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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Epitaxial Design of Complex Nickelates as Electrocatalysts for the Oxygen Evolution Reaction

Abstract The oxygen evolution reaction (OER) is a crucial process in electrochemical water splitting, a promising technology to renewably yield hydrogen gas from water. Designing and developing earth‐abundant, efficient, and stable OER electrocatalysts to replace the most widely used but scarce RuO 2 and IrO 2 are thus of critical interest. Recently, ABO 3 ‐structured perovskite oxides, especially rare‐earth nickelates, are extensively studied for their potential use as OER electrocatalysts. In particular, the epitaxial synthesis of complex oxide thin films allows flexible and precise control over the materials so that their structure–stability–property relationships can be established. Using nickelate thin films as model systems, this review illustrates how epitaxial design allows researchers to test different hypotheses and proposed descriptors, as well as formulate new design principles. Following a brief introduction to the background of OER mechanisms, proposed activity descriptors, and synthesis methods, various epitaxial design strategies are surveyed including strain tuning, composition control, surface termination/orientation selection, defect engineering, and interface design. These have led to precise control over the atomic structures and electronic properties of nickelates which in turn determine their electrochemical performance. Finally, the remaining challenges and perspectives toward a deeper understanding and use of complex oxides as OER catalysts are discussed.

Choi, Min‐Ju↗
DOE OSTI2021

Edge-Mediated Annihilation of Vacancy Clusters in Monolayer Molybdenum Diselenide (MoSe 2 ) under Electron Beam Irradiation

Here annihilation of vacancy clusters in monolayer molybdenum diselenide (MoSe2) under electron beam irradiation is reported. In situ high-resolution transmission electron microscopy observation reveals that the annihilation is achieved by diffusion of vacancies to the free edge near the vacancy clusters. Monte Carlo simulations confirm that it is energetically favorable for the vacancies to locate at the free edge. By computing the minimum energy path for the annihilation of one vacancy cluster as a case study, it is further shown that electron beam irradiation and pre-stress in the suspended MoSe2 monolayer are necessary for the vacancies to overcome the energy barriers for diffusion. The findings suggest a new mechanism of vacancy healing in 2D materials and broaden the capability of electron beam for defect engineering of 2D materials, a promising way of tuning their properties for engineering applications.

2D materials↗
DOE OSTI2024

Direct Fabrication of Atomically Defined Pores in MXenes Using Feedback-Driven STEM

Controlled fabrication of nanopores in 2D materials offer the means to create robust membranes needed for ion transport and nanofiltration. Techniques for creating nanopores have relied upon either plasma etching or direct irradiation; however, aberration-corrected scanning transmission electron microscopy (STEM) offers the advantage of combining a sub-Å sized electron beam for atomic manipulation along with atomic resolution imaging. Here, for this work, a method for automated nanopore fabrication is utilized with real-time atomic visualization to enhance the mechanistic understanding of beam-induced transformations. Additionally, an electron beam simulation technique, Electron-Beam Simulator (E-BeamSim) is developed to observe the atomic movements and interactions resulting from electron beam irradiation. Using the MXene Ti 3 C 2 T x , the influence of temperature on nanopore fabrication is explored by tracking atomic transformations and find that at room temperature the electron beam irradiation induces random displacement and results in titanium pileups at the nanopore edge, which is confirmed by E-BeamSim. At elevated temperatures, after removal of the surface functional groups and with the increased mobility of atoms results in atomic transformations that lead to the selective removal of atoms layer by layer. This work can lead to the development of defect engineering techniques within functionalized MXene layers and other 2D materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhancing the Multifunctional Photocatalytic Activity of Sustainable Magnetic Nanoparticles

