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Results for “synthesis (scalable processing)”

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 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Selective Production of Aromatics by Catalytic Fast Pyrolysis of Furan with In Situ Dehydrogenation of Propane

Catalytic fast pyrolysis (CFP) of furan was studied with the co-feeding of propane over ZSM-5, CrOx/Al2O3, and mixed catalysts with both ZSM-5 and CrOx/Al2O3 to combine the dehydrogenation of propane and CFP of furan in the presence of in situ generated propylene. With 15 vol % propane co-feeding, a slight increase in aromatic yield was observed over ZSM-5 catalyst. These enhancement was further improved by using mixed catalysts consisting of CrOx/Al2O3 and ZSM-5 with different weight ratios. Over the best mixed catalyst with CrOx/Al2O3 to ZSM-5 weight ratio of 2, a nearly 2-fold increase in the aromatic yield was obtained. The toluene selectivity was also increased from 37% to 50%. The increase in aromatic yield is directly dependent on the propane to total flow volume ratio. Moreover, the coke formation within ZSM-5 was also reduced, leading to a slower catalyst deactivation. From mechanistic studies, a two-step cascade reaction pathway was observed over the bifunctional mixed catalysts. It was proposed that propane dehydrogenates to propylene over CrOx/Al2O3. The propylene then reacts with furan within ZSM-5 catalyst to selectively form aromatics. This work demonstrates a simple and economical strategy to further improve the CFP technique.

bio-inspired↗
DOE OSTI2017

Collateral Advantages of a Gel Electrolyte for MnO 2 Nanowire Capacitors: Higher Voltage and Reduced Volume

Recently we demonstrated that symmetric, all Au@δ-MnO 2 core@shell nanowire capacitors can achieve cycle stability to 100 000 cycles and beyond in a poly(methyl methacrylate) (PMMA) gel electrolyte. Here we examine the limits of the PMMA gel to confer this extraordinary stability, in terms of the accessible maximum voltage, Vmax, and the thickness of the PMMA gel electrolyte layer. Two conclusions are (1) the PMMA gel permits the Vmax to be increased by 50% from 1.2 V to 1.8 V, allowing the specific energy to be increased 5–6 fold, and (2) the PMMA gel layer thickness can be reduced from 180 μm (previously) to 2 μm while simultaneously utilizing two layers of nanowires and patterning nanowires in each layer at 5× higher density. For this nanowire “sandwich” architecture, a net increase in volumetric capacity of 600× up to 500 mF/cm3 can be achieved while retaining cycle stability to 100 000 cycles.

25 ENERGY STORAGE↗
DOE OSTI2018

Dynamic Hosts for High-Performance Li–S Batteries Studied by Cryogenic Transmission Electron Microscopy and in Situ X-ray Diffraction

Developing a high-performance sulfur host is central to the commercialization and general development of lithium–sulfur batteries. Here, for the first time, we propose the concept of dynamic hosts for lithium–sulfur batteries and elucidate the mechanism through which TiS 2 acts in such a fashion, using in situ X-ray diffraction and cryogenic scanning transmission electron microscopy (cryo-STEM). A TiS 2 –S composite electrode delivered a reversible capacity of 1120 mAh g –1 at 0.3 C after 200 cycles with a capacity retention of 97.0% and capacities of 886 and 613 mAh g –1 at 1.0 C up to 200 and 1000 cycles, respectively. Finally, our results indicate that it is Li x TiS 2 (0 < x ≤ 1), rather than TiS 2 , that effectively traps polysulfides and catalytically decomposes Li 2 S.

25 ENERGY STORAGE↗
DOE OSTI2019

Manifesto on the Thermochemistry of Nanoscale Redox Reactions for Energy Conversion

Advancements in the use of nanoscale materials for energy conversions will rely on a clear understanding of reaction thermochemistry. While band edge and Fermi energies can be rigorous thermodynamic descriptors of bulk materials, we show here that their application to nanoscale systems is problematic. A change of one electron at a 1000 atom nanoparticle or a localized surface site on a catalyst/electrode causes significant nuclear reorganization of the system. Electron transfer is often coupled with solvent reorganization and/or with the transfer of ions, including ion intercalation, surface binding, and movement within the surrounding double layer. These effects can be significant (even for some bulk materials). However, Fermi and band energies, as typically used, do not include the energetics of nuclear reorganizations or cation coupling. A comprehensive approach to nanoscale charge transfer thermodynamics must explicitly consider these effects in order to have a more complete understanding and greater control of nanoscale redox reactivity.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2019

Semiconductor Quantum Dots Are Efficient and Recyclable Photocatalysts for Aqueous PET-RAFT Polymerization

