Modulating temperature for Cu2ZnSnS4 (CZTS) synthesis via hot injection method and studying the photocatalytic efficiencies for the degradation of rhodamine 6G and methylene blue pollutants.

Cu2ZnSnS4 (CZTS) was synthesized following hot injection method and the process was optimized by varying temperature conditions. Four samples at different temperatures viz., 200, 250, 300 and 350 °C were prepared and analyzed using different characterization techniques. Based on the correlation between XRD, Raman and XPS, we conclude that the formation of ZnS and SnS2 occurs at 350 °C but at 200 °C there is no breakdown of the complex as per XRD. According to Raman and XPS analysis, as the temperature rises, the bonds between the metals become weaker, which is visibly seen in Raman and XPS due to the minor peaks of copper sulfide. Scanning electron microscopic analysis confirmed nanometric particles which increase in size with temperature. The photocatalytic evaluation showed that CZTS synthesized at 200 °C performed efficiently in the removal of the two colorants, methylene blue and Rhodamine 6G, achieving 92.80% and 90.65%, respectively. The photocatalytic degradation efficiencies decreased at higher temperatures due to bigger sized CZTS particles as confirmed by SEM results. Computational simulations confirm that CZTS has a highly negative energy -25,764 Ry, confirming its structural stability and higher covalent than ionic character.

Mesostructured lead dioxide grown on titania nanotubes for diclofenac water removal through electrocatalytic and photoelectrocatalytic processes.

Mesostructured PbO2/TiO2 materials were synthesized to perform electrocatalysis (as electrooxidation, EO) and photoelectrocatalysis for removing diclofenac (DCF), 15 ppm concentration in 0.1 M NaSO4 solutions, at different pH conditions (3.0, 6.0 and 9.0) by applying 30 mA cm-2. Titania nanotubes (TiO2NTs)-based materials were prepared to synthetize with a massive PbO2 deposit on this support to obtain TiO2NTs/PbO2 and a TiO2NTs:PbO2 material consisting in a dispersed PbO2 deposit on TiO2-NTs that allowed the formation of a heterostructured surface of combined composition (TiO2 and PbO2). Organics removal (DCF and byproducts) was monitored through UV-vis spectrophotometry and high-performance liquid chromatography (HPLC) during degradation tests. TiO2NTs/PbO2 electrode was tested in both processes, removing DCF at neutral and alkaline solution conditions in EO while an unimportant photoactivity was registered at this material. Conversely, TiO2NTs:PbO2 was used as electrocatalytic material in EO experiments, achieving more than 50% of DCF removal at pH 6.0 by applying 30 mA cm-2. Also, for first time, the synergic effect was investigated when it was exposed to UV irradiation in photoelectrocatalytic experiments, enhancing its efficacy (⁓more than 20%) to remove DCF from a solution with 15 ppm over performance removals achieved (56%) when EO was applied under similar conditions. Chemical Oxygen Demand (COD) analyses showed that significantly higher DCF degradation is reached under photoelectrocatalysis, since COD values decrease a 76% against a 42% decrease achieved with electrocatalysis. Scavenging experiments showed a significant participation on the pharmaceutical oxidation process through the generation of photoholes (h+), hydroxyl radicals and sulfate-based oxidants.

Real-Time Detection of Hydroxyl Radical Generated at Operating Electrodes via Redox-Active Adduct Formation Using Scanning Electrochemical Microscopy.

The hydroxyl radical (•OH) is one of the most attractive reactive oxygen species due to its high oxidation power and its clean (photo)(electro)generation from water, leaving no residues and creating new prospects for efficient wastewater treatment and electrosynthesis. Unfortunately, in situ detection of •OH is challenging due to its short lifetime (few ns). Using lifetime-extending spin traps, such as 5,5-dimethyl-1-pyrroline N-oxide (DMPO) to generate the [DMPO-OH]• adduct in combination with electron spin resonance (ESR), allows unambiguous determination of its presence in solution. However, this method is cumbersome and lacks the necessary sensitivity and versatility to explore and quantify •OH generation dynamics at electrode surfaces in real time. Here, we identify that [DMPO-OH]• is redox-active with E0 = 0.85 V vs Ag|AgCl and can be conveniently detected on Au and C ultramicroelectrodes. Using scanning electrochemical microscopy (SECM), a four-electrode technique capable of collecting the freshly generated [DMPO-OH]• from near the electrode surface, we detected its generation in real time from operating electrodes. We also generated images of [DMPO-OH]• production and estimated and compared its generation efficiency at various electrodes (boron-doped diamond, tin oxide, titanium foil, glassy carbon, platinum, and lead oxide). Density functional calculations, ESR measurements, and bulk calibration using the Fenton reaction helped us unambiguously identify [DMPO-OH]• as the source of redox activity. We hope these findings will encourage the rapid, inexpensive, and quantitative detection of •OH for conducting informed explorations of its role in mediated oxidation processes at electrode surfaces for energy, environmental, and synthetic applications.

