Search NASA⌕ Search

SEARCH · Search NASA

Results for “functionalized metal nanoparticles”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Building Minimalist Models for Functionalized Metal Nanoparticles

In our opinion, the presented strategy includes all the crucial elements of an optimal low resolution model: the choice of the minimal possible resolution, compatibility between different levels of resolution, a parameterization including the specific coating present on the NP by means of superficial higher resolution interacting sites. The effective charges could be further optimized by directly adopting a RESP procedure for their fitting. This task and the model validation at different concentrations and ionic strengths vs. the aggregation tendency are currently in due course (Brancolini et al., submitted). The following steps will be the use of the model in combination with proteins models at the same CG level (minimalist), to verify their effective capability of preventing the amyloids aggregation. Furthermore, the strategy here outlined is extensible to larger NPs and different functionalization, which opens the possibility of in silico optimization of the NPs size and chemistry for therapeutic use.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Improved Models for Metallic Nanoparticle Cores from Atomic Pair Distribution Function (PDF) Analysis

X-ray atomic pair distribution functions (PDFs) were collected from a range of canonical metallic nanomaterials, both elemental and alloyed, prepared using different synthesis methods and exhibiting drastically different morphological properties. Widely applied shape-tuned attenuated crystal (AC) fcc models proved inadequate, yielding structured, coherent, and correlated fit residuals. However, equally simple discrete cluster models could account for the largest amplitude features in these difference signals. A hypothesis testing based approach to nanoparticle structure modeling systematically ruled out effects from crystallite size, composition, shape, and surface faceting as primary factors contributing to the AC misfit. On the other hand, decahedrally twinned cluster cores were found to be the origin of the AC structure misfits for a majority of the nanomaterials reported here. It is further motivated that the PDF can readily differentiate between the arrangement of domains in these multiply twinned motifs. Most of the nanomaterials surveyed also fall within the sub-5 nm size regime where traditional electron microscopy cannot easily detect and quantify domain structures, with sampling representative of the average nanocrystal synthesized. Here, the results demonstrate that PDF analysis is a powerful method for understanding internal atomic interfaces in small noble metallic nanomaterials. Such core cluster models, easily built algorithmically, should serve as starting structures for more advanced models able to capture atomic positional disorder, ligand induced or otherwise, near nanocrystal surfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Molecular Dynamics Simulations of a Catalytic Multivalent Peptide–Nanoparticle Complex

Molecular modeling of a supramolecular catalytic system is conducted resulting from the assembling between a small peptide and the surface of cationic self-assembled monolayers on gold nanoparticles, through a multiscale iterative approach including atomistic force field development, flexible docking with Brownian Dynamics and µs-long Molecular Dynamics simulations. Self-assembly is a prerequisite for the catalysis, since the catalytic peptides do not display any activity in the absence of the gold nanocluster. Atomistic simulations reveal details of the association dynamics as regulated by defined conformational changes of the peptide due to peptide length and sequence. Our results show the importance of a rational design of the peptide to enhance the catalytic activity of peptide–nanoparticle conjugates and present a viable computational approach toward the design of enzyme mimics having a complex structure–function relationship, for technological and nanomedical applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Low-Resolution Models for the Interaction Dynamics of Coated Gold Nanoparticles with β2-microglobulin

A large number of low-resolution models have been proposed in the last decades to reduce the computational cost of molecular dynamics simulations for bio-nano systems, such as those involving the interactions of proteins with functionalized nanoparticles (NPs). For the proteins, “minimalist” models at the one-bead-per residue (Cα-based) level and with implicit solvent are well established. For the gold NPs, widely explored for biotechnological applications, mesoscale (MS) models treating the NP core with a single spheroidal object are commonly proposed. In this representation, the surface details (coating, roughness, etc.) are lost. These, however, and the specificity of the functionalization, have been shown to have fundamental roles for the interaction with proteins. We presented a mixed-resolution coarse-grained (CG) model for gold NPs in which the surface chemistry is reintroduced as superficial smaller beads. We compared molecular dynamics simulations of the amyloid β2-microglobulin represented at the minimalist level interacting with NPs represented with this model or at the MS level. Our finding highlights the importance of describing the surface of the NP at a finer level as the chemical-physical properties of the surface of the NP are crucial to correctly understand the protein-nanoparticle association.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Synergistic Integration of Chemo-Resistive and SERS Sensing for Label-Free Multiplex Gas Detection

