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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 19 records

Supported Oxygen Evolution Catalysts by Design: Toward Lower Precious Metal Loading and Improved Conductivity in Proton Exchange Membrane Water Electrolyzers

Reducing the precious metal content of water oxidation catalysts for proton-exchange-membrane water electrolyzers remains a critical barrier to their large-scale deployment. Herein, we present an engineered architecture for supported iridium catalysts, which enables decreased precious metal content and improved activity and conductivity. The improvement in performance at lower precious metal loading is realized by the deposition of a conformal layer of platinum nanoparticles on titanium dioxide (TiO 2 ) using a facile photoreduction method to prepare conductive layer coated supports (CCSs). Platinum nanoparticles are homogeneously dispersed on TiO 2 , and the conductivity of the subsequent catalysts with 39 wt % precious group metal loadings is significantly higher than the commercial 75 wt % loaded IrO 2 -TiO 2 catalysts. The conformal conductive layer also maintains an enhanced conductivity and electrochemical activity upon thermal annealing when compared to catalysts without the conductive layer and nonconformal heterogeneous conductive layer. The iridium mass activity from half-cell studies shows a 141% improvement for CCS supported catalysts at 42% lower loadings compared to the commercial catalysts. The conductive layer also improves the single cell electrolyzer performance at a similar catalyst loading in comparison to a commercial state-of-the-art catalyst. Here, we correlate the physical properties of the engineered catalysts with their electrochemical performance in electrolyzers to understand structure-activity relationships, and we anticipate further performance improvements upon synthesis and materials optimizations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

General synthesis of single-atom catalysts with high metal loading using graphene quantum dots

Transition-metal single-atom catalysts present extraordinary activity per metal atomic site, but suffer from low metal-atom densities (typically less than 5 wt% or 1 at.%), which limits their overall catalytic performance. Here we report a general method for the synthesis of single-atom catalysts with high transition-metal-atom loadings of up to 40 wt% or 3.8 at.%, representing several-fold improvements compared to benchmarks in the literature. Graphene quantum dots, later interweaved into a carbon matrix, were used as a support, providing numerous anchoring sites and thus facilitating the generation of high densities of transition-metal atoms with sufficient spacing between the metal atoms to avoid aggregation. A significant increase in activity in electrochemical CO 2 reduction (used as a representative reaction) was demonstrated on a Ni single-atom catalyst with increased Ni loading.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machine learning prediction and experimental verification of Pt-modified nitride catalysts for ethanol reforming with reduced precious metal loading

Ethanol is the smallest molecule containing C–O, C–C, C–H, and O–H bonds present in biomass-derived oxygenates. The development of inexpensive and selective catalysts for ethanol reforming is important towards the renewable generation of hydrogen from biomass. Transition metal nitrides (TMN) are interesting catalyst support materials that can effectively reduce precious metal loading for the catalysis of ethanol and other oxygenates. Herein theoretical and experimental methods were used to probe platinum-modified molybdenum nitride (Pt/Mo 2 N) surfaces for ethanol reforming. Computations using density-functional theory and machine learning predicted monolayer Pt/Mo 2 N to be highly active and selective for ethanol reforming. Temperature-programmed desorption (TPD) experiments verified that ethanol primarily underwent decomposition on Mo 2 N, and the reaction pathway shifted to reforming on Pt/Mo 2 N surfaces. Additionally, high-resolution electron energy loss spectroscopy (HREELS) results further indicated that while Mo2N decomposed the ethoxy intermediate by cleaving C–C, C–O, and C–H bonds, Pt-modification preserved the C–O bond, resulting in ethanol reforming.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave-assisted ammonia synthesis over Cs-Ru/CeO 2 catalyst at ambient pressure: Effects of metal loading and support particle size

Industrially, ammonia is produced by Haber-Bosch process under high temperatures and pressures, consuming more than >2% of the world's energy production. This paper presents microwave-assisted catalytic synthesis of ammonia operated at atmospheric pressure and temperatures from 260 to 360 °C. A Cs-promoted Ru catalyst supported on cerium oxide with different metal loading (4–24 wt% Ru) and support particle size (25nm, 50nm and 5μm) was investigated. The small size cerium oxide support resulted in the highest activity while the large cerium oxide support was less favorable, leading to lower activity associated to large Ru particle size and lower dispersion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extraction of Neptunium, Plutonium, Americium, Zirconium, and Technetium by Di-(2-Ethylhexyl)- Iso -Butyramide (DEH i BA) at High Metal Loadings

