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Control over the morphology of nanomaterials to have a 2D structure and manipulating the surface strain of nanostructures through defect control have proved to be promising for developing efficient catalysts for sustainable chemical and energy conversion. Here a one-pot aqueous synthesis route of freestanding Pd nanosheets with a penta-twinned structure (PdPT NSs) is presented. The generation of the penta-twinned nanosheet structure can be succeeded by directing the anisotropic growth of Pd under the controlled reduction kinetics of Pd precursors. Experimental and computational investigations showed that the surface atoms of the PdPT NSs are effectively under a compressive environment due to the strain imposed by their twin boundary defects. Due to the twin boundary-induced surface strain as well as the 2D structure of the PdPT NSs, they exhibited highly enhanced electrocatalytic activity for oxygen reduction reaction compared to Pd nanosheets without a twin boundary, 3D Pd nanocrystals, and commercial Pd/C and Pt/C catalysts.
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A three-dimensional (3D) microstructural volume is reconstructed from a stack of two-dimensional sections which was obtained by serial sectioning coupled with electron back scattering diffraction (EBSD) mapping of a 316L austenitic stainless steel. A new alignment algorithm named linear translation by minimising the indicator (LTMI) is proposed to reduce the translational misalignments between adjacent sections by referencing to coherent twin boundaries which are flat and lying on {111} planes. The angular difference between the measured orientation of a flat twin boundary and that of the {111} plane is used as an indicator of the accuracy of the alignment operations. This indicator is minimised through linear translations of the centroids of triangular facets, which constitute grain boundaries at a distance not restricted by the in-plane step size of the EBSD maps. And hence the systematic trend in the translational misalignments can be effectively reduced. The LTMI alignment procedure proposed herein effectively corrects the misalignments remained by other methods on a 3D-EBSD data prepared using serial sectioning methods. The accuracy in distinguishing between coherent and incoherent twin boundaries is significantly improved.
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Periodic gyroid network materials have many interesting properties (band gaps, topologically protected modes, superior charge and mass transport, and outstanding mechanical properties) due to the space-group symmetries and their multichannel triply continuous morphology. The three-dimensional structure of a twin boundary in a self-assembled polystyrene-b-polydimethylsiloxane (PS-PDMS) double-gyroid (DG) forming diblock copolymer is directly visualized using dual-beam scanning microscopy. The reconstruction clearly shows that the intermaterial dividing surface (IMDS) is smooth and continuous across the boundary plane as the pairs of chiral PDMS networks suddenly change their handedness. The boundary plane therefore acts as a topological mirror. The morphology of the normally chiral nodes and strut loops within the networks is altered in the twin-boundary plane with the formation of three new types of achiral nodes and the appearance of two new classes of achiral loops. The boundary region shares a very similar surface/volume ratio and distribution of the mean and Gaussian curvatures of the IMDS as the adjacent ordered DG grain regions, suggesting the twin is a low-energy boundary.
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Ferroelectricity (Valasek, J. Phys. Rev. 1921, 17, 475), a spontaneous formation of electric polarization, is a solid state phenomenon, usually, associated with ionic compounds or complex materials. Here we show that, atypically for elemental solids, few-layer graphenes can host an equilibrium out-of-plane electric polarization, switchable by sliding the constituent graphene sheets. The systems hosting such effect include mixed-stacking tetralayers and thicker (5-9 layers) rhombohedral graphitic films with a twin boundary in the middle of a flake. The predicted electric polarization would also appear in marginally (small-angle) twisted few-layer flakes, where lattice reconstruction would give rise to networks of mesoscale domains with alternating value and sign of out-of-plane polarization.
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Utilizing advanced transmission electron microscopy (TEM), the structure at the (110)-type twin boundary (TB) of Ce-doped GdFeO3 (C-GFO) has been investigated with picometer precision. Such a TB is promising to generate local ferroelectricity within a paraelectric system, while precise knowledge about its structure is still largely missing. In this work, a direct measurement of the cation off-centering with respect to the neighboring oxygen is enabled by integrated differential phase contrast (iDPC) imaging, and up to 30 pm Gd off-centering is highly localized at the TB. Further electron energy loss spectroscopy (EELS) analysis demonstrates a slight accumulation of oxygen vacancies at the TB, a self-balanced behavior of Ce at the Gd sites, and a mixed occupation of Fe2+ and Fe3+ at the Fe sites. Our results provide an informative picture with atomic details at the TB of C-GFO, which is indispensable to further push the potential of grain boundary engineering.
