New insights into water splitting at mesoporous α-Fe₂O₃ films: a study by modulated transmittance and impedance spectroscopies

Closed access. This article was published in the Journal of the American Chemical Society [© American Chemical Society] and the definitive version is available at: http://dx.doi.org/10.1021/ja209530sThin mesoporous films of α-Fe2O3 have been prepared on conducting glass substrates using layer-by-layer self-assembly of ca. 4 nm hydrous oxide nanoparticles followed by calcining. The electrodes were used to study the oxygen evolution reaction (OER) in the dark and under illumination using in situ potential-modulated absorption spectroscopy (PMAS) and light-modulated absorption spectroscopy (LMAS) combined with impedance spectroscopy. Formation of surface-bound higher-valent iron species (or “surface trapped holes”) was deduced from the PMAS spectra measured in the OER onset region. Similar LMAS spectra were obtained at more negative potentials in the onset region of photoelectrochemical OER, indicating involvement of the same intermediates. The impedance response of the mesoporous α-Fe2O3 electrodes exhibits characteristic transmission line behavior that is attributed to slow hopping of holes, probably between surface iron species. Frequency-resolved PMAS and LMAS measurements revealed slow relaxation behavior that can be related to the impedance response and that indicates that the lifetime of the intermediates (or trapped holes) involved in the OER is remarkably long

The upper critical field of filamentary Nb3Sn conductors

We have examined the upper critical field of a large and representative set of present multi-filamentary Nb3Sn wires and one bulk sample over a temperature range from 1.4 K up to the zero field critical temperature. Since all present wires use a solid-state diffusion reaction to form the A15 layers, inhomogeneities with respect to Sn content are inevitable, in contrast to some previously studied homogeneous samples. Our study emphasizes the effects that these inevitable inhomogeneities have on the field-temperature phase boundary. The property inhomogeneities are extracted from field-dependent resistive transitions which we find broaden with increasing inhomogeneity. The upper 90-99 % of the transitions clearly separates alloyed and binary wires but a pure, Cu-free binary bulk sample also exhibits a zero temperature critical field that is comparable to the ternary wires. The highest mu0Hc2 detected in the ternary wires are remarkably constant: The highest zero temperature upper critical fields and zero field critical temperatures fall within 29.5 +/- 0.3 T and 17.8 +/- 0.3 K respectively, independent of the wire layout. The complete field-temperature phase boundary can be described very well with the relatively simple Maki-DeGennes model using a two parameter fit, independent of composition, strain state, sample layout or applied critical state criterion.Comment: Accepted Journal of Applied Physics Few changes to shorten document, replaced eq. 7-

Measurement and modeling of volume scattering functions for phytoplankton from Norwegian coastal waters

The volume scattering function (VSF) describes the angular distribution of scattered light, and the VSF of phytoplankton is one of the most important inherent optical properties of oceanic water. Despite its importance, relatively few measurements of the VSF have been carried out in aquatic environments, and we present here data and analyses of measured VSFs at 442, 490, and 550 nm for 15 representative phytoplankton species from Norwegian coastal waters. In addition, the analytic scattering phase functions Henyey-Greenstein (HG) and Fournier-Forand, as well as Mie theory, were fitted and compared to the measured VSFs. The measured VSFs for all the species were strongly, but unequally forward peaked with HG-fitted asymmetry factors in the range 0.897–0.988. The VSF of Synechococcus sp., Phaeodactylum tricornutum, and Emiliania huxleyi (naked) had shoulders in the forward direction, whereas the VSF of the cylindrically shaped Chaetoceros calcitrans and Chaetoceros wighamii had minima in the backward direction. Results from this work indicate that internal structures influence the angular and spectral shape of the VSF more significantly than the morphology and size of the phytoplankton cells

Voltammetric optimisation of TEMPO-mediated oxidations at cellulose fabric

A simple method for rapid voltammetric screening of N-oxyl based mediators and reaction conditions for electrochemical oxidation of cellulose is described. Using immobilised cellulose (cotton cloth) the screening requires small quantities of mediator and yet yields information about relative efficiency of mediator, optimum pH, and preferred buffer identity.</p

Utilization of a Pt(II) di-yne Chromophore incorporating a 2,2ʹ-bipyridine-5,5ʹ-diyl spacer as a Chelate to Synthesize a Green and Red Emitting d-f-d Heterotrinuclear Complex

