Electrochemical dechlorination of chlorobenzene in organic solutions was studied. Electrolysis of chlorobenzene in acetonitrile solution in a one-compartment cell fitted with a platinum cathode and a zinc anode at 60mA/cm(2) and 0 degrees C was found to be the optimum conditions, which gave complete dechlorination of chlorobenzene. However, similar result could not be achieved when applying these conditions to 1,3-dichlorobenzene and 1,2,4-trichlorobenzene. We found that the use of naphthalene which reacted as a mediator in the appropriate system could accelerate the reduction and gave complete dechlorination of those chlorobenzenes. Moreover, in the presence of naphthalene the reaction time could be shortened by half compared to dechlorination in the absence of naphthalene.
Electrochemical dechlorination of chlorobenzenes in the presence of various arene mediators such as naphthalene, biphenyl, phenanthrene, anthracene, and pyrene, was studied. The amount of mediator required was able to be reduced to 0.01 equiv. for all mediators except for anthracene, with the complete dechlorination of mono-, 1,3-di- and 1,2,4-trichlorobenzene still achieved. This catalytic amount of mediator plays an important role in accelerating the dechlorination through the rapid formation of radical anions prior to reduction of the chlorobenzenes.
The incorporation of a spacer among membranes has a major influence on fluid dynamics and performance metrics. Spacers create feed channels and operate as turbulence promoters to increase mixing and reduce concentration/temperature polarization effects. However, spacer geometry remains unoptimized, and studies continue to investigate a wide range of commercial and custom-made spacer designs. The in-depth discussion of the present systematic review seeks to discover the influence of Reynolds number or solution flowrate on flow hydrodynamics throughout a spacer-filled channel. A fast-flowing solution sweeping one membrane's surface first, then the neighboring membrane's surface produces good mixing action, which does not happen commonly at laminar solution flowrates. A sufficient flowrate can suppress the polarization layer, which may normally require the utilization of a simple feed channel rather than complex spacer configurations. When a recirculation eddy occurs, it disrupts the continuous flow and effectively curves the linear fluid courses. The higher the flowrate, the better the membrane performance, the higher the critical flux (or recovery rate), and the lower the inherent limitations of spacer design, spacer shadow effect, poor channel hydrodynamics, and high concentration polarization. In fact, critical flow achieves an acceptable balance between improving flow dynamics and reducing the related trade-offs, such as pressure losses and the occurrence of concentration polarization throughout the cell. If the necessary technical flowrate is not used, the real concentration potential for transport is relatively limited at low velocities than would be predicted based on bulk concentrations. Electrodialysis stack therefore may suffer from the dissociation of water molecules. Next studies should consider that applying a higher flowrate results in greater process efficiency, increased mass transfer potential at the membrane interface, and reduced stack thermal and electrical resistance, where pressure drop should always be indicated as a consequence of the spacer and circumstances used, rather than a problem.
Hematite (α-Fe2O3) nanoparticles were synthesized by the solid transformation of ferrous hydroxide and ferrihydrite in hydrothermal condition. The as-prepared α-Fe2O3 nanoparticles were characterized by UV-vis, PL, XRD, Raman, TEM, AFM, FESEM, and EDX analysis. The experimental results indicated the formation of uniform hematite nanoparticles with an average size of 45 nm and perfect crystallinity. The electrochemical behavior of a GC/α-Fe2O3 electrode was studied using CV and EIS techniques with an electrochemical probe, [Fe(CN)6](3-/4-) redox couple. The electrocatalytic activity was investigated toward DA oxidation in a phosphate buffer solution (pH 6.8) by varying different experimental parameters. The chronoamperometric study showed a linear response in the range of 0-2 μM with LoD of 1.6 μM for DA. Square wave voltammetry showed a linear response in the range of 0-35 μM with LoD of 236 nM for DA.
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.
Graphene and its hybrids are being employed as potential materials in light-sensing devices due to their high optical and electronic properties. However, the absence of a bandgap in graphene limits the realization of devices with high performance. In this work, a boron-doped reduced graphene oxide (B-rGO) is proposed to overcome the above problems. Boron doping enhances the conductivity of graphene oxide and creates several defect sites during the reduction process, which can play a vital role in achieving high-sensing performance of light-sensing devices. Initially, the B-rGO is synthesized using a modified microwave-assisted hydrothermal method and later analyzed using standard FESEM, FTIR, XPS, Raman, and XRD techniques. The content of boron in doped rGO was found to be 6.51 at.%. The B-rGO showed a tunable optical bandgap from 2.91 to 3.05 eV in the visible spectrum with an electrical conductivity of 0.816 S/cm. The optical constants obtained from UV-Vis absorption spectra suggested an enhanced surface plasmon resonance (SPR) response for B-rGO in the theoretical study, which was further verified by experimental investigations. The B-rGO with tunable bandgap and enhanced SPR could open up the solution for future high-performance optoelectronic and sensing applications.
