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At least 289 records · Page 16

All sources NASA NTRS DOE OSTI

DOE OSTI2025

Organic Modulators Enable Morphological Diversity in Colloidal Crystals Engineered with DNA

Colloidal crystal engineering with DNA is a powerful way of generating a wide variety of crystals spanning over 90 different symmetries. However, in many cases, crystals with well-defined habits are difficult, if not impossible, to make, in part due to rapid crystal defect formation and propagation. This is especially true in the case of face-centered cubic (FCC) structures. Herein, we report a strategy that uses formamide as a chemical modulator to slow down colloidal crystal growth, which decreases defect formation and yields higher-quality crystals. Formamide forms hydrogen bonds with DNA bases and destabilizes the DNA duplex; in the context of colloidal crystallization, formamide leads to the disassembly of undercoordinated particles (defect architectures) and facilitates their reassembly into structures with the maximum number of nearest-neighbor contacts and DNA bonds. Here, when targeting an FCC lattice comprised of DNA-modified spherical 20 nm particles, formamide promotes the formation of its Wulff polyhedron (a truncated octahedron), never observed before in colloidal crystal engineering with DNA. Importantly, kinetic habits, including tetrahedra, octahedra, icosahedra, and decahedra, are also observed depending on formamide concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Rheology and dynamics of a solvent segregation driven gel (SeedGel)

Bicontinuous structures promise applications in a broad range of research fields, such as energy storage, membrane science, and biomaterials. Kinetically arrested spinodal decomposition is found responsible for stabilizing such structures in different types of materials. A recently developed solvent segregation driven gel (SeedGel) is demonstrated to realize bicontinuous channels thermoreversibly with tunable domain sizes by trapping nanoparticles in a particle domain. As the mechanical properties of SeedGel are very important for its future applications, a model system is characterized by temperature-dependent rheology. The storage modulus shows excellent thermo-reproducibility and interesting temperature dependence with the maximum storage modulus observed at an intermediate temperature range (around 28 °C). SANS measurements are conducted at different temperatures to identify the macroscopic solvent phase separation during the gelation transition, and solvent exchange between solvent and particle domains that is responsible for this behavior. Further, the long-time dynamics of the gel is further studied by X-ray Photon Correlation Spectroscopy (XPCS). The results indicate that particles in the particle domain are in a glassy state and their long-time dynamics are strongly correlated with the temperature dependence of the storage modulus.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Effect of Intermediate Semiconducting TiOx Thin Films on Nanoparticle-Mediated Electron Transfer: Electrooxidation of CO

The concept of nanoparticle-mediated electron transfer (eT) across insulating thin films was elucidated theoretically by Allongue and Chazalviel in 2011. In their model, metal nanoparticles (NPs) are immobilized atop passivating, self-assembled monolayers (SAMs). They found that under certain conditions, related to the thickness of the SAM and the size of the NPs, efficient faradaic oxidation and reduction reactions could proceed at the NP surface. In the absence of NPs, however, eT was suppressed by the insulating SAM thin films. Allongue and Chazalviel concluded that, within certain bounds, eT is mediated by fast tunneling between the conductive electrode and the metal NPs, while the kinetics of the redox reaction are controlled by the NPs. This understanding has been confirmed using a variety of experimental models. The theory is based on electron tunneling; therefore, the nature of the intervening medium (the insulator in prior studies) should not affect the eT rate. In the present manuscript, however, we show that the theory breaks down under certain electrochemical conditions when the medium between conductors is an n-type semiconductor. Specifically, we find that in the presence of either Au or Pt NPs immobilized on a thin film of TiOx, CO electrooxidation does not proceed. In contrast, the exact same systems lead to the efficient reduction of oxygen. At present, we are unable to explain this finding within the context of the model of Allongue and Chazalviel.

