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Results for “palladium catalyst”

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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Hydrogen Uptake Kinetics of 1,4-Bis(phenylethynyl)benzene (DEB) Rubberized Coating on Silicone Foam Substrate

The hydrogen uptake kinetics of 1,4-bis(phenylethynyl)benzene, or DEB, mixed with palladium (Pd) on activated carbon in a rubber matrix coating on top of a porous silicone foam substrate are investigated. First, isothermal isobaric hydrogenation experiments were performed under different temperatures and H 2 pressures to extract the uptake kinetics. The H 2 uptake models based on the measured kinetic parameters were then employed to investigate/simulate the performance of the getter under dynamic application environments. The actual hydrogenation characteristics in this type of getter is multifaceted and involve actual H 2 concentration in the getter matrix, micrometer scale diffusion of atomic hydrogen away from Pd sites, precipitation of hydrogenated DEB crystals at the coating surfaces, and mobility of fresh DEB molecules. The kinetic analysis/modeling methodology described in this report can serve as a template for other gas-solid reactions as well. Aside from possessing a good hydrogen capacity and excellent performance, this type of rubberized getter also offers some unique advantages over traditional solid getter: flexible structure and protection of Pd catalyst from exposure to the environment.

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

Facile Synthesis of Palladium-Based Nanocrystals with Different Crystal Phases and a Comparison of Their Catalytic Properties

A relatively unexplored aspect of noble-metal nanomaterials is polymorphism, or their ability to crystallize in different crystal phases. Here, in this work, a method is reported for the facile synthesis of Ru@Pd core–shell nanocrystals featuring polymorphism, with the core made of hexagonally close-packed (hcp)-Ru while the Pd shell takes either an hcp or face-centered cubic (fcc) phase. The polymorphism shows a dependence on the shell thickness, with shells thinner than ≈1.4 nm taking the hcp phase whereas the thicker ones revert to fcc. The injection rate provides an experimental knob for controlling the phase, with one-shot and drop-wise injection of the Pd precursor corresponding to fcc-Pd and hcp-Pd shells, respectively. When these nanocrystals are tested as catalysts toward formic acid oxidation, the Ru@Pd hcp nanocrystals outperform Ru@Pd fcc in terms of both specific activity and peak potential. Density functional theory calculations are also performed to elucidate the origin of this performance enhancement.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Non-reactive facet specific adsorption as a route to remediation of chlorinated organic contaminants

The present work quantifies metal-contaminant interactions between palladium substrates and three salient chlorinated organic contaminants, namely trichloroethylene 1,3,5-trichlorobenzene (TCB), and 3,3′,4,4′-tetrachlorobiphenyl (PCB77). Given that Pd is one of the conventional catalytically active materials known for contaminant removal, maximizing catalytic efficiency through optimal adsorption dynamics reduces the cost of remediation of contaminants that are persistent water pollutants chronically affecting public health. Adsorption efficiency analyses from all-atom molecular dynamics (MD) simulations advance the understanding of reaction mechanisms available from density functional theory (DFT) calculations to an extractable feature scale that can fit the parametric design of supported metal catalytic systems and feed into high throughput catalyst selection. Data on residence time, site-specific adsorption, binding energies, packing geometries, orientation profiles, and the effect of adsorbate size show the anomalous behaviour of organic contaminant adsorption on the undercoordinated {110} surface as compared to the {111} and {100} surfaces. The intermolecular interaction within contaminants from molecular dynamics simulation exhibits refreshing results than ordinary single molecule density functional theory calculation. Since complete adsorption and dechlorination is an essential step for chlorinated organic contaminant remediation pathways, the presented profiles provide essential information for designing efficient remediation systems through facet-controlled palladium nanoparticles.

Guo, Hao↗
DOE OSTI2025

Bidirectional Suzuki Catalyst Transfer Polymerization of Poly( p -phenylene)

Suzuki catalyst transfer polymerization (SCTP) has emerged as an effective method for accessing length-controlled π-conjugated poly(p-phenylene). Regio-controlled functional group sequencing along the backbone and the chain ends of synthetic polymers remains a challenge for the successful integration of organic semiconductors in sensors and electronic devices. Here, we report a bidirectional SCTP system based on dinuclear palladium(II) initiators. Functional groups transferred during the initiation and termination steps unlock independently addressable synthetic handles at the polymer core and respective chain ends. These functional groups open opportunities for late-stage regio-controlled and chemoselective derivatizations. Control over key polymer parameters, including molecular weight (M n ), dispersity ( Đ = M w /M n ), degree of polymerization ( DP ), termination efficiency, and functional group interconversion, is corroborated by size exclusion chromatography (SEC) and NMR spectroscopy. The modular design of SCTP initiators, in combination with commercially available terminating groups, represents a highly flexible toolbox for late-stage polymer conjugation, e.g., chemoselective anchoring groups for integration with functional electronics or bioorthogonal conjugation for molecular sensing.

