The reduction of oxygen on iron(II) oxide/poly(3,4-ethylenedioxythiophene) composite thin film electrodes

© 2014 Elsevier Ltd. All rights reserved. Conducting polymers (CPs) are currently being investigated for use in many applications owing to their abilities to catalyze a wide range of electrochemical reactions and act as an effective electrode support for various inorganic and organic electrocatalyst materials. Here, we have found that the deposition of poly(3,4-ethylenedioxythiophene) (PEDOT) through the use of an established base-inhibited chemical vapor-phase polymerization (VPP) procedure using an iron(III) tosylate oxidant results in the co-deposition of electrocatalytic iron(II) oxide species within the film. The presence of these species accounts for the 2-electron reduction of hydrogen peroxide that occurs on these electrodes during the series 4-electron oxygen reduction reaction. Furthermore, this realization leads to the possibility of fabricating thin film inorganic/CP composites of various compositions through careful choice of oxidant in a facile, one-step process. A combination of in situ Raman (487.77 nm laser) and in situ UV-Vis spectroscopy was used to probe the oxidation state of PEDOT in the thin film composite electrodes while reducing oxygen in alkaline conditions. These measurements show that the 2-electron electroreduction of hydrogen peroxide (or HO2 -) occurs only on the iron(II) oxide species in a reaction that is facilitated by an effective electron transfer from the delocalized electron orbitals of the PEDOT matrix. This approach could potentially be used in situ to monitor the electrocatalyst/electrode interface quality of conducting polymer-supported electrocatalysts.

Ionic liquid electrolytes as a platform for rechargeable metal–air batteries: a perspective

Metal-air batteries are a well-established technology that can offer high energy densities, low cost and environmental responsibility. Despite these favourable characteristics and utilisation of oxygen as the cathode reactant, these devices have been limited to primary applications, due to a number of problems that occur when the cell is recharged, including electrolyte loss and poor efficiency. Overcoming these obstacles is essential to creating a rechargeable metal-air battery that can be utilised for efficiently capturing renewable energy. Despite the first metal-air battery being created over 100 years ago, the emergence of reactive metals such as lithium has reinvigorated interest in this field. However the reactivity of some of these metals has generated a number of different philosophies regarding the electrolyte of the metal-air battery. Whilst much is already known about the anode and cathode processes in aqueous and organic electrolytes, the shortcomings of these electrolytes (i.e. volatility, instability, flammability etc.) have led some of the metal-air battery community to study room temperature ionic liquids (RTILs) as non-volatile, highly stable electrolytes that have the potential to support rechargeable metal-air battery processes. In this perspective, we discuss how some of these initial studies have demonstrated the capabilities of RTILs as metal-air battery electrolytes. We will also show that much of the long-held mechanistic knowledge of the oxygen electrode processes might not be applicable in RTIL based electrolytes, allowing for creative new solutions to the traditional irreversibility of the oxygen reduction reaction. Our understanding of key factors such as the effect of catalyst chemistry and surface structure, proton activity and interfacial reactions is still in its infancy in these novel electrolytes. In this perspective we highlight the key areas that need the attention of electrochemists and battery engineers, in order to progress the understanding of the physical and electrochemical processes in RTILs as electrolytes for the various forms of rechargeable metal-air batteries.

Improvement of the biomedical properties of titanium using SMAT and thermal oxidation

Titanium and its alloys are excellent candidates for biomedical implant. However, they exhibit relatively poor tribological properties. In this study, a two-step treatment including surface mechanical attrition treatment (SMAT) combined with thermal oxidation process has been developed to improve the tribological properties and biocompatibility of Ti. Ti after two-step treatment shows excellent wear-resistance and biocompatibility among all Ti samples, which can be ascribed to the highest surface energy, well crystallinity of rutile layer on its surface. Overall, the two-step treatment is a prospective method to produce excellent biomedical Ti materials.

