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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Nanocomposites from Solution-Synthesized PbTe-BiSbTe Nanoheterostructure with Unity Figure of Merit at Low-Medium Temperatures (500-600 K)

The large-scale implementation of thermoelectric devices is inhibited, in part, by the limited temperature range where each material can operate at its highest efficiency, as evaluated by the dimensionless figure of merit ( zT = S 2 σT/κ ). To date, Bi 2 Te 3 -based materials have been restricted to zT ≥ 1 between 300-500 K, before the onset of bipolar conduction reduces the zT significantly. Herein, we show that a scalable, low-temperature solution process method can be used to synthesize precursor material for Pb-doped Bi x Sb 2-x Te 3 bulk nanocomposites with a zT = 1 over the 500-600 K range, making this material suitable for low-grade waste heat recovery for the first time. Our success in increasing the efficiency of p-type Bi x Sb 2-x Te 3 at higher temperatures can be largely explained by the increase in the optical band gap, according to the Burstein-Moss shift, due to Pb doping, thus delaying the onset of bipolar conduction. Furthermore, the solution synthesis method enabled controlled nanostructuring of the bulk materials, which greatly reduced the thermal conductivity over the investigated temperature range. Lastly, our scalable synthesis processing method may be applicable to not only other thermoelectrics, but also in fields such as photocatalysis, electronics and optoelectronics.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Modeling Mesoscale Processes of Scalable Synthesis

Brown University is part of the Collaboratory on Mathematics for Mesoscopic Modeling of Materials (CM4), led by PNNL. The Collaboratory focuses on developing rigorous mathematical foundations for understanding and controlling fundamental mechanisms in mesoscale processes to enable scalable synthesis of complex materials, through the design of efficient modeling methods and corresponding scalable algorithms.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2019

Modeling Mesoscale Processes of Scalable Synthesis (Final Report)

The main objective of the center is to develop tools that can help for the understanding of equilibrium and non-equilibrium properties of nanoparticles in aqueous electrolytes. To achieve this goal, we need to develop new computational methodologies that can integrate molecular level description such as the electronic structure analysis to mesoscale description such as generalized hydrodynamics. The challenge is to develop systematic coarse graining techniques that can adaptively choose the level of description needed for the particular task. For example, if bonding breaking is involved, then one should use appropriate models from quantum mechanics to accurately model the time scale and molecular mechanism for the breaking process. However, to model transport process or the process of self-assembly, much less detailed models can be used. There are two main components to this task. One is to develop accurate models that bridge different levels of description. The classical example is the QM/MM model that bridges quantum mechanics and molecular mechanics for studying chemical reactions of large molecules. This work was awarded the Nobel prize this year. For our purpose, we also need to develop methods that bridge molecular and continuum levels of description. Another main task is to develop systematic coarse-graining methods that can give rise to accurate mesoscale and macroscale models, starting from more detailed models at the atomic or molecular scale. None of these ideas are new. By now they have been fashionable topics for quite some time. But neither problem is satisfactorily resolved. The main problem is that uncontrolled approximations are used. As a result, we have very little idea about the validity and accuracy of these models. The main purpose of the center is to exploit the Mori-Zwanzig formalism to achieve the goals stated above. The Mori-Zwanzig formalism is a general tool for eliminating degrees of freedom from existing models. What is attractive about this formalism is its generality. The flip side is that it is also somewhat of a tautology. In order to make it a practical tool, one has to make approximations and this is where the trouble comes. Instead of focusing on Mori-Zwanzig formalism, the PI proposes to study the closely related renormalization group formalism (RG). Like Mori-Zwanzig, RG is a general strategy for eliminating small scale degrees of freedom in a model. Unlike Mori-Zwanzig, RG has the advantage that at least for some problems, one can write a PDE (partial differential equation) type of model for the exact RG flow, without any approximation. This gives us a solid starting point for discussing and analyzing approximations. The PI studied approximate RG flows for turbulent diffusion and related problems. However, extending it to more practical problems proved to be hard. The second line that the PI has pursued is to develop special numerical algorithms for studying particularly important events for dynamics processes in meso-scale systems. The PI succeeded in doing so for the problem of understanding phase transition in metallic systems.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

Modeling Mesoscale Processes of Scalable Synthesis Final Scientific/Technical Report

