Enhancing Aqueous Chlorate Reduction Using Vanadium Redox Cycles and pH Control.

Chlorate (ClO3-) is a toxic oxyanion pollutant from industrial wastes, agricultural applications, drinking water disinfection, and wastewater treatment. Catalytic reduction of ClO3- using palladium (Pd) nanoparticle catalysts exhibited sluggish kinetics. This work demonstrates an 18-fold activity enhancement by integrating earth-abundant vanadium (V) into the common Pd/C catalyst. X-ray photoelectron spectroscopy and electrochemical studies indicated that VV and VIV precursors are reduced to VIII in the aqueous phase (rather than immobilized on the carbon support) by Pd-activated H2. The VIII/IV redox cycle is the predominant mechanism for the ClO3- reduction. Further reduction of chlorine intermediates to Cl- could proceed via VIII/IV and VIV/V redox cycles or direct reduction by Pd/C. To capture the potentially toxic V metal from the treated solution, we adjusted the pH from 3 to 8 after the reaction, which completely immobilized VIII onto Pd/C for catalyst recycling. The enhanced performance of reductive catalysis using a Group 5 metal adds to the diversity of transition metals (e.g., Cr, Mo, Re, Fe, and Ru in Groups 6-8) for water pollutant treatment via various unique mechanisms.

Magnetite interaction with arsenic during sorptive removal from groundwater: a mechanistic study.

A magnetic mixed iron oxide, magnetite (Fe3O4), was synthesized in the laboratory and characterized before its use as sorbent for arsenic removal. The characterization techniques used were X-ray diffraction (XRD), specific surface area, zeta potential and particle size measurements. The sorbent was applied for arsenic removal, without any pre or post treatment, from groundwater. The efficiency of sorption can only be improved by understanding the sorbent-sorbate interaction. For onsite monitoring of the sorbent-sorbate interaction, an electrochemical investigation using cyclic voltammetry (CV) measurement was developed. The study confirmed that the sorption of As(III) on Fe3O4 is dynamic (reversible) whereas that of As(V) is static (irreversible) in nature. Detailed investigation after the sorption was carried out utilizing X-ray photoelectron spectroscopy (XPS) measurement. The complexation of As(III)-Fe3O4 and As(V)-Fe3O4 without any redox transformation was evident from the XPS data. By careful examination of the results, a mechanism of arsenic removal by Fe3O4 was proposed.

Electrochemical Study of Semiconductor Properties for Bismuth Silicate-Based Photocatalysts Obtained via Hydro-/Solvothermal Approach.

Three bismuth silicate-based photocatalysts (composites of Bi2SiO5 and Bi12SiO20) prepared via the hydro-/solvothermal approach were studied using electrochemical methods. The characteristic parameters of semiconductors, such as flat band potential, donor density, and mobility of their charge carriers, were obtained and compared with the materials' photocatalytic activity. An attempt was made to study the effect of solution components on the semiconductor/liquid interface (SLI). In particular, the Mott-Schottky characterization was made in a common model electrolyte (Na2SO4) and with the addition of glycerol as a model organic compound for photocatalysis. Thus, a medium close to those in photocatalytic experiments was simulated, at least within the limits allowed by electrochemical measurements. Zeta-potential measurements and electrochemical impedance spectroscopy were used to reveal the processes taking place at the SLI. It was found that the medium in which measurements were carried out dramatically impacted the results. The flat band potential values (Efb) obtained via the Mott-Schottky technique were shown to differ significantly depending on the solution used in the experiment, which is explained by different processes taking place at the SLI. A strong influence of specific adsorption of commonly used sulfate ions and neutral molecules on the measured values of Efb was shown.

Exploring the Functional Properties of Sodium Phytate Doped Polyaniline Nanofibers Modified FTO Electrodes for High-Performance Binder Free Symmetric Supercapacitors.