A new heterotrinuclear (d-f-d) complex [Eu(btfa)31c] (btfa = 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 1c = [(Ph)(Et3P)2Pt–C≡C–R–C≡C–Pt(Et3P)2(Ph)] (R = 2,2’-bipyridine-5,5’-diyl) has been synthesized by utilizing the N,N-donor sites of the organometallic chromophore. The complex was characterized by analytical and spectroscopic methods. Photophysical properties of the complex were analysed in detail using both steady-state and time-resolved emission and excitation spectroscopy. The optical absorption spectrum of the complex is dominated by the spin allowed π–π* transitions of the btfa and 1c units in the UV-visible region (200 – 418 nm) and thus is excitable over a wide range of wavelengths across the UV into the visible region of the electromagnetic spectrum. The complex displays typical red Eu(III) emission when excited at 345 nm. However, it also shows green emission when excited at 464 nm and, thus could be an interesting candidate for full colour display applications. The change in the colour could be a result of the high value of the energy back-transfer rate (6.73 105 s–1) from the triplet state of the organometallic chromophore to the 5D1 state of Eu(III). Judd-Ofelt (J-O) intensity parameters ( and ), radiative (AR), non-radiative (AR) decay rates and intrinsic quantum yield ( ) have been calculated

Polymer of Intrinsic Microporosity (PIM-7) Coating Affects Triphasic Palladium Electrocatalysis

A film of the polymer of intrinsic microporosity PIM-7 is coated onto a glassy carbon electrode and the resulting effects on electron transfer reactions are studied for three different types of processes: (i) aqueous solution based, (ii) solid state surface immobilised, and (iii) electrocatalytic processes on electrodeposited palladium. The effects on reactivity for hydroquinone oxidation in aqueous phosphate buffer are shown to be linked to microporosity causing a slightly lower rate of mass transport without detrimental effects on electron transfer and reaction kinetics. Next, water-insoluble microcrystalline anthraquinone is immobilised directly into the PIM-7 film and shown to give a chemically reversible reduction process, which is enhanced in the presence of PIM-7, when compared to the case of anthraquinone immobilised directly onto bare glassy carbon. Electrodeposition of a film of nano-palladium is demonstrated to give catalytically active electrodes for the reduction/oxidation of protons/hydrogen, the reduction of oxygen, and for the oxidation of formic acid and methanol. With the PIM-7 film applied onto palladium, a mechanical stabilisation effect occurs. In addition, both the hydrogen insertion and the hydrogen evolution reactions as well as formic acid oxidation are enhanced. Effects are discussed in terms of PIM-7 beneficially affecting the interfacial reaction under triphasic conditions. The microporous polymer acts as an interfacial “gas management” layer.</p

Ferromagnetic material in the superconductor and its effect on the magnetization sextupole and decapole in the SSC dipoles at injection

It has been shown that the magnetization of a multifilamentary superconductor can be altered by adding nickel to the composite strand. This report presents the results of calculations of the magnetization sextupole and higher multipoles in a five centimeter SSC dipole with and without nickel as part of the strand composite. The relative distribution of the nickel in the inner and outer coil conductors can be used to effectively eliminate sextupole and decapole at the SSC dipole injection field. Calculations of magnetization sextupole in the dipole are presented for strand with substituted nickel filaments and strand with electroplated nickel. The effect of nickel in the strand on the SSC dipole field quality at fields above the injection field is described. The effect of nickel in the strand on magnetization sextupole flux creep decay and the magnetization sextupole temperature dependence is also discussed. 11 refs., 7 figs., 1 tab

A general scaling relation for the critical current density in Nb3Sn

We review the scaling relations for the critical current density (Jc) in Nb3Sn wires and include recent findings on the variation of the upper critical field (Hc2) with temperature (T) and A15 composition. We highlight deficiencies in the Summers/Ekin relations, which are not able to account for the correct Jc(T) dependence. Available Jc(H) results indicate that the magnetic field dependence for all wires can be described with Kramer's flux shear model, if non-linearities in Kramer plots are attributed to A15 inhomogeneities. The strain (eps) dependence is introduced through a temperature and strain dependent Hc2*(T,eps) and Ginzburg- Landau parameter kappa1(T,eps) and a strain dependent critical temperature Tc(eps). This is more consistent than the usual Ekin unification, which uses two separate and different dependencies on Hc2*(T) and Hc2*(eps). Using a correct temperature dependence and accounting for the A15 inhomogeneities leads to a remarkable simple relation for Jc(H,T,eps). Finally, a new relation for s(eps) is proposed, based on the first, second and third strain invariants.Comment: Accepted Topical Review for Superconductor, Science and Technolog

A Review of the Properties of Nb3Sn and Their Variation with A15 Composition, Morphology and Strain State

This article gives an overview of the available literature on simplified, well defined (quasi-)homogeneous laboratory samples. After more than 50 years of research on superconductivity in Nb3Sn, a significant amount of results are available, but these are scattered over a multitude of publications. Two reviews exist on the basic properties of A15 materials in general, but no specific review for Nb3Sn is available. This article is intended to provide such an overview. It starts with a basic description of the Niobium-Tin intermetallic. After this it maps the influence of Sn content on the the electron-phonon interaction strength and on the field-temperature phase boundary. The literature on the influence of Cu, Ti and Ta additions will then be briefly summarized. This is followed by a review on the effects of grain size and strain. The article is concluded with a summary of the main results.Comment: Invited Topical Review for Superconductor, Science and Technology. Provisionally scheduled for July 200