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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Trace level of atomic copper in N-doped graphene quantum dots switching the selectivity from C 1 to C 2 products in CO electroreduction

To unravel the relationship between trace Cu on the metal-free catalysts toward CO/CO 2 reduction reaction (CO/CO 2 RR), we investigated the effect of trace Cu loading in N-doped graphene quantum dots (NGQDs) on CO/CO 2 RR. A general trend is that increasing the Cu loading in NGQDs switches the selectivity from C 1 (CH 4 ) to C 2 products in CORR. When 2.5 μg/cm 2 Cu with the atomic size is loaded on NGQDs, the selectivity shifts from 62% Faradaic efficiency (FE) of CH 4 to 52% FE of C 2 products in CORR. Further increasing the atomic Cu loading to 3.8 μg/cm 2 promotes the FE of C 2 products to 78%. CO 2 RR requires one order of magnitude higher Cu loading than CORR to switch the selectivity from C 1 to C 2 products due to the low partial pressure of CO. Finally, this study clarifies the distinct impact of trace (ppm level) Cu on the activity/selectivity between CORR and CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Charge density wave and superconductivity competition in Lu 5 Ir 4 Si 10 : A proton irradiation study

Real-space modulated charge density waves (CDW) are a ubiquitous feature in many families of superconductors. In particular, how CDW relates to superconductivity is an active and open question that has recently gathered much interest since CDWs have been discovered in many cuprates superconductors. Here we show that disorder induced by proton irradiation is a full-fledged tuning parameter that can bring essential information to answer this question as it affects CDW and superconductivity with different and unequivocal mechanisms. Specifically, in the model CDW superconductor Lu 5 Ir 4 Si 10 that develops a 1D CDW below 77 K and s-wave superconductivity below 4 K, we show that disorder enhances the superconducting critical temperature T c and H c2 while it suppresses the CDW. Discussing how disorder affects both superconductivity and the CDW, we make a compelling case that superconductivity and CDW are competing for electronic density of states at the Fermi level in Lu 5 Ir 4 Si 10 , and we reconcile the results obtained via the more common tuning parameters of pressure and doping. Owing to its prototypical, 1D, Peierls type CDW and the s-wave, weak-coupling nature of its superconductivity, this irradiation study of Lu 5 Ir 4 Si 10 provides the basis to understand and extend such studies to the more complex cases of density waves and superconductivity coexistence in heavy fermions, Fe-based, or cuprates superconductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

CHARGED POINT DEFECTS AND DEFECT COMPLEXES IN PHOSPHORENE AND STRUCTURAL PREDICTION OF TAU-11, A DENSITY FUNCTIONAL THEORY APPROACH

With the advent of powerful computers, first principle calculations have become a robust and reliable tool to complement experiments in the study of materials. First principle calculations such as density functional theory can be used to guide experiments to save time and effort when it comes to new and advanced materials discovery. Study of charge defects in materials and crystal structure prediction are such areas in which density functional theory calculations facilitate the prediction of defect formation energy, charge transition levels and elemental site occupations. Experimentally, studying charge defects requires inferring results from various techniques. Likewise, determining site occupancies for similar elements using experimental techniques is challenging and sometimes impossible. In this work, we study the charged intrinsic and extrinsic defects and defect complexes in phosphorene and determine the site occupancies of Al, Fe and Si in the τ11 phase using density functional theory. In the defect work, we calculate the defect formation energy, charge transition level, binding energies and Stokes shift for vacancy, dopant substitution and dopant-vacancy defect complexes in phosphorene. We found that vacancy defect in phosphorene becomes negatively charged in n-type doping and may passivate the dopants and reduce carrier concentration and mobility. For non-metal dopants in phosphorene, we predict that O, S and Si prefer to form dopant-vacancy complexes removing the vacancy defect states from the band gap. Mn dopant-vacancy defect complex exhibits possibility of switching between two magnetic spin states. Lastly, using density functional theory, we complement the results from neutron powder diffraction to determine the site occupancies of Al and Si in τ11 phase which was used to determine the alloying element to develop a high temperature and low density alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Suppression of thermal conductivity and electronic correlations in Fe 1– x Ru x Sb 2 (0 ≤ x ≤ 0.6)

