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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Nanofaceted C/Re(11$\bar{21}$): Fabrication, structure, and template for synthesizing nanostructured model Pt electrocatalyst for hydrogen evolution reaction

Here, we report the first observation of carbon-induced nanofaceting of a Re single crystal and its application in synthesizing a nanostructured. model Pt electrocatalyst investigated using multiple surface science techniques, including low:energy electron diffraction, Auger electron spectroscopy, X-ray photoelectron spectroscopy, low-energy ion scattering, and scanning tunneling microscopy, combined with electrochemical reaction measurements. Upon annealing In acetylene at 700 K followed by annealing in vacuum at 1100 K, an Initially planar Re(11$\overline{2}$1) surface becomes completely faceted and covered with three-sided nanopyramids exposing ($1\overline{1}1$), ($10\overline{1}1$), and ($11\overline{2}0$) faces. Using the faceted C/Re($11\overline{2}1$) surface as a template, we have successfully fabricated a nanostructured Pt monolayer (ML) electrocatalyst. The Pt ML supported on the C/Re nanotemplate exhibits higher activity for the hydrogen evolution reaction than Pt(111). This is the first application of faceted metal surfaces as templates for synthesis of nanoscale model electrocatalyst with well-defined (facet) surface structure and controlled (facet) size on the nanometer scale, illustrating the potential for future studies of nanostructured bimetallic systems relevant to electrocatalytic reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Anomalous Shape Evolution of Ag 2 O 2 Nanocrystals Modulated by Surface Adsorbates during Electron Beam Etching

An understanding of nanocrystal shape evolution is significant for the design, synthesis, and applications of nanocrystals with surface-enhanced properties such as catalysis or plasmonics. Surface adsorbates that are selectively attached to certain facets may strongly affect the atomic pathways of nanocrystal shape development. However, it is a great challenge to directly observe such dynamic processes in situ with a high spatial resolution. In this work, we report the anomalous shape evolution of Ag 2 O 2 nanocrystals modulated by the surface adsorbates of Ag clusters during electron beam etching, which is revealed through in situ transmission electron microscopy (TEM). In contrast to the Ag 2 O 2 nanocrystals without adsorbates, which display the near-equilibrium shape throughout the etching process, Ag 2 O 2 nanocrystals with Ag surface adsorbates show distinct facet development during etching by electron beam irradiation. Three stages of shape changes are observed: a sphere-to-a cube transformation, side etching of a cuboid, and bottom etching underneath the surface adsorbates. We find that the Ag adsorbates modify the Ag 2 O 2 nanocrystal surface configuration by selectively capping the junction between two neighboring facets. They prevent the edge atoms from being etched away and block the diffusion path of surface atoms. Finally, our findings provide critical insights into the modulatory function of surface adsorbates on the shape control of nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Formation of open ruthenium branched structures with highly exposed active sites for oxygen evolution reaction electrocatalysis

The formation of exposed active sites that have high activity and stability for oxygen evolution reaction (OER) catalysis is a significant opportunity for improving water electrolysers. Low-index facets surface Ru can achieve both high activity and stability for OER. Here, we present a new catalyst design where low-index faceted Ru branches are grown off the corners of Pt nanocubes, forming open Ru branched nanoparticles. This open branched structure, exposing low-index facets on its length-tunable branch, enables a high electrochemically active surface area (ECSA), achieving high activity and stability for OER. This design strategy and synthetic control provide a principle for achieving high-performance OER nanocatalysts.

Xiao, Sa [The University of New South Wales, Sydne↗
DOE OSTI2026

4D-STEM Coupled with Unsupervised Machine Learning to Reveal at Large-Scale the Microstructural Evolution in Li- and Mn-Rich Cathodes

