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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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166 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Coupled uptake and conversion of C 12 H 26 and NO on Pd/SSZ-13: Experiments and modeling

The uptake of NO in the presence of C 12 H 26 (dodecane) and H 2 O over a Pd/SSZ-13 washcoated Passive NOx Adsorber (PNA) monolith is reported. When a co-feed containing C 12 H 26 and NO is supplied to an unsaturated (with C 12 H 26 ) sample, the NO uptake is unaffected but during the subsequent temperature ramp the release of trapped NO is delayed from 175°C to over 220°C. The release delay is beneficial for PNA performance as the primary NO x aftertreatment technology, Selective Catalytic Reduction (SCR), is not operated below 200°C. However, pre-saturation of C 12 H 26 followed by the same NO and C 12 H 26 co-feed results in a decrease in the NO uptake compared to the NO-only feed. We conjecture that C 12 H 26 pre-adsorbed on the exterior surface of the sample blocks NO access to the pores, decreasing the number of available sites for NO uptake. Oxidation of C 12 H 26 leads to the generation of partial oxidation product CO at lower temperatures (<250°C) and deep oxidation product CO 2 at higher temperatures. Carbon monoxide binds strongly to Pd sites with NO and can delay NO release. A Pd/SSZ-13 washcoated monolith model developed in an earlier study [Ambast et al., Appl. Catal. B. Environmental (2021)] is upgraded to include C 12 H 26 storage, release, and conversion. Through a systematic combination of judicious experiments, model tuning, and validation, we provide evidence for the underlying NO uptake and release mechanisms in the presence of C 12 H 26 .

42 ENGINEERING↗
DOE OSTI2022

Development, characterization, and modeling of a high-performance Ru/B2CA catalyst for ammonia synthesis

This paper documents the development and performance of a nano-phase Ru catalyst on a (BaO) x (CaO) y (Al 2 O 3 ) support. Extensive screening of the support’s ternary composition shows the best stoichiometry is (BaO) 2 (CaO)(Al 2 O 3 ), denoted B2CA. The paper first describes catalyst preparation and characterization. The paper reports a detailed 12-step reaction mechanism that represents ammonia synthesis over wide ranges of temperature, pressure, space velocity, and feed composition. Additionally, the mechanism is developed and validated using results of packed-bed experiments. The elementary reaction pathways consider surface adsorbates, including catalyst-poisoning behaviors. The rate expressions include important coverage-dependent activation barriers. Machine learning models assist interpretation of the catalyst-support interactions. The detailed chemistry is much more predictive than is possible with global representations (N 2 + 3H 2 ⇌ 2NH 3 ). The validated models can be applied to assist optimizing reactor design and operating conditions.

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

Direct Comparison of the Activity and Selectivity of Rh 1 Cu and Ni 1 Cu Single-Atom Alloy Sites for Ethanol Decomposition

Ethanol is an important source of clean hydrogen, acetaldehyde, acetic acid, acetate esters, and light hydrocarbons. Controlling the divergent reaction pathways to these products requires understanding how different active sites influence the elementary steps involved. Herein, we present a combined surface science, theory, and nanoparticle catalysis study demonstrating how two single-atom dopants (Rh and Ni) in a Cu host can distinctively alter the selectivity of alcohol conversion. Specifically, our model studies reveal that ethanol reacts on Ni 1 Cu single-atom alloys to selectively produce acetaldehyde, whereas methane and CO are also formed on Rh 1 Cu single-atom alloys. Interestingly, these different reactivities are in contrast to the behavior of the pure metals as Ni(111) and Rh(111) surfaces favor methane/CO and surface carbon/CO, respectively. DFT calculations of reaction pathways and simulated product desorption based on microkinetic analyses explain these reactivity differences, demonstrating that C–C cleavage leading to methane formation has a lower barrier on Rh single-atom sites. To test the catalytic relevance of these fundamental results we synthesized and characterized supported Ni 1 Cu and Rh 1 Cu single-atom alloy nanoparticles with dopant:Cu ratios of 1:200. Flow reactor results revealed that both Ni and Rh increased ethanol conversion over Cu and that Ni 1 Cu catalysts were >99.9% selective to acetaldehyde, while Rh 1 Cu also produced 0.6%–2.6% of equimolar methane and CO between 433 and 493 K, demonstrating that C–C bond cleavage is enabled by isolated Rh sites. Furthermore, these catalytic results bridge the pressure and materials gaps, and together, this study provides insights into how different isolated dopant sites promote different catalytic pathways.

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

Surface molecular pump enables ultrahigh catalyst activity

The performance of electrocatalysts is critical for renewable energy technologies. While the electrocatalytic activity can be modulated through structural and compositional engineering following the Sabatier principle, the insufficiently explored catalyst-electrolyte interface is promising to promote microkinetic processes such as physisorption and desorption. By combining experimental designs and molecular dynamics simulations with explicit solvent in high accuracy, we demonstrated that dimethylformamide can work as an effective surface molecular pump to facilitate the entrapment of oxygen and outflux of water. Dimethylformamide disrupts the interfacial network of hydrogen bonds, leading to enhanced activity of the oxygen reduction reaction by a factor of 2 to 3. This strategy works generally for platinum-alloy catalysts, and we introduce an optimal model PtCuNi catalyst with an unprecedented specific activity of 21.8 ± 2.1 mA/cm 2 at 0.9 V versus the reversible hydrogen electrode, nearly double the previous record, and an ultrahigh mass activity of 10.7 ± 1.1 A/mg Pt .

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