The performance of high-rate supercapacitors requires fine morphological and electrical properties of the electrode. Polyaniline (PANI), as one of the most promising materials for energy storage, shows different behaviour on different substrates. The present study reports on the surface modification of fluorine doped tin oxide (FTO) with the sodium phytate doped PANI without any binder and its utilization as a novel current collector in symmetric supercapacitor devices. The electrochemical behaviour of the sodium phytate doped PANI thin film with and without a binder on fluorine doped tin oxide (FTO) as current collector was investigated by cyclic voltammetry (CV). The electrode without a binder showed higher electrocatalytic efficiency. A symmetrical cell configuration was therefore constructed with the binder-free electrodes. The device showed excellent electrochemical performance with high specific capacities of 550 Fg-1 at 1 Ag-1 and 355 Fg-1 at 40 Ag-1 calculated from galvanostatic discharge curves. The low charge transfer and solution resistances (RCT and RS) of 7.86 Ωcm² and 3.58 × 10-1 Ωcm², respectively, and superior rate capability of 66.9% over a wide current density range of 1 Ag-1 to 40 Ag-1 and excellent cycling stability with 90% of the original capacity over 1000 charge/discharge cycles at 40 Ag-1, indicated it to be an efficient energy storage device. Moreover, the gravimetric energy and power density of the supercapacitor was remarkably high, providing 73.8 Whkg-1 at 500 Wkg-1, respectively. The gravimetric energy density remained stable as the power density increased. It even reached up to 49.4 Whkg-1 at a power density of up to 20 Wkg-1.

Au-modified organic/inorganic MWCNT/Cu/PANI hybrid nanocomposite electrode for electrochemical determination of nitrate ions.

A new electrochemical sensor is reported for the based on the application of noble bimetal nanoparticles (gold and copper) to polymeric-carbon-modifiers for the reduction of nitrate. This sensor was designed for nitrate ion measurement at the surface of pencil graphite electrode modified by a nanocomposite. The modification was the electrosynthesis of gold nanoparticles on the MWCNT/copper-polyaniline (Cu-PANI) nanocomposite. Physicochemical properties of the synthesized hybrid nanocomposites and their surface performance efficiency are characterized using microscopic, spectroscopic, and electrochemical techniques. At optimized pH, the nitrate peak current (at working potential of 1084 mV versus Ag/AgCl reference electrode) was linear in the concentration range 0.8-30.0 µM with a detection limit of 0.09 µM using differential pulse voltammetry. Modified sensor was successfully implemented to quantify nitrate ions in wastewater resulting from the production line for industrial barium chromate and an example of aqueduct water with appropriate recovery levels. • Aniline was polymerized in phosphoric acid solution using peroxydisulfate as an initiator. • MWCNT@CuNPs@PANNSs@AuNPs nanocomposite on PGE electrode was revealed specific recognition for NO3-. • The electrochemical sensor displayed high selectivity and sensitivity for the detection of NO3-.

Effect of the Thickness of TiO2 Films on the Structure and Corrosion Behavior of Mg-based Alloys.

This article discusses the influence of the thickness of TiO2 films deposited onto MgCa2Zn1 and MgCa2Zn1Gd3 alloys on their structure, corrosion behavior, and cytotoxicity. TiO2 layers (about 200 and 400 nm thick) were applied using magnetron sputtering, which provides strong substrate adhesion. Such titanium dioxide films have many attractive properties, such as high corrosion resistance and biocompatibility. These oxide coatings stimulate osteoblast adhesion and proliferation compared to alloys without the protective films. Microscopic observations show that the TiO2 surface morphology is homogeneous, the grains have a spherical shape (with dimensions from 18 to 160 nm). Based on XRD analysis, it can be stated that all the studied TiO2 layers have an anatase structure. The results of electrochemical and immersion studies, performed in Ringer's solution at 37 °C, show that the corrosion resistance of the studied TiO2 does not always increase proportionally with the thickness of the films. This is a result of grain refinement and differences in the density of the titanium dioxide films applied using the physical vapor deposition (PVD) technique. The results of 24 h immersion tests indicate that the lowest volume of evolved H2 (5.92 mL/cm2) was with the 400 nm thick film deposited onto the MgCa2Zn1Gd3 alloy. This result is in agreement with the good biocompatibility of this TiO2 film, confirmed by cytotoxicity tests.

High carbon iron filings (HCIF) and metal reducing bacteria (Serratia sp.) co-assisted Cr (VI) reduction: Kinetics, mechanism and longevity.

