Atmospheric pressure chemical vapour deposition of boron doped titanium dioxide for photocatalytic water reduction and oxidation

Boron-doped titanium dioxide (B-TiO) films were deposited by atmospheric pressure chemical vapour deposition of titanium(iv) chloride, ethyl acetate and tri-isopropyl borate on steel and fluorine-doped-tin oxide substrates at 500, 550 and 600 °C, respectively. The films were characterised using powder X-ray diffraction (PXRD), which showed anatase phase TiO at lower deposition temperatures (500 and 550 °C) and rutile at higher deposition temperatures (600 °C). X-ray photoelectron spectroscopy (XPS) showed a dopant level of 0.9 at% B in an O-substitutional position. The ability of the films to reduce water was tested in a sacrificial system using 365 nm UV light with an irradiance of 2 mW cm. Hydrogen production rates of B-TiO at 24 μL cm h far exceeded undoped TiO at 2.6 μL cm h. The B-TiO samples were also shown to be active for water oxidation in a sacrificial solution. Photocurrent density tests also revealed that B-doped samples performed better, with an earlier onset of photocurrent. © 2013 The Owner Societies.

Hydrogen adsorption on boron doped graphene: an ab initio study

(i) The electronic and structural properties of boron doped graphene sheets, and (ii) the chemisorption processes of hydrogen adatoms on the boron doped graphene sheets have been examined by ab initio total energy calculations. In (i) we find that the structural deformations are very localized around the boron substitutional sites, and in accordance with previous studies (Endo et al 2001 J. Appl. Phys. 90 5670) there is an increase of the electronic density of states near the Fermi level. Our simulated scanning tunneling microscope (STM) images, for occupied states, indicate the formation of bright (triangular) spots lying on the substitutional boron (center) and nearest-neighbor carbon (edge) sites. Those STM images are attributed to the increase of the density of states within an energy interval of 0.5 eV below the Fermi level. For a boron concentration of similar to 2.4%, we find that two boron atoms lying on the opposite sites of the same hexagonal ring (B1-B2 configuration) represents the energetically most stable configuration, which is in contrast with previous theoretical findings. Having determined the energetically most stable configuration for substitutional boron atoms on graphene sheets, we next considered the hydrogen adsorption process as a function of the boron concentration, (ii). Our calculated binding energies indicate that the C-H bonds are strengthened near boron substitutional sites. Indeed, the binding energy of hydrogen adatoms forming a dimer-like structure on the boron doped B1-B2 graphene sheet is higher than the binding energy of an isolated H(2) molecule. Since the formation of the H dimer-like structure may represent the initial stage of the hydrogen clustering process on graphene sheets, we can infer that the formation of H clusters is quite likely not only on clean graphene sheets, which is in consonance with previous studies (Hornekaer et al 2006 Phys. Rev. Lett. 97 186102), but also on B1-B2 boron doped graphene sheets. However, for a low concentration of boron atoms, the formation of H dimer structures is not expected to occur near a single substitutional boron site. That is, the formation (or not) of H clusters on graphene sheets can be tuned by the concentration of substitutional boron atoms.

A New Indirect Electroanalytical Method to Monitor the Contamination of Natural Waters with 4-Nitrophenol Using Multiwall Carbon Nanotubes

The electrochemical detection of the hazardous pollutant 4-nitrophenol (4-NP) at low potentials, in order to avoid matrix interferences, is an important research challenge. This study describes the development, electrochemical characterization and utilization of a multiwall carbon nanotube (MWCNT) film electrode for the quantitative determination of 4-NP in natural water. Electrochemical impedence spectroscopy measurements showed that the modified surface exhibits a decrease of ca. 13 times in the charge transfer resistance when compared with a bare glassy carbon (GC) surface. Voltammetric experiments showed the possibility to oxidize a hydroxylamine layer (produced by the electrochemical reduction of 4-NP on the GC/MWNCT surface) in a potential region which is approximately 700 mV less positive than that needed to oxidize 4-NP, thus minimizing the interference of matrix components. The limit of detection for 4-NP obtained using square-wave voltammetry (0.12 mu mol L(-1)) was lower than the value advised by EPA. A natural water sample from a dam located in Sao Carlos (Brazil) was spiked with 4-NP and analyzed by the standard addition method using thee GC/MWCNT electrode, without any further purification step. the recovery procedure yielded a value of 96.5% for such sample, thus confirming the suitability of the developed method to determine 4-NP in natural water samples. The electrochemical determination was compared with that obtained by HPLC with UV-vis detection.

