Search NASA⌕ Search

SEARCH · Search NASA

Results for “catalyst efficiency”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Highly efficient Pt catalyst on newly designed CeO 2 -ZrO 2 -Al 2 O 3 support for catalytic removal of pollutants from vehicle exhaust

Pt-CeO 2 catalysts have been widely studied for the vehicle emission control. Designing novel CeO 2 based supports with improved physical-chemical properties has become a research hotspot to further promote the catalytic performance and stability of Pt-CeO 2 catalysts. In this work, through utilizing a unique, two-step incipient wetness impregnation (T-IWI) method for ceria-zirconia-alumina (CZA-T) support preparation, a Pt single site catalyst (Pt/CZA-T) with excellent thermal stability was synthesized. Higher oxidation activity and Oxygen storage capacity (OSC) were achieved on activated Pt/CZA-T, comparing to Pt catalysts on regular CeO 2 /Al 2 O 3 (Pt/CA) and one-step prepared CeZrO x /Al 2 O 3 (Pt/CZA). Via the modification of hydrophilic/hydrophobic properties of γ-Al 2 O 3 by this unique T-IWI method, finer Ce 0.9 Zr 0.1 O 2 particles with higher density of surface defects were formed on CZA-T, on which a higher Pt dispersion and stronger Pt-O-Ce interaction were achieved. Upon activation, smaller, well-dispersed Pt clusters on CZA-T were generated. It was concluded that the CO oxidation performance and OSC were highly related to the size of Pt clusters on different supports that we have developed. Finally, more Pt sites located at Pt cluster-CeZrO x interfaces, which were the real active sites, were responsible for the highest OSC function and CO oxidation activity of activated Pt/CZA-T catalyst.

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

Deactivation by Potassium Accumulation on a Pt/TiO 2 Bifunctional Catalyst for Biomass Catalytic Fast Pyrolysis

Biomass-derived feedstocks bring significant challenges to the longevity of the catalysts used for their conversion, and alkali metals, for example, K, in the feedstock have been widely ascribed as one of the important factors causing catalyst deactivation. To address this challenge, it is critical to understand the mechanism of catalyst deactivation caused by K accumulation to guide the improvement of catalysts and processes and the development of catalyst regeneration strategies. In this work, we report a deep understanding of the impact of K on a bifunctional Pt/TiO 2 catalyst, which is an efficient catalyst for the ex situ catalytic fast pyrolysis of biomass. We simulated the K-poisoning of Pt/TiO 2 catalysts by purposely loading different amounts of K (100-6000 ppm by weight) on the catalysts. A series of characterization approaches, including scanning transmission electron microscopy, Fourier transform infrared spectroscopy, and chemical titration, were combined with a kinetic assessment of multiple probe reactions to elucidate the mechanism of Pt/TiO 2 deactivation by K accumulation. At low K loadings (<800 ppm), K preferentially poisons the strong Lewis acid sites, leading to significantly reduced activity for acid-catalyzed alcohol dehydration. However, acetone condensation is less sensitive to the poisoning of strong Lewis acid sites. Reactions that occur on Pt sites or at the metal-support interface, including alkene hydrogenation, m-cresol hydrodeoxygenation (HDO), and CO oxidation, were not impacted. At high K loadings (>800 ppm), K starts to accumulate on the Pt-TiO 2 interfacial area, poisoning the interfacial active sites for HDO and CO oxidation reactions. We further found that the poisoning of the Pt/TiO 2 catalyst by K is reversible, and water washing can successfully remove the accumulated K and recover the activities for both alcohol dehydration and m-cresol HDO reactions.

09 BIOMASS FUELS↗
DOE OSTI2025

Discovering Ni/Cu Single-Atom Alloy as a Highly Active and Selective Catalyst for Direct Methane Conversion to Ethylene: A First-Principles Kinetic Study

Direct methane conversion to liquid fuels or value-added chemicals is a promising technology to utilize natural resources without resorting to further petroleum extraction. However, discovering efficient catalysts for this reaction is challenging due to either coke formation or unfavorable C-H bond activation. Herein, we design single-atom alloy (SAA) catalysts to simultaneously eliminate the above two bottlenecks based on mechanism-guided strategies: (1) the active single atom enables favorable C-H bond breaking and (2) the less reactive host metal facilitates C-C coupling and thus avoids strong binding of carbonaceous species. Employing electronic structure theory calculations, we screened the stability of multiple SAAs with 3d-5d transition metals atomically dispersed on a copper surface in terms of avoiding dopant aggregation and segregation. We then evaluated reactivities of the stable SAAs as catalysts for direct methane conversion to C2 products, including methane dehydrogenation and C-C coupling mechanisms. Combining selectivity analysis with kinetic modeling, we predicted that nickel dispersed on copper, i.e., Ni/Cu SAA, is a highly active and selective catalyst that can efficiently transform methane to ethylene. This work designs efficient SAA catalysts for direct methane activation and provides chemical insights into engineering compositions of SAAs to tune their catalytic performances.