Li- and Mn-rich (LMR) layered oxides are known to exhibit a thin surface reconstruction layer, which grows during electrochemical cycling in a manner that depends on exposed crystallographic facets, cycling conditions, and electrolyte chemistry. Direct characterization of this layer has traditionally relied on high-resolution electron microscopy, which is inherently limited to small fields of view. Here, we employ four-dimensional scanning transmission electron microscopy (4D-STEM) combined with unsupervised machine-learning clustering to quantitatively map phase distributions over large areas and track their evolution in LMR cathodes during electrochemical aging. Our results show that the surface reconstruction layer consists predominantly of a rocksalt phase, whose thickness varies across different facets following activation cycling and becomes substantially thicker and more uniform during calendar aging. In contrast, a spinel-like phase is observed within the particle bulk. Large-area phase mapping and correlative high-resolution imaging reveal that this spinel-like phase preferentially nucleates at bulk crystallographic defects, including boundaries between 60°-rotated layered domains and associated mixed-phase regions, rather than exclusively at the particle surface. Our findings establish a mechanistic distinction between surface-driven rocksalt formation and bulk-defect-mediated spinel nucleation while demonstrating the unique capability of 4D-STEM to provide statistically robust, mesoscale insight into complex phase-evolution processes in LMR cathodes.

4D-STEM↗
DOE OSTI2015

Atomic Scale Analysis of the Enhanced Electro- and Photo-Catalytic Activity in High-Index Faceted Porous NiO Nanowires

Catalysts play a significant role in clean renewable hydrogen fuel generation through water splitting reaction as the surface of most semiconductors proper for water splitting has poor performance for hydrogen gas evolution. The catalytic performance strongly depends on the atomic arrangement at the surface, which necessitates the correlation of the surface structure to the catalytic activity in well-controlled catalyst surfaces. Herein, we report a novel catalytic performance of simple-synthesized porous NiO nanowires (NWs) as catalyst/co-catalyst for the hydrogen evolution reaction (HER). The correlation of catalytic activity and atomic/surface structure is investigated by detailed high resolution transmission electron microscopy (HRTEM) exhibiting a strong dependence of NiO NW photo- and electrocatalytic HER performance on the density of exposed high-index-facet (HIF) atoms, which corroborates with theoretical calculations. Significantly, the optimized porous NiO NWs offer long-term electrocatalytic stability of over one day and 45 times higher photocatalytic hydrogen production compared to commercial NiO nanoparticles. Our results open new perspectives in the search for the development of structurally stable and chemically active semiconductor-based catalysts for cost-effective and efficient hydrogen fuel production at large scale.

08 HYDROGEN↗
DOE OSTI2023

Ferroelectric Polarization in BaTiO 3 Nanocrystals Controls Photoelectrochemical Water Oxidation and Photocatalytic Hydrogen Evolution

Ferroelectric (FE) semiconductors such as BaTiO 3 support a remnant polarization after the application of an electric field that can promote the separation of photogenerated charge carriers. Here, we demonstrate FE-enhanced photocatalytic hydrogen evolution and photoelectrochemical water oxidation with barium titanate nanocrystals for the first time. Nanocrystals of the ferroelectric tetragonal structure type were obtained by a hydrothermal synthesis from TiO 2 and barium hydroxide in 63% yield. BaTiO 3 nanocrystal films on tantalum substrates exhibit water oxidation photocurrents of 0.141 mA cm –2 at 1.23 V RHE under UV light (60 mW cm –2 ) illumination. Electric polarization at 52.8 kV cm –1 normal to the film plane increases the photocurrent by a factor of 2 or decreases it by a factor of 3.5, depending on the field polarity. It also shifts the onset potential by –0.15 or +0.09 V and it modifies the surface photovoltage signal. Lastly, exposure to an electric field increases the H 2 evolution rate of Pt/BaTiO 3 by a factor of ~1.5, and it raises the selectivity of photodeposition of silver onto the (001) facets of the nanocrystal. All FE enhancements can be removed by heating samples above the Curie temperature of BaTiO 3 . Furthermore, these findings can be explained by FE dipole-induced changes to the potential drop across the space charge layer of the material. The ability to use the ferroelectric effect to enhance hydrogen evolution and water oxidation is of potential interest for the development of improved solar energy for fuel conversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2 O 4 spinel in oxidizing atmosphere

With the capability of MgAl2O4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement in Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. A dynamic stabilization mechanism involving wetting\nucleation seems to be responsible for the evolution of surface compositions upon cyclic oxidizing and reducing ther-mal treatments.

