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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 1,405 records · Page 78
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Platinum Supported on NbRuyOz as Electrocatalyst for Ethanol Oxidation in Acid and Alkaline Fuel Cells

Platinum supported on a mixed metal oxide, NbRu{sub y}O{sub z} (8Nb:1Ru), was evaluated as an electrocatalyst for the ethanol oxidation reaction (EOR) in 0.1 M HClO{sub 4} and 1 M KOH. The support was synthesized from a liquid precursor solution of metal chlorides that was aerosolized and thermally decomposed into a powder via the spray pyrolysis (SP) process. Two samples were of primary interest: 30%Pt deposited onto the support by dry impregnation and 60%Pt as part of the precursor solution that underwent in situ SP Pt dispersion. TEM, SEM, and XRD were used to confirm morphology and deposition of Pt. XPS and XAS studies confirmed elemental distribution and oxidation state of Pt catalyst. In situ IRRAS studies in 0.1 M HClO{sub 4} show that these electrocatalysts are capable of facilitating the complete oxidation pathway of EOR, involving scission of the C-C bond and CO oxidation.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2012

A Theoretical Study of Methanol Oxidation Catalyzed by Isolated Vanadia Clusters Supported on the (101) Surface of Anatase

A theoretical model has been developed for describing isolated vanadate species dispersed on the (101) surface of anatase that takes into account the equilibration of the supported species with gas-phase oxygen. The lowest energy of the combined solid and gas phases identifies the VOx species with the optimal structure and composition. This model of VOx species supported on the surface of anatase is then used to analyze the reaction path for methanol oxidation to formaldehyde. The chemisorption of methanol is found to proceed preferentially by addition across a V-O-Ti bond to form V-OCH3 and Ti-OH species. The rate-limiting step for the formation of formaldehyde takes place via the transfer of a hydrogen atom from V-OCH3 bound to an oxygen atom bridging two Ti atoms, i.e., a Ti-O-Ti group located adjacent to the supported vanadate species. This step is found to have the lowest apparent activation energy of all pathways explored for the formation of formaldehyde.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2013

State of Supported Pd during Catalysis in Water

In operando X-ray absorption was used to measure the structure and chemical state of supported Pd nanoparticles with 3 -10 nm diameter in contact with H2 saturated water at 298-473 K. The Pd-Pd distances determined were consistent with the presence of subsurface hydrogen, i.e., longer than those measured by others for bare, reduced Pd particles, and within the range of distances for Pd hydrides. During the Pd-catalyzed hydrogenation of phenol, cyclohexanone, cyclohexanol or cyclohexene in the presence of water, the Pd nanoparticles exhibited a lengthening of the Pd-Pd bond that we attribute to a change in the concentration of sorbed H related to the steady state of H at the surface of the Pd particles. This steady state is established by all reactions involving H2, i.e., the sorption/desorption into the bulk, the sorption at the surface, and the reaction with adsorbed unsaturated reactants. Thus, first insight into the chemical state of Pd and the H/Pd ratio during catalysis in water is provided. The Pd particles did not change upon their exposure to water or reactants; nor did the spectra show any effect from the interaction of the Pd particles with various supports. The experimental results are consistent with ab initio molecular dynamic simulations, which indicate that Pd-water interactions are relatively weak for Pd metal and that these interactions become even weaker, when hydrogen is incorporated into the metal particles. This work was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is a multi-program national laboratory operated for DOE by Battelle through Contract DE-AC05-76RL01830.

hydrodeoxygenation↗
DOE OSTI2014

Understanding Atom Probe Tomography of Oxide-Supported Metal Nanoparticles by Correlation with Atomic Resolution Electron Microscopy and Field Evaporation Simulation

Metal-dielectric composite materials, specifically metal nanoparticles supported on or embedded in metal oxides, are widely used in catalysis. The accurate optimization of such nanostructures warrants the need for detailed three-dimensional characterization. Atom probe tomography is uniquely capable of generating sub-nanometer structural and compositional data with part-per-million mass sensitivity, but there are reconstruction artifacts for composites containing materials with strongly differing fields of evaporation, as for oxide-supported metal nanoparticles. By correlating atom probe tomography with scanning transmission electron microscopy for Au nanoparticles embedded in an MgO support, deviations from an ideal topography during evaporation are demonstrated directly, and correlated with compositional errors in the reconstructed data. Finite element simulations of the field evaporation process confirm that protruding Au nanoparticles will evolve on the tip surface, and that evaporation field variations lead to an inaccurate assessment of the local composition, effectively lowering the spatial resolution of the final reconstructed dataset. Cross-correlating the experimental data with simulations results in a more detailed understanding of local evaporation aberrations during APT analysis of metal-oxide composites, paving the way towards a more accurate three-dimensional characterization of this technologically important class of materials.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2016

