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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 OSTI2018

Quinone-mediated electrochemical O2 reduction accessing high power density with an off-electrode heterogeneous catalyst

New methods for interconversion of electrical and chemical energy are crucial to address emerging challenges in renewable energy storage and conversion. Dissolved redox mediators provide an effective means to transport electrons (and protons) between an electrode and catalysts that are not in direct physical contact with an electrode. Mediators are widely implemented in biofuel cells, but such devices typically exhibit low power densities. Here, we report the development of a tetrasubstituted quinone mediator that exhibits excellent stability under strongly acidic conditions and supports electrochemical reduction of O2 at an off-electrode heterogeneous cobalt catalyst contained within a packed-bed reactor. Efficient oxidation of the hydroquinone by O2 in the reactor provides the basis for mediator regeneration, and an integrated “flow cathode” system supports high fuel-cell power densities. These results establish the combination of organic mediators with off-electrode heterogeneous catalysts as a versatile platform for development of new electrode-driven chemical redox transformations.

Preger, Yuliya↗
DOE OSTI2016

Accessing alkali-free NASICON-type compounds through mixed oxoanion sol–gel chemistry: Hydrogen titanium phosphate sulfate, H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1)

We report a direct sol–gel synthesis and characterization of new proton-containing, rhombohedral NASICION-type titanium compounds with mixed phosphate and sulfate oxoanions. The synthetic conditions were established by utilizing peroxide ion as a decomposable and stabilizing ligand for titanyl ions in the presence of phosphates in a strong acidic medium. Thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), induction-coupled plasma optical emission spectroscopic (ICP-OES) elemental analysis, and Raman and {sup 1}H magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopic studies have determined the presence of sulfate and proton ions in the structure, for which the compositional range has been found to be H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1). The particulate products exhibit a nanocrystalline nature observed through characterization with scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The N{sub 2} sorption isotherm measurements and subsequent Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) analyses confirmed the presence of the textural meso- and macropores in the materials. Future studies would determine the potential of the new compounds in various applications as battery materials, proton conductors and solid acid catalysts. - Graphical abstract: A series of proton-containing NASICON-type compounds, H{sub 1−x}Ti{sub 2}(PO{sub 4}){sub 3−x}(SO{sub 4}){sub x} (x=0.5–1), were discovered through a new sol–gel synthetic method that utilizes peroxide ion as a decomposable and stabilizing ligand for titanyl ions in the presence of phosphates in a strong acidic medium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electrochemical Oxidation of Organic Molecules at Lower Overpotential: Accessing Broader Functional Group Compatibility with Electron-Proton Transfer Mediators

CONSPECTUS: Electrochemical organic oxidation reactions are highly appealing because protons are often effective terminal electron acceptors, thereby avoiding undesirable stoichiometric oxidants. These reactions are often plagued by high overpotentials, however, that greatly limit their utility. Single-electron transfer (SET) from organic molecules generates high energy radical-cations. Formation of such intermediates often requires electrode potentials far above the thermodynamic potentials of the reaction and frequently causes decomposition and/or side reactions of ancillary functional groups. In this Account, we show how electrocatalytic electron-proton transfer mediators (EPTMs) address this challenge. EPTMs bypass the formation of radical-cation intermediates by supporting mechanisms that operate at electrode potentials much lower (=1 V) than analogous direct electrolysis reactions. The stable aminoxyl radical TEMPO (2,2,6,6-tetramethylpiperidine N-oxyl) is an effective mediator for electrochemical alcohol oxidation, and we have employed such processes for applications ranging from pharmaceutical synthesis to biomass conversion. A complementary electrochemical alcohol oxidation method employs a cooperative Cu/TEMPO mediator system that operates at 0.5 V lower electrode potential than the TEMPO-only mediated process. This difference, which arises from a different catalytic mechanism, rationalizes the broad functional group tolerance of Cu/TEMPO-based aerobic alcohol oxidation catalysts. Aminoxyl mediators address long-standing challenges in the "Shono oxidation", an important method for a-C–H oxidation of tertiary amides and carbamates. Shono oxidations are initiated by a high-potential SET step that limits their utility. Aminoxyl-mediated Shono-type oxidations have been developed that operate at much lower potentials and tolerate diverse functional groups. Analogous reactivity underlies a-C–H cyanation of secondary cyclic amines, a new method that enables efficient diversification of piperidine-based pharmaceutical building blocks and preparation of non-natural amino acids. Electrochemical oxidations of benzylic C–H bonds are commonly initiated by SET to generate radical cations, but such methods are again plagued by large overpotentials. Mediated electrolysis methods that promote hydrogen-atom-transfer (HAT) from benzylic C–H bonds to Fe-oxo species and phthalimide N-oxyl (PINO) support C–H oxygenation, iodination, and oxidative-coupling reactions. A complementary method merges photochemistry with electrochemistry to achieve amidation of C(sp3)–H bonds. This unique process operates at much lower overpotentials compatible with diverse functional groups. These results have broad implications for organic electrochemistry, highlighting the importance of "overpotential" considerations and the prospects for expanding synthetic utility by using mediators to bypass high-energy outer-sphere electron-transfer mechanisms. Principles demonstrated here for oxidation are equally relevant to electrochemical reductions.

