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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Mechanisms of Hydrogen-Assisted Magnesiothermic Reduction of TiO{sub 2}

Direct reduction of TiO{sub 2} powder has been attempted for decades by researchers in an effort to decrease titanium (Ti) metal production costs. The main objective has been to avoid energy-intensive steps involved in production of primary Ti by the Kroll process. The emerging hydrogen-assisted magnesiothermic reduction process, which uses Mg to directly reduce TiO{sub 2} powder under a H{sub 2} atmosphere, has been shown to have the potential to compete directly with the Kroll process. The present studies represent an effort to understand the reduction reaction mechanisms of this process. Phase transformations and the reaction pathways are examined by SEM/EDX analysis of partially reduced powder cross-sectional, X-ray diffraction, and other analytical techniques. The results show important morphological changes, the prominent intermediate and final phases under the H{sub 2} atmosphere, as well as the local deposition behavior of the MgO byproduct. The effect of the specific surface areas of the initial particles is also discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The selective catalytic reduction of NO x over Ag/Al 2 O 3 with isobutanol as the reductant

Here, this study investigates the potential of isobutanol (iBuOH) as a reductant for the selective catalytic reduction (SCR) of NO x over 2 wt% Ag/Al 2 O 3 between 150 and 550 °C and gas hourly space velocities (GHSV) between 10,000 and 35,000 h -1 . The feed gas consists of 500 ppm NO, 5% H 2 O, 10% O 2 , and 375-1500 ppm iBuOH (C 1 :N ratios of 3-12); additionally, blends of 24 and 48% iBuOH in gasoline are evaluated. Over 90% NO x conversion is achieved between 300 and 400 C using pure iBuOH, including a 40% peak selectivity towards NH 3 that could be utilized in a dual HC/NH 3 SCR configuration. The iBuOH/gasoline blends are only able to achieve greater than 90% NOx conversion when operated at a GHSV of 10,000 h -1 and employing a C 1 :N ratio of 12. Iso-butyraldehyde and NO 2 appear to function as intermediates in the iBuOH-SCR mechanism, which mirrors the mechanism observed for EtOH-SCR. In general, the performance of iBuOH in the SCR of NO x over a Ag/Al 2 O 3 catalyst is comparable with that of EtOH, although EtOH/gasoline blends display higher NO x reduction than iBuOH/gasoline blends. The key parameter in employing alcohols in SCR appears to be the C-OH:N ratio rather than the C 1 :N ratio.

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

Oxygen Vacancies Enriched Bi Based Catalysts for Enhancing Electrocatalytic CO2 Reduction to Formate

The practical application of CO2 conversion through electrochemical reduction is still hindered by the lack of high performance and cost-effective catalysts. It is thus imperative to explore feasible strategies for scalable fabrication of catalysts for CO2 reduction to targeting products with high efficiency. Herein, for the first time, a hybrid of BiOx encapsulated in carbon thin layer is developed as high active electrocatalyst for CO2 conversion, which is synthesized by pyrolysis using Bi MOF as precursor and sacrificial template. The carbon layer overcoating BiOx catalyst exhibits superior performance for CO2 reduction to formate, achieving a maximum Faradaic efficiency of 89.3 % and a maximum current density of 37.8 mA cm-2. It is found that the as-prepared BiOx catalyst is enriched with oxygen vacancies stabilized by the encapsulating carbon layer. Both the carbon layer and oxygen vacancies improve the charge transfer of the catalyst, in favor of the high formate current density. The defects of oxygen vacancies play a vital role in CO2 adsorption and activation and thereby further enhancing the electrocatalytic ability for formate production.

oxygen vacancy, bismuth, carbon coating, CO2 elect↗
DOE OSTI2015

Synthesis of carbon supported ordered tetragonal pseudo-ternary Pt 2 M'M'' (M = Fe, Co, Ni) nanoparticles and their activity for oxygen reduction reaction

