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At least 1,549 records · Page 86
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Atomically Ordered PdCu Electrocatalysts for Selective and Stable Electrochemical Nitrate Reduction

Electrochemical nitrate reduction (NO 3 RR) has attracted attention as an emerging approach to mitigate nitrate pollution in groundwater. Here, we report that a highly ordered PdCu alloy-based electrocatalyst exhibits selective (91% N 2 ), stable (480 h), and near complete (94%) removal of nitrate without loss of catalyst. In situ and ex situ XAS provide evidence that structural ordering between Pd and Cu improves long-term catalyst stability during NO 3 RR. In contrast, we also report that a disordered PdCu alloy-based electrocatalyst exhibits non-selective (44% N 2 and 49% NH 4 + ), unstable, and incomplete removal of nitrate. The copper within disordered PdCu alloy is vulnerable to accepting electrons from hydrogenated neighboring Pd atoms. This resulted in copper catalyst losses which were 10× greater than that of the ordered catalyst. The design of stable catalysts is imperative for water treatment because loss of the catalyst adds to the system cost and environmental impacts.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electron-Beam Induced Emergence of Mesoscopic Ordering in Layered MnPS 3

Ordered mesoscale structures in 2D materials induced by small misorientations have allowed for a wide variety of electronic, ferroelectric, and quantum phenomena to be explored. Until now, the only mechanism to induce this periodic ordering was via mechanical rotations between the layers, with the periodicity of the resulting moiré pattern being directly related to twist angle. Here we report a fundamentally distinct mechanism for emergence of mesoscopic periodic patterns in multilayer sulfur-containing metal phosphorus trichalcogenide, MnPS3, induced by the electron beam. The formation under the beam of periodic hexagonal patterns with several characteristic length scales, nucleation and transitions between the phases, and local dynamics are demonstrated. The associated mechanisms are attributed to the relative contraction of the layers caused by beam-induced sulfur vacancy formation with subsequent ordering and lattice parameter change. As a result, the plasmonic response of the system is locally altered, suggesting an element of control over plasmon resonances by electron beam patterning. To conclude, we pose that harnessing this phenomenon provides both insight into fundamental physics of quantum materials and enables device applications by enabling controlled periodic potentials on the atomic scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Double epitaxy as a paradigm for templated growth of highly ordered three-dimensional mesophase crystals

Molecular templating and self-assembly are fundamental mechanisms for controlling the morphology of biominerals, while in synthetic two-dimensional layered materials similar levels of control over materials structure can be achieved through the epitaxial relationship with the substrate. In this study these two concepts are combined to provide an approach for the nucleation and growth of three-dimensional ordered mesophases on solid surfaces. A combined experimental and theoretical study revealed how atomic ordering of the substrate controls the structure of surfactant template and the orientation and morphology of the epitaxially grown inorganic material. Such dual epitaxial relationship between the substrate, surfactant template and inorganic mesophase gives rise to a highly ordered porous mesophase with a well-defined cubic lattice of pores. The level of control over material’s three-dimensional architecture achieved in this one-step synthesis is reminiscent to that in biomineralization.

crystal growth↗
DOE OSTI2018

Proximity-Induced Magnetic Order in a Transferred Topological Insulator Thin Film on a Magnetic Insulator

Breaking the time reversal symmetry (TRS) in a topological insulator (TI) by introducing a magnetic order gives rise to exotic quantum phenomena. One of the promising routes to inducing a magnetic order in a TI is utilizing magnetic proximity effect between a TI and a strong magnetic insulator (MI). Here, we demonstrate a TI/MI heterostructure prepared through transferring a molecular beam epitaxy (MBE)-grown Bi 2 Se 3 film onto a yttrium iron garnet (YIG) substrate via wet transfer. The transferred Bi 2 Se 3 exhibits excellent quality over a large scale. Moreover, through wet transfer we are able to engineer the interface and perform a comparative study to probe the proximity coupling between Bi 2 Se 3 and YIG under different interface conditions. A detailed investigation of both the anomalous Hall effect and quantum corrections to the conductivity in magnetotransport measurements reveals an induced magnetic order as well as TRS breaking in the transferred Bi 2 Se 3 film on YIG. In contrast, a thin layer of AlO x at the interface obstructs the proximity coupling and preserves the TRS, indicating the critical role of the interface in mediating magnetic proximity effect.

