Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “FACET”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Surface Structure Dependence of SO 2 Interaction with Ceria Nanocrystals with Well-defined Surface Facets

The effects of the surface structure of ceria (CeO 2 ) on the nature, strength, and amount of species resulting from SO 2 adsorption were studied using in situ IR and Raman spectroscopies coupled with mass spectrometry, along with first-principles calculations based on density functional theory (DFT). CeO 2 nanocrystals with different morphologies, namely, rods (representing a defective structure), cubes (100 facet), and octahedra (111 facet), were used to represent different CeO 2 surface structures. IR and Raman spectroscopic studies showed that the structure and binding strength of adsorbed species from SO 2 depend on the shape of the CeO 2 nanocrystals. SO 2 adsorbs mainly as surface sulfites and sulfates at room temperature on CeO 2 rods, cubes, and octahedra that were either oxidatively or reductively pretreated. The formation of sulfites is more evident on CeO 2 octahedra, whereas surface sulfates are more prominent on CeO 2 rods and cubes. This is explained by the increasing reducibility of the surface oxygen in the order octahedra < cubes < rods. Bulk sulfites are also formed during SO 2 adsorption on reduced CeO 2 rods. The formation of surface sulfites and sulfates on CeO 2 cubes is in good agreement with our DFT results of SO 2 interactions with the CeO 2 (100) surface. CeO 2 rods desorb SO2 at higher temperatures than cubes and octahedra nanocrystals, but bulk sulfates are formed on CeO 2 rods and cubes after high-temperature desorption whereas only some surface sulfates/sulfites are left on octahedra. This difference is rationalized by the fact that CeO 2 rods have the highest surface basicity and largest amount of defects among the three nanocrystals, so they bind and react with SO 2 strongly and are the most degraded after SO 2 adsorption cycles. The fundamental understanding obtained in this work on the effects of the surface structure and defects on the interaction of SO 2 with CeO 2 provides insights for the design of more sulfur-resistant CeO 2 -based catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Electrochemical Reactivity of Faceted β-Co(OH) 2 Single Crystal Platelet Particles in Alkaline Electrolytes

Oxygen evolution reaction is the kinetic bottleneck in the generation of H 2 gas through the electrolysis of water. Understanding how water is electrochemically converted to oxygen is key to the development of high-performance electrocatalysts that can enable energy storage technologies based on water to hydrogen fuel generation. The use of well-defined metal oxide systems allows for the isolation of spatial reactivity in bulk redox conversion and oxygen evolution reactions. Herein, we investigate the electrochemical reactivity of well-faceted single-crystalline β-Co(OH) 2 platelet particles in alkaline solutions as a function of pH, potential, and mass loading. A geometrical model that describes the electrochemically active surface area contributions for a porous electrode of stacked high-aspect ratio particles is developed, which pinpoints the origin of reactivity for redox conversion processes and oxygen evolution at the edge facets of the particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

The role of surface passivation in controlling Ge nanowire faceting

In situ transmission electron microscopy observations of nanowire morphologies indicate that during Au-catalyzed Ge nanowire growth, Ge facets can rapidly form along the nanowire sidewalls when the source gas (here, digermane) flux is decreased or the temperature is increased. This sidewall faceting is accompanied by continuous catalyst loss as Au diffuses from the droplet to the wire surface. We suggest that high digermane flux and low temperatures promote effective surface passivation of Ge nanowires with H or other digermane fragments inhibiting diffusion and attachment of Au and Ge on the sidewalls. Furthermore, these results illustrate the essential roles of the precursor gas and substrate temperature in maintaining nanowire sidewall passivation, necessary to ensure the growth of straight, untapered, <111>-oriented nanowires.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Enhanced Oxygen Reduction Performance on {101} CoMn 2 O 4 Spinel Facets

Here, we present a facile colloidal synthesis method for producing {101}-facet-tailored CoMn 2 O 4 spinel nano-octahedra with uniform size (9 nm). These nano-octahedra exhibit superior electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media compared to their spherical counterparts and previously reported spinel electrocatalysts. At 0.85 V, they achieve a high mass activity (MA) of 60.0 A/g, surpassing the spherical counterparts (38.6 A/g). Furthermore, the CoMn 2 O 4 nano-octahedra demonstrate excellent stability, maintaining an MA of 47.2 A/g after 10,000 durability cycles. This work highlights a promising approach for synthesizing advanced spinel nano-oxides with controlled crystal facets, offering potential as non-precious metal ORR electrocatalysts. The exposed active catalyst surfaces and well-defined structures contribute to their enhanced ORR performance.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Theoretical Study of the Initial Stages of Self-Assembly of a Carboxysome’s Facet

