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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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9 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Low-Temperature Catalyst Redispersion: A Route to Enhanced Stability of Supported Metal Catalysts?

Sintering poses a significant challenge to achieving the long-term stability of supported metal catalysts under reaction conditions. Here, in this study, we report a low-temperature catalyst redispersion mechanism, in which platinum single atoms, which aggregate into nanoparticles under Reverse Water Gas Shift (RWGS) conditions at elevated temperatures, fragment into atomically dispersed species upon cooling. Using multimodal operando characterization combined with first-principles theoretical modeling, we track the structural evolution of Pt single atoms supported on ceria nanodomes, deposited either on ceria or ceria–titania mixed oxides. We find that fragmentation is more pronounced when cooling occurs under RWGS conditions compared to CO alone, owing to a synergistic interplay of the effects of H 2 , CO 2 , and CO. The support architecture has a strong influence on the extent of redispersion: while CO alone induces fragmentation on ceria, interfacial confinement and vacancy pinning at the ceria–titania interface suppress restructuring. In contrast, RWGS conditions overcome these barriers, enabling redispersion across both supports. These findings point toward a pathway for catalyst stabilization via reaction-induced redispersion under mild conditions.

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

Dynamic Copper Site Redispersion through Atom Trapping in Zeolite Defects

Single-site copper-based catalysts have shown remarkable activity and selectivity for a variety of reactions. However, deactivation by sintering in high-temperature reducing environments remains a challenge and often limits their use due to irreversible structural changes to the catalyst. Here, we report zeolite-based copper catalysts in which copper oxide agglomerates formed after reaction can be repeatedly redispersed back to single sites using an oxidative treatment in air at 550 °C. Under different environments, single-site copper in Cu–Zn–Y/deAlBeta undergoes dynamic changes in structure and oxidation state that can be tuned to promote the formation of key active sites while minimizing deactivation through Cu sintering. For example, single-site Cu 2+ reduces to Cu 1+ after catalyst pretreatment (270 °C, 101 kPa H 2 ) and further to Cu0 nanoparticles under reaction conditions (270–350 °C, 7 kPa EtOH, 94 kPa H 2 ) or accelerated aging (400–450 °C, 101 kPa H 2 ). After regeneration at 550 °C in air, agglomerated CuO was dispersed back to single sites in the presence and absence of Zn and Y, which was verified by imaging, in situ spectroscopy, and catalytic rate measurements. Ab initio molecular dynamics simulations show that solvation of CuO monomers by water facilitates their transport through the zeolite pore, and condensation of the CuO monomer with a fully protonated silanol nest entraps copper and reforms the single-site structure. Importantly, the capability of silanol nests to trap and stabilize copper single sites under oxidizing conditions could extend the use of single-site copper catalysts to a wider variety of reactions and allows for a simple regeneration strategy for copper single-site catalysts.

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

Thermodynamics and kinetics of interconversion between platinum nanoparticles and cations in zeolites

In metal-containing zeolites, sintering and redispersion processes exercise control over the identity of metal site structures, but the thermodynamic and kinetic factors that influence these molecular-level processes are not completely understood. Furthermore, we assess the ability of first principles informed free energy models (for supported and unsupported nanoparticles) and kinetic models integrating Ostwald ripening with atom trapping to describe the interconversion between Pt cations and nanoparticles encapsulated in chabazite (CHA) zeolites. Density functional theory-derived thermodynamic phase diagrams show that the interconversion between cations, favored in oxidizing environments, and particles, favored in reducing environments, is fully reversible within a wide range of their respective conditions (temperatures and pressures) for CHA and several other zeolite topologies. Kinetic Monte Carlo simulations of Pt redispersion are consistent with experimentally observed redispersion kinetics of encapsulated Pt nanoparticles in CHA zeolites, and model results suggest the zeolite host imparts additional stability for Pt nanoparticles. We envision our thermodynamic and kinetic models for Pt-CHA are also capable of describing nanoparticle and cation interconversions for other zeolite frameworks under similar conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Structurally Regenerable High Entropy Aluminate Spinel Catalysts for Dry Reforming of Methane

The dry reforming of methane reaction is a promising means to convert two potent greenhouse gases, methane and carbon dioxide, into industrially valuable synthesis gas. However, the presence of reducing gases and high operating temperatures degrade conventional nickel catalysts via excessive coke formation and particle sintering. These catalysts are not readily regenerated because the oxidative heat treatments employed to remove coke further promote active particle sintering. In this work, we designed high entropy aluminate spinel oxides (MAl 2 O 4 where M = Co, Mg, Ni, and divalent site vacancies in nominal equimolar concentration) as selective and regenerable reforming catalysts. Under reaction conditions, reducible nickel and cobalt cations exsolved from the spinel lattice to form highly selective bimetallic particles on the oxide surface. Instead of sintering, these particles uniquely redissolved back into the aluminate lattice upon reoxidation and regained the original spinel structure. This phenomenon is ascribed to entropic stabilization, wherein an increase in configurational entropy creates a thermodynamic driving force for redispersing supported metal particles back into the multi‐cationic oxide structure. During the dry reforming reaction, nickel atoms similarly exsolved from a NiAl 2 O 4 sample and reduced to form metallic nickel particles. However, subsequent oxidation of this sample promoted sintering and oxidation of the nickel particles to an inactive state. High entropy materials thus provide a unique mechanism of regeneration, which is inaccessible in conventional catalysts.