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

Descriptors for Cu facets for CO2 reduction reaction activity

Computation screening is crucial for designing efficient electrochemical catalysts for carbon dioxide (CO2R) reduction to valuable hydrocarbons and oxygenates. Herein, leveraging density functional theory calculations of the CO adsorption energy ΔE_CO on seventeen Cu terminations, we discover a strong linear correlation between ΔE_CO and the recently experimentally measured CO2R electrochemical currents (ACS Catal. 2022, 12, 11, 6578–6588). Examining the ab initio thermodynamics of the early critical intermediates CO*, COH*, and CHO*, we find that CO* → CHO* is the thermodynamically preferred step, and notably shows a volcano trend with the experimental currents where the maximum CO2R current corresponds to the moderate CHO* formation energy. Importantly, we show that increasing the step and kink density of the Cu termination not only enhances CO adsorption strength but also modulates the CO* → CHO* pathway, as respectively exemplified in the (941) and (741) facets. We also explain why (741) is exceptional with high CO2R activity as measured experimentally due to its relatively low activity toward the hydrogen evolution reaction compared with the other Cu surfaces. Beyond the general CO adsorption energy that only shows a linear trend with CO2R activity, we show that the reaction CO* → CHO* free energy is a descriptor that displays a volcano relationship with the overall CO2R activity on Cu facets.

machine learning↗
DOE OSTI2024

Theoretical Investigation of the Adsorbate and Potential–Induced Stability of Cu Facets During Electrochemical CO 2 and CO Reduction

The activity and product selectivity of electrocatalysts for reactions like the carbon dioxide reduction reaction (CO 2 RR) are intimately dependent on the catalyst's structure and composition. While engineering catalytic surfaces can improve performance, discovering the key sets of rational design principles remains challenging due to limitations in modeling catalyst stability under operating conditions. Herein, we perform first-principles density functional calculations adopting implicit solvation methods with potential control to study the influence of adsorbates and applied potential on the stability of different facets of model Cu electrocatalysts. Using coverage dependencies extracted from microkinetic models, we describe an approach for calculating potential and adsorbate-dependent contributions to surface energies under reaction conditions, where Wulff constructions are used to understand the morphological evolution of Cu electrocatalysts under CO 2 RR conditions. Here we identify that CO*, a key reaction intermediate, exhibits higher kinetically and thermodynamically accessible coverages on (100) relative to (111) facets, which can translate into an increased relative stabilization of the (100) facet during CO 2 RR. Our results support the known tendency for increased (111) faceting of Cu nanoparticles under more reducing conditions and that the relative increase in (100) faceting observed under CO 2 RR conditions is likely attributed to differences in CO* coverage between these facets.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Computational descriptor for electrochemical currents of carbon dioxide reduction on Cu facets

Computation screening is crucial for designing efficient electrochemical catalysts for carbon dioxide (CO 2 R) reduction that produce valuable hydrocarbons and oxygenates. In this work, leveraging density functional theory calculations for the CO adsorption energy ΔE CO on seventeen Cu terminations, we discover a strong linear correlation between ΔE CO and the experimentally measured CO 2 R electrochemical currents (ACS Catal. 2022, 12, 11, 6578–6588). Examining ab initio thermodynamics of early critical intermediates CO*, COH*, and CHO*, we find that CO* → CHO* is the thermodynamically controlling step. Beyond the general CO adsorption energy that only shows a linear trend with CO 2 R activity, we show that the reaction free energy of CO* → CHO* is the descriptor for the overall CO 2 R activity for Cu facets, as it displays a volcano relationship with the experimental current. Importantly, we show that high step and kink density of the Cu terminations not only enhances CO adsorption strength but also modulates the CO* → CHO* pathway, as respectively exemplified in the (941) and (741) facets. In addition, we explain that the high activity of (741) is due to its relatively low hydrogen evolution reaction activity compared with the other Cu surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Facet-Dependent Thermal Instability in LiCoO2