Bacterial microcompartments, BMCs, are organelles that exist within wide variety of bacteria and act as nanofactories. Among the different types of known BMCs, the carboxysome has been studied the most. The carboxysome plays an important role in the light-independent part of the photosynthesis process, where its icosahedral-like proteinaceous shell acts as a membrane that controls the transport of metabolites. Although a structural model exists for the carboxysome shell, it remains largely unknown how the shell proteins self-assemble. Understanding the self-assembly process can provide insights into how the shell affects the carboxysome s function and how it can be modified to create new functionalities, such as artificial nanoreactors and artificial protein membranes. Here, we explain a theoretical framework that employs Monte Carlo simulations with a coarse-grain potential that reproduces well the atomistic potential of mean force; employing this framework, we are able to capture the initial stages of the 2D self-assembly of CcmK2 hexamers, a major protein-shell component of the carboxysome's facet. The simulations reveal that CcmK2 hexamers self-assemble into clusters that resemble what was seen experimentally in 2D layers. Further analysis of the simulation results suggests that the 2D self-assembly of carboxysome s facets is driven by a nucleation growth process, which in turn could play an important role in the hierarchical self- assembly of BMC shells in general.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

A Three-Component Strategy for Synthesizing High-Entropy Alloy Nanoparticles with High-Index Facets

Controlling the shapes and, more importantly, exposed facets (high-index facets (HIFs), especially) of high-entropy alloy (HEA) nanoparticles is not yet possible. Herein, a three-component synthetic strategy for obtaining tetrahexahedral (THH)-shaped HIF-HEA nanoparticles through a combined alloying-dealloying strategy and liquid-metal mediation process is reported. Metal precursors are first alloyed with Ga to form multielemental nanoparticles and then alloyed with a volatile metal. Selectively dealloying the volatile metal from the nanoparticles is used to regulate their surface energies; the Ga stabilizes the HEA phase, and the trace element stabilizes the HIFs, resulting in THH-shaped HEA nanoparticles (seven different types) with {210} HIFs. Finally, nanoparticle megalibraries containing millions of THH-shaped HIF-HEAs on 4 cm 2 chips with size and composition control shows generalizability and scalability for materials discovery purposes.

alloys↗
DOE OSTI2019

Facet-dependent active sites of a single Cu 2 O particle photocatalyst for CO 2 reduction to methanol

Atomic level understanding of the active sites and transformation mechanisms under realistic working conditions are pre-requisites for rational design of high performance photocatalysts. By using correlated scanning fluorescence x-ray microscopy and environmental transmission electron microscopy at atmospheric pressure, in operando, we directly observed that the (110) facet of a single Cu 2 O photocatalyst particle is photocatalytically active for CO 2 reduction to methanol while the (100) facet is inert. The oxidation state of the active sites changed from Cu(I) towards Cu(II) due to CO 2 and H 2 O coadsorption and changed back to Cu+ after CO 2 conversion under visible light illumination. The Cu 2 O photocatalyst oxidized water as it reduced CO 2 . At the same time, the crystal lattice expanded due to CO 2 adsorption then reverted after CO 2 conversion. The internal quantum yield for unassisted wireless photocatalytic reduction of CO 2 to methanol using Cu 2 O crystals is ~ 72% with 10% solar to fuel efficiency.

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

The role of faceting and elongation on the magnetic anisotropy of magnetite Fe3O4 nanocrystals

Abstract Fe 3 O 4 nanoparticles are one of the most promising candidates for biomedical applications such as magnetic hyperthermia and theranostics due to their bio-compatibility, structural stability and good magnetic properties. However, much is unknown about the nanoscale origins of the observed magnetic properties of particles due to the dominance of surface and finite size effects. Here we have developed an atomistic spin model of elongated magnetite nanocrystals to specifically address the role of faceting and elongation on the magnetic shape anisotropy. We find that for faceted particles simple analytical formulae overestimate the magnetic shape anisotropy and that the underlying cubic anisotropy makes a significant contribution to the energy barrier for moderately elongated particles. Our results enable a better estimation of the effective magnetic anisotropy of highly crystalline magnetite nanoparticles and is a step towards quantitative prediction of the heating effects of magnetic nanoparticles.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Imaging the surface morphology, chemistry and conductivity of LiNi 1/3 Fe 1/3 Mn 4/3 O 4 crystalline facets using scanning transmission X-ray microscopy

We have employed scanning transmission X-ray microscopy (STXM) using the X-ray fluorescence mode in order to elucidate the chemical structures at Ni, Fe, Mn and O sites from the (111) and (100) facets of micron-sized LiNi 1/3 Fe 1/3 Mn 4/3 O 4 energy material particles. Furthermore, STXM imaging using electron yield mode has mapped out the surface conductivity of the crystalline particles. Our study presents a novel approach that visualizes local element segregation, chemistry and conductivity variation among different crystal facets, which will assist further tailoring of the morphology and surface structure of this high voltage spinel lithium ion battery cathode material.