We present simultaneous suppression of FeSb 2 thermal conductivity and electronic correlations in Fe 1– x Ru x Sb 2 (0 ≤ x ≤ 0.6) single crystal alloys. Small energy gap Δ 1 in Kondo-insulator-like semiconductor FeSb 2 associated with impurity in-gap state increases whereas the intrinsic bandgap Δ 2 decreases upon Ru substitution on Fe atomic site. Thermopower is suppressed along with the intrinsic bandgap and with the thermal conductivity. The more delocalized 4 d character of atomic orbital of Ru brings suppression of electronic correlations, but also an increase in impurity density which reduces phonon mean free path and surface scattering length. Our results indicate a range of Ru doping x where nanostructuring could be used to suppress thermal conductivity further, potentially toward the amorphous limit.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Deep level defects in low-pressure chemical vapor deposition grown (010) β-Ga 2 O 3

This study provides the full-bandgap evaluation of defect state distributions in beta phase gallium oxide (β-Ga 2 O 3 ) grown by low-pressure chemical vapor deposition (LPCVD) on (010) β-Ga 2 O 3 substrates at high growth of up to 20 µm/h. Deep-level optical spectroscopy and deep-level transient spectroscopy measurements applied to Ni/β-Ga 2 O 3 Schottky diodes revealed the presence of a previously unreported defect state at E C -3.6 eV, which dominated the overall trap distribution in LPCVD grown material. However, states at E C -0.8 eV, E C -2.0 eV, and E C -4.4. eV were also detected, similar to prior studies on β-Ga 2 O 3 grown by other methods, with similar or lower concentrations for the LPCVD samples. The E C -0.8 eV and E C -2.0 eV states were previously connected to residual Fe impurities and gallium vacancies, respectively. The total concentration of traps in the LPCVD material was on par with or lower than the state-of-the-art metal–organic chemical vapor deposition-grown materials despite the much higher growth rate, and the distribution of states showed negligible dependence on SiCl 4 flow rate and doping concentration. These results demonstrate that the high growth rate of LPCVD-grown β-Ga 2 O 3 is very promising for achieving thick, low defect density, and high-quality layers needed for multi-kV device applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Cation Migration and LSCF/SDC Decomposition Related to Long-Term Operation Mode as Revealed by Electron Microscopy

This study utilized energy dispersive spectroscopy (EDS) in a scanning electron microscope (SEM) and a scanning transmission electron microscope (STEM) in order to track cation migration and related particle decomposition for air electrode components of solid oxide cells. The influence of a Sm-doped ceria (SDC) barrier layers was assessed for three operation modes (fuel cell, electrolysis, reversible) over long time periods (1000-1500 hours). Composition profiles across air electrode/electrolyte interfaces indicated negligible accumulation of La/Sr cations to the yttria-stabilized zirconia (YSZ) electrolyte during operation. Instead, air electrode particles composed of SDC and/or La-Sr-Co-Fe-oxides (LSCF) exhibited decomposition by Sr evaporation and Sm migration to LSCF particle edges.

Picard, Yoosuf↗
DOE OSTI2021

Microscopic Phase Diagram of Eu(Fe 1-x Ni x )As 2 ( x = 0,0.04) Under Pressure

This study will go to establish the microscopic P-T phase diagram of recent 112-type iron-pnictides Eu(Fe 1-x Ni x )As- 2 (x = 0,0.04), high-pressure synchrotron Mossbauer spectroscopy experiments in 151 Eu and 57 Fe have been performed. In EuFeAs 2 application of pressure completely suppresses the itinerant electron magnetism from the Fe sublattice and the local-moment magnetism in Eu ions at similar to ~10 and similar to ~11.6 GPa, respectively. High-pressure x-ray diffraction experiments in EuFeAs 2 reveal an anomalous change in the lattice parameters and a discontinuity in volume around 10 GPa, suggesting an isostructural transition at this pressure. With Ni-doping (x = 0.04), a collapse of local magnetic order occurs at similar to ~8GPa, a lower critical pressure compared with the parent compound. In both systems, the suppression of local-moment magnetism is associated with a significant increase of mean valence in Eu ions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Quantitative relationship between structural orthorhombicity, shear modulus, and heat capacity anomaly of the nematic transition in iron-based superconductors

Electronic nematicity in iron pnictide materials has been extensively studied by various experimental techniques, yet its heat capacity anomaly at the phase transition has not been examined quantitatively. In this paper, we review the thermodynamic description of nematicity in Ba(Fe 1- x Cox) 2 As 2 using the Landau free energy, which defines the behavior of three thermodynamic quantities: the structural orthorhombicity that develops below the nematic transition, the softening shear modulus above the transition, and the discontinuous heat capacity at the transition. We derive a quantitative relationship between these three quantities, which is found to hold for a range of dopings. We report this result shows that the nematic transition is exceedingly well described by a mean-field model in the underdoped regime of the phase diagram.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Nematic Fluctuations in the Non-Superconducting Iron Pnictide BaFe 1.9-x Ni 0.1 Cr x As 2

