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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 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

LiMn 2 O 4 Surface Chemistry Evolution during Cycling Revealed by in Situ Auger Electron Spectroscopy and X-ray Photoelectron Spectroscopy

This work utilizes in situ electrochemical and analytical characterization during cycling of LiMn 2 O 4 (LMO) equilibrated at different potentials in an ultrahigh vacuum (UHV) environment. The LMO reacts with organic molecules in the vacuum to form a high surface concentration of Li 2 CO 3 (≈50% C) during initial charging to 4.05 V. Charging to higher potentials reduces the overall Li 2 CO 3 concentration (≈15% C). Discharging to 3.0 V increases the Li 2 CO 3 concentration (≈30% C) and over discharging to 0.1 V again reduces its concentration (≈15% C). This behavior is reproducible over 5 cycles. The model geometry utilized suggests that oxygen from LMO can participate in redox of carbon, where LMO contributes oxygen to form the carbonate in the solid electrolyte interphase (SEI). Similar results were obtained from samples cycled ex situ , suggesting that the model in situ geometry provides reasonably representative information about surface chemistry evolution. Finally, carbon redox at LMO and the inherent voltage instability of the Li 2 CO 3 likely contributes significantly to its capacity fade.

25 ENERGY STORAGE↗
DOE OSTI2018

Simple Fabrication Method for Mixed Matrix Membranes with in Situ MOF Growth for Gas Separation

Metal organic framework (MOF)/polymer composite membranes are of interest for gas separations, as they often have performance that exceeds the neat polymer. However, traditional composite membranes, known as mixed matrix membranes (MMMs), can have complex and time-consuming preparation procedures. The MOF and polymer are traditionally prepared separately and require priming and mixing to ensure uniform distribution of particles and compatibility of the polymer–particle interface. In this study, we reduce the number of steps using an in situ MOF growth strategy. Herein, MMMs are prepared by growing MOF (UiO-66) in situ within a Matrimid polymer matrix while simultaneously curing the matrix. The gas separation performance for MMMs, prepared using this approach, was evaluated for the CO 2 /N 2 separation and compared with MMMs made using the traditional postsynthesis mixing. It was found that MMMs prepared using both the in situ MOF growth strategy and by traditional postsynthesis mixing are equivalent in performance. Finally, using the in situ MOF growth allows for a simpler, faster, and potentially more economical fabrication alternative for MMMs.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Adipic Acid Production via Metal-Free Selective Hydrogenolysis of Biomass-Derived Tetrahydrofuran-2,5-Dicarboxylic Acid

Biomass-derived furans offer sustainable routes to adipic acid (AA), a key chemical in Nylon-6,6 synthesis. In this work, we show that tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) is a viable precursor for AA production, achieving up to 89% yield in a metal-free system containing HI and molecular H 2 in a propionic acid solvent at 160 °C. Reactivity studies demonstrate that the interplay between HI, H 2 , and the solvent is essential for effective THFDCA ring opening. By measuring the reaction orders of HI and molecular H 2 and calculating an acid–base equilibrium constant in a nonaqueous solvent, we show that HI plays a multifaceted role in the reaction by acting both as a proton source and an iodide source to selectively cleave C–O bonds without overhydrogenation of carboxylic acid groups. Using reactivity studies, kinetic measurements, and first-principles computational insights, we demonstrate that metal-free activation of molecular H 2 plays a key role in the reaction, following HI-mediated cleavage of the etheric C–O bond in THFDCA.

09 BIOMASS FUELS↗
DOE OSTI2018

Redox-Mediator-Assisted Electrocatalytic Hydrogen Evolution from Water by a Molybdenum Sulfide-Functionalized Metal–Organic Framework

The Zr 6 -based metal–organic framework NU-1000 was successfully functionalized with candidate catalysts—MoS x units—via SIM (solvothermal deposition in MOFs) of molybdenum(VI), followed by reaction with H2S gas. The structure of the material, named MoS x - SIM, was characterized spectroscopically and through a single-crystal X-ray diffraction measurement. These measurements and others established that the catalyst is monometallic, with mixed oxygen and sulfur coordination, and that it forms from a MOF-node-supported molybdenum-based cluster featuring only oxy ligands. Notably, the formal potential for the MOF-grafted complex, like that for the metal–sulfur active site of hydrogenase, is nearly coincident with the formal potential for the hydrogen couple. Its effective concentration within the mesoporous MOF is several hundred millimolar, and its porous-framework-based immobilization/heterogenization obviates the need for aqueous solubility as a condition for use as a well-defined catalyst. MoS x - SIM was evaluated as an electrocatalyst for evolution of molecular hydrogen from aqueous acid. Although the MoS x - functionalized framework exhibits catalytic behavior, the highly insulating nature of the support inhibits high electrocatalytic performance. Introduction of an archetypal redox mediator (RM), methyl viologen (MV 2+ ), resulted in more than 20-fold enhancement in its catalytic performance on a turnover frequency basis, implying efficient RM-assisted electron transfer to otherwise electrochemically non-addressable MoS x moieties. Electrochemical kinetic studies with additional viologens as mediators reveal an unexpected square-root dependence of overall reaction rate on mediator concentration, as well as sensitivity to the strength of RM •+ as a reductant. These observations, together with observations of potential-dependent H/D isotope effects and potential-dependent pH effects, provide useful insights into the catalysis mechanism and help to explain how the MOF-affixed monometallic catalyst can effectively catalyze a two-electron reduction reaction, i.e., hydrogen evolution from acidified water.

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

Synergy between Ceria Oxygen Vacancies and Cu Nanoparticles Facilitates the Catalytic Conversion of CO 2 to CO under Mild Conditions

The performance of supported metal catalysts can depend on many factors, including metal particle size and dispersion and metal–support interactions, and differentiation of these effects is challenging because of their interwoven relationship. Copper/ceria catalysts are well-known redox catalysts studied in the conversion of CO and CO 2 via oxidation and/or reduction pathways. The redox behaviors of each species, Cu-CuO and CeO x -CeO 2 , are often suggested to be interlinked, allowing ceria-supported copper domains to outperform copper species on other, nonredox active supports. In this work, the catalytic activity of nanosized Cu supported on either cerium oxide or mesoporous silica is explored using samples where the Cu weight loading, particle size, and dispersion of Cu are held constant to highlight the impact of the two supports on catalytic performance without additional influencing factors. The Cu/CeO 2 catalysts are synthesized via a space-confined method to limit the growth of CeO 2 particles and to achieve a high dispersion of Cu. Through in situ XRD and XAS, it is shown that the presence of Cu nanoparticles on the CeO 2 support lowers the reduction temperature of CeO 2 , allowing formation of oxygen vacancies at low temperatures <300 °C. The Cu/CeO x catalyst demonstrates 100% CO selectivity in the low temperature (300 °C) and ambient pressure conversion of CO 2 to CO, even when approaching equilibrium conversion. Moreover, this catalyst is approximately 4 times more active than the corresponding Cu/SiO 2 catalyst with otherwise similar structural attributes. The potential reaction pathways are probed by in situ FTIR and in situ XAS at various temperatures, identifying Cu + -CO species and oxygen vacancies forming under some conditions. The collected experimental evidence also suggests a reaction sequence for CO 2 hydrogenation over Cu/CeO x catalysts, consistent with DFT reports in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