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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

High surface area nanocrystalline hausmannite synthesized by a solvent-free route

Highlights: ► High surface area Mn{sub 3}O{sub 4} nanoparticles obtained by a solvent-free low temperature route. ► 3,6,9-Trioxadecanoic acid allows to obtain nanocrystalline hausmannite. ► Tape casted electrodes show up to 300 mAh g{sup −1} capacity after more than 40 cycles at a C/3 rate. ► Upper cut off voltage strongly influences capacity retention upon cycling at high C rates. -- Abstract: Nanocrystalline high surface area Mn{sub 3}O{sub 4} powder was obtained at low temperature by a solvent-free route. The precursor was a mixture of manganese (II) acetate, 3,6,9-trioxadecanoic acid (TODA) and ammonium acetate that were intimately mixed by grounding in an agate mortar. Nanocrystalline Mn{sub 3}O{sub 4} was obtained by thermal treatment at 120 °C. Powder X-ray diffraction, selected area electron diffraction, high resolution transmission electron microscopy, and Fourier transformed infrared characterization confirmed the formation of the hausmannite phase. The as-prepared mesoporous material has high specific surface area (120 m{sup 2} g{sup −1}). The performances of tape casted Mn{sub 3}O{sub 4} nanopowder electrodes were investigated as anode material for lithium ion batteries. High capacity values were achieved at diverse C rates. Capacity fading was found to be dependent on the upper cut off voltage, the presence of a plateau at 2.25 V vs. Li{sup +}/Li being detrimental for long term cyclability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Preparation and nonlinear optical properties of indium nanocrystals in sodium borosilicate glass by the sol–gel route

Graphical abstract: The sodium borosilicate glass doped with indium nanocrystals have been successfully prepared by sol–gel methods. And the indium nanocrystals in tetragonal crystal system have formed uniformly in the glass, and the average diameter of indium nanocrystals is about 30 nm. The third-order optical nonlinear refractive index γ, absorption coefficient β, and susceptibility χ{sup (3)} of the glass are determined to be −4.77 × 10{sup −16} m{sup 2}/W, 2.67 × 10{sup −9} m/W, and 2.81 × 10{sup −10} esu, respectively. Highlights: ► Indium nanocrystals embedded in glass matrix have been prepared by sol–gel route. ► The crystal structure and composition are investigated by XRD and XPS. ► Size and distribution of indium nanocrystals is determined by TEM. ► The third-order optical nonlinearity is investigated by using Z-scan technique. -- Abstract: The sodium borosilicate glass doped with indium nanocrystals have been successfully prepared by sol–gel route. The thermal stability behavior of the stiff gel is investigated by thermogravimetric (TG) and differential thermal (DTA) analysis. The crystal structure of the glass is characterized by X-ray powder diffraction (XRD). Particle composition is determined by X-ray photoelectron spectroscopy (XPS). Size and distribution of the nanocrystals are characterized by transmission electron microscopy (TEM) as well as high-resolution transmission electron microscopy (HRTEM). Results show that the indium nanocrystals in tetragonal crystal structure have formed in glass, and the average diameter is about 30 nm. Further, the glass is measured by Z-scan technique to investigate the nonlinear optical (NLO) properties. The third-order NLO coefficient χ{sup (3)} of the glass is determined to be 2.81 × 10{sup −10} esu. The glass with large third-order NLO coefficient is promising materials for applications in optical devices.

36 MATERIALS SCIENCE↗
DOE OSTI2012

The effect of different annealing temperatures on tin and cadmium telluride phases obtained by a modified chemical route

Graphical abstract: Display Omitted Highlights: ► Synthesis of cadmium and tin telluride. ► Chemical route to obtain pure crystalline cadmium and tin telluride. ► Effect of the annealing temperature on the crystalline phases. ► Removal of tin oxide as side product through thermal treatment. -- Abstract: In this work tin and cadmium telluride were prepared by a modification of a chemical route reported in the literature to obtain metallacycles formed by oxidative addition of tin-tellurium bonds to platinum (II). Through this procedure it was possible to obtain tin and cadmium telluride. X-ray diffraction and X-ray photoelectron spectroscopy were used to identify the crystalline phases obtained as well as the presence of side products. In the case of tin telluride it was identified potassium chloride, metallic tellurium and tin oxide as contaminants. The tin oxidation states were also monitored by {sup 119}Sn Mössbauer spectroscopy. The annealing in hydrogen atmosphere was chosen as a strategy to reduce the tin oxide and promote its reaction with the excess of tellurium present in the medium. The evolution of this tin oxide phase was studied through the annealing of the sample at different temperatures. Cadmium telluride was obtained with high degree of purity (98.5% relative weight fraction) according to the Rietveld refinement of X-ray diffraction data. The modified procedure showed to be very effective to obtain amorphous tin and cadmium telluride and the annealing at 450 °C has proven to be useful to reduce the amount of oxide produced as side product.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Influence of crystalline phase and defects in the ZrO{sub 2} nanoparticles synthesized by thermal plasma route on its photocatalytic properties