Aldehydes↗
DOE OSTI2023

Low temperature hydrogen superpermeation in vanadium composite metal foil pumps

Palladium-based foil membranes are an effective option for hydrogen isotope recovery from the plasma exhaust of future fusion plants, but cost and availability are concerns. Vanadium (V) is a relatively low cost, neutron tolerant material with high hydrogen permeability. It has been well-studied as a superpermeable membrane at high temperature (>500 °C), but V displays negligible superpermeation at low temperature (75–200 °C) due to catalytic limitations. Composite membranes were fabricated by depositing thin layers (~100 nm) of either Pd or BCC PdCu on sputter-cleaned vanadium foils (100 μm). Symmetric membranes elevated superpermeation to levels approaching bulk Pd or PdCu foils, with ~5X higher flux in the latter reflecting the superior properties of PdCu. Asymmetric membranes revealed that the Pd-based catalyst layer was critical for both efficient absorption of superthermal hydrogen upstream as well as catalyzing re-combinative desorption downstream. At T ≥ 150 °C composite membrane superpermeation was equivalent to the Pd-based foils, but the flux was attenuated by a factor of 2-3X as the temperature was reduced. This deviation from pure foil performance coincided with the formation of vanadium hydride (β-V 2 H), which also impacted the transient response. Nevertheless, no embrittlement was observed under the conditions examined and elevating the temperature >150 °C removed the hydride and restored full performance. The achievement of palladium-level performance with a >99% reduction in Pd inventory makes these V composite metal foils pumps an attractive option for low temperature hydrogen isotope recovery in future fusion plants.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1981

Demonstration of catalytic combustion with residual fuel

An experimental program was conducted to demonstrate catalytic combustion of a residual fuel oil. Three catalytic reactors, including a baseline configuration and two backup configurations based on baseline test results, were operated on No. 6 fuel oil. All reactors were multielement configurations consisting of ceramic honeycomb catalyzed with palladium on stabilized alumina. Stable operation on residual oil was demonstrated with the baseline configuration at a reactor inlet temperature of about 825 K (1025 F). At low inlet temperature, operation was precluded by apparent plugging of the catalytic reactor with residual oil. Reduced plugging tendency was demonstrated in the backup reactors by increasing the size of the catalyst channels at the reactor inlet, but plugging still occurred at inlet temperature below 725 K (845 F). Operation at the original design inlet temperature of 589 K (600 F) could not be demonstrated. Combustion efficiency above 99.5% was obtained with less than 5% reactor pressure drop. Thermally formed NO sub x levels were very low (less than 0.5 g NO2/kg fuel) but nearly 100% conversion of fuel-bound nitrogen to NO sub x was observed.

Dodds, W. J.↗
DOE OSTI2022

Efficient transfer hydrodehalogenation of halophenols catalyzed by Pd supported on ceria

We report the transfer hydrodehalogenation (THD) of halophenols is efficiently catalyzed by palladium supported on high surface area ceria (Pd/CeO 2 ) under mild conditions (65 °C) using isopropanol (iPrOH) as hydrogen source. The reactivity of 4-halophenols (4-X-PhOH) varies in the order 4-F-PhOH > 4-Cl-PhOH > 4-Br-PhOH > > 4-I-PhOH and appears to be controlled by the desorption of halides from the catalyst surface. Kinetic analysis of the reactions and temperature programmed surface reaction (TPSR) experiments indicate that oxidative addition of C-X bonds and H-abstraction from isopropoxide compete for the same active sites on Pd. The catalyst was able to conduct the THD of various hazardous pollutants and emerging contaminants (dichlorodiphenyltrichloroethane (DDT), pentachlorophenol, pentafluorophenol and triclosan).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

An investigation of the physical and chemical changes of Pd nanoparticles on carbon supports in response to the release of hydrogen from aqueous formate solutions