Redox sulfur chemistry of the copper chaperone Atox1 is regulated by the enzyme glutaredoxin 1, the reduction potential of the glutathione couple GSSG/2GSH and the availability of Cu(I)

Glutaredoxins have been characterised as enzymes regulating the redox status of protein thiols via cofactors GSSG/GSH. However, such a function has not been demonstrated with physiologically relevant protein substrates in in vitro experiments. Their active sites frequently feature a Cys-xx-Cys motif that is predicted not to bind metal ions. Such motifs are also present in copper-transporting proteins such as Atox1, a human cytosolic copper metallo-chaperone. In this work, we present the first demonstration that: (i) human glutaredoxin 1 (hGrx1) efficiently catalyses interchange of the dithiol and disulfide forms of the Cys(12)-xx-Cys(15) fragment in Atox1 but does not act upon the isolated single residue Cys(41); (ii) the direction of catalysis is regulated by the GSSG/2GSH ratio and the availability of Cu(I); (iii) the active site Cys(23)-xx-Cys(26) in hGrx1 can bind Cu(I) tightly with femtomolar affinity (K(D) = 10(-15.5) M) and possesses a reduction potential of E(o)' = -118 mV at pH 7.0. In contrast, the Cys(12)-xx-Cys(15) motif in Atox1 has a higher affinity for Cu(I) (K(D) = 10(-17.4) M) and a more negative potential (E(o)' = -188 mV). These differences may be attributed primarily to the very low pKa of Cys23 in hGrx1 and allow rationalisation of conclusion (ii) above: hGrx1 may catalyse the oxidation of Atox1(dithiol) by GSSG, but not the complementary reduction of the oxidised Atox1(disulfide) by GSH unless Cu(aq)(+) is present at a concentration that allows binding of Cu(I) to reduced Atox1 but not to hGrx1. In fact, in the latter case, the catalytic preferences are reversed. Both Cys residues in the active site of hGrx1 are essential for the high affinity Cu(I) binding but the single Cys(23) residue only is required for the redox catalytic function. The molecular properties of both Atox1 and hGrx1 are consistent with a correlation between copper homeostasis and redox sulfur chemistry, as suggested by recent cell experiments. These proteins appear to have evolved the features necessary to fill multiple roles in redox regulation, Cu(I) buffering and Cu(I) transport.

Reduction of oxygen in a trialkoxy ammonium-based ionic liquid and the role of water

The oxygen reduction reaction in a novel trialkoxy ammonium-based ionic liquid, N-ethyl-2-(2-methoxyethoxy)-N,N-bis(2-(2-methoxyethoxy)ethyl)ethan-1-aminium bis(trifluoromethylsulfonyl)imide, [N2(20201)(20201)(20201)] [NTf2] has been studied on glassy carbon and gold electrodes, showing faster electrokinetics on glass carbon because of weaker adsorption of the IL. This has been demonstrated by theoretical calculations and electrochemical studies. In the neat IL, the oxygen is reduced to superoxide (O2 -) through a one electron process; however, better performance is attained in the presence of water (42 mol%), in terms of current density, and onset potential of the reduction process via a reversible 2-electron process. Furthermore, a remarkable increase in cyclic coulombic efficiency is observed for the wet IL (66% in comparison with the neat IL (24%), showing the practicality of a reversible O2/H2O2 system for energy storage.

Proton transport in choline dihydrogen phosphate/H3PO4 mixtures

Mixtures of the plastic crystal material choline dihydrogen phosphate [Choline][DHP] and phosphoric acid, from 4.5 mol% to 18 mol% H₃PO₄, were investigated and shown to have significantly higher proton conductivity compared to the pure [Choline][DHP]. This was particularly evident from the electrochemical hydrogen reduction reaction and the proton NMR diffusion measurements, in addition to ionic conductivity measured from the impedance spectroscopy. The ionic conductivity was observed to increase by more than an order of magnitude in phase I (i.e. the highest temperature solid phase in [Choline][DHP]) reaching up to 10⁻² S cm⁻¹. The multinuclear NMR spectroscopy data suggest that, at least on the timescale of the NMR measurement, the H⁺ cations and [DHP] anions are equivalent in both phases. The pulsed field gradient NMR diffusion measurements of the 18 mol% acid sample indicate that all three ions are mobile, however the H⁺ diffusion coefficient is an order of magnitude higher than for the [Choline] cation or the [DHP] anion, and therefore conduction in these materials is dominated by proton conductivity. The thermal stability, as measured by TGA, is unaffected with increasing acid additions and remains high; i.e. no significant mass loss below 200 °C.

