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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Interfacial Unit-Dependent Catalytic Activity for CO Oxidation over Cerium Oxysulfate Cluster Assemblies

Atomically precise cerium oxo clusters offer a platform to investigate structure–property relationships that are much more complex in the ill-defined bulk material cerium dioxide. We investigated the activity of the MCe 70 torus family (M = Cd, Ce, Co, Cu, Fe, Ni, and Zn), a family of discrete oxysulfate-based Ce 70 rings linked by monomeric cation units, for CO oxidation. CuCe 70 emerged as the best performing MCe 70 catalyst among those tested, prompting our exploration of the role of the interfacial unit on catalytic activity. Temperature-programmed reduction (TPR) studies of the catalysts indicated a lower temperature reduction in CuCe 70 as compared to CeCe 70 . In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) indicated that CuCe 70 exhibited a faster formation of Ce 3+ and contained CO bridging sites absent in CeCe 70 . Isothermal CO adsorption measurements demonstrated a greater uptake of CO by CuCe 70 as compared to CeCe 70 . The calculated energies for the formation of a single oxygen defect in the structure significantly decreased with the presence of Cu at the linkage site as opposed to Ce. Furthermore, this study revealed that atomic-level changes in the interfacial unit can change the reducibility, CO binding/uptake, and oxygen vacancy defect formation energetics in the MCe 70 family to thus tune their catalytic activity.

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

Impacts of engine lubrication oil-derived ash on soot oxidative reactivity on a catalytic gasoline particulate filter

Characterizing soot oxidation kinetics is crucial for understanding how gasoline particulate filters (GPFs) perform both in terms of filtration efficiency and pressure drop. The most common method for measuring soot oxidative reactivity is thermogravimetric analysis (TGA). Because TGA is an offline method, it may inaccurately predict how soot oxidizes on a GPF, especially if a catalytic washcoat is present that may enhance oxidation rates through surface interactions as the soot loads on the filter. In this work, a novel in-situ soot oxidative reactivity measurement method was developed. The method involved loading a catalytic GPF under high temperature conditions conducive to soot oxidation and measuring the filtration efficiency of 100 nm particles. A correlation was made between filtration efficiency and loaded soot mass on the filter to allow calculation of the soot oxidation rate. The method was evaluated in experiments using a 2.0 L gasoline direct injection (GDI) engine with three oils of varying additive packages, including an oil with a high zinc dialkyldithiophosphate (ZDDP) concentration, a non-additive, pure poly-alpha olefin (PAO) oil, and an oil with a high concentration of calcium sulfonate. Calculated specific soot oxidation rates ranged from ~0.06–0.6 min –1 and showed strong dependence on GPF inlet gas temperature and lubrication oil additive type. The results clearly demonstrated a catalytic effect of calcium-containing ash particles. Reactivity of soot produced by the engine running with the high calcium containing lubrication oil was increased. Similarly, the results indicated that the catalytic washcoat on the filter increased soot oxidation rates on-filter, especially at low soot loading. Conversely, the ZDDP oil additive exhibited a reactivity inhibiting effect, resulting in lower soot oxidation rates. Finally, this work represents the first known in-situ soot oxidative reactivity measurements on a GPF and elucidates the effect of lubrication oil additives and catalytic washcoat on oxidation rate.

42 ENGINEERING↗
DOE OSTI2026

Evaluation of a catalytically aided thermal regeneration method for quartz filter-based black carbon sensing

Black carbon (BC)–a strong indicator of diesel particulate matter and other sources of incomplete carbonaceous fuel combustion–is an important air pollutant that affects public health, yet low-cost sensors capable of long-term, autonomous BC monitoring remain underdeveloped. We report on the development and evaluation of a novel BC prototype sensor that integrates soot collection on a quartz filter, in-situ optical transmission measurement, and thermal filter regeneration. To enable regeneration at lower temperatures, we evaluated the catalytic effects of various alkali metal salts pre-applied to the filter. Among these, cesium carbonate (Cs 2 CO 3 ) exhibited the strongest catalytic activity, lowering the temperature required for complete BC removal by up to 190 °C and reducing energy consumption by more than 75% compared to that required for untreated filters. The catalytic effect persisted through 10 BC collection–regeneration cycles. These findings demonstrate the potential of catalytically aided thermal regeneration in BC sensors and suggest a pathway toward energy-efficient and reduced maintenance air quality monitoring suitable for distributed BC monitoring networks.

