N-doped pierced graphene microparticles as a highly active electrocatalyst for li-air batteries

In this work we report a novel scalable strategy to prepare a lithium-air battery electrode from 3D Ndoped pierced graphene microparticles (N-PGM) with highly active performance. This approach has combined the merits of spray drying technology and the hard template method. The pierced structured graphene microparticles were characterized physically and electrochemically. An x-ray
photoelectron spectrometer and Raman spectra have revealed that the novel structure possesses a higher N-doping level than conventional graphene without the pierced structure. A much higher BET surface area was also achieved for the N-PGMthan the conventional N-doped graphene microparticles (N-GM). Cyclic voltammetry indicated that the lithium-air battery with the N-PGM electrode has a better utilization for the graphene mass and a higher void volume for Li2O2 formation than that of theN-GMelectrode. N-PGMalso exhibits improved decomposition kinetics for Li oxide
species yielded in the cathodic reaction. Charge and discharge measurements showed that theN-PGM lithium-air battery achieved an improved specific capacity and an enhanced cycle performance than when anN-GMelectrode is used.

Experimental and theoretical investigation on corrosion inhibition of AA5052 aluminium alloy by l-cysteine in alkaline solution

The corrosion inhibition of l-cysteine on AA5052 aluminium alloy in 4 mol/L NaOH solution was investigated by hydrogen gas evolution experiment, polarisation curve, galvanostatic discharge, electrochemical impedance spectroscopy measurements and quantum chemical calculations. The adsorption of l-cysteine on aluminium alloy surface obeyed the amended Langmuir's adsorption isotherm. The polarisation curves indicated that l-cysteine acted as a cathodic inhibitor to inhibit cathodic reaction. The inhibition mechanism was dominated by the geometric covering effect. The galvanostatic discharge shows that the additives restrain the hydrogen evolution and increase the anodic utilization rate. Quantum chemical calculations indicated that l-cysteine molecules mainly interacted with on the carboxyl groups on the aluminium alloy surface. A strong hybridization occurred between the s-orbital and p-orbital of reactive sites in the l-cysteine molecule and the sp-orbital of Aluminium.

Effects of Mg17Sr2 Phase on the bio-corrosion behavior of Mg-Zr-Sr alloys

The effect of the second phase Mg17Sr2 on the biocorrosion behavior of Mg5ZrxSr (x = 0, 2, 5 wt%) alloys before and after solution treatment was investigated. Electrochemical impedance spectroscopy, cathodic polarization and hydrogen evolution were used to evaluate the biocorrosion of Mg5ZrxSr. We found that Mg17Sr2 precipitated on boundary zones and enhanced the galvanic effect, leading to a severer corrosion of the Mg matrix adjacent to Mg17Sr2. The corrosion subsequently spread gradually from the regions adjacent to the Mg17Sr2 to the central Mg matrix. However, a high volume fraction of Mg17Sr2 could also form a continuous network, isolate the Mg matrix and act as a barrier of corrosion.

Visualising dynamic passivation and localised corrosion processes occurring on buried steel surfaces under the effect of anodic transients

A new method of visualising dynamically changing electrode processes has been demonstrated by mapping localised corrosion processes occurring on buried steel surfaces under the effect of anodic transients. Dynamically shifting external electrical interferences such as anodic transients are known to affect the efficiency of cathodic protection (CP) of underground pipelines; however unfortunately conventional techniques including electrochemical methods have difficulties in measuring such effects. In this paper we report that the wire beam electrode has necessary temporal and spatial resolutions required for measuring and visualising the dynamic effects of anodic transients on CP, passivation and localised corrosion processes occurring on buried steel surfaces. For the first time a critical anodic transient duration has been observed and explained as the incubation period for the breakdown of passivity and the initiation of localised corrosion.

On the fundamental mechanisms of active screen plasma nitriding

The nitriding mechanisms of conventional DC plasma treatments have been extensively studied and discussed, but no general agreement has been reached thus far. The sputtering and redeposition theory is among the most accepted ones but, even though this mechanism is feasible, its contribution to the nitriding effect is under question. Furthermore, the novel active screen plasma nitriding technique has been successful in treating samples left at floating potential, where sputtering can not be considered to play a major role. Therefore, it has been proposed that the material sputtered from the cathodic mesh of the active screen furnace (auxiliary cathode) and deposited onto the treated specimens is involved in the mass transfer of nitrogen. The contribution made by this transferred material is the focus of attention of the present study. The hardening effect on the treated specimens showed considerable correlation with the deposition layer, and the XRD analysis of this deposited material yielded possible FeN and FexN peaks. This finding supports the deposition of iron nitrides and their subsequent decomposition on the treated substrate as a mechanism of significance to the plasma nitriding treatments conducted in active screen experimental settings.

