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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Solvent‐free enzymatic esterification of free fatty acids with glycerol for biodiesel application: Optimized using the Taguchi experimental method

Abstract Presence of free fatty acids along with glycerides poses a technical difficulty for biodiesel production. This work used a Taguchi L9 design to optimize the solvent‐free enzymatic process to result in the esterification of oleic acid with glycerol. Under optimal conditions the esterification reaction temperature of 60°C, enzyme dose of 5 wt%, glycerol: oleic acid molar ratio of 5:1, and reaction time of 3 h, a 75.235 ± 2.19% conversion of oleic acid to esters was achieved. With the addition of molecular sieves, the conversion increased to 86.73% ± 1.09%. However, using the parameters predicted by Taguchi design (60°C, 5 wt%, 5:1, and 4.5 h), 88.5% ± 1.11% of oleic acid could be converted to esters derivative. Diglycerides were the major product, and the reaction equilibrium was attained after 4 h. The immobilized enzyme could be used up to seven times with only a 10% reduction in the conversion. Thus, the process can efficiently reduce the free fatty acid content of oil to make it suitable for biodiesel production.

09 BIOMASS FUELS↗
DOE OSTI2020

Solvent‐Free Self‐Assembly for Scalable Preparation of Highly Crystalline Mesoporous Metal Oxides

Abstract Mesoporous metal oxides (MMOs) have been demonstrated great potential in various applications. Up to now, the direct synthesis of MMOs is still limited to the solvent induced inorganic‐organic self‐assembly process. Here, we develop a facile, general, and high throughput solvent‐free self‐assembly strategy to synthesize a series of MMOs including single‐component MMOs and multi‐component MMOs (e.g., doped MMOs, composite MMOs, and polymetallic oxide) with high crystallinity and remarkable porous properties by grinding and heating raw materials. Compared with the traditional solution self‐assembly process, the avoidance of solvents in this method not only greatly increases the yield of target products and synthesis efficiency, but also reduces the environmental pollution and the consumption of cost and energy. We believe the presented approach will pave a new avenue for scalable production of advanced mesoporous materials for various applications.

Xiong, Hailong↗
DOE OSTI2022

Data for Solvent-Free Enzymatic Esterification of Free Fatty Acids with Glycerol for Biodiesel Application: Optimized Using the Taguchi Experimental Method

Presence of free fatty acids along with glycerides poses a technical difficulty for biodiesel production. This work used a Taguchi L9 design to optimize the solvent-free enzymatic process to result in the esterification of oleic acid with glycerol. Under optimal conditions the esterification reaction temperature of 60°C, enzyme dose of 5 wt%, glycerol: oleic acid molar ratio of 5:1, and reaction time of 3 h, a 75.235 ± 2.19% conversion of oleic acid to esters was achieved. With the addition of molecular sieves, the conversion increased to 86.73% ± 1.09%. However, using the parameters predicted by Taguchi design (60°C, 5 wt%, 5:1, and 4.5 h), 88.5% ± 1.11% of oleic acid could be converted to esters derivative. Diglycerides were the major product, and the reaction equilibrium was attained after 4 h. The immobilized enzyme could be used up to seven times with only a 10% reduction in the conversion. Thus, the process can efficiently reduce the free fatty acid content of oil to make it suitable for biodiesel production.

Conversion↗
DOE OSTI2019

Solvent-free synthesis of organometallic halides CH 3 NH 3 PbI 3 and (CH 3 NH 3 ) 3 Bi 2 I 9 and their thermoelectric transport properties

Organometallic halides are great candidates for optoelectronics. As an important family of semiconductors, understanding their thermoelectric transport properties is also important. This has been a challenging task as many of such compounds are highly intrinsic. In this work, we synthesized two halides, CH 3 NH 3 PbI 3 and (CH 3 NH 3 ) 3 Bi 2 I 9 , using a solvent-free method. We found an extraordinarily high Seebeck coefficient of +2600 ± 200 μ V/K in (CH 3 NH 3 ) 3 Bi 2 I 9 . For CH 3 NH 3 PbI 3 , our synthesis method led to a negative Seebeck coefficient of –1350 ± 50 μ V/K, in contrast to positive values observed in solvent synthesized samples. We also found the thermal conductivity of CH 3 NH 3 PbI 3 to be 0.38 W/m K, largely independent of temperature from 300 K to 450 K, despite a tetragonal-to-cubic phase transition. (CH 3 NH 3 ) 3 Bi 2 I 9 has an even lower thermal conductivity of 0.21 W/m K (also temperature independent) which is due to its soft phonon dispersion and weak bonds.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High‐Loading Lithium‐Sulfur Batteries with Solvent‐Free Dry‐Electrode Processing

