Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “nanoparticle assembly”

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 379 records · Page 21

Particle emission with identification from an atmospheric pressure plasma liquid interface

A conspicuous emission phenomenon of luminous particles from the liquid anode surface of an atmospheric pressure DC glow discharge is reported. The emission has been shown to occur when the plasma forms a pattern on the surface of the liquid electrolyte. Here, the spatial-temporal evolutions of the trajectories of emitted particles were studied using a high-speed imaging system. Particles were sampled in flight using a witness plate for analysis. Critical particle characteristics were examined using electron microscope technologies. The morphology of the resulting splats and compositions suggest that they are molten droplets with a great deal of structure, including evidence of nanoprecipitation. A theoretical model was employed to estimate the particle size from the measured splats, which provides a radius range within a hundred micrometers. This experiment leads to the postulation of a mechanism in which particle emission at the plasma liquid interface is likely driven by the Taylor cone effect.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Reducing module soiling with scalable and robust photocatalytic coatings

The air-glass interface at the front of a photovoltaic (PV) module reflects approximately 4% of incident light, decreasing the potential power output of the module by the same amount. Today’s modules reduce this loss by adding a low-refractive-index (1.25-1.30) SiO2 coating to the sunward side of the module glass; this antireflection coating recovers approximately 3% of the 4% light that would otherwise be lost. While such antireflection coatings work very well on clean, new modules, they do not inhibit soiling—the accumulation of soilants such as dust, pollen, soot, or other foreign material—on the module glass, and soilants reflect and scatter incident light. An improved coating would serve provide not only an antireflection effect, but also an anti-soiling effect. The goal of this project was to develop such a coating and provide a path for it to be manufactured in the U.S. The project successfully designed and fabricated coatings that provided >3% transmittance gain compared to bare glass (matching the performance of commercial antireflection coatings) and displayed anti-soiling behavior in standard laboratory soiling effects. This was achieved by using a Swift Coat proprietary coating deposition technique, aerosol impact-driven assembly (AIDA), to control the porosity and thus refractive index of coatings of photocatalytic materials—such as TiO2—that would otherwise increase (instead of decrease) reflection. These combined antireflection/anti-soiling coatings passed PV industry standard module reliability tests as well as coating-specific abrasion tests, showing that they have the durability needed for decades in the field. Swift Coat scaled the AIDA hardware and deposition process to make mini-modules that were monitored for nearly two years during field tests administered by a third party, as well as demonstrated scaling to the widths of full-sized modules. The fielded mini-modules outperformed reference modules (with commercial antireflection coatings) in two locations, providing a 1% absolute average performance boost and larger increases during periods of heavier soiling. Swift Coat’s cost analysis indicated a coating manufacturing cost below the sales price of today’s antireflection coatings. More than five module manufacturers sampled and assessed the coatings, and three provided letters of support. The coating developed in this project increases the energy output of PV modules, thereby decreasing the cost per kilowatt-hour of solar energy generated. Cheaper solar electricity benefits the public by accelerating the transition to a stable, affordable, carbon-free energy economy. In addition, for select applications in which PV modules are highly visible—such as on residential rooftops—the coating provides an aesthetic benefit because it stays cleaner than today’s modules. Finally, Swift Coat and its prospective customers are U.S. companies, and successful commercialization of this technology will provide U.S. jobs and a secure solar supply chain.

14 SOLAR ENERGY↗

Bis-polymer lipid-peptide conjugates and nanoparticles thereof

The present invention provides bis-polymer lipid-peptide conjugates containing a hydrophobic block and headgroup containing a helical peptide and two polymer blocks. The conjugates can self-assemble to form helix bundle subunits, which in turn assemble to provide micellar nanocarriers for drug cargos and other agents. Particles containing the conjugates and methods for forming the particles are also disclosed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Block copolymer self-assembly derived mesoporous magnetic materials with three-dimensionally (3D) co-continuous gyroid nanostructure

