Identifying the trend of reactivity for sp2 materials: an electron delocalization model from first principles calculations

The reactivity of sp² carbon materials is studied using the adsorption and dissociation of O₂ on graphene and graphene oxide as model systems. The reactions on the basal plane, zigzag and armchair edges of graphene and graphene oxide with different oxygen-containing groups are calculated using first principles calculations. Two Brønsted-Evans- Polanyi relationships are identified and an electron delocalization model is suggested to understand the general trend of reactivity for sp² carbon materials.

Diamond microelectrodes for corrosion studies

Este trabalho teve como objetivos a produção, caracterização e aplicação de microelétrodos (MEs) de diamante como sensores amperométricos e potenciométricos em sistemas de corrosão nos quais a agressividade do meio e a presença de produtos de corrosão, constituem obstáculos que podem diminuir o desempenho, ou inviabilizar a utilização, de outros tipos de sensores. Os microeléctrodos são baseados em filmes finos de diamante dopado com boro (BDD – Boron Doped Diamond) depositados sobre fios de tungsténio afiados, através do método de deposição química a partir da fase vapor, assistida por filamento quente (HFCVD – Hot Filament Chemical Vapor Deposition). A otimização das diversas etapas de fabricação dos MEs deu origem ao desenvolvimento de um novo sistema de afiamento eletroquímico para obtenção destes fios e a várias opções para a obtenção dos filmes de diamante condutor e seu isolamento com resinas para exposição apenas da ponta cilíndrica. A qualidade cristalina dos filmes de diamante foi avaliada por espectroscopia de Raman. Esta informação foi complementada com uma caracterização microestrutural dos filmes de diamante por microscopia eletrónica de varrimento (SEM), em que se fez a identificação da tipologia dos cristais como pertencendo às gamas de diamante nanocristalino ou microcristalino. Os filmes de BDD foram utilizados na sua forma não modificada, com terminações em hidrogénio e também com modificação da superfície através de tratamentos de plasma RF de CF4 e O2 indutores de terminações C-F no primeiro caso e de grupos C=O, C-O-C e C-OH no segundo, tal como determinado por XPS. A caracterização eletroquímica dos MEs não modificados revelou uma resposta voltamétrica com elevada razão sinal/ruído e baixa corrente capacitiva, numa gama de polarização quasi-ideal com extensão de 3 V a 4 V, dependente dos parâmetros de crescimento e pós-tratamentos de superfície. Estudou-se a reversibilidade de algumas reações heterogéneas com os pares redox Fe(CN)6 3-/4- e FcOH0/+ e verificou-se que a constante cinética, k0, é mais elevada em elétrodos com terminações em hidrogénio, nos quais não se procedeu a qualquer modificação da superfície. Estes MEs não modificados foram também testados na deteção de Zn2+ onde se observou, por voltametria cíclica, que a detecção da redução deste ião é linear numa escala log-log na gama de 10-5-10-2 M em 5 mM NaCl. Realizaram-se também estudos em sistemas de corrosão modelares, em que os microeléctrodos foram usados como sensores amperométricos para mapear a distribuição de oxigénio e Zn2+ sobre um par galvânico Zn-Fe, com recurso a um sistema SVET (Scanning Vibrating Electrode Technique). Foi possível detetar, com resolução lateral de 100 μm, um decréscimo da concentração de O2 junto a ambos os metais e produção de catiões de zinco no ânodo. Contudo verificou-se uma significativa deposição de zinco metálico na superfície dos ME utilizados. Os MEs com superfície modificada por plasma de CF4 foram testados como sensores de oxigénio dissolvido. A calibração dos microeléctrodos foi efetuada simultaneamente por voltametria cíclica e medição óptica através de um sensor de oxigénio comercial. Determinou-se uma sensibilidade de ~0.1422 nA/μM, com um limite de deteção de 0.63 μM. Os MEs modificados com CF4 foram também testados como sensores amperométricos com os quais se observou sensibilidade ao oxigénio dissolvido em solução, tendo sido igualmente utilizados durante a corrosão galvânica de pares Zn-Fe. Em alguns casos foi conseguida sensibilidade ao ião Zn2+ sem que o efeito da contaminação superficial com zinco metálico se fizesse sentir. Os microeléctrodos tratados em plasma de CF4 permitem uma boa deteção da distribuição de oxigénio, exibindo uma resposta mais rápida que os não tratados além de maior estabilidade de medição e durabilidade. Nos MEs em que a superfície foi modificada com plasma de O2 foi possível detetar, por cronopotenciometria a corrente nula, uma sensibilidade ao pH de ~51 mV/pH numa gama de pH 2 a pH 12. Este comportamento foi associado à contribuição determinante de grupos C-O e C=O, observados por XPS com uma razão O/C de 0,16. Estes MEs foram igualmente testados durante a corrosão galvânica do par Zn-Fe onde foi possível mapear a distribuição de pH associada ao desenvolvimento de regiões alcalinas causadas pela redução do oxigénio, acima da região catódica, e de regiões ácidas decorrentes da dissolução anódica do ânodo de zinco. Com o par galvânico imerso em 50 mM NaCl registou-se uma variação de pH aproximadamente entre 4,8 acima do ânodo de zinco a 9,3 sobre o cátodo de ferro. A utilização pioneira destes MEs como sensores de pH é uma alternativa promissora aos elétrodos baseados em membranas seletivas.