Increased focus on carbon neutral energy has generated a resurgence of interest in nuclear power, and in particular advanced reactors which are likely to utilize high assay low enriched uranium (HALEU). This in turn could increase the economic attractiveness of recovering still partially enriched uranium from used nuclear fuel. Concomitant to development of advanced reactors, advanced reprocessing schemes should be developed which address the disadvantages to well established reprocessing schemes. The present study focuses on using di-(2-ethylhexyl)-iso-butyramide (DEHiBA) under high metal loading conditions for the reprocessing of used nuclear fuel. The elements examined in the study include the dominant transuranic actinides (Np, Pu, Am) as well as the often-problematic Tc and Zr. Further, by increasing the concentration of the extractant from the more commonly reported 1.0 M – 1.5 M, the extraction of hexavalent actinides is substantially increased, while maintaining effective rejection of tri, tetra, and pentavalent actinides, particularly in the presence of high loadings of uranium. In conclusion, the extraction of Zr by 1.5 M DEHiBA is noted to be negligible by comparison to tributyl phosphate (TBP), however the coextraction of Tc with U is observed to be nominally twice the quantity that is extracted by TBP indicating a need for effective Tc management.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

On the effect of metal loading on the reducibility and redox chemistry of ceria supported Pd catalysts

The effect of Pd loading on the redox characteristics of a ceria support was examined using in situ Pd K-edge XAS, Ce L 3 -edge XAS and in situ X-ray diffraction techniques. Analysis of the data obtained from these techniques indicates that the onset temperature for the partial reduction of Ce(IV) to Ce(III), by exposure to H 2 , varies inversely with the loading of Pd. Whilst the onset and completion temperatures of the reduction of Ce(IV) to Ce(III) are different, both samples yield the same maximal fraction of Ce(III) formation independent of Pd loading. Furthermore, the partial reduction of Ce is found to be concurrent with the reduction of PdO and demonstrated that the presence of metallic Pd is necessary for the reduction of the CeO 2 support. Upon passivation by room temperature oxidation, a full oxidation of the reduced ceria support was observed. However, only a mild surface oxidation of Pd was identified. The mild passivation of the Pd is found to lead to a highly reactive sample upon a second reduction by H 2 . The onset of the reduction of Pd and Ce has been demonstrated to be independent of the Pd loading after a mild passivation with both samples exhibiting near room temperature reduction in the presence of H 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the Catalytic Requirements of Perovskite Fuel Electrodes Using Ultra-Low Metal Loadings

Solid Oxide Fuel Cells (SOFC) with La 0.3 Sr 0.7 TiO 3 (LST)–yttria-stabilized ZrO 2 (YSZ) anodes were prepared by impregnation of LST into porous YSZ scaffolds and then modified by Atomic Layer Deposition (ALD) of Ni, Pt, Pd, Fe, Co. and CeO 2 . Weight loadings as low as 0.01% of Pt, Ni, and Pd were sufficient to decrease anode impedances by orders of magnitude for operation in humidified H 2 at 973 K. The effects of CeO 2 , Co, and Fe were less but still significant. Sintering at higher temperatures was important. Furthermore, possible ways of stabilizing the metal particles and implications for developing ceramic anodes are discussed.

25 ENERGY STORAGE↗

Low and High LET Degradation Studies of Metal-Loaded Organic Phase Ligands in the ALSEP Process

Organic solutions comprising the Actinide Lanthanide Separation Process (ALSEP) solvent consisting of 0.5 M 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and 0.05 M N,N,N’,N’-tetra(2-ethylhexyl)diglycolamide (T2EHDGA) in n-dodecane were subjected to low LET and high LET irradiation before and after equilibration with an aqueous phase of 3 M HNO 3 . Degradation dose constants revealed greater ligand degradation due to gamma irradiation than alpha irradiation for both ligands. Furthermore, equilibration with nitric acid did not have a significant impact on ligand degradation for either irradiation source. Identified degradation products were similar for both gamma and alpha irradiation and occurred mostly through the rupture of the N–C carbonyl and C–O ether bonds for T2EHDGA and the C–Oether bond in HEH[EHP]. Acid contact appears to alter the degradation pathway by favoring the formation of higher molecular weight recombination products. Furthermore, mixed T2EHDGA-HEH[EHP]-NO 3 complexes were formed with Nd(III) after extraction from 3 M HNO 3 , and low LET gamma irradiation of the Nd(III) loaded organic solution produced similar degradation products as the organic solution absent of Nd(III). Interestingly, and likely due to the greater radiolytic susceptibility of T2EHDGA than HEH[EHP], a HEH[EHP]-Nd(III) complex appears to form as the T2EHDGA degrades with increasing absorbed dose.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electrocatalyst comprising a crumpled transition metal dichalcogenide support loaded with monodispersed metal nanoparticles