Magnetic nanomaterials are gaining interest for their many applications in technological areas from information science and computing to next-generation quantum energy materials. While magnetic materials have historically been nanostructured through techniques such as lithography and molecular beam epitaxy, there has recently been growing interest in using soft matter self-assembly. In this work, a triblock terpolymer, poly(isoprene-block-styrene-block-ethylene oxide) (ISO), is used as a structure directing agent for aluminosilicate sol nanoparticles and magnetic material precursors to generate organic–inorganic bulk hybrid films with co-continuous morphology. After thermal processing into mesoporous materials, results from a combination of small angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) are consistent with the double gyroid morphology. Nitrogen sorption measurements reveal a type IV isotherm with H1 hysteresis, and yield a specific surface area of around 200 m 2 g −1 and an average pore size of 23 nm. The magnetization of the mesostructured material as a function of applied field shows magnetic hysteresis and coercivity at 300 K and 10 K. Comparison of magnetic measurements between the mesoporous gyroid and an unstructured bulk magnetic material, derived from the identical inorganic precursors, reveals the structured material exhibits a coercivity of 250 Oe, opposed to 148 Oe for the unstructured at 10 K, and presence of remnant magnetic moment not conventionally found in bulk hematite; both of these properties are attributed to the mesostructure. This scalable route to mesoporous magnetic materials with co-continuous morphologies from block copolymer self-assembly may provide a pathway to advanced magnetic nanomaterials with a range of potential applications.

Chemistry↗

The Features of Self-Assembling Organic Bilayers Important to the Formation of Anisotropic Inorganic Materials in Microgravity Conditions

There is a growing need for inorganic anisotropic particles in a variety of materials science applications. Structural, optical, and electrical properties can be greatly augmented by the fabrication of composite materials with anisotropic microstructures or with anisotropic particles uniformly dispersed in an isotropic matrix. Examples include structural composites, magnetic and optical recording media, photographic film, certain metal and ceramic alloys, and display technologies including flat panel displays. While considerable progress has been made toward developing an understanding of the synthesis of powders composed of monodispersed, spherical particles, these efforts have not been transferred to the synthesis of anisotropic nanoparticles. The major objective of the program is to develop a fundamental understanding of the growth of anisotropic particles at organic templates, with emphasis on the chemical and structural aspects of layered organic assemblies that contribute to the formation of anisotropic inorganic particles.

Talham, Daniel R.↗

Photosynthetic Biohybrid System for Enhanced Abiotic N 2 -to-NH 3 Conversion under Ambient Conditions

Photosynthetic biohybrid systems (PBSs) offer an eco-friendly approach to transforming solar energy into value-added products by integrating biological entities with inorganic semiconductors. However, the chemical conversion capacity of most PBSs has inherent limitations, as whole-cell bacteria and isolated enzymes require fine-tuning of environmental conditions. Here, in this study, we report a new PBS developed by introducing free-standing ceria nanoparticles into the purple membrane (PM) of Halobacterium salinarum archaea, which can unidirectionally transfer charge carriers in response to incident photons, even after separation from living archaea at various conditions. Our microscopy, spectroscopy, and synchrotron X-ray scattering analyses confirm that the electrostatic assembly between ceria and PM creates seamless interfacial contact, thereby enhancing the photocatalytic capacity of ceria. Although the conversion of dinitrogen (N 2 ) to ammonia (NH 3 ) is thermodynamically challenging due to the triple bond in N 2 and a series of charge-transfer reactions, our PM–ceria (PMC) hybrid nanoparticle efficiently produces NH 3 by reducing N 2 using solar energy even under atmospheric pressure and room temperature while simultaneously converting glycerol into value-added derivatives. Additionally, our PMC nanoparticle involves neither toxic/precious metals nor bioengineering processes to achieve enhanced photocatalytic N 2 -to-NH 3 conversion. This study sheds light on the new aspect of PBSs by employing PM to potentially resolve the global energy and environmental challenges posed by the conventional Haber–Bosch process.