Palladium nanoparticles on carbon supports (Pd/C) are effective for catalyzing hydrogen release from aqueous formate solutions but typically suffer from a gradual decrease of activity. This study finds two primary factors influencing activity: (i) the number of available surface Pd sites, and (ii) metal-support interactions which depend on the nature of the C support. We propose that the Pd/C catalyst is structure insensitive and undergoes Ostwald ripening to yield an active ‘conditioned’ catalyst with dispersion plateauing between ca. 15–20 %. Contrary to earlier studies, in-situ XANES experiments show that PdO is not an active catalyst for formate dehydrogenation. Calcination of Pd/C before dehydrogenation increases the catalytic activity which suggests a beneficial, albeit temporary, modification of the metal support interaction. N-containing supports minimize nanoparticle growth and also increase activity through a metal-support interaction. In conclusion, these findings advance our understanding of catalyst evolution and stability in formate dehydrogenation systems.

Formate dehydrogenation↗
DOE OSTI2022

Multi-state Catalysts Modulated by Mechanical Force (Final Report)

The development of more efficient catalytic processes and new approaches to control catalytic activity and selectivity are central to the realization of more selective, atom economic, and energy efficient routes to value added chemicals and polymers. The reactivity and selectivity of a transition metal catalyst is intimately related to the ligand-sphere geometry and, in many cases, the ideal ligand geometry for one step of a catalytic cycle is poorly matched to the ideal ligand geometry for another, resulting in sub-optimal efficiency. Macroscopic mechanical forces are both large, potentially much larger than interatomic forces, and are directional and localized to an extent that differentiates them from other forms of energy input such as heat or light. As such, mechanical force represents a heretofore untapped approach to modulate catalyst geometry, with the potential to reversibly modulate catalyst geometry on the timescale of catalytic turnover or monomer enchainment. This project has addressed the fundamental challenges in material-to-molecule strain coupling associated with the development of a new class of mechanically responsive catalysts (mechanocatalysts) in which active organotransition metal catalysts are strategically embedded in a flexible polymer network such that application of external mechanical force (stretching or deformation) leads to modulation of catalyst geometry, and hence reactivity and selectivity. Our efforts during the tenure of this grant were directed toward the elucidation of force-reactivity relationships of elementary transformations that occur within the first coordination sphere of a transition metal complex employing stiff stilbene photoswitches tethered to a flexible bidentate phosphine ligand derived from MeOBiphep as molecular force probes which provide a range of compressive and extension forces to the coupled transition metal complex depending on the geometry of the stiff stilbene and length of the tethering chains. During the tenure of this grant, we have quantified the rate of C(sp 2 )-C(sp 2 ) reductive elimination from platinum(II) diaryl complexes containing bis(phosphine) force probe ligands as a function of mechanical force; compressive forces decreased the rate of reductive elimination whereas extension forces increased the rate relative to the strain-free MeOBiphep complex with a 3.4-fold change in rate over a ~290 pN range of restoring forces. In a similar manner, we have quantified the rate of oxidative addition of bromobenzene to low-ligated palladium(0) complexes containing force probe ligands as a function of mechanical force; compressive forces increase the rate of oxidative addition, whereas tensile forces decrease the rate with a ~6 fold change in rate across ~340 pN of force applied to the complexes. In both cases, experimental and computational analyses argue strongly against any significant force-induced perturbation of ground state geometry within the first coordination sphere of the reactant complexes. Rather, the force/rate behavior observed for these transformations across these ranges of forces is attributed to the coupling of force to the nuclear motion comprising the reaction coordinates for reductive elimination and oxidative addition. These results together inform the development of catalysts whose activity can be tuned by an external force that is adjusted within a catalytic cycle and suggest opportunities to experimentally map geometry changes associated with reactions in transition metal complexes and potential strategies for force-modulated catalysis.

99 GENERAL AND MISCELLANEOUS↗
NASA NTRS1984

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

Stonehart, P.↗
DOE OSTI2022

Dynamical Study of Adsorbate-Induced Restructuring Kinetics in Bimetallic Catalysts Using the PdAu(111) Model System