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New pathways to controlling the morphology of superconducting vortex latticesâand their subsequent dynamicsâare required to guide and scale vortex world-lines into a computing platform. We have found that the nematic twin boundaries align superconducting vortices in the adjacent terraces due to the incommensurate potential between vortices surrounding twin boundaries and those trapped within them. With the varying density and morphology of twin boundaries, the vortex lattice assumes several distinct structural phases, including square, regular, and irregular one-dimensional lattices. Through concomitant analysis of vortex lattice models, we have inferred the characteristic energetics of the twin boundary potential and furthermore predicted the existence of geometric size effects as a function of increasing confinement by the twin boundaries. These findings extend the ideas of directed control over vortex lattices to intrinsic topological defects and their self-organized networks, which have direct implications for the future design and control of strain-based topological quantum computing architectures.
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Bornite (Cu5 FeS4 ) is an Earth-abundant, nontoxic thermoelectric material. Herein, twin engineering and Se alloying are combined in order to further improve its thermoelectric performance. Cu5 FeS4-x Sex (0 ≤ x ≤ 0.4) icosahedral nanoparticles, containing high-density twin boundaries, have been synthesized by a colloidal method. Spark plasma sintering retains twin boundaries in the pellets sintered from Cu5 FeS4-x Sex colloidal powders. Thermoelectric property measurement demonstrates that alloying Se increases the carrier concentration, leading to much-improved power factor in Se-substituted Cu5 FeS4 , for example, 0.84 mW m-1 K-2 at 726 K for Cu5 FeS3.6 Se0.4 ; low lattice thermal conductivity is also achieved, due to intrinsic structural complexity, distorted crystal structure, and existing twin boundaries and point defects. As a result, a maximum zT of 0.75 is attained for Cu5 FeS3.6 Se0.4 at 726 K, which is about 23% higher than that of Cu5 FeS4 and compares favorably to that of reported Cu5 FeS4 -based materials. In addition, the Cu5 FeS4-x Sex samples containing twin boundaries also obtain improved hardness compared to the ones fabricated by melting-annealing or ball milling. This work demonstrates an effective twin engineering-composition tuning strategy toward enhanced thermoelectric and mechanical properties of Cu5 FeS4 -based materials.
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Penta-twinned nanomaterials often exhibit unique mechanical properties. However, the intrinsic deformation behavior of penta-twins remains largely unclear, especially under the condition of high shear stress. In this study, we show that the deformation of penta-twins often subject to a structural destruction via dislocation-mediated coordinated twin boundary (TB) deformation, resulting in a reconstructed pentagon-shaped core. This reconstructed core region is mainly induced by the coordinated TB migration along different directions (for the nucleation and growth) and accelerated by the TB sliding (for the growth). The destructed penta-twin core can effectively accommodate the intrinsic disclination of the penta-twin, which further collapses beyond a critical size, as predicted by an energy-based criterion. These intrinsic deformation behaviors of penta-twins would enable the possibility of controlling the morphology of penta-twinned nanomaterials with unique properties.
Assuntos
Nanoestruturas , Rubiaceae , Estresse MecânicoRESUMO
Twinning is a common deformation mechanism in metals, and twin boundary (TB) segregation of impurities/solutes plays an important role in the performances of alloys such as thermostability, mobility, and even strengthening. The occurrence of such segregation phenomena is generally believed as a one-layer coverage of solutes alternately distributed at extension/compression sites, in an orderly, continuous manner. However, in the Mn-free and Mn-containing Mg-Nd model systems, we reported unexpected three- and five-layered discontinuous segregation patterns of the coherent {101Ì 1} TBs, and not all the extension sites occupied by solutes larger in size than Mg, and even some larger sized solutes taking the compression sites. Nd/Mn solutes selectively segregate at substitutional sites and thus to generate two new types of ordered two-dimensional TB superstructures or complexions. These findings refresh the understanding of solute segregation in the perfect coherent TBs and provide a meaningful theoretical guidance for designing materials via targeted TB segregation.
Assuntos
Ligas , Ligas/químicaRESUMO
Electroreduction of carbon dioxide (CO2RR) has been regarded as a promising approach to realize the production of useful fuels and to decrease greenhouse gas levels simultaneously, where high-efficiency catalysts are required. Herein, we report La2CuO4 nanobamboo (La2CuO4 NBs) perovskite with rich twin boundaries showing a high Faraday efficiency (FE) of 60% toward ethylene (C2H4), whereas bulk La2CuO4 exhibits a FECO of 91%. X-ray absorption spectroscopy (XAS) reveals that the Cu in La2CuO4 NBs is in the Cu2+ state, and no obvious change can be observed during the catalytic process, as monitored by in situ XAS. Density functional theory calculations reveal that the superior FEC2H4 of La2CuO4 NBs originates from the active (113) surfaces with intrinsic strain. The formation of gap states annihilates the electron transfer barrier of C-C coupling, resulting in the high FEC2H4. This work provides a new perspective for developing efficient perovskite catalysts via grain boundary engineering.