coke deposition↗
DOE OSTI2024

Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Methane dehydroaromatization (MDA) is a promising approach for direct methane transformation to aromatics and hydrogen. The benchmark catalyst Mo/H-ZSM-5 struggles to find commercial adoption because of thermodynamically-limited yields and rapid coking on Brønsted acid and molybdenum carbide species, especially on zeolite external surfaces. Here, gas-phase atomic layer deposition (ALD) overcoats H-ZSM-5 external surfaces with SiO 2 or Al 2 O 3 . NH 3 -TPD, HRTEM, and textural properties show that these overcoats exclusively passivate zeolite external surfaces. Under MDA conditions, SiO 2 gives softer coke and increases cumulative benzene yields by 25%, while Al 2 O 3 strongly decreases yields. H 2 -TPR and UV-visible and Raman spectroscopy show how the overcoats redisperse the MoO x precatalysts, especially over multiple deactivation and isothermal oxidative regeneration cycles. Combined with 27 Al-MAS NMR, MoO x redistribution and dealumination are seen as the causes of long-term deactivation over multiple regeneration cycles, and this process continues to occur regardless of the overcoat. Altogether, the deposition of a small amount of silica on the outer surface of Mo/H-ZSM-5 reduces the formation of hard coke, which could be regenerated by milder methods such as hydrogen treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Reconstruction and Dissolution of Copper Catalysts during Electrocatalytic Nitrate Reduction

Copper-based electrocatalysts are widely explored for electrochemical nitrate remediation, yet their stability under operating conditions remains poorly understood. While nanoscale and subnanoscale Cu motifs are known to restructure during the nitrate reduction reaction (NO 3 RR), how these transformations translate into irreversible material loss remains unclear. Here, we quantify Cu dissolution during NO 3 RR as a function of catalyst architecture and electrolyte chemistry using two model systems: single-atom Cu (Cu 1 ) and Cu nanoparticles (Cu NP ). Time-resolved leaching measurements, integrated with in situ X-ray absorption spectroscopy (XAS), reveal measurable Cu loss for both catalysts during NO 3 RR. Dissolution is concentrated at the initiation of electrolysis, coinciding with rapid restructuring, and depends strongly on morphology, with Cu NP consistently exhibiting greater Cu loss than Cu 1 . In situ XAS reveals that Cu 1 forms transient metallic clusters under reduction that largely redisperse upon returning to open-circuit voltage, whereas Cu NP undergoes reduction of an oxidized surface layer accompanied by sustained Cu loss during electrolysis. Notably, the presence of nitrate significantly intensifies restructuring and Cu loss, highlighting the critical role of electrolyte composition. Furthermore, these findings establish a direct link between electrochemical restructuring and Cu dissolution, unveiling electrolyte-dependent interactions as key determinants of catalyst durability in electrochemical nitrate conversion.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Evolution of size-selected Pt cluster catalysts on prototypical oxide supports

The current quest for new pathways into sustainable, efficient and durable energy conversion technologies makes the used for a fundamental understanding of the atomic-scale phenomena underlying catalytic processes ever more pressing. In this context, characterizing catalyst particles in situ provides valuable information about the evolution of their composition, structure, oxidation state and charge state during an ongoing process. To disentangle the influence of individual parameters – temperature, pressure, gas composition, cluster size, as well as support acidity, redox state and defect density – it is crucial to control them precisely and separately in experiments. At the example of size-selected Pt n clusters – i.e. sub-nm particles defined to the exact number of atoms – on flat oxide supports, we follow their rich evolution phenomena via (synchrotron-based) X-ray photoelectron spectroscopy (XPS) and scanning tunnelling microscopy (STM) during temperature ramps and in various gas environments. Here, we present our experience with these highly defined, yet complicated-to-create samples in ultra-high vacuum (UHV) and at mbar pressures. We discuss their stability during transport to synchrotrons and under reaction conditions on three prototypical oxide supports and show the various phenomena that can be disentangled. Ptn clusters on the non-reducible silicon dioxide, SiO 2 , remain size-selected and show remarkable stability. Doping strongly influences the size-dependent binding energy shifts and changes the Pt response to oxidative and reaction conditions, which we attribute to different cluster geometries: p-type doping leads to wetting, enhanced sinter resistance and a diminished response to oxidative environments, compared to clusters on n-type doped samples. We compare the system with our previous findings of a similar change in dimensionality for Pt 20 clusters on the reducible ceria, CeO 2 (111), support, induced by modulation of its O vacancy density. The Pt n /CeO 2 system is particularly interesting for strategies to stabilize and redisperse Pt clusters dynamically. Finally, we study the evolution of Pt n clusters on another reducible oxide support, magnetite, Fe 3 O 4 (001), in 0.1 mbar alternating redox conditions at RT and elevated temperature. In analogy to findings previously reported for Pt/TiO 2 (110), the clusters either become encapsulated by a thin oxide film via strong metal–support interaction (SMSI) or deeply buried in the magnetite. Overall, our approach of following the evolution of size-selected clusters on oxide supports leads to fundamental atomic-scale insights on nano-scale catalyst materials, on our path to sustainable, dynamic and self-repairing catalysts.