Tang, Xiaochen [Lawrence Berkeley National Laborat↗
DOE OSTI2023

Microwave-enhanced methane cracking for clean hydrogen production in shale rocks

Here, steam methane reforming (SMR) generates about 95% of hydrogen (H 2 ) in the U.S. using natural gas as a main feedstock. However, this technology also generates a large amount of carbon dioxide (CO 2 ), a major greenhouse gas causing global warming. Carbon capture and storage (CCS) technique is required, but the cost and safety of storing CO 2 underground are a concern. Here we propose a new approach using microwave/electromagnetic irradiation to produce clean hydrogen from unrecovered hydrocarbons within petroleum reservoirs. Solid carbon or CO 2 produced during this process will be simultaneously sequestrated underground without involving CCS. In this paper, we perform a series of experiments to investigate the in-situ hydrogen production from shale gas (methane) conversion by passing a methane stream through a packed shale rock sample heated by microwave. We found that methane conversion was significantly enhanced in the presence of Fe and Fe 3 O 4 particles as catalysts, with a conversion of 40.5% and 100% at reaction temperature of 500 °C and 600 °C, respectively. Methane conversion is promoted at a lower reaction temperature by the catalytic effect of minerals in shale. Additionally, the influences of catalysts, shale rock, and methane flow rate are characterized.

08 HYDROGEN↗
DOE OSTI2021

Submonolayer Is Enough: Switching Reaction Channels on Pt/SiO 2 by Atomic Layer Deposition

The reaction mechanism of CO 2 with H 2 is studied on platinum nanoparticles supported on fumed silica. It is found that platinum nanoparticle size, reaction temperature, and metal oxide promoters play important roles in determining the reaction rate and the mechanism of forming surface carbonyl species. Metal oxide promoters consist of sub-monolayer titanium oxide or aluminum oxide overcoated onto the catalysts by atomic layer deposition (ALD). Furthermore, these alter the CO formation rate, influence the adsorption and desorption behavior, and switch the surface reaction channel from Eley-Rideal to Langmuir-Hinshelwood mechanism due to an enhancement of CO 2 affinity to the metal-metal oxide interface. At the temperatures relevant for catalytic turnover, ALD overcoating significantly increases catalytic activity in CO 2 hydrogenation to CH 4 and CO, while the identity of the oxide overcoat helps control product selectivity.

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

Structural and Chemical Evolution of an Inverse CeO x /Cu Catalyst under CO 2 Hydrogenation: Tunning Oxide Morphology to Improve Activity and Selectivity

Small nanoparticles of ceria deposited on a powder of CuO display a very high selectivity for the production of methanol via CO 2 hydrogenation. CeO 2 /CuO catalysts with ceria loadings of 5%, 20%, and 50% were investigated. Among these, the system with 5% CeO x showed the best catalytic performance at temperatures between 200 and 350 °C. The evolution of this system under reaction conditions was studied using a combination of environmental transmission electron microscopy (E-TEM), in situ X-ray absorption spectroscopy (XAS), and time-resolved X-ray diffraction (TR-XRD). For 5% CeO x /Cu, the in situ studies pointed to a full conversion of CuO into metallic copper, with a complete transformation of Ce 4+ into Ce 3+ . Images from E-TEM showed drastic changes in the morphology of the catalyst when it was exposed to H 2 , CO 2 , and CO 2 /H 2 mixtures. Under a CO 2 /H 2 feed, there was a redispersion of the ceria particles that was detected by E-TEM and in situ TR-XRD. Finally, these morphological changes were made possible by the inverse oxide/metal configuration and facilitate the binding and selective conversion of CO 2 to methanol.

03 NATURAL GAS↗
DOE OSTI2024

Synthesizing Highly Crystalline Graphite Powder from Bulk Polyethylene Waste for Lithium-Ion Battery Anodes

Upcycling plastic waste into graphite can potentially be used, in conjunction with other methods, to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing, and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create a stable carbon char that does not readily decompose during high-temperature processing. This method employs solid additives in the form of salts, which are combined with the PE melt during air processing to increase the effective surface area of the melt and improve the oxygen-driven chemistry that stabilizes the PE for high-temperature processing. After removing the solid salt additives from the PE-derived char, it is converted into a highly crystalline bulk graphite powder using a Fe-based low-temperature (<1500 °C) catalytic process. The PE-derived graphite powder showed excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs) with a capacity of up to 302 mAh/g at 0.5 discharge/charge cycles per hour (0.5 C) and capacity retention of 100% after 415 cycles.