Graphical abstract: Thermal plasma synthesized nanophase zirconia showing the blue shift in the band gap of monoclinic phase as found from the photoabsorption spectroscopy was found to be the dominant parameter for the enhancement in its photocatalytic activity. The existence of different defect states and their concentration in as synthesized samples also inferred from the photoabsorption measurements were also found to be responsible for the enhanced photocatalytic activity of the samples. Highlights: ► Phase controlled structural formation of nanophase ZrO{sub 2} by thermal plasma route. ► Enhanced photocatalytic degradation rate of methylene blue dye. ► The blue shift in the band gap of monoclinic phase of nanocrystalline ZrO{sub 2}. ► Existence of different defect states in the as synthesized nano phase ZrO{sub 2}. ► Several competing processes which controls the photocatalytic degradation rate. -- Abstract: The photocatalytic activity of pure ZrO{sub 2} samples, prepared by a thermal plasma route, and characterized by X-ray diffraction technique was tested for the degradation of methylene blue, which is known to be a hazardous dye. Although, all these samples synthesized at different operating pressures of the thermal plasma reactor showed the photocatalytic activity; the sample synthesized at 1.33 bar of operating pressure showed the highest photocatalytic activity. The blue shift in the band gap of monoclinic phase, as observed from the photo-absorption spectroscopy, may be attributed to the enhanced photocatalytic activity. The existence of different defect states and their concentration as, inferred from the photo-absorption measurements were also found to be responsible for the enhanced photocatalytic activity of the as synthesized samples.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Thermal quenching mechanisms of the Eu{sup 3+} luminescence in Ca{sub 9}Al(PO{sub 4}){sub 7} obtained by citric route

Graphical abstract: Display Omitted Highlights: ► Convenient citric route was used for preparation of the Ca{sub 9}Al(PO{sub 4}){sub 7}:Eu{sup 3+} powders. ► We found that the thermal dependency of the Eu{sup 3+} emission shows two different temperature ranges. ► 80% of Eu{sup 3+} luminescence intensity is kept at 430 K. ► The possible quenching pathways were constructed using simplified one coordinate energy diagram. -- Abstract: The citric route was employed for synthesis of the pure phase Ca{sub 9}Al(PO{sub 4}){sub 7}:Eu{sup 3+} (CAlP:Eu{sup 3+}) powders as an attractive alternative to the solid state reaction (no need of multistep and long thermal treatment). Structural properties of the final product were studied by means of X-ray diffraction as well as Rietveld refinement was conducted in order to calculate the cell parameters. The thermal behavior of the emission was studied using excitation line well matched with the {sup 7}F{sub 0} → {sup 5}D{sub 4} absorption band covering broad range of temperature. Activation energy was estimated to be equal to 10,550 cm{sup −1}. The thermal behavior of the Eu{sup 3+} luminescence in CAlP crystal lattice shown that the almost 80% of intensity is kept up to 430 K.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Investigation of nanocrystalline zinc chromite obtained by two soft chemical routes

Graphical abstract: - Highlights: • Two soft chemical routes to synthesize zinc chromites are described. • Glycine is used as chelating agent (precursor method) and fuel (solution combustion method). • The synthesized chromites have crystallite size in the range of 18–27 nm. • An antiferromagnetic (AFM) transition is observed at about T{sub N} ∼ 18 K. - Abstract: Zinc chromite (ZnCr{sub 2}O{sub 4}) nanocrystalline powders were obtained by two different chemical routes: the precursor method and the solution combustion method involving glycine-nitrates. The complex compound precursors, [ZnCr{sub 2}(NH{sub 2}CH{sub 2}COO){sub 8}]·9H{sub 2}O and [ZnCr{sub 2}(NH{sub 2}CH{sub 2}COOH){sub 4.5}]·(NO{sub 3}){sub 8}·6H{sub 2}O, were characterized by chemical analysis, infrared spectroscopy (IR), ultraviolet–visible spectroscopy (UV–vis) and thermal analysis. The structure, morphology, surface chemistry and magnetic properties of ZnCr{sub 2}O{sub 4} powders were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), infrared and Raman spectroscopy (RS), ultraviolet–visible spectroscopy (UV–vis) and magnetic measurements. X-ray diffraction patterns indicated the chromite spinel phase with good crystallinity and an average crystallite size of approximately 18–27 nm. The band gap values ranged between 3.31 and 3.33 eV. The magnetic measurements indicated an antiferromagnetic transition at T{sub N} ∼ 17.5/18 K.