Galyamova, Aigerim↗

NASA NTRS2015

Observation Platform for Dynamic Biomedical and Biotechnology Experiments Using the International Space Station (ISS) Light Microscopy Module (LMM)

Techshot, Inc., has developed an observation platform for the LMM on the ISS that will enable biomedical and biotechnology experiments. The LMM Dynamic Stage consists of an electronics module and the first two of a planned suite of experiment modules. Specimens and reagent solutions can be injected into a small, hollow microscope slide-the heart of the innovation-via a combination of small reservoirs, pumps, and valves. A life science experiment module allows investigators to load up to two different fluids for on-orbit, real-time image cytometry. Fluids can be changed to initiate a process, fix biological samples, or retrieve suspended cells. A colloid science experiment module conducts microparticle and nanoparticle tests for investigation of colloid self-assembly phenomena. This module includes a hollow glass slide and heating elements for the creation of a thermal gradient from one end of the slide to the other. The electronics module supports both experiment modules and contains a unique illuminator/condenser for bright and dark field and phase contrast illumination, power supplies for two piezoelectric pumps, and controller boards for pumps and valves. This observation platform safely contains internal fluids and will greatly accelerate the research and development (R&D) cycle of numerous experiments, products, and services aboard the ISS.

Kurk, Michael A. (Andy)↗

NASA NTRS2015

Observation Platform for Dynamic Biomedical and Biotechnology Experiments Using the International Space Station (ISS) Light Microscopy Module (LMM)

Kurk, Michael A. (Andy)↗

DOE OSTI2023

pH- and Redox-Responsive Pickering Emulsions Based on Cellulose Nanocrystal Surfactants

Nanoparticle surfactants (NPSs), formed by using dynamic interactions between nanoparticles and complementary ligands at the liquid-liquid interface, have emerged as “smart emulsifiers” with attributes of high emulsification efficiency, long-term stability, and on-demand emulsification/demulsification capabilities. However, only pH-responsiveness can be adopted for the assembly of reported NPSs formed by electrostatic interactions. Here, we propose an alternative design strategy, by taking advantage of the ferrocenium (Fc + ) sulfate ion pair, to develop a new type of cellulose nanocrystal (CNC) surfactant. In conclusion, the Fc + groups are sensitive to pH, redox reagents and voltage, imparting the CNC surfactants and derived Pickering emulsions with multi-stimuli-responsiveness, and showing promising applications in controllable delivery, release, and biphasic biocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Colloidal Clusters and Networks Formed by Oppositely Charged Nanoparticles with Varying Stiffnesses

Colloidal clusters and gels are ubiquitous in science and technology. Particle softness has a strong effect on interparticle interactions; however, our understanding of the role of this factor in the formation of colloidal clusters and gels is only beginning to evolve. Here, we report the results of experimental and simulation studies of the impact of particle softness on the assembly of clusters and networks from mixtures of oppositely charged polymer nanoparticles (NPs). Experiments were performed below or above the polymer glass transition temperature, at which the interaction potential and adhesive forces between the NPs were significantly varied. Hard NPs assembled in fractal clusters that subsequently organized in a kinetically arrested colloidal gel, while soft NPs formed dense precipitating aggregates, due to the NP deformation and the decreased interparticle distance. Importantly, interactions of hard and soft NPs led to the formation of discrete precipitating NP aggregates at a relatively low volume fraction of soft NPs. A phenomenological model was developed for interactions of oppositely charged NPs with varying softnesses. Furthermore, the experimental results were in agreement with molecular dynamics simulations based on the model. This work provides insight on interparticle interactions before, during, and after the formation of hard–hard, hard–soft, and soft–soft contacts and has impact for numerous applications of reversible colloidal gels, including their use as inks for additive manufacturing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2020

Synthesis and catalytic performance of polydopamine supported metal nanoparticles

Polydopamine (PDA) is an emerging nature-inspired biopolymer material that possesses many interesting properties including self-assembly and universal adhesion. PDA is also able to form coordination bonds with various metal ions, which can be reduced to metal nanoparticles (NPs) as a result of thermal annealing under protective environment. In this study, PDA has been utilized as a support material to synthesize Pt NPs in an aqueous solution at room temperature. The catalytic performance of the resulting PDA-Pt nanocomposite was evaluated using an electrochemical workstation which showed comparable activity to Pt/C material for hydrogen evolution reaction (HER). Furthermore, Cu, Ni, and Cu–Ni NPs supported on PDA were also obtained using this strategy with assistance of subsequent thermal annealing. The phase evolution of the NPs was studied by in-situ X-ray diffraction while the morphology of the nanoparticles was investigated using electron microscopic techniques. Preliminary results showed the NPs supported on PDA also possessed HER activity. This work demonstrates that PDA can be utilized as a potential support for synthesis of metal NPs that can be exploited in engineering applications such as catalysts.