Huynh, Ngoc Tien↗
DOE OSTI2024

Synthesizing Highly Crystalline Graphite Powder from Bulk Polyethylene Waste for Lithium-Ion Battery Anodes

Upcycling plastic waste into graphite can potentially be used, in conjunction with other methods, to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing, and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create a stable carbon char that does not readily decompose during high-temperature processing. This method employs solid additives in the form of salts, which are combined with the PE melt during air processing to increase the effective surface area of the melt and improve the oxygen-driven chemistry that stabilizes the PE for high-temperature processing. After removing the solid salt additives from the PE-derived char, it is converted into a highly crystalline bulk graphite powder using a Fe-based low-temperature (<1500 °C) catalytic process. The PE-derived graphite powder showed excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs) with a capacity of up to 302 mAh/g at 0.5 discharge/charge cycles per hour (0.5 C) and capacity retention of 100% after 415 cycles. This method illustrates there are opportunities for upcycling large quantities of PE waste to produce graphite powders.

Huynh, Ngoc Tien [NETL Site Support Contractor, Na↗
DOE OSTI2024

Hydrothermally and thermally stable catalytic materials based on theta-alumina

A material and a method of making hydrothermally stable (catalytic) materials on the basis of theta-alumina support that is thermally and hydrothermally stable up to 1,150 C with metal, mixed metal-, metal-oxide nanoparticles dispersed upon it. Such materials did not lose significant amounts of their catalytic activity at temperature ranges for industrially relevant applications (including hydrocarbon oxidation, nitric oxide reduction, carbon monoxide oxidation) even after hydrothermal aging up to 1,150° C.

Khivantsev, Konstantin↗
DOE OSTI2023

Modeling plasma-induced surface charge effects on CO 2 activation by single atom catalysts supported on reducible and irreducible metal oxides

Abstract The accumulation of negative surface charge on catalytic surfaces in the presence of low-temperature plasma (LTP) could influence catalytic performance. However, it is difficult to disentangle the role of surface charging and other LTP catalytic effects in experiment. Herein, we use density functional theory (DFT) modeling to understand the effect of plasma-induced surface charging on CO 2 activation by atomically dispersed single atom (SA) catalysts on both reducible and irreducible metal oxide supports. We model CO 2 adsorption strength and CO 2 dissociation barriers for Co 1 , Ni 1 , Cu 1 , Rh 1 , Pd 1 , and Ag 1 SAs on both reducible and irreducible supports, namely, CeO 2 (100), TiO 2 (101), and γ -Al 2 O 3 (110), to elucidate trends. We find that accumulated surface charge on the SA increases the CO 2 adsorption strength and decreases the CO 2 dissociation barrier for all studied SA/support combinations. For both charged and uncharged (neutral) systems, SAs on the reducible CeO 2 (100) support generally adsorb CO 2 more weakly compared to when on irreducible supports like γ -Al 2 O 3 (110). SAs on γ -Al 2 O 3 (110) typically have larger barriers for CO 2 dissociation for both charged and uncharged systems compared to TiO 2 (101) and CeO 2 (100). The magnitude of surface charging effects on CO 2 binding energies and dissociation barriers depends sensitively on both the SA and the support. In some cases, the CO 2 activation trends qualitatively change between neutral and charged systems for a fixed SA across different supports. This DFT modeling study demonstrates that surface charging should be considered in strong electric fields because it can have a large effect on molecule adsorption and bond-breaking on catalytic surfaces.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Selective catalytic reduction of NOx with NH 3 over Ce-Mn oxide and Cu-SSZ-13 composite catalysts – Low temperature enhancement

A composite catalyst comprised of ceria-manganese oxide and Cu-SSZ-13 components represents a potential solution for improving selective catalytic reduction (SCR) of NOx by ammonia. Here, clarity is provided to the pathway of promotion on these catalysts at low temperatures (< 200 °C), and it is shown that improved performance comes solely from interaction of the oxide phase with Brønsted acid bound NH 3 . We demonstrate that at low temperatures, the catalytic components interact via oxide-derived nitrites/nitrite-precursors (e.g., HONO, N 2 O 3 ) reacting with Brønsted acid bound NH3 from the zeolite. Then, only at elevated temperatures is the influence of the oxide phase on Cu redox in the Cu-SSZ-13 observed. Furthermore, we show how the oxide component has the great potential to circumvent NH 4 NO 3 inhibition on Cu-SSZ-13 in the composite catalysts at low temperatures by bypassing the formation of nitrates from NO 2 disproportionation, thus providing a practical solution to improving low temperature SCR reactivity.