A single-step synthesized cobalt-free barium ferrites-based composite cathode for intermediate temperature solid oxide fuel cells

Cobalt-free perovskite cathode with excellent oxygen reduction reaction (ORR) properties below 800 °C is a key material toward wide implementation of intermediate-temperature solid oxide fuel cells. This work reports the phase structure, microstructure and performance of such cathode based on the composite phases of triclinic Ba0.9Bi0.1FeO3-δ, cubic BaFeO3 and orthorhombic BaFe2O4 prepared by sol–gel route. The resultant barium ferrites composite cathode exhibits uniform particles, pores and elements distribution. In particular, favorable ORR properties of this cathode is demonstrated by very low interfacial resistance of only 0.036 and 0.072 Ω cm2 at 750 and 700 °C and maximum power density of 1295 and 840 mW cm−2 at 750 and 700 °C.

Plastic crystal phases with high proton conductivity

The addition of up to 4 mol% of the strong acids, trifluoromethane sulfonic acid (TfOH) and bis-trifluoromethanesulfonyl imide [HN(Tf) 2], to the organic ionic plastic crystal (OIPC) [Choline][DHP] has been shown to dramatically increase the ionic conductivity by up to three orders of magnitude whilst still retaining the crystalline structure of the OIPC matrix. This enhanced proton diffusivity led to a significant proton reduction reaction in the electrochemical measurements. Powder XRD and DSC thermal analyses strongly suggest that these mixtures are single phase, crystalline materials. The work here also confirms that an increase in TfOH acid concentration (8 mol% and 12 mol%) results in a higher content of the amorphous phase as previously observed for the H 3PO 4/[Choline][DHP] system. © 2012 The Royal Society of Chemistry.

Enhancing bi-functional electrocatalytic activity of perovskite by temperature shock : a case study of LaNiO3-ᵟ

Perovskite oxide offers an attractive alternative to precious metal electrocatalysts given its low cost and high oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity. The results obtained in this work suggest a correlation of crystal structure with ORR and OER activity for LaNiO3-?. LaNiO3-? perovskites with different crystal structure were obtained by heating at different temperatures, e.g., 400, 600, and 800 C followed by quenching into room temperature. Cubic structure (relative to rhombohedral) leads to higher ORR and OER activity as well as enhanced bi-functional electrocatalytic activity, e.g., lower difference in potential between the ORR at -3 mA cm-2 and OER at 5 mA cm -2 (?E). Therefore, this work shows the possibility to adjust bi-functional activity through a simple process. This correlation may also extend to other perovskite oxide systems.

Bi-functional oxygen electrocatalysts based on Palladium oxide-Ruthenium oxide composites

Bi-functional oxygen electrodes are an enabling component for rechargeable metal-air batteries and regenerative fuel cells, both of which are regarded as the next-generation energy devices with zero emission. Nonetheless, at the present, no single metal oxide component can catalyze both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with high performance which leads to large overpotential between ORR and OER. This work strives to address this limitation by studying the bi-functional electrocatalytic activity of the composite of a good ORR catalyst compound (e.g. palladium oxide, PdO) and a good OER catalyst compound (e.g. ruthenium oxide, RuO2) in alkaline solution (0.1M KOH) utilizing a thin-film rotating disk electrode technique. The studied compositions include PdO, RuO2, PdO/RuO2 (25wt.%/75wt.%), PdO/RuO2 (50wt.%/50wt.%) and PdO/RuO2 (75wt.%/25wt.%). The lowest overpotential (e.g. E (2 mA cm−2) - E (-2 mA cm−2)) of 0.82 V is obtained for PdO/RuO2 (25wt.%/75wt.%) (versus Ag|AgCl (3M NaCl) reference electrode).