Electrochemically assisted dewatering for the removal of oxyfluorfen from a coagulation/flocculation sludge.

This work focuses on the evaluation of the electrochemical dewatering of sludge obtained in the coagulation of wastes polluted with oxyfluorfen. To do this, sludge samples were treated, aiming not only to reduce the sludge volume, but also to facilitate the degradation of oxyfluorfen contained in the cake via electrolysis with a boron-doped diamond anode. Results show that water can be effectively recovered through three sequential stages. First, a gravity-driven stage, that can recover around 60% of initial volume and where no oxyfluorfen is dragged. Then, a second stage that involves the application of pressure and which accounts for the recuperation of an additional 25% of the total volume of the water removed and in which oxyfluorfen also remained in the cake. Finally, an electrochemical stage, which involves the application of electricity with increasing electric fields (1.0, 2.0, 4.0, and 16.0 V cm-1), accounting for the recovery of the rest of water released and where an electrolytic degradation of oxyfluorfen is obtained, whose extension depends on the electrode configuration used in the electro-dewatering cell. This electrode configuration also influences the retention or loss of oxyfluorfen from the cake, being the optimum choice the placement of the cathode downstream, next to the outlet of the dewatering cell.

Electrokinetic - Enhanced ryegrass cultures in soils polluted with organic and inorganic compounds.

The effect of electric fields on seed germination and development of ryegrass (Lolium perenne L.) was studied in clean and contaminated soil with heavy metals and/or PAHs. The application of 0.2 DCV/cm in clean soil near ryegrass seeds enhanced the germination by 75%. The presence of contaminants in soil hindered the germination and growing of ryegrass. However, the application of DC electric field favored the germination and growing of plants compensating the negative effects of the contaminants. The electrode material in anodes has a decisive influence in the germination and growing of ryegrass. Stable anode materials have to be used to avoid the release of toxic ions in the soil that affect the development of the plant. Graphite anodes are very appropriate because they are inexpensive and does not generate toxic effects on plants. The electro-phytoremediation of mixed contaminated soil with ryegrass showed very promising results, especially AC electric fields. The tests with AC current showed the highest biomass production in a treatment of 1 month. The more biomass production the more removal of heavy metals and PAHs from soil.

Design, Synthesis, and Use of Peptides Derived from Human Papillomavirus L1 Protein for the Modification of Gold Electrode Surfaces by Self-Assembled Monolayers.

In order to obtain gold electrode surfaces modified with Human Papillomavirus L1 protein (HPV L1)-derived peptides, two sequences, SPINNTKPHEAR and YIK, were chosen. Both have been recognized by means of sera from patients infected with HPV. The molecules, Fc-Ahx-SPINNTKPHEAR, Ac-C-Ahx-(Fc)KSPINNTKPHEAR, Ac-C-Ahx-SPINNTKPHEAR(Fc)K, C-Ahx-SPINNTKPHEAR, and (YIK)2-Ahx-C, were designed, synthesized, and characterized. Our results suggest that peptides derived from the SPINNTKPHEAR sequence, containing ferrocene and cysteine residues, are not stable and not adequate for electrode surface modification. The surface of polycrystalline gold electrodes was modified with the peptides C-Ahx-SPINNTKPHEAR or (YIK)2-Ahx-C through self-assembly. The modified polycrystalline gold electrodes were characterized via infrared spectroscopy and electrochemical measurements. The thermodynamic parameters, surface coverage factor, and medium pH effect were determined for these surfaces. The results indicate that surface modification depends on the peptide sequence (length, amino acid composition, polyvalence, etc.). The influence of antipeptide antibodies on the voltammetric response of the modified electrode was evaluated by comparing results obtained with pre-immune and post-immune serum samples.

Hemodialysis Wastewater Treatment via Electrocoagulation and Electro-Oxidation: Modular Pilot-Level Modeling and Simulation.