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.
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.
In this study, the kinetics of adsorption of Pb(II) from aqueous solution onto palm shell-based activated carbon (PSAC) were investigated by employing ion selective electrode (ISE) for real-time Pb(II) and pH monitoring. Usage of ISE was very appropriate for real-time adsorption kinetics data collection as it facilitated recording of adsorption data at very specific and short time intervals as well as provided consistent kinetics data. Parameters studied were initial Pb(II) concentration and agitation speed. It was found that increases in initial Pb(II) concentration and agitation speed resulted in higher initial rate of adsorption. Pseudo first-order, pseudo second-order, Elovich, intraparticle diffusion and liquid film diffusion models were used to fit the adsorption kinetics data. It was suggested that chemisorption was the rate-controlling step for adsorption of Pb(II) onto PSAC since the adsorption kinetics data fitted both the pseudo second-order and Elovich models well.
Fibres from oil palm empty fruit bunches, generated in large quantities by palm oil mills, were processed into self-adhesive carbon grains (SACG). Untreated and KOH-treated SACG were converted without binder into green monolith prior to N2-carbonisation and CO2-activation to produce highly porous binderless carbon monolith electrodes for supercapacitor applications. Characterisation of the pore structure of the electrodes revealed a significant advantage from combining the chemical and physical activation processes. The electrochemical measurements of the supercapacitor cells fabricated using these electrodes, using cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge techniques consistently found that approximately 3h of activation time, achieved via a multi-step heating profile, produced electrodes with a high surface area of 1704m(2)g(-1) and a total pore volume of 0.889cm(3)g(-1), corresponding to high values for the specific capacitance, specific energy and specific power of 150Fg(-1), 4.297Whkg(-1) and 173Wkg(-1), respectively.
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.
Vibrio parahaemolyticus (V. parahaemolyticus) is a common foodborne pathogen that contributes to a large proportion of public health problems globally, significantly affecting the rate of human mortality and morbidity. Conventional methods for the detection of V. parahaemolyticus such as culture-based methods, immunological assays, and molecular-based methods require complicated sample handling and are time-consuming, tedious, and costly. Recently, biosensors have proven to be a promising and comprehensive detection method with the advantages of fast detection, cost-effectiveness, and practicality. This research focuses on developing a rapid method of detecting V. parahaemolyticus with high selectivity and sensitivity using the principles of DNA hybridization. In the work, characterization of synthesized polylactic acid-stabilized gold nanoparticles (PLA-AuNPs) was achieved using X-ray Diffraction (XRD), Ultraviolet-visible Spectroscopy (UV-Vis), Transmission Electron Microscopy (TEM), Field-emission Scanning Electron Microscopy (FESEM), and Cyclic Voltammetry (CV). We also carried out further testing of stability, sensitivity, and reproducibility of the PLA-AuNPs. We found that the PLA-AuNPs formed a sound structure of stabilized nanoparticles in aqueous solution. We also observed that the sensitivity improved as a result of the smaller charge transfer resistance (Rct) value and an increase of active surface area (0.41 cm2). The development of our DNA biosensor was based on modification of a screen-printed carbon electrode (SPCE) with PLA-AuNPs and using methylene blue (MB) as the redox indicator. We assessed the immobilization and hybridization events by differential pulse voltammetry (DPV). We found that complementary, non-complementary, and mismatched oligonucleotides were specifically distinguished by the fabricated biosensor. It also showed reliably sensitive detection in cross-reactivity studies against various food-borne pathogens and in the identification of V. parahaemolyticus in fresh cockles.
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.