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Due to its in-plane structural anisotropy and highly polymorphic nature, borophene has been shown to form a diverse set of linear superlattice structures that are not observed in other two-dimensional materials. Here, we show both theoretically and experimentally that concentric superlattice structures can also be realized in borophene via the energetically preferred self-assembly of coherent twin boundaries. Since borophene twin boundaries do not require the creation of additional lattice defects, they are exceptionally low in energy and thus easier to nucleate and even migrate than grain boundaries in other two-dimensional materials. Due to their high mobility, borophene twin boundaries naturally self-assemble to form novel phases consisting of periodic concentric loops of filled boron hexagons that are further preferred energetically by the rotational registry of borophene on the Ag(111) surface. Compared to defect-free borophene, concentric superlattice borophene phases are predicted to possess enhanced mechanical strength and localized electronic states. Overall, these results establish defect-mediated self-assembly as a pathway to unique borophene structures and properties.
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The seed-mediated growth of noble metal nanostructures with planar geometries requires the use of seeds lined with parallel stacking faults so as to provide a break in symmetry in an otherwise isotropic metal. Although such seeds are now routinely synthesized using colloidal pathways, equivalent pathways have not yet been reported for the fabrication of substrate-based seeds with the same internal defect structures. The challenge is not merely to form seeds with planar defects but to do so in a deterministic manner so as to have stacking faults that only run parallel to the substrate surface while still allowing for the lithographic processes needed to regulate the placement of seeds. Here, we demonstrate substrate-imposed epitaxy as a viable synthetic control able to induce planar defects in Au seeds while simultaneously dictating nanostructure in-plane alignment and crystallographic orientation. The seeds, which are formed in periodic arrays using nanoimprint lithography in combination with a vapor-phase assembly process, are subjected to a liquid-phase plasmon-mediated synthesis that uses light as an external stimuli to drive a reaction yielding periodic arrays of hexagonal Au nanoplates. These achievements not only represent the first of their kind demonstrations but also advance the possibility of integrating wafer-based technologies with a rich and exciting nanoplate colloidal chemistry.
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Ultrathin bimetallic nanowires are of importance and interest for applications in electronic devices such as sensors and heterogeneous catalysts. In this work, we have designed a new, highly reproducible and generalized wet chemical method to synthesize uniform and monodispersed Au-based alloy (AuCu, AuPd, and AuPt) nanowires with tunable composition using microwave-assisted reduction at the liquid-liquid interface. These ultrathin alloy nanowires are below 4 nm in diameter and about 2 µm long. Detailed microstructural characterization shows that the wires have an face centred cubic (FCC) crystal structure, and they have low-energy twin-boundary and stacking-fault defects along the growth direction. The wires exhibit remarkable thermal and mechanical stability that is critical for important applications. The alloy wires exhibit excellent electrocatalytic activity for methanol oxidation in an alkaline medium.
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Using a homemade, novel, in situ transmission electron microscopy (TEM) double tilt tensile device, plastic behavior of single crystalline Cu nanowires of around 150 nm are studied. Deformation twins occur during the tests as predesigned before the experiments. In situ observation of twin boundary sliding (TBS) caused by full dislocation (extended dislocation) is first revealed at the atomic scale which is confirmed by molecular dynamics (MD) simulation results. Combined with twin boundary migration and multiple dislocations nucleated from surface, TBS causes a superlarge fracture strain which is over 166% and a severe necking which is over 93%, far beyond the typical values for most nanomaterials without twins.
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We demonstrate that optical second harmonic generation (SHG) can be utilized to determine the exact nature of nanotwins in noncentrosymmetric crystals, which is challenging to resolve via conventional transmission electron or scanned probe microscopies. Using single-crystalline nanotwinned CdTe nanobelts and nanowires as a model system, we show that SHG polarimetry can distinguish between upright (Cd-Te bonds) and inverted (Cd-Cd or Te-Te bonds) twin boundaries in the system. Inverted twin boundaries are generally not reported in nanowires due to the lack of techniques and complexity associated with the study of the nature of such defects. Precise characterization of the nature of defects in nanocrystals is required for deeper understanding of their growth and physical properties to enable their application in future devices.