An electrocatalyst comprises a crumpled transition metal dichalcogenide support loaded with catalytic metal nanoparticles through spontaneous reduction reactions. The support can be prepared by hydrothermal conversion of 2D nanosheets to 3D hierarchically crumpled sheets. As an example, using crumpled MoS 2 as a support, highly tunable Ru loadings were obtained using the electrostatic interaction between MoS 2 and RuCl 3 in solution. Control over Ru loading was leveraged to produce Ru—MoS 2 electrocatalysts that demonstrate different nitrogen reduction reaction activities, and which show varying resistance to electrochemical sintering and deactivation. Further, these high surface area materials can be utilized for many applications, including electrocatalysts, supercapacitors, and batteries.

Percival, Stephen↗

Metal boride aerogels

A metal boride aerogel includes a three-dimensional aerogel structure comprising metal boride particles having an average diameter of less than one micron. A method is disclosed for forming a metal boride aerogel including dispersing boron nanoparticles in a solution of a metal salt, forming a boron-loaded metal oxide precursor gel using the dispersed boron nanoparticles in the solution of the metal salt, drying the boron-loaded metal oxide precursor gel to form a boron-loaded metal oxide precursor aerogel, and heating the boron-loaded metal oxide precursor aerogel to form a metal boride aerogel. The metal boride aerogel is essentially free of metal oxide.

Worsley, Marcus A.↗

Zeolitic catalytic conversion of alcohols to hydrocarbon fractions with reduced gaseous hydrocarbon content

A method for converting an alcohol to a hydrocarbon fraction reduced in gaseous hydrocarbon content, the method comprising: (i) contacting said alcohol with a metal-loaded zeolite catalyst under conditions suitable for converting said alcohol to a first hydrocarbon fraction containing liquid hydrocarbons having at least five carbon atoms along with gaseous hydrocarbons having less than five carbon atoms, wherein said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said first hydrocarbon fraction; and (ii) selectively removing said gaseous hydrocarbons from the first hydrocarbon fraction and contacting said gaseous hydrocarbons with a metal-loaded zeolite catalyst under conditions suitable for converting said gaseous hydrocarbons into liquid hydrocarbons having at least five carbon atoms to produce a second hydrocarbon fraction reduced in gaseous hydrocarbon content, wherein the metal-loaded zeolite catalyst in steps (i) and (ii) are the same or different.

09 BIOMASS FUELS↗

Degradation Mechanisms in Advanced MEAs for PEM Water Electrolyzers Fabricated by Reactive Spray Deposition Technology

Proton exchange membrane water electrolyzers (PEMWEs) have demonstrated enormous potential as the next generation hydrogen production technology. The main challenges that the state-of-the-art PEMWEs are currently facing are excessive cost and poor durability. Understanding the failure modes in PEMWEs is a key factor for improving their durability, lowering the precious metal loading, and hence cost reduction. Here, reactive spray deposition technology (RSDT) has been used to fabricate a membrane electrode assembly (MEA) with one order of magnitude lower Pt and Ir catalyst loadings (0.2–0.3 mg PGM cm –2 ) in comparison to the precious metal loadings in the stat-of-the-art commercial MEAs (2–3 mg PGM cm –2 ). As fabricated MEA with an active area of 86 cm 2 , has been tested for over 5000 h at steady-state conditions that are typical for an industrial hydrogen production system. Herein, we present and discuss the results from a comprehensive post-test analysis of the MEA of interest. The main degradation mechanisms, governing the performance loss in the RSDT fabricated MEA with ultra-low precious metal loadings, have been identified and discussed in detail. All failure modes are critically compared and the main degradation mechanism with the highest impact on the MEA performance loss among the others is identified.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