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Lithium-sulfur (Li-S) batteries show extraordinary promise as a next-generation battery technology due to their high theoretical energy density and the cost efficiency of sulfur. However, the sluggish reaction kinetics, uncontrolled growth of lithium sulfide (Li2S), and substantial Li2S oxidation barrier cause low sulfur utilization and limited cycle life. Moreover, these drawbacks get exacerbated at high current densities and high sulfur loadings. Here, a heterostructured WOx/W2C nanocatalyst synthesized via ultrafast Joule heating is reported, and the resulting heterointerfaces contribute to enhance electrocatalytic activity for Li2S oxidation, as well as controlled Li2S deposition. The densely distributed nanoparticles provide abundant binding sites for uniform deposition of Li2S. The continuous heterointerfaces favor efficient adsorption and promote charge transfer, thereby reducing the activation barrier for the delithiation of Li2S. These attributes enable Li-S cells to deliver high-rate performance and high areal capacity. This study provides insights into efficient catalyst design for Li2S oxidation under practical cell conditions.
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Kingham [(1982). The post-ionization of field evaporated ions: A theoretical explanation of multiple charge states. Surf Sci116(2), 273-301] provided equations for the probability of observing higher charge states in atom probe tomography (APT) experiments. These "Kingham curves" have wide application in APT, but cannot be analytically transformed to provide the electric field in terms of the easily measured charge state ratio (CSR). Here we provide a numerical scheme for the calculation of Kingham curves and the variation in electric field with CSR. We find the variation in electric field with CSR is well described by a simple two- or three-parameter equation, and the model is accurate to most elements and charge states. The model is applied to experimental APT data of pure aluminium and a microalloyed steel, demonstrating that the methods described in this work can be easily applied to a variety of APT problems to understand electric field variations.
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There has been an increasing interest in atom probe tomography (APT) to characterize hydrated and biological materials. A major benefit of APT compared to microscopy techniques more commonly used in biology is its combination of outstanding three-dimensional (3D) spatial resolution and mass sensitivity. APT has already been successfully used to characterize biominerals, revealing key structural information at the atomic scale, however there are many challenges inherent to the analysis of soft hydrated materials. New preparation protocols, often involving specimen preparation and transfer at cryogenic temperature, enable APT analysis of hydrated materials and have the potential to enable 3D atomic scale characterization of biological materials in the near-native hydrated state. In this study, samples of pure water at the tips of tungsten needle specimens were prepared at room temperature by graphene encapsulation. A comparative study was conducted where specimens were transferred at either room temperature or cryo-temperature and analyzed by APT by varying the flight path and pulsing mode. The differences between the analysis workflows are presented along with recommendations for future studies, and the compatibility between graphene coating and cryogenic workflows is demonstrated.
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The application of atom probe tomography (APT) to frozen liquids is limited by difficulties in specimen preparation. Here, we report on the use of nanoporous Cu needles as a physical framework to hold water ice for investigation using APT. Nanoporous Cu needles are prepared by electropolishing and dealloying Cu-Mn matchstick precursors. Cryogenic scanning electron microscopy and focused ion beam milling reveal a hierarchical, dendritic, highly wettable microstructure. The atom probe mass spectrum is dominated by peaks of Cu+ and H(H2O)n+ up to n ≤ 3, and the reconstructed volume shows the protrusion of a Cu ligament into an ice-filled pore. The continuous Cu ligament network electrically connects the apex to the cryostage, leading to an enhanced electric field at the apex and increased cooling, both of which simplify the mass spectrum compared to previous reports.
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In the archetypal antiferroelectric PbZrO_{3}, antiparallel electric dipoles cancel each other, resulting in zero spontaneous polarization at the macroscopic level. Yet in actual hysteresis loops, the cancellation is rarely perfect and some remnant polarization is often observed, suggesting the metastability of polar phases in this material. In this work, using aberration-corrected scanning transmission electron microscopy methods on a PbZrO_{3} single crystal, we uncover the coexistence of the common antiferroelectric phase and a ferrielectric phase featuring an electric dipole pattern of ↓↑↓. This dipole arrangement, predicted by Aramberri et al. to be the ground state of PbZrO_{3} at 0 K, appears at room temperature in the form of translational boundaries. The dual nature of the ferrielectric phase, both a distinct phase and a translational boundary structure, places important symmetry constraints on its growth. These are overcome by sideways motion of the boundaries, which aggregate to form arbitrarily wide stripe domains of the polar phase embedded within the antiferroelectric matrix.
