Photocatalyzed hydrodecarboxylation of fatty acids: a prospective method to produce drop-in biofuels.

A direct and practical method for photocatalyzed hydrodecarboxylation of fatty acids is reported herein. The catalytic system consists of a commercially available acridinium salt as the photocatalyst and thiophenol as the Hydrogen Atom Transfer (HAT) co-catalyst. Results evidenced that Cn-1 alkanes were obtained in yields up to 77%. Furthermore, the protocol was employed for a complex mixture of fatty acids bio-derived from a real sample of licuri oil to obtain hydrocarbons in the range of C9-C17 with high selectivity and excellent conversion (>90%). This work provides a powerful strategy for producing drop-in biofuels under mild conditions. Finally, an energetic assessment of our proposed protocol (∼22.9 kW h) reveals the benefit of a sustainable production of renewable hydrocarbons.

Ketorolac removal through photoelectrocatalysis using TiO2 nanotubes in water system.

Ketorolac, a highly persistent NSAID of environmental concern, was significantly removed from water (80% removal) through photoelectrocatalysis where titanium dioxide nanotubes prepared by Ti foil electrochemical anodization at 30 V were used as photoanodes. Fifteen milligrams per liter of ketorolac solutions in a 0.05 M Na2SO4 aqueous medium was subjected to irradiation from a 365-nm light with an intensity of 1 mWcm-2 and under an applied potential of 1.3 V (vs. Hg/Hg2SO4/sat.K2SO4) at pH 6.0. When each process (photo and electrocatalysis) was carried out separately, less than 20% drug removal was achieved as monitored through UV-vis spectrophotometry. Through scavenging experiments, direct oxidation on the photogenerated holes and oxidation by hydroxyl radical formation were found to play a key role on ketorolac's degradation. Chemical oxygen demand (COD) analyses also showed a significant COD decreased (68%) since the initial COD value was 31.3 mg O2/L and the final COD value was 10.1 mg O2/L. A 48% mineralization was also achieved, as shown by total organic carbon (TOC) analyses. These results showed that electrodes based on titania nanotubes are a promising alternative material for simultaneous photocatalytic and electrocatalytic processes in water remediation.

Development of recycled and miniaturized electroanalytical sensor: Probing isoniazid determination in environmental water matrices.

Surface water pollution has become relevant because growing population and intense industrial activities. Thus, to protect the environment from contamination, recently the electroanalytical sensors that require small sample volume and easy preparation have shown a prominent performance for pharmaceuticals monitoring. For this purpose, a miniaturized electrochemical platform was developed based on recycling obsolete computer integrated circuits (microchips), fitting with the ideals of green chemistry and circular economy. The gold microelectrodes array (Au-µEA) was easily exposed by polishing the device surface and then characterized by optical microscopy, scanning electron microscopy and cyclic voltammetry. To enhance the analytical performance for isoniazid detection, the Au-µEA was modified with electrochemically reduced graphene oxide (ERGO). The developed sensor presented a linear range between 5 and 100 µmol L-1 and a limit of detection of 1.38 µmol L-1 demonstrating a reliable performance. Looking to its environmental application, the ERGO/Au-µEA sensor was used for isoniazid quantification in lagoon, river, tap water and synthetic effluent spiked samples with recovery values between 92.5 and 108.4%. Thus, this research field opens up new possibilities in global water-related issues contributing with innovative sustainable solutions.

An Electroanalytical Solution for the Determination of Pb2+ in Progressive Hair Dyes Using the Cork-Graphite Sensor.

Lead is one of the most toxic metals for living organisms: once absorbed by soft tissues, it is capable of triggering various pathologies, subsequently bioaccumulating in the bones. In consideration of this, its detection and quantification in products for human consumption and use is of great interest, especially if the procedure can be carried out in an easy, reproducible and economical way. This work presents the results of the electroanalytical determination of lead in three different commercial products used as progressive hair dyes. Analyses were performed by cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV) using a composite cork-graphite sensor in 0.5M H2SO4 solution or 0.1M acetate buffer (pH 4.5), in the presence and absence of hair dye samples. The H2SO4 solution gave better results in terms of analyte sensitivity than the acetate buffer electrolyte. In both cases, well-defined signals for lead were obtained by DPSV analyses, enabling the calibration curve and figures of merit to be determined. The limits of detection (LOD) were found to be approximately 1.06 µM and 1.26 µM in H2SO4 and acetate buffer, respectively. The DPSV standard addition method was successfully applied to quantify the lead in hair dye samples, yielding values below 0.45% in Pb. All three analyzed samples were shown to comply with the limit set by the Brazilian Health Regulatory Agency, i.e., 0.6% lead in this type of product. The comparison of the electroanalytical results with those obtained by the reference method, based on the use of inductively coupled plasma optical emission spectrometry (ICP-OES), confirmed that the electroanalytical detection approach is potentially applicable as a strategy for quality control.