25 ENERGY STORAGE↗
DOE OSTI2025

Faceted NiO(111) nanosheets: morphological and catalytic evolution for the oxygen evolution reaction

The renaissance of the energy system through the use of green hydrogen by water electrolysis lies behind the development of abundant, active, and scalable catalysts for the oxygen evolution reaction (OER). A fundumental understanding of the surface properties for these materials is of vital importance in producing viable heterogenous catalysts. In this feature article, we summarize several years of collaborative work on a uniquely faceted NiO(111) nanosheet possessing hexagonal holes with a focus on understanding how the evolution of the catalyst surface and bulk composition effects OER performance. The importance of surface faceting, morphological evolution, and metal combination by different doping strategies are all analyzed and summarized to further improve the material's performance. Furthermore, microwave and supercritical synthesis processes are utilized to understand how varying wet-chemical techniques effect the formation of the NiO(111) nanosheet and activity of the material. We discuss our chosen strategies and the difficulties encountered with optimizing a catalyst surface for the OER.

08 HYDROGEN↗
DOE OSTI2025

Supercritical preparation of doped (111) facetted nickel oxide for the oxygen evolution reaction

Green hydrogen is of great interest as a replacement for traditional fossil fuels in a variety of energy applications. However, due to the poor kinetics present in the oxygen evolution reaction (OER) half-reaction, nanostructured catalysts are needed to reduce the reaction overpotential. Nickel oxide has previously been shown to be a promising alternative to expensive Pt-group based catalysts for the OER in alkaline media. Herein, facetted NiO nanosheets have been doped with Fe, Mn, or Co to reduce its catalytic overpotential for the OER. A supercritical synthesis process was used to promote the mass transport of the reactants while preserving catalytic surface area. Microscopy, diffraction, spectroscopy, and adsorption techniques were used to understand the morphological changes resulting from the inclusion of each dopant, as well as characterize the surface chemistry presented by the doped (111) facet. The pH was found to affect the properties of mixing due to difference in hydrolysis rates and catalysis of the hydrolysis/condensation. The dopants exhibited distinct effects on OER activity: Mn increased the overpotential to 742 mV vs. RHE, while Co and Fe reduced it to 502 mV and 457 mV, respectively. In summary, a straightforward and novel synthesis method is presented to prepare doped NiO(111) nanosheets, and their surface characteristics are explored to understand their varied electrochemical performances.

08 HYDROGEN↗
DOE OSTI2014

Faceting oscillations in nano-ferroelectrics

We observe periodic faceting of 8-nm diameter ferroelectric disks on a 10 s time-scale when thin Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3} film is exposed to constant high-resolution transmission electron microscopy beams. The oscillation is between circular disk geometry and sharply faceted hexagons. The behavior is analogous to that of spin structure and magnetic domain wall velocity oscillations in permalloy [Bisig et al., Nat. Commun. 4, 2328 (2013)], involving overshoot and de-pinning from defects [Amann et al., J. Rheol. 57, 149–175 (2013)].

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Facet-controlled phase separation in supersaturated Au-Ni nanoparticles upon shape equilibration

Solid-state dewetting is used to fabricate supersaturated, submicron-sized Au-Ni solid solution particles out of thin Au/Ni bilayers by means of a rapid thermal annealing technique. Phase separation in such particles is studied with respect to their equilibrium crystal (or Wulff) shape by subsequent annealing at elevated temperature. It is found that (100) faceting planes of the equilibrated particles are enriched with Ni and (111) faces with Au. Both phases are considered by quantum-mechanical calculations in combination with an error-reduction scheme that was developed to compensate for a missing exchange-correlation potential that would reliably describe both Au and Ni. The observed phase configuration is then related to the minimization of strongly anisotropic elastic energies of Au- and Ni-rich phases and results in a rather unique nanoparticle composite state that is characterized by nearly uniform value of elastic response to epitaxial strains all over the faceted surface. The same conclusion is yielded also by evaluating bi-axial elastic moduli when employing interpolated experimental elastic constants. This work demonstrates a useful route for studying features of physical metallurgy at the mesoscale.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Comparison of S-adsorption on (111) and (100) facets of Cu nanoclusters