Jang, Jinhyeong [Argonne National Laboratory (ANL)↗

End-exclusion zones in strongly stretched, molten polymer brushes of arbitrary shape

Theories of strongly stretched polymer brushes, particularly the parabolic brush theory, are valuable for providing analytically tractable predictions for the thermodynamic behavior of surface-grafted polymers in a wide range of settings. Furthermore, the parabolic brush limit fails to describe polymers grafted to convex curved substrates, such as the surfaces of spherical nanoparticles or the interfaces of strongly segregated block copolymers. It has previously been shown that strongly stretched curved brushes require a boundary layer devoid of free chain ends, requiring modifications of the theoretical analysis. While this “end-exclusion zone” has been successfully incorporated into the descriptions of brushes grafted onto the outer surfaces of cylinders and spheres, the behavior of brushes on surfaces of arbitrary curvature has not yet been studied. We present a formulation of the strong-stretching theory for molten brushes on the surfaces of arbitrary curvature and identify four distinct regimes of interest for which brushes are predicted to possess end-exclusion zones, notably including regimes of positive mean curvature but negative Gaussian curvature. Through numerical solutions of the strong-stretching brush equations, we report predicted scaling of the size of the end-exclusion zone, the chain end distribution, the chain polarization, and the free energy of stretching with mean and Gaussian surface curvatures. Through these results, we present a comprehensive picture of how the brush geometry influences the end-exclusion zones and exact strong-stretching free energies, which can be applied, for example, to model the full spectrum of brush geometries encountered in block copolymer melt assembly.

36 MATERIALS SCIENCE↗

One-Step Facile Synthesis of High-Activity Nitrogen-Doped PtNiN Oxygen Reduction Catalyst

PtM alloy electrocatalysts (M = Fe, Co, Ni) have been the subject of many investigations aimed at increasing their attractive properties, in particular oxygen reduction reaction (ORR) activity, while reducing total platinum-group-metal content and improving durability. Despite some success, these catalysts still have relatively high Pt content and lack the necessary durability as M metals leach out from the alloys during potential cycling. Previously, we synthesized nitrogen (N)-doped PtMN/C catalysts consisting of thin Pt shells on M nitride cores by a two-step method, which showed higher ORR activity and stability than their PtM counterparts. In the present work, we developed a facile one-step synthesis method, which comprises a single thermal annealing process of the N-doped PtNiN/C alloy. The ORR performance of the one-step synthesized PtNiN/C catalyst is much higher than that of the two-step synthesized PtNiN/C, as revealed by rotating disk electrode measurements. Membrane electrode assembly fuel cell testing demonstrated superb durability and high activity. Formation of Pt monolayer shells on the nitrided (Pt x Ni 1-x ) 4 N cores was confirmed by in situ X-ray absorption spectroscopy. The origins of the enhanced activity and stability of the one-step synthesized PtNiN/C catalyst are elucidated based on density functional theory calculations together with the experimental results.

30 DIRECT ENERGY CONVERSION↗

Sol–Gel‐Based Advanced Porous Silica Materials for Biomedical Applications

Abstract Porous silica‐based materials have burgeoning applications ranging from fillers and additives, to adsorbents, catalysts, and recently therapeutic agents and vaccines in nanomedicine. The preponderance of these materials is made by sol–gel processing wherein soluble silica precursors are reacted to form amorphous networks composed of siloxane bonds. The facile sol–gel approach allows for an unlimited variety of binary tertiary and more complex chemical compositions including organic ligands and networks resulting in so‐called organic–inorganic hybrid materials. Here, a brief review of the recent progress in sol–gel‐derived silica materials prepared as particles, thin films, biosilica/silica bioreplicas (of molecules, cells and organisms), and their related preparation, properties, and bioapplications is provided. First, it highlights the recent achievements of mesoporous silica nanoparticles in biomedical applications, including therapeutic agent delivery, multimodal imaging and theranostics, and bone tissue engineering and repair. Second, the research in evaporation‐induced self‐assembly (EISA)‐based mesostructured silica thin films and cell‐directed EISA in bio/nano interfaces for various bioapplications, such as bioactive coatings, biosensing, and living cell immobilization, has been reviewed. Third, the pioneering work in biomimetic silicification/immobilization of biomolecules and bio‐organisms and silica bioreplication of complex bio‐organisms is summarized. Finally, it is concluded with personal perspectives on the directions of future work on this field.