Wang, Fei↗
DOE OSTI2017

Adsorption of a catalytically accessible polyoxometalate in a mesoporous channel-type metal–organic framework

A Keggin-type polyoxometalate (H 3 PW 12 O 40 ) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW 12 @NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Lastly, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW 12 @NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Accessing Organonitrogen Compounds via C–N Coupling in Electrocatalytic CO 2 Reduction

Given the limited product variety of electrocatalytic CO 2 reduction reactions solely from CO 2 and H 2 O as the reactants, it is desirable to expand the product scope by introducing additional reactants that provide elemental diversity. The integration of inorganic heteroatom-containing reactants into electrocatalytic CO 2 reduction could in principle enable the sustainable synthesis of valuable products, such as organonitrogen compounds, which have widespread applications but typically rely on NH 3 derived from the energy-intensive and fossil-fuel-dependent Haber-Bosch process for their industrial scale production. Here, in this Perspective, research progress towards building C-N bonds in N-integrated electrocatalytic CO 2 reduction is highlighted, and the electrosyntheses of urea, acetamides, and amines are examined from the standpoint of reactivity, catalyst structure, and most fundamentally, mechanism. Mechanistic discussions of C-N coupling in these advances are emphasized and critically evaluated, with the aim of directing future investigations on improving the product yield and broadening the product scope of N-integrated electrocatalytic CO 2 reduction.

electrochemical reduction↗
DOE OSTI2015

Accessing a growth window for SrVO{sub 3} thin films

Stoichiometric SrVO{sub 3} thin films were grown over a range of cation fluxes on (001) (La{sub 0.3}Sr{sub 0.7})(Al{sub 0.65}Ta{sub 0.35})O{sub 3} substrates using hybrid molecular beam epitaxy, where a thermal effusion cell was employed to generate a Sr flux and V was supplied using the metal-organic precursor vanadium oxytriisopropoxide (VTIP). By systematically varying the VTIP flux while keeping the Sr flux constant, a range of flux ratios were discovered in which the structural and electronic properties of the SrVO{sub 3} films remained unaltered. The intrinsic film lattice parameter and residual resistivity were found to be the smallest inside the growth window, indicating the lowest defect concentration of the films, and rapidly increased for cation flux ratios deviating from ideal growth condition. Reflection high-energy electron diffraction showed that films grown within this range had smooth surfaces and diffraction patterns were free of additional spots, while otherwise the growing surface was rough and contained additional crystalline phases. Results show the existence of a SrVO{sub 3} growth window at sufficiently high growth temperature, in which high-quality, stoichiometric films can be grown in a robust, highly reproducible manner that is invulnerable to unintentional flux variation.

36 MATERIALS SCIENCE↗