Electrochemistry of room temperature protic ionic liquids

Eighteen protic ionic liquids containing different combinations of cations and anions, hydrophobicity, viscosity, and conductivity have been synthesized and their physicochemical properties determined. In one series, the diethanolammonium cations were combined with acetate, formate, hydrogen sulfate, chloride, sulfamate, and mesylate anions. In the second series, acetate and formate anions were combined with amine bases, triethylamine, diethylamine, triethanolamine, di-n-propylamine, and di-n-butylamine. The electrochemical characteristics of the eight protic ionic liquids that are liquid at room temperature (RTPILs) have been determined using cyclic, microelectrode, and rotating disk electrode voltammetries. Potential windows of the RTPILs have been compared at glassy carbon, platinum, gold, and boron-doped diamond electrodes and generally found to be the largest in the case of glassy carbon. The voltammetry of IUPAC recommended potential scale reference systems, ferrocene/ferrocenium and cobaltocenium/cobaltocene, have been evaluated and found to be ideal in the case of the less viscous RTPILs but involve adsorption in the highly viscous ones. Other properties such as diffusion coefficients, ionic conductivity, and double layer capacitance also have been measured. The influence of water on the potential windows, viscosity, and diffusion has been studied systematically by deliberate addition of water to the dried ionic liquids. The survey highlights the problems with voltammetric studies in highly viscous room temperature protic ionic liquids and also suggests the way forward with respect to their possible industrial use.

Aplicação das técnicas eletroanalíticas (voltametria cíclica e de pulso diferencial) usando o eletrodo de diamante dopado com boro para o estudo da isoniazida, etambutol, rifampicina e pirazinamida

In this work a study was done using electrochemical cyclic voltammetry and differential pulse voltammetry for isoniazida (INH), ethambutol (EMB), rifampicina (RIF) and pyrazinamide (PZA) using the electrode boron-doped diamond (BDD) as working electrode. It also verified the applicability of the technique of differential pulse voltammetry in the quantification of the active compounds used in the treatment of tuberculosis, subsequently applying in samples of pharmaceutical formulation. Among the four active compounds studied, isoniazid showed the best results for the detection and quantification using differential pulse voltammetry. At pH 4 and pH 8, for the calibration curves to INH showed good linearity, with quantification limits of 6.15 mmol L-1 (0,844 ppm) and 4.08 mmol L-1 (0.560 ppm) for the respective pH. The proposed method can be used to determine drug isoniazid, for recovery values were obtained in approximately 100%

Electroanalytical determination of carbendazim and fenamiphos in natural waters using a diamond electrode

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Desenvolvimento de detector eletroquímico para cromatografia líquida de alta eficiência baseado em um eletrodo modificado com nanopartículas metálicas para determinação de ácidos carboxílicos em vinhaça de cana-de-açúcar

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

DESENVOLVIMENTO E AVALIAÇÃO DE ELETRODOS DE DIFUSÃO GASOSA (EDG) PARA GERAÇÃO DE H2O2 IN SITU E SUA APLICAÇÃO NA DEGRADAÇÃO DO CORANTE REATIVO AZUL 19

DEVELOPMENT AND EVALUATION OF GAS DIFFUSION ELECTRODES (GDE) FOR GENERATION OF H2O2 IN SITU AND THEIR APPLICATION IN THE DEGRADATION OF REACTIVE BLUE 19 DYE. This work reports the development of GDE for electrogeneration of H2O2 and their application in the degradation process of Reactive Blue 19 dye. GDE produced by carbon black with 20% polytetrafluoroethylene generated up to 500 mg L-1 of H2O2 through the electrolysis of acidic medium at -0.8 V vs Ag/AgCl. Reactive Blue 19 dye was degraded most efficiently with H2O2 electrogenerated in the presence of Fe(II) ions, leading to removal of 95% of the original color and 39% of TOC at -0.8 V vs Ag/AgCl.

