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

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At least 397 records · Page 22

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↗

Discovery of two-dimensional binary nanoparticle superlattices using global Monte Carlo optimization

Binary nanoparticle (NP) superlattices exhibit distinct collective plasmonic, magnetic, optical, and electronic properties. Here, we computationally demonstrate how fluid-fluid interfaces could be used to self-assemble binary systems of NPs into 2D superlattices when the NP species exhibit different miscibility with the fluids forming the interface. We develop a basin-hopping Monte Carlo (BHMC) algorithm tailored for interface-trapped structures to rapidly determine the ground-state configuration of NPs, allowing us to explore the repertoire of binary NP architectures formed at the interface. By varying the NP size ratio, interparticle interaction strength, and difference in NP miscibility with the two fluids, we demonstrate the assembly of an array of exquisite 2D periodic architectures, including AB-, AB 2 -, and AB 3 -type monolayer superlattices as well as AB-, AB 2 -, A 3 B 5 -, and A 4 B 6 -type bilayer superlattices. Our results suggest that the interfacial assembly approach could be a versatile platform for fabricating 2D colloidal superlattices with tunable structure and properties.

36 MATERIALS SCIENCE↗

The Role of Phase Separation on Rayleigh-Plateau Type Instabilities in Alloys

Classical molecular dynamics (MD) simulations are used to investigate the role of phase separation (PS) on the Rayleigh-Plateau (RP) instability. Ni–Ag bulk structures are created at temperatures (2000 K and 1400 K) that generate different PS length scales, λ PS , relative to the RP instability length scale, λRP. Rectanguloids are then cut from the bulk structures and patterned with a perturbation of certain amplitude and wavelength, λ RP . It is found that when λ PS << λ RP (2000 K), the patterned rectanguloids break up into nanoparticles in a manner consistent with classical RP theory, whereas when λ PS << λ RP (1400 K), soluto-capillarity affects the RP instability significantly. Specifically, since Ag has a lower surface energy than Ni, Ag migrates to cover neighboring Ni regions, therefore modifying the RP instability. Thus, we demonstrate that the phase separation length scale of an immiscible alloy can be exploited to direct the assembly of functional bimetallic alloys.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spherical Congeners of Polyaromatic Compounds Approaching C 20 - and C 60 -Fullerene-Type Structures

A series of three symmetric, hollow spherical, and shape-persistent molecular organic cages analogous to C 20 and C 60 were examined by computational modeling, analyzing structural elements, strain indicators, and physical properties relevant for potential applications. The compounds are covalent aromatic cages based on 1,3,5-substituted benzene nodes linked by paraphenylene or para-pyrenylene-connectors, with diameters varying from 2.3 to 4.2 nm. The apertures in the cage interior are varied by virtue of the cage type (C 20 - or C 60 -type cage) and the linear connectors placed between the C 6 H 3 -units. NBO and MESP analyses indicate the presence of electrophilic and nucleophilic sites in the molecular skeleton. In the cages with the phenylene-connectors, the HOMO−LUMO gaps are close to 4.0 eV. In the cage coated with an enlarged polyaromatic spacer (pyrene-unit), the gap is reduced by approximately 0.4 eV.

Aromatic compounds↗

Tuning the dynamics in Fe 3 O 4 nanoparticles for hyperthermia optimization

The AC magnetic susceptibility (ACS) of Fe 3 O 4 nanoparticles was measured between 10 kHz and 4 MHz at different temperatures and in applied DC fields. In this frequency range, magnetostatic interactions impact magnetization dynamics even for dilute assemblies. The ACS spectrum of relaxation frequencies changes both with temperature and the addition of a small DC field. Because both the relaxation peak frequency and amplitude can be tuned with the DC field, these results could be applied to magnetic hyperthermia applications to optimize heat delivery.

Physics↗

Transmission Measurement of the Third-Order Susceptibility of Gold

Gold nanoparticle composites are known to display large optical nonlinearities. In order to assess the validity of generalized effective medium theories (EMT's) for describing the linear and nonlinear optical properties of metal nanoparticle composites, knowledge of the linear and nonlinear susceptibilities of the constituent materials is a prerequisite. In this study the inherent nonlinearity of the metal is measured directly (rather than deduced from a suitable EMT) using a very thin gold film. Specifically, we have used the z-scan technique at a wavelength near the transmission window of bulk gold to measure the third-order susceptibility of a continuous thin gold film deposited on a quartz substrate surface-modified with a self-assembled monolayer to promote adhesion and uniformity without affecting the optical properties. We compare our results with predictions which ascribe the nonlinear response to a Fermi-smearing mechanism. Further, we note that the sign of the nonlinear susceptibility is reversed from that of gold nanoparticle composites.