The main driven force of the electronic nematic phase in iron-based superconductors is still under debate. Here, we report a comprehensive study on the nematic fluctuations in a non-superconducting iron pnictide system BaFe 1.9-x Ni 0.1 Cr x As 2 by electronic transport, angle-resolved photoemission spectroscopy (ARPES), and inelastic neutron scattering (INS) measurements. Previous neutron diffraction and transport measurements suggested that the collinear antiferromagnetism persists to x = 0.8, with similar Néel temperature TN and structural transition temperature Ts around 32 K, but the charge carriers change from electron type to hole type around x = 0.5. In this study, we have found that the in-plane resistivity anisotropy also highly depends on the Cr dopings and the type of charge carriers. While ARPES measurements suggest possibly weak orbital anisotropy onset near Ts for both x = 0.05 and x = 0.5 compounds, INS experiments reveal clearly different onset temperatures of low-energy spin excitation anisotropy, which is likely related to the energy scale of spin nematicity. These results suggest that the interplay between the local spins on Fe atoms and the itinerant electrons on Fermi surfaces is crucial to the nematic fluctuations of iron pnictides, where the orbital degree of freedom may behave differently from the spin degree of freedom, and the transport properties are intimately related to the spin dynamics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Atomically Dispersed Iron–Nitrogen Sites on Hierarchically Mesoporous Carbon Nanotube and Graphene Nanoribbon Networks for CO 2 Reduction

Atomically dispersed metal and nitrogen co-doped carbon (M-N/C) catalysts hold great promise for electrochemical CO 2 conversion. However, there is a lack of cost-effective synthesis approaches to meet the goal of economic mass production of single-atom M-N/C with desirable carbon support architecture for efficient CO 2 reduction. Herein, we report facile transformation of commercial carbon nanotube (CNT) into isolated Fe-N 4 sites anchored on carbon nanotube and graphene nanoribbon (GNR) networks (Fe-N/CNT@GNR). The oxidization-induced partial unzipping of CNT results in the generation of GNR nanolayers attached to the remaining fibrous CNT frameworks, which reticulates a hierarchically mesoporous complex and thus enables a high electrochemical active surface area and smooth mass transport. The Fe residues originating from CNT growth seeds serve as Fe sources to form isolated Fe-N-4 moieties located at the CNT and GNR basal plane and edges with high intrinsic capability of activating CO 2 and suppressing hydrogen evolution. The Fe-N/CNT@GNR delivers a stable CO Faradaic efficiency of 96% with a partial current density of 22.6 mA cm -2 at a low overpotential of 650 mV, making it one of the most active M-N/C catalysts reported. This work presents an effective strategy to fabricate advanced atomistic catalysts and highlights the key roles of support architecture in single-atom electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thermodynamic approach for enhancing superconducting critical current performance

Abstract The addition of artificial pinning centers has led to an impressive increase in the critical current density ( J c ) of superconductors, enabling record-breaking all-superconducting magnets and other applications. The J c of superconductors has reached ~0.2–0.3 J d , where J d is the depairing current density, and the numerical factor depends on the pinning optimization. By modifying λ and/or ξ, the penetration depth and coherence length, respectively, we can increase J d . For (Y 0.77 Gd 0.23 )Ba 2 Cu 3 O y ((Y,Gd)123), we can achieve this by controlling the carrier density, which is related to λ and ξ. We can also tune λ and ξ by controlling the chemical pressure in Fe-based superconductors, i.e., BaFe 2 (As 1− x P x ) 2 films. The variation in λ and ξ leads to an intrinsic improvement in J c via J d , allowing extremely high values of J c of 130 MA/cm 2 and 8.0 MA/cm 2 at 4.2 K, consistent with an enhancement in J d of a factor of 2 for both incoherent nanoparticle-doped (Y,Gd)123 coated conductors (CCs) and BaFe 2 (As 1− x P x ) 2 films, showing that this new material design is useful for achieving high critical current densities in a wide array of superconductors. The remarkably high vortex-pinning force in combination with this thermodynamic and pinning optimization route for the (Y,Gd)123 CCs reached ~3.17 TN/m 3 at 4.2 K and 18 T ( H || c ), the highest values ever reported for any superconductor.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Ion Implantation-Induced Plastic Phenomena in Metallic Alloys