Análise de acetona em ar exalado: desenvolvimento de método eletroanalítico e algoritmo para processamento de sinais

Propõe-se método novo e completo para análise de acetona em ar exalado envolvendo coleta com pré-concentração em água, derivatização química e determinação eletroquímica assistida por novo algoritmo de processamento de sinais. Na literatura recente a acetona expirada vem sendo avaliada como biomarcador para monitoramento não invasivo de quadros clínicos como diabetes e insuficiência cardíaca, daí a importância da proposta. Entre as aminas que reagem com acetona para formar iminas eletroativas, estudadas por polarografia em meados do século passado, a glicina apresentou melhor conjunto de características para a definição do método de determinação por voltametria de onda quadrada sem a necessidade de remoção de oxigênio (25 Hz, amplitude de 20 mV, incremento de 5 mV, eletrodo de gota de mercúrio). O meio reacional, composto de glicina (2 mol·L-1) em meio NaOH (1 mol·L-1), serviu também de eletrólito e o pico de redução da imina em -1,57 V vs. Ag|AgCl constituiu o sinal analítico. Para tratamento dos sinais, foi desenvolvido e avaliado um algoritmo inovador baseado em interpolação de linha base por ajuste de curvas de Bézier e ajuste de gaussiana ao pico. Essa combinação permitiu reconhecimento e quantificação de picos relativamente baixos e largos sobre linha com curvatura acentuada e ruído, situação em que métodos convencionais falham e curvas do tipo spline se mostraram menos apropriadas. A implementação do algoritmo (disponível em http://github.com/batistagl/chemapps) foi realizada utilizando programa open source de álgebra matricial integrado diretamente com software de controle do potenciostato. Para demonstrar a generalidade da extensão dos recursos nativos do equipamento mediante integração com programação externa em linguagem Octave (open source), implementou-se a técnica da cronocoulometria tridimensional, com visualização de resultados já tratados em projeções de malha de perspectiva 3D sob qualquer ângulo. A determinação eletroquímica de acetona em fase aquosa, assistida pelo algoritmo baseado em curvas de Bézier, é rápida e automática, tem limite de detecção de 3,5·10-6 mol·L-1 (0,2 mg·L-1) e faixa linear que atende aos requisitos da análise em ar exalado. O acetaldeído, comumente presente em ar exalado, em especial, após consumo de bebidas alcoólicas, dá origem a pico voltamétrico em -1,40 V, contornando interferência que prejudica vários outros métodos publicados na literatura e abrindo possibilidade de determinação simultânea. Resultados obtidos com amostras reais são concordantes com os obtidos por método espectrofotométrico, em uso rotineiro desde o seu aperfeiçoamento na dissertação de mestrado do autor desta tese. Em relação à dissertação, também se otimizou a geometria do dispositivo de coleta, de modo a concentrar a acetona num volume menor de água gelada e prover maior conforto ao paciente. O método completo apresentado, englobando o dispositivo de amostragem aperfeiçoado e o novo e efetivo algoritmo para tratamento automático de sinais voltamétricos, está pronto para ser aplicado. Evolução para um analisador portátil depende de melhorias no limite de detecção e facilidade de obtenção eletrodos sólidos (impressos) com filme de mercúrio, vez que eletrodos de bismuto ou diamante dopado com boro, entre outros, não apresentaram resposta.

Tecnologia eletroquímica como tratamento alternativo de efluentes derivados da indústria têxtil e petroquímica