36 MATERIALS SCIENCE↗

DOE OSTI2023

All‐Liquid Reconfigurable Electronics Using Jammed MXene Interfaces

Abstract Rigid, solid‐state components represent the current paradigm for electronic systems, but they lack post‐production reconfigurability and pose ever‐increasing challenges to efficient end‐of‐life recycling. Liquid electronics may overcome these limitations by offering flexible in‐the‐field redesign and separation at end‐of‐life via simple liquid phase chemistries. Up to now, preliminary work on liquid electronics has focused on liquid metal components, but these devices still require an encapsulating polymer and typically use alloys of rare elements like indium. Here, using the self‐assembly of jammed 2D titanium carbide (Ti 3 C 2 T x ) MXene nanoparticles at liquid–liquid interfaces, “all‐liquid” electrically conductive sheets, wires, and simple functional devices are described including electromechanical switches and photodetectors. These assemblies combine the high conductivity of MXene nanosheets with the controllable form and reconfigurability of structured liquids. Such configurations can have applications not only in electronics, but also in catalysis and microfluidics, especially in systems where the product and substrate have affinity for solvents of differing polarity.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Surface Decoration of Platinum Catalysts by ZrO 2– x Nanoclusters for Durable Fuel Cell Applications

Improving the activity and durability of carbon-supported platinum catalysts for the oxygen-reduction reaction (ORR) in acidic electrolytes is crucial to reducing the high overpotentials and power loss over time in proton-exchange membrane fuel cells (PEMFCs). We found that platinum nanoparticle catalyst deposited on an engineered carbon support in the presence of zirconium enabled higher ORR activity and 25% better retention in electrochemically active surface area (ECSA), thereby improving durability. The use of zirconium precursor in the carbon synthesis process led to the formation of atomically dispersed Zr and ZrO 2 nanoparticles on the support. Upon Pt deposition and subsequent heat treatment, the ZrO 2 particles preferentially rearranged on and around the platinum nanoparticles in a chemically reduced form as zirconium suboxide (ZrO 2-x ) surface-decorated nanoclusters, which mitigated Pt nanoparticle coarsening. Finally, analysis of the here-to-fore unknown catalyst structure as well as its performance and durability in a PEM fuel cell membrane electrode assembly (MEA) is discussed.

25 ENERGY STORAGE↗

DOE OSTI2020

Programmable Anisotropy and Percolation in Supramolecular Patchy Particle Gels

Patchy particle interactions are predicted to facilitate the controlled self-assembly and arrest of particles into phase-stable and morphologically tunable "equilibrium" gels, which avoids the arrested phase separation and subsequent aging that is typically observed in traditional particle gels with isotropic interactions. Despite these promising traits of patchy particle interactions, such tunable equilibrium gels have yet to be realized in the laboratory due to experimental limitations associated with synthesizing patchy particles in high yield. Here, we introduce a supramolecular metal-coordination platform consisting of metallic nanoparticles linked by telechelic polymer chains, which validates the predictions associated with patchy particle interactions and facilitates the design of equilibrium particle hydrogels through limited valency interactions. We demonstrate that the interaction valency and self-assembly of the particles can be effectively controlled by adjusting the relative concentration of polymeric linkers to nanoparticles, which enables the gelation of patchy particle hydrogels with programmable local anisotropy, morphology, and low mechanical percolation thresholds. Moreover, by crowding the local environment around the patchy particles with competing interactions, we introduce an independent method to control the self-assembly of the nanoparticles, thereby enabling the design of highly anisotropic particle hydrogels with substantially reduced percolation thresholds. We thus establish a canonical platform that facilitates multifaceted control of the self-assembly of the patchy nanoparticles en route to the design of patchy particle gels with tunable valencies, morphologies, and percolation thresholds. These advances lay important foundations for further fundamental studies of patchy particle systems and for designing tunable gel materials that address a wide range of engineering applications.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Ultrastrong colloidal crystal metamaterials engineered with DNA

Lattice-based constructs, often made by additive manufacturing, are attractive for many applications. Typically, such constructs are made from microscale or larger elements; however, smaller nanoscale components can lead to more unusual properties, including greater strength, lighter weight, and unprecedented resiliencies. Here, solid and hollow nanoparticles (nanoframes and nanocages; frame size: ~15 nanometers) were assembled into colloidal crystals using DNA, and their mechanical strengths were studied. Nanosolid, nanocage, and nanoframe lattices with identical crystal symmetries exhibit markedly different specific stiffnesses and strengths. Unexpectedly, the nanoframe lattice is approximately six times stronger than the nanosolid lattice. Nanomechanical experiments, electron microscopy, and finite element analysis show that this property results from the buckling, densification, and size-dependent strain hardening of nanoframe lattices. Last, these unusual open architectures show that lattices with structural elements as small as 15 nanometers can retain a high degree of strength, and as such, they represent target components for making and exploring a variety of miniaturized devices.