Practical sensing applications such as real-time safety alerts and clinical diagnoses require sensor devices to differentiate between various target molecules with high sensitivity and selectivity, yet conventional devices such as oxide-based chemo-resistive sensors and metal-based surface-enhanced Raman spectroscopy (SERS) sensors usually do not satisfy such requirements. In this report a label-free, chemo-resistive/SERS multimodal sensor based on a systematically assembled 3D cross-point multifunctional nanoarchitecture (3D-CMA), which has unusually strong enhancements in both “chemo-resistive” and “SERS” sensing characteristics is introduced. 3D-CMA combines several sensing mechanisms and sensing elements via 3D integration of semiconducting SnO 2 nanowire frameworks and dual-functioning Au metallic nanoparticles. It is shown that the multimodal sensor can successfully estimate mixed-gas compositions selectively and quantitatively at the sub-100 ppm level, even for mixtures of gaseous aromatic compounds (nitrobenzene and toluene) with very similar molecular structures. This is enabled by combined chemo-resistive and SERS multimodal sensing providing complementary information.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Functionalization of carbon nanotubes with metallic moieties

A method of functionalizing carbon nanotubes with metallic moieties is disclosed. Carbon nanotubes are first associated with one or more binding moieties to provide carbon nanotubes encapsulated by the binding moieties. The encapsulated carbon nanotubes are then contacted with a metal salt or a metal complex that binds to the binding moieties. Reduction of the metal salt or metal complex provides carbon nanotubes functionalized with metal nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Growth of Nanoparticles with Desired Catalytic Functions by Controlled Doping-Segregation of Metal in Oxide

Here, the size and morphology of metal nanoparticles (NPs) often play a critical role in defining the catalytic performance of supported metal nanocatalysts. However, common synthetic methods struggle to produce metal NPs of appropriate size and morphological control. Thus, facile synthetic methods that offer controlled catalytic functions are highly desired. Here we have identified a new pathway to synthesize supported Rh nanocatalysts with finely tuned spatial dimensions and controlled morphology using a doping-segregation method. We have analyzed their structure evolutions during both the segregation process and catalytic reaction using a variety of in situ spectroscopic and microscopic techniques. A correlation between the catalytic functional sites and activity in CO 2 hydrogenation over supported Rh nanocatalysts is then established. This study demonstrates a facile strategy to design and synthesize nanocatalysts with desired catalytic functions.

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

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Making the most of your electrons: Challenges and opportunities in characterizing hybrid interfaces with STEM

Inspired by the unique architectures composed of hard and soft materials in natural and biological systems, synthetic hybrid structures and associated hard-soft interfaces have recently evoked significant interest. Soft matter is typically dominated by structural fluctuations even at room temperature, while hard matter is governed by rigid mechanical behavior. This dichotomy offers considerable opportunities to leverage the disparate properties offered by these components across a wide spectrum spanning from basic science to engineering insights with significant technological overtones. Such hybrid structures, which include polymer nanocomposites, DNA functionalized nanoparticle superlattices, and metal organic frameworks to name a few, have delivered promising insights into the technologically relevant applications such as catalysis, environmental remediation, optoelectronics, and medicine. The interfacial structure between the hard and soft phases demonstrates features across a variety of length scales and often strongly influence the functionality of hybrid systems. While scanning/transmission electron microscopy (S/TEM) has proven to be a valuable tool for acquiring intricate molecular and nanoscale details of these interfaces, the unusual nature of hybrid composites presents a suite of challenges that make assessing or establishing structure–property relationships especially difficult. There are additional considerations at all stages of sample analysis from preparing electron-transparent samples to obtaining sufficient contrast to resolve the interface between dissimilar materials given the dose sensitivity of soft materials. Here, we discuss each of these challenges and supplement a review of recent developments in the field with additional experimental investigations and simulations to present solutions for attaining a nano or molecular-level understanding of these interfaces. These solutions present a host of opportunities for investigating the role interfaces play in this unique class of functional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Design and optimization of nanoparticle-pigmented solar selective absorber coatings for high-temperature concentrating solar thermal systems

In this paper, we present a systematic approach for the design and optimization of nanoparticle-pigmented solar selective absorbers for operation at 750 °C. Using the scattering and absorption cross-sections calculated by Lorenz-Mie scattering theory as input, we employ a four-flux radiative transfer method to investigate the solar selectivity mechanism and optimize the optical-to-thermal conversion efficiency (η therm ) as a function of the metallic nanoparticle material, the nanoparticle diameter, the volume fraction, and the coating thickness. Among the nanoparticle material candidates in this study, C54-TiSi 2 is the best option with an optimized η therm = 87.0% for a solar concentration ratio of C = 100 and η therm = 94.4% for C = 1000 at 750 °C. NiSi is also a promising candidate comparable to TiSi 2 in thermal efficiency, Experimentally, an un-optimized 200 nm-diameter TiSi 2 nanoparticle-silicone solar selective coating has already achieved η therm = 89.8% for C = 1000 at 750 °C. This performance is consistent with the theoretical model and close to the thermal efficiency of the commercial Pyromark 2500 coatings (90.1%). We also demonstrate that Ni/NiSi core-shell structures embedded in the SiO 1.5 matrix is thermally stable at 750 °C for 1000 h in air. Lastly, these results indicate that silicide cermet coatings are promising to achieve high optical performance and high temperature thermal stability simultaneously.