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Eletricidade , Movimento (Física)RESUMO
Transition-metal oxides with a strain effect have attracted immense interest as cathode materials for fuel cells. However, owing to the introduction of heterostructures, substrates, or a large number of defects during the synthesis of strain-bearing catalysts, not only is the structure-activity relationship complicated but also their performance is mediocre. In this study, a mode of strain introduction is reported. Transition-metal ions with different electronegativities are intercalated into the cryptomelane-type manganese oxide octahedral molecular sieves (OMS-2) structure with K ions as the template, resulting in the octahedral structural distortion of MnO6 and producing strains of different degrees. Experimental studies reveal that Ni-OMS-2 with a high compressive strain (4.12%) exhibits superior oxygen reduction performance with a half-wave potential (0.825 V vs RHE) greater than those of other reported manganese-based oxides. This result is related to the increase in the covalence of MnO6 octahedral configuration and shifting down of the eg band center caused by the higher compression strain. This research avoids the introduction of new chemical bonds in the main structure, weakens the effect of eg electron filling number, and emphasizes the pure strain effect. This concept can be extended to other transition-metal-oxide catalysts.
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Óxidos , Oxigênio , Íons , Compostos de Manganês , Oxirredução , Óxidos/químicaRESUMO
Owing to dwindling fossil fuels reserves, the development of alternative renewable energy sources is globally important. Photocatalytic hydrogen (H2 ) evolution represents a practical and affordable alternative to convert sunlight into carbon-free H2 fuel. Recently, 2D/2D van der Waals heterostructures (vdWHs) have attracted significant research attention for photocatalysis. Here, for the first time a ReS2 /In2 ZnS4 2D/2D vdWH synthesized via a facile physical mixing is reported. It exhibits a highly promoted photocatalytic H2 -evolution rate of 2515 µmol h-1 g-1 . Importantly, this exceeds that for pristine In2 ZnS4 by about 22.66 times. This, therefore, makes ReS2 /In2 ZnS4 one of the most efficient In2 ZnS4 -based photocatalysts without noble-metal cocatalysts. Advanced characterizations and theoretical computations results show that interlayer electronic interaction within ReS2 /In2 ZnS4 vdWH and atomic-level S active centers along the edges of ReS2 NSs work collaboratively to result in the boosted light-induced H2 evolution. Results will be of immediate benefit in the rational design and preparation of vdWHs for applications in catalysis/(opto)electronics.
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Current reconstruction methodologies for atom probe tomography (APT) contain serious geometric artifacts that are difficult to address due to their reliance on empirical factors to generate a reconstructed volume. To overcome this limitation, a reconstruction technique is demonstrated where the analyzed volume is instead defined by the specimen geometry and crystal structure as determined by transmission electron microscopy (TEM) and diffraction acquired before and after APT analysis. APT data are reconstructed using a bottom-up approach, where the post-APT TEM image is used to define the substrate upon which APT detection events are placed. Transmission electron diffraction enables the quantification of the relationship between atomic positions and the evaporated specimen volume. Using an example dataset of ZnMgO:Ga grown epitaxially on c-plane sapphire, a volume is reconstructed that has the correct geometry and atomic spacings in 3D. APT data are thus reconstructed in 3D without using empirical parameters for the reverse projection reconstruction algorithm.