The dynamic restructuring of bimetallic catalysts plays a crucial role in their catalytic activity and selectivity. In particular, catalyst pretreatment with species such as carbon monoxide and oxygen has been shown to be an effective strategy for tuning the surface composition and morphology. Mechanistic and kinetic understanding of such restructuring are fundamental to the chemistry and engineering of surface active sites but have remained challenging due to the large structural, chemical, and temporal degrees of freedom. Here, we combine time-resolved temperature-programmed infrared reflection absorption spectroscopy, ab initio thermodynamics, and machine-learning molecular dynamics to uncover previously unidentified timescale and kinetic parameters of in situ restructuring in Pd/Au(111), a highly relevant model system for dilute Pd-in-Au nanoparticle catalysts. The key innovation lies in utilizing CO not only as a chemically sensitive probe of surface Pd, but also as an agent that induces restructuring of the surface. Upon annealing in vacuum, as-deposited Pd islands became encapsulated by Au and partially dissolved into the subsurface, leaving behind isolated Pd monomers on the surface. Subsequent exposure to 0.1 mbar CO enabled Pd monomers to repopulate the surface up to 373 K, above which complete Pd dissolution occurred by 473 K, with apparent activation energies of 0.14 and 0.48 eV, respectively. Furthermore, these restructuring processes occurred over the span of ~1000 s at a given temperature. Such a minute-timescale dynamics not only elucidates the fluxional nature of alloy catalysts but also presents an opportunity to fine-tune the surface at moderate temperature and pressure conditions.

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

Catalytic Conversion of Ethylene to Value-added Materials (Final Report)

The general goal of the work was to develop new late metal Ni(II)- and Pd(II)-based catalysts and processes to convert ethylene and other readily available α-olefins via polymerization and oligomerization reactions to an array of new value-added materials with high efficiency. An emphasis was placed on invention of new catalysts and processes guided by rational design and detailed mechanistic studies. These investigations have generated new knowledge which may underpin technological advances directed towards new and more efficient methods for utilizing ethylene and α-olefins derived from ethylene.

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

Substrate–Support Interactions Mediate Hydrogenation of Phenolic Compounds by Pd/CeO 2 Nanorods

Ceria-supported palladium (Pd/CeO 2 ) has spawned significant attention in recent years due to its ability to catalyze selective hydrogenation of phenolic compounds to cyclohexanones and cyclohexanols at a mild temperature and pressure. However, the mechanistic basis by which ceria enhances catalytic conversion is still unclear. Here, we use the increase in the 13 C transverse relaxation rate upon the addition of nanoparticles (NPs) ( 13 C ΔR 2 ) to investigate the adsorption of phenolic compounds on the surface of the Pd/CeO 2 catalyst by solution NMR. We show that hydroxyphenols adsorb on the support more efficiently than underivatized phenol and methoxyphenols and that phenol derivatives with an oxygen atom at position 2 (i.e., 2-hydroxyphenol and 2-methoxyphenol) form very stable interactions with the Pd site of Pd/CeO 2 . An analysis of the kinetics of hydrogenation revealed that catalytic conversion is linearly correlated with the ability of the substrate to form interactions with the CeO 2 support and is inhibited by the formation of stable substrate–Pd adducts. Our data suggest that CeO 2 –substrate interactions mediate phenol hydrogenation more efficiently than Pd–substrate interactions and explain the exceptional catalytic performance reported for Pd/CeO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Insights into Supported Subnanometer Catalysts Exposed to CO via Machine-Learning-Enabled Multiscale Modeling

Subnanometer catalysts offer high noble metal utilization and superior performance for several reactions. However, understanding their structures and properties on an atomic scale under working conditions is challenging due to the large configurational space. Here, we introduce an efficient multiscale framework to predict their stability exposed to an adsorbate. The framework integrates a comprehensive toolset including density functional theory (DFT) calculations, cluster expansion, machine learning, and structure optimization. The end-to-end machine-learning workflow guides DFT data generation and enables significant computational acceleration. We demonstrate the approach for CO-adsorbed Pdn (n = 1–55) clusters on CeO 2 (111). Simulation results reveal that CO can facilitate restructuring by stabilizing smaller planar structures and bilayer structures of specific intermediate sizes, consistent with experimental reports. Metal–support interactions, preferential CO adsorption, and metal nuclearity and structure control catalyst stability. As a result, the framework allows automatic discovery of stable catalyst structures and a systematic strategy to exploit properties in the subnanometer scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrochemical production of H 2 O 2 on palladium-based clusters driven by metal–support interaction