Ion implantation is widely used for doping semiconductors or electroceramic materials and probing material behaviors in extreme radiation environments. However, implanted ions can induce compressive stresses into the host material, which can induce plasticity and mesoscopic deformation. However, these phenomena have almost exclusively been observed in brittle ionic and/or covalently bonded materials. Here, in this study, we present transmission electron microscopy observations of unusual implantation-induced plasticity in two metallic alloys. First, Fe 2+ ions induce dislocation plasticity below the implanted layer in a model Fe-P alloy. Next, He+ ions form pressurized cavities which activate the fcc-to-hcp strain-induced martensitic transformation in Alloy 625. In both cases, the plasticity can be explained by a combination of implanted ions being incorporated into the lattice and the creation of irradiation defects. These findings have significant implications for mechanical testing of ion-implanted layers, while also opening pathways for using ion implantation to tune stress distributions in metallic alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of the sample work function on alkali metal dosing induced electronic structure change

Alkali metal dosing (AMD) has been widely used as a way to control doping without chemical substitution. This technique, in combination with angle resolved photoemission spectroscopy (ARPES), often provides an opportunity to observe unexpected phenomena. However, the amount of transferred charge and the corresponding change in the electronic structure vary significantly depending on the material. Here, we report study on the correlation between the sample work function and alkali metal induced electronic structure change for three iron-based superconductors: FeSe, Ba(Fe 0.94 Co 0.06 ) 2 As 2 and NaFeAs which share a similar Fermi surface topology. Electronic structure change upon monolayer of alkali metal dosing and the sample work function were measured by ARPES. In this work, our results show that the degree of electronic structure change is proportional to the difference between the work function of the sample and Mulliken's absolute electronegativity of the dosed alkali metal. This finding provides a possible way to estimate the AMD induced electronic structure change.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Cascade electrocatalysis via AgCu single-atom alloy and Ag nanoparticles in CO 2 electroreduction toward multicarbon products

Electrocatalytic CO 2 reduction into value-added multicarbon products offers a means to close the anthropogenic carbon cycle using renewable electricity. However, the unsatisfactory catalytic selectivity for multicarbon products severely hinders the practical application of this technology. In this paper, we report a cascade AgCu single-atom and nanoparticle electrocatalyst, in which Ag nanoparticles produce CO and AgCu single-atom alloys promote C-C coupling kinetics. As a result, a Faradaic efficiency (FE) of 94 ± 4% toward multicarbon products is achieved with the as-prepared AgCu single-atom and nanoparticle catalyst under ~720 mA cm -2 working current density at -0.65 V in a flow cell with alkaline electrolyte. Density functional theory calculations further demonstrate that the high multicarbon product selectivity results from cooperation between AgCu single-atom alloys and Ag nanoparticles, wherein the Ag single-atom doping of Cu nanoparticles increases the adsorption energy of *CO on Cu sites due to the asymmetric bonding of the Cu atom to the adjacent Ag atom with a compressive strain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Evolution of size-selected Pt cluster catalysts on prototypical oxide supports

The current quest for new pathways into sustainable, efficient and durable energy conversion technologies makes the used for a fundamental understanding of the atomic-scale phenomena underlying catalytic processes ever more pressing. In this context, characterizing catalyst particles in situ provides valuable information about the evolution of their composition, structure, oxidation state and charge state during an ongoing process. To disentangle the influence of individual parameters – temperature, pressure, gas composition, cluster size, as well as support acidity, redox state and defect density – it is crucial to control them precisely and separately in experiments. At the example of size-selected Pt n clusters – i.e. sub-nm particles defined to the exact number of atoms – on flat oxide supports, we follow their rich evolution phenomena via (synchrotron-based) X-ray photoelectron spectroscopy (XPS) and scanning tunnelling microscopy (STM) during temperature ramps and in various gas environments. Here, we present our experience with these highly defined, yet complicated-to-create samples in ultra-high vacuum (UHV) and at mbar pressures. We discuss their stability during transport to synchrotrons and under reaction conditions on three prototypical oxide supports and show the various phenomena that can be disentangled. Ptn clusters on the non-reducible silicon dioxide, SiO 2 , remain size-selected and show remarkable stability. Doping strongly influences the size-dependent binding energy shifts and changes the Pt response to oxidative and reaction conditions, which we attribute to different cluster geometries: p-type doping leads to wetting, enhanced sinter resistance and a diminished response to oxidative environments, compared to clusters on n-type doped samples. We compare the system with our previous findings of a similar change in dimensionality for Pt 20 clusters on the reducible ceria, CeO 2 (111), support, induced by modulation of its O vacancy density. The Pt n /CeO 2 system is particularly interesting for strategies to stabilize and redisperse Pt clusters dynamically. Finally, we study the evolution of Pt n clusters on another reducible oxide support, magnetite, Fe 3 O 4 (001), in 0.1 mbar alternating redox conditions at RT and elevated temperature. In analogy to findings previously reported for Pt/TiO 2 (110), the clusters either become encapsulated by a thin oxide film via strong metal–support interaction (SMSI) or deeply buried in the magnetite. Overall, our approach of following the evolution of size-selected clusters on oxide supports leads to fundamental atomic-scale insights on nano-scale catalyst materials, on our path to sustainable, dynamic and self-repairing catalysts.