14 SOLAR ENERGY↗
DOE OSTI2022

Active learning of polarizable nanoparticle phase diagrams for the guided design of triggerable self-assembling superlattices

Polarizable nanoparticles are of interest in materials science because of their rich and complex phase behavior that can be used to engineer nanostructured materials with long-range crystalline order. To understand and rationally navigate the design space of polarizable nanoparticles for self-assembling highly ordered superlattices, we developed a coarse-grained computational model to describe the nanoparticle-nanoparticle interactions in implicit solvent and employ the computationally efficient image method to model many-body polarization interactions. We conducted high-throughput virtual screening over a five-dimensional particle design space spanned by temperature, particle size, particle charge, particle dielectric, and solvent dielectric using enhanced sampling molecular dynamics calculations within an active learning framework to efficiently map out the regions of thermodynamic stability of the self-assembled aggregates. We validate our predictions in comparisons against small angle x-ray scattering measurements of gold nanoparticles surface functionalized with metal chalcogenide ligands. Lastly, we use our validated phase maps to computationally design switchable nanostructured materials capable of triggered assembly and disassembly as a function of temperature and solvent dielectric with potential applications as sensors, smart windows, optoelectronic devices, and in medical diagnostics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Continual–quantum plasmonics with kinematical functions: dipolar resonance and nonlocal polarizability of simple metal made nanoparticles

In this work we formulate the theory of a mesoscopic oscillator equivalent to sp-electron excitations in simple metal made nanoparticles illuminated by incident light. The principles of continuum mechanics have been applied to maintain this goal: the primary hypotheses about the dependences of electron density function upon kinematical generalized coordinates, the stationary action principle, and the perturbation method. On their grounds, dynamic equations describing the motion of electron gas subject to alternating potentials together with the ground state equations have been derived. A methodological advantage of the latter is in the correct (qualitative and quantitative) prediction of Friedel oscillations and electron spill-out through an ion lattice with no demands to use high power computer resources as opposed to the orbital density functional theory. The dynamic equations allow studying of the nanoparticle resonant properties in an analytical form without need of numerically solving them. It has been shown with their use that the resonant frequency of the main dipolar resonance becomes the density functional of the ground state. On the basis of the dynamic equations, the theory of nonlocal polarizability has been deduced that does not impose the homogeneity (or weak inhomogeneity) constraints on the electron gas density. In this context the two following results are of importance. We manage to: (1) to demonstrate the effect of giant nonlocality of the dipole moment—its formation by the events separated by distances significantly larger than nanoparticle dimensions and temporal intervals much larger than the mean free time; (2) to derive the expression of the volumetric mode of compression-tension that is resonant on frequency of the main dipolar resonance.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Surfactant-free syntheses and pair distribution function analysis of osmium nanoparticles

A surfactant-free synthesis of precious metal nanoparticles (NPs) performed in alkaline low-boiling-point solvents has been recently reported. Monoalcohols are here investigated as solvents and reducing agents to obtain colloidal Os nanoparticles by using low-temperature (<100 °C) surfactant-free syntheses. The effect of the precursor (OsCl 3 or H 2 OsCl 6 ), precursor concentration (up to 100 mM), solvent (methanol or ethanol), presence or absence of a base (NaOH), and addition of water (0 to 100 vol %) on the resulting nanomaterials is discussed. It is found that no base is required to obtain Os nanoparticles as opposed to the case of Pt or Ir NPs. The robustness of the synthesis for a precursor concentration up to 100 mM allows for the performance of X-ray total scattering with pair distribution function (PDF) analysis, which shows that 1–2 nm hexagonal close packed (hcp) NPs are formed from chain-like [OsO x Cl y ] complexes.

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

Tuning nanoparticle size for enhanced functionality in perovskite thin films deposited by metal organic deposition

Because of pressing global environmental challenges, focus has been placed on materials for efficient energy use, and this has triggered the search for nanostructural modification methods to improve performance. Achieving a high density of tunable-sized second-phase nanoparticles while ensuring the matrix remains intact is a long-sought goal. In this paper, we present an effective, scalable method to achieve this goal using metal organic deposition in a perovskite system REBa 2 Cu 3 O 7 (rare earth (RE)) that enhances the superconducting properties to surpass that of previous achievements. We present two industrially compatible routes to tune the nanoparticle size by controlling diffusion during the nanoparticle formation stage by selecting the second-phase material and modulating the precursor composition spatially. Combining these routes leads to an extremely high density (8 × 10 22 m -3 ) of small nanoparticles (7 nm) that increase critical currents and reduce detrimental effects of thermal fluctuations at all magnetic field strengths and temperatures. This method can be directly applied to other perovskite materials where nanoparticle addition is beneficial.

36 MATERIALS SCIENCE↗