The corrosion inhibition of aluminium alloy 7075-T651 with cerium and Mischmetal di phenyl phosphate

Previous studies have shown that cerium diphenyl phosphate (Cedpp) 3 is a very effective inhibitor of corrosion of aluminium alloys in chloride solutions. This paper describes the results of further studies using electrochemical and constant immersion corrosion tests to compare the effectiveness of Ce(dpp) 3 and Mischmetal diphenyl phosphate Mm(dpp) 3 as inhibitors of corrosion pitting on AA7075-T651 aluminium alloy. The results shows that both Ce(dpp) 3 and Mm(dpp) 3 are excellent inhibitors of pitting corrosion of this alloy in very aggressive environments of continuously aerated 0.1M and 1.0M sodium chloride (NaCl) solutions. Polarisation tests indicate that these compounds act as a cathodic inhibitors by reducing the rate of the oxygen reduction reaction, which results in a decreased corrosion current density and a separation of the corrosion potential from the pitting potential. This inhibition is thought to be due to the formation of a surface film consisting of rare earth metal oxide, aluminium oxide and a cerium-aluminium organo-phosphate complex. Surface analysis data from scanning electron microscopy and X-ray Energy Dispersive Spectroscopy show the complex nature of this protective film. This work further develops our understanding about the mechanisms through which these complex films form, and how inhibition occurs in the presence of these compounds.

High N-content holey few-layered graphene electrocatalysts: Scalable solvent-less production

Few layered nitrogen doped graphene (NG) attracts great interest in energy storage and conversion applications due to its electronic and catalytic properties. However, its bulk production cannot be envisioned by the current synthetic methods. Here we report a facile, solvent-less, low cost and high yield process for the synthesis of NG. Mechanochemical solid-state exfoliation allows scalable synthesis of holey and crumple nitrogen-doped few-layered graphene from graphite with controlled high concentration N doping and a high surface area through ball-milling. By adjusting the ratio of starting materials, the nitrogen content can be modulated from 4.87 to 17.83 at.%. Furthermore, the types of nitrogen-containing species in few-layered graphene can also be controlled. The resultant NG exhibits superior oxygen reduction reaction performance and more reliable stability than commercial Pt/C catalysts. This journal is

Ionic liquids for energy, materials, and medicine.

As highlighted by the recent ChemComm web themed issue on ionic liquids, this field continues to develop beyond the concept of interesting new solvents for application in the greening of the chemical industry. Here some current research trends in the field will be discussed which show that ionic liquids research is still aimed squarely at solving major societal issues by taking advantage of new fundamental understanding of the nature of these salts in their low temperature liquid state. This article discusses current research trends in applications of ionic liquids to energy, materials, and medicines to provide some insight into the directions, motivations, challenges, and successes being achieved with ionic liquids today.

A water-soluble antimicrobial acrylamide copolymer containing sulfitobetaine for enhanced oil recovery

Herein, we report a novel acrylamide copolymer with antimicrobial property as an enhanced oil recovery chemical. The copolymer was synthesized from acrylamide (AM), acrylic acid (AA) and 2-((2-(acryloyloxy)ethyl)dimethylammonio)ethyl sulfite (ADMES) using oxidation-reduction initiation system. Subsequently, the copolymer AM/AA/ADMES was evaluated and characterized on several aspects such as IR, ¹H NMR, intrinsic viscosity, and dissolubility. The AM/AA/ADMES solution exerted remarkable thickening ability, salt tolerance ability and viscoelasticity. In addition, the rheological properties, temperature resistance ability and long-term stability of AM/AA/ADMES were investigated systematically in the presence of sulfate-reducing bacteria and relatively low viscosity loss could be obtained compared to partially hydrolyzed polyacrylamide. On the basis of core flooding experiments, AM/AA/ADMES was found to be a valuable prospect with 10.5 resistance factor, 4.6 residual resistance factor and up to 11.0% enhanced oil recovery.