36 MATERIALS SCIENCE↗
DOE OSTI2014

A facile gel-combustion route for fine particle synthesis of spinel ferrichromite: X-ray and Mössbauer study on effect of Mg and Ni content

Highlights: • A novel and facile synthesis route. • Transformation of system from random to inverse spinel. • Appearance of superparamagnetism phase. - Abstract: A novel nitrate–citrate gel combustion route was used to prepare fine particle of a series Mg{sub 1−x}Ni{sub x}FeCrO{sub 4} (0.0 ≤ x ≤ 1.0) and its structural properties were investigated. The in situ oxidizing environment provided by the nitrate ions in the gel increases the rate of oxidation and lowers the decomposition temperature of component. All the samples after sintering were characterized at room temperature by X-ray diffraction (XRD) method and Mössbauer spectroscopy techniques. The X-ray and Mössbauer studies confirmed the single phase cubic spinel structure with all Fe ions in 3+ charge state. XRD and Mössbauer studies revealed that the samples of x = 0.0, and 0.2 are random spinel and show rather broad lines, while x = 0.4–1.0 are inverse spinel.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Non-toxic novel route synthesis and characterization of nanocrystalline ZnS{sub x}Se{sub 1−x} thin films with tunable band gap characteristics

Highlights: • A simple, inexpensive, and non-toxic CBD route is used to deposit ZnS thin films. • The ZnS{sub x}Se{sub 1−x} thin films formation takes place via annealing of ZnS thin films in Se atmosphere. • S/(S + Se) ratio found to be temperature dependent and easy tuning of band gap has been done by Se atom deposition. - Abstract: An environmentally benign chemical bath deposition (CBD) route was employed to deposit zinc sulfide (ZnS) thin films. The CBD-ZnS thin films were further selenized in a furnace at various temperatures viz. 200, 300, 400, and 500 °C and the S/(S + Se) ratio was found to be dependent on the annealing temperature. The effects of S/(S + Se) ratio on the structural, compositional and optical properties of the ZnS{sub x}Se{sub 1−x} (ZnSSe) thin films were investigated. EDS analysis showed that the S/(S + Se) ratio decreased from 0.8 to 0.6 when the film annealing temperature increased from 200 to 500 °C. The field emission scanning electron microscopy and atomic force microscopy studies showed that all the films were uniform, pin hole free, smooth, and adhered well to the glass substrate. The X-ray diffraction study on the ZnSSe thin films showed the formation of the cubic phase, except for the unannealed ZnSSe thin film, which showed an amorphous phase. The X-ray photoelectron spectroscopy revealed Zn-S, Zn-Se, and insignificant Zn-OH bonds formation from the Zn 2p{sub 3/2}, S 2p, Se 3d{sub 5/2}, and O 1s atomic states, respectively. The ultraviolet–visible spectroscopy study showed ∼80% transmittance in the visible region for all the ZnSSe thin films having various absorption edges. The tuning of the band gap energy of the ZnSSe thin films was carried out by selenizing CBD-ZnS thin films, and as the S/(S + Se) ratio decreased from 0.8 to 0.6, the band gap energy decreased from 3.20 to 3.12 eV.

36 MATERIALS SCIENCE↗
DOE OSTI2015

A facile route to synthesize core/shell structured carbon/magnetic nanoparticles hybrid and their magnetic properties

