Hysteresis and stepwise structure in MR curves of granular superconducting ruthenocuprates RuSr2_2(Gd1.5_{1.5}Ce0.5)_{0.5})Cu2_2O10−δ_{10-\delta}}

Granular superconductivity effects in a polycrystalline sample of ruthenocuprate RuSr$_2$(Gd$_{1.5}$Ce$_{0.5})$Cu$_2$O$_{10-\delta}$ are studied. The main attention has been devoted to manifestation of these effects in current and magnetic-field dependences of resistive transition to superconducting state. It is found that current dependences of differential resistance taken at different temperatures intersect strictly at two definite values of current demonstrating crossing point effect. This phenomenon has been explained taking into account inhomogeneous state of intergrain medium which can be considered as a two-component system. The particular attention has been given to magnetoresistance (MR) hysteresis in mixed state of this inhomogeneous system and to influence of applied current and temperature on this phenomenon. Two types of hysteresis (clockwise and anticlockwise) have been found with transition from clockwise to anticlockwise hysteresis with increasing temperature. Stepwise structure in MR hysteretic curves has been observed in low-field range. Possible reasons of the change in hysteresis behavior with increasing temperature and appearance of the stepwise structure in MR curves are discussed taking into consideration inhomogeneous state of the granular superconductor studied.Comment: 31 pages, 13 figure

Stainless steel made to rust: a robust water-splitting catalyst with benchmark characteristics

The oxygen evolution reaction (OER) is known as the efficiency-limiting step for the electrochemical cleavage of water mainly due to the large overpotentials commonly used materials on the anode side cause. Since Ni–Fe oxides reduce overpotentials occurring in the OER dramatically they are regarded as anode materials of choice for the electrocatalytically driven water-splitting reaction. We herewith show that a straightforward surface modification carried out with AISI 304, a general purpose austenitic stainless steel, very likely, based upon a dissolution mechanism, to result in the formation of an ultra-thin layer consisting of Ni, Fe oxide with a purity >99%. The Ni enriched thin layer firmly attached to the steel substrate is responsible for the unusual highly efficient anodic conversion of water into oxygen as demonstrated by the low overpotential of 212 mV at 12 mA cm−2 current density in 1 M KOH, 269.2 mV at 10 mA cm−2 current density in 0.1 M KOH respectively. The Ni, Fe-oxide layer formed on the steel creates a stable outer sphere, and the surface oxidized steel samples proved to be inert against longer operating times (>150 ks) in alkaline medium. In addition Faradaic efficiency measurements performed through chronopotentiometry revealed a charge to oxygen conversion close to 100%, thus underpinning the conclusion that no “inner oxidation” based on further oxidation of the metal matrix below the oxide layer occurs. These key figures achieved with an almost unrivalled-inexpensive and unrivalled-accessible material, are among the best ever presented activity characteristics for the anodic water-splitting reaction at pH 13

Atomically dispersed Pt-N-4 sites as efficient and selective electrocatalysts for the chlorine evolution reaction

Chlorine evolution reaction (CER) is a critical anode reaction in chlor-alkali electrolysis. Although precious metal-based mixed metal oxides (MMOs) have been widely used as CER catalysts, they suffer from the concomitant generation of oxygen during the CER. Herein, we demonstrate that atomically dispersed Pt-N-4 sites doped on a carbon nanotube (Pt-1/CNT) can catalyse the CER with excellent activity and selectivity. The Pt-1/CNT catalyst shows superior CER activity to a Pt nanoparticle-based catalyst and a commercial Ru/Ir-based MMO catalyst. Notably, Pt-1/CNT exhibits near 100% CER selectivity even in acidic media, with low Cl- concentrations (0.1M), as well as in neutral media, whereas the MMO catalyst shows substantially lower CER selectivity. In situ electrochemical X-ray absorption spectroscopy reveals the direct adsorption of Cl- on Pt-N-4 sites during the CER. Density functional theory calculations suggest the PtN4C12 site as the most plausible active site structure for the CER

Oxidized mild steel S235: an efficient anode for the electrocatalytically initiated water-splitting

The surface of steel S235 was oxidized by Cl₂ gas and checked for its electrocatalytic efficiency regarding oxygen formation in aqueous solution. If exposed to humid Cl₂ gas for 110 min, steel S235 became an electrocatalyst that exhibits an overpotential for the oxygen evolution reaction (OER) of 462 mV at 1 mA cm² at pH 7. The OER activity of the same sample at pH 13 was moderate (347 mV overpotential at 2.0 mA cm² current density) in comparison with OER electrocatalysts developed recently. Potential versus time plots measured at a constant current demonstrate the sufficient stability of all samples under catalysis conditions at pH 7 and 13 for tens of hours. High-resolution X-ray photoelectron spectra could be reasonably resolved with the proviso that Fe₂O₃, FeO(OH), MnO(OH), and Mn₂O₃ are the predominant Fe and Mn species on the surface of the oxidized steel S235

The Role of TiO2 Doping on RuO2-Coated Electrodes for the Water Oxidation Reaction

Electrochemical water splitting into H2 and O2 presents a significant and challenging energy loss due to the high overpotential required at the anode. Today, in industrially relevant applications, dimensionally stable anodes (DSA) based on the electrocatalytic active RuO2 are conventionally utilized. To enhance the resistance against corrosion, incorporation of TiO2 in the RuO2-coated electrodes is widely employed. In the present work we have used scanning electrochemical microscopy (SECM) to demonstrate that TiO2-doped RuO2-coated electrodes, in addition to being more durable, also show an electrocatalytic activity that is, on average, 13% higher as compared to the pure RuO2-coated electrodes. We also demonstrate that cracks in the pure RuO2 coating are the most active zones, probably because Ti from the Ti support has diffused into the first applied layer of the RuO2 coating. To reveal the nature of this enhanced activity for water oxidation displayed on TiO2-doped RuO2 electrodes, we have employed X-ray photoelectron spectroscopy (XPS) for material characterization. The results show that the electrocatalytic activity enhancement displayed on the mixed (Ru1–x:Tix)O2 coating is promoted through a charge transfer from the RuO2 to the TiO2, which provides new and more reactive sites designated as activated RuO2δ+.This study has partly been carried out in the framework of the European Commission FP7 Initial Training Network “ELCAT”, Grant Agreement No. 214936-2. Portions of this research were performed at SPring-8 with the approval of Japan Synchrotron Radiation Research Institute as Nanotechnology Support Project of the Ministry of Education, Culture, Sports, Science and Technology (Proposal No. 2007A2005 and 2008A1671/BL-47XU)