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Findings of laser-assisted atom probe tomography experiments on boron carbide elucidate an approach for characterizing the atomic structure and interatomic bonding of molecules associated with extraordinary structural stability. The discovery of crystallographic planes in these boron carbide datasets substantiates that crystallinity is maintained to the point of field evaporation, and characterization of individual ionization events gives unexpected evidence of the destruction of individual icosahedra. Statistical analyses of the ions created during the field evaporation process have been used to deduce relative atomic bond strengths and show that the icosahedra in boron carbide are not as stable as anticipated. Combined with quantum mechanics simulations, this result provides insight into the structural instability and amorphization of boron carbide. The temporal, spatial, and compositional information provided by atom probe tomography makes it a unique platform for elucidating the relative stability and interactions of primary building blocks in hierarchically crystalline materials.
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In this work, we demonstrate a new system for the examination of gas interactions with surfaces via atom probe tomography. This system provides capability of examining the surface and subsurface interactions of gases with a wide range of specimens, as well as a selection of input gas types. This system has been primarily developed to aid the investigation of hydrogen interactions with metallurgical samples, to better understand the phenomenon of hydrogen embrittlement. In its current form, it is able to operate at pressures from 10-6 to 1000 mbar (abs), can use a variety of gasses, and is equipped with heating and cryogenic quenching capabilities. We use this system to examine the interaction of hydrogen with Pd, as well as the interaction of water vapor and oxygen in Mg samples.
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Covering a broad optical spectrum, ternary InxGa1-xAs nanowires, grown by bottom-up methods, have been receiving increasing attention due to the tunability of the bandgap via In composition modulation. However, inadequate knowledge about the correlation between growth and properties restricts our ability to take advantage of this phenomenon for optoelectronic applications. Here, three different InGaAs nanowires were grown under different experimental conditions and atom probe tomography was used to quantify their composition, allowing the direct observation of the nanowire composition associated with the different growth conditions.
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Understanding oxide-metal interfaces is crucial to the advancement of materials and components for many industries, most notably for semiconductor devices and power generation. Atom probe tomography provides three-dimensional, atomic scale information about chemical composition, making it an excellent technique for interface analysis. However, difficulties arise when analyzing interfacial regions due to trajectory aberrations, such as local magnification, and reconstruction artifacts. Correlative microscopy and field simulation techniques have revealed that nonuniform evolution of the tip geometry, caused by heterogeneous field evaporation, is partly responsible for these artifacts. Here we attempt to understand these trajectory artifacts through a study of the local evaporation field conditions. With a better understanding of the local evaporation field, it may be possible to account for some of the local magnification effects during the reconstruction process, eliminating these artifacts before data analysis.
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Atom probe tomography was used to analyze self-assembled monolayers of thiophene on different surfaces, including tungsten, platinum, and aluminum, where the tungsten was examined in both pristine and oxidized forms. A glovebag with controlled atmospheres was used to alter the level of oxidation for tungsten. It was shown that different substrates lead to substantial changes in the way thiophene adsorbs on the surface. Furthermore, the oxidation of the surface strongly influenced the adsorption behavior of the thiophene molecules, leading to clear differences in the amounts and compositions of field evaporated ions and molecular ions.
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The application of atom probe tomography to the study of minerals is a rapidly growing area. Picosecond-pulsed, ultraviolet laser (UV-355 nm) assisted atom probe tomography has been used to analyze trace element mobility within dislocations and low-angle boundaries in plastically deformed specimens of the nonconductive mineral zircon (ZrSiO4), a key material to date the earth's geological events. Here we discuss important experimental aspects inherent in the atom probe tomography investigation of this important mineral, providing insights into the challenges in atom probe tomography characterization of minerals as a whole. We studied the influence of atom probe tomography analysis parameters on features of the mass spectra, such as the thermal tail, as well as the overall data quality. Three zircon samples with different uranium and lead content were analyzed, and particular attention was paid to ion identification in the mass spectra and detection limits of the key trace elements, lead and uranium. We also discuss the correlative use of electron backscattered diffraction in a scanning electron microscope to map the deformation in the zircon grains, and the combined use of transmission Kikuchi diffraction and focused ion beam sample preparation to assist preparation of the final atom probe tip.