Permeable reactive barriers (PRBs) have been an area of interest for in-situ remediation of groundwater. However, the corrosion of iron used in PRBs has been an area of concern. This study was aimed to enhance the long term performance for reduction of Cr (VI) by high carbon iron filings (HCIF) co-assisted with Serratia sp. Cr (VI) reduction by HCIF alone followed pseudo-first order kinetics and the reaction rate was 0.382 h-1 for 50 mg/L of Cr (VI) which declined to 0.0017 mg-1 L h-1 in combined system. But in cyclic studies, the reduction of Cr (VI) with HCIF alone system declined to 70% after 2 cycles whereas more than 90% reduction was observed in combined system up to four cycles. The corrosion potential and XRD data supported that Serratia sp. have positive effect on longevity of HCIF for Cr (VI) reduction.

Synthesis of a novel Au nanoparticles decorated Ni-MOF/Ni/NiO nanocomposite and electrocatalytic performance for the detection of glucose in human serum.

A nonenzymatic glucose electrochemical sensor was constructed based on Au nanoparticles (AuNPs) decorated Ni metal-organic-framework (MOF)/Ni/NiO nanocomposite. Ni-MOF/Ni/NiO nanocomposite was synthesized by one-step calcination of Ni-MOF. Then AuNPs were loaded onto the Ni-based nanocomposites' surface through electrostatic adsorption. Through characterization by transmission electron microscopy (TEM), high resolution TEM (HRTEM) and energy disperse spectroscopy (EDS) mapping, it is found that the AuNPs were well distributed on the surface of Ni-based nanocomposite. Cyclic voltammetric (CV) study showed the electrocatalytic activity of Au-Ni nanocomposite was highly improved after loading AuNPs onto it. Amperometric study demonstrated that the Au-Ni nanocomposites modified glassy carbon electrode (GCE) exhibited a high sensitivity of 2133.5 mA M-1 cm-2 and a wide linear range (0.4-900 µM) toward the oxidation of glucose with a detection limit as low as 0.1 µM. Moreover, the reproducibility, selectivity and stability of the sensor all exhibited outstanding performance. We applied the as-fabricated high performance sensor to measure the glucose levels in human serum and obtained satisfactory results. It is believed that AuNPs decorated Ni MOF/Ni/NiO nanocomposite provides a new platform for developing highly performance electrochemical sensors in practical applications.

Facile synthesis of ZnFe2O4 photocatalysts for decolourization of organic dyes under solar irradiation.

ZnFe2O4 was fabricated by a simple solution-combustion method. The structural, optical and electronic properties are investigated by XRD, TEM, FESEM, UV-vis DRS, PL, FTIR and photocurrent measurements. The photocatalytic activity of the prepared material is studied with regard to the degradation of rhodamine B (Rh B) and Congo red under solar irradiation. The kinetic study showed that the material exhibits zeroth and first order reaction kinetics for the degradation of Rh B and Congo red, respectively. The photocatalytic behaviour of ZnFe2O4 was systematically studied as a function of the activation temperature. ZnFe2O4 prepared at 500 °C showed the highest activity in degrading Rh B and Congo red. The highest activity of ZnFe2O4-500 °C correlates well with the lowest PL intensity, highest photocurrent and lowest particle size.

Hydrazinylpyridine based highly selective optical sensor for aqueous source of carbonate ions: Electrochemical and DFT studies.

A series of new receptors PDZ1-3 based on 2-(arylidenehydrazinyl)pyridines have been designed and synthesized for the detection of biologically and environmentally important ions. The colorimetric detection of CO32- using neutral organic receptor PDZ-1 has been achieved with characteristic visual colour change from yellow to green accompanied by a large redshift of 215nm in absorption maxima. UV-Vis spectroscopic and cyclic voltammetric studies reveal the stoichiometry of binding and electrochemistry of host-guest complex formation. The binding constant was found to be 0.77×104M-2. In addition, electrochemical studies provide an insight into the stability of the complex. DFT studies performed on the PDZ-1 and PDZ-1-CO32- complex reveal the binding mechanism involved in the anion detection process. PDZ-1 is highly selective for carbonate and does not show any colorimetric response towards any other anions or cations, while PDZ-2 and PDZ-3 remain inactive in the ion detection process. The limit of detection (LOD) and limit of quantification (LOQ) of PDZ-1 for carbonate was found to be 0.11mM and 0.36mM respectively. Considerable binding constant and limit of detection make PDZ-1 to be used as a real time sensor for the detection of carbonate in environmental and biological samples.