Graphical abstract: Controllable synthesis of core/shell structured carbon/magnetic nanoparticles hybrid and their tunable magnetic properties. - Highlights: • The paper reports a simple route for core/shell structured carbon/magnetic nanoparticles hybrid. • By controlling the temperature, Fe{sub 3}O{sub 4}@CNCs, Fe@HCNTs and Fe@LCNTs were produced selectively. • The magnetic properties of the obtained core/shell structured hybrid could be tuned effectively. - Abstract: By controlling the pyrolysis temperature, core/shell structured Fe{sub 3}O{sub 4}/carbon nanocages, Fe/helical carbon nanotubes and Fe/low helicity of carbon nanotubes could be synthesized selectively over Fe{sub 2}O{sub 3} nanotubes generated by a hydrothermal method. The transmission electron microscopic and scanning electron microscopic investigations revealed that the efficiency of generating core/shell structured hybrid was high, exceeding 90%. Because of the magnetic nanoparticles tightly wrapped in graphitic layers, the obtained core/shell structured hybrids showed high stability and good magnetic properties. And the magnetic properties of the obtained core/shell structured hybrid could be tuned by the decomposition temperature and time. Therefore, a simple, inexpensive and environment-benign route was proposed to produce magnetism-tunable core/shell structured hybrid in large quantities.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2017

Routes for realizing high-performing Si solar cells by using periodic structures

Highlights: • The record high-efficiency of 16.9% for periodically patterned Si solar cells. • Optical and electrical benefits of periodic microscale Si structures. • Design routes for realizing high-performing periodic Si solar cells. - Abstract: Theoretical suggestion indicated the substantial improvement of solar cells by using periodic structures. Yet, the promise has not been practically realized due to the lack of electrical analyses of periodical light-absorbing structure. Here, we report the record high-efficiency of 16.9% for periodically patterned silicon (Si) solar cells. Periodic Si micro-pillars were fabricated for large-scale solar cells. The Si pillars with a height of about 5 μm provided significantly enlarged light-active surface, which improved the photo-generated carrier collection efficiency. From optical aspects, the pillar structures reduced light reflection and hence effectively drove more photons into the absorber layer. Additionally, the enhanced pillar-structured Si surface definitely contributed to reduce an electrical resistance of a solar cell. We demonstrated that the surficial enhanced Si design could be a promising approach for high-efficient solar cell applications. We may suggest a route for the optimum electrical designs of periodic structured solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Structural and optical characterizations of Cu2SnS3 (CTS) nanoparticles synthesized by one-step green hydrothermal route

Highlights: • Pure quasi-stoichiometric CTS nanoparticles obtained by green hydrothermal route. • Cubic structure of CTS nanoparticles without secondary phases was acheived. • A formation mechanism of the CTS nanoparticles is proposed. • CTS has a band gap of Eg = 1.4 eV, which is optimal for photovoltaïc absorber. - Abstract: In this study, nanoparticles of Cu{sub 2}SnS{sub 3} (CTS) have been synthesized by a simple one-step hydrothermal route without annealing. Metal chlorides and sodium sulphide precursors were dissolved in green solvent (water) and maintained at 230 °C for 24 h in a laboratory scale autoclave. Structural, morphological and optical characterization of synthesized CTS nanoparticles has been performed by Energy Dispersive Spectrometry (EDS), X-Ray Diffraction (XRD), Raman Spectroscopy, Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM) and UV–vis-NIR Spectroscopy. The results appear to confirm the formation of pure and quasi-stoichiometric cubic CTS nanoparticles. No secondary phases have been detected. The average size of the synthesized nanoparticles is estimated to be about 30 nm. From the absorption measurements, the optical band gap energy of the CTS nanoparticles was estimated to be 1.4 eV. This is very close to the optimal value required for an absorber material in photovoltaic (PV) solar energy conversion. In order to improve the understanding of the formation mechanism of CTS nanoparticles, the precipitate recovered prior to the hydrothermal reaction was analysed by EDS and XRD. The obtained results suggest that the formation of CTS nanoparticles takes place in two stages. Firstly, it is initiated from the formation of precipitates of Cu{sub 2}S, CuS and SnS binary compounds in the starting precursors solution prior to the hydrothermal reaction and thereafter it is completed under hydrothermal conditions. This study shows the feasibility of synthesizing CTS nanoparticles with abundant elements using an environmentally-friendly and low cost process.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Structural and optical analysis of Fe doped NiO nanoparticles synthesized by chemical precipitation route