Alloying Pt with 3d transition metals has attracted much attention due to their reduced Pt content and reports of enhanced electrocatalytic activity for proton exchange membrane fuel cell applications. However, synthesizing ordered nanocrystalline intermetallics in the sub-10 nm range can be challenging. Here, we report on the co-reduction synthesis of ordered ternary Pt-base transition metal intermetallics with particle sizes in the regime of 3–5 nm. Since differences in the activity of PtM (M = Fe, Co, Ni) for oxygen reduction reaction (ORR) have been reported, we explored their combinations: Pt 2 FeCo, Pt 2 FeNi, and Pt 2 CoNi. These ternary intermetallic nanoparticles crystallized in P4/mmm space group upon annealing in a protective KCl matrix. The electrocatalysts were prepared by dispersing these intermetallics onto a carbon support using ethylene glycol and various sonication techniques. A combination of analytical techniques including powder X-ray diffraction, thermogravimetric analysis, electron microscopy and electrochemical methods have been used in this study. The oxygen reduction reaction activity and stability of the catalysts were tested in 0.1 M HClO 4 and 0.1 M H 2 SO 4 using cyclic voltammetry and rotating disk electrode voltammetry. The correlations between the composition, structure, morphology and activity of the intermetallics have been established and are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Reductive Dissolution Mechanisms at the Hematite-Electrolyte Interface Probed by In Situ X-ray Scattering

The electron-catalyzed dissolution and reprecipitation of iron (oxyhydr)oxides constitute critical steps in natural geochemical iron cycling. However, the atomic-scale mechanisms of reductive dissolution and oxidative precipitation of Fe2+ remain poorly understood because they are difficult to directly experimentally probe. Using in situ synchrotron X-ray scattering and a novel electrochemical cell, we interrogate the interfacial structure between the hematite (?-Fe2O3) (11 ¯02) surface and acidic aqueous solution (5 mM Na2SO4, pH 4.0) under controlled electrochemical potential from open circuit to cathodic bias as the reductive dissolution potential is approached and then exceeded. The crystalline order of the surface improves under mild reducing conditions, and the surface Fe stoichiometry changes with cathodic bias. After significant reductive dissolution occurs and cathodic bias is removed, dissolved Fe is re-deposited, forming a disordered interface. Unlike at circumneutral pH, water layers at the hematite interface with acidic solution are poorly ordered, likely due to the adsorption of sulfate from the electrolyte. These results provide a novel atomic-scale view into the behavior of reducible transition metal oxide surfaces under fluctuating (electro)chemical conditions.

McBriarty, Martin E.↗
DOE OSTI2020

Reduction of Oxidized Pd/Ag(111) Surfaces by H 2 : Sensitivity to PdO Island Size and Dispersion

Understanding the migration of species across interfaces in bimetallic systems is key to exploiting their bifunctionality for chemical reactivity and heterogeneous catalysis. The present study demonstrates that the sizes and dispersion of oxidized Pd islands present on oxidized Ag(111) in addition to the concentration of active Pd sites have a significant influence on the rate of surface reduction by H 2 . Two distinct types of Pd oxide islands were generated for this investigation and characterized using X-ray photoelectron spectroscopy and scanning tunneling microscopy. Small, uniformly-dispersed PdO x islands (1-5 nm diameter) were created by depositing Pd onto AgO x surfaces, while larger, non-uniformly dispersed PdO x agglomerates (30-50 nm) were produced by depositing Pd on Ag(111) prior to oxidizing. Based on X-ray photoelectron spectroscopy, the small PdO x islands have a higher concentration of undercoordinated Pd atoms than the large agglomerates. Both types of PdO x are found to dramatically enhance the reduction of AgO x by H 2 at 300 K due to the ability of the PdO x to dissociate H 2 ; the pure AgO x surfaces are unreactive toward H 2 . The rate of reduction at 300 K is found to be 2-4 times larger for the AgO x surface covered by small, uniformly dispersed PdO x islands. The higher reactivity of this surface is attributed to enhanced migration of oxygen and hydrogen atoms between the PdO x and AgO x phases due to the sizes and high dispersion of the small PdO islands as well as the higher concentration of active Pd sites on the PdO x . Furthermore, the results of this study demonstrate that reactant migration between co-existing surface phases is highly sensitive to both the intrinsic chemical activity and morphological properties of the active phase (PdO x ) and reveal that these properties can be significantly influenced by the method of synthesizing the oxidized bimetallic surfaces.