The development of efficient photocatalytic materials has intensified in response to increasing emphasis on sustainable energy conversion and environmental restoration. However, the excessive use and indiscriminate release of heavy metals from photocatalytic nanoparticles pose potential environmental risks. This study provides insights into optimizing visible-light-active photocatalysts to enhance their photocatalytic properties and stability. Specifically, cobalt doping and controlled pH modulation are employed on the modified Fe 3 O 4 , forming two distinct samples: Co@Fe 3 O 4 -B (base-treated) and Co@Fe 3 O 4 -A (acid-treated) nanoparticles. Microscopic characterization reveals that Co@Fe 3 O 4 -A undergoes a phase transition to hematite, whereas Co@Fe 3 O 4 -B retains its mixed-phase configuration. Spectroscopic analyses confirm that the cobalt dopants decorate the outskirts of each nanoparticle, forming a core–shell structure. However, Co@Fe 3 O 4 -B exhibit Co 2+ states with a high oxygen vacancy content, whereas Co@Fe 3 O 4 -A contain mixed Co 2+/3+ states. The high density of defect states in the Co@Fe 3 O 4 -B results in superior photocatalytic efficiency, achieving near-complete oxidation of furfuraldehyde (97% conversion) and 5-hydroxymethylfurfural (94% conversion), as well as effective degradation of toluene (78% conversion). This study demonstrates that the combined approach of doping and pH treatment is promising for the surface-defect engineering of photocatalysts, enhancing their multifunctional performance and reusability for sustainable energy conversion.

Fe3 O4 nanoparticles↗
DOE OSTI2022

High performance high-power textured Mn/Cu-doped PIN-PMN-PT ceramics

Piezoelectric ceramics with combinatory soft and hard characteristics are highly desired for high-power applications. However, it remains grand challenge to achieve simultaneous presence of hard (e.g. high coercive field, E c ; high mechanical quality factor, Q m ) and soft (e.g. high piezoelectric constant, d; high electromechanical coupling factor, k) piezoelectric properties in piezoelectric ceramics since the mechanism controlling the hard behavior (pinned domain walls) will significantly reduce the soft behavior. Here, we address this grand challenge and demonstrate <001> textured MnO 2 and CuO co-doped Pb(In 1/2 Nb 1/2 )O 3- Pb(Mg 1/3 Nb 2/3 )O 3- PbTiO 3 (PIN-PMN-PT) ceramics exhibiting ultrahigh combined soft and hard piezoelectric properties (d 33 = 713 pC N –1 , k 31 = 0.52, Q m ≈950, E c = 9.6 kV cm –1 , tan δ = 0.45%). The outstanding electromechanical properties are explained by considering composition/phase selection, crystallographic anisotropy and defect engineering. Phase-field model in conjunction with high resolution electron microscopy and diffraction techniques is utilized to delineate the contributions arising from intrinsic piezoelectric response, domain dynamics, and local structural heterogeneity. Furthermore, these results will have significant impact in the development of high-power transducers and actuators.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Distinctive features of structural evolution and thermodynamic response in wide-bandgap semiconductors driven by intense electronic excitation

Radiation-tolerant material selection requires balancing lattice rigidity, defect dynamics, and electronic stability, as shown by covalent SiC outperforming ionic Ga 2 O 3 and GaN under extreme environments. Responding to intense electronic excitation, irradiation-driven phase segregation (β → δ/κ in Ga 2 O 3 ) and core–shell track (disordered structure in GaN), accompanied by elemental redistribution, contrastingly, exceptional radiation tolerance manifested by comparatively minimal lattice distortion (0.17 % strain variation) was demonstrated in SiC. These differential responses are primarily attributed to two fundamental mechanisms: (i) thermodynamic driving forces governing defect migration and phase separation, and (ii) the synergistic effects of robust covalent bonding composition coupled with efficient defect recombination processes. Here, the stronger electron–phonon (e-ph) coupling in Ga 2 O 3 (4.34 × 1018 W m −3 K −1 ) and GaN (3.55 × 10 18 W m −3 K −1 ) enhances lattice energy deposition, triggering thermal spikes (ΔT ≫ T m ) and structural transition behaviors, whereas weaker e-ph coupling in SiC (3.69 × 10 18 W m −3 K −1 ), relatively high thermodynamic parameters and efficient energy dissipation suppress thermal spikes to maintaining lattice integrity. The photoresponse degradation driven by enhanced radiative recombination is dominant in N-doped SiC, while V-doped systems achieve defect-mediated photoconduction optimization characterized by abrupt current transitions, matching fluorescence yield evolutions, and directly connecting defect engineering to optoelectronic performance.

