Surface Protonic Conduction in Porous Oxides

Acknowledgment. This review is in part enabled through work in the projects SUPROX (280868) and MoZEES (257653) financed by the Research Council of Norway (RCN)

DFT+U studies including spin-orbit coupling - a case study for f-electrons in praseodymium-doped ceria

The mixed ionic electronic conductor Ceria exhibits not only a high concentration of Anti-Frenkel defects with high mobility, resulting in ionic conductivity of oxygen ions, but also enables an additional electronic conduction mechanism in form of small polaron hopping between the f-states of the cations. This promotes the reversible exchange of oxygen with the surrounding atmosphere and thus the oxygen storage capacity of the binary oxide CeO2-δ. The material has been established as a model system to describe both ionic and electronic transport processes in bulk material to gain deeper insights into the characteristics of polaron hopping and defect-defect interactions in mixed conductors. By introducing the redox active lanthanide Praseodymium to the Ceria host lattice, both electronic and ionic conductivities are increased in temperature and oxygen partial pressure regions where pure Ceria lacks of good performance. The redox properties of Pr-ions, shifting the equilibrium from Pr4+ to Pr3+ and forming oxygen vacancies, is key to understand the additional contribution to the total electrical conductivity and the enhanced catalytic activity. So far in literature, only the effect of Pr3+-ions in the Ceria host lattice has been investigated by means of density functional theory. To complement these investigations with the impact of Pr-ions in both oxidation states, density functional theory was applied, including a Hubbard-U correction for electronic correlation in the f-states of both cations in Ce1-xPrxO2-δ. A systematic study of spin polarization, antiferromagnetic coupling and spin-orbit interaction of the unpaired 4f-electrons was performed to investigate the influence of magnetic interactions on the description of localized polarons. The preferred localization of the excess electrons on Pr- rather than Ce-ions as well as the defect formation and configuration is discussed by analyzing the resulting energy levels and densities of states of the investigated ideal and defective super cells

Extraction of thermal and electromagnetic properties in 45Ti

The level density and gamma-ray strength function of 45Ti have been determined by use of the Oslo method. The particle-gamma coincidences from the 46Ti(p,d gamma)45Ti pick-up reaction with 32 MeV protons are utilized to obtain gamma-ray spectra as function of excitation energy. The extracted level density and strength function are compared with models, which are found to describe these quantities satisfactorily. The data do not reveal any single-particle energy gaps of the underlying doubly magic 40Ca core, probably due to the strong quadruple deformation

Lithium Phthalocyanine: A Probe for Electron Paramagnetic Resonance Oximetry in Viable Biological Systems.

Lithium phthalocyanine (LiPc) is a prototype of another generation of synthetic, metallic-organic, paramagnetic crystallites that appear very useful for in vitro and in vivo electron paramagnetic resonance oximetry. The peak-to-peak line width of the electron paramagnetic resonance spectrum of LiPc is a linear function of the partial pressure of oxygen (pO2); this linear relation is independent of the medium surrounding the LiPc. It has an extremely exchange-narrowed spectrum (peak-to-peak line width = 14 mG in the absence of O2). Physicochemically LiPc is very stable; its response to pO2 does not change with conditions and environments (e.g., pH, temperature, redox conditions) likely to occur in viable biological systems. These characteristics provide the sensitivity, accuracy, and range to measure physiologically and pathologically pertinent O2 tensions (0.1-50 mmHg; 1 mmHg = 133 Pa). The application of LiPc in biological systems is demonstrated in measurements of pO2 in vivo in the heart, brain, and kidney of rats

Creation of high mobility two-dimensional electron gases via strain induced polarization at an otherwise nonpolar complex oxide interface

The discovery of two-dimensional electron gases (2DEGs) in SrTiO3-based heterostructures provides new opportunities for nanoelectronics. Herein, we create a new type of oxide 2DEG by the epitaxial-strain-induced polarization at an otherwise nonpolar perovskite-type interface of CaZrO3/SrTiO3. Remarkably, this heterointerface is atomically sharp, and exhibits a high electron mobility exceeding 60,000 cm2V-1s-1 at low temperatures. The 2DEG carrier density exhibits a critical dependence on the film thickness, in good agreement with the polarization induced 2DEG scheme.Comment: 19 pages, 4 figs; Nano Letters,2015, published onlin

Investigation of the electrostatic potential of a grain boundary in Y-substituted BaZrO3 using inline electron holography

We apply inline electron holography to investigate the electrostatic potential across an individual BaZr0.9Y0.1O3 grain boundary. With holography, we measure a grain boundary potential of -1.3 V. Electron energy loss spectroscopy analyses indicate that barium vacancies at the grain boundary are the main contributors to the potential well in this sample. Furthermore, geometric phase analysis and density functional theory calculations suggest that reduced atomic density at the grain boundary also contributes to the experimentally measured potential well

CO2 Enhancement of Forest Productivity Constrained by Limited Nitrogen Availability