42 ENGINEERING↗

DOE OSTI2020

Theoretical insight into thermodynamics of particle-based crystallization

Crystallization process often does not follow the monomer-by-monomer addition pathway, as described by classical nucleation theory. Instead, initial step may involve the formation of larger building blocks, such as crystalline or amorphous nanoparticles, droplets, clusters, complexes or oligomers, which subsequently undergo assembly into a crystal. These multistep crystallization processes are ubiquitous in mineral formation and biomineralization. In materials synthesis utilizing non-classical crystallization pathways is particularly attractive as the restriction on which crystalline faces can grow is lifted in a multistep crystallization process adding to the versatility of materials architectures that can be obtained. Predicting the outcomes of non-classical crystallization through the understanding of the control parameters influencing crystallization pathways is an important and challenging task essential for utilizing the full potential of non-classical crystallization in the design of functional materials. Here, the current status of the development of a predictive theoretical framework for modeling non-classical crystallization is reviewed.

Sushko, Maria L.↗

DOE OSTI2022

Laser diagnostics to characterize the in-flame growth of platinum nanoparticles manufactured by the reactive spray deposition technology

Reactive Spray Deposition Technology (RSDT) is an atmospheric pressure, flame-based advanced manufacturing method used to fabricate Membrane Electrode Assemblies (MEAs) for proton exchange fuel cells and water electrolyzers. RSDT combines the flame synthesis of catalyst nanoparticles and their deposition onto the membrane in one step. The properties of the synthesized nanoparticles, such as their Size Distribution Function (SDF), determine the manufactured electrodes’ performance, which can be evaluated when the deposition is complete via ex-situ characterization of the products. Efforts to improve RSDT for manufacturing state-of-the-art MEAs can be significantly enhanced with integrated laser diagnostics that enable in situ measurement of the synthesized catalyst nanoparticles. This paper reports the implementation of laser diagnostics in an RSDT facility and evaluates their potential to assist the manufacturing process. Laser Light Scattering (LS) and Laser-Induced Incandescence (LII) measurements are performed in the oxygen-rich zone of the flame at various distances from the flame fuel jet nozzle downstream of its luminous region. The measurements quantitatively track the evolution in size and volume fraction of platinum-based nanoparticles in two flames that yield different catalytic properties in the manufactured electrodes. The profiles of the measured nanoparticles’ volume fraction along the flame axis can be estimated a priori so that the average nanoparticle sizes can be measured in quasi-real time via LS. Nanoparticles experience an extremely slow growth rate while being convected at distances from 150 nm to 300 nm from the fuel nozzle. Complementary characterizations of the synthesized nanoparticles are performed ex-situ via High-Angle Annular Darkfield Scanning Transmission Electron Microscopy (HAADF-STEM) image analyses of samples collected on grids at a fixed distance from the fuel jet nozzle. Comparing the results from laser and microscopy techniques not only cross-validates the findings but also provides the parameters to infer the bimodal SDF in-situ and yields evidence that the coagulation efficiency of the synthesized nanoparticles has extremely low values in the investigated zone of the flames.

Rayleigh Light Scattering (LS)↗

DOE OSTI2021

Low coordination number copper catalysts for electrochemical CO 2 methanation in a membrane electrode assembly

The electrochemical conversion of CO 2 to methane provides a means to store intermittent renewable electricity in the form of a carbon-neutral hydrocarbon fuel that benefits from an established global distribution network. The stability and selectivity of reported approaches reside below technoeconomic-related requirements. Membrane electrode assembly-based reactors offer a known path to stability; however, highly alkaline conditions on the cathode favour C-C coupling and multi-carbon products. In computational studies herein, we find that copper in a low coordination number favours methane even under highly alkaline conditions. Experimentally, we develop a carbon nanoparticle moderator strategy that confines a copper-complex catalyst when employed in a membrane electrode assembly. In-situ XAS measurements confirm that increased carbon nanoparticle loadings can reduce the metallic copper coordination number. At a copper coordination number of 4.2 we demonstrate a CO 2 -to-methane selectivity of 62%, a methane partial current density of 136 mA cm –2 , and > 110 hours of stable operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