Lei, Qi↗

Direct Integration of Strained-Pt Catalysts into Proton-Exchange-Membrane Fuel Cells with Atomic Layer Deposition

The design and fabrication of lattice-strained platinum catalysts achieved by removing a soluble core from a platinum shell synthesized via atomic layer deposition, is reported. The remarkable catalytic performance for the oxygen reduction reaction (ORR), measured in both half-cell and full-cell configurations, is attributed to the observed lattice strain. By further optimizing the nanoparticle geometry and ionomer/carbon interactions, mass activity close to 0.8 A mg Pt -1 @0.9 V iR-free is achievable in the membrane electrode assembly. Nevertheless, active catalysts with high ORR activity do not necessarily lead to high performance in the high-current-density (HCD) region. More attention shall be directed toward HCD performance for enabling high-power-density hydrogen fuel cells.

25 ENERGY STORAGE↗

Covalent Triazine-Based Frameworks with Ru-tda Based Catalyst Anchored via Coordination Bond for Photoinduced Water Oxidation

Light-induced water splitting (hν-WS) for the production of hydrogen as a solar fuel is considered a promising sustainable strategy for the replacement of fossil fuels. An efficient system for hν-WS involves a photoactive material that, upon shining light, is capable of separating and transferring charges to catalysts for the hydrogen and oxygen evolution processes. Covalent triazine-based frameworks (CTFs) represent an interesting class of 2D organic light-absorbing materials that have recently emerged thanks to their tunable structural, optical and morphological properties. Typically, catalysts (Cat) are metallic nanoparticles generated in situ after photoelectroreduction of metal precursors or directly drop-casted on top of the CTF material to generate Cat-CTF assemblies. Here, in this work, the synthesis, characterization and photocatalytic performance of a novel hybrid material, Ru-CTF, is reported, based on a CTF structure featuring dangling pyridyl groups that allow the Ru-tda (tda is [2,2':6',2'“-terpyridine]-6,6'”-dicarboxylic acid) water oxidation catalyst (WOC) unit to coordinate via covalent bond. The Ru-CTF molecular hybrid material can carry out the light-induced water oxidation reaction efficiently at neutral pH, reaching values of maximum TOF of 17 h -1 and TONs in the range of 220 using sodium persulfate as a sacrificial electron acceptor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ formed catalysts for active, durable, and thermally stable ammonia protonic ceramic fuel cells at 550 °C

Ammonia protonic ceramic fuel cells (NH 3 -PCFCs) are promising and attractive energy-conversion devices owing to their high energy density, zero-carbon emission, and safety. The development of NH 3 -PCFCs, however, depends largely on the insufficient activity and poor durability of typical Ni-based anodes for ammonia decomposition, especially at low temperatures such as 550 °C. Herein, we report a self-assembled heterostructured Ru 0.95 Cu 0.05 Ni x (RCN) catalyst obtained through an in situ reaction between the surface-decorated Ru 0.95 Cu 0.05 nanoparticles and the Ni grain in the anode under typical processing conditions. At 550 °C, Ni–BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3 anode-supported PCFCs with RCN catalysts exhibit a high peak power density of 0.732 W cm -2 and a significantly enhanced durability of 100 h in NH 3 . Moreover, the cells demonstrate improved thermal stability compared with the bare cell during a 31-cycle thermal cycling test in NH 3 between 550 and 700 °C. In conclusion, the enhanced performance is likely attributed to the synergistic effects of Ru and Cu in RCN for NH 3 decomposition, resulting in a more vital interaction of NH 3 than that of the bare anode surfaces, as confirmed by NH 3 thermal conversion, electrochemical performance, and theoretical simulations.