Falling, Lorenz J. [Technical Univ. of Munich (Ger↗
DOE OSTI2025

In situ Gas Cell TEM Investigation of Nanoporous and Zeolite-based Nanocatalysts

A crucial application of in situ transmission electron microscopy is the understanding of nanocatalysts and the effect of the environment on their structure. Pre-treatments, such as calcination or annealing, can dramatically impact the catalytic properties by modifying the morphology and composition of nanostructures. Zeolites and nanoporous structures are particularly sensitive to reactive environments as the porosity or the chemical state can substantially change during the interaction with gases at elevated temperatures.[1] For instance, it has been shown that heating in air causes redispersion of sintered Cu clusters on zeolite, improving the catalytic properties.[2] These observations are possible though innovative in situ TEM gas holders, where the samples are enclosed into a small cell with SiNx windows, isolating the reactive environment from the rest of the column. [3] Here, we present in situ gas cell experiments of sensitive nanoporous structure and zeolite-based nanocatalysts. Scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy were used to understand migration of Al during calcination. In situ diagnostics also help distinguish Al as Bronsted sites, extra-framework Lewis sites, or bulk alumina. More broadly, in situ gas-heating TEM experiments are useful to determine chemical changes and modification of morphology of sensitive nanocatalysts upon pre-treatment (Figure 1).[4] Detailed in situ STEM and energy-dispersive X-ray spectroscopy (EDS) demonstrated compositional changes in nanoporous CuAlTi structures for hydrogen-deuterium exchange (H2-D2) reaction. Coarsening due to annealing at high temperature, a necessary steps for the preparation of catalysts, can be reversed by applying a redox cycle. Using the wide range of gases and temperature, the diagnostics are helpful to derive fundamental understanding of these catalysts at the atomic scale and also provide general guidelines to improve their design.

Foucher, Alexandre [ORNL] (ORCID:0000000150424002)↗
NASA NTRS2003

Flame Synthesis Of Single-Walled Carbon Nanotubes And Nanofibers

Carbon nanotubes are widely sought for a variety of applications including gas storage, intercalation media, catalyst support and composite reinforcing material [1]. Each of these applications will require large scale quantities of CNTs. A second consideration is that some of these applications may require redispersal of the collected CNTs and attachment to a support structure. If the CNTs could be synthesized directly upon the support to be used in the end application, a tremendous savings in post-synthesis processing could be realized. Therein we have pursued both aerosol and supported catalyst synthesis of CNTs. Given space limitations, only the aerosol portion of the work is outlined here though results from both thrusts will be presented during the talk. Aerosol methods of SWNT, MWNT or nanofiber synthesis hold promise of large-scale production to supply the tonnage quantities these applications will require. Aerosol methods may potentially permit control of the catalyst particle size, offer continuous processing, provide highest product purity and most importantly, are scaleable. Only via economy of scale will the cost of CNTs be sufficient to realize the large-scale structural and power applications on both earth and in space. Present aerosol methods for SWNT synthesis include laser ablation of composite metalgraphite targets or thermal decomposition/pyrolysis of a sublimed or vaporized organometallic [2]. Both approaches, conducted within a high temperature furnace, have produced single-walled nanotubes (SWNTs). The former method requires sophisticated hardware and is inherently limited by the energy deposition that can be realized using pulsed laser light. The latter method, using expensive organometallics is difficult to control for SWNT synthesis given a range of gasparticle mixing conditions along variable temperature gradients; multi-walled nanotubes (MWNTs) are a far more likely end products. Both approaches require large energy expenditures and produce CNTs at prohibitive costs, around $500 per gram. Moreover these approaches do not possess demonstrated scalability. In contrast to these approaches, flame synthesis can be a very energy efficient, low-cost process [3]; a portion of the fuel serves as the heating source while the remainder serves as reactant. Moreover, flame systems are geometrically versatile as illustrated by innumerable boiler and furnace designs. Addressing scalability, flame systems are commercially used for producing megatonnage quantities of carbon black [4]. Although it presents a complex chemically reacting flow, a flame also offers many variables for control, e.g. temperature, chemical environment and residence times [5]. Despite these advantages, there are challenges to scaling flame synthesis as well.

Wal, Randy L. Vander↗