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2016

Gold-supported cerium-doped NiO x catalysts for water oxidation

Here, the development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiO x films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeO x –Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highly active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeO x –Au catalyst is further demonstrated in a device context by pairing it with a nickel–molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Synthesis of high-entropy alloy nanoparticles on supports by the fast moving bed pyrolysis

High-entropy alloy nanoparticles (HEA-NPs) are important class of materials with significant technological potential. However, the strategies for synthesizing uniformly dispersed HEA-NPs on granular supports such as carbon materials, γ-Al 2 O 3 , and zeolite, which is vital to their practical applications, are largely unexplored. Herein, we present a fast moving bed pyrolysis strategy to immobilize HEA-NPs on granular supports with a narrow size distribution of 2 nm up to denary (MnCoNiCuRhPdSnIrPtAu) HEA-NPs at 923 K. Fast moving bed pyrolysis strategy ensures the mixed metal precursors rapidly and simultaneously pyrolyzed at high temperatures, resulting in nuclei with a small size. The representative quinary (FeCoPdIrPt) HEA-NPs exhibit high stability (150 h) toward hydrogen evolution reaction with high mass activity, which is 26 times higher than the commercial Pt/C at an overpotential of 100 mV. Our strategy provides an improved methodology for synthesizing HEA-NPs on various supports.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite oxide supports

Single-atom catalysts (SACs) have attracted considerable attention in the catalysis community. However, fabricating intrinsically stable SACs on traditional supports (N-doped carbon, metal oxides, etc.) remains a formidable challenge, especially under high-temperature conditions. Here, we report a novel entropy-driven strategy to stabilize Pd single-atom on the high-entropy fluorite oxides (CeZrHfTiLa)O x (HEFO) as the support by a combination of mechanical milling with calcination at 900 °C. Characterization results reveal that single Pd atoms are incorporated into HEFO (Pd1@HEFO) sublattice by forming stable Pd–O–M bonds (M = Ce/Zr/La). Compared to the traditional support stabilized catalysts such as Pd@CeO 2 , Pd 1 @HEFO affords the improved reducibility of lattice oxygen and the existence of stable Pd–O–M species, thus exhibiting not only higher low-temperature CO oxidation activity but also outstanding resistance to thermal and hydrothermal degradation. This work therefore exemplifies the superiority of high-entropy materials for the preparation of SACs.

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

Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction

Oxide-supported noble metal catalysts have been extensively studied for decades for the water gas shift (WGS) reaction, a catalytic transformation central to a host of large volume processes that variously utilize or produce hydrogen. There remains considerable uncertainty as to how the specific features of the active metal-support interfacial bonding—perhaps most importantly the temporal dynamic changes occurring therein—serve to enable high activity and selectivity. Here we report the dynamic characteristics of a Pt/CeO 2 system at the atomic level for the WGS reaction and specifically reveal the synergistic effects of metal-support bonding at the perimeter region. We find that the perimeter Pt 0 -O vacancy -Ce 3+ sites are formed in the active structure, transformed at working temperatures and their appearance regulates the adsorbate behaviors. We find that the dynamic nature of this site is a key mechanistic step for the WGS reaction.

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

Self-regeneration of supported transition metals by a high entropy-driven principle

The sintering of Supported Transition Metal Catalysts (STMCs) is a core issue during high temperature catalysis. Perovskite oxides as host matrix for STMCs are proven to be sintering-resistance, leading to a family of self-regenerative materials. However, none other design principles for self-regenerative catalysts were put forward since 2002, which cannot satisfy diverse catalytic processes. Herein, inspired by the principle of high entropy-stabilized structure, a concept whether entropy driving force could promote the self-regeneration process is proposed. To verify it, a high entropy cubic Zr 0.5 (NiFeCuMnCo) 0.5 O x is constructed as a host model, and interestingly in situ reversible exsolution-dissolution of supported metallic species are observed in multi redox cycles. Notably, in situ exsolved transition metals from high entropy Zr 0.5 (NiFeCuMnCo) 0.5 O x support, whose entropic contribution (TΔS config = T$\star$12.7 J mol -1 K -1 ) is predominant in ΔG, affording ultrahigh thermal stability in long-term CO 2 hydrogenation (400 °C, >500 h). Current theory may inspire more STWCs with excellent sintering-resistance performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Interplay between copper redox and transfer and support acidity and topology in low temperature NH 3 -SCR