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

Lithium cuprate, a multifunctional material for NO selective catalytic reduction by CO with subsequent carbon oxide capture at moderate temperatures

Li 2 CuO 2 was evaluated as a possible catalyst for the NO selective catalytic reduction (NO SCR) by CO. The initial idea was supported by ab initio thermodynamic analysis. This analysis showed that NO SCR was favored by using Li 2 CuO 2 as a catalyst, based on the calculated heat of reaction and Gibbs free energy. The NO SCR reaction was evaluated under dynamic, isothermal and cyclic conditions using different NO : CO ratios (2 : 1, 1 : 1 and 1 : 2). The dynamic and isothermal experiments showed that Li 2 CuO 2 does reduce NO in the presence of CO to reach higher conversions (>90%) between 400 and 450 °C. However, it must be mentioned that the catalytic process was reduced once some of the produced CO 2 was captured on the ceramic. At that point, Li 2 CuO 2 acts as a bifunctional material, catalyzing the NO SCR reaction and capturing some of the produced CO 2 . Moreover, cyclic experiments evidenced high NO reduction. Finally, a different set of experiments showed that this catalytic reduction performed differently if NO and CO were previously fed. Finally, when lithium cuprate is previously carbonated (initial CO feed), the catalytic reaction does not complete. In contrast, when there was a previous nitrate formation (initial NO feed), the reaction reached 100% efficiency.

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

Facilitating Hydrogen Dissociation over Dilute Nanoporous Ti–Cu Catalysts

The dissociation of H 2 is an essential elementary step in many industrial chemical transformations, typically requiring precious metals. Here, we report a hierarchical nanoporous Cu catalyst doped with small amounts of Ti (npTiCu) that increases the rate of H 2 –D 2 exchange by approximately one order of magnitude compared to the undoped nanoporous Cu (npCu) catalyst. The promotional effect of Ti was measured via steady-state H 2 –D 2 exchange reaction experiments under atmospheric pressure flow conditions in the temperature range of 300–573 K. Pretreatment with flowing H 2 is required for stable catalytic performance, and two temperatures, 523 and 673 K, were investigated. The experimentally determined H 2 –D 2 exchange rate is 5–7 times greater for npTiCu vs the undoped Cu material under optimized pretreatment and reaction temperatures. The H 2 pretreatment leads to full reduction of Cu oxide and partial reduction of surface Ti oxide species present in the as-prepared catalyst as demonstrated using in situ ambient pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. The apparent activation energies and pre-exponential factors measured for H 2 –D 2 exchange are substantially different for Ti-doped vs undoped npCu catalysts. Density functional theory calculations suggest that isolated, metallic Ti atoms on the surface of the Cu host can act as the active surface sites for hydrogen recombination. Furthermore, the increase in the rate of exchange above that of pure Cu is caused primarily by a shift in the rate-determining step from dissociative adsorption on Cu to H/D atom recombination on Ti-doped Cu, with the corresponding decrease in activation entropy that it produces.

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

Pressure Driven Alkane Dehydrogenation by Palladium Metal

Abstract Dehydrogenation of alkanes is of increasing importance in fulfilling global demand for olefins and offers a potential source of carbon‐neutral hydrogen as a co‐product. Currently commercial dehydrogenation processes occur at high‐temperatures (500–900 °C) which is energy intensive and results in side reactions and rapid coking of the catalysts. In addition, the hydrogen produced is often burned to maintain temperature and to inhibit the back reaction. Here, pressure is utilized as a parameter to enable novel chemical catalytic processes, and ambient‐temperature dehydrogenation of alkanes by palladium is observed at 50–100 MPa, with both hydrogen gas and olefins recovered on decompression. This reaction follows a fundamentally different path to current commercial high‐temperature low‐pressure dehydrogenation processes with the palladium catalyst reversibly forming a hydride intermediate.