Copper(II) complexes of embelin and 2-aminobenzimidazole encapsulated in zeolite Y-potential as catalysts

Copper(II) complexes of two biologically important ligands, viz., embelin (2,5-dihydroxy-3-undecyl-2,5-cyclohexadien 1,4-dione) and 2-aminobenzimidazole were entrapped in the cages of zeolite Y by the flexible ligand method. The capability of these compounds in catalyzing the reduction of oxygen (industrially known as deoxo reaction) was explored and the results indicate an enhancement of the catalytic properties from that of the simple copper ion exchanged zeolite. These point to the ability of the ligands in enhancing the oxygen binding capability of the metal ion. Elemental analyses, Fourier transform infrared (FTIR), diffuse reflectance and EPR spectral studies, magnetic susceptibility measurements, TG, surface area analyses and powder X-ray diffraction studies were used in understanding the presence, composition and structure of the complexes inside the cages. The study also reveals the increased thermal and mechanical stability of the complexes as a result of encapsulation.

Electrochemical fabrication and electrocatalytic properties of nanostructured mesoporous platinum microelectrodes

Electrodeposition from a lyotropic liquid crystal template medium was used to produce nanostructured platinum microelectrodes with high specific surface area and high mass transport efficiency. Compared to polished and conventional platinized microelectrodes, well-ordered nanostructured platinum microelectrodes exhibited enhanced electrocatalytic properties for oxygen and ascorbic acid, whilst well-ordered nanostructured platinum microelectrodes offered improved electrocatalytic properties for oxygen reduction compared to disordered nanostructured platinum microelectrodes.

Approaches for multicopper oxidases in the design of electrochemical sensors for analytical applications

We report an effective approach for the construction of a biomimetic sensor of multicopper oxidases by immobilizing a cyclic-tetrameric copper(II) species, containing the ligand (4-imidazolyl)ethylene-2-amino-1-ethylpyridine (apyhist), in the Nafion (R) membrane on a vitreous carbon electrode surface. This complex provides a tetranuclear arrangement of copper ions that allows an effective reduction of oxygen to water, in a catalytic cycle involving four electrons. The electrochemical reduction of oxygen was studied at pH 9.0 buffer solution by using cyclic voltammetry, chronoamperometry, rotating disk electrode voltammetry and scanning electrochemical microscopy techniques. The mediator shows good electrocatalytic ability for the reduction of O(2) at pH 9.0, with reduction of overpotential (350 mV) and increased current response in comparison with results obtained with a bare glassy carbon electrode. The heterogeneous rate constant (k(ME)`) for the reduction of O(2) at the modified electrode was determined by using a Koutecky-Levich plot. In addition, the charge transport rate through the coating and the apparent diffusion coefficient of O(2) into the modifier film were also evaluated. The overall process was found to be governed by the charge transport through the coating, occurring at the interface or at a finite layer at the electrode/coating interface. The proposed study opens up the way for the development of bioelectronic devices based on molecular recognition and self-organization. (C) 2010 Elsevier Ltd. All rights reserved.