This Letter describes the use of CdSe quantum dots (QDs) as photocatalysts for photoinduced electron transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization of a series of aqueous acrylamides and acrylates. In this work, the high colloidal solubility and photostability of these QDs allowed polymerization to occur with high efficiency (>90% conversion in 2.5 h), low dispersity (PDI < 1.1), and ultralow catalyst loading (<0.5 ppm). The use of protein concentrators enabled the removal of the photocatalyst from the polymer and monomer with tolerable metal contamination (8.41 ug/g). These isolated QDs could be recycled for four separate polymerizations without a significant decrease in efficiency. By changing the pore size of the protein concentrators, the QDs and polymer could be separated from the remaining monomer, allowing for the synthesis of block copolymers using a single batch of QDs with minimal purification steps and demonstrating the fidelity of chain ends.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Solid-State Solvation and Enhanced Exciton Diffusion in Doped Organic Thin Films under Mechanical Pressure

Direct modification of exciton energy has been previously used to optimize the operation of organic optoelectronic devices. One demonstrated method for exciton energy modification is through the use of the solvent dielectric effects in doped molecular films. To gain a deeper appreciation of the underlying physical mechanisms, we test the solid-state solvation effect in molecular thin films under applied external pressure. We observe that external mechanical pressure increases dipole–dipole interactions, leading to shifts in the Frenkel exciton energy and enhancement of the time-resolved spectral red shift associated with the energy-transfer-mediated exciton diffusion. Measurements are performed on host:dopant molecular thin films, which show bathochromic shifts in photoluminescence (PL) under increasing pressure. This is in agreement with a simple solvation theory model of exciton energetics with a fitting parameter based on the mechanical properties of the host matrix material. We measure no significant change in exciton lifetime with increasing pressure, consistent with unchanged aggregation in molecular films under compression. However, we do observe an increase in exciton spectral thermalization rate for compressed molecular films, indicating enhanced exciton diffusion for increased dipole–dipole interactions under pressure. The results highlight the contrast between molecular energy landscapes obtained when dipole–dipole interactions are increased by the pressure technique versus the conventional dopant concentration variation methods, which can lead to extraneous effects such as aggregation at higher doping concentrations. The present work demonstrates the use of pressure-probing techniques in studying energy disorder and exciton dynamics in amorphous molecular thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Understanding Diffusion in Hierarchical Zeolites with House-of-Cards Nanosheets

Introducing mesoporosity to conventional microporous sorbents or catalysts is often proposed as a solution to enhance their mass transport rates. Here, we show that diffusion in these hierarchical materials is more complex and exhibits non-monotonic dependence on sorbate loading. Our atomistic simulations of n-hexane in a model system containing microporous nanosheets and mesopore channels indicate that diffusivity can be smaller than in a conventional zeolite with the same micropore structure, and this observation holds true even if we confine the analysis to molecules completely inside the microporous nanosheets. Only at high sorbate loadings or elevated temperatures, when the mesopores begin to be sufficiently populated, does the overall diffusion in the hierarchical material exceed that in conventional microporous zeolites. Here, our model system is free of structural defects, such as pore blocking or surface disorder, that are typically invoked to explain slower-than-expected diffusion phenomena in experimental measurements. Examination of free energy profiles and visualization of molecular diffusion pathways demonstrates that the large free energy cost (mostly enthalpic in origin) for escaping from the microporous region into the mesopores leads to more tortuous diffusion paths and causes this unusual transport behavior in hierarchical nanoporous materials. This knowledge allows us to re-examine zero-length-column chromatography data and show that these experimental measurements are consistent with the simulation data when the crystallite size instead of the nanosheet thickness is used for the nominal diffusional length.

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

Speed Limit for Triplet-Exciton Transfer in Solid-State PbS Nanocrystal-Sensitized Photon Upconversion

Hybrid interfaces combining inorganic and organic materials underpin the operation of many optoelectronic and photocatalytic systems and allow for innovative approaches to photon up- and down-conversion. However, the mechanism of exchange-mediated energy transfer of spin-triplet excitons across these interfaces remains obscure, particularly when both the macroscopic donor and acceptor are composed of many separately interacting nanoscopic moieties. Here, we study the transfer of excitons from colloidal lead sulfide (PbS) nanocrystals to the spin-triplet state of rubrene molecules. By reducing the length of the carboxylic acid ligands on the nanocrystal surface from 18 to 4 carbon atoms, thinning the effective ligand shell from 13 to 6 Å, we are able to increase the characteristic transfer rate by an order of magnitude. However, we observe that the energy transfer rate asymptotes for shorter separation distances (≤10 Å) which we attribute to the reduced Dexter coupling brought on by the increased effective dielectric constant of these solid-state devices when the aliphatic ligands are short. This implies that the shortest ligands, which hinder long-term colloidal stability, offer little advantage for energy transfer. Indeed, we find that hexanoic acid ligands are already sufficient for near-unity transfer efficiency. Using nanocrystals with these optimal-length ligands in an improved solid-state device structure, we obtain an upconversion efficiency of (7 ± 1)% with excitation at λ = 808 nm.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Charge Transport Modulation in PbSe Nanocrystal Solids by Au x Ag 1– x Nanoparticle Doping