Low-temperature standard NH 3 -SCR over copper-exchanged zeolite catalysts occurs on NH 3 -solvated Cu-ion active sites in a quasi-homogeneous manner. As key kinetically relevant reaction steps, the reaction intermediate Cu II (NH 3 ) 4 ion hydrolyzes to Cu II (OH)(NH 3 ) 3 ion to gain redox activity. The Cu II (OH)(NH 3 ) 3 ion also transfers between neighboring zeolite cages to form highly reactive reaction intermediates. Via operando electron paramagnetic resonance spectroscopy and SCR kinetic measurements and density functional theory calculations, we demonstrate here that such kinetically relevant steps become energetically more difficult with lower support Brønsted acid strength and density. Consequently, Cu/LTA displays lower Cu atomic efficiency than Cu/CHA and Cu/AEI, which can also be rationalized by considering differences in their support topology. By carrying out hydrothermal aging to eliminate support Brønsted acid sites, both Cu II (NH 3 ) 4 ion hydrolysis and Cu II (OH)(NH 3 ) 3 ion migration are hindered, leading to a marked decrease in Cu atomic efficiency for all catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Tuning metal-support interactions in nickel–zeolite catalysts leads to enhanced stability during dry reforming of methane

Ni-based catalysts are highly reactive for dry reforming of methane (DRM) but they are prone to rapid deactivation due to sintering and/or coking. In this study, we present a straightforward approach for anchoring dispersed Ni sites with strengthened metal-support interactions, which leads to Ni active sites embedded in dealuminated Beta zeolite with superior stability and rates for DRM. The process involves solid-state grinding of dealuminated Beta zeolites and nickel nitrate, followed by calcination under finely controlled gas flow conditions. By combining in situ X-ray absorption spectroscopy and ab initio simulations, it is elucidated that the efficient removal of byproducts during catalyst synthesis is conducted to strengthen Ni–Si interactions that suppress coking and sintering after 100 h of time-on-stream. Transient isotopic kinetic experiments shed light on the differences in intrinsic turnover frequency of Ni species and explain performance trends. This work constructs a fundamental understanding regarding the implication of facile synthesis protocols on metal-support interaction in zeolite-supported Ni sites, and it lays the needed foundations on how these interactions can be tuned for outstanding DRM performance.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Single-atom Zr promoter boosts oxygen activation on ceria-supported Pt catalysts

Activation of surface lattice oxygen and chemisorbed oxygen on catalyst surfaces constitutes a pivotal step in heterogeneous oxidative catalysis. Herein, we report a strategy for enhancing oxygen activation by rational design of catalysts with single-atom promoters. Single-site Zr species in CeO 2 (Zr 1 -CeO 2 ) are synthesized using the atom-trapping method. The Zr 1 -CeO 2 -supported Pt catalyst exhibits enhanced catalytic performance over the CeO 2 -supported Pt catalyst in the oxidation of CO, C 3 H 8 , and C 3 H 6 , achieving significantly lower T 50 values (temperature required to reach 50% conversion). This enhanced catalytic activity is attributed to the formation of an asymmetric Zr 1 -O-Pt 1 structure, which favors the activation of the adjacent surface lattice oxygen and chemisorbed molecular oxygen. This work exemplifies that incorporating single-site atoms into oxide support facilitates oxygen activation, providing new insights into the role of atomically dispersed promoters in heterogeneous catalysis.

Science & Technology - Other Topics↗
DOE OSTI2026

Non-equilibrium reducing flame aerosol process to create supported high-entropy alloy nanoparticles

High-entropy alloy (HEA) nanomaterials provide opportunities and property combinations for energy and electronic applications, but their practical synthesis faces challenges of elemental immiscibility, metal reducibility, and particle aggregation during their synthesis. Herein, we report a broadly applicable non-equilibrium, scalable, and in-situ reducing flame aerosol process for synthesis of supported HEA nanoparticles. This versatile process can directly load a high concentration of 2 ~ 4 nm HEA nanoparticles on various 1- to 3-dimensional supports. Notably, simultaneous formation of HEA nanoparticles and a mesoporous silica support was successfully realized in a single step. Exploration of this process demonstrates the role of kinetics and entropy on decreasing alloy particle size and altering the reducibility of elements. We propose an entropy-induced reduction mechanism to incorporate oxidizable elements into HEAs, which extends the compositional space of HEA nanoparticles. As a representative catalytic application, we present a RuPdOsIrPt/graphene electrocatalyst with high activity and stability for hydrogen oxidation reaction. Our findings open horizons for high-performance HEA design and applications in diverse fields such as catalysis, electrochemistry, and sensing.

organic↗
DOE OSTI2011

Synthesis of Silica Supported AuCu Nanoparticle Catalysts and the Effects of Pretreatment Conditions for the CO Oxidation Reaction