Kothakonda, Manish↗
DOE OSTI2020

Engineering Catalysts for Selective Ester Hydrogenation

The development of efficient catalysts and processes for synthesizing functionalized (olefinic and/or chiral) primary alcohols and fluoral hemiacetals is currently needed. These are valuable building blocks for pharmaceuticals, agrochemicals, perfumes, and so forth. From an economic standpoint, bench-stable Takasago Int. Corp.’s Ru-PNP, more commonly known as Ru-MACHO, and Gusev’s Ru-SNS complexes are arguably the most appealing molecular catalysts to access primary alcohols from esters and H 2 . This work introduces economically competitive Ru-SNP(O) z complexes ( z = 0, 1), which combine key structural elements of both of these catalysts. In particular, the incorporation of SNP heteroatoms into the ligand skeleton was found to be crucial for the design of a more product-selective catalyst in the synthesis of fluoral hemiacetals under kinetically controlled conditions. Based on experimental observations and computational analysis, this paper further extends the current state-of-the-art understanding of the accelerative role of KO- t -C 4 H 9 in ester hydrogenation. Finally, it attempts to explain why a maximum turnover is seen to occur starting at ~25 mol % base, in contrast to only ~10 mol % with ketones as substrates.

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

Silica accelerates the selective hydrogenation of CO 2 to methanol on cobalt catalysts

The reaction pathways on supported catalysts can be tuned by optimizing the catalyst structures, which helps the development of efficient catalysts. Such design is particularly desired for CO 2 hydrogenation, which is characterized by complex pathways and multiple products. Here, we report an investigation of supported cobalt, which is known for its hydrocarbon production and ability to turn into a selective catalyst for methanol synthesis in CO 2 hydrogenation which exhibits good activity and stability. The crucial technique is to use the silica, acting as a support and ligand, to modify the cobalt species via Co-O-SiOn linkages, which favor the reactivity of spectroscopically identified *CH 3 O intermediates, that more readily undergo hydrogenation to methanol than the C-O dissociation associated with hydrocarbon formation. Cobalt catalysts in this class offer appealing opportunities for optimizing selectivity in CO 2 hydrogenation and producing high-grade methanol. By identifying this function of silica, we provide support for rationally controlling these reaction pathways.

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

Electrocatalytic Reductive Amination of Aldehydes and Ketones with Aqueous Nitrite

The electrocatalytic utilization of oxidized nitrogen waste for C–N coupling chemistry is an exciting research area with great potential to be adopted as a sustainable method for generation of organonitrogen molecules. The most widely used C–N coupling reaction is reductive amination. In this work, we develop an alternative electrochemical reductive amination reaction that can proceed in neutral aqueous electrolyte with nitrite as the nitrogenous reactant and via an oxime intermediate. We develop a selection criterion for nitrite reduction electrocatalysts suited for oxime electrosynthesis and, in doing so, find Pd to be a highly efficient catalyst for this reaction, reaching an oxime Faradaic efficiency of 82% at −0.21 V vs the reversible hydrogen electrode. The aliphatic or aromatic structure of the carbonyl reactant impacts the efficacy of the catalyst, with aromatic substrates leading to suppressed oxime formation and detrimental reduction of the carbonyl to the alcohol. We developed a Pb/PbO electrocatalyst that selectively performs oxime reduction in the neutral aqueous electrolyte. With acetone as a model substrate, we demonstrate an efficient one-pot, two-step electrochemical reaction for the conversion of acetone to isopropyl amine with 85% yield and 50% global Faradaic efficiency.

catalysts↗
NASA NTRS2016

Development of Advanced ISS-WPA Catalysts for Organic Oxidation at Reduced Pressure/Temperature

The Water Processor Assembly (WPA) at International Space Station (ISS) processes a waste stream via multi-filtration beds, where inorganic and non-volatile organic contaminants are removed, and a catalytic reactor, where low molecular weight organics not removed by the adsorption process are oxidized at elevated pressure in the presence of oxygen and elevated temperature above the normal water boiling point. Operation at an elevated pressure requires a more complex system design compared to a reactor that could operate at ambient pressure. However, catalysts currently available have insufficient activity to achieve complete oxidation of the organic load at a temperature less than the water boiling point and ambient pressure. Therefore, it is highly desirable to develop a more active and efficient catalyst at ambient pressure and a moderate temperature that is less than water boiling temperature. This paper describes our efforts in developing high efficiency water processing catalysts. Different catalyst support structures and coating metals were investigated in subscale reactors and results were compared against the flight WPA catalyst. Detailed improvements achieved on alternate metal catalysts at ambient pressure and 200 F will also be presented in the paper.