Nanocrystal (NC) solids are an exciting class of materials, whose physical properties are tunable by choice of the NCs as well as the strength of the interparticle coupling. One can consider these NCs as “artificial atoms” in analogy to the formation of condensed matter from atoms. Akin to atomic doping, the doping of a semiconducting NC solid with impurity NCs can drastically alter its electronic properties. A high degree of complexity is possible in these artificial structures by adjusting the size, shape, and composition of the building blocks, which enables “designer” materials with targeted properties. Here, we present the doping of the PbSe NC solids with a series of Au x Ag 1–x alloy nanoparticles (NPs). A combination of temperature-dependent electrical conductance and Seebeck coefficient measurements and room-temperature Hall effect measurements demonstrates that the incorporation of metal NPs both modifies the charge carrier density of the NC solids and introduces energy barriers for charge transport. These studies point to charge carrier injection from the metal NPs into the PbSe NC matrix. The charge carrier density and charge transport dynamics in the doped NC solids are adjustable in a wide range by employing the Au x Ag 1–x NP with different Au:Ag ratio as dopants. Furthermore, this doping strategy could be of great interest for thermoelectric applications taking advantage of the energy filtering effect introduced by the metal NPs.

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

Single Nanocrystal Spectroscopy of Shortwave Infrared Emitters

Short-wave infrared (SWIR) emitters are at the center of ground-breaking applications in biomedical imaging, next-generation optoelectronic devices, and optical communications. Colloidal nanocrystals based on indium arsenide are some of the most promising SWIR emitters to date. However, the lack of single-particle spectroscopic methods accessible in the SWIR has prevented advances in both nanocrystal synthesis and fundamental characterization of emitters. In this paper, we demonstrate an implementation of a solution photon correlation Fourier spectroscopy (s-PCFS) experiment utilizing the SWIR sensitivity and time resolution of superconducting nanowire single-photon detectors to extract single-particle emission linewidths from colloidal indium arsenide/cadmium selenide (InAs/CdSe) core/shell nanocrystals emissive from 1.2 to 1.6 μm. We show that the average single InAs/CdSe nanocrystal fluorescence linewidth is, remarkably, as narrow as 52 meV, similar to what has been observed in some of the most narrowband nanostructured emitters in the visible region. Additionally, the single nanocrystal fluorescence linewidth increases with increasing shell thickness, suggesting exciton–phonon coupling as the dominant emission line-broadening mechanism in this system. The development of the SWIR s-PCFS technique has enabled measurements of spectral linewidths of colloidal SWIR-emissive NCs in solution and provides a platform to study the single NC spectral characteristics of SWIR emitters.

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

Tunable Light-Emitting Diodes Utilizing Quantum-Confined Layered Perovskite Emitters

Organic–inorganic perovskites have been shown to have excellent optoelectronic properties. Further, layered perovskites have been demonstrated, utilizing quantum confinement to achieve emission blue-shifted from the bulk band gap. Here, we tune this blue-shift to build LEDs that span the visible spectrum. We demonstrate that electroluminescence from red-shifted layers dominates emission from mixed-thickness devices and that the addition of excess ligand is necessary to drive emission toward blue-shifted layers. By tuning the thickness of the layers, we build LEDs with blue emission utilizing the lead bromide system and orange emission utilizing the lead iodide system. Lastly, we demonstrate that these materials suffer reversible degradation under an applied electric field. The spectrally narrow emission, combined with the favorable electronic properties of perovskite materials and access to shorter emission wavelengths through quantum confinement, demonstrates the promise of these materials as a new platform for low-cost, high-performance light-emitting devices.

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

Engineering a Full Gamut of Structural Colors in All-Dielectric Mesoporous Network Metamaterials

Structural colors are a result of the scattering of certain frequencies of the incident light on micro- or nanoscale features in a material. This is a quite different phenomenon from that of colors produced by absorption of different frequencies of the visible spectrum by pigments or dyes, which is the most common way of coloring used in our daily life. However, structural colors are more robust and can be engineered to span most of the visible spectrum without changing the base material, only its internal structure. They are abundant in nature, with examples as colorful as beetle shells and butterfly wings, but there are few ways of preparing them for large-scale commercial applications for real-world uses. In this work, we present a technique to create a full gamut of structural colors based on a low-cost, robust, and scalable fabrication of periodic network structures in porous alumina as well as the strategy to theoretically predict and engineer different colors on demand. We experimentally demonstrate mesoporous network metamaterial structures with engineered colors spanning the whole optical spectrum and discuss their applications in sensing, environmental monitoring, biomimetic tissues engineering, etc.

36 MATERIALS SCIENCE↗