08 HYDROGEN↗
DOE OSTI2020

Structural Rearrangements of Subnanometer Cu Oxide Clusters Govern Catalytic Oxidation

Sub-nanometer metal oxide clusters are very important materials that are widely used, for example, in catalysis or electronic devices such as sensors. Hence, it is critical to understand the atomic structures and properties of sub-nanometer metal oxide clusters under a reactive gas environment, such as O 2 . We consider here experimentally accessible precise-size Cu clusters (Cu 4 ) supported on partially hydroxylated amorphous alumina and show that such clusters can access, in catalytic conditions at high temperature under a pressure of O 2 , a large ensemble of oxidized structures, representing a large variety of oxygen content, of geometries in link with the support, and of catalytic activities for oxidation reactions, as seen from their reducibilities. A grand canonical basin hopping method based on first-principles energy reveals an ensemble of 24 configurations for the Cu 4 O x cluster of low free energy, less than 0.8 eV above the global minimum. The low free energy ensemble consists of clusters of different stoichiometries, which are mainly Cu 4 O 3 and Cu 4 O 4 in the temperature range of 200–400 °C and under a pressure of 0.5 bar of O 2 . The presence of several competitive isomers at each composition implies that cluster fluxionality impacts the phase diagram, which should be ensemble-averaged. In terms of catalytic oxidation activity, Cu 4 O 3 isomers present highly variable O abstraction energy: the most stable isomers are inactive for alkane oxidative dehydrogenation, but isomerization to metastable isomers, that proceed with low barrier, enable to create active configurations with low O abstraction energy. O atoms with the lowest anionic character, and thus of more electrophilic nature, present the best oxidation capability. In contrast, all Cu 4 O 4 isomers show a low O abstraction energy and a high potential catalytic activity. Here, this manuscript demonstrates the unique structural and electronic properties of sub-nano Cu oxide clusters and illustrates the critical roles of configuration ensembles and rearrangement to highly reactive metastable cluster isomers in nanocatalysis.

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

Bioinspired Catalyst Design Principles: Progress in Emulating Properties of Enzymes in Synthetic Catalysts

Catalysis enables many aspects of modern life, including fuels, products, plastics, and medicines. Recent advances in catalysis have enabled us to realize higher efficiencies and new processes. Ideally, we seek to achieve high rates of selective conversions using catalysts derived from abundantly available elements and operating under mild conditions, specifically lower reaction temperatures and pressures. Such catalysts could enable decentralized, on-demand synthesis of chemicals and energy carriers. Nature has demonstrated the feasibility of this approach with enzymes, which showcase catalytic processes at low temperatures and pressures with nonprecious metals. Current thinking holds that in addition to the active site, the complexity of the enzyme structure, specifically the protein scaffold, is also critical to achieving this performance. Recreating this environment has been a long-standing scientific goal. However, we still understand the functions of enzymes better than we understand the de novo design of catalysts that mimic enzymes features, while also retaining their activity and selectivity under more demanding conditions. Here, in this Perspective, we will critically examine four key areas of catalyst design that incorporate the chemical and structural properties of enzymes into synthetic catalysts: (i) the use of confinement to enhance catalytic activity, (ii) tailoring the environment around the active site, (iii) proton transport, and (iv) bifunctionality and cooperativity.

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

Stress-Alteration Enhancement of the Reactivity of Aluminum Nanoparticles in the Catalytic Decomposition of exo -Tetrahydrodicyclopentadiene (JP-10)

High energy density aluminum nanoparticles (AlNP) upon thermal annealing followed by super-quenching results in elevated stress levels in the metallic core and reduced surface energy at the core-shell interface. Isomer-selective vacuum ultraviolet based photoionization mass spectrometry coupled to a high temperature chemical microreactor reveals that these stress-altered (SA) AlNPs exhibit distinctive temperature-dependent reactivities towards catalytic decomposition of the hydrocarbon jet fuel exo-tetrahydrodicyclopentadiene (JP-10, C 10 H 16 ) compared to untreated (UN) AlNPs. SA-AlNPs show a delayed initiation of the decomposition for JP-10 by 200 K relative to the UN-AlNPs, however, the full decomposition is achieved at 100 K lower temperature. Furthermore, there is less oxygenated products that are generated from the alumina surface-induced heterogeneous oxidation process, and a larger fraction of closed and open-shell hydrocarbons. Furthermore, chemical insight bridging the reactivity order of SA-AlNPs at low and high temperatures, simultaneously, is obtained via a detailed examination of the product branching ratios obtained in this study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