Physical and electrochemical evaluation of ATO supported IrO2 catalyst for proton exchange membrane water electrolyser

Antimony doped tin oxide (ATO) was studied as a support material for IrO₂ in proton exchange membrane water electrolyser (PEMWE). Adams fusion method was used to prepare the IrO₂-ATO catalysts. The physical and electrochemical characterisation of the catalysts were carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder conductivity, cyclic voltammetry (CV) and membrane electrode assembly (MEA) polarisation. The BET surface area and electronic conductivity of the supported catalysts were found to be predominantly arisen from the IrO₂. Supported catalyst showed higher active surface area than the pristine IrO₂ in CV analysis with 85% H₃PO₄ as electrolyte. The MEA performance using Nafion®−115 membrane at 80 °C and atmospheric pressure showed a better performance for IrO₂ loading ≥60 wt.% than the pristine IrO₂ with a normalised current density of 1625 mA cm⁻² @1.8 V for the 60% IrO₂-ATO compared to 1341 mA cm⁻² for the pristine IrO₂ under the same condition. The higher performance of the supported catalysts was mainly attributed to better dispersion of active IrO₂ on electrochemically inactive ATO support material, forming smaller IrO₂ crystallites. A 40 wt.% reduction in the IrO₂ was achieved by utilising the support material.

Optimised extraction of heterocyclic aromatic amines from blood using hollow fibre membrane liquid-phase microextraction and triple quadrupole mass spectrometry

Heterocyclic aromatic amines (HCA) are carcinogenic mutagens formed during cooking of proteinaceous foods, particularly meat. To assist in the ongoing search for biomarkers of HCA exposure in blood, a method is described for the extraction from human plasma of the most abundant HCAs: 2-Amino-1-methyl-6-phenylimidazo(4,5-b)pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx) (and its isomer 7,8-DiMeIQx), using Hollow Fibre Membrane Liquid-Phase Microextraction. This technique employs 2.5 cm lengths of porous polypropylene fibres impregnated with organic solvent to facilitate simultaneous extraction from an alkaline aqueous sample into a low volume acidic acceptor phase. This low cost protocol is extensively optimised for fibre length, extraction time, sample pH and volume. Detection is by UPLC-MS/MS using positive mode electrospray ionisation with a 3.4 min runtime, with optimum peak shape, sensitivity and baseline separation being achieved at pH 9.5. To our knowledge this is the first description of HCA chromatography under alkaline conditions. Application of fixed ion ratio tolerances for confirmation of analyte identity is discussed. Assay precision is between 4.5 and 8.8% while lower limits of detection between 2 and 5 pg/mL are below the concentrations postulated for acid-labile HCA-protein adducts in blood.

Preparation of Aqueous Core/Polymer Shell Microcapsules by Internal Phase Separation

Aqueous core/polymer shell microcapsules with mommuclear and polynuclear core morphologies have been formed by internal phase separation from water-in-oil emulsions. The water-in-oil emulsions were prepared with the shell polymer dissolved in the aqueous phase by adding a low boiling point cosolvent. Subsequent removal of this cosolvent (by evaporation) leads to phase separation of the polymer and, if the spreading conditions are correct, formation of a polymer shell encapsulating the aqueous core. Poly(tetrahydrofuran) (PTHF) shell/aqueous core microcapsules, with a single (mononuclear) core, have been prepared, but the low T-g (-84 degreesC) of PTHF makes characterization of the particles more difficult. Poly(methyl methacrylate) and poly(isobutyl methacrylate) have higher T-g values (105 and 55 degreesC, respectively) and can be dissolved in water at sufficiently high acetone concentrations, but evaporation of the acetone from the emulsion droplets in these cases mostly resulted in polynuclear capsules, that is, having cores with many very small water droplets contained within the polymer matrix. Microcapsules with fewer, larger aqueous droplets in the core could be produced by reducing the rate of evaporation of the acetone. A possible mechanism for the formation of these polynuclear cores is suggested. These microcapsules were prepared dispersed in an oil-continuous phase. They could, however, be successfully transferred to a water-continuous phase, using a simple centrifugation technique. In this way, microcapsules with aqueous cores, dispersed in an aqueous medium, could be made. It would appear that a real challenge with the water-core systems, compared to the previous oil-core systems, is to obtain the correct order of magnitude of the three interfacial tensions, between the polymer, the aqueous phase, and the continuous oil phase; these control the spreading conditions necessary to produce shells rather than "acorns".