Thermal runaways triggered by the oxygen release from oxide cathode materials pose a major safety concern for widespread application of lithium ion batteries. Utilizing in situ aberration-corrected scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) at high temperatures, we show that oxygen release from LixCoO2 cathode crystals is occurring at the surface of particles. We correlated this local oxygen evolution from the LixCoO2 structure with local phase transitions spanning from layered to spinel and then to rock salt structure upon exposure to elevated temperatures. Ab initio molecular dynamics simulations (AIMD) results show that oxygen release is highly dependent on LixCoO2 facet orientation. While the [001] facets are stable at 300 degrees C, oxygen release is observed from the [012] and [104] facets, where under-coordinated oxygen atoms from the delithiated structures can combine and eventually evolve as O-2. The novel understanding that emerges from the present study piovides in-depth insights into the thermal runaway mechanism of Li-ion batteries and can assist the design and fabrication of cathode crystals with the most thermally stable facets.

ab initio molecular dynamics↗
DOE OSTI2016

Facet control of gold nanorods

While great success has been achieved in fine-tuning the aspect ratios and thereby the plasmon resonances of cylindrical Au nanorods, facet control with atomic level precision on the highly curved nanorod surfaces has long been a significantly more challenging task. The intrinsic structural complexity and lack of precise facet control of the nanorod surfaces remain the major obstacles for the atomic-level elucidation of the structure–property relationships that underpin the intriguing catalytic performance of Au nanorods. Here we demonstrate that the facets of single-crystalline Au nanorods can be precisely tailored using cuprous ions and cetyltrimethylammonium bromide as a unique pair of surface capping competitors to guide the particle geometry evolution during nanorod overgrowth. By deliberately maneuvering the competition between cuprous ions and cetyltrimethylammonium bromide, we have been able to create, in a highly controllable and selective manner, an entire family of nanorod-derived anisotropic multifaceted geometries whose surfaces are enclosed by specific types of well-defined high-index and low-index facets. This facet-controlled nanorod overgrowth approach also allows us to fine-tune the particle aspect ratios while well-preserving all the characteristic facets and geometric features of the faceted Au nanorods. Furthermore, taking full advantage of the combined structural and plasmonic tunability, we have further studied the facet-dependent heterogeneous catalysis on well-faceted Au nanorods using surface-enhanced Raman spectroscopy as an ultrasensitive spectroscopic tool with unique time-resolving and molecular finger-printing capabilities.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Radiation induced nanovoid shrinkage in Cu at room temperature: An in situ study

Radiation induced void swelling is widely observed in a variety of metallic materials. Here, by using sputtering deposition technique, we have introduced faceted nanovoids into Cu films. In-situ Kr ion irradiation was subsequently performed at room temperature to investigate the evolution of nanovoids. Most nanovoids found to shrink gradually with increasing dose. Irradiation induced high-density vacancy clusters exist mostly in the formof stacking fault tetrahedrons. Phase fieldmodeling reveales that void shrinkage arises from biased absorption of interstitials. These findings provide insights to the physical mechanisms of radiation response of nanovoids in metallic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Various facets of magnetic charge correlation: Micromagnetic and distorted-wave Born approximation simulations study

The emergent concept of the magnetic charge quasiparticle provides a new realm to study the evolution of magnetic properties in two-dimensional artificially frustrated magnets. Here we report on the exploration of magnetic phases due to various magnetic charge correlation using the complementary numerical techniques of micromagnetic and distorted-wave Born approximation simulations in artificial permalloy honeycomb lattice. The honeycomb element length varies between 10 nm and 100 nm, while the width and thickness are kept within the single domain limit. In addition to the charge ordered loop state, we observe disordered charge arrangement, characterized by the random distribution of ±Q charges, in single domain size honeycomb lattice. As the length of the honeycomb element increases, low multiplicity magnetic charges tend to form contiguous bands in thinner lattice. Thin honeycomb lattice with 100 nm element length exhibits a perfect spin ice pattern, which remains unaffected by the modest increase in the width of element size. We simulate scattering profiles under the pretext of distorted-wave Born approximation formalism for the micromagnetic phases. The results are expected to provide useful guidance in the experimental investigation of magnetic phases in an artificial honeycomb magnet.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Versatile stochastic model for predictive KMC simulation of fcc metal nanostructure evolution with realistic kinetics