Stimulation of terrestrial productivity by rising CO~2~ concentration is projected to reduce the airborne fraction of anthropogenic CO~2~ emissions; coupled climate-carbon (C) cycle models, including those used in the IPCC Fourth Assessment Report (AR4), are sensitive to this negative feedback on atmospheric CO~2~^1^. The representation of the so-called CO~2~ fertilization effect in the 11 models used in AR4 and subsequent models^2,3^ was broadly consistent with experimental evidence from four free-air CO~2~ enrichment (FACE) experiments, which indicated that net primary productivity (NPP) of forests was increased by 23 +/- 2% in response to atmospheric CO~2~ enrichment to 550 ppm^4^. Substantial uncertainty remains, however, because of the expectation that feedbacks through the nitrogen (N) cycle will reduce the CO~2~ stimulation of NPP^5,6^; these feedbacks were not included in the AR4 models and heretofore have not been confirmed by experiments in forests^7^. Here, we provide new evidence from a FACE experiment in a deciduous Liquidambar styraciflua (sweetgum) forest stand in Tennessee, USA, that N limitation has significantly reduced the stimulation of NPP by elevated atmospheric CO~2~ concentration (eCO~2~). Isotopic evidence and N budget analysis support the premise that N availability in this forest ecosystem has been declining over time, and declining faster in eCO~2~. Model analyses and evidence from leaf- and stand-level observations provide mechanistic evidence that declining N availability constrained the tree response to eCO2. These results provide a strong rationale and process understanding for incorporating N limitation and N feedback effects in ecosystem and global models used in climate change assessments

Hydrothermal Transformation of Microporous Lithium Zinc Phosphates; A Kinetic Study using in situ Synchrotron Radiation Powder Diffraction.

The solution mediated phase transformation of a lithium zinc phosphate has been investigated. The zeolite type ABW phase, LiZnPO{sub 4}. H{sub 2}O, suspended in an aqueous solution of LiNO{sub 3}, transforms to the more dense phase, (delta tau) LiZnPO{sub 4} (crystobalite type structure). In situ time resolved powder diffraction using synchrotron radiation, has been utilized to obtain isothermal crystallization curves in the temperature range 179 {degrees} C to 210 {degrees} C. A power law was used for the kinetic analysis, giving an apparent activation energy for the reaction, Ea = 93.1 kJ/mole. The order of the power law varies from 2. 80 to 4.41 in the observed temperature range. This indicates a continuous change in the mechanism of the nucleation

C-type related order in the defective fluorites La2Ce2O7 and Nd2Ce2O7 studied by neutron scattering and ab initio MD simulations

This work presents a structural investigation of La2-xNdxCe2O7 (x = 0.0, 0.5, 1.0, 1.5, 2.0) using X-ray powder diffraction and total scattering neutron powder diffraction, analysed using Rietveld and the reverse Monte Carlo method (RMC). Ab initio molecular dynamics (MD) modelling is also performed for further investigations of the local order. The main intensities in the neutron diffraction data for the La2-xNdxCe2O7 series correspond to the fluorite structure. However, additional C-type superlattice peaks are visible for x > 0 and increase in intensity with increasing x. The Nd-containing compositions (x > 0) are best fitted with Rietveld analysis by using a combination of oxygen deficient fluorite and oxygen excess C-type structures. No indications of cation order are found in the RMC or Rietveld analysis, and the absence of cation order is supported by the MD modelling. We argue that the superlattice peaks originate from oxygen vacancy ordering and associated shift in the cation position away from the ideal fluorite site similar to that in the C-type structure, which is seen from the Rietveld refinements and the observed ordering in the MD modelling. The vacancies favour alignments in the , and especially the direction. Moreover, we find that such ordering might also be found to a small extent in La2Ce2O7, explaining the discernible modulated background between the fluorite peaks. The observed overlap of the main Bragg peaks between the fluorite and C-type phase supports the co-existence of vacancy ordered and more disordered domains. This is further supported by the observed similarity of the radial distribution functions as modelled with MD. The increase in long range oxygen vacancy order with increasing Nd-content in La2-xNdxCe2O7 corresponds well with the lower oxide ion conductivity in Nd2Ce2O7 compared to La2Ce2O7 reported earlier

The effect of the annealing temperature on the local distortion of La0.67_{0.67}Ca0.33_{0.33}MnO3_3 thin films

Mn $K$-edge fluorescence data are presented for thin film samples (3000~\AA) of Colossal Magnetoresistive (CMR) La$_{0.67}$Ca$_{0.33}$MnO$_3$: as-deposited, and post-annealed at 1000 K and 1200 K. The local distortion is analyzed in terms of three contributions: static, phonon, and an extra, temperature-dependent, polaron term. The polaron distortion is very small for the as-deposited sample and increases with the annealing temperature. In contrast, the static distortion in the samples decreases with the annealing temperature. Although the local structure of the as-deposited sample shows very little temperature dependence, the change in resistivity with temperature is the largest of these three thin film samples. The as-deposited sample also has the highest magnetoresistance (MR), which indicates some other mechanism may also contribute to the transport properties of CMR samples. We also discuss the relationship between local distortion and the magnetization of the sample.Comment: 11 pages of Preprint format, 8 figures in one tar fil