Photocatalytic degradation of Novacron blue and Novacron yellow textile dyes by the TiO2/palygorskite nanocomposite.

The photocatalytic discoloration of industrial dyes, Novacron blue (NB) and Novacron yellow (NY), was investigated using composites based on TiO2 and natural palygorskite (Pal-Ti10 and Pal-Ti30). The method consisted of synthesizing the composites starting from a physical mixture of TiO2 and natural palygorskite in the presence of alcohol, for impregnation through calcination under conditions of temperature equal to 450 °C and atmospheric air. The characterization techniques used in this work were FTIR, XRD, XRF, SEM, particle size analysis and zeta potential. The photocatalysis for the NB dye was investigated through the application of a factorial 24 experimental design, aiming at the best experimental conditions and finally applying them in another NY industrial dye. The investigated concentrations of NB were 10 ppm and 30 ppm, the composites were synthesized using 10 and 30% (p/p) of titanium dioxide in palygorskite, the two pH values were 2.0 and 6.0 and the light intensities 9 and 18 W were used. Tests performed at pH 2.0, Pal-Ti30 composite, power 18 W and 10 ppm of dye showed 100% color removal of both dyes in 90 min. The bleaching process followed the pseudo-first order kinetic model, and the apparent constants (Kapp) were 0.0216 min-1 and 0.0193 min-1 for NB and NY dyes, respectively. The results of total organic carbon (TOC) showed mineralization of 61.70% and 58.06% for NB and NY, respectively, in 90 min of treatment, and the by-products were detected by GC-MS.

Electrochemical treatment of real petrochemical effluent: current density effect and toxicological tests.

This work aims to investigate the electrochemical treatment of petrochemical industry effluents (from the northwest region of Brazil) mediated by active chlorine species electrogenerated at ruthenium-titanium oxide supported in titanium (Ti/Ru0.3Ti0.7O2) and boron doped diamond (BDD) anodes by applying 15 and 45 mA cm-2. Chemical oxygen demand (COD) determinations and toxicity analyses were carried out in order to evaluate the process extension as well as the possible reuse of the wastewater after treatment. Toxicity was evaluated by assessing the inhibition of lettuce (Lactuca sativa) stem growth, seed germination, and the production of nitrite (NO-2) and nitrate (NO-3) species. Results clearly showed that the best COD reduction performances were reached at the BDD anode, achieving almost 100% of removal in a short time. Degradation of nitrogen-organic compounds generated NO-2 and NO-3 which act as nutrients for lettuce. Toxicity results also indicated that the electrogenerated active chlorine species are persistent in the effluent after the treatment, avoiding the stem growth, and consequently affecting the germination.

Real time monitoring of in situ generated hydrogen peroxide in electrochemical advanced oxidation reactors using an integrated Pt microelectrode.

This work propose the fabrication and characterization of a Pt microelectrode integrated with a silver quasi-reference counter electrode (Pt/AgQRCE) for real time amperometric measurements of hydrogen peroxide electrochemically generated by water oxidation on Nb-supported boron doped diamond (Ni/BDD) anode. The developed electroanalytical method requires a very small sample volume and has higher sensitivity when compared to the conventional spectrophotometric analysis using ammonium metavanadate. The experiments were performed with Nb/BDD anode applying current densities of 30, 60, 90 and 120 mA cm-2 in 0.10 mol L-1 HClO4 supporting electrolyte showed that H2O2 production increase in the first 90 min of electrolysis and then reaches a plateau in both off-line and real time measurements. For the first 90 min, the electrogeneration of H2O2 exhibited a pseudo zero-order kinetics. The results obtained by the electrochemical amperometric analysis were compared to a spectrophotometric methodology reported on the literature and, at 95% confidence level the two methods do not demonstrated significant difference.

Synthesis of Highly Functionalized N,N-Diarylamides by an Anodic C,N-Coupling Reaction.

We report an innovative, sustainable and straightforward protocol for the synthesis of N,N-diarylamides equipped with nonprotected hydroxyl groups by using electrosynthesis. The concept allows the application of various substrates furnishing diarylamides with yields up to 57 % within a single and direct electrolytic protocol. The method is thereby easy to conduct in an undivided cell with constant current conditions offering a versatile and short-cut alternative to conventional pathways.

Electrochemical measurements and theoretical studies for understanding the behavior of catechol, resorcinol and hydroquinone on the boron doped diamond surface.

