Alkaline-stable anion exchange membranes: A review of synthetic approaches
Not provided.
catalysis (heterogeneous), electrocatalysis, hydro↗
SEARCH · Engineering Papers
Results for “Heterogeneous material”
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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Direct Correlation of Charge Carrier Transport to Local Crystal Quality in Lead Halide Perovskites
Although solution processing methods provide an attractive route toward development of low-cost functional materials, these accessible fabrication approaches can engender high concentrations of microscopic structural defects that are detrimental to performance. In lead halide perovskites, structural disorder derived from solution processing has been implicated as an important determiner of photophysical properties. However, a direct correlation between the functional properties of these materials and the local crystal structure in which non-equilibrium states evolve has remained elusive, in part because structural heterogeneities occur on length scales that defy conventional characterization techniques. To address this knowledge gap, in this work we have combined ultrafast pump–probe microscopy and electron backscattering diffraction to directly correlate charge carrier transport with the local diffraction pattern contrast, an indicator of crystal quality. Spatial correlation of these measurements strongly suggests that even on individual single crystal CsPbBr3 domains, microscopic variability in the crystal quality profoundly impacts the efficiency of charge carrier transport.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Multifunctional Electrocatalysts: Ru–M (M = Co, Ni, Fe) for Alkaline Fuel Cells and Electrolyzers
Not provided.
catalysis (heterogeneous), electrocatalysis, hydro↗
Multimodal Nanoscale Mapping of Local Structure and CO 2 Adsorption in Metal–Organic Frameworks
Diamine functionalization of the metal−organic framework Mg 2 (dobpdc) (dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) significantly enhances its selectivity for CO 2 capture from flue gases and air. The structure and CO 2 capacity of such materials are typically assessed using bulk techniques that rely on averaging signal over large ensembles of unit cells, obscuring local heterogeneities, such as variations in CO 2 occupancy across individual nanocrystals. To resolve this limitation, we demonstrate a multimodal, nanoscale characterization of Mg 2 (dobpdc) appended with 1,3-diaminopropane. By employing recently developed characterization techniques at progressively smaller length scales, we uncover insights from correspondingly smaller populations of unit cells. First, we use parallel-beam 3D electron diffraction (3D ED) to identify a prominent expansion in lattice parameters upon desorption of CO 2 , as observed at the level of single nanocrystals. Second, we use convergent-probe 4D scanning transmission electron microscopy (4D-STEM) to quantify associated differences in lattice strain as a function of gas loading and diamine appending. These measurements sample small subvolumes within individual nanocrystals. Finally, we apply infrared scattering scanning near-field optical microscopy (IR s- SNOM) to confirm variable CO 2 chemisorption across adsorption sites at the surface of single nanocrystals. This multimodal, multiscale approach allows us to map heterogeneity within individual nanocrystals. Collectively, these findings emphasize the importance of local, nanoscale characterization of metal−organic frameworks in revealing previously unresolvable features that impact their performance.
Karstens, Sarah L. [University of California, Berk↗
Combinatorial Studies of Palladium-Based Oxygen Reduction Electrocatalysts for Alkaline Fuel Cells
Not provided.
catalysis (heterogeneous), electrocatalysis, hydro↗
The influence of counterion structure identity on conductivity, dynamical correlations, and ion transport mechanisms in polymerized ionic liquids
We used equilibrium and non-equilibrium atomistic simulations to probe the influence of anion chemistry on the true conductivity, dynamical correlations, and ion transport mechanisms in polymeric ionic liquids. An inverse correlation was found between anion self-diffusivities, ionic mobilities, and the anion size for spherical anions. While some larger asymmetric anions had higher diffusivities than smaller spherical anions, their diffusivities and mobilities did not exhibit a direct correlation to the anion volumes. Here, the conductivity and anion dynamical correlations also followed the same trends as displayed by the diffusivity and mobility of anions. All the systems we examined displayed positively correlated motion among anions, suggesting a contribution that enhances the conductivity beyond the ideal Nernst–Einstein value. Analysis of ion transport mechanisms demonstrated very similar hopping characteristics among the spherical anions despite differences in their sizes.
36 MATERIALS SCIENCE↗
Group-velocity-dispersion engineering of tantala integrated photonics
Designing integrated photonics, especially to leverage Kerr-nonlinear optics, requires accurate and precise knowledge of the refractive index across the visible to infrared spectral ranges. Tantala ( T a 2 O 5 ) is an emerging material platform for integrated photonics and nanophotonics that offers broadband ultralow loss, moderately high nonlinearity, and advantages for scalable and heterogeneous integration. We present refractive index measurements on a thin film of tantala, and we explore the efficacy of this data for group-velocity-dispersion (GVD) engineering with waveguide and ring-resonator devices. In particular, the observed spectral extent of supercontinuum generation in fabricated waveguides and the wavelength dependence of free spectral range (FSR) in optical resonators provide a sensitive test of our integrated photonics design process. Our work opens up new design possibilities with tantala, including with octave-spanning soliton microcombs.