In order to gain insight into the nature of chemical bonding of sulfur atoms on coinage metal surfaces, we compare the adsorption energy and structural parameters for sulfur at four-fold hollow (4fh) sites on (100) facets and at three-fold hollow (3fh) sites on (111) facets of Cu nanoclusters. Consistent results are obtained from localized atomic orbital and plane-wave based density functional theory using the same functionals. PBE and its hybrid counterpart (PBE0 or HSE06) also give similar results. 4fh sites are preferred over 3fh sites with stronger bonding by ~0.6 eV for nanocluster sizes above ~280 atoms. However, for smaller sizes there are strong variations in the binding strength and the extent of the binding site preference. In addition, we show that suitable averaging over clusters of different sizes, or smearing the occupancy of orbitals, provide useful strategies to aid assessment of the behavior in extended surface systems. From site-projected density of states analysis using the smearing technique, we show that S adsorbed on a 4fh site has similar bonding interactions with the substrate as that on a 3fh site, but with much weaker antibonding interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Nucleation-mediated reshaping of facetted metallic nanocrystals: Breakdown of the classical free energy picture

Shape stability is key to avoiding degradation of performance for metallic nanocrystals synthesized with facetted non-equilibrium shapes to optimize properties for catalysis, plasmonics, and so on. Reshaping of facetted nanocrystals is controlled by the surface diffusion-mediated nucleation and growth of new outer layers of atoms. Here, Kinetic Monte Carlo (KMC) simulation of a realistic stochastic atomistic-level model is applied to precisely track the reshaping of Pd octahedra and nanocubes. Unexpectedly, separate constrained equilibrium Monte Carlo analysis of the free energy profile during reshaping reveals a fundamental failure of the classical nucleation theory (CNT) prediction for the reshaping barrier and rate. Why? Nucleation barriers can be relatively low for these processes, so the system is not locally equilibrated before crossing the barrier, as assumed in CNT. This claim is supported by an analysis of a first-passage problem for reshaping within a master equation framework for the model that reasonably captures the behavior in KMC simulations.

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

Facet-dependent structure and dissociation of water at pristine IrO 2 /water interfaces

Understanding the microscopic structure of water at metal oxide interfaces is crucial for advancing electrocatalysis. IrO 2 , specifically, has shown exceptional activity for electrochemical water oxidation, but we currently lack a fundamental understanding of how the surface structure of IrO 2 impacts water reactivity. In this work, we developed a machine learning potential trained to first-principles accuracy for modeling IrO 2 /water interfaces across different facets: (110), (100), (101), and (001). Using extensive machine learning molecular dynamics simulations, we investigated the spontaneous dissociation of water molecules at these interfaces. Our results reveal a distinct dissociation probability trend: (110) > (100) ≈ (101) > (001), which we attribute primarily to the reaction thermodynamics of surface water dissociation. A strong correlation is observed between the surface Ir–O bond distances and the dissociation probabilities, highlighting the role of surface geometry in modulating reactivity. As a consequence, the interfacial solvation structures and hydrogen bonding environments are dynamically tuned by the varying water dissociation capabilities across facets. This work elucidates how water dissociation energetics depend on surface orientation and interfacial structure, offering atomistic insights into manipulating reaction chemistry at electrocatalytic interfaces.

organic↗
DOE OSTI2018

Beam Diagnostic Challenges for FACET-II

FACET-II, the Facility for Advanced Accelerator Experimental Tests II, is a new accelerator R&D test facility to be constructed at SLAC. It will provide high-energy, high-density electron and positron beams to advance the development of beam driven plasma wakefield acceleration and support a broad range of experiments. The FACET-II beams are expected to have 10 GeV energy, contain 2 nC of charge, have a transverse normalized emittance of 7 microns, be compressed to about 1 micron long and focused to about 6 micron wide at the interaction point. Additionally, the nominal peak current is 20 kA and is expected to fluctuate up to 200 kA. Most experiments desire complete knowledge of the incoming beam parameters on a pulse-to-pulse basis. However, the extreme beam densities and strong fields of the beam current will destroy any diagnostics intercepting the beam in a single shot and impose unique challenges for beam diagnostics. Moreover, non-intercepting diagnostics are desirable to provide feedback for machine setup and characterization. Finally, we need to look beyond conventional diagnostics to seek new solutions for measurements of the high charge, small beam size, short bunch length, and low emittance.

43 PARTICLE ACCELERATORS↗