Intense electronic excitation↗
DOE OSTI2025

Atomically precise synthesis of oxides with hybrid molecular beam epitaxy

Advancements in synthesis science are revolutionizing the way we create atomically precise materials. Techniques like molecular beam epitaxy (MBE) have set the benchmark for addressing long-standing questions in materials science by leveraging improved control over the composition and structure of existing materials and enabling materials discovery. In this review, we discuss recent innovations in MBE that are redefining its capabilities, enabling the fabrication of ultra-pure, defect-engineered films and the stabilization of metastable phases that were previously unattainable. These advancements are unlocking new opportunities in electronic, magnetic, and quantum technologies, where the precise tuning of material properties is essential for advancing device functionality and performance.

complex oxides↗
DOE OSTI2022

Promoting the water dissociation of nickel sulfide electrocatalyst through introducing cationic vacancies for accelerated hydrogen evolution kinetics in alkaline media

Developing cost-effective non-precious electrocatalysts with excellent HER performance in alkaline media is of significance for industrial hydrogen production. Herein, we successfully endow Ni 3 S 2 with unprecedentedly enhanced alkaline HER activities by introducing nickel vacancies. The Ni 3 S 2 catalyst with nickel vacancies exhibits an ultralow overpotential of 35 mV at 10 mA cm –2 in 1 M KOH electrolyte, outperforming commercial Pt/C (56 mV) and most reported non-precious electrocatalysts. The electron paramagnetic resonance and X-ray absorption fine structure etc. validates the formation of Ni vacancies and the change of the geometric/electronic structure of Ni 3 S 2 . Additionally, the theoretical calculations reveal that the Ni sites with higher valence state neighbouring the Ni vacancies can promote the water dissociation, playing a vital role in accelerating HER kinetics in alkaline media. Finally, this work may provide a universal strategy to enhance the HER activity of transition-metal compound catalysts in alkaline media by means of cationic defect engineering.

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

Nanostructures evolution assessment and spectroscopic properties modification induced by electronic energy loss in KTaO 3 crystal

Modifications of micro/nanostructure and photoelectric properties under swift ion irradiation (645 MeV Xe 35+ ) of KTaO 3 crystal with varying electronic energy losses (7.2–31.4 keV/nm) and ion velocities (0.18–5.00 MeV/u) have been studied by combining experimental and calculated approaches. The i-TS calculations combined with molecular dynamics simulations are compared with the experimental observations, revealing the inner track fine structures from individual spherical defects to continuous ion tracks with core–shell morphologies, and a quantitative relationship, including the melting (0.42 eV/atom), damage (0.75 eV/atom), and amorphous (1.71 eV/atom) thresholds, is established to successfully predict the inner disorder/amorphous proportions and track damage morphologies. The surface nanostructures of nanohillocks (isolated or partial overlaps) and nanopits (serious overlaps) directly depend on the combined action of the deposited potential and kinetic energies of incident ions, which induce local melting and sublimation in the near-surface region. Owing to the decreased recombination and the increased separation efficiency between electrons and holes, the higher photogenerated charge carrier mobility enhanced the photocurrent effect, further optimizing the photoconductivity performance in Xe 35+ -irradiated KTaO 3 . Therefore, controlled defect engineering using the ion irradiation technique, as an effective strategy, could design tailored nanostructure systems and regulate photoelectric properties, further promoting the development of novel technological applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Catalytic materials for lithium-sulfur batteries: mechanisms, design strategies and future perspective

Lithium-sulfur batteries (LSBs) are attractive candidates for post-lithium-ion battery technologies because of their ultrahigh theoretical energy density and low cost of active cathode materials. However, the commercialization of LSBs remains extremely challenging primarily due to poor cycling performance and safety concerns, which are inherently caused by low conductivity of S 8 and Li 2 S, severe polysulfide shuttling, and high polarization by solid Li 2 S 2 /Li 2 S deposition. Catalytic materials could facilitate the large-scale practical application of LSBs by overcoming all these challenges. In this review, we investigate the sulfur species evolution in LSBs and explore the roles of catalytic materials in charge/discharge processes, highlighting the catalysis of solid S 8 to liquid polysulfides and solid Li 2 S 2 to Li 2 S. Furthermore, we offer systematic strategies from atomic to macro levels, including defect engineering, morphology engineering and catalyst compositing, to enhance catalysis efficiency in terms of sulfur supercooling, fast charge transfer, thiosulfate generation, disulfide bond cleavage, tuneable Li 2 S growth and Li 2 S decomposition enhancement. Finally, the design and availability of the proposed catalytic materials will further advance LSB technology from coin cells and pouch cells to the subsequent commercialization scale.