This is the final scientific and technical report for this award. Molecular dynamics (MD) is a powerful tool to study biomolecules at the nanoscale. One of its main limitations however is that such simulations typically require a timestep of 1 femtosecond while reactions and conformational changes typically happen on the time scale of 1 microsecond or more. This discrepancy severely restricts the impact of this method. We have developed a series of algorithms to mitigate this problem and allow predicting long-time scale events using much shorter simulations. The method is based on the concurrent adaptive sampling method. It consists in using probabilistic weights for trajectories and biasing the sampling such that rare but important trajectories, e.g., those that go over energy barriers and lead to relevant conformational changes in the molecule, are observed with much higher frequency that in a standard MD simulation. We will demonstrate below that this approach has been very successful. In collaboration with Jay Grate at PNNL we have applied this novel method to the study the triazine polymers, which can be con gured using different types of side chains in order to adopt different 3-dimensional structures. We have found novel stable con- formations and have analyzed the impact of side chain modifcations on the native folded shape of the polymer. Direct MD simulations would have been untractable for this problem. The method of replica exchange was also used successfully to calculate free energy profiles, in particular for cis-trans torsional angle changes with high energy barriers. Studying molecules at the atomistic scale is essential to design new molecules in chemical engineering, such as the triazine polymers developed by Grate, in material science to study the strength of metals for examples (e.g., dislocation dynamics), or in biochemistry to understand how proteins fold and how they interact with ligands (a key step in designing drugs). Although new hardware makes these simulations increasingly faster (e.g., GPU, Anton from DE Shaw Research), new algorithms are key to making these methods more tractable and increase their impact. At this point, because of limitations in modeling, one of the main techniques for advancing science remains to a large extent numerous and costly experiments. For exam- ple, when designing drug, where multiple variants must be screened, the ability to run tests on a computer rather than experimentally testing with high throughput methods thousands of compounds would represent a signi cant advance with broad benefits for the public at large.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Modeling Mesoscale Processes of Scalable Synthesis. Final report

The newly developed solvers during the project address the coupling of multiple physics using both pure algebraic approach and analytic approach and provide optimal and scalable performance for wide-range numerical simulations. Such solvers and their theoretical framework are expected to have significant impact to other DoE-related multi-physics and multi-scale applications. Moreover, these solvers have been implemented in FASP package developed by the Penn State team.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

Some nanoporous, crystalline materials possess dynamic constituents, for example, rotatable moieties. These moieties can undergo a conformation change in response to the adsorption of guest molecules, which qualitatively impacts adsorption behavior. Here, we pose and solve a statistical mechanical model of gas adsorption in a porous crystal whose cages share a common ligand that can adopt two distinct rotational conformations. Guest molecules incentivize the ligands to adopt a different rotational configuration than maintained in the empty host. Our model captures inflections, steps, and hysteresis that can arise in the adsorption isotherm as a signature of the rotating ligands. The insights disclosed by our simple model contribute a more intimate understanding of the response and consequence of rotating ligands integrated into porous materials to harness them for gas storage and separations, chemical sensing, drug delivery, catalysis, and nanoscale devices. Particularly, our model reveals design strategies to exploit these moving constituents and engineer improved adsorbents with intrinsic thermal management for pressure-swing adsorption processes.

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

Insights into Azetidine Polymerization for the Preparation of Poly(propylenimine)-Based CO 2 Adsorbents

The cationic ring-opening polymerization of azetidine to form branched poly(propylenimine) (PPI) is investigated for the purpose of evaluating the utility of PPI/silica composite adsorbents for CO 2 capture. The polymerization kinetics and primary:secondary:tertiary amine distribution are monitored with 1H NMR during reaction with varied synthesis conditions (i.e., reaction time 20–150 h), temperature (343–353 K), and monomer to acid initiator (here, HClO 4 ) ratio. It is found that primary amines are converted to tertiary amines with increased polymerization time, while the addition of monomer over the first 6 h of polymerization increases the primary amine content. This suggests a mechanism where the monomer is rapidly consumed, leaving dimers or small oligomers that still contain rings as key reaction centers. The synthesized polymer is neutralized with either NH 4 OH or a basic resin and impregnated into mesoporous silica (SBA-15). The CO 2 capture properties of these composite adsorbents are investigated, giving information about the effectiveness of the acid neutralization processes.

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

Solar-driven interfacial evaporation

As a ubiquitous solar-thermal energy conversion process, solar-driven evaporation has attracted tremendous research attention owing to its high conversion efficiency of solar energy and transformative industrial potential. In recent years, solar-driven interfacial evaporation by localization of solar-thermal energy conversion to the air/liquid interface has been proposed as a promising alternative to conventional bulk heating-based evaporation, potentially reducing thermal losses and improving energy conversion efficiency. In this Review, we discuss the development of the key components for achieving high-performance evaporation, including solar absorbers, evaporation structures, thermal insulators and thermal concentrators, and discuss how they improve the performance of the solar-driven interfacial evaporation system. We describe the possibilities for applying this efficient solar-driven interfacial evaporation process for energy conversion applications. The exciting opportunities and challenges in both fundamental research and practical implementation of the solar-driven interfacial evaporation process are also discussed.

charge transport↗
DOE OSTI2016

Critical design of heterogeneous catalysts for biomass valorization: current thrust and emerging prospects

Catalysis in the heterogeneous phase plays a crucial role in the valorization of biorenewable substrates with controlled reactivity, efficient mechanical process separation, greater recyclability and minimization of environmental effects. In this minireview, we have critically analyzed the design aspects of catalysts with multifunctional properties in making biomass conversion processes more productive and sustainable. The catalytic systems have been categorized into subgroups such as metal oxides and phosphates, supported metals, functionalized porous materials, acidic and ion-exchange resins, zeolites and carbonaceous materials to discuss their structural features and active sites towards intrinsic reactivity and selectivity in the transformation of biomass intermediates via hydrolysis, dehydration, hydrodeoxygenation and oxidation pathways. Recent advances in photocatalytic materials for the oxidation of biomass-derived small molecules (such as sugars, alcohols, carboxylic acids) and lignin model compounds and the role of different heteroatoms in improving photo-electronic properties are discussed. The synergistic effect of metal nanoparticulate sites and acid–base supports of bimetallic catalytic systems in performing multistep cascade processes in one-pot are analyzed.