Oxygen reduction reaction mechanism on nitrogen-doped graphene:A density functional theory study

Nitrogen-doped graphene (N-graphene) was reported to exhibit a good activity experimentally as an electrocatalyst of oxygen reduction reaction (ORR) on the cathode of fuel cells under the condition of electropotential of similar to 0.04 V (vs. NNE) and pH of 14. This material is promising to replace or partially replace the conventionally used Pt. In order to understand the experimental results. ORR catalyzed by N-graphene is studied using density functional theory (DFT) calculations under experimental conditions taking the solvent, surface adsorbates, and coverages into consideration. Two mechanisms, i.e., dissociative and associative mechanisms, over different N-doping configurations are investigated. The results show that N-graphene surface is covered by O with 1/6 monolayer, which is used for reactions in this work. The transition state of each elementary step was identified using four different approaches, which give rise to a similar chemistry. A full energy profile including all the reaction barriers shows that the associative mechanism is more energetically favored than the dissociative one and the removal of O species from the surface is the rate-determining step. (C) 2011 Elsevier Inc. All rights reserved.

Diabetic retinopathy:morphometric analysis of basement membrane thickening of capillaries in different retinal layers within arterial and venous environments

AIMS: To assess quantitatively variations in the extent of capillary basement membrane (BM) thickening between different retinal layers and within arterial and venous environments during diabetes.

METHODS: One year after induction of experimental (streptozotocin) diabetes in rats, six diabetic animals together with six age-matched control animals were sacrificed and the retinas fixed for transmission electron microscopy (TEM). Blocks of retina straddling the major arteries and veins in the central retinal were dissected out, embedded in resin, and sectioned. Capillaries in close proximity to arteries or veins were designated as residing in either an arterial (AE) or a venous (VE) environment respectively, and the retinal layer in which each capillary was located was also noted. The thickness of the BM was then measured on an image analyser based two dimensional morphometric analysis system.

RESULTS: In both diabetics and controls the AE capillaries had consistently thicker BMs than the VE capillaries. The BMs of both AE and VE capillaries from diabetics were thicker than those of capillaries in the corresponding retinal layer from the normal rats (p < or = 0.005). Also, in normal AE and VE capillaries and diabetic AE capillaries the BM in the nerve fibre layer (NFL) was thicker than that in either the inner (IPL) or outer (OPL) plexiform layers (p < or = 0.001). However, in diabetic VE capillaries the BMs of capillaries in the NFL were thicker than those of capillaries in the IPL (p < or = 0.05) which, in turn, had thicker BMs than capillaries in the OPL (p < or = 0.005).

CONCLUSIONS: The variation in the extent of capillary BM thickening between different retinal layers within AE and VE environments may be related to differences in levels of oxygen tension and oxidative stress in the retina around arteries compared with that around veins.

In situ catalyst activity control in a novel membrane reactor-Reaction driven wireless electrochemical promotion of catalysis

A dual chamber membrane reactor was used in order to study the effect of macroscopically applied oxygen chemical potential differences to a platinum catalyst supported on a mixed oxygen ion and electronic conducting membrane. It is believed that the oxygen chemical potential difference imposed by the use of an oxygen sweep in one of the reactor chambers causes the back-spillover of oxygen species from the support onto the catalyst surface, resulting in the modification of the catalytic activity. The use of different sweep gases, such as ethylene and hydrogen was investigated as the means to reverse the rate modification by removing the spilt over species from the catalyst surface and returning the system to its initial state. Oxygen sweep in general had a positive effect on the reaction rate with rate increases up to 20% measured. Experimental results showed that hydrogen is a more potent sweep gas than ethylene in terms of the ability to reverse rate modification. A 10% rate loss was observed when using an ethylene sweep as compared with an almost 60% rate decrease when hydrogen was used as the sweep gas. © 2009 Elsevier Ltd. All rights reserved.