High-Current Density Durability of Pt/C and PtCo/C Catalysts at Similar Particle Sizes in PEMFCs

The durability of carbon supported PtCo-alloy based nanoparticle catalysts play a key role in the longevity of proton-exchange membrane fuel cells (PEMFC) in electric vehicle applications. To improve its durability, it is important to understand and mitigate the various factors that cause PtCo-based cathode catalyst layers (CCL) to lose performance over time. These factors include i) electrochemical surface area (ECSA) loss, ii) specific activity loss, iii) H + /O 2 -transport changes and iv) Co 2+ contamination effects. We use a catalyst-specific accelerated stress test (AST) voltage cycling protocol to compare the durability of Pt and PtCo catalysts at similar average nanoparticle size and distribution. Our studies indicate that while Pt and PtCo nanoparticle catalysts suffer from similar magnitudes of electrochemical surface area (ECSA) losses, PtCo catalyst shows a significantly larger cell voltage loss at high current densities upon durability testing. The distinctive factor causing the large cell voltage loss of PtCo catalyst appears to be the secondary effects of the leached Co 2+ cations that contaminate the electrode ionomer. A 1D performance model has been used to quantify the cell voltage losses arising from various factors causing degradation of the membrane electrode assembly (MEA).

08 HYDROGEN↗

DOE OSTI2023

Mixed Nanosphere Assemblies at a Liquid–Liquid Interface

The in-plane packing of gold (Au), polystyrene (PS), and silica (SiO 2 ) spherical nanoparticle (NP) mixtures at a water–oil interface is investigated in situ by UV–vis reflection spectroscopy. All NPs are functionalized with carboxylic acid such that they strongly interact with amine-functionalized ligands dissolved in an immiscible oil phase at the fluid interface. This interaction markedly increases the binding energy of these nanoparticle surfactants (NPSs). The separation distance between the Au NPSs and Au surface coverage are measured by the maximum plasmonic wavelength (λ max ) and integrated intensities as the assemblies saturate for different concentrations of non-plasmonic (PS/SiO 2 ) NPs. Further, as the PS/SiO 2 content increases, the time to reach intimate Au NP contact also increases, resulting from their hindered mobility. λ max changes within the first few minutes of adsorption due to weak attractive inter-NP forces. Additionally, a sharper peak in the reflection spectrum at NP saturation reveals tighter Au NP packing for assemblies with intermediate non-plasmonic NP content. Grazing incidence small angle X-ray scattering (GISAXS) and scanning electron microscopy (SEM) measurements confirm a decrease in Au NP domain size for mixtures with larger non-plasmonic NP content. The results demonstrate a simple means to probe interfacial phase separation behavior using in situ spectroscopy as interfacial structures densify into jammed, phase-separated NP films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Interfacial and Confinement-Mediated Organization of Gas Hydrates, Water, Organic Fluids, and Nanoparticles for the Utilization of Subsurface Energy and Geological Resources

Harnessing the subsurface geologic environments in an efficient and environmentally sustainable manner is challenged by uncertainties associated with predicting the fate of fluids and sustaining porosity and permeability in subsurface geologic environments. Some of these uncertainties arise from confined and interfacially induced structures of fluids in subsurface geologic environments. The formation of gas hydrates, phase transitions of confined fluids, assembly and deposition of heavy hydrocarbons, and the agglomeration and fate of nanoparticles in confined environments are summarized in this review. Nanoscale confinement contributes to anisotropic structures and dynamics of fluids, which is the basis for anomalous phase transition thermodynamics, reactivity, transport, and geomechanical behavior. In this review, we discuss the structures of confined fluids and deviation in observed properties from bulk fluids. The factors influencing the structures of confined fluids can be generally divided into two groups: (a) pore characteristics including pore size, pore surface chemistry, and pore geometry and (b) confined fluid/solid characteristics such as molecular structure, concentrations, charges, pore filling, and presence of additives. Scientific advancements and knowledge gaps in our understanding of the structures of confined fluids and the associated differences in observed properties compared to bulk fluids are discussed. Here, the phenomena discussed in this review are of particular relevance to our efforts in harnessing the subsurface environments for a low carbon future by increasing the utilization of geothermal energy, using CO 2 as a working fluid, and storing CO 2 in subsurface geologic environments.

42 ENGINEERING↗