Using electrochemical techniques (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)) with a boron-doped diamond (BDD) electrode it was possible to study the behavior of hydroquinone (HQ), catechol (CT) and resorcinol (RS), in aqueous solutions as well as to associate the electrochemical profiles with computational simulations. It led to understanding the factors that influence the direct electrooxidation of HQ, CT and RS on the BDD surface. Theoretical calculations demonstrated that the compounds with lower HOMO energy and high ionization potential (IP) are more stable, showing a higher E pa, denoting that HOMO energies and IP are related to the difficulty of oxidizing (losing an electron) a specific compound. Analyzing the electro-oxidation reactions of HQ, CT and RS by using computational calculations, it was possible to verify the reversibility behavior, direct oxidation pathway and the possible intermediates formed during electron-transfer. The results clearly demonstrated that the reversibility was attained for HQ and CT, while this behavior is not feasible, thermodynamically speaking, for RS and this was confirmed by DFT calculations. For direct oxidation mechanisms, HQ and CT are quickly oxidized, but RS produces stable intermediates. These experimental and theoretical results also explain the behavior when the compounds were analyzed by electroanalytical techniques, suggesting that the interactions by direct electron-transfer determine the stability of response (sensitivity) as well as the limit of detection. The results are described and discussed in light of the existing literature.

Electrochemical advanced oxidation processes as decentralized water treatment technologies to remediate domestic washing machine effluents.

Water scarcity is one of the major concerns worldwide. In order to secure this appreciated natural resource, management and development of water treatment technologies are mandatory. One feasible alternative is the consideration of water recycling/reuse at the household scale. Here, the treatment of actual washing machine effluent by electrochemical advanced oxidation processes was considered. Electrochemical oxidation and electro-Fenton technologies can be applied as decentralized small-scale water treatment devices. Therefore, efficient decolorization and total organic abatement have been followed. The results demonstrate the promising performance of solar photoelectro-Fenton process, where complete color and organic removal was attained after 240 min of treatment under optimum conditions by applying a current density of 66.6 mA cm-2. Thus, electrochemical technologies emerge as promising water-sustainable approaches.

Functional group influences on the reactive azo dye decolorization performance by electrochemical oxidation and electro-Fenton technologies.

Electrochemical water treatment technologies are highly promising to achieve complete decolorization of dyebath effluents, as demonstrated by several studies reported in the literature. However, these works are focused on the treatment of one model pollutant and generalize the performances of the processes which are not transposable since they depend on the pollutant treated. Thus, in the present study, we evaluate, for the first time, the influence of different functional groups that modify the dye structure on the electrochemical process decolorization performance. The textile azo dyes Reactive Orange 16, Reactive Violet 4, Reactive Red 228, and Reactive Black 5 have been selected because they present the same molecular basis structure with different functional groups. The results demonstrate that the functional groups that reduce the nucleophilicity of the pollutant hinder the electrophilic attack of electrogenerated hydroxyl radical. Thereby, the overall decolorization efficiency is consequently reduced as well as the decolorization rate. Moreover, the presence of an additional chromophore azo bond in the molecule enhances the recalcitrant character of the azo dyes as pollutants. The formation of a larger and more stable conjugated π system increases the activation energy required for the electrophyilic attack of •OH, affecting the performance of electrochemical technologies on effluent decolorization.

Solar photocatalytic application of NbO2OH as alternative photocatalyst for water treatment.

Water recycling and industrial effluents remediation are a hot topic of research to reduce the environmental impact of the human activity. Persistent organic pollutants are highly recalcitrant compounds with hazardous effects associated to their fate in water bodies. Several novel technologies have been developed during the last decades to deal with this novel contamination. However, the natural sources and idiosyncrasy of each country lead to the potential application of different technologies. In this context, we have focused on the development of phocotalytic treatment of solutions containing dyes using a novel photocatalytic material, the NbO2OH. The NbO2OH was synthesized and characterized with different techniques. Several assays demonstrated the solar photoactivity of this novel oxyhydroxide catalyst, achieving complete decolorizations after 10min of treatment under optimal conditions of 1.0gL-1 NbO2OH photocatalyst loading, 0.1M of H2O2 as electron scavenger, pH4.0 and methyl orange concentrations up to 15mgL-1. Also, the catalyst recuperation demonstrated the potential reuse of this photocatalyst without losing catalytic response after five cycles. This work is of significant importance because niobium is a natural resource, mainly extracted in Brazil and the annual global sunlight irradiation in the near-equatorial region of northeast Brazil is over the average solar irradiation of the planet. Thus, the solar photocatalytic treatment using NbO2OH in northeast Brazil appears as a highly potential environmental-friendly nanotechnology to mitigate the water pollution.

Electrochemical treatment of shrimp farming effluent: role of electrocatalytic material.

This study investigated the electrochemical oxidation of organic matter present in shrimp farming effluent using three types of electrocatalytic materials: Ti/Ru0.34Ti0.66O2, Ti/Pt, and boron-doped diamond (BDD). An electrochemical cell with 300 mL under stirring agitation was used by applying 20, 40, and 60 mA cm-2. A Ti/Ru0.34Ti0.66O2 anode showed a reduction of chemical oxygen demand (COD) about 84 % after 1 h of electrolysis, while at the same time, 71 % of COD decay was achieved at Ti/Pt. Conversely, only 71 % of COD was removed after 2 h with a BDD anode. Regarding the temperature effect, BDD showed better performances than those achieved for Ti/Ru0.34Ti0.66O2 and Ti/Pt anodes during an electrochemical treatment of a shrimp farming effluent, obtaining 72 % of COD removal by applying 20 mA cm-2 at 40 °C after 15 min. Energy consumption and cost were estimated in order to established the engineering applicability of this alternative process.

Removal of oxyfluorfen from ex-situ soil washing fluids using electrolysis with diamond anodes.

In this research, firstly, the treatment of soil spiked with oxyfluorfen was studied using a surfactant-aided soil-washing (SASW) process. After that, the electrochemical treatment of the washing liquid using boron doped diamond (BDD) anodes was performed. Results clearly demonstrate that SASW is a very efficient approach in the treatment of soil, removing the pesticide completely by using dosages below 5 g of sodium dodecyl sulfate (SDS) per Kg of soil. After that, complete mineralization of organic matter (oxyflourfen, SDS and by-products) was attained (100% of total organic carbon and chemical oxygen demand removals) when the washing liquids were electrolyzed using BDD anodes, but the removal rate depends on the size of the particles in solution. Electrolysis of soil washing fluids occurs via the reduction in size of micelles until their complete depletion. Lower concentrations of intermediates are produced (sulfate, chlorine, 4-(trifluoromethyl)-phenol and ortho-nitrophenol) during BDD-electrolyzes. Finally, it is important to indicate that, sulfate (coming from SDS) and chlorine (coming from oxyfluorfen) ions play an important role during the electrochemical organic matter removal.

Acid blue 29 decolorization and mineralization by anodic oxidation with a cold gas spray synthesized Sn-Cu-Sb alloy anode.

The elevated cost of anodic materials used in the anodic oxidation for water treatment of effluents undermines the real application of these technologies. The study of novel alternative materials more affordable is required. In this work, we report the application of Sn-Cu-Sb alloys as cheap anodic material to decolorize azo dye Acid Blue 29 solutions. These anodes have been synthesized by cold gas spray technologies. Almost complete decolorization and COD abatement were attained after 300 and 600 min of electrochemical treatment, respectively. The influence of several variables such as supporting electrolyte, pH, current density and initial pollutant concentration has been investigated. Furthermore, the release and evolution of by-products was followed by HPLC to better understand the oxidative power of Sn-Cu-Sb electrodes.

Combined soil washing and CDEO for the removal of atrazine from soils.

In this work, it is studied the removal of atrazine from spiked soils by soil washing using surfactant fluids, followed by the treatment of the resulting washing waste by electrolysis with boron doped diamond (BDD) anode. Results confirm that combination of both technologies is efficient for the removal and total mineralization of atrazine. Ratio surfactant/soil is a key parameter for the removal of atrazine from soil and influences significantly in the characteristic of the wastewater produced, affecting not only to the total organic load but also to the mean size of micelles. The higher the ratio surfactant soil, the lower is the size of the particles. Electrolyses of this type of waste attain the complete mineralization. TOC and COD are removed from the start of the treatment but the key of the treatment is the reduction in size of the micelles, which lead to a higher negative charge in the surface and to the faster depletion of the surfactant as compared with the pesticide.

Decontamination of produced water containing petroleum hydrocarbons by electrochemical methods: a minireview.

Produced water (PW) is the largest waste stream generated in oil and gas industries. The drilling and extraction operations that are aimed to maximize the production of oil may be counterbalanced by the huge production of contaminated water (called PW) with pollutants, such as heavy metals, dissolved/suspended solids, and organic compounds. PW is conventionally treated through different physical, chemical, and biological methods. In offshore platforms, because of space constraints, compact physical and chemical systems are used. However, major research efforts are being developed with innovative technologies for treating PW in order to comply with reuse and discharge limits. Among them, electrochemical technologies have been proposed as a promising alternative for the treatment of this kind of wastewaters. Then, this paper presents a minireview of efficient electrochemical technologies used until now for treating PW generated by petrochemical industry.