09 BIOMASS FUELS↗
DOE OSTI2017

Interactions on External MOF Surfaces: Desorption of Water and Ethanol from CuBDC Nanosheets

The external surfaces of metal-organic framework (MOF) materials are difficult to experimentally isolate due to the high porosities of these materials. MOF surface surrogates in the form of copper benzenedicarboxylate (CuBDC) nanosheets were synthesized using a bottomup approach and the surface interactions of water and ethanol were investigated by temperature programmed desorption (TPD). A method of analysis of diffusion-influenced TPD was developed to measure the desorption properties of these porous materials. This approach also allows the extraction of diffusion coefficients from TPD data. The transmission Fourier transform infrared spectra, powder X-ray diffraction patterns and TPD data indicate that water desorbs from CuBDC nanosheets with activation energies of 44±2 kJ/mol at edge sites and 58 ± 1 kJ/mol at external surface and internal and pore sites. Ethanol desorbs with activation energies of 58 ± 1 kJ/mol at internal pore sites and 66 ± 0.4 kJ/mol at external surface sites. Co-adsorption of water and ethanol was also investigated. The presence of ethanol was found to inhibit the desorption of water that results in a water desorption process with an activation energy of 68 ± 0.7 kJ/mol.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Sub-Micrometer Zeolite Films on Gold-Coated Silicon Wafers with Single-Crystal-Like Dielectric Constant and Elastic Modulus

A low-temperature synthesis coupled with mild activation produces zeolite films exhibiting low dielectric constant (low-k) matching the theoretically predicted and experimentally measured values for single crystals. This synthesis and activation method allows for the fabrication of a device consisting of a b-oriented film of the pure-silica zeolite MFI (silicalite-1) supported on a gold-coated silicon wafer. The zeolite seeds are assembled by a manual assembly process and subjected to optimized secondary growth conditions that do not cause corrosion of the gold underlayer, while strongly promoting in-plane growth. The traditional calcination process is replaced with a non-thermal photochemical activation to ensure preservation of an intact gold layer. The dielectric constant (k), obtained through measurement of electrical capacitance in a metal-insulator-metal configuration, highlights the ultralow k approximate to 1.7 of the synthetized films, which is among the lowest values reported for an MFI film. There is large improvement in elastic modulus of the film (E approximate to 54 GPa) over previous reports, potentially allowing for integration into silicon wafer processing technology.

Tiriolo, Raffaele↗
DOE OSTI2016

Intrinsic ultralow lattice thermal conductivity of the unfilled skutterudite FeSb 3

It is generally accepted that unfilled skutterudites process high lattice thermal conductivity $κ_l$ that can be efficiently reduced upon filling. Here by using first-principles Boltzmann-Peierls transport calculations, we find pure skutterudite of FeSb 3 with no filler in fact has an intrinsic ultralow $κ_l$ smaller than that of CoSb 3 by one order of magnitude. The value is even smaller than those of most of the fully filled skutterudites. This finding means that with FeSb 3 as a reference, filling does not necessarily lower $κ_l$. The ultralow $κ_l$ of FeSb 3 is a consequence of the overall softening of phonon spectrum, especially the lowering in frequency of optical phonon branches associated with the weakly bonded Sb 4 rings. They overlap more with heat-carrying acoustic phonons and significantly increase the phase space for three-phonon anharmonic scattering processes. This provides an alternative non-filling-related mechanism for lowering the $κ_l$ of skutterudites.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Graphene-Modified Tin Dioxide for Efficient Planar Perovskite Solar Cells with Enhanced Electron Extraction and Reduced Hysteresis

Tin dioxide (SnO 2 ) as an efficient electron transport layer (ETL) has been demonstrated for emerging high-performance organic–inorganic hybrid perovskite solar cells (PSCs). However, the low-temperature solution-processed SnO 2 usually results in high trap-state density and current–voltage hysteresis. Here, we reported an effective strategy to solve this problem by incorporating graphene ink into the low-temperature processed SnO 2 for planar structure PSCs. The electron extraction efficiency has been significantly improved with graphene-doped SnO2 ETL coupled with attenuated charge recombination at the ETL/perovskite interface. The power conversion efficiency (PCE) of PSCs based on the graphene–SnO 2 ETL reached over 18% with negligible hysteresis. Incorporation of graphene into the ETL layer also enhanced the device stability retaining 90% of the initial PCE value after storing in ambient condition with a relative humidity of 40 ± 5% for 300 h. Our results provide an important insight into further efficiency boost in SnO 2 -based low-temperature processed PSCs.

36 MATERIALS SCIENCE↗