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By employing 3,5-bis(trifluoromethyl) pyrazole (TFMP) as an electrolyte additive in both aqueous and non-aqueous mediums, a versatile interphase strategy is achieved. This facilitates stable Zn anodes with improved efficiency and longer cycling life.
Luminescence-based detection of economically critical rare earth elements is enhanced by immobilizing a metal–organic framework sensitization material onto an optical fiber, facilitating sensor regeneration and solvent removal for better signal.
N-doped carbon/FeCoCu catalysts exhibit excellent ORR performance, demonstrating outstanding rechargeability in Zn–air batteries. DFT calculations reveal enhanced conductivity and a favorable surface electronic structure for oxygen reactions.
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We demonstrate ferroelectricity in Mg-substituted ZnO thin films with the wurtzite structure. Zn 1–x Mg x O films are grown by dual-cathode reactive magnetron sputtering on (111)-Pt // (0001)-Al 2 O 3 substrates at temperatures ranging from 26 to 200 °C for compositions spanning from x = 0 to x = 0.37. X-ray diffraction indicates a decrease in the c-lattice parameter and an increase in the a-lattice parameter with increasing Mg content, resulting in a nearly constant c/a axial ratio of 1.595 over this composition range. Transmission electron microscopy studies show abrupt interfaces between Zn 1–x Mg x O films and the Pt electrode. When prepared at pO 2 = 0.025, film surfaces are populated by abnormally oriented grains as measured by atomic force microscopy for Mg concentrations >29%. Raising pO 2 to 0.25 eliminates the misoriented grains. Optical measurements show increasing bandgap values with increasing Mg content. When prepared on a 200 °C substrate, films display ferroelectric switching with remanent polarizations exceeding 100 μC cm –2 and coercive fields below 3 MVcm –1 when the Mg content is between ~30% and ~7%. Substrate temperature can be lowered to ambient conditions, and when doing so, capacitor stacks show only minor sacrifices to crystal orientation and nearly identical remanent polarization values; however, coercive fields drop below 2 MV/cm. Using ambient temperature deposition, we demonstrate ferroelectric capacitor stacks integrated directly with polymer substrate surfaces.
Zn 0.64 Mg 0.36 O (ZMO) is a newly discovered ferroelectric oxide with the wurtzite structure. Epitaxial Zn 0.64 Mg 0.36 O films from 0.036 to 0.5 μm in thickness are grown on Pt/sapphire with the crystallographic c-axis out of plane. At room temperature, the remanent polarization is ~80 μC/cm 2 and the coercive field is ~3 MV/cm. The coercive field is strongly temperature dependent up to 240 °C with a pseudo-activation energy of 23 ± 0.3 meV, suggesting that polarization reversal occurs through an extrinsic process such as domain wall motion. ZMO films can be woken up in 20 electric field cycles on driving near the coercive field; they wake up in a single loop at fields in excess of 4 MV/cm. A thermally activated fluid imprint process, with a pseudo-activation energy of 67 ± 8 meV, enlarges the coercive field by several hundred kV cm –1 after switching the polarization. Additionally, ZMO films exhibit excellent retention characteristics; no reduction in the polarization is observed up to 1000 h from room temperature to 200 °C bakes. Here, this current early generation of ZMO films can survive several thousand switching cycles before dielectric breakdown occurs.
This study reports the thickness scaling of sputtered ferroelectric Zn 0.61 Mg 0.39 O (ZMO) thin films down to 43 nm. Encapsulated IrO 2 /ZMO/Ir capacitors exhibited switchable polarizations exceeding 50 μC cm −2 and coercive fields that increased from 3.9 to 4.4 MV cm −1 as the thickness decreased. Switching kinetics are best described by the simultaneous non-linear nucleation and the growth model. Bimodal switching is prevalent at low thicknesses, with the fastest switching times measured to be approximately 400 ns. Device encapsulation made ZMO switching kinetics more abrupt, potentially due to changes in the concentration of atmosphere-induced defects such as hydroxides. These results demonstrate stable ferroelectricity and sub-microsecond switching in sub-50 nm wurtzite ZMO, highlighting its potential as a low-voltage ferroelectric for integrated nonvolatile memory applications.
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YiiP is a secondary transporter that couples Zn 2+ transport to the proton motive force. Structural studies of YiiP from prokaryotes and Znt8 from humans have revealed three different Zn 2+ sites and a conserved homodimeric architecture. These structures define the inward-facing and outward-facing states that characterize the archetypal alternating access mechanism of transport. To study the effects of Zn 2+ binding on the conformational transition, we use cryo-EM together with molecular dynamics simulation to compare structures of YiiP from Shewanella oneidensis in the presence and absence of Zn 2+ . To enable single-particle cryo-EM, we used a phage-display library to develop a Fab antibody fragment with high affinity for YiiP, thus producing a YiiP/Fab complex. To perform MD simulations, we developed a nonbonded dummy model for Zn 2+ and validated its performance with known Zn 2+ -binding proteins. Using these tools, we find that, in the presence of Zn 2+ , YiiP adopts an inward-facing conformation consistent with that previously seen in tubular crystals. After removal of Zn 2+ with high-affinity chelators, YiiP exhibits enhanced flexibility and adopts a novel conformation that appears to be intermediate between inward-facing and outward-facing states. This conformation involves closure of a hydrophobic gate that has been postulated to control access to the primary transport site. Comparison of several independent cryo-EM maps suggests that the transition from the inward-facing state is controlled by occupancy of a secondary Zn 2+ site at the cytoplasmic membrane interface. This work enhances our understanding of individual Zn 2+ binding sites and their role in the conformational dynamics that govern the transport cycle.