Abstract Lithium‐sulfur (Li‐S) batteries, with their high energy density, nontoxicity, and the natural abundance of sulfur, hold immense potential as the next‐generation energy storage technology. To maximize the actual energy density of the Li‐S batteries for practical applications, it is crucial to escalate the areal capacity of the sulfur cathode by fabricating an electrode with high sulfur loading. Herein, ultra‐high sulfur loading (up to 12 mg cm −2 ) cathodes are fabricated through an industrially viable and sustainable solvent‐free dry‐processing method that utilizes a polytetrafluoroethylene binder fibrillation. Due to its low porosity cathode architecture formed by the binder fibrillation process, the dry‐processed electrodes exhibit a relatively lower initial capacity compared to the slurry‐processed electrode. However, its mechanical stability is well maintained throughout the cycling without the formation of electrode cracking, demonstrating significantly superior cycling stability. Additionally, through the optimization of the dry‐processing, a single‐layer pouch cell with a loading of 9 mg cm −2 and a novel multi‐layer pouch cell that uses an aluminum mesh as its current collector with a total loading of 14 mg cm −2 are introduced. To address the reduced initial capacity of dry‐processed electrodes, strategies such as incorporating electrocatalysts or employing prelithiated active materials are suggested.

Chemistry↗
DOE OSTI2019

Solvent-Free Synthesis of CuO/HKUST-1 Composite and Its Photocatalytic Application

A metal–organic framework (MOF) is one kind of crystalline microporous material and is increasingly used as a host of catalytically active guests. Nanostructured materials supported on MOFs have presented enhanced catalytic activity and stability. Templates or several steps are essential to the synthesis of MOF composites. Simple and effective MOF synthesis methods are still challenging. In this work, nanosized copper oxide particles in MOF composites, described as nanosized CuO@HKUST-1, were prepared by a facile solvent-free reaction. These series of CuO@HKUST-1 composites exhibited excellent photocatalytic activity for production of hydrogen and methylene blue (MB) degradation under visible light. This synthesis method provides an effective way to fabricate MOF-related nanocomposite catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Iron Single‐Atom Catalyzed N‐Alkylation of Amines with Alcohols via Solvent‐Free Borrowing Hydrogen Strategy

Abstract Industrial hydrogenation is a pivotal process in chemical synthesis. However, it has significant drawbacks, including high cost, safety risks associated with the use of molecular hydrogen gas, and substantial energy demands due to the need for elevated temperatures and pressures to achieve satisfactory yields. The borrowing hydrogen synthesis, which enables the transfer of hydrogen between molecules, offers a promising approach for green, one‐pot synthesis of industrially important chemicals and intermediates. Despite its potential, the broad application remains limited due to the reliance on toxic solvents, expensive noble metal catalysts, and the still restricted efficiency and substrate scope. In this study, the first solvent‐free strategy for theN‐alkylation of amines with alcohols is presented, employing an N‐doped graphene‐supported Fe single‐atom catalyst (Fe SA @N‐G; 1.06 wt.%). This approach achieves superior conversion and selectivity (up to 99%) along with record values for turnover number (TON, 1032.7) and turnover frequency (TOF, 413.1 h -1 ) for the coupling reaction of aniline with benzyl alcohol, surpassing all previously reported catalysts. DFT calculations, combined with experimental data, elucidated the reaction mechanism and identified the Fe 1 (III)‐N 4 active site participating in Fe‐H hydride transfer and containing two pyrrolic and two pyridinic nitrogens bound to the Fe center. The developed technology is further supported by the catalyst's excellent scalability, reusability, and performance under continuous‐flow conditions. Additionally, the exceptional efficiency of the single‐atom catalyst is demonstrated across more than 50 substrates, including reactions involving both aliphatic and aromatic amines with aliphatic and aromatic alcohols. The industrial applicability of this technology is validated through the synthesis of pharmaceutically relevant compounds, including stimulant drugs, antihistamines, and pharmaceutical intermediates.