Utilizing palladium (Pd) clusters as active sites offers a promising route to minimize noble metal consumption in electrochemical hydrogen peroxide (H 2 O 2 ) production. In this work, we present a synthesis approach for anchoring Pd-based clusters onto carbon-supported CeO 2 nanosubstrates to enable efficient H 2 O 2 generation via the two-electron oxygen reduction reaction (ORR) pathway. By systematically adjusting Pd loading, we evaluated its impact on H 2 O 2 yield and production rate. The catalyst with the lowest Pd content (0.027 wt%) exhibited outstanding performance, achieving 97% H 2 O 2 selectivity, 94.2 faradaic efficiency at 0.7 V vs. RHE, and a peak production rate of 195.8 mol g Pd −1 h −1 . A formulation containing 0.35 wt% Pd delivered a peak ORR mass activity nearly three times as high as that of commercial 10 wt% Pd/C, while retaining comparable electrochemical stability. These enhancements are attributed to synergistic effects among isolated PdO clusters, CeO 2 nanocrystals, and the conductive carbon support, which together facilitate oxygen adsorption and promote the two-electron ORR pathway. Analysis after accelerated durability testing further revealed a tendency toward cluster agglomeration and mass transfer from smaller to larger nanocrystals, indicative of a coarsening mechanism. Overall, this study underscores the promise of low-Pd PdO–CeO 2 –carbon hybrid catalysts for scalable and efficient H 2 O 2 electrosynthesis, while highlighting stability as a critical area for future improvement.

36 MATERIALS SCIENCE↗
NASA NTRS2003

Catalyzed Combustion of Bipropellants for Micro-Spacecraft Propulsion

This paper addresses the need to understand the physics and chemistry involved in propellant combustion processes in micro-scale combustors for propulsion systems on micro-spacecraft. These spacecraft are planned to have a mass less than 50 kilograms with attitude control estimated to be in the 10 milli-Newton thrust class. These combustors are anticipated to be manufactured using Micro Electrical Mechanical Systems (MEMS) technology and are expected to have diameters approaching the quenching diameter of the propellants. Combustors of this size are expected to benefit significantly from surface catalysis processes. Miniature flame tube apparatus is chosen for this study because microtubes can be easily fabricated from known catalyst materials and their simplicity in geometry can be used in fundamental simulations for validation purposes. Experimentally, we investigated the role of catalytically active surfaces within 0.4 and 0.8 mm internal diameter microtubes, with special emphases on ignition processes in fuel rich gaseous hydrogen and gaseous oxygen. Flame thickness and reaction zone thickness calculations predict that the diameters of our test apparatus are below the quenching diameter of the propellants in sub-atmospheric tests. Temperature and pressure rise in resistively heated platinum and palladium microtubes was used as an indication of exothermic reactions. Specific data on mass flow versus preheat temperature required to achieve ignition are presented. With a plug flow model, the experimental conditions were simulated with detailed gas-phase chemistry, thermodynamic properties, and surface kinetics. Computational results generally support the experimental findings, but suggest an experimental mapping of the exit temperature and composition is needed.

Schneider, Steven J.↗
DOE OSTI2025

Nickel Enhances InPd-Catalyzed Nitrate Reduction Activity and N 2 Selectivity

Palladium–indium (PdIn) is a well-established bimetallic composition for reductively degrading nitrate anions, one of the most ubiquitous contaminants in the groundwater. However, the scarcity and the variable price of these rare-earth and platinum group critical metals may hinder their use for water treatment. Nickel (Ni), a nonprecious metal in the same element group as Pd, could partially replace and lower Pd usage if the resulting trimetallic composition is sufficiently catalytically active. Herein, we report the synthesis and nitrate reduction catalysis of activated carbon-supported “In-on-Pd-on-Ni” catalysts (InPdNi/AC). While bimetallic InPd/AC (0.05 wt % In, 1.3 wt % Pd) was expectedly active, trimetallic InPdNi/AC containing the same In amount, much less Pd (0.1 wt %), and 1 wt % Ni was >17 more active (k cat ≈ 20 vs 349 L min –1 g surface metal –1 ). X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations showed that Pd gained electron density from Ni, correlating to the increased nitrate reduction activity. Ammonium byproduct selectivity for InPdNi/AC (18% at 50% nitrate conversion) was lower compared to that of InPd/AC (48%), suggestive of the higher surface coverage of NO or its greater reactivity with NO 2 – , which led to more N 2 . Accounting for the catalyst precursor, manufacturing costs, and spent metal recovery, we calculated that Ni incorporation lowered the net catalyst cost significantly (from $\$$1028/kg to $\$$170/kg). The trimetallic composition lowered, by ∼26 times, the catalyst cost of a stirred tank reactor sized to the same treatment capacity as that for the bimetallic case. In conclusion, the results demonstrate that the partial replacement of the precious metal with an earth-abundant one leads to a higher efficiency and lower cost denitrification catalyst, via a material strategy that should be beneficial for other clean-water catalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