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

Understanding trends in electrochemical carbon dioxide reduction rates

Electrochemical carbon dioxide reduction to fuels presents one of the great challenges in chemistry. Herein we present an understanding of trends in electrocatalytic activity for carbon dioxide reduction over different metal catalysts that rationalize a number of experimental observations including the selectivity with respect to the competing hydrogen evolution reaction. We also identify two design criteria for more active catalysts. The understanding is based on density functional theory calculations of activation energies for electrochemical carbon monoxide reduction as a basis for an electrochemical kinetic model of the process. Furthermore, we develop scaling relations relating transition state energies to the carbon monoxide adsorption energy and determine the optimal value of this descriptor to be very close to that of copper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Electrochemical Reduction of Ag 2 VP 2 O 8 Composite Electrodes Visualized via In situ Energy Dispersive X-ray Diffraction (EDXRD). Unexpected Conductive Additive Effects

In our study, we characterize the deposition of silver metal nanoparticles formed during discharge of Li/Ag 2 VP 2 O 8 cells with composite cathodes containing conductive carbon additive. Using in situ energy dispersive X-ray diffraction (EDXRD) of an intact battery, the location and distribution of silver metal nanoparticles generated upon reduction-displacement deposition within an Ag 2 VP 2 O 8 cathode containing a pre-existing percolation network can be observed for the first time. Our study yielded unexpected results where higher rate initial discharge generated a more effective conductive matrix. This stands in contrast to cells with cathodes with no conductive additive where a low rate initial discharge proved more effective. Our results provide evidence that using conductive additives in conjunction with an in situ reduction-displacement deposition of silver metal provides a path toward the ultimate goal of complete electrical contact and full utilization of all electroactive particles.

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

The short-term reduction of uranium by nanoscale zero-valent iron (nZVI): role of oxide shell, reduction mechanism and the formation of U( v )-carbonate phases

Nanoscale zero-valent iron (nZVI) is a potential remediation agent for uranium-contaminated groundwaters, however, a complete mechanistic understanding of the processes that lead to uranium immobilization has yet to be achieved. In this study, the short-term anoxic reaction of U(VI) with fresh, (anoxic) aged and corroded nZVI particles was investigated under aqueous conditions conducive to the formation of thermodynamically stable U(VI)-Ca-CO3 ternary aqueous complexes. The first stage of the reaction between U(VI) and nZVI was assigned to sorption processes with the formation of surface U(VI)-carbonate complexes. Aged nZVI removed U(VI) faster than either fresh or corroded nZVI and it is hypothesized that U reduction initially occurs through the transfer of one electron from Fe(II) in the nZVI surface oxide layer. Evidence for reduction to U(V) was obtained through X-ray photoelectron spectroscopy and by determination of U-O bond distances of ~2.05 Å and 2.27 Å by U LIII-edge X-ray absorption spectroscopy detection of U-O bond distances at ~2.05 Å and 2.27 Å with these distances , similar to thoseat observed for the U(V) site in the mixed U(V)/U(VI) carbonate mineral wyartite. Scanning transmission electron microscopy also demonstrated that U was present as a nanoparticulate phase after one day of reaction, rather than a surface complex. Further reduction to U(IV), as observed in previous studies, would appear to be rate-limiting and coincident with the transformation of this meta-stable U-carbonate phase to uraninite (UO2).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