Chemistry↗
DOE OSTI2018

A Solvent-Free Synthesis of Lignin-Derived Renewable Carbon with Tunable Porosity for Supercapacitor Electrodes

Synthesis of multiphase materials from lignin, a biorefinery coproduct, offers limited success owing to the inherent difficulty in controlling dispersion of these renewable hyperbranched macromolecules in the product or its intermediates. Effective use of the chemically reactive functionalities in lignin, however, enables tuning morphologies of the materials. Here in this study, we bind lignin oligomers with a rubbery macromolecule followed by thermal crosslinking to form a carbon precursor with phase contrasted morphology at submicron scale. The solvent-free mixing is conducted in a high-shear melt mixer. With this, the carbon precursor is further modified with potassium hydroxide for a single-step carbonization to yield activated carbon with tunable pore structure. A typical precursor with 90 % lignin yields porous carbon with 2120 m 2 g -1 surface area and supercapacitor with 215 F g -1 capacitance. Lastly, the results show a simple route towards manufacturing carbon-based energy-storage materials, eliminating the need for conventional template synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Solvent-free synthesis of lanthanide oxide and mixed lanthanide oxide nanoparticles

Lanthanide oxides and mixed lanthanide oxides can be produced using furnace or microwave assisted solid-state synthesis. The use of Ln-tri(methylsilyl)amide-based precursors yields spherical nanoparticles. The formation of spherical shaped nanoparticles is likely due to the preferential single-step decomposition of the Ln-TMS as well as the low activation energy to overcome decomposition. Reaction temperature, initial metal ion ratio, and reaction dwell time can be used to control the final nanoparticle size. The method enables solvent-free, high-yield synthesis of morphology-controlled lanthanide oxides.

Treadwell, LaRico Juan↗
NASA NTRSDate not supplied

Solvent-Free Preparation of High Energy, Binder-Free Electrodes Enabled by Dry Compressible Holey Graphene

Graphene is an atomically thick sheet consisting of a graphitic carbon network with excellent mechanical strength, electrical and thermal conductivity, and chemical stability. Holey graphene, a structural derivative of graphene, has an array of through-the-thickness holes across the lateral surface of the nanosheet. The presence of these holes has minimal detrimental effect on the graphene properties and leads to enhanced performance in applications such as electronics, sensors, and energy storage. For example, these holes allow more facile cross-plane ion and gas transport than intact graphene, making holey graphene an ideal electrode material for electrochemical energy storage. This presentation will focus on the ability of holey graphene to be compression molded into robust articles or architectures under solvent-free conditions without the need for potentially parasitic binders. The unique dry compressibility of holey graphene has enabled facile fabrication of high mass loading electrodes with both high density and high porosity, which have found use in supercapacitors and various high-energy battery systems such as lithium-oxygen, lithium-sulfur, and lithium-selenium batteries.

Yi Lin↗
DOE OSTI2021

Organic Solvent Free Process to Fabricate High Performance Silicon/Graphite Composite Anode

Cycling stability is a key challenge for application of silicon (Si)-based composite anodes as the severe volume fluctuation of Si readily leads to fast capacity fading. The binder is a crucial component of the composite electrodes. Although only occupying a small amount of the total composite mass, the binder has major impact on the long-term electrochemical performance of Si-based anodes. In recent years, water-based binders including styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) have attracted wide research interest as eco-friendly and low-cost alternatives for the conventional poly(vinylidene difluoride) (PVDF) binder in Si anodes. In this study, Si-based composite anodes are fabricated by simple solid mixing of the active materials with subsequent addition of SBR and CMC binders. This approach bypasses the use of toxic and expansive organic solvents. The factors of binder, silicon, and graphite materials have been systematically investigated. It is found that the retained capacities of the anodes are more than 440 mAh/g after 400 cycles. These results indicate that organic solvent free process is a facile strategy for producing high performance silicon/graphite composite anodes.

Fang, Chen (ORCID:0000000321011991)↗
DOE OSTI2025

Solvent-Free Dimerization of Isoprene at Ambient Temperature: A Green Route to Biofuel-Range Hydrocarbons

In order to achieve a net-zero carbon footprint by 2050, the global aviation industry must reduce its dependence on fossil fuels. In this regard, there is a global challenge to produce sufficient sustainable aviation fuel (SAF) from renewable sources. Isoprene is an intermediate molecule that can be derived from multiple biomass-based or biosynthetic routes. Here, in this work, we report a green route for the catalytic conversion of isoprene to hydrocarbons that are suitable for aviation fuel. By using an Amberlyst-15 catalyst without metal loading at ambient temperature (19–23 °C), as well as 40 °C, 50 °C, and 60 °C, isoprene was converted into olefinic precursors for SAF and/or blending with conventional aviation fuels. Specifically, at ambient temperature, the process achieved approximately 70 wt % conversion of isoprene with over 50 mol % carbon selectivity toward the aviation fuel range. The resulting SAF-range hydrocarbons were composed of iso-alkenes, branched olefinic monocyclic compounds, and bicyclic compounds, covering a wide range of aviation fuel components. Our work demonstrates, for the first time, the formation of diverse hydrocarbon families for SAF and/or aviation fuel blending at ambient temperature from isoprene.