Black, Jennifer A.↗
Facet-dependent Catalysis of CuNi Nanocatalysts toward 4-Nitrophenol Reduction Reaction
Not provided.
catalysis (heterogeneous), electrocatalysis, hydro↗
The Reactivity and Structural Dynamics of Supported Metal Nanoclusters Using Electron Microscopy, in-situ X-Ray Spectroscopy, Electronic Structure Theories, and Molecular Dynamics Simulations
This research will provide new methods to determine the structures and compositions of heterogeneous catalysts as they exist in reaction conditions. The new tools will make it possible to understand how extremely small material structures—ones in a size range spanning from single atoms to larger polyatomic clusters—make it possible to carry out highly selective chemical transformations required to synthesize useful materials as well as for efficient energy production and utilization. The tools will make it possible to see how the atomic structures of catalytic materials evolve over time under the conditions of their use, and in this way provide understandings to guide the design of new energy-efficient catalysts. The work will make it possible to answer long standing questions that include the following. How does catalyst structure help guide molecules along specific reaction pathways? What are the important intermediates involved in these transformations? How do the structures and reactivity of catalytic materials, as well as the chemistry of their interfaces, vary with reaction conditions? Is it possible to develop new catalytic materials using new knowledge of the active structures and reaction mechanisms? The work will provide heretofore unavailable experimental tools that can be applied in advanced programs of research addressing such questions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Hard–Soft Core–Shell Architecture Formation from Cubic Cobalt Ferrite Nanoparticles
Cubic bi-magnetic hard–soft core–shell nanoarchitectures were prepared starting from cobalt ferrite nanoparticles, prevalently with cubic shape, as seeds to grow a manganese ferrite shell. The combined use of direct (nanoscale chemical mapping via STEM-EDX) and indirect (DC magnetometry) tools was adopted to verify the formation of the heterostructures at the nanoscale and bulk level, respectively. The results showed the obtainment of core–shell NPs (CoFe 2 O 4 @MnFe 2 O 4 ) with a thin shell (heterogenous nucleation). In addition, manganese ferrite was found to homogeneously nucleate to form a secondary nanoparticle population (homogenous nucleation). This study shed light on the competitive formation mechanism of homogenous and heterogenous nucleation, suggesting the existence of a critical size, beyond which, phase separation occurs and seeds are no longer available in the reaction medium for heterogenous nucleation. These findings may allow one to tailor the synthesis process in order to achieve better control of the materials’ features affecting the magnetic behaviour, and consequently, the performances as heat mediators or components for data storage devices.
36 MATERIALS SCIENCE↗
Electrochemical impregnation of nickel hydroxide in porous electrodes
The electrochemical impregnation of nickel hydroxide in porous electrode was investigated both experimentally and theoretically. The loading level and plaque expansion were the most important parameters to be considered. The effects of applied current density, stirring, ratio of solution to electrode volume and pH were identified. A novel flow through electrochemical impregnation is proposed in which the electrolyte is forced through the porous nickel plaque. The thickening of the plaque can be reduced while maintaining high loading capacity. A mathematical model is presented which describes the transport of the nitrate, nickel and hydroxyl ions and the consecutive heterogeneous electrochemical reduction of nitrate and the homogeneous precipitation reaction of nickel hydroxide. The distributions of precipitation rate and active material within the porous electrode are obtained. A semiempirical model is also proposed which takes into account the plugging of the pores.
Ho, Kuo-Chuan↗
Comets after Hyakutake and Hale-Bopp
Being icy, cometary nuclei are the most easily modified bodies in the solar system - even modest heating is sufficient to induce significant weight loss. This sublimative loss and longterm storage far from the sun protect the nucleus against internal warming and ensure that cometary nuclei today contain the least processed material remaining from the early nebula - or perhaps from the natal cloud. The chemical compositions of ices, low temperature-refractory organics, and refractory minerals (and their physical states) provide sensitive probes of the origin and history of this material. The fortunate appearance of Hyakutake and Hale-Bopp has provided a wealth of information on these Oort cloud comets, obtained with a wide range of astronomical approaches. I will review certain key results for these comets, such as chemical abundances, isotopic abundance ratios, nuclear spin statistics, and nuclear vs extended production of "parent volatiles", and will illustrate how these test the origins of cometary material. A comparison with 1P/Halley--a third comet from the giant planet nebular region--will be discussed in the context of heterogeneity among these bodies.