Yu, Ping↗
DOE OSTI2024

Mechanism-Guided Kinetic Analysis of Electrocatalytic Proton Reduction Mediated by a Cobalt Catalyst Bearing a Pendant Basic Site

Cobalt polypyridyl complexes stand out as efficient catalysts for electrochemical proton reduction, but investigations into their operating mechanisms, with broad-reaching implications in catalyst design, have been limited. Herein, we investigate the catalytic activity of a cobalt(II) polypyridyl complex bearing a pendant pyridyl base with a series of organic acids spanning 20 pKa units in acetonitrile. Structural analysis, as well as electrochemical studies, reveals that the Co(III) hydride intermediate is formed through reduction of the Co(II) catalyst followed by direct metal protonation in the initial EC step despite the presence of the pendant base, which is commonly thought of as a more kinetically accessible protonation site. Protonation of the pendant base occurs after the Co(III) hydride intermediate is further reduced in the overall ECEC pathway. Additionally, when the acid used is sufficiently strong, the Co(II) catalyst can be protonated, and the Co(III) hydride can react directly with acid to release H 2 . With thorough mechanistic understanding, the appropriate electroanalytical methods were identified to extract rate constants for the elementary steps over a range of conditions. Thermodynamic square schemes relating catalytic intermediates proposed in the three electrocatalytic HER mechanisms were constructed. Furthermore, these findings reveal a full description of the HER electrocatalysis mediated by this molecular system and provide insights into strategies to improve synthetic fuel-forming catalysts operative through metal hydride intermediates.

08 HYDROGEN↗
DOE OSTI2024

A Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO 2 hydrogenation to methanol

CO 2 hydrogenation to chemicals and fuels is a significant approach for achieving carbon neutrality. It is essential to rationally design the chemical structure and catalytic active sites towards the development of efficient catalysts. Here we show a Ce-CuZn catalyst with enriched Cu/Zn-OV-Ce active sites fabricated through the atomic-level substitution of Cu and Zn into Ce-MOF precursor. The Ce-CuZn catalyst exhibits a high methanol selectivity of 71.1% and a space-time yield of methanol up to 400.3 g·kg cat -1 ·h -1 with excellent stability for 170 h at 260°C, comparable to that of the state-of-the-art CuZnAl catalysts. Controlled experiments and DFT calculations confirm that the incorporation of Cu and Zn into CeO 2 with abundant oxygen vacancies can facilitate H 2 dissociation energetically and thus improve CO 2 hydrogenation over the Ce-CuZn catalyst via formate intermediates. This work offers an atomic-level design strategy for constructing efficient multi-metal catalysts for methanol synthesis through precise control of active sites.

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

Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

Abstract Although hexagonal boron nitride (h‐BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas‐phase methyl radicals (CH 3 . ) in the ODHP reaction over boron‐based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV‐PIMS), which uncovers the existence of gas‐phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C−H activation of propane, while C 2 and C 1 products can be formed via both surface‐mediated and gas‐phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron‐based catalysts.

Zhang, Xuanyu↗
DOE OSTI2020

Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

Although hexagonal boron nitride (h-BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas-phase methyl radicals (CH 3 . ) in the ODHP reaction over boron-based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV-PIMS), which uncovers the existence of gas-phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C-H activation of propane, while C 2 and C 1 products can be formed via both surface-mediated and gas-phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron-based catalysts.

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

Aqueous-Based Granulation Method Towards Syngas Production

An aqueous-based granulation method is developed to combat the structural changes associated with binder-based granulation techniques. Microwave-assisted methane reforming studies showed an improved catalyst efficiency for these aqueous-based granules compared to the powder catalysts. This granulation method has been extended to other practical applications (chemical looping gasification and air separations).

aqueous-based granulation↗
DOE OSTI2024

The role of manganese in CoMnO x catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis

Cobalt is an efficient catalyst for Fischer–Tropsch synthesis (FTS) of hydrocarbons from syngas (CO + H 2 ) with enhanced selectivity for long-chain hydrocarbons when promoted by Manganese. However, the molecular scale origin of the enhancement remains unclear. Here we present an experimental and theoretical study using model catalysts consisting of crystalline CoMnO x nanoparticles and thin films, where Co and Mn are mixed at the sub-nm scale. Employing TEM and in-situ X-ray spectroscopies (XRD, APXPS, and XAS), we determine the catalyst’s atomic structure, chemical state, reactive species, and their evolution under FTS conditions. We show the concentration of CH x , the key intermediates, increases rapidly on CoMnO x , while no increase occurs without Mn. DFT simulations reveal that basic O sites in CoMnO x bind hydrogen atoms resulting from H 2 dissociation on Co 0 sites, making them less available to react with CH x intermediates, thus hindering chain termination reactions, which promotes the formation of long-chain hydrocarbons.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Toward efficient single-atom catalysts for renewable fuels and chemicals production from biomass and CO 2