Smith, David D.↗

Ordered nanoparticle arrays formed on engineered chaperonin protein templates

Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques. Alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Some proteins, for example, have been used to form ordered two-dimensional arrays. Here, we fabricated nanoscale ordered arrays of metal and semiconductor quantum dots by binding preformed nanoparticles onto crystalline protein templates made from genetically engineered hollow double-ring structures called chaperonins. Using structural information as a guide, a thermostable recombinant chaperonin subunit was modified to assemble into chaperonins with either 3 nm or 9 nm apical pores surrounded by chemically reactive thiols. These engineered chaperonins were crystallized into two-dimensional templates up to 20 microm in diameter. The periodic solvent-exposed thiols within these crystalline templates were used to size-selectively bind and organize either gold (1.4, 5 or 10nm) or CdSe-ZnS semiconductor (4.5 nm) quantum dots into arrays. The order within the arrays was defined by the lattice of the underlying protein crystal. By combining the self-assembling properties of chaperonins with mutations guided by structural modelling, we demonstrate that quantum dots can be manipulated using modified chaperonins and organized into arrays for use in next-generation electronic and photonic devices.

Chaperonins/chemistry/ultrastructure↗

Biologically Derived Nanoparticle Arrays via a Site-Specific Reconstitution of Ferritin and their Electrochemistry

Nanoparticle arrays biologically derived from an electrochemically-controlled site-specific biomineralization were fabricated on a gold substrate through the immobilization process of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, the fabrication of self-assembled arrays with the immobilized ferritin, and the electrochemical characterization of various core materials. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of electrochemical site-specific biomineralization with a protein cage loads ferritins with different core materials such as Pt, Co, Mn, and Ni. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. The nano-sized metalcored ferritins on a gold substrate displayed a good electrochemical activity for the electron transport and storage, which is suitable for bioelectronics applications such as biofuel cell, bionanobattery, biosensors, etc. Keywords: Ferritin, immobilization, site-specific reconstitution, biomineralization, and bioelectronics

Kim, Jae-Woo↗

Stabilized hole-selective layer for high-performance inverted p-i-n perovskite solar cells

P-i-n geometry perovskite solar cells (PSCs) offer simplified fabrication, greater amenability to charge extraction layers, and low-temperature processing over n-i-p counterparts. Self-assembled monolayers (SAMs) can enhance the performance of p-i-n PSCs but ultrathin SAMs can be thermally unstable. Here we report a thermally robust hole-selective layer comprised of nickel oxide (NiO x ) nanoparticle film with a surface-anchored (4-(3,11-dimethoxy-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonic acid (MeO-4PADBC) SAM that can improve and stabilize the NiO x /perovskite interface. The energetic alignment and favorable contact and binding between NiO x /MeO-4PADBC and perovskite reduced the voltage deficit of PSCs with various perovskite compositions and led to strong interface toughening effects under thermal stress. The resulting 1.53–electron-volt devices achieved 25.6% certified power conversion efficiency and maintained >90% of their initial efficiency after continuously operating at 65 degrees Celsius for 1200 hours under 1-sun illumination.

14 SOLAR ENERGY↗

Stability of Polyethylene Glycol-Coated Copper Nanoparticles and Their Optical Properties

Oxidation is a corrosion reaction where the corroded metal forms an oxide. Prevention of oxidation at the nanoscale is critically important to retain the physicochemical properties of metal nanoparticles. In this work, we studied the stability of polyethylene glycol (PEG) coated copper nanoparticles (PEGylated CuNPs) against oxidation. The freshly-prepared PEGylated CuNPs mainly consist of metallic Cu which are quite stable in air although their surfaces are typically covered with a few monolayers of cuprous oxide. However, they are quickly oxidized in water due to the presence of protons that facilitate oxidation of the cuprous oxide to cupric oxide. PEG with carboxylic acid terminus could slightly delay the oxidation process compared to that with thiol terminus. It was found that a solvent with reducing power such as ethanol could greatly enhance the stability of PEGylated CuNPs by preventing further oxidation of the cuprous oxide to cupric oxide and thus retain the optical properties of CuNPs. The reducing environment also assists the galvanic replacement of these PEGylated CuNPs to form hollow nanoshells; however, they consist of ultra-small particle assemblies due to the co-reduction of gold precursor during the replacement reaction. As a result, these nanoshells do not exhibit strong optical properties in the near-infrared region. This study highlights the importance of solvent effects on PEGylated nonprecious metal nanoparticles against oxidation corrosion and its applications in preserving physicochemical properties of metallic nanostructures.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Creating Favorable Pt/Co Interfaces via a Two‐Step Approach for Constructing Highly Durable PtCo Intermetallic Fuel Cell Catalysts