Mumma, Michael J.↗
FIB-TEM Investigations of Fe-NI-Sulfides in the CI Chondrites Alais and Orgueil
The CI chondrites are primitive meteorites with bulk compositions matching the solar photosphere for all but the lightest elements. They have been extensively aqueously altered, and are composed primarily of fine-grained phyllosilicate matrix material which is host to carbonates, sulfates, sulfides, and minor amounts of olivine and pyroxene. The alteration, while extensive, is heterogeneous. For example, CI-chondrite cubanite and carbonate grains differ on mm to sub-mm scales, demonstrating multiple aqueous episodes. CI-chondrite variability is also evidenced by degree of brecciation, abundance and size of coarse-grained phyllosilicates, olivine and pyroxene abundance, as well as Ni-content and size of sulfide grains. Our previous work revealed Orgueil sulfide grains with variable Ni-contents, metal:S ratios, crystal structures and textures. We continue to explore the variability of CI-chondrite pyrrhotite (Po, (FeNi)1-xS) and pentlandite (Pn, (Fe,Ni)9S8) grains. We investigate the microstructure of sulfides within and among CI-chondrite meteorites in order to place constraints on the conditions under which they formed.
Berger, Eve L.↗
Conceive, Believe and Achieve; A Path to Miniaturization, COTS Infusion, and Size Weight and Power Realization for Flight
JPL along with other aerospace agencies such as the US Air Force Space Pro-grams and a packaging technology innovator, i3 Electronics, Inc., are evaluating the use of state-of-the-art (SOA) commercial off-the-shelf (COTS) and alternative packaging technologies for future high performance and high reliability space applications. Utilization of SOA COTS technologies have resulted in large scale reduction in electronics volume, weight, power, cost and schedule with outstanding electrical performance and high reliability. We will share JPL’s joint design, architectural approach, alternative substrate materials selection, associated processes, and mission assurance role in identifying reliability and qualification risks, as part of the three year Heterogeneous Packaging/Device Integration effort under the guidance and leadership of JPL’s Mission Assurance Directorate.
Hunter, Don J.↗
Nanoscale Three-Dimensional Imaging of Degradation in Composite Si-Containing Anodes
The use of silicon (Si) in next-generation lithium-ion battery (LIB) anodes has the potential to dramatically improve electrochemical performance over current LIB graphite (Gr) anodes, due to silicon’s higher specific capacity.1 However, widespread implementation of Si-containing anodes is inhibited by issues such as significant Si volume expansion during lithiation and an unstable solid-electrolyte interphase (SEI), resulting in unreliable performance and poor cycle life. Currently, composite anodes with both Si and graphite active materials are used to increase capacity and mitigate some of the limitations associated with Si. In composite electrodes with a heterogeneous distribution of components with varying electrical properties (including Si, Gr, conductive carbon additive, and binder), it is important to understand the local distribution of each component to correlate with electrochemical processes, particularly localized degradation and heterogeneous aging, and to optimize performance. To investigate Si-containing composite anodes in the nanoscale, we use scanning spreading resistance microscopy (SSRM), a form of scanning probe microscopy (SPM) that probes local electronic resistivity. By examining the intrinsic electronic resistivity contrast between the anode components, separate phases can be distinguished and understood within the composite structure.2 This work studies the effect of electrochemical cycling in two different electrolytes on component distribution and aging by comparing the electrical and structural evolution of composite Si-graphite electrodes and SEI before and after charge-discharge cycling. 1. W. J. Zhang. A review of the electrochemical performance of alloy anodes for lithium-ion batteries J. Power Sources 196 13–24 (2011). 2. C. Stetson, Z. Huey, A. Downard, Z. Li, B. To, A. Zakutayev, C.-S. Jiang, M. Al-Jassim, D. Finegan, S.-D. Han and S. DeCaluwe: Three-Dimensional Mapping of Resistivity and Microstructure of Composite Electrodes for Lithium-Ion Batteries. ACS Nano Letters Accepted (2020).