Hemodialysis treatment in specialized clinics within the same hospital significantly impacts environmental water health due to contaminated wastewater. The issues observed included changes in electrical conductivity, the presence of dangerous bacterial loads, toxicity from heavy metals, total cyanide content, and helminth parasite eggs. The level of damage is dependent on the patient's health under treatment. This research will use a modular system that employs electrocoagulation and electro-oxidation processes at the laboratory and pilot levels to treat hemodialysis wastewater using synthetically prepared and real samples extracted from local clinics. The results showed that these hybrid systems improved various physicochemical parameters. Specifically, decreases in electrical conductivity of 49 %, total suspended solids of 27-100 %, chemical oxygen demand of 49 %, biochemical oxygen demand of 49 %, and cation and anion loading were observed at 96-100 % and pH 8.13 UpH in accordance with the established standards. With these results and the experimental conditions used, the proposed treatment system was modeled using the GPS-X program, and it was concluded that the modular system used and the electrocoagulation/electro-oxidation/activated carbon configuration is suitable for treating wastewater from hemodialysis and that scaling up this process to facilities that have dialysate machines more advanced than those considered in this work is possible.

Novel electro-fenton approach for regeneration of activated carbon.

An electro-Fenton-based method was used to promote the regeneration of granular activated carbon (GAC) previously adsorbed with toluene. Electrochemical regeneration experiments were carried out using a standard laboratory electrochemical cell with carbon paste electrodes and a batch electrochemical reactor. For each system, a comparison was made using FeSO4 as a precursor salt in solution (homogeneous system) and an Fe-loaded ion-exchange resin (Purolite C-100, heterogeneous system), both in combination with electrogenerated H2O2 at the GAC cathode. In the two cases, high regeneration efficiencies were obtained in the presence of iron using appropriate conditions of applied potential and adsorption-polarization time. Consecutive loading and regeneration cycles of GAC were performed in the reactor without great loss of the adsorption properties, only reducing the regeneration efficiency by 1% per cycle during 10 cycles of treatment. Considering that, in the proposed resin-containing process, the use of Fe salts is avoided and that GAC cathodic polarization results in efficient cleaning and regeneration of the adsorbent material, this novel electro-Fenton approach could constitute an excellent alternative for regenerating activated carbon when compared to conventional methods.

Electrochemical degradation of amoxicillin in acidic aqueous medium using TiO2-based electrodes modified by oxides of transition metals.

One of the most widely used antibiotics is amoxicillin (AMX), which is the most widely used in humans and animals, but it is discharged metabolically due to its indigestibility. Conventional biological and physicochemical methods for removing AMX from water are not enough to mineralize it; it is only concentrated and transferred to produce new residues that require further processing to remove the new residues. In this research, naked and modified surfaces with TiO2 nanotubes (TiO2,nt) electrophoretically modified with PbO2, IrO2, RuO2, and Ta2O5 were used to evaluate their efficiency in the electrochemical degradation of AMX in acid media (0.1 mol L-1 H2SO4). After their comparison, Pb-Ta 50:50|TiO2,nt|Ti showed the highest removal efficiency of AMX (44.71%) with the lowest specific energy consumption (8.69 ± 0.78 kWh Kg COD-1) and the average instant current efficiency of 26.67 ± 9.19%, in comparison with the others naked and modified surfaces of TiO2,nt∣Ti.

Bauhinia forficata Link, Antioxidant, Genoprotective, and Hypoglycemic Activity in a Murine Model.

Bauhinia forficata L. is a tree used in alternative medicine as an anti-diabetic agent, with little scientific information about its pharmacological properties. The hypoglycemic, antioxidant, and genoprotective activities of a methanolic extract of B. forficata leaves and stems combined were investigated in mice treated with streptozotocin (STZ). Secondary metabolites were determined by qualitative phytochemistry. In vitro antioxidant activity was determined by the DPPH method at four concentrations of the extract. The genoprotective activity was evaluated in 3 groups of mice: control, anthracene (10 mg/kg), and anthracene + B. forficata (500 mg/kg) and the presence of micronuclei in peripheral blood was measured for 2 weeks. To determine the hypoglycemic activity, the crude extract was prepared in a suspension and administered (500 mg/kg, i.g.) in previously diabetic mice with STZ (120 mg/kg, i.p.), measuring blood glucose levels every week as well as the animals' body weight for six weeks. The extract showed good antioxidant activity and caused a decrease in the number of micronuclei. The diabetic mice + B. forficata presented hypoglycemic effects in the third week of treatment, perhaps due to its secondary metabolites. Therefore, B. forficata is a candidate for continued use at the ethnomedical level as an adjuvant to allopathic therapy.