30 DIRECT ENERGY CONVERSION↗

Strong Effect of Nonpolar Solvent Molecular Structure on CdSe Nanoplatelet Stacking

We report a drastic difference in stacking behavior of oleic acid-stabilized 4-monolayer (4 ML) CdSe nanoplatelets (NPLs) in toluene and methylcyclohexane (MCH), two nonpolar solvents that differ in the conformational flexibility of their molecules. Using liquid cell transmission electron microscopy (TEM) and small angle scattering (SAXS) techniques, we show that NPLs form microns-long ribbons consisting of 4 ML CdSe NPLs in toluene, the solvent widely used to form stable colloidal solutions of a broad range of quasi-spherical nanoparticles. In contrast, 4 ML CdSe NPLs are well dispersed in MCH. The difference in stacking behavior of NPLs in toluene and MCH suggests that the conformational flexibility of the solvent molecules, such as the ability to adopt multiple chair conformations, modulates nanoplatelet interactions. Molecular dynamics (MD) simulations reveal that solvent molecules subtly alter the structure of the organic ligand shell. These solvent-dependent changes propagate to the inorganic core, modulating the degree of CdSe nanoplatelet (NPL) twisting and, consequently, the properties of the nanoparticles. We show that toluene better solvates oleate ligands while MCH induces a bimodal oleate span distribution, which can lead to increased solubility of CdSe NPLs. In addition, the solvent can also influence the inorganic core, which, in turn, can modify the nanoparticle properties. We demonstrate that destabilization of toluene solution containing ribbons of 4 ML CdSe NPLs without CdS shells results in the formation of NPL assemblies with amplified spontaneous emission (ASE) with a low threshold of 14 µJ cm−2 that is comparable with that of CdSe/CdS core/shell NPLs. Our results emphasize that the solvent plays a major role in mediating interactions between NPLs and hence their processability for fabrication of functional structures.

CdSe↗

Supported Pt Nanoparticles on Mesoporous Titania for Selective Hydrogenation of Phenylacetylene

Semi-hydrogenation of alkynes to alkenes is one of the most important industrial reactions. However, it remains technically challenging to obtain high alkene selectivity especially at a high alkyne conversion because of kinetically favorable over hydrogenation. In this contribution, we show that supported ultrasmall Pt nanoparticles (2.5 nm) on mesoporous TiO2 (Pt@mTiO2) remarkably improve catalytic performance toward semi-hydrogenation of phenylacetylene. Pt@mTiO2 is prepared by co-assembly of Pt and Ti precursors with silica colloidal templates via an evaporation-induced self-assembly process, followed by further calcination for thermal decomposition of Pt precursors and crystallization of mTiO2 simultaneously. As-resultant Pt@mTiO2 discloses a high hydrogenation activity of phenylacetylene, which is 2.5 times higher than that of commercial Pt/C. More interestingly, styrene selectivity over Pt@mTiO2 remains 100% in a wide phenylacetylene conversion window (20–75%). The styrene selectivity is >80% even at 100% phenylacetylene conversion while that of the commercial Pt/C is 0%. The remarkable styrene selectivity of the Pt@mTiO2 is derived from the weakened styrene adsorption strength on the atop Pt sites as observed by diffuse reflectance infrared Fourier transform spectroscopy with CO as a probe molecule (CO-DRIFTS). Our strategy provides a new avenue for promoting alkyne to alkene transformation in the kinetically unfavorable region through novel catalyst preparation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge‐Programmable Photopolymers for 3D Electronics via Additive Manufacturing

Charge‐programmed 3D printing enables the fabrication of 3D electronics with lightweight and high precision via selective patterning of metals. This selective metal deposition is catalyzed by Pd nanoparticles that are specifically immobilized onto the charged surface and promises to fabricate a myriad of complex electronic devices with self‐sensing, actuation, and structural elements assembled in a designed 3D layout. However, the achievable property space and the material‐performance correlation of the charge‐programmed printing remain unexplored. Herein, a series of photo‐curable resins are designed for unveiling how the charge and crosslink densities synergistically impact the nanocatalyst‐guided selective deposition in catalytic efficiency and properties of the 3D printed charge‐programmed architectures, leading to high‐quality 3D patterning of solid and liquid metals. The findings offer a wide tunability of the structural properties of the printed electronics, ranging from stiff to extreme flexibility. Capitalizing on these results, the printing and successful application of an ultralight‐weight and deployable 3D multi‐layer antenna system operating at an ultrahigh‐frequency of 19 GHz are demonstrated.