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With the increased need for high-rate Li-ion batteries, it has become apparent that new electrode materials with enhanced Li-ion transport should be designed. Interfaces, such as twin boundaries (TBs), offer new opportunities to navigate the ionic transport within nanoscale materials. Here, we demonstrate the effects of TBs on the Li-ion transport properties in single crystalline SnO2 nanowires. It is shown that the TB-assisted lithiation pathways are remarkably different from the previously reported lithiation behavior in SnO2 nanowires without TBs. Our in situ transmission electron microscopy study combined with direct atomic-scale imaging of the initial lithiation stage of the TB-SnO2 nanowires prove that the lithium ions prefer to intercalate in the vicinity of the (101Ì ) TB, which acts as conduit for lithium-ion diffusion inside the nanowires. The density functional theory modeling shows that it is energetically preferred for lithium ions to accumulate near the TB compared to perfect neighboring lattice area. These findings may lead to the design of new electrode materials that incorporate TBs as efficient lithium pathways, and eventually, the development of next generation rechargeable batteries that surpass the rate performance of the current commercial Li-ion batteries.
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Metallic nanowires usually exhibit ultrahigh strength but low tensile ductility owing to their limited strain hardening capability. Here we study the unique strain hardening behavior of the five-fold twinned Ag nanowires by nanomechanical testing and atomistic modeling. In situ tensile tests within a scanning electron microscope revealed strong strain hardening behavior of the five-fold twinned Ag nanowires. Molecular dynamics simulations showed that such strain hardening was critically controlled by twin boundaries and pre-existing defects. Strain hardening was size dependent; thinner nanowires achieved more hardening and higher ductility. The size-dependent strain hardening was found to be caused by the obstruction of surface-nucleated dislocations by twin boundaries. Our work provides mechanistic insights into enhancing the tensile ductility of metallic nanostructures by engineering the internal interfaces and defects.
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Atomistic simulations reveal a new and unique strengthening mechanism in nanotwinned metals governed by the collective motion of multiple necklace-like extended jogged dislocations. This mechanism prevails in a columnar-grained nanotwinned metal subject to an external stress parallel to the twin planes, provided the twin boundary spacing falls below a critical value. A theoretical model based on the depinning of unit jogs on twin planes is proposed to determine the flow stress associated with this deformation mechanism and is shown to be in agreement with atomistic simulations.
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The precise design and synthesis of active sites to improve catalyst's performance has emerged as a promising tactic for electrochemistry. However, it is challenging to combine different types of active sites and manipulate them simultaneously at atomic resolution. Here, we present a strategy to synthesize Re atom-doped Cu twin boundaries (TBs), through pulsed electrodeposition and boundary segregation. The Re-doped Cu TBs demonstrate a highly efficient nitrogen reduction reaction (NRR) performance. Re-doped Cu TBs showed a turnover frequency of â¼5889 s-1, â¼800 times higher than the pure Cu TB active centers (â¼7 s-1). In addition to the "acceptance-donation" activation of N2 molecules, theoretical calculations also reveal that the Re-Re dimer on TB can boost the NRR and impede the hydrogen evolution reaction synchronously, rendering Re-doped Cu TB catalysts with high NRR activity and selectivity.
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The development of proton exchange membrane water electrolysis is a promising technology for hydrogen production, which has always been restricted by the slow kinetics of the oxygen evolution reaction (OER). Although IrOx is one of the benchmark acidic OER electrocatalysts, there are still challenges in designing highly active and stable Ir-based electrocatalysts for commercial application. Herein, a Ru-doped IrOx electrocatalyst with abundant twin boundaries (TB-Ru0.3Ir0.7Ox@ITO) is reported, employing indium tin oxide with high conductivity as the support material. Combing the TB-Ru0.3Ir0.7Ox nanoparticles with ITO support could expose more active sites and accelerate the electron transfer. The TB-Ru0.3Ir0.7Ox@ITO exhibits a low overpotential of 203 mV to achieve 10 mA cm-2 and a high mass activity of 854.45 A g-1noble metal at 1.53 V vs RHE toward acidic OER, which exceeds most reported Ir-based OER catalysts. Moreover, improved long-term stability could be obtained, maintaining the reaction for over 110 h at 10 mA cm-2 with negligible deactivation. DFT calculations further reveal the activity enhancement mechanism, demonstrating the synergistic effects of Ru doping and strains on the optimization of the d-band center (εd) position and the adsorption free energy of oxygen intermediates. This work provides ideas to realize the trade-off between high catalytic activity and good stability for acidic OER electrocatalysts.