Valorization of high-salinity effluents for CO2 fixation and hypochlorite generation.

In this work, it is evaluated the fixation of carbon dioxide using the alkali generated in the chloralkaline process, as a new way to face the treatment of highly saline wastewater, in which it is aimed not to separate the wastewater into concentrated and diluted streams but to recover value-added products (VAPs) while contributing to minimize the carbon fingerprint of other processes. The electrolytic process is combined with a reactive absorption and with a crystallization, demonstrating the formation of pure nahcolite, hypochlorite (or chlorine) and hydrogen from the waste. Carbon dioxide is captured with a current efficiency over 90% and the energy required is around 0.65 kWh kg-1, which is very promising from the view point of sustainability, considering that the system can be easily powered with green energies.

Electrochemical detector based on a modified graphite electrode with phthalocyanine for the elemental analysis of actinides.

The quantification of actinides in aqueous solutions involves complex and expensive separation processes. Electrochemical methods have been widely used for the quick and accurate identification and quantification of organic and inorganic compounds directly or indirectly. Therefore, this work proposes the use of modified graphite with phthalocyanine for electrochemical detection and quantification of Th, U, Pu, Am, and Cm, in aqueous media by cyclic voltammetry. The electrodes were characterized by Raman and infrared spectroscopy, and the cyclic voltammetry data were modeled with Aoki's model. The detection limits (DL) and the quantification limits (QL) reached by the electrochemical detection of these actinides were of the order of ppt. Aoki's model fitted perfectly with the experimental data. The functionalization of graphite electrodes promotes the formation of phthalic anhydride, and the phthalocyanine is anchored on the epoxy groups of the graphite. The electrochemical detection process of these actinides is indirect. This electrochemical detector is cheap and disposable and can be an alternative for an initial characterization of actinides in liquid waste.

Decontamination of radioactive metal surfaces by electrocoagulation.

The decontamination of noncompactable radioactive wastes, such as tools and equipment, aims to reduce the waste volume to be conditioned and stored. The electrocoagulation (EC) application in the decontamination of noncompactable radioactive waste from stainless steel containing uranium, was studied to evaluate its technical viability. The first studies were carried out with stainless steel plates coated with WO3 to simulate a fixed contamination and to determine the best tungsten removal conditions via EC considering pH, electrolyte support, distance between the electrodes, cell potential and counter-electrode material. The best removal conditions for WO3 were applied to plates contaminated with UO2(NO3)2 to evaluate the viability of the EC decontamination process. Uranium removal efficiencies of 90% were obtained in 1 h, at pH of 1, 2.4 V and 1 cm of distance between anode / cathode in a circular array. The EC process, under the previously obtained conditions, was applied to two metallic pieces contaminated with U. It proved feasible to decontaminate metallic pieces through the EC process, thus being able to obtain up to 90% U removal efficiency; however, it is important that the surfaces of the parts are free of grease and dust.

Analysis of the biological recovery of soils contaminated with hydrocarbons using an electrokinetic treatment.

There are various treatments available for soil decontamination, including physical, chemical, thermal and biological treatments. However, when pollutants are persistent or toxic, it is often necessary to use an integrated set of techniques, to enhance decontamination effects. Integrated treatments typically include soil washing, heat treatment, stabilization processes or phytoremediation. The biological recovery of soils contaminated with hydrocarbons or heavy metals is a topic of central interest, since many treatment processes are often extremely aggressive and destroy the flora and microflora of the treated environments and can interfere with the natural properties of the soil. The objective of this work was to analyze the biological recovery of soils treated with an electrokinetic remediation (ER) method at laboratory, pilot and field-scale tests which measure the germination of seeds and growth of maize (Zea mays L.) using a 2D circular arrangement of electrodes (IrO2-Ta2O5 |Ti| |Ti). The hydrocarbon removal rates obtained were greater than 80% for both the hydrocarbon's medium and heavy fractions; after this ER method was employed a phytoremediation treatment was also completed, using maize, which increased the removal rates up to 90%. A coupled electro- and phyto-remediation process was develop at the field-scale within an oil refinery property in Guanajuato, Mexico to demonstrate the successful biological recovery of soils contaminated with hydrocarbons as proved by the germination of seeds and growth of maize in the on-site fields.