Study of active screen plasma processing conditions for carburising and nitriding austenitic stainless steel

Active screen (AS) is an advanced technology for plasma surface engineering, which offers some advantages over conventional direct current (DC) plasma treatments. Such surface defects and process instabilities as arcing, edge and hollow cathode effects can be minimised or completely eliminated by the AS technique, with consequent improvements in surface quality and material properties. However, the lack of information and thorough understanding of the process mechanisms generate scepticism in industrial practitioners. In this project, AISI 316 specimens were plasma carburised and plasma nitrided at low temperature in AS and DC furnaces, and the treated samples were comparatively analysed. Two diagnostic techniques were used to study the plasma: optical fibre assisted optical emission spectroscopy, and a planar electrostatic probe. Optimum windows of treatment conditions for AS plasma nitriding and AS plasma carburising of austenitic stainless steel were identified and some evidence was obtained on the working principles of AS furnaces. These include the sputtering of material from the cathodic mesh and its deposition on the worktable, the generation of additional active species, and the electrostatic confinement of the plasma within the operative volume of the furnace.

Desenvolvimento de métodos electroquímicos de quantificação de fármacos em amostras de água contaminadas

Este trabalho teve como objectivo, o desenvolvimento de um método electroquímico, para quantificação do fármaco carbamazepina (CBZ) em águas contaminadas. Neste trabalho foram utilizados quatro métodos voltamétricos: a voltametria cíclica, a voltametria de varrimento linear, a voltametria de onda quadrada e a voltametria de impulso diferencial. Os eléctrodos de trabalho utilizados foram, o eléctrodo de mercúrio de gota suspensa, o eléctrodo de carbono vítreo clássico e um eléctrodo de carbono vítreo modificado com um filme de nanotubos de carbono de paredes múltiplas (MWCNTs). O eléctrodo de mercúrio de gota suspensa permitiu o estudo da redução da CBZ numa região de potencial mais catódico, e os eléctrodos de carbono vítreo, com e sem modificação, permitiram o estudo da oxidação da CBZ numa região de potencial mais anódico. Nas condições experimentais estudadas, o eléctrodo de mercúrio de gota suspensa revelou ser um sensor voltamétrico pouco eficaz na determinação quantitativa da carbamazepina, em amostras com uma matriz complexa. Entre os eléctrodos de carbono vítreo, o eléctrodo de carbono vítreo modificado com os MWCNTs revelou ser o sensor voltamétrico mais eficaz e sensível, na detecção e determinação da carbamazepina. Modificado com um filme de nanotubos de carbono de paredes múltiplas, que previamente foram dispersos em dihexadecilhidrogenofosfato (DHP) e água, este novo eléctrodo permitiu obter uma resposta electroquímica da CBZ, consideravelmente superior ao eléctrodo não modificado. Utilizando a voltametria de varrimento linear e as condições experimentais consideradas óptimas, o eléctrodo nanoestruturado permitiu obter uma relação linear entre o sinal medido e a concentração da CBZ no intervalo 0.13- 1.60 M (30.7- 378 g -1), com os limites de detecção e quantificação mais baixos, até à data reportados com métodos electroquímicos (0.04 e 0.14M, respectivamente). O eléctrodo modificado foi aplicado na quantificação da CBZ, em formulações farmacêuticas, em águas naturais tratadas e em amostras de águas residuais, ambas dopadas, obtendo-se taxas de recuperação consideravelmente elevadas (100.6%, 98.0%,95.8%, respectivamente). Os resultados obtidos, na análise da CBZ em amostras ambientais, com o eléctrodo modificado, foram comparados com resultados obtidos por HPLC-UV e LC­ ESI-MS/MS, validando o método electroquímico desenvolvido neste trabalho. ABSTRACT: The aim of this work was to develop a new electrochemical method for the quantification of carbamazepine (CBZ) in contaminated waters. ln this study, four voltammetric methods were used: cyclic voltammetry, linear sweep voltammetry, square wave voltammetry and differential pulse voltammetry. the working electrodes used were the hanging mercury drop electrode (HMDE), the classical glassy carbon electrode (GCE), and a glassy carbon electrode modified with a film of multi-walled carbon nanotubes (MWCNls). Using HMDE, the reduction of CBZ was studied in the cathodic potential region. the CGE sensors, with or without modification, allowed the study of CBZ oxidation in the anodic potential region. ln the tested conditions, the results obtained for the quantification of CBZ using the HMDE sensor were not very satisfactory, especially when more complex samples were analysed. When the MWCNls-dihexadecyl hydrogen phosphate (DHP) film­ coated GCE was used for the voltammetric determination of CBZ, the results obtained showed that this modified electrode exhibits excellent enhancement effects on the electrochemical oxidation of CBZ. the oxidation peak current of CBZ at this film­ modified electrode increased significantly, when compared with that at a bare glassy carbon electrode. The enhanced electrooxidation and voltammetry of CBZ at the surface of MWCNTs-DHP film coated GCE in phosphate buffer solution (pH 6.71) was attributed to the unique properties of MWCNTs such as large specific surface area and strong adsorptive properties providing more reaction sites. The proposed method was applied to the quantification of CBZ in pharmaceutical formulations, drinking water and wastewater samples with good recoveries and low limits of detection and quantification (0.04 and 0.14 M, respectively), and was positively compared with chromatographic techniques usually used in the quantification of pharmaceutical compounds in environmental samples. HPLC-UV and LC-ESI-MS/MS were also used in the quantification of CBZ in pharmaceutical formulations and wastewater samples to prove the importance and accuracy of his voltammetric method.