Electrochemical evaluation of troponin T imprinted polymer receptor.

The selective detection and quantification of macromolecular targets is a fundamental biological mechanism in nature. Molecularly imprinted polymers (MIPs) have been identified as one of the most promising synthetic alternatives to bioreceptors. However, expanding this methodology towards selective recognition of bulky templates such as proteins appears to be extremely challenging due to problems associated with removal of the template from the polymeric network. In this study, polymer imprinted with troponin T (TnT) was assessed using electrochemical methods and the influence of various extraction methods, including conventional immersion extraction, thermal annealing and ultrasonic-assisted extraction, on the binding characteristics of the troponin-to-imprinted polymer receptor was elucidated. Cyclic voltammetric deposition of o-phenylenediamine (o-PD) film in the presence of TnT as a template was performed in acetate buffer (0.5 M, pH 5.2) on a gold substrate. Solvent extraction of the target molecule was optimised and followed by subsequent washing with water. The electrochemistry of a ferro/ferricyanide probe was used to characterise the TnT MIP receptor film. The incubation of the TnT MIP receptor-modified electrode with respect to TnT concentration resulted in a suppression of the ferro/ferricyanide redox current. The dissociation constant (KD) was calculated using a two-site model of template affinity for the TnT MIP receptor. The synthetic TnT MIP receptor had high affinity for TnT with a KD of 2.3×10(-13) M.

Effect of immediate and delayed post space preparation on the apical seal of root canals obturated with different sealers and techniques

During mechanical preparation of the post space, the root canal filling may be twisted or vibrated, depending on several factors associated with the preparation technique and quality of filling. OBJECTIVE: The purpose of this study was to investigate the effect of immediate and delayed post space preparation on the integrity of the apical seal. MATERIAL AND METHODS: Sixty-four extracted human incisors were biomechanically prepared using the step-back technique. Sixty roots were randomly assigned to 6 experimental groups of 10 teeth each and the remaining 4 roots served as positive and negative controls (n=2). The root canals in the different groups were obturated with cold lateral and warm vertical condensation of gutta-percha and one of two sealers (Sealapex and Diaket). Post space was prepared either individually or simultaneously. An insulated copper wire was cut into 10-cm-long pieces. In each canal, one piece was inserted to maintain contact with gutta-percha and extended to the outside as one of two working electrodes. A stainless steel wire with the same dimensions of those of the copper wire, used as the other working electrode, was immersed into the background electrolyte from the center of the bottle. The electrical current between standard and experimental electrodes in canals was measured over a period of 10 days applying a conductivity meter. The Kruskal-Wallis test (p=0.05) determined whether there was a significant difference in microleakage among the groups and the Mann-Whitney U test (p=0.01) was used for multiple comparison grouping variables. RESULTS: The results suggest that only the differences between the root canal filling techniques were statistically significant (p<0.01). There were no statistically significant difference in the sealers and the times of filling removal for post space preparation (p>0.01). CONCLUSION: The quality of the root canal filling is important for the integrity of the apical seal.

An electrochemical study of the sealing ability of three retrofilling materials / 대한치과보존학회지

The purpose of this study was to evaluate the apical sealing ability of Super-EBA, MTA and Dyract-flow as retrofilling materials. Forty-eight extracted human teeth with straight and single root canal were used in this study. The root canals were prepared to a #40 apical canal size and obturated with gutter-percha. Apicoectomies were performed and root end cavities were prepared to a depth of 3mm using an ultrasonic device. The root end cavities were filled with Super-EBA, MTA or Dyract-flow. Leakage was measured using an electrochemical technique for 4 weeks. According to this study, the results were as follows. 1. Increasing leakage with time was observed in all groups. 2. No significant difference was noted among the 3 groups with time (p = 0.216). 3. No significant difference was noted among the 3 groups when measured within the same time interval (p = 0.814). The results of this study suggest that the sealing ability of Dyract-flow is equal to that of Super-EBA and MTA, and Dyract-flow may be an alternative to other materials for root-end filling.