Preparation of IrO2-Ta2O5|Ti electrodes by immersion, painting and electrophoretic deposition for the electrochemical removal of hydrocarbons from water.

After intense years of great development, the electrochemical technologies have become very suitable alternatives in niche markets like industrial wastewater reclamation and soil remediation. A key role to achieve a high efficiency in such treatments is played by the characteristics of the coating of the electrodes employed. This paper compares three techniques, namely immersion, painting and electrophoresis, for the preparation of IrO2-Ta2O5ǀTi, so-called dimensionally stable anodes (DSA(®)). The quality of the coatings has been investigated by means of surface and electrochemical analysis. Their ability to generate hydroxyl radicals and degrade aqueous solutions of hydrocarbons like phenanthrene, naphthalene and fluoranthene has been thoroughly assessed. Among the synthesis techniques, electrophoretic deposition yielded the best results, with DSA(®) electrodes exhibiting a homogeneous surface coverage that led to a good distribution of active sites, thus producing hydroxyl radicals that were able to accelerate the degradation of hydrocarbons.

Preparation, characterization and photoelectrochemical study of mixed C60-Starburst PAMAM G0.0 dendrimer films anchored on the surface of nanocrystalline TiO2 semiconductor electrodes.

Nanocrystalline TiO2 silanized electrodes were prepared and further modified in a sequential fashion with C60 and Starburst PAMAM G0.0 dendrimers, resulting in a novel photoelectrochemical sensitization film that showed particularly high photocurrent (IPCE) and global photoconversion efficiencies (eta).

Design, self-assembly, and photophysical properties of pentameric metallomacrocycles: [M5(N-hexyl[1,2-bis(2,2':6',2''-terpyridin-4-yl)]carbazole)5][M = Fe(II), Ru(II), and Zn(II)].

A novel family of metallopentacycles was constructed by the facile self-assembly of a bis(terpyridine)-carbazole monomer utilizing terpyridine-metal(II)-terpyridine connectivity; its photophysical properties were investigated.

Chemically pretreating slaughterhouse solid waste to increase the efficiency of anaerobic digestion.

The combined effect of temperature and pretreatment of the substrate on the anaerobic treatment of the organic fraction of slaughterhouse solid waste was studied. The goal of the study was to evaluate the effect of pretreating the waste on the efficiency of anaerobic digestion. The effect was analyzed at two temperature ranges (the psychrophilic and the mesophilic ranges), in order to evaluate the effect of temperature on the performance of the anaerobic digestion process for this residue. The experiments were performed in 6 L batch reactors for 30 days. Two temperature ranges were studied: the psychrophilic range (at room temperature, 18°C average) and the mesophilic range (at 37°C). The waste was pretreated with NaOH before the anaerobic treatment. The result of pretreating with NaOH was a 194% increase in the soluble chemical oxygen demand (COD) with a dose of 0.6 g NaOH per g of volatile suspended solids (VSS). In addition, the soluble chemical oxygen demand/total chemical oxygen demand ratio (sCOD/tCOD) increased from 0.31 to 0.7. For the anaerobic treatment, better results were observed in the mesophilic range, achieving 70.7%, 47% and 47.2% removal efficiencies for tCOD, total solids (TS), and volatile solids (VS), respectively.

Glassy carbon electrodes modified with composites of starburst-PAMAM dendrimers containing metal nanoparticles for amperometric detection of dopamine in urine.

Composites of hydroxyl-terminated PAMAM dendrimers, generation 4.0 (64 peripheral OH groups) containing either Ir, Pt or Rh nanoparticles were synthesized and characterized in solution. Each one of these composites was then immobilized on a glassy carbon electrode (GC) and incorporated as an amperometric detector for dopamine in a high-performance liquid chromatograph (HPLC). Comparison of the analytical performance of the novel electrochemical detectors with a typical UV-vis optical detector for dopamine revealed that the sensitivity of the GC electrode modified with dendrimer-Rh composite is comparable to that of the spectroscopic detector, with a detection limit of 0.15muM, and is linear up to at least 1.0mM (R(2)=0.998). Furthermore, it was found that the electroanalytical approach suffers minimal matrix effects that arise in the analysis of dopamine in samples of urine.