Highlights: • The Fe doped NiO nanoparticles were synthesized by chemical precipitation route. • XRD analysis reveals cubic rock-salt fcc structure of the synthesized nanoparticles. • The Ni-O and Fe-O bonding were confirmed through FTIR spectroscopy. • Existence of nickel or interstitial oxygen vacancies indicates p-type nature of nanoparticles. - Abstract: The Ni{sub 1-x}Fe{sub x}O (x = 0.00, 0.02, 0.04 and 0.06) nanoparticles are synthesized by chemical precipitation route using polyvinyl-pyrrolidone (PVP) and nitrate metal salts. The results of thermogravimetric analysis (TGA) of the synthesized dried hydroxide powders showed that thermal decomposition occurs up to 500 °C so as to form pure Ni{sub 1-x}Fe{sub x}O. Therefore, all synthesized samples were calcined at 500 °C for 4 h and then used for further characterization. Energy dispersive X-ray spectroscopy (EDS) of all the samples showed the presence of Ni, O and Fe without any other impurities. From X-ray diffraction (XRD) and transmission electron microscopy (TEM) we could prove that the samples are polycrystalline in nature and are in single phase. The different vibrational modes in Ni{sub 1-x}Fe{sub x}O (x = 0.00, 0.02, 0.04 and 0.06) nanoparticles were studied by Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). Further, we analyzed the optical response from ultraviolet-visible spectra and Photoluminescence (PL) spectra.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Serpentine Ultralong Path with Extended Routing (SUPER) High Resolution Traveling Wave Ion Mobility-MS using Structures for Lossless Ion Manipulations

Ion mobility (IM) separations have a broad range of analytical applications, but insufficient resolution limits many applications. Here we report on traveling wave (TW) ion mobility (IM) separations in a Serpentine Ultra-long Path with Extended Routing (SUPER) Structures for Lossless Ion Manipulations (SLIM) module in conjunction with mass spectrometry (MS). The extended routing utilized multiple passes was facilitated by the introduction of a lossless ion switch at the end of the ion path that either directed ions to the MS detector or to another pass through the serpentine separation region, providing theoretically unlimited TWIM path lengths. Ions were confined in the SLIM by rf fields in conjunction with a DC guard bias, enabling essentially lossless TW transmission over greatly extended paths (e.g., ~1094 meters over 81 passes through the 13.5 m serpentine path). In this multi-pass SUPER TWIM provided resolution approximately proportional to the square root of the number of passes (or path length). More than 30-fold higher IM resolution for Agilent tuning mix m/z 622 and 922 ions (~340 vs. ~10) was achieved for 40 passes compared to commercially available drift tube IM and other TWIM-based platforms. An initial evaluation of the isomeric sugars Lacto-N-hexaose and Lacto-N-neohexaose showed the isomeric structures to be baseline resolved, and a new conformational feature for Lacto-N-neohexaose was revealed after 9 passes. The new SLIM SUPER high resolution TWIM platform has broad utility in conjunction with MS and is expected to enable a broad range of previously challenging or intractable separations.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2026

A Chemocatalytic Route to Stereoregular Poly(3-hydroxyhexanoate) and Its Statistical and Tri-Block Copolymers

Poly(3-hydroxyhexanoate) (P3HHx)-based poly(3- hydroxyalkanoate)s (PHAs) are biologically produced, commercially implemented PHAs, but little is known in the open literature about the structure and property characterizations of discrete, authentic homopolymer P3HHx, and its copolymers with poly(3- hydroxybutyrate) (P3HB). Here, we introduce a chemocatalytic route to stereoregular (both isotactic and syndiotactic) P3HHx and PHA copolymers with P3HB, including statistical copolymer P3HBHx with various levels of 3HHx incorporation and discrete hard−soft−hard triblock copolymer P3HB-b-P3HHx-b-P3HB, and present extensive characterizations of their structures, thermal properties, and mechanical performance. The synthesis is efficiently achieved by one-pot polymerization of eight-membered di(n-propyl) and dimethyl (for copolymerization) diolides catalyzed by chiral molecular catalysts. Notably, P3HBHx can be rapidly produced in quantitative yield and exhibits high molar mass (M n up to 551 kg/mol) as well as both high modulus (up to 1.39 GPa) and ductility (up to 445%), while P3HB-b-P3HHx-b-P3HB further extends application temperature windows by possessing a unique combination of low T g (−18 °C) and high T m (154 °C) values. These findings highlight the stereomicrostructural and architectural versatility of chemocatalytic routes to PHAs, which, in turn, can be utilized to largely tune the PHA thermal properties and mechanical performance.