Supported gold nanoparticles have generated an immense interest in the field of catalysis due to their extremely high reactivity and selectivity. Recently, alloy nanoparticles of gold have received a lot of attention due to their enhanced catalytic properties. Here we report the synthesis of silica supported AuCu nanoparticles through the conversion of supported Au nanoparticles in a solution of Cu(C{sub 2}H{sub 3}O{sub 2}){sub 2} at 300 C. The AuCu alloy structure was confirmed through powder XRD (which indicated a weakly ordered alloy phase), XANES, and EXAFS. It was also shown that heating the AuCu/SiO{sub 2} in an O{sub 2} atmosphere segregated the catalyst into a Au-CuO{sub x} heterostructure between 150 C to 240 C. Heating the catalyst in H{sub 2} at 300 C reduced the CuO{sub x} back to Cu{sup 0} to reform the AuCu alloy phase. It was found that the AuCu/SiO{sub 2} catalysts were inactive for CO oxidation. However, various pretreatment conditions were required to form a highly active and stable Au-CuO{sub x}/SiO{sub 2} catalyst to achieve 100% CO conversion below room-temperature. This is explained by the in situ FTIR result, which shows that CO molecules can be chemisorbed and activated only on the Au-CuOx/SiO{sub 2} catalyst but not on the AuCu/SiO{sub 2} catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Dehydration, Dehydrogenation, and Condensation of Alcohols on Supported Oxide Catalysts Based on Cyclic (WO3)3 and (MoO3)3 Clusters

Supported early transition metal oxides have important applications in numerous catalytic reactions. In this article we review preparation and activity of well-defined model WO3 and MoO3 catalysts prepared via deposition of cyclic gas-phase (WO3)3 and (MoO3)3 clusters generated by sublimation of WO3 and MoO3 powders. Conversion of small aliphatic alcohols to alkenes, aldehydes/ketons, and ethers is employed to probe the structure-activity relationships on model WO3 and MoO3 catalysts ranging from unsupported (WO3)3 and (MoO3)3 clusters embedded in alcohol matrices, to (WO3)3 clusters supported on surfaces of other oxides, and epitaxial and nanoporous WO3 films. Detailed theoretical calculations reveal the underlying reaction mechanisms and provide insight into the origin of the differences in the WO3 and MoO3 reactivity. For the range of interrogated (WO3)3 they further shed light into the role structure and binding of (WO3)3 clusters with the support play in determining their catalytic activity.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Nanoscale conductive niobium oxides made through low temperature phase transformation for electrocatalyst support

We report an effective approach to synthesize nanoscale Nb2O5 coated on carbon nanotubes (CNTs) and transform it at low temperatures to the conductive form of NbO2. The latter, when used as a Pt electrocatalyst support, shows significant enhancement in catalyst activity and durability in the oxygen reduction reaction (ORR). Direct phase transformation of Nb2O5 to NbO2 often requires temperatures above 1000 degrees C. Here we show that this can be achieved at a much lower temperature (e.g. 700 degrees C) if the niobium oxide is first activated with carbon. Low temperature processing allows retaining nanostructures of the oxide without sintering, keeping its high surface areas needed for being a catalyst support. We further show that Pt supported on the conductive oxides on CNTs has two times higher mass activity for the ORR than on bare CNTs. The electrochemical stability of Pt was also outstanding, with only ca. 5% loss in electrochemical surface areas and insignificant reduction in half-wave potential in ORR after 5000 potential cycles.

Huang, K↗
DOE OSTI2015

Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles

Mechanistic aspects of deconstruction and hydrodeoxygenation of organosolv lignin using supported Ni catalysts with (Ni/HZSM-5 and Ni/HBEA) and without Brønsted acid sites (Ni/SiO2) are reported. Lignin was deconstructed and converted to saturated cyclic hydrocarbons ranging from C5 to C14. In the one-stage reaction, full conversion with total yield of 70 ± 5 wt.% saturated hydrocarbons was achieved at 593 K and 20 bar H2. The organosolv lignin used consists of seven to eight monolignol subunits and has an average molecular weight of ca. 1200 g mol-1. The monolignols were mainly guaiacyl, syringyl and phenylcoumaran, randomly interconnected through β-O-4, 4-O-5, β-1, 5-5’ and β-β ether bonds. In situ IR spectroscopy was used to follow the changes in lignin constituents during reaction. The proposed reaction pathways for the catalytic transformation of this organosolv lignin to alkanes start with the hydrogenolysis of aryl alkyl ether bonds, followed by hydrogenation of the aromatic compounds on Ni to cyclic alcohols. Oxygen is removed from the alcohols via dehydration on Brønsted acid sites to yield cyclic alkenes that are further hydrogenated to alkanes. Formation of condensation products may occur via intermolecular recombination of aromatic monomers or alkylation of aromatic compounds by alkenes. The financial support from TUM-PNNL cooperation project “Development of new methods for in situ characterization in liquid phase reactions” (CN-177939) is highly appreciated. The work by S.K., H.S., and J.A.L was partially supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

Kasakov, Stanislav↗