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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Numerical Investigation of Susceptor-Catalyst Design for Ethylene Generation in Radio Frequency Based Reactors

Ethylene is the most widely produced petrochemical component in the world. Whether reactors are heated directly or indirectly via steam, manufacturers use economies of scale to overcome inherent thermodynamic inefficiencies when burning fossil fuels. While allowing large-scale operations to use alternative sources of energy and raw materials, new methods of supplying energy to chemical reactor systems can reduce the energy waste produced by conventional processes. One viable method for effectively supplying energy to reactor systems is electromagnetic (EM) induction heating. Using the properties of radio frequency (RF) waves, heterogeneous catalysts can be precisely targeted for heating inside reactors. Site-selective heating can greatly lower the energy requirements of the process by supplying heat to reaction sites while reducing needless heat transfer elsewhere. In this study, a microscale model was used to help create guidelines for susceptors and catalysts to improve ethylene production. The oxidative dehydrogenation of ethane is investigated by utilizing several catalysts and potential catalyst/susceptor combinations, with heat provided by an EM susceptor. Having the susceptors and catalyst function separately results in higher gradients in both heat and mass transfer, which drives transport through the catalyst region, while still providing adequate heating for endothermic reactions. However, using a susceptive core with a catalyst covering produces the maximum ethylene concentration.

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

Direct Observation of Hydroxyls Formed from Water and Oxygen on Ag(100)

The interaction of oxygen with silver is a key descriptor of the catalytic reactivity of silver nanoparticles which are ubiquitous in large-scale partial oxidation reactions like ethylene epoxidation. Despite Ag(100) being proposed as the most selective facet, it is less studied than (111) and (110) surfaces. Using scanning tunneling microscopy and synchrotron X-ray photoelectron spectroscopy, we report that, in addition to the well-known O adatoms formed from O 2 dissociation on Ag(100), hydroxyl groups (OH), at a binding energy of ∼ 531 eV, are also present. The O/OH ratio depends on exposure to water and surface temperature. These assignments are consistent with our density functional theory calculations, which indicate that the formation of two OH groups from an O atom and H 2 O molecule is exothermic. These results indicate that, in addition to O, OH is present even under ultrahigh vacuum conditions and therefore should be considered in proposed catalytic pathways.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Spectroscopic Probe Molecule Selection Using Quantum Theory, First-Principles Calculations, and Machine Learning

Probe molecule vibrational spectra have a long history of being used to characterize materials including metals, oxides, metal-organic frameworks, and even human proteins. Furthermore, recent advances in machine learning have enabled computationally generated spectra to aid in detailed characterization of complex surfaces with probe molecules. Despite widespread use of probe molecules, the science of probe molecule selection is underdeveloped. Here, we develop physical concepts, including orbital interaction energy and the energy overlap integral, to explain and predict the ability of probe molecules to discriminate structural descriptors. We resolve the crystal orbital overlap population (COOP) to specific molecular orbitals and quantify their bonding character, which directly influences vibrational frequencies. Using only a single adsorbate calculation from density function theory (DFT), we compute the interaction energy of individual adsorbate molecular orbitals with adsorption site atomic orbitals across many different sites. Combining the molecular orbital resolved COOP and changes in orbital interaction energy enables probe molecule selection for improved discrimination of various sites. We demonstrate these concepts by comparing the predicted effectiveness of carbon monoxide (CO), nitric oxide (NO), and ethylene (C 2 H 4 ) to probe Pt adsorption sites. Finally, using a previously developed machine learning framework, we show that models trained on hundreds of thousand C 2 H 4 spectra, computed from DFT, which regress surface binding-type and generalized coordination number (GCN), outperform those trained using CO and NO spectra. Lastly, a python package, pDOS_overlap, for implementing the electron density based analysis on any combination of adsorbates and materials, is also made available.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Recent Advances in the Understanding of Boron-Containing Catalysts for the Selective Oxidation of Alkanes to Olefins

The production of ethylene and propylene through aerobic alkane oxidation without significant coproduction of CO and CO 2 (CO x ) presents a challenge to academic and industrial researchers alike. Recently, boron-containing materials such as hexagonal boron nitride (hBN) have been identified as active and selective catalysts for the oxidative dehydrogenation (ODH) of propane to propylene with minimal CO x selectivity. Additionally, high olefin selectivity is also obtained in the oxidation of other alkanes and other materials such as metal borides and supported B/SiO 2 have been successfully applied to this transformation. Here, recent advances in the understanding of these catalysts in the oxidation of light alkanes are presented here providing a framework for further study of this exciting field.

03 NATURAL GAS↗
DOE OSTI2023

Numerical modeling of chemical looping oxidative dehydrogenation of ethane in parallel packed beds

Chemical looping oxidative dehydrogenation (CL-ODH) of ethane has the potential to be a highly efficient alternative to steam cracking for ethylene production. Accurate reactor modeling is of critical importance to efficiently scale up and optimize this new technology. This study reports a one-dimensional