Biopolymers↗
DOE OSTI2015

A Facile Molecular Precursor Route to Metal Phosphide Nanoparticles and Their Evaluation as Hydrodeoxygenation Catalysts

Metal phosphides have been identified as a promising class of materials for the catalytic upgrading of bio-oils, which are renewable and potentially inexpensive sources for liquid fuels. Herein, we report the facile synthesis of a series of solid, phase-pure metal phosphide nanoparticles (NPs) (Ni 2 P, Rh 2 P, and Pd 3 P) utilizing commercially available, air-stable metal–phosphine complexes in a one-pot reaction. This single-source molecular precursor route provides an alternative method to access metal phosphide NPs with controlled phases and without the formation of metal NP intermediates that can lead to hollow particles. The formation of the Ni 2 P NPs was shown to proceed through an amorphous Ni–P intermediate, leading to the desired NP morphology and metal-rich phase. This low-temperature, rapid route to well-defined metal NPs is expected to have broad applicability to a variety of readily available or easily synthesized metal–phosphine complexes with high decomposition temperatures. Hydrodeoxygenation of acetic acid, an abundant bio-oil component, was performed to investigate H 2 activation and deoxygenation pathways under conditions that are relevant to ex situ catalytic fast pyrolysis (high temperatures, low pressures, and near-stoichiometric H 2 concentrations). The catalytic performance of the silica-supported metal phosphide NPs was compared to the analogous incipient wetness (IW) metal and metal phosphide catalysts over the range 200–500 °C. Decarbonylation was the primary pathway for H 2 incorporation in the presence of all of the catalysts except NP-Pd 3 P, which exhibited minimal productive activity, and IW-Ni, which evolved H 2 . The highly controlled NP-Ni2P and NP-Rh2P catalysts, which were stable under these conditions, behaved comparably to the IW-metal phosphides, with a slight shift to higher product onset temperatures, likely due to the presence of surface ligands. Most importantly, the NP-Ni 2 P catalyst exhibited H 2 activation and incorporation, in contrast to IW-Ni, indicating that the behavior of the metal phosphide is significantly different from that of the parent metal, and more closely resembles that of noble metal catalysts.

09 BIOMASS FUELS↗
DOE OSTI2021

Electrochemical Routes for the Valorization of Biomass-Derived Feedstocks: From Chemistry to Application

The drive to reduce consumption of fossil resources, coupled with expanding capacity for renewable electricity, invites the exploration of new routes to utilize this energy for the sustainable production of fuels, chemicals, and materials. Biomass represents a possible source of platform precursors for such commodities due to its inherent ability to fix CO2 in the form of multi-carbon organic molecules. Electrochemical methods for the valorization of biomass are thus intriguing, but there is a need to objectively evaluate this field and define the opportunity space by identifying pathways suited to electrochemistry. In this contribution we offer a comprehensive, critical review of recent advances in low-temperature (liquid phase), electrochemical reduction and oxidation of biomass-derived intermediates (polyols, furans, carboxylic acids, amino acids, and lignin), with emphasis on identifying the state-of-the-art for each documented reaction. Progress in computational modeling is also reviewed. We further suggest a number of possible reactions that have not yet been explored but which are expected to proceed based on established routes to transform specific functional groups. We conclude with a critical discussion of technological challenges for scale-up, fundamental research needs, process intensification opportunities (e.g., by pairing compatible oxidations and reductions), and new benchmarking standards that will be necessary to accelerate progress toward application in this still-nascent field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effect of Diel Cycling Temperature, Relative Humidity, and Synthetic Route on the Surface Morphology and Hydrolysis of α -U 3 O 8

The speciation and morphological changes of α-U 3 O 8 following aging under diel cycling temperature and relative humidity (RH) have been examined. This work advances the knowledge of U-oxide hydration as a result of synthetic route and environmental conditions, ultimately giving novel insight into nuclear material provenance. α-U 3 O 8 was synthesized via the washed uranyl peroxide (UO 4 ) and ammonium uranyl carbonate (AUC) synthetic routes to produce unaged starting materials with different morphologies. α-U 3 O 8 from UO 4 is comprised of subrounded particles, while α-U 3 O 8 from AUC contains blocky, porous particles approximately an order of magnitude larger than particles from UO 4 . For aging, a humidity chamber was programmed for continuous daily cycles of 12 “high” hours of 45 °C and 90% RH, and 12 “low” hours of 25 °C and 20% RH. Samples were analyzed at varying intervals of 14, 24, 36, 43, and 54 days. At each aging interval, crystallographic changes were measured via powder X-ray diffraction coupled with whole pattern fitting for quantitative analysis. Morphologic effects were studied via scanning electron microscopy and 12-way classification via machine learning. While all samples were found to have distinguishing morphologic characteristics (93.2% classification accuracy), α-U 3 O 8 from UO 4 had more apparent change with increasing aging time. Nonetheless, α-U 3 O 8 from AUC was found to hydrate more quickly than α-U 3 O 8 from UO 4 , which can likely be attributed to its larger surface area and porous starting material morphology.

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