The exploration of unconventional catalysts for the vapor-liquid-solid synthesis of one-dimensional materials promises to yield new morphologies and functionality. Here, we show, for the model ZnO system, that unusual nanostructures can be produced via a semiconductor (Ge) catalyst. As well as the usual straight nanowires, we describe two other distinct morphologies: twisted nanowires and twisted nanotubes. The twisted nanotubes show large hollow cores and surprisingly high twisting rates, up to 9°/μm, that cannot be easily explained through the Eshelby twist model. A combination of ex situ and in situ transmission electron microscopy measurements suggest that the hollow core results from a competition between growth and etching at the Ge-ZnO interface during synthesis. The twisting rate is consistent with a softening of elastic rigidity. Finally, these results indicate that the use of unconventional, nonmetallic catalysts provides opportunities to synthesize unusual oxide nanostructures with potentially useful properties.
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Both Zn doping and c-axis magnetic fields have been observed to increase the spin stripe order in La 2-x Ba x CuO 4 with x close to 1/8. For x = 0.095, the applied magnetic field also causes superconducting layers to decouple, presumably by favoring pair-density-wave order that consequently frustrates interlayer Josephson coupling. Here we show that introducing 1% Zn also leads to an initial onset of two-dimensional (2D) superconductivity, followed by 3D superconductivity at lower temperatures, even in zero field. Overall, we infer that the Zn pins pair-density-wave order locally, establishing the generality of such behavior.
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Under ambient conditions, Zn is a hexagonal metal with a large c / a ratio of 1.856. Plastic deformation is predominantly accommodated by basal 〈 a 〉 slip and compression twins on the { 10 1 ¯ 2 } planes. Increasing hydrostatic pressure drastically reduces the c / a ratio of Zn and, when a critical threshold of c / a = 3 at about 10 GPa is crossed, the { 10 1 ¯ 2 } twins are predicted to change from compressive to tensile in nature. What happens at the transition point, when c / a = 3 , remains unknown. Here, we strain-cycle a textured polycrystalline sample of pure Zn at uniform hydrostatic pressures ranging between 2 and 17 GPa, over which the c / a ratio crosses the c / a = 3 compressive-tensile transition for { 10 1 ¯ 2 } twins. During deformation, the state of the sample is monitored through x-ray diffraction to extract texture and internal strain evolution. By comparing the experimental results with the predictions of an elastoviscoplastic polycrystal simulation, we confirm the androgynous nature of { 10 1 ¯ 2 } twin response at low and high pressures. When c / a = 3 , polycrystalline Zn does not display any evidence of twinning and its plastic behavior is controlled by mostly basal and pyramidal 〈 c + a 〉 slip activity, with a very small contribution of prismatic 〈 a 〉 slip. Evidence for the activity of other { 10 1 ¯ n } twinning modes, which have been suggested for Zn under high pressure, are not observed. Published by the American Physical Society 2024
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The high hot strength of MgO–Cr 2 O 3 refractory is often ascribed to its intimate aggregate/matrix bonding. For a fundamental comparison with it, ~2 mm aggregates of MgO and Al 2 O 3 were separately embedded in ZnAl 2 O 4 and MgAl 2 O 4 matrices, sintered at 1600°C, and examined. It was found that similarity of thermal expansion coefficient (TEC) between the aggregate and the matrix is critical to achieve good bonding and this is more important than the extent of interdiffusion. The TEC mismatch of ≥ 5.7 × 10 -6 K -1 caused significant undesirable debonding in MgO aggregate/MgAl 2 O 4 matrix sample and MgO/ZnAl 2 O 4 despite >736 μm Zn 2+ diffusion depth in the latter. Direct bonding, as inferred from a thicker interfacial reaction layer and a greater shift of the aggregate/matrix interface before and after firing, was better in MgAl 2 O 4 /ZnAl 2 O 4 combination, followed by tabular Al 2 O 3 /ZnAl 2 O 4 and Al 2 O 3 /MgAl 2 O 4 . Powder X-ray diffraction indicated that the volatilization of ZnAl 2 O 4 at 1600°C in air was negligible compared to MgO–Cr 2 O 3 .
Volatile recycling and storage in the mantle transition zone (MTZ) is important for the refertilization of the upper mantle and is associated with the generation of high-µ (HIMU, where µ is 238 U/ 204 Pb) mantle. One way to probe the MTZ and the processes associated with mantle convection is to sample lavas that originate from the shallow mantle and were contaminated by upwelling from the MTZ, such as at the previously proposed shallow plume of Bermuda. Here we present the first δ 66 Zn isotopic compositions of Bermuda silica-undersaturated and silica-saturated lavas to explore the origin of the carbon-rich lithologies and the genesis of the large seamount found in the western North Atlantic Ocean. Contrasting with global δ 66 Zn data sets, our results (δ 66 Zn between 0.24 ± 0.04 and 0.41 ± 0.04) do not support direct sampling of recycled marine carbonates in the Bermuda HIMU mantle. Instead, we show that δ 66 Zn fractionation toward higher values is associated with magmatic processes and incorporation of carbon sourced from deep fluids associated with the formation of carbonatites. These carbon-rich fluids are likely sourced from the metasomatic reactions between the subducted cold slab of the Iapetus oceanic lithosphere ca. 500 Ma and the thickened continental lithospheric mantle of Pangea. Melting of this metasomatized mantle was triggered by the arrival of the Farallon slab to the eastern North American margin in the late Cenozoic via shallow convection.