ADVANCED PROPULSION SYSTEMS↗
Operando methods: A new era of electrochemistry
One of the grand challenges facing electrochemistry is to directly resolve the complex nature of (electro)catalyst active sites and capture real-time “movies” of reaction dynamics, i.e. “watching chemistry in action”. The need for such fundamental understanding has stimulated the development of operando/in situ methods, which have greatly enhanced our ability to identify activity descriptors of electrocatalysts and establish structure–property relationships of energy materials. Here, this review summarizes the frontiers of operando electrochemical liquid-cell scanning transmission electron microscopy and correlative synchrotron X-ray methods, which are complementary tools to comprehensively investigate reaction dynamics across multiple spatiotemporal scales. In an effort to encourage greater adoption of advanced operando methods by the general electrochemistry community, this review points out the need to benchmark electrochemistry in confined and heterogenous liquid environment with minimal beam-induced damage. We anticipate that multimodal operando methods will become indispensable for understanding interfacial reaction mechanisms for the broad chemistry and energy materials communities.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Carbon-rich Chondritic Clast PV1 from the Plainview H-chondrite Regolith Formation from H3 Chondrite Material by Possible Cometary Impact
Chondritic clast PV1 from the Plainview H-chondrite regolith breccia is a subrounded, 5-mm diameter unequilibrated chondritic fragment that contains 13 wt% C occurring mainly within irregularly shaped 30-400-micron-size opaque patches. The clast formed from H3 chondrite material as indicated by the mean apparent chondrule diameter (310 micron vs. approximately 300 micron in H3 chondrites), the mean Mg-normalized refractory lithophile abundance ratio (1.00 +/- 0.09 XH), the previously determined 0-isotopic composition (Delta O-17 = 0.66% vs. 0.68 +/- 0.04%0 in H3 chondrites and 0.73 +/- 0.09% in H4-6 chondrites), the heterogeneous olivine compositions in grain cores (with a minimum range of Fal-19), and the presence of glass in some chondrules. Although the clast lacks the fine-grained, ferroan silicate matrix material present in type 3 ordinary chondrites, PV1 contains objects that appear to be recrystallized clumps of matrix material. Similarly, the apparent dearth of radial pyroxene and cryptocrystalline chondrules in PV1 is accounted for by the presence of some recrystallized fragments of these chondrule textural types. All of the chondrules in PV1 are interfused indicating that temperatures must have briefly reached approximately 1100C (the approximate solidus temperature of H-chondrite silicate). The most likely source of this heating was by an impact. Some metal was lost during impact heating as indicated by the moderately low abundance of metallic Fe-Ni in PV1 (approximately 14 wt%) compared to that in mean H chondrites (approximately 18 wt%). The carbon enrichment of the clast may have resulted from a second impact event, one involving a cometary projectile, possibly a Jupiter-family comet. As the clast cooled, it experienced hydrothermal alteration at low water/rock ratios as evidenced by the thick rims of ferroan olivine around low-FeO olivine cores. The C-rich chondritic clast was later incorporated into the H-chondrite parent-body regolith and extensively fractured and faulted.
Rubin, Alan E.↗
On Lateral Viscosity Contrast in the Mantle and the Rheology of Low-Frequency Geodynamics
Mantle-wide heterogeneity is largely controlled by deeply penetrating thermal convective currents. These thermal currents are likely to produce significant lateral variation in rheology, and this can profoundly influence overall material behaviour. How thermally related lateral viscosity variations impact models of glacio-isostatic and tidal deformation is largely unknown. An important step towards model improvement is to quantify, or bound, the actual viscosity variations that characterize the mantle. Simple scaling of viscosity to shear-wave velocity fluctuations yields map-views of long- wavelength viscosity variation. These give a general quantitative description and aid in estimating the depth dependence of rheological heterogeneity throughout the mantle. The upper mantle is probably characterized by two to four orders of magnitude variation (peak-to-peak). Discrepant time-scales for rebounding Holocene shorelines of Hudson Bay and southern Iceland are consistent with this characterization. Results are given in terms of a local average viscosity ratio, (Delta)eta(bar)(sub i), of volumetric concentration, phi(sub i). For the upper mantle deeper than 340 km the following reasonable limits are estimated for (delta)eta(bar) approx. equal 10(exp -2): 0.01 less than or equal to phi less than or equal to 0.15. A spectrum of ratios (Delta)eta(bar)(sub i) less than 0.1 at concentration level eta(sub i) approx. equal 10(exp -6) - 10(exp -1) in the lower mantle implies a spectrum of shorter time-scale deformational response modes for second-degree spherical harmonic deformations of the Earth. Although highly uncertain, this spectrum of spatial variation allows a purely Maxwellian viscoelastic rheology simultaneously to explain all solid tidal dispersion phenomena and long-term rebound-related mantle viscosity. Composite theory of multiphase viscoelastic media is used to demonstrate this effect.
Ivins, Erik R.↗