Quantification of N-acetylcysteine in pharmaceuticals using cobalt phthalocyanine modified graphite electrodes

Flow injection analysis (FIA) with amperometric detection was employed for the quantification of N-acetylcysteine (NAC) in pharmaceutical formulations, utilizing an ordinary pyrolytic graphite (OPG) electrode modified with cobalt phthalocyanine (CoPc). Cyclic voltammetry was used in preliminary studies to establish the best conditions for NAC analysis. In FIA-amperometric experiments the OPG-CoPc electrode exhibited sharp and reproducible current peaks over a wide linear working range (5.0 x 10(-5)-1.0 x 10(-3) mol L(-1)) in 0.1 mol L(-1) NaOH solution. High sensitivity (130 mA mol(-1) cm(2)) and a low detection limit (9.0 x 10(-7) mol L(-1)) were achieved using the sensor. The repeatability (R.S.D.%) for 13 successive flow injections of a solution containing 5.0 x 10(-4) mol L(-1) NAC was 1.1%. The new procedure was applied in analyses of commercial pharmaceutical products and the results were in excellent agreement with those obtained using the official titrimetric method. The proposed amperometric method is highly suitable for quality control analyses of NAC in pharmaceuticals since it is rapid, precise and requires much less work than the recommended titrimetric method. (C) 2010 Elsevier B.V. All rights reserved.

Investigation of the CO tolerance mechanism at several Pt-based bimetallic anode electrocatalysts in a PEM fuel cell

The electrocatalysis of CO tolerance of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C at a PEM fuel cell anode has been investigated using single cell polarization and online electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), in situ X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO(2) start at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particulary for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H(2)/CO, the formation of CO(2) is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction. (C) 2008 Elsevier Ltd. All rights reserved.

Electrocatalysis of ethanol oxidation on Pt monolayers deposited on carbon-supported Ru and Rh nanoparticles

Pt monolayers deposited on carbon- supported Ru and Rh nanoparticles were investigated as electrocatalysts for ethanol oxidation. Electronic features of the Pt monolayers were studied by in situ XANES (X-ray absorption near-edge structure). The electrochemical activity was investigated by cyclic voltammetry and cronoamperometric experiments. Spectroscopic and electrochemical results were compared to those obtained on carbon-supported Pt-Ru and Pt-Rh alloys, and Pt E-TEK. XAS results indicate a modification of the Pt 5d band due to geometric and electronic interactions with the Ru ant Rh substrates, but the effect of withdrawing electrons from Pt is less pronounced in relation to that for the corresponding alloys. Electrochemical stripping of adsorbed CO, which is one of the intermediates, and the currents for the oxidation of ethanol show faster kinetics on the Pt monolayer deposited on Ru nanoparticles, and an activity that exceeds that of conventional catalysts with much larger amounts of platinum. (c) 2007 Elsevier B.V. All rights reserved.

Ethanol electro-oxidation on carbon-supported Pt-Ru, Pt-Rh and Pt-Ru-Rh nanoparticles

This work investigates the effects of carbon-supported Pt, Pt-Ru, Pt-Rh and Pt-Ru-Rh alloy electrocatalysts oil the yields of CO2 and acetic acid as electro-oxidation products of ethanol. Electronic and structural features of these metal alloys were studied by in situ X-ray absorption spectroscopy (XAS). The electrochemical activity was investigated by polarization experiments and the reaction intermediates and products were analyzed by in situ Fourier Transform Infra-Red Spectroscopy (FTIR). Electrochemical stripping of CO. which is one of the adsorbed intermediates, presented a faster oxidation kinetics on the Pt-Ru electrocatalyst, and similar rates of reaction on Pt-Rh and Pt. The electrochemical current of ethanol oxidation showed a higher value and the onset potential was less positive oil Pt-Ru. However, in situ FTIR spectra evidenced that the CO2/acetic acid ratio is higher for the materials with Rh, mainly at lower potentials. These results indicate that the Ru atoms act mainly by providing oxygenated species for the oxidation of ethanol intermediates, and point out ail important role of Rh on the C-C bond dissociation. (C) 2007 Elsevier Ltd. All rights reserved.