09 BIOMASS FUELS↗
DOE OSTI2019

Solvent-free and one-pot synthesis of ultramicroporous carbons with ultrahigh nitrogen contents for sulfur dioxide capture

SO 2 from industrial tail gas is of great significance to control the environmental issues potentially induced by SO 2 emission. In the present work, porous carbons with rich ultramicropores and ultrahigh N contents (11.5–17.3 wt%) were synthesized by directly pyrolyzing the mixtures of glucose and urea at 700 °C, without the use of any solvents. Additionally, the synthesized porous carbons were characterized for porosity, morphology and elemental compositions, and also systematically investigated for SO 2 capture performance. Furthermore, it is found that the adsorption of SO 2 on synthesized porous carbons shows chemical behavior, owing to the strong acid-based interaction between SO 2 and pyridinic N. As consequence, the SO 2 capacities of synthesized porous carbons are very high, especially at low pressures (4.16 mmol/g at 296.2 K and 10 kPa). The synthesized porous carbons also display impressive adsorption selectivities for SO 2 /CO 2 /N 2 mixed gas, and good reversibility for SO 2 adsorption. Thus, it is believed that the synthesized porous carbons are promising candidates for selective and reversible SO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

Single-Step, Solvent-Free, Catalyst-Free Preparation of Holey Carbon Allotropes

Methods for forming holey carbon allotropes and graphene nanomeshes are provided by the various embodiments. The various embodiments may be applicable to a variety of carbon allotropes, such as graphene, graphene oxide, reduced graphene oxide, thermal exfoliated graphene, graphene nanoribbons, graphite, exfoliated graphite, expanded graphite, carbon nanotubes (e.g., single-walled carbon nanotubes, double-walled carbon nanotubes, few-walled carbon nanotubes, multi-walled carbon nanotubes, etc.), carbon nanofibers, carbon fibers, carbon black, amorphous carbon, fullerenes, etc. The methods may produce holey carbon allotropes without the use of solvents, catalysts, flammable gas, additional chemical agents, or electrolysis to produce the pores (e.g., holes, etc.) in the carbon allotropes. In an embodiment, a carbon allotrope may be heated at a working window temperature for a working period of time to create holes in the carbon allotrope.

Lin, Yi↗
DOE OSTI2013

Au/SiO{sub x} composite thin film as catalyst for solvent-free hydrocarbon oxidation

Graphical abstract: Au/SiO{sub x} composite thin film possesses high catalytic activity and stability for selective oxidation of cis-cyclooctene. - Highlights: • Au/SiO{sub x} composite thin film was synthesized by a facile and efficient chemical approach. • The Au/SiO{sub x} composite thin film exhibits high catalytic ability for the selective oxidation. • The Au/SiO{sub x} composite thin film possesses high structural and catalytic stability. - Abstract: We report a facile and efficient chemical approach for the controllable preparation of Au/SiO{sub x} composite thin film using silicon quantum dots as SiO{sub x} sources. Au/SiO{sub x} composite thin film exhibits high catalytic activity (65.04% conversion based on cis-cyclooctene and 78.34% selectivity for 2-hydroxycyclooctanone) and stability for selective oxidation of cis-cyclooctene in the absence of solvent using TBHP as radical initiator and oxygen (in the air) as oxidant at 80 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Elastomeric Nanocomposite with Solvent‐Free, One Step, In Situ Shear Exfoliation of Graphite to Graphene

A graphene nanoflake (GNF)‐enhanced elastomeric nanocomposite (G‐EMC) is fabricated following an innovative, cost‐effective, single‐step, in situ shear exfoliation (ISE) method from low‐cost bulk material, graphite, where uniform mixing happens simultaneously within the elastomer matrix. Electron microscopy, atomic force microscopy, and photo‐induced force microscopy results show good dispersion of GNFs with exfoliation to a few layers and uniform distribution in the elastomer matrix. X‐ray photoelectron spectroscopy analysis shows less than 1% oxygen‐containing functional groups/impurity, enhanced bonding through the formation of edge sites as fracture occurs across the GNF basal plane, and pi‐pi interactions with newly exfoliated planar basal plane surfaces of the GNFs. Raman spectroscopy results confirm the formation of GNFs with only a few layers of graphene formed by the ISE process. Fabricated 10 wt.% G‐EMC nanocomposites show a 400%–500% increase in strength and fracture toughness. And 35 wt.% G‐EMCs provide an electrical conductivity of 25.64 S m −1 and a sensor gauge factor of 45. The resulting intrinsic piezo resistivity of the fabricated nanocomposite has been exploited to fabricate a multi‐functional wired and wireless sensor for detecting different body movements, speech, human vital functions, solvents, and biomolecules.

36 MATERIALS SCIENCE↗