36 MATERIALS SCIENCE↗

Surface structure of mass-selected niobium oxide nanoclusters on Au(111)

The structures formed by the deposition of mass-selected niobium oxide clusters, Nb 3 O y ( y = 5, 6, 7), onto Au(111) were studied by scanning tunneling microscopy. The as-deposited Nb 3 O 7 clusters assemble into large dendritic structures that grow on the terraces as well as extend from the top and bottom of step edges. The Nb 3 O 6 cluster also forms dendritic assemblies but they are generally much smaller in size. The assemblies are composed of smaller discrete structures (<1 nm) which are likely to be single clusters. Furthermore, the dendritic assemblies for both the Nb 3 O 7 and Nb 3 O 6 clusters have fractal dimensions of about 1.7 which is very close to that expected for simple diffusion limited aggregation. Annealing the Nb 3 O 7,6 /Au(111) surfaces up to 550 K results in changes in assembly sizes and increases in heights, while heating to 700 results in the disruption of the assemblies into smaller structures. By contrast, the as-deposited Nb 3 O 5 /Au(111) surface at RT exhibits compact cluster structures which become 3D nanoparticles when annealed above 550 K. Differences in the observed surface structures and thermal stability are attributed to differences in metal-oxygen stoichiometry which can influence cluster binding energies, mobility and inter-cluster interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Constructing Highly Durable Fuel Cell Catalysts Through Integrating Graphitic Shell‐Protected Composite Carbon Support with Gaseous Co Deposition‐Driven PtCo Intermetallics

Metal dissolution, nanoparticle agglomeration, and carbon support corrosion cause significant performance degradation of current PtCo catalysts under acidic and oxidative oxygen reduction reaction. Here, in this study, an integrated strategy is presented to design high-performance Pt 3 Co intermetallic catalysts by regulating gaseous Co deposition-driven diffusion into Pt nanoparticles supported on a composite carbon. The composite carbon is derived from ZIF-8/polyaniline, consisting of a high-surface-area (HSC) core and a protective graphitic shell (GS), which is employed to design 40 wt.% Pt/HSC@GS catalyst. The corresponding membrane electrode assemblies (MEAs) can maintain 1.09 A cm −2 at 0.7 V (20. 7% loss) after 10 000 cycles (1.0–1.5 V for carbon stability) and 1.15 A cm −2 (16.1% loss) after 150 000 cycles (0.60–0.95 V for catalyst stability). A ordered Pt 3 Co intermetallic is synthesized via a gaseous Co-deposition process, which yields a homogeneous Co-rich layer onto the Pt nanoparticles on the composite support, thereby facilitating Co diffusion into Pt crystal during subsequent ordering annealing to form the ordered intermetallic structure. This gaseous deposition leads to a thin carbon layer on PtCo nanoparticles, inhibiting particle growth during the annealing and mitigating Co dissolution under dynamic electrochemical conditions. The PtCo catalyst achieves impressive MEA performance and long-term durability (1.45 A cm −2 at 0.7 V after 120 000 cycles) under heavy-duty conditions.

30 DIRECT ENERGY CONVERSION↗

Spontaneous formation of anisotropic microrods from paraffin wax in an aqueous environment

The construction of functional nano-/micro-architectures through self-assembly and self-organization of organic molecules and polymeric materials plays an important role in the development of many technologies. In this study, we report the spontaneous formation of uniform polymer microrods with lengths of up to a few tens of micrometers from paraffin wax. Through a solvent attrition approach, colloidal structures of paraffin wax are introduced into water. After the initial growth stage, the microrods undergo morphological transformation and end-to-end aggregation, processes likely driven by thermodynamics to create equilibrium structures with minimal interfacial energies. Here, the polymer microrods can effectively absorb hydrophobic nanoparticles, indicating their potential to serve as host materials for functional components. The formation of polymer microrods from paraffin wax and their spontaneous growth mechanism discovered in this study may provide new insights to the self-assembly of microstructures.

36 MATERIALS SCIENCE↗