Ethanol oxidation reactions using SnO(2)@Pt/C as an electrocatalyst

This paper presents a study on the ethanol oxidation reaction using SnO(2)@Pt/C core-shell structures as electrocatalysts. All the materials used, including Pt/C and PtSn/C E-tek, were 20% (w/w) metal on carbon. The formation of core-shell nanoparticles (SnO(2)@Pt/C) was measured by UV-vis spectrophotometry. X-ray diffraction measurements showed Pt (shell) diffraction patterns without influence from the SnO(2) core and without any shift in 2 theta values for Pt. The diameters of the core-shell particle structures, measured using high-resolution transmission electron microscopy images, were in the range of 3-16 nm. The electrochemical profile for SnO(2)@Pt/C in an acidic medium (H(2)SO(4) at a concentration of 0.5 mol L(-1)) was almost the same as the typical electrochemical behavior for Pt in an acidic medium. Furthermore, the onset potential for the ethanol oxidation reaction using SnO(2)@Pt/C was almost the same as that for PtSn/C E-tek (0.23 V versus the reversible hydrogen electrode). However, the mass current peak densities for ethanol oxidation were 50% higher on SnO(2)@Pt/C than on PtSn/C E-tek. In the polarization curve, the mass current density for ethanol oxidation was higher at all potentials for SnO(2)@Pt/C when compared to Pt/C and PtSn/C E-tek. At 0.5 V, the current mass density for ethanol oxidation on SnO(2)@Pt was 2.3 times of that for the same process on the commercial material. The electrocatalytic activity of SnO(2)@Pt/C for ethanol oxidation was associated with an increase in the electrochemically active surface area. However, an electronic effect should also be considered because the Pt shell changes its electronic structure in the presence of the foreign core. (C) 2010 Elsevier B.V. All rights reserved.

Mass transport effects in the borohydride oxidation reaction-Influence of the residence time on the reaction onset and faradaic efficiency

The borohydride oxidation reaction (BOR) was studied on Pt and Au electrodes by cyclic voltammetry in dilute alkaline borohydride solutions (0.1 M NaOH + 10(-3) mol L(-1) NaBH(4)). More specifically, the electrodes were considered as either Vulcan XC72-supported Pt or Au (noted as Pt/C and Au/C, respectively) active layers or smooth Pt or Au surfaces, the latter possibly being covered by a layer of (non-metalized) Vulcan XC72 carbon powder. The BOR onset potential and the number of electrons (n(e-)) exchanged per BH(4)(-) anion (faradaic efficiency) were investigated for these electrodes, to determine whether the residence time of reaction intermediates (at the electrode surface or inside the porous layer) does influence the overall reaction pathway/completion. For the carbon-supported platinum, n(e-) strongly depends on the thickness of the active layer. While thin (ca. 0.5 mu m-thick) Pt/C active layers yield n(e-) < 4, thick layers (approximately 3 mu m) yield n(e-)approximate to 8, which can be ascribed to the sufficient residence time of the molecules formed within the active layer (H(2), by heterogeneous hydrolysis, or BOR intermediates) enabling further (near-complete) oxidation. This puts into evidence that not only the nature of the electrocatalyst is important to reach high BOR efficiency, but also the structure/thickness of the active layer. The same trend applies for Au/C active layers and for smooth Pt or Au surfaces covered with a layer of (inactive) Vulcan XC72. In addition, the BOR onset usually shifts negative when the reaction intermediates are trapped, which suggests that some of the intermediates are more easily oxidized than BH(4)(-) itself; based on literature data, BH(3)OH(-) species is a likely candidate. (C) 2011 Elsevier B.V. All rights reserved.

Perpendicularly self-oriented and shape-controlled L1(0)-FePt nanorods directly synthesized by a temperature-modulated process

The synthesis and self-assembly of tetragonal phase-containing L1(0)-Fe(55)Pt(45) nanorods with high coercive field is described. The experimental procedure resulted in a tetragonal/cubic phase ratio close to 1:1 for the as-synthesized nanoparticles. Using different surfactant/solvent proportions in the process allowed control of particle morphology from nanospheres to nanowires. Monodisperse nanorods with lengths of 60 +/- 5 nm and diameters of 2-3 nm were self-assembled in a perpendicular oriented array onto a substrate surface using hexadecylamine as organic spacer. Magnetic alignment and properties assigned, respectively, to the shape anisotropy and the tetragonal phase suggest that the self-assembled materials are a strong candidate to solve the problem of random magnetic alignment observed in FePt nanospheres leading to applications in ultrahigh magnetic recording (UHMR) systems capable of achieving a performance of the order of terabits/in(2).