Structurally ordered PtCo intermetallics are one of the most promising oxygen-reduction catalysts in proton exchange membrane fuel cells (PEMFCs) due to their intrinsically improved catalytic activity and stability relative to PtCo solid-solution alloys. However, increasing the heating temperature to achieve a desirable high degree of ordering results in severe particle agglomeration and low mass activity and stability. Herein, a two-step synthesis approach is developed to create an L1 2 -Pt 3 Co intermetallic structure with an increased ordering degree and well-dispersed ultrafine particles. The first step of the synthesis yields ultrafine Pt nanoparticles that are well-dispersed on the ZIF-8-derived carbon support. The second adsorption step enables us to fine-tune the Pt and Co interfaces, assisted by optimal amino acids, to establish a favorable Co-rich environment around fine Pt nanoparticles, facilitating Co diffusion into the Pt crystalline under mild thermal conditions (<800 °C). In conclusion, this two-step ordered L1 2 -Pt 3 Co catalyst is systematically evaluated using membrane electrode assemblies under heavy-duty vehicle (HDV) conditions and demonstrated exceptional performance and durability, retaining 1.35 A cm -2 only a 7% loss in current density at 0.7 V after an extensive accelerated stress test of 150,000 voltage cycles.

30 DIRECT ENERGY CONVERSION↗

Surfactant-Induced Interfacial Aggregation of Porphyrins for Structuring Color-Tunable Liquids

Locking nonequilibrium shapes of liquids into targeted architectures by interfacial jamming of nanoparticles is an emerging area in material science. 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (H 6 TPPS) shows three different aggregation states that present an absorption imaging platform to monitor the assembly and jamming of supramolecular polymer surfactants (SPSs) at the liquid/liquid interface. The interfacial interconversion of H 6 TPPS, specifically H 4 TPPS 2- dissolved in water, from J- to an H-aggregation was induced by strong electrostatic interactions with amine-terminated polystyrene dissolved in toluene at the water/toluene interface. We find that this resulted in color-tunable liquids due to interfacial jamming of the SPSs formed between H 4 TPPS 2- and amine-terminated polystyrene. However, the formed SPSs cannot lock in nonequilibrium shapes of liquids. In addition, a self-wrinkling behavior was observed when amphiphilic triblock copolymers of PS-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) were used to interact with H 4 TPPS 2- . Subsequently, the SPSs formed can lock in nonequilibrium shapes of liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recent developments in Pt–Co catalysts for proton-exchange membrane fuel cells

Development of Pt-based oxygen reduction reaction catalysts with high efficiency and high durability is central to the application of proton-exchange membrane fuel cell systems. Pt–Co bimetallic catalysts have drawn extensive attention owing to their capability of delivering high performance and long lifetime for fuel cell applications including light-duty and heavy-duty vehicles. However, further improvements in durability and performance are needed to meet market requirements. To fully exploit the potential of Pt–Co catalysts, new insights into the relationship between catalyst properties and fuel cell performance and durability are needed, and more effective methods to tailor the features of Pt–Co catalysts need to be developed. This review provides a summary and perspective on recent efforts, including work on customizing the Pt shell and Pt:Co ratio, tailoring the crystal structure, and improving carbon support properties, with a particular emphasis on mechanisms leading to enhancement of mass activity, power density, and durability in membrane electrode assembly testing.

25 ENERGY STORAGE↗

Photoresponsive Structured Liquids Enabled by Molecular Recognition at Liquid–Liquid Interfaces

Using host-guest molecular recognition at the oil-water interface, a new type of photoresponsive nanoparticle surfactant (NPS) was designed and prepared to structure liquids. With the help of a polymeric surfactant, the interfacial host-guest interactions can be significantly enhanced, leading to the rapid formation and assembly of a NP monolayer and offering sufficient binding energy to hold the NPs in a jammed state. The assembly of the NPSs can be reversibly manipulated via a photoswitchable jamming-to-unjamming transition, endowing the interface as well as the macroscopic assemblies with responsiveness to the external trigger (photons). Finally, this study for the first time opens a pathway for the construction of multiresponsive, structured all-liquid systems by introducing host-guest chemistry, showing promising potential applications in encapsulation, delivery systems, and unique microfluidic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