Falling, Lorenz J. [Technical Univ. of Munich (Ger↗
NASA NTRS2006

Experimental Partitioning of Cr(3+) and Sc(3+) into Olivine: Mechanisms and Implications

Olivine (Mg, Fe)Si2O4 does not, by stoichiometry, accept cations such as Sc(3+) or Cr(3+). However, the partition coefficients of Sc and Cr between olivine and liquid are significant 0.2-1.0. We have measured Cr(3+) partition coefficients of near unity and have grown olivines with nearly 3 wt.% Sc2O3. Therefore, there must be a simple means of charge balancing 3+ ions in a crystal structure that was obviously not designed to receive other than 2+ ions on the olivine M sites. The simplest explanation is that two 3+ ions enter the olivine structure by displacing three 2+ ions and creating an M site vacancy. Even this explanation has difficulties. For minor elements in our experiments (~1 wt.%) the odds of a minor element 3+ ion finding a second 3+ for charge balance are of the order of 100:1 against. Because of the reducing conditions of our experiments, Fe(3+) will not suffice; and Al(3+) is not in sufficient quantity in olivine for charge balance. Therefore, Cr or Sc must, in effect, charge balance itself. For true trace elements, the problem is compounded many times. For an ion at the 10 ppm level the chances of finding a second (for example) Sc ion is approx.10(exp 5):1 against. Of course, any other 3+ ion would suffice but comparisons between percent level doping experiments and trace level partitioning indicate that Henry s law is obeyed. This implies that the same substitution mechanism occurs at both the percent and tens of ppm levels. There are two simple solutions to this problem: (i) The electrical conductivity of olivine is such that charge balance need not be local. This requires substantial domains within the olivine crystal in electrical contact by migration of vacancies or electronic defects. (ii) The 3+ cation brings along its own charge-balancing ion because it existed as a dimer in the silicate liquid. Olivine is not a true insulator but is actually a p-type semiconductor. Even so, electrical communication by this means is unlikely over the tens or hundreds of unit cells that would be required for charge balance to be local. Therefore, we cautiously favor the idea that melt speciation is the means by which 3+ ions enter the olivine structure. Possibly this model might be tested by in situ XAFS measurements or by molecular dynamical calculations.

Jones, John↗
DOE OSTI2023

Magnetic properties of intercalated quasi-2D Fe 3-x GeTe 2 van der Waals magnet

Among several well-known transition metal-based compounds, cleavable van der Waals (vdW) Fe 3-x GeTe 2 (FGT) magnet is a strong candidate for use in two-dimensional (2D) magnetic devices due to its strong perpendicular magnetic anisotropy, sizeable Curie temperature (T C ~154 K), and versatile magnetic character that is retained in the low-dimensional limit. While the T C remains far too low for practical applications, there has been a successful push toward improving it via external driving forces such as pressure, irradiation, and doping. Here we present experimental evidence of a room temperature (RT) ferromagnetic phase induced by the electrochemical intercalation of common tetrabutylammonium cations (TBA+) into quasi-2D FGT. We obtained Curie temperatures as high as 350 K with chemical and physical stability of the intercalated compound. The temperature-dependent Raman measurements, in combination with vdW-corrected ab initio calculations, suggest that charge transfer (electron doping) upon intercalation could lead to the observation of RT ferromagnetism. This work demonstrates that molecular intercalation is a viable route in realizing high-temperature vdW magnets in an inexpensive and reliable manner and has the potential to be extended to bilayer and few-layer vdW magnets.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