In the present study, Electrochemical Oxidation was used to remove COD and color from semi-aerobic landfill leachate collected from Pulau Burung Landfill Site (PBLS), Penang, Malaysia. Experiments were conducted in a batch laboratory-scale system in the presence of NaCl as electrolyte and aluminum electrodes. Central composite design (CCD) under Response surface methodology (RSM) was applied to optimize the electrochemical oxidation process conditions using chemical oxygen demand (COD) and color removals as responses, and the electrolyte concentrations, current density and reaction time as control factors. Analysis of variance (ANOVA) showed good coefficient of determination (R(2)) values of >0.98, thus ensuring satisfactory fitting of the second-order regression model with the experimental data. In un-optimized condition, maximum removals for COD (48.77%) and color (58.21%) were achieved at current density 80 mA/cm(2), electrolyte concentration 3,000 mg/L and reaction time 240 min. While after optimization at current density 75 mA/cm(2), electrolyte concentration 2,000 mg/L and reaction time 218 min a maximum of 49.33 and 59.24% removals were observed for COD and color respectively.
Nitrates in different water and wastewater streams raised concerns due to severe impacts on human and animal health. Diverse methods are reported to remove nitrate from water streams which almost fail to entirely treat nitrate, except biological denitrification which is capable of reducing inorganic nitrate compounds to harmless nitrogen gas. Review of numerous studies in biological denitrification of nitrate containing water resources, aquaculture wastewaters and industrial wastewater confirmed the potential of this method and its flexibility towards the remediation of different concentrations of nitrate. The denitrifiers could be fed with organic and inorganic substrates which have different performances and subsequent advantages or disadvantages. Review of heterotrophic and autotrophic denitrifications with different food and energy sources concluded that autotrophic denitrifiers are more effective in denitrification. Autotrophs utilize carbon dioxide and hydrogen as the source of carbon substrate and electron donors, respectively. The application of this method in bio-electro reactors (BERs) has many advantages and is promising. However, this method is not so well established and documented. BERs provide proper environment for simultaneous hydrogen production on cathodes and appropriate consumption by immobilized autotrophs on these cathodes. This survey covers various designs and aspects of BERs and their performances.
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 toxicity electrochemical DNA biosensor has been constructed for the detection of carcinogens using 24 base guanine DNA rich single stranded DNA, and methylene blue (MB) as the electroactive indicator. This amine terminated ssDNA was immobilized onto silica nanospheres and deposited on gold nanoparticle modified carbon-paste screen printed electrodes (SPEs). The modified SPE was initially exposed to a carcinogen, followed by immersion in methylene blue for an optimized duration. The biosensor response was measured using differential pulse voltammetry. The performance of the biosensor was identified on several anti-cancer compounds. The toxicity DNA biosensor demonstrated a linear response range to the cadmium chloride from 0.0005 ppm to 0.01 ppm (R2 = 0.928) with a limit of detection at 0.0004 ppm. The biosensor also exhibited its versatility to screen the carcinogenicity of potential anti-cancer compounds.
With the expanded use of the combination of artesunate (AS) and amodiaquine (AQ) for the treatment of falciparum malaria and the abundance of products on the market, comes the need for rapid and reliable bioanalytical methods for the determination of the parent compounds and their metabolites. While the existing methods were developed for the determination of either AS or AQ in biological fluids, the current validated method allows simultaneous extraction and determination of AS and AQ in human plasma. Extraction is carried out on Supelclean LC-18 extraction cartridges where AS, its metabolite dihydroartemisinin (DHA) and the internal standard artemisinin (QHS) are separated from AQ, its metabolite desethylamodiaquine (DeAQ) and the internal standard, an isobutyl analogue of desethylamodiaquine (IB-DeAQ). AS, DHA and QHS are then analysed using Hypersil C4 column with acetonitrile-acetic acid (0.05M adjusted to pH 5.2 with 1.00M NaOH) (42:58, v/v) as mobile phase at flow rate 1.50ml/min. The analytes are detected with an electrochemical detector operating in the reductive mode. Chromatography of AQ, DeAQ and IB-DeAQ is carried out on an Inertsil C4 column with acetonitrile-KH(2)PO(4) (pH 4.0, 0.05M) (11:89, v/v) as mobile phase at flow rate 1.00ml/min. The analytes are detected by an electrochemical detector operating in the oxidative mode. The recoveries of AS, DHA, AQ and DeAQ vary between 79.1% and 104.0% over the concentration range of 50-1400ng/ml plasma. The accuracies of the determination of all the analytes are 96.8-103.9%, while the variation for within-day and day-to-day analysis are <15%. The lower limit of quantification for all the analytes is 20ng/ml and limit of detection is 8ng/ml. The method is sensitive, selective, accurate, reproducible and suited particularly for pharmacokinetic study of AS-AQ drug combination and can also be used to compare the bioavailability of different formulations, including a fixed-dose AS-AQ co-formulation.