Transformation of biomass and CO 2 into renewable value-added chemicals and fuels has been identified as a promising strategy to fulfill high energy demands, lower greenhouse gas emissions, and exploit under-utilized resources. Cost-effective and performance-efficient catalysts are of great importance to lowering the conversion cost of biomass and CO 2 . Significant progress has been made to advance the catalyst design for these processes, with metal catalysts playing a critical role in many involved catalytic reactions. Traditional nanoparticle-based metal catalysts still require improvement in metal utilization rates, stability, and selectivity tunability. Single-atom catalysts, which have maximum atomic efficiency and a uniform and tunable metal center, as well as an adjustable metal-support interaction, provide potential opportunities to boost catalyst efficiency and thermal stability. Their well-defined and uniform structure also provides advantages to fundamental studies for understanding of the intrinsic reaction mechanism and site requirement in biomass and CO 2 conversion. In this article, we summarize and highlight the recent advances in converting biomass and CO 2 to renewable fuels and chemicals using single-atom catalysts. We discuss the design principles of single-atom catalysts and their potential applications to biomass and CO 2 upgrading as well as the origins of catalytic activity. Moreover, we compare the catalytic efficiency of various catalysts reported thus to provide a fair assessment of these catalysts. Finally, perspectives are given on the interesting fields that may guide future studies.

09 BIOMASS FUELS↗
DOE OSTI2021

Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst

Electrochemically converting nitrate, a widespread water pollutant, back to valuable ammonia is a green and delocalized route for ammonia synthesis, and can be an appealing and supplementary alternative to the Haber-Bosch process. However, as there are other nitrate reduction pathways present, selectively guiding the reaction pathway towards ammonia is currently challenged by the lack of efficient catalysts. Here we report a selective and active nitrate reduction to ammonia on Fe single atom catalyst, with a maximal ammonia Faradaic efficiency of ~ 75% and a yield rate of up to ~ 20,000 μg h –1 mg cat. –1 (0.46 mmol h –1 cm –2 ). Our Fe single atom catalyst can effectively prevent the N-N coupling step required for N 2 due to the lack of neighboring metal sites, promoting ammonia product selectivity. Density functional theory calculations reveal the reaction mechanisms and the potential limiting steps for nitrate reduction on atomically dispersed Fe sites.

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

Insights into Heterogeneous Catalysts under Reaction Conditions by In Situ/Operando Electron Microscopy

The advancement of clean energy and environment depends strongly on the development of efficient catalysts in a wide range of heterogeneous catalytic reactions, which has benefited from transmission electron microscopic techniques in determining the atomic-scale morphologies and structures. However, it is the morphology and structure under the catalytic reaction conditions that determine the performance of the catalyst, which has captured a surge of interest in developing and applying in situ/operando transmission electron microscopic techniques in heterogeneous catalysis. The major theme of this review is to highlight some of the most recent insights into heterogeneous catalysts under the relevant reaction conditions using in situ/operando transmission electron microscopic techniques. Rather than a comprehensive overview of the basic principles of in situ/operando techniques, this review focuses on the insights into the atomic-scale/nanoscale details of various catalysts ranging from single-component to multicomponent catalysts under heterogeneous catalytic, electrocatalytic, and photocatalytic reaction conditions involving both gas–solid and liquid–solid interfaces. Here, this focus is coupled with discussions of the correlation of the atomic, molecular, and nanoscale morphology, composition, and structure with the catalytic properties under the reaction conditions, shining light on the challenges and opportunities in design of nanostructured catalysts for clean and sustainable energy applications.

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

A measure of active interfaces in supported catalysts for high-temperature reactions

Formulating knowledge of structure-function relationships in heterogeneous catalysis is central to the design of efficient catalysts; yet, the elucidation of dominant reaction sites has remained as a challenge. Here, in this paper, we present a methodology that can be used to visualize metal-gas and metal-oxide-gas interfaces in three dimensions and to quantify their catalytic activity levels. As a case study, CH 4 oxidation occurring in a Pt/CeO 2 system is chosen. By employing thermally robust Pt@CeO 2 model catalysts with size-tunable and monodisperse cores, and gas-permeable shells, we reconstruct a series of structures in 3D via electron tomography and match the information to activity data and theoretical calculations. This strategy reveals that two different interfaces catalyze the CH 4 oxidation and that their contribution to the overall rate changes with the Pt size, temperature, and gas atmosphere. Our results provide an analytic platform on which to explore reaction pathways and mechanisms applicable to multiple reactions and materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