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We study the electrolyte-gate-induced conductance at the surface of SrTiO(3)(001). We find two distinct transport regimes as a function of gate voltage. At high carrier densities, a percolative metallic state is induced in which, at low temperatures, clear signatures of a Kondo effect are observed. At lower carrier densities, the resistance diverges at low temperatures and can be well described by a 2D variable range hopping model. We postulate that this derives from nonpercolative transport due to inhomogeneous electric fields from imperfectly ordered ions at the electrolyte-oxide interface.
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Complex oxides--containing at least two different cations on crystallographically distinct sites--have recently been shown to display redox cycling of platinum group metals (PGMs), such as Pd; for example, Pd-substituted complex oxides can reversibly extrude metallic Pd under reducing conditions and then reincorporate Pd(2+) ions into the lattice under oxidizing conditions. The title compounds, YMn(0.5)Fe(0.5-x)Pd(x)O(3-δ) (0 ≤ x ≤ 0.07) crystallizing in the noncentrosymmetric YMnO(3) structure, were prepared using a sol-gel process at 800 °C, and the structures were refined from high-resolution synchrotron X-ray powder diffraction data. Their redox cycling behavior was monitored using synchrotron X-ray diffraction and EXAFS studies. In contrast to the previously studied complex oxide host compounds, YMn(0.5)Fe(0.5-x)Pd(x)O(3-δ) is only modestly tolerant to cycling: repeated redox cycling leads to the formation of PdO, which, on the time-scale of the oxidation cycles, does not reincorporate in the complex oxide lattice. Both oxidized and reduced samples were tested for the oxidation of CO to CO(2) under CO-lean conditions. YMn(0.5)Fe(0.5-x)Pd(x)O(3-δ) performs essentially as well as previously studied YFe(1-x)Pd(x)O(3-δ). The CO oxidation light-off characteristics of the hexagonal hosts are very similar to finely dispersed PdO. Despite evidence that Pd is almost fully dispersed as divalent ions in the host lattice, which is presumably accompanied by the concurrent creation of oxygen vacancies (2 Pd(2+):1 V(O(2-))), the as-prepared hexagonal materials do not display any significant improvement in catalytic activity as a function of Pd substitution level. This suggests that the corner-connected trigonal bipyramids that characterize this structural family do not enable the transport of oxygen through the bulk of the lattice. The study casts light on factors in the solid-state chemistry of precious metal-substituted complex oxides that influence the efficacy of redox cycling of the precious metal, and catalytic performance.
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The design and fabrication of lattice-strained platinum catalysts achieved by removing a soluble core from a platinum shell synthesized via atomic layer deposition, is reported. The remarkable catalytic performance for the oxygen reduction reaction (ORR), measured in both half-cell and full-cell configurations, is attributed to the observed lattice strain. By further optimizing the nanoparticle geometry and ionomer/carbon interactions, mass activity close to 0.8 A mgPt -1 @0.9 V iR-free is achievable in the membrane electrode assembly. Nevertheless, active catalysts with high ORR activity do not necessarily lead to high performance in the high-current-density (HCD) region. More attention shall be directed toward HCD performance for enabling high-power-density hydrogen fuel cells.
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Dielectrics are an important class of materials that are ubiquitous in modern electronic applications. Even though their properties are important for the performance of devices, the number of compounds with known dielectric constant is on the order of a few hundred. Here, we use Density Functional Perturbation Theory as a way to screen for the dielectric constant and refractive index of materials in a fast and computationally efficient way. Our results constitute the largest dielectric tensors database to date, containing 1,056 compounds. Details regarding the computational methodology and technical validation are presented along with the format of our publicly available data. In addition, we integrate our dataset with the Materials Project allowing users easy access to material properties. Finally, we explain how our dataset and calculation methodology can be used in the search for novel dielectric compounds.
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The electric-field-induced metallization of insulating oxides is a powerful means of exploring and creating exotic electronic states. Here we show by the use of ionic liquid gating that two distinct facets of rutile TiO2, namely, (101) and (001), show clear evidence of metallization, with a disorder-induced metal-insulator transition at low temperatures, whereas two other facets, (110) and (100), show no substantial effects. This facet-dependent metallization can be correlated with the surface energy of the respective crystal facet and, thus, is consistent with oxygen vacancy formation and diffusion that results from the electric fields generated within the electric double layers at the ionic liquid/TiO2 interface. These effects take place at even relatively modest gate voltages.
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Electrolyte gating with ionic liquids is a powerful tool for inducing novel conducting phases in correlated insulators. An archetypal correlated material is vanadium dioxide (VO(2)), which is insulating only at temperatures below a characteristic phase transition temperature. We show that electrolyte gating of epitaxial thin films of VO(2) suppresses the metal-to-insulator transition and stabilizes the metallic phase to temperatures below 5 kelvin, even after the ionic liquid is completely removed. We found that electrolyte gating of VO(2) leads not to electrostatically induced carriers but instead to the electric field-induced creation of oxygen vacancies, with consequent migration of oxygen from the oxide film into the ionic liquid. This mechanism should be taken into account in the interpretation of ionic liquid gating experiments.
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The synthesis of multifunctional magnetic nanoparticles (NPs) is a highly active area of current research located at the interface between materials science, biotechnology and medicine. By virtue of their unique physical properties magnetic nanoparticles are emerging as a new class of diagnostic probes for multimodal tracking and as contrast agents for MRI. Furthermore, they show great potential as carriers for targeted drug and gene delivery, since reactive agents, such as drug molecules or large biomolecules (including genes and antibodies), can easily be attached to their surface. On the other hand, the fate of the nanoparticles inside the body is mainly determined by the interactions with its local environment. These interactions strongly depend upon the size of the magnetic NPs but also on the individual surface characteristics, like charge, morphology and surface chemistry. This review not only summarizes the most common synthetic approaches for the generation of magnetic NPs, it also focuses on different surface modification strategies that are used today to enhance the biocompatibility of these NPs. Finally, key considerations for the application of magnetic NPs in biomedicine, as well as various examples for the utilization in multimodal imaging and targeted gene delivery are presented.
Assuntos
Nanopartículas de Magnetita/química , Meios de Contraste/síntese química , Meios de Contraste/uso terapêutico , Portadores de Fármacos/síntese química , Portadores de Fármacos/uso terapêutico , Humanos , Imageamento por Ressonância Magnética , Nanopartículas de Magnetita/uso terapêutico , Neoplasias/diagnóstico , Neoplasias/terapiaRESUMO
We demonstrate a simple route to making hierarchically porous MnO. Macropores in Mn3O4 are induced through a process of powder sintering. The loss of volume associated with the reduction of Mn3O4 to MnO results in the formation of mesopores in the walls of a macroporous monolith of MnO. The mesopores are regenerative, in that oxidation closes them up and reduction opens them again.