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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Economizing on Precious Metals in Three-Way Catalysts: Thermally Stable and Highly Active Single-Atom Rhodium on Cera for NO Abatement under Dry and Industrially Relevant Conditions

We show for the first time that atomically dispersed Rh cations on ceria, prepared via high-temperature atom trapping synthesis, are the active species for (CO+NO) reaction. This provides a direct link with the organometallic homogeneous Rh(I) complexes capable of catalyzing dry (CO+NO) reaction but without the stability concern. In particular, thermally stable Rh cations in 0.1wt% Rh1/CeO2 achieve full NO conversion with a TOF of ~ 330 hr-1 per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N2 with N2O being the minor product. The presence of water promotes low-temperature activity of 0.1wt% Rh1/CeO2 starting at 50 °C with full NO conversion at ~120 °C. In the case with the wet stream, however, ammonia and nitrogen are the main products with only minor N2O amounts. NH3 formation at such low temperatures is attractive because of the potential to use this as a passive SCR system. Because of the uniformity of Rh ions on the support, we are able to observe the intermediates of (CO+NO) reaction via infrared measurements on Rh cations on zeolite and ceria. Furthermore, we show that ammonia formation correlates with the WGS activity of the material and thus, rhodium hydride Rh-H species are involved in this reaction: we detect Rh(CO)Hx species on ceria using isotopic IR measurements. These findings provide new mechanistic understanding for the catalytically active species in TWC catalysis and open up a new avenue for the synthesis of novel emissions control catalysts with 100% atom economy of ultra-expensive precious metals such as Rh.

Khivantsev, Konstantin↗
DOE OSTI2021

Comparative Study on the Machine Learning-Based Prediction of Adsorption Energies for Ring and Chain Species on Metal Catalyst Surfaces

Computation of adsorption and transition state energies for a large number of surface intermediates for numerous active site models pose significant computational overhead in computational screening of catalysts. Machine learning (ML) techniques can be used to predict part of these energies. To predict the energies, ML models need to be fed appropriate metal and species descriptors. For complex surface chemistries, the structures of the intermediate species can vary greatly. In this paper, working with the hydrodeoxygenation of succinic acid on six different metal surfaces, we have studied the effect of linear and non-linear ML models used along with pen-and-paper based species descriptors and two categories of metal descriptors on two different categories of intermediate species: chain and ring. More specifically, our computations include the prediction of chain species when trained on only chain species and also when trained on both chain and ring species. Similar computations were performed for predictions of ring species. In each case, results of linear ML models were compared with kernel based non-linear models. Our results indicate that ring species data does not improve the prediction of chain species. Similarly, chain species data does not improve the prediction of ring species. The use of non-linear ML models, however, did help to minimize the prediction errors compared to the linear models. Furthermore, the study also shows that electronic or adsorption energy based metal descriptors along with bond count based species fingerprints can achieve a mean absolute error (MAE) of less than 0.2 eV for complex chain molecules when used with an appropriate machine learning model.

Adsorption↗
DOE OSTI2017

Characterizing substrate–surface interactions on alumina-supported metal catalysts by dynamic nuclear polarization-enhanced double-resonance NMR spectroscopy [Characterizing substrate-surface interactions on alumina supported metal catalysts by DNP-enhanced double-resonance NMR spectroscopy]

The characterization of nanometer-scale interactions between carbon-containing substrates and alumina surfaces is of paramount importance to industrial and academic catalysis applications, but it is also very challenging. Here, we demonstrate that dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP SENS) allows the unambiguous description of the coordination geometries and conformations of the substrates at the alumina surface through high-resolution measurements of 13 C– 27 Al distances. We apply this new technique to elucidate the molecular-level geometry of 13 C-enriched methionine and natural abundance poly(vinyl alcohol) adsorbed on γ-Al 2 O 3 -supported Pd catalysts, and we support these results with element-specific X-ray absorption near-edge measurements. Furthermore, this work clearly demonstrates a surprising bimodal coordination of methionine at the Pd–Al 2 O 3 interface.

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

Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts [Balancing activity, stability and conductivity of nanoporous core-shell Ir/IrO 2 oxygen evolution catalysts]

The selection of oxide materials for catalyzing the Oxygen Evolution Reaction in acid-based electrolyzers must be guided by the proper balance between activity, stability and conductivity – a challenging mission of great importance for delivering affordable and environmentally friendly hydrogen. Here we report that the highly conductive nanoporous architecture of an iridium oxide shell on a metallic iridium core, formed through the fast dealloying of osmium from an Ir 25 Os 75 alloy, exhibits an exceptional balance between oxygen evolution activity and stability as quantified by the Activity-Stability FactorASF. Based on this metric, the nanoporous Ir/IrO 2 morphology of dealloyed Ir 25 Os 75 shows a factor of ~30 improvement ASFrelative to conventional Ir-based oxide materials and a ~8 times improvement over dealloyed Ir 25 Os 75 nanoparticles due to optimized stability and conductivity, respectively. Here, we propose that the Activity-Stability FactorASF is the key “metric” for determining the technological relevance of oxide-based anodic water electrolyzer catalysts.

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

Highly active Au/δ-MoC and Au/β-Mo 2 C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2 C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and the Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Mesoporous cobalt/manganese oxide: a highly selective bifunctional catalyst for amine–imine transformations

Here, we discuss a heterogeneous catalytic protocol using cobalt doped mesoporous manganese oxide for amine–alcohol cross-coupling to selectively produce symmetric or asymmetric imines. Thorough investigations on the surface chemistry and physical properties of the material revealed its outstanding oxidation–reduction properties and reaction mechanism which was supported by quantum mechanical calculations done by using density functional theory (DFT).

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

Examining Ohmic Losses in Fuel-Cell Catalyst Layers with Different Pt/C Ratios

A model of a fuel-cell cathode with distinct proton conductivities at the agglomerate and electrode scales was used to simulate polarization curves under conditions with facile oxygen transport. Here, the model was applied to electrodes containing agglomerates with different ratios of platinum to carbon in order to examine the hypothesis that intra-agglomerate proton conductivity is substantially lower than ionomer conductivity. The model predicts decreasing performance and increasing sensitivity to Pt/C ratio as intra-agglomerate conductivity declines relative to a constant through-electrode conductivity. Experiments on catalyst layers with Vulcan supports do not show the predicted trend indicating that mesoscale intra-agglomerate conductivity is not orders of magnitude lower than bulk ionomer conductivity.

08 HYDROGEN↗
NASA NTRS1980

Non-noble catalysts and catalyst supports for phosphoric acid fuel cells

Tungsten carbide, which is known to be active for hydrogen oxidation and CO tolerant has a hexagonal structure. Titanium carbide is inactive and has a cubic structure. Four different samples of the cubic alloys Wx-1TixC were prepared and found to be active and CO tolerant. These alloys are of interest as possible phosphoric acid fuel cell catalysts. They also are of interest as opportunities to study the activity of W in a different crystalline environment and to correlate the activities of the surface sites with surface composition.

Mcalister, A. J.↗