25 ENERGY STORAGE↗
DOE OSTI2025

Substitutional doping of 2D transition metal dichalcogenides for device applications: Current status, challenges and prospects

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have emerged as a class of materials with exceptional electronic, optical, and mechanical properties, making them highly tunable for diverse applications in nanoelectronics, optoelectronics, and catalysis. Here, this review focuses on substitutional doping of TMDs, a key strategy to tailor their properties and enhance device performance, with a focus on its applications over the past five years (2019–2024). We delve into both theoretical and experimental doping approaches, including established methods like chemical vapor transport (CVT) and chemical vapor deposition (CVD) alongside liquid phase exfoliation (LPE) and post-synthesis treatments. Advanced growth techniques are also explored. Challenges like dopant uniformity, concentration control, and stability are addressed. The influence of various dopants on the electronic band structure, carrier concentration, and defect engineering is analyzed in detail. We further explore recent advancements in utilizing doped TMDs for field-effect transistors (FETs), photodetectors, sensors, photovoltaics, optoelectronic devices, energy storage and conversion, and even quantum computers. By examining both the potential and limitations of substitutional doping, this review aims to propel future research and technological advancements in this exciting field.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Dislocation-induced large local polarization inhomogeneity of ferroelectric materials

Dislocations in ferroelectrics play important roles in ferroelectricity, piezoelectricity, and dielectricity. However, the intrinsic charge-lattice coupling mechanism in ferroelectric crystals containing dislocations is still not well understood. Here, we report a large local polarization inhomogeneity of ~100 μCcm –2 induced by a single a[001] dislocation in the PbZr 0.2 Ti 0.8 O 3 /SrTiO 3 film/substrate heterostructure, the tensile region (~120 μCcm –2 ) and the compressive strain region (~21 μCcm –2 ) around the dislocation forms a butterfly-like area. Furthermore, this study reveals the dramatic effects of dislocations on local polarization and provides a strategy to manipulate the polarization magnitude and orientation of local polarization by defect engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ferroelectric Switching in Hybrid Molecular-Beam-Epitaxy-Grown BaTiO 3 Films

Molecular beam epitaxy (MBE) is a promising synthesis technique for both heterostructure growth and epitaxial integration of ferroelectric BaTiO 3 . However, direct measurement of the remnant polarization (P r ) has not been previously reported in MBE-grown BaTiO 3 films. We report the in situ growth of an all-epitaxial SrRuO 3 /BaTiO 3 /SrRuO 3 heterostructure on Nb-doped SrTiO 3 (001) substrates by hybrid MBE using metal–organic precursors. This capacitor structure consisting of 16 nm SrRuO 3 /40 nm BaTiO 3 /16 nm SrRuO 3 shows hysteretic polarization–electric field (P–E) curves with P r ∼ 15 μC cm –2 at frequencies ranging from 500 Hz to 20 kHz, after isolating the intrinsic ferroelectric response from non-ferroelectric contributions using the Positive-Up-Negative-Down (PUND) method. We hypothesize that the asymmetry in switching behavior and current leakage has origins in structural defects. Furthermore, this work opens the door to defect-engineered ferroelectric BaTiO 3 -based heterostructures grown by hybrid MBE for future electronic, photonic and spintronic applications.