The impact of water concentration on the catalytic oxidation of ethanol on platinum electrode in concentrated phosphoric acid

The electro-oxidation of ethanol on platinum in phosphoric acid opens the door to promote the oxidation reaction at higher temperatures. However, the effect of the presence of water is not well understood. In this work, the electro-oxidation of ethanol on platinum was studied in concentrated phosphoric acid containing different concentrations of water at room temperature. The results show that effect of bulk water on the rate electro-oxidation is highest at 0.60 V and decreases for increasing potentials. This was suggested as due to the increasing formation of oxygenated species on the electrode surface with potential, which in turn is more efficient than the increase of water content in the electrolyte. Altogether, these results were interpreted as an evidence of a Langmuir-Hinshelwood step involving oxygenated species as one of the adsorbed partners. (C) 2009 Elsevier B.V. All rights reserved.

Synthesis, Characterization, and Electrocatalytic Activity toward Methanol Oxidation of Carbon-Supported Pt(x)-(RuO(2)-M)(1-x) Composite Ternary Catalysts (M = CeO(2), MoO(3), or PbO(x))

Carbon-supported platinum is commonly used as an anode electrocatalyst in low-temperature fuel cells fueled with methanol. The cost of Pt and the limited world supply are significant barriers for the widespread use of this type of fuel cell. Moreover, Pt used as anode material is readily poisoned by carbon monoxide produced as a byproduct of the alcohol oxidation. Although improvements in the catalytic performance for methanol oxidation were attained using Pt-Ru alloys, the state-of-the-art Pt-Ru catalyst needs further improvement because of relatively low catalytic activity and the high cost of noble Pt and Ru. For these reasons, the development of highly efficient ternary platinum-based catalysts is an important challenge. Thus, various compositions of ternary Pt(x)-(RuO(2)-M)(1-x)/C composites (M = CeO(2), MoO(3), or PbO(x)) were developed and further investigated as catalysts for the methanol electro-oxidation reaction. The characterization carried out by X-ray diffraction, energy-dispersive X-ray analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry point out that the different metallic oxides were successfully deposited on the Pt/C, producing small and well-controlled nanoparticles in the range of 2.8-4.2 nm. Electrochemical experiments demonstrated that the Pt(0.50)(RuO(2)-CeO(2))(0.50)/C composite displays the higher catalytic activity toward the methanol oxidation reaction (lowest onset potential of 207 mV and current densities taken at 450 mV, which are 140 times higher than those at commercial Pt/C), followed by the Pt(0.75)(RuO(2)-MoO(3))(0.25)/C composite. In addition, both of these composites produced low quantities of formic acid and formaldehyde when compared to a commercially available Pt(0.75)-Ru(0.25)/C composite (from E-Tek, Inc.), suggesting that the oxidation of methanol occurs mainly by a pathway that produces CO(2) forming the intermediary CO(ads).

A comparative study of the electrogeneration of hydrogen peroxide using Vulcan and Printex carbon supports

A comparative study of two different conductive carbon-black pigments, Vulcan XC-72 R and Printex L6, for the electrogeneration of hydrogen peroxide (H(2)O(2)) by reducing dissolved oxygen in an alkaline solution was performed. The materials were physically characterized by X-ray diffraction (XRD), Fourier transform infrared attenuated total reflection (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). XRD shows the presence of SO(2) and ATR-FTIR technique indicates a difference in NO and SO(2) functional groups between the two carbon pigments. XPS indicated presence of SO and NO and more oxygenated acid species on Printex L6. A rotating ring-disk electrode was used for electrochemical analysis of the oxygen reduction reaction (ORR). The results showed that the Printex L6 was better than Vulcan XC-72 R for H(2)O(2) production. Results also indicate that the number of electrons transferred in the ORR for Printex L6 and Vulcan XC-72 R were 2.2 and 2.9, respectively, while the percentages of H(2)O(2) formed were 88% and 51%. Scanning electrochemistry microscopy images confirmed the higher amount of H(2)O(2) formed in the Printex L6 pigment. Printex L6 was shown to be a more promising for H(2)O(2) production than Vulcan XC-72 R, while the latter was shown to have more potential for fuel cells. (C) 2011 Elsevier Ltd. All rights reserved.