Remote control of the activity of a Pt catalyst supported on a mixed ionic electronic conducting membrane

A novel configuration for the in situ control of the catalytic activity of a polycrystalline Pt catalyst supported on a mixed ionic electronic conducting (MIEC) substrate is investigated. The modification of the catalytic activity is achieved by inducing the reverse spillover of oxygen promoting species from the support onto the catalyst surface, thus modifying the chemisorptive bond energy of the gas phase adsorbed reactants. This phenomenon is known as Electrochemical Promotion of Catalysis (EPOC). In this work we investigate the use of a wireless system that takes advantage of the mixed ionic electronic conductivity of the catalyst support (internally short-circuiting the system) in a dual chamber reactor. In this wireless configuration, the reaction takes place in one chamber of the membrane reactor while introduction of the promoting species is achieved by the use of an appropriate sweep gas (and therefore control of the oxygen chemical potential difference across the membrane) on the other chamber. Experimental results have shown that the catalytic rate can be enhanced by using an oxygen sweep, while a hydrogen sweep can reverse the changes. Total rate enhancement ratios of up to 3.5 were measured. © 2008 Elsevier B.V. All rights reserved.

Electrochemical promotion of catalysis controlled by chemical potential difference across a mixed ionic-electronic conducting ceramic membrane - An example of wireless NEMCA

A La_0.6Sr_0.4Co_0.2F_0.8O₃ mixed ionic electronic conducting (MIEC) membrane was used in a dual chamber reactor for the promotion of the catalytic activity of a platinum catalyst for ethylene oxidation. By controlling the oxygen chemical potential difference across the membrane, a driving force for oxygen ions to migrate across the membrane and backspillover onto the catalyst surface is established. The reaction is then promoted by the formation of a double layer of oxide anions on the catalyst surface. Thelectronic conductivity of the membrane material eliminates the need for an external circuit to pump the promoting oxide ion species through the membrane and onto the catalyst surface. This renders this "wireless" system simpler and more amenable for large-scale practical application. Preliminary experiments show that the reaction rate of ethylene oxidation can indeed be promoted by almost one order of magnitude upon exposure to an oxygen atmosphere on the sweep side of the membrane reactor, and thus inducing an oxygen chemical potential difference across the membrane, as compared to the rate under an inert sweep gas. Moreover, the rate does not return to its initial unpromoted value upon cessation of the oxygen flow on the sweep side, but remains permanently promoted. A number of comparisons are drawn between the classical electrochemical promotion that utilises an external circuit and the "wireless" system that utilises chemical potential differences. In addition a 'surface oxygen capture' model is proposed to explain the permanent promotion of the catalyst activity. © 2007 Springer Science+Business Media, LLC.

In situ modification of a Pt catalyst supported on a mixed ionic-electronic conducting membrane

The electrochemical promotion of a platinum catalyst for ethylene oxidation on a dual chamber membrane reactor was studied. The catalyst was supported on a La_0.6Sr_0.4Co_0.2Fe_0.803 membrane. Due the supporting membrane's electronic conductivity it is possible to promote the reaction by controlling the oxygen chemical potential difference across the membrane. Upon establishment of an oxygen potential difference across the membrane, oxygen species can migrate and spillover onto the catalyst surface, modifying the catalytic activity. Initial experiments showed an overall promotion of approximately one order of magnitude of the reaction rate of ethylene, under an oxygen atmosphere on the sweep side of the membrane reactor, as compared with the rate under an inert sweep gas. The reaction rate can keep its promoted state even after the flow of oxygen on the sweep side was interrupted. This behavior caused further promotion with every experiment cycle. The causes of permanent promotion and on demonstrating controllable promotion of the catalytic activity are presented. This is an abstract of a paper presented at the AIChE Annual Meeting (San Francisco, CA 11/12-17/2006).