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Correlative microscopy approaches offer synergistic solutions to many research problems. One such combination, that has been studied in limited detail, is the use of atom probe tomography (APT) and transmission Kikuchi diffraction (TKD) on the same tip specimen. By combining these two powerful microscopy techniques, the microstructure of important engineering alloys can be studied in greater detail. For the first time, the accuracy of crystallographic measurements made using APT will be independently verified using TKD. Experimental data from two atom probe tips, one a nanocrystalline Al-0.5Ag alloy specimen collected on a straight flight-path atom probe and the other a high purity Mo specimen collected on a reflectron-fitted instrument, will be compared. We find that the average minimum misorientation angle, calculated from calibrated atom probe reconstructions with two different pole combinations, deviate 0.7° and 1.4°, respectively, from the TKD results. The type of atom probe and experimental conditions appear to have some impact on this accuracy and the reconstruction and measurement procedures are likely to contribute further to degradation in angular resolution. The challenges and implications of this correlative approach will also be discussed.
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Atom probe is a powerful technique for studying the composition of nano-precipitates, but their morphology within the reconstructed data is distorted due to the so-called local magnification effect. A new technique has been developed to mitigate this limitation by characterizing the distribution of the surrounding matrix atoms, rather than those contained within the nano-precipitates themselves. A comprehensive chemical analysis enables further information on size and chemistry to be obtained. The method enables new insight into the morphology and chemistry of niobium carbonitride nano-precipitates within ferrite for a series of Nb-microalloyed ultra-thin cast strip steels. The results are supported by complementary high-resolution transmission electron microscopy.
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To be able to correlate the catalytic properties of nanoparticles with their structure, detailed knowledge about their make-up on the atomic level is required. Herein, we demonstrate how atom-probe tomography (APT) can be used to quantitatively determine the three-dimensional distribution of atoms within a Au@Ag nanoparticle with near-atomic resolution. We reveal that the elements are not evenly distributed across the surface and that this distribution is related to the surface morphology and residues from the particle synthesis.
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Kesterite is an earth-abundant energy material with high predicted power conversion efficiency, making it a sustainable and promising option for photovoltaics. However, a large open circuit voltage Voc deficit due to non-radiative recombination at intrinsic defects remains a major hurdle, limiting device performance. Incorporating Ge into the kesterite structure emerges as an effective approach for enhancing performance by manipulating defects and morphology. Herein, how different amounts of Ge affect the kesterite growth pathways through the combination of advanced microscopy characterization techniques are systematically investigated. The results demonstrate the significance of incorporating Ge during the selenization process of the CZTSSe thin film. At high temperature, the Ge incorporation effectively delays the selenization process due to the formation of a ZnSe layer on top of the metal alloys through decomposition of the Cu-Zn alloy and formation of Cu-Sn alloy, subsequently forming of Cu-Sn-Se phase. Such an effect is compounded by more Ge incorporation that further postpones kesterite formation. Furthermore, introducing Ge mitigates detrimental "horizontal" grain boundaries by increasing the grain size on upper layer. The Ge incorporation strategy discussed in this study holds great promise for improving device performance and grain quality in CZTSSe and other polycrystalline chalcogenide solar cells.
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Hydrogen embrittlement reduces the durability of the structural steels required for the hydrogen economy. Understanding how hydrogen interacts with the materials plays a crucial role in managing the embrittlement problems. Theoretical models have indicated that carbon vacancies in metal carbide precipitates are effective hydrogen traps in steels. Increasing the number of carbon vacancies in individual metal carbides is important since the overall hydrogen trapping capacity can be leveraged by introducing abundant metal carbides in steels. To verify this concept, we compare a reference steel containing titanium carbides (TiCs), which lack carbon vacancies, with an experimental steel added with molybdenum (Mo), which form Ti-Mo carbides comprising more carbon vacancies than TiCs. We employ theoretical and experimental techniques to examine the hydrogen trapping behavior of the carbides, demonstrating adding Mo alters the hydrogen trapping mechanism, enabling hydrogen to access carbon vacancy traps within the carbides, leading to an increase in trapping capacity.