SrRuO3 electrode↗
DOE OSTI2022

Capture Instead of Release: Defect-Modulated Radionuclide Leaching Kinetics in Metal–Organic Frameworks

Comparison of defect-controlled leaching-kinetics modulation of metal–organic frameworks (MOFs) and porous functionalized silica-based materials was performed on the example of a radionuclide and radionuclide surrogate for the first time, revealing an unprecedented readsorption phenomenon. On a series of zirconium-based MOFs as model systems, we demonstrated the ability to capture and retain >99% of the transuranic 241 Am radionuclide after 1 week of storage. Here, we report the possibility of tailoring radionuclide release kinetics in MOFs through framework defects as a function of postsynthetically installed organic ligands including cation-chelating crown ether-based linkers. Based on comprehensive analysis using spectroscopy (EXAFS, UV–vis, FTIR, and NMR), X-ray crystallography (single crystal and powder), and theoretical calculations (nine kinetics models and structure simulations), we demonstrated the synergy of radionuclide integration methods, topological restrictions, postsynthetic scaffold modification, and defect engineering. This combination is inaccessible in any other material and highlights the advantages of using well-defined frameworks for gaining fundamental knowledge necessary for the advancement of actinide-based material development, providing a pathway for addressing upcoming challenges in the nuclear waste administration sector.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

To Substitute Rather Than Intercalate: Chimie douce Approach to Induce Ferromagnetism in Metastable Pt 0.8 M 0.2 Se 2 ( M = Cr, Co, Ni)

Two-dimensional (2D) magnetic materials with exotic magnetic properties have garnered significant interest due to their potential applications in spintronics and data storage technologies. However, the limited availability of intrinsic 2D magnetic materials has driven efforts to induce and manipulate magnetism in otherwise nonmagnetic 2D systems through approaches such as chemical intercalation, defect engineering, and substitutional doping. Herein, we present a facile, chimie douce method for incorporating 3d transition metals (Cr, Co, and Ni) into the nonmagnetic PtSe 2 sublattice. This synthetic approach enables control over layer thickness of Pt 1–x M x Se 2 (M = Cr, Co, Ni) nanosheets by varying the M identity and annealing conditions. Comprehensive scattering and spectroscopic characterizations confirm the successful and homogeneous substitution of M atoms at the Pt site, rather than intercalation, and reveal a strong correlation between nanosheet thickness and the identity of the substituting metal. High-temperature annealing of the nanosheets promotes an irreversible transformation toward the bulk phase, allowing for detailed characterization of structural and magnetic properties. A case study of Pt 0.8 Cr 0.2 Se 2 reveals that nanosheet thickness plays a critical role in modulating local magnetic interactions. While Cr atoms in the as-synthesized few-layers-thick nanosheets exhibit predominantly short-range antiferromagnetic interactions, the emergence of short-range ferromagnetic exchange is revealed in the bulk material. Detailed ac susceptibility and remanent magnetization measurements further demonstrate that bulk Pt 0.8 Cr 0.2 Se 2 adopts a frustrated magnetic ground state with clear signatures of ferromagnetic cluster-glass behavior. The systematic investigation presented herein establishes a clear and robust protocol for the synthesis and in-depth characterization of 2D transition-metal-substituted PtSe2 materials with varying layer thickness and paves a path toward their realization in spintronic and magnetic device applications.

crystallinity↗
DOE OSTI2021

Defect-driven selective metal oxidation at atomic scale

Nanoscale materials modified by crystal defects exhibit significantly different behaviours upon chemical reactions such as oxidation, catalysis, lithiation and epitaxial growth. However, unveiling the exact defect-controlled reaction dynamics (e.g. oxidation) at atomic scale remains a challenge for applications. Here, using in situ high-resolution transmission electron microscopy and first-principles calculations, we reveal the dynamics of a general site-selective oxidation behaviour in nanotwinned silver and palladium driven by individual stacking-faults and twin boundaries. The coherent planar defects crossing the surface exhibit the highest oxygen binding energies, leading to preferential nucleation of oxides at these intersections. Planar-fault mediated diffusion of oxygen atoms is shown to catalyse subsequent layer-by-layer inward oxide growth via atomic steps migrating on the oxide-metal interface. These findings provide an atomistic visualization of the complex reaction dynamics controlled by planar defects in metallic nanostructures, which could enable the modification of physiochemical performances in nanomaterials through defect engineering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