Stochastic lattice-gas models provide the natural framework for analysis of the surface diffusion-mediated evolution of crystalline metal nanostructures on the appropriate time scale (often 10 1 –10 4 s) and length scale. Model behavior can be precisely assessed by kinetic Monte Carlo simulation, typically incorporating a rejection-free algorithm to efficiently handle the broad range of Arrhenius rates for hopping of surface atoms. The model should realistically prescribe these rates, or the associated barriers, for a diversity of local surface environments. However, commonly used generic choices for barriers fail, even qualitatively, to simultaneously describe diffusion for different low-index facets, for terrace vs step edge diffusion, etc. We introduce an alternative Unconventional Interaction–Conventional Interaction formalism to prescribe these barriers, which, even with few parameters, can realistically capture most aspects of behavior. Here, the model is illustrated for single-component fcc metal systems, mainly for the case of Ag. It is quite versatile and can be applied to describe both the post-deposition evolution of 2D nanostructures in homoepitaxial thin films (e.g., reshaping and coalescence of 2D islands) and the post-synthesis evolution of 3D nanocrystals (e.g., reshaping of nanocrystals synthesized with various faceted non-equilibrium shapes back to 3D equilibrium Wulff shapes).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Local Chemical Ordering and Negative Thermal Expansion in PtNi Alloy Nanoparticles

An atomic insight into the local chemical ordering and lattice strain is particular interesting to recent emerging bimetallic nanocatalysts such as PtNi alloys. Here in this paper, we reported the atomic distribution, chemical environment and lattice thermal evolution in full-scale structural description of PtNi alloy nanoparticles (NPs). The different segregation of elements in the well-faceted PtNi nanoparticles is convinced by extended X-ray absorption fine structure (EXAFS). Atomic pair distribution function (PDF) study evidences the co-existence of the face-centered cubic and tetragonal ordering parts in the local environment of PtNi nanoparticles. Further reverse monte carlo (RMC) simulation with PDF data obviously exposed the segregation as Ni and Pt in the centers of {111} and {001} facets respectively. Layer-by-layer statistical analysis up to 6 nm for the local atomic pairs revealed the distribution of local tetragonal ordering on the surface. This local coordination environment facilitates the distribution of heteroatomic Pt-Ni pairs, which plays an important role in the negative thermal expansion of Pt 41 Ni 59 NPs. The present study on PtNi alloy NPs from local short-range coordination to long-range average lattice provides a new perspective on tailoring physical properties in nanomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Modeling the Economic and Environmental Impacts of Land Scarcity Under Deep Uncertainty

Abstract Land scarcity is increasing over time, driven by complex multisector dynamics. The impacts of land scarcity on the economy and environment are multi‐faceted and regional, so any action to convert land will contain inherent tradeoffs. These impacts are complicated by the deeply uncertain evolution of the various sectors influencing land scarcity. A need therefore exists to provide multi‐metric and multi‐sector assessments that are robust to myriad uncertainties. Land conservation effectively limits the supply of productive land, while biofuel consumption increases the demand and competition for that land, and how these dynamics individually and jointly propagate to economic and environmental impacts is an important open question. To address this, we adopt the Global Change Analysis Model (GCAM) that has representations of various important systems including the climate, macroeconomic, energy, agriculture and land, and water resources systems. Various scenarios of increased land demand (from biofuels) and decreased land supply (from conservation) under various socioeconomic scenarios drawn from the SSPs were simulated using GCAM. We find that while biofuel consumption and land conservation reduce carbon emissions, this comes at the cost of higher food prices, reduced crop production, and increased water withdrawals. Additionally, some regions experience these tradeoffs more severely than others and are more heavily impacted from the same biofuel mandate or by an additional percent of protected land. These and other findings highlight the importance of multisector modeling frameworks that capture many cross‐sector linkages, and acknowledge the important uncertainties confronting the human‐Earth system when making any analysis of land scarcity impacts.

54 ENVIRONMENTAL SCIENCES↗