42 ENGINEERING↗
DOE OSTI2019

Unsaturated Ligands Seed an Order to Disorder Transition in Mixed Ligand Shells of CdSe/CdS Quantum Dots

A phase transition within the ligand shell of core/shell quantum dots is studied in the prototypical system of colloidal CdSe/CdS quantum dots with a ligand shell composed of bound oleate (OA) and octadecylphosphonate (ODPA). The ligand shell composition is tuned using a ligand exchange procedure and quantified through proton NMR spectroscopy. Temperature-dependent photoluminescence spectroscopy reveals a signature of a phase transition within the organic ligand shell. Surprisingly, the ligand order to disorder phase transition triggers an abrupt increase in the photoluminescence quantum yield (PLQY) and full-width at half-maximum (FWHM) with increasing temperature. The temperature and width of the phase transition show a clear dependence on ligand shell composition, such that QDs with higher ODPA fractions have sharper phase transitions that occur at higher temperatures. In order to gain a molecular understanding of the changes in ligand ordering, Fourier transform infrared and vibrational sum frequency generation spectroscopies are performed. These measurements confirm that an order/disorder transition in the ligand shell tracks with the photoluminescence changes that accompany the ligand phase transition. The phase transition is simulated through a lattice model that suggests that the ligand shell is well-mixed and does not have completely segregated domains of OA and ODPA. Finally, we show that the unsaturated chains of OA seed disorder within the ligand shell.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Elucidation of Local Ordering and Atomic-Scale Structure in Polymer-Derived SiOC

Silicon oxycarbide (SiOC) is a versatile ceramic material with tunable microstructure and compositions that can be modulated through precursor chemistry and processing conditions. Though there are several noteworthy uses of SiOC across a range of application spaces, the difficulties in elucidating the short- to medium-range order within these materials have limited the maturation of strategies to precisely control SiC x O 4–x compositions for user-tailored applications. In this contribution, we implement a range of synchrotron scattering and spectroscopy methods coupled with stochastic modeling techniques to elucidate changes in local chemistry and structure associated with the pyrolysis of a commercially available SiOC polymer precursor. Stochastic modeling approaches provide valuable insights into decoupling local Si–O and Si–C environments while confirming predominate heterogeneous phases in materials. Using pyrolysis temperatures between 250 to 800 °C results in a heterogeneous material predominately composed of SiOC and amorphous SiO 2 domains. At 1100 °C, redistribution of Si–C pairs in the SiOC network and Si–O from the SiO 2 domains create a more ordered SiOC phase with local cubic SiC-like ordering. In addition, residual carbon leads to a detectable carbon phases at 1100 °C that persist at higher temperatures. These efforts address the difficulties of obtaining atomic-scale insights into the local structure and nanoscale heterogeneities in SiOC, providing pathways toward establishing structure–property relationships for future materials development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Commodity Thermoplastic Elastomer-Enabled Templated Synthesis of Large-Pore Ordered Mesoporous Materials

Fabrication of ordered mesoporous materials (OMMs) has predominantly relied on templating-based methods. However, these methods are constrained by several limitations, especially the limited pore sizes attainable with commercially available surfactants used as structure-directing agents. To unlock the full potential of the OMMs, it is essential to develop synthetic strategies that facilitate the production of large-pore OMMs using scalable processes and cost-effective precursors. This work demonstrates the use of thermoplastic elastomer (TPE)-derived carbon replicas for synthesizing ordered mesoporous silica (OMS) and metal oxides (OMMOs) via precursor infiltration and template removal. The nanostructural evolution of the resulting inorganic materials was systematically investigated. Specifically, using tetraethyl orthosilicate (TEOS) as a silica precursor, this method can produce an OMS with relatively large pores. To establish the generalizability of this process, the fabrication approach was extended to other commercially available TPEs with varied chemical compositions and molecular weights while consistently resulting in ordered structures. Additionally, this synthetic strategy can be successfully applied to the production of OMMOs, including tin and titanium oxide matrix chemistries, yielding pore sizes of 16.0 and 19.2 nm, respectively. By developing a general method and using low-cost precursors, this work presents a scalable approach for fabricating large-pore OMMs with tunable pore textures and matrix chemistries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Many Body Effects and Icosahedral Order in Superlattice Self-Assembly

