphene-counterpart for equivalent pH values. The results confirm that the conductance of the sensor is decreased and Vg-min is obviously right-shifted by increasing value of pH. The authors demonstrate that although there is not the experimental evidence reported in the part of literature for TGN sensor, but the model can assist in comprehending experiments involving nanoscale pH sensors.
The development of free and total cholesterol nanobiosensors based on a single step electrochemical integration of gold nanoparticles (AuNPs), cholesterol oxidase (COx), cholesterol esterase (CE) and a mediator with polypyrrole (PPy) films is described. The incorporation of the various components in the PPy films was confirmed by chronopotentiometry, cyclic voltammetry (CV), scanning electron microscopy, energy dispersive X-ray analysis (SEM-EDX), and Fourier transformed infrared (FTIR) spectroscopy. The free cholesterol, PPy-NO3--Fe(CN)64--AuNPs-COx, nanobiosensor achieved a minimum detectable concentration of 5 μM, a linear concentration range of 5-25 μM and a sensitivity of 1.6 µA cm-2 µM-1 in 0.05 M phosphate buffer (pH 7.00). For the total cholesterol, PPy-NO3--Fe(CN)64--AuNPs-COx-CE, nanobiosensor which also involved the co-incorporation of cholesterol esterase (CE) with the other components, the achieved performances include a minimum detectable total cholesterol concentration of 25 μM, a broader linear concentration range of 25-170 μM and a lower sensitivity of 0.1 µA µM-1 cm-2. Owing to its high selectivity, the presence of common interferants did not affect the total cholesterol measurement with the PPy-NO3--Fe(CN)64--AuNPs-COx-CE nanobiosensor. Both nanobiosensors were successfully used for direct and indirect determination of total cholesterol in human blood serum samples.
The effluent discharge treatment for controlling the environment from non biodegradable metal contaminants using plant extract is an efficient technique. The reduction of hexavalent chromium by abundantly available weed, Aerva lanata L. was investigated using batch equilibrium technique. The variables studied were Cr(VI) concentration, Aerva lanata L. dose, contact time, pH, temperature and agitation speed. Cyclic voltammetry and ICP-MS analysis confirmed the reduction of Cr(VI) to Cr(III). Electrochemical analysis proved that, the chromium has not been degraded and the valency of the chromium has only been changed. ICP-MS analysis shows that 100ng/L of hexavalent chromium was reduced to 97.01ng/L trivalent chromium. These results suggest that components present in the Aerva lanata L. are responsible for the reduction of Cr(VI) to Cr(III). The prime components ferulic acid, kaempherol and β-carboline present in the Aerva lanata L. may be responsible for the reduction of Cr(VI) as evident from LC-MS analysis.
The effect of pH and redox potential on the redox equilibria of iron oxides in aqueous-based magnetite dispersions was investigated. The ionic activities of each dissolved iron species in equilibrium with magnetite nanoparticles were determined and contoured within the Eh-pH framework of a composite stability diagram. Both standard redox potentials and equilibrium constants for all major iron oxide redox equilibria in magnetite dispersions were found to differ from values reported for noncolloidal systems. The "triple point" position of redox equilibrium among Fe(II) ions, magnetite, and hematite shifted to a higher standard redox potential and an equilibrium constant which was several orders of magnitude higher. The predominant area of magnetite stability was enlarged to cover a wider range of both pH and redox potentials as compared to that of a noncolloidal magnetite system.