In this work, the treatment of wastewater from the textile industry, containing dyes as Yellow Novacron (YN), Red Remazol BR (RRB) and Blue Novacron CD (NB), and also, the treatment of wastewater from petrochemical industry (produced water) were investigated by anodic oxidation (OA) with platinum anodes supported on titanium (Ti/Pt) and boron-doped diamond (DDB). Definitely, one of the main parameters of this kind of treatment is the type of electrocatalytic material used, since the mechanisms and products of some anodic reactions depend on it. The OA of synthetic effluents containing with RRB, NB and YN were investigated in order to find the best conditions for the removal of color and organic content of the dye. According to the experimental results, the process of OA is suitable for decolorization of wastewaters containing these textile dyes due to electrocatalytic properties of DDB and Pt anodes. Removal of the organic load was more efficient at DDB, in all cases; where the dyes were degraded to aliphatic carboxylic acids at the end of the electrolysis. Energy requirements for the removal of color during OA of solutions of RRB, NB and YN depends mainly on the operating conditions, for example, RRB passes of 3.30 kWh m-3 at 20 mA cm-2 for 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (estimated data for volume of treated effluent). On the other hand, in the study of OA of produced water effluent generated by petrochemical industry, galvanostatic electrolysis using DDB led to the complete removal of COD (98%), due to large amounts of hydroxyl radicals and peroxodisulphates generated from the oxidation of water and sulfates in solution, respectively. Thus, the rate of COD removal increases with increasing applied current density (15-60 mAcm-2 ). Moreover, at Pt electrode, approximately 50% removal of the organic load was achieved by applying from 15 to 30 mAcm-2 while 80% of COD removal was achieved for 60 mAcm-2 . Thus, the results obtained in the application of this technology were satisfactory depending on the electrocatalytic materials and operating conditions used for removal of organic load (petrochemical and textile effluents) as well as for the removal of color (in the case of textile effluents). Therefore, the applicability of electrochemical treatment can be considered as a new alternative like pretreatment or treatment of effluents derived from textiles and petrochemical industries.

Aplicação de tratamentos eletroquímicos integrados para remediação de solos e águas contaminadas com petróleo e pesticidas

Electrochemical technologies have been proposed as a promising alternative for the treatment of effluents and contaminated soils. Therefore, the objective of this work was to study the treatment of contaminated soils and wastewaters using electrochemical technologies. Thus, the study regarding the scale-up of the electrochemical system with continuous flow treatment of wastewater of the petrochemical industry was investigated using platinum electrodes supported on titanium (Ti / Pt), and boron-doped diamond (BDD). The results clearly showed that under the operating conditions studied and electrocatalytic materials employed, the better removal efficiency was achieved with BDD electrode reducing the chemical oxygen demand (COD) from 2746 mg L-1 to 200 mg L-1 in 5 h consuming 56.2 kWh m-3 . The decontamination of soils and effluents by petrochemical products was evaluated by studying the effects of electrokinetic remediation for removal of total petroleum hydrocarbons (HTP) from contaminated soil with diesel. The efficiency of this process was dependent on the electrolyte used Na2SO4 (96.46%), citric acid (81.36%) and NaOH (68.03%) for 15 days. Furthermore, the effluent after treatment of the soil was treated by electrochemical oxidation, achieving a good elimination of the organic polluting load dissolved. Depending on the physical behavior of wastewater contaminated with oil (emulsified state); atrazine emulsified effluents were investigated. The main characteristics of the effluent produced during the washing of contaminated soil were studied, being dependent on the surfactant dosage used; which determined its electrolytic treatment with BDD. The electrochemical oxidation of emulsified effluent of atrazine was efficient, but the key to the treatment is reducing the size of micelles.

Estudo da produção eletroquímica de espécies de cloro ativo para tratamento de efluentes sintéticos

The treatment of wastewater is essential to human health. One of the most important steps is the disinfection treatment which uses chlorine to eliminate bacteria as required by environmental agencies. However, the identification of potentially toxic byproducts generated by this method, such as trihalomethanes, has stimulated the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered suitable alternatives to the chlorination method. Thus, the present dissertation analyzes the evolution of active chlorine species in a synthetic NaCl solution and it is tested to treat a synthetic solution of the dye Reactive Blue 19 using boron-doped diamond (BDD) and ruthenium oxide (Ti/Ru0.3Ti0.7O2) as anodes. The indirect electrochemical process was discussed in terms of mineralization of the total organic load and percentage of color removal in order to evaluate the applicability of electrochemical technology. Electrochemical experiments were carried out with different current densities (25, 50 and 75 mA.cm-2) during 120 minutes. On the other hand, other important parameter in this study was the influence of the proportion sp3/sp2 on BDD anode on the performance of the evolution of active chlorine species which was investigated by electrolytic techniques (linear polarization), with the intention of determining the related training oxidizing species and consumption energy to chemical or electrochemical reactions. From the results, it can be noted that the BDD electrode showed better efficiency throughout the electrochemical process.

Estudo da produção eletroquímica de espécies de cloro ativo para tratamento de efluentes sintéticos

The treatment of wastewater is essential to human health. One of the most important steps is the disinfection treatment which uses chlorine to eliminate bacteria as required by environmental agencies. However, the identification of potentially toxic byproducts generated by this method, such as trihalomethanes, has stimulated the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered suitable alternatives to the chlorination method. Thus, the present dissertation analyzes the evolution of active chlorine species in a synthetic NaCl solution and it is tested to treat a synthetic solution of the dye Reactive Blue 19 using boron-doped diamond (BDD) and ruthenium oxide (Ti/Ru0.3Ti0.7O2) as anodes. The indirect electrochemical process was discussed in terms of mineralization of the total organic load and percentage of color removal in order to evaluate the applicability of electrochemical technology. Electrochemical experiments were carried out with different current densities (25, 50 and 75 mA.cm-2) during 120 minutes. On the other hand, other important parameter in this study was the influence of the proportion sp3/sp2 on BDD anode on the performance of the evolution of active chlorine species which was investigated by electrolytic techniques (linear polarization), with the intention of determining the related training oxidizing species and consumption energy to chemical or electrochemical reactions. From the results, it can be noted that the BDD electrode showed better efficiency throughout the electrochemical process.

Electrocombustion of humic acid and removal of algae from aqueous solutions

This paper reports experiments involving the electrochemical combustion of humic acid (HA) and removal of algae from pond water. An electrochemical flow reactor with a boron-doped diamond film anode was used and constant current experiments were conducted in batch recirculation mode. The mass transfer characteristics of the electrochemical device were determined by voltammetric experiments in the potential region of water stability, followed by a controlled current experiment in the potential region of oxygen evolution. The average mass transfer coefficient was 5.2 x 10(-5) m s(-1). The pond water was then processed to remove HA and algae in the conditions in which the reaction combustion occurred under mass transfer control. To this end, the mass transfer coefficient was used to estimate the initial limiting current density applied in the electrolytic experiments. As expected, all the parameters analyzed here-solution absorbance at 270 nm, total phenol concentration and total organic carbon concentration-decayed according to first-order kinetics. Since the diamond film anode successfully incinerated organic matter, the electrochemical system proved to be predictable and programmable.

Ethanol oxidation reaction on PtCeO(2)/C electrocatalysts prepared by the polymeric precursor method

This paper presents a study of the electrocatalysis of ethanol oxidation reactions in an acidic medium on Pt-CeO(2)/C (20 wt.% of Pt-CeO(2) on carbon XC-72R), prepared in different mass ratios by the polymeric precursor method. The mass ratios between Pt and CeO(2) (3:1, 2:1, 1:1, 1:2, 1:3) were confirmed by Energy Dispersive X-ray Analysis (EDAX). X-ray diffraction (XRD) structural characterization data shows that the Pt-CeO(2)/C catalysts are composed of nanosized polycrystalline non-alloyed deposits, from which reflections corresponding to the fcc (Pt) and fluorite (CeO(2)) structures were clearly observed. The mean crystallite sizes calculated from XRD data revealed that, independent of the mass ratio, a value close to 3 nm was obtained for the CeO(2) particles. For Pt, the mean crystallite sizes were dependent on the ratio of this metal in the catalysts. Low platinum ratios resulted in small crystallites. and high Pt proportions resulted in larger crystallites. The size distributions of the catalysts particles, determined by XRD, were confirmed by Transmission Electron Microscope (TEM) imaging. Cyclic voltammetry and chronoamperometic experiments were used to evaluate the electrocatalytic performance of the different materials. In all cases, except Pt-CeO(2)/C 1:1, the Pt-Ceo(2)/C catalysts exhibited improved performance when compared with Pt/C. The best result was obtained for the Pt-CeO(2)/C 1:3 catalyst, which gave better results than the Pt-Ru/C (Etek) catalyst. (C) 2009 Elsevier B.V. All rights reserved.