Here, we elucidate how nanocrystals “bond” to form ordered structures. For that purpose we consider nanocrystal configurations consisting of regular polygons and polyhedra, which are the motifs that constitute single component and binary nanocrystal superlattices, and simulate them using united atom models. We compute the free energy and quantify many body effects, i.e., those that cannot be accounted for by pair potential (two-body) interactions, further showing that they arise from coalescing vortices of capping ligands. We find that such vortex textures exist for configurations with local coordination number ≤6. For higher coordination numbers, vortices are expelled and nanocrystals arrange in configurations with tetrahedral or icosahedral order. We provide explicit formulas for the optimal separations between nanocrystals, which correspond to the minima of the free energies. Our results quantitatively explain the structure of superlattice nanocrystals as reported in experiments and reveal how packing arguments, extended to include soft components, predict ordered nanocrystal aggregation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Charge Recombination with Fractional Reaction Orders in Water-Splitting Dye-sensitized Photoelectrochemical Cells

In water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs), charge recombination competes with catalytic water oxidation to determine the overall efficiency of the system. The kinetics of these processes have been difficult to understand because transient absorbance (TA) experiments typically show nearly complete charge recombination on the sub-millisecond timescale; in contrast, electrochemical measurements such as open circuit photovoltage decay suggest a charge recombination timescale that is 2-3 orders of magnitude longer. Here we explore these processes with dye-sensitized nanocrystalline TiO 2 and TiO 2 /Ta 2 O 5 core-shell photoanodes in aqueous electrolytes using TA spectroscopy, intensity-modulated photovoltage spectroscopy (IMVS), and photoelectrochemical impedance spectroscopy (PEIS). The fast recombination rates measured by TA result from strong laser excitation that leads to high electron occupancy in TiO 2 , whereas IMVS modulates the concentration of charge-separated states near solar irradiance levels. The recombination processes measured by electrochemical methods such as IMVS, PEIS, and transient photovoltage are the discharging of injected electrons in TiO 2 , as evidenced by the close agreement betweeen the nearly first-order recombination rates probed by IMVS and the RC time constants derived from PEIS data. However, IMVS measurements at variable probe light intensity reveal that the reaction orders for the recombination of injected electrons with oxidized sensitizer molecules are far from unity. In conclusion, this kinetic analysis is relevant to understanding steady-state recombination rates in full WS-DSPECs in which molecular and nanoparticle catalysts are used to oxidize water.

14 SOLAR ENERGY↗
DOE OSTI2018

Ag 2 Se to KAg 3 Se 2 : Suppressing Order–Disorder Transitions via Reduced Dimensionality

Here we report an order–disorder phase transition in the 2D semiconductor KAg 3 Se 2 , which is a dimensionally reduced derivative of 3D Ag 2 Se. At ~695 K, the room temperature β-phase (CsAg 3 S 2 structure type, monoclinic space group C2/m) transforms to the high temperature α-phase (new structure type, hexagonal space group R$ \overline{3}\ $m, a = 4.5638(5) Å, c = 25.4109(6) Å), as revealed by in situ temperature-dependent X-ray diffraction. Significant Ag + ion disorder accompanies the phase transition, which resembles the low temperature (~400 K) superionic transition in the 3D parent compound. Ultralow thermal conductivity of ~0.4 W m –1 K –1 was measured in the “ordered” β-phase, suggesting anharmonic Ag motion efficiently impedes phonon transport even without extensive disordering. The optical and electronic properties of β-KAg 3 Se 2 are modified as expected in the context of the dimensional reduction framework. UV–vis spectroscopy shows an optical band gap of ~1 eV that is indirect in nature as confirmed by electronic structure calculations. Electronic transport measurements on β-KAg 3 Se 2 yielded n-type behavior with a high electron mobility of ~400 cm 2 V –1 s –1 at 300 K due to a highly disperse conduction band. Finally, our results thus imply that dimensional reduction may be used as a design strategy to frustrate order–disorder phenomena while retaining desirable electronic and thermal properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Emergent order in the kagome Ising magnet Dy 3 Mg 2 Sb 3 O 14

The Ising model—in which degrees of freedom (spins) are binary valued (up/down)—is a cornerstone of statistical physics that shows rich behaviour when spins occupy a highly frustrated lattice such as kagome. Here we show that the layered Ising magnet Dy 3 Mg 2 Sb 3 O 14 hosts an emergent order predicted theoretically for individual kagome layers of in-plane Ising spins. Neutron-scattering and bulk thermomagnetic measurements reveal a phase transition at ~ 0.3 K from a disordered spin-ice-like regime to an emergent charge ordered state, in which emergent magnetic charge degrees of freedom exhibit three-dimensional order while spins remain partially disordered. Monte Carlo simulations show that an interplay of inter-layer interactions, spin canting and chemical disorder stabilizes this state. Our results establish Dy 3 Mg 2 Sb 3 O 14 as a tuneable system to study interacting emergent charges arising from kagome Ising frustration.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2016

Electric-field-induced spin disorder-to-order transition near a multiferroic triple phase point

Here, the emergence of a triple phase point in a two-dimensional parameter space (such as pressure and temperature) can offer unforeseen opportunities for the coupling of two seemingly independent order parameters. On the basis of this, we demonstrate the electric control of magnetic order by manipulating chemical pressure: lanthanum substitution in the antiferromagnetic ferroelectric BiFeO 3 . Our demonstration relies on the finding that a multiferroic triple phase point of a single spin-disordered phase and two spin-ordered phases emerges near room temperature in Bi 0.9 La 0.1 FeO 3 ferroelectric thin films. By using spatially resolved X-ray absorption spectroscopy, we provide direct evidence that the electric poling of a particular region of the compound near the triple phase point results in an antiferromagnetic phase while adjacent unpoled regions remain magnetically disordered, opening a promising avenue for magnetoelectric applications at room temperature.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Structure and properties of densified silica glass: characterizing the order within disorder

The broken symmetry in the atomic-scale ordering of glassy versus crystalline solids leads to a daunting challenge to provide suitable metrics for describing the order within disorder, especially on length scales beyond the nearest neighbor that are characterized by rich structural complexity. Here, we address this challenge for silica, a canonical network-forming glass, by using hot versus cold compression to (i) systematically increase the structural ordering after densification and (ii) prepare two glasses with the same high-density but contrasting structures. The structure was measured by high-energy X-ray and neutron diffraction, and atomistic models were generated that reproduce the experimental results. The vibrational and thermodynamic properties of the glasses were probed by using inelastic neutron scattering and calorimetry, respectively. Traditional measures of amorphous structures show relatively subtle changes upon compacting the glass. The method of persistent homology identifies, however, distinct features in the network topology that change as the initially open structure of the glass is collapsed. The results for the same high-density glasses show that the nature of structural disorder does impact the heat capacity and boson peak in the low-frequency dynamical spectra. Densification is discussed in terms of the loss of locally favored tetrahedral structures comprising oxygen-decorated SiSi 4<:sub> tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Self-assembly of ordered graphene nanodot arrays

Our ability to fabricate nanoscale domains of uniform size in two-dimensional materials could potentially enable new applications in nanoelectronics and the development of innovative metamaterials. But, achieving even minimal control over the growth of two-dimensional lateral heterostructures at such extreme dimensions has proven exceptionally challenging. Here we show the spontaneous formation of ordered arrays of graphene nano-domains (dots), epitaxially embedded in a two-dimensional boron–carbon–nitrogen alloy. These dots exhibit a strikingly uniform size of 1.6 ± 0.2 nm and strong ordering, and the array periodicity can be tuned by adjusting the growth conditions. Furthemore, we explain this behaviour with a model incorporating dot-boundary energy, a moiré-modulated substrate interaction and a long-range repulsion between dots. This new two-dimensional material, which theory predicts to be an ordered composite of uniform-size semiconducting graphene quantum dots laterally integrated within a larger-bandgap matrix, holds promise for novel electronic and optoelectronic properties, with a variety of potential device applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Ordered hydroxyls on Ca 3 Ru 2 O 7 (001)

As complex ternary perovskite-type oxides are increasingly used in solid oxide fuel cells, electrolysis and catalysis, it is necessary to obtain a better understanding of their surface chemical properties. Here we report a pronounced ordering of hydroxyls on the cleaved (001) surface of the Ruddlesden-Popper perovskite Ca 3 Ru 2 O 7 upon water adsorption at 105 K and subsequent annealing to room temperature. Density functional theory calculations predict the dissociative adsorption of a single water molecule (E ads = 1.64 eV), forming an (OH) ads group adsorbed in a Ca-Ca bridge site, with an H transferred to a neighboring surface oxygen atom, O surf . Scanning tunneling microscopy images show a pronounced ordering of the hydroxyls with (2 × 1), c(2 × 6), (1 × 3), and (1 × 1) periodicity. The present work demonstrates the importance of octahedral rotation and tilt in perovskites, for influencing surface reactivity, which here induces the ordering of the observed OH overlayers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Generating high-order optical and spin harmonics from ferromagnetic monolayers

High-order harmonic generation (HHG) in solids has entered a new phase of intensive research, with envisioned band-structure mapping on an ultrashort time scale. This partly benefits from a flurry of new HHG materials discovered, but so far has missed an important group. HHG in magnetic materials should have profound impact on future magnetic storage technology advances. Here we introduce and demonstrate HHG in ferromagnetic monolayers. We find that HHG carries spin information and sensitively depends on the relativistic spin–orbit coupling; and if they are dispersed into the crystal momentum k space, harmonics originating from real transitions can be k-resolved and carry the band structure information. Geometrically, the HHG signal is sensitive to spatial orientations of monolayers. Different from the optical counterpart, the spin HHG, though probably weak, only appears at even orders, a consequence of SU(2) symmetry. Our findings open an unexplored frontier—magneto-high-order harmonic generation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Nonequilibrium charge-density-wave order beyond the thermal limit

The interaction of many-body systems with intense light pulses may lead to novel emergent phenomena far from equilibrium. Recent discoveries, such as the optical enhancement of the critical temperature in certain superconductors and the photo-stabilization of hidden phases, have turned this field into an important research frontier. Here, we demonstrate nonthermal charge-density-wave (CDW) order at electronic temperatures far greater than the thermodynamic transition temperature. Using time- and angle-resolved photoemission spectroscopy and time-resolved X-ray diffraction, we investigate the electronic and structural order parameters of an ultrafast photoinduced CDW-to-metal transition. Tracking the dynamical CDW recovery as a function of electronic temperature reveals a behaviour markedly different from equilibrium, which we attribute to the suppression of lattice fluctuations in the transient nonthermal phonon distribution. A complete description of the system’s coherent and incoherent order-parameter dynamics is given by a time-dependent Ginzburg-Landau framework, providing access to the transient potential energy surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2021

X-ray study of ferroic octupole order producing anomalous Hall effect

Recently found anomalous Hall, Nernst, magnetooptical Kerr, and spin Hall effects in the antiferromagnets Mn 3 X (X = Sn, Ge) are attracting much attention for spintronics and energy harvesting. Since these materials are antiferromagnets, the origin of these functionalities is expected to be different from that of conventional ferromagnets. Here, we report the observation of ferroic order of magnetic octupole in Mn 3 Sn by X-ray magnetic circular dichroism, which is only predicted theoretically so far. The observed signals are clearly decoupled with the behaviors of uniform magnetization, indicating that the present X-ray magnetic circular dichroism is not arising from the conventional magnetization. We have found that the appearance of this anomalous signal coincides with the time reversal symmetry broken cluster magnetic octupole order. Our study demonstrates that the exotic material functionalities are closely related to the multipole order, which can produce unconventional cross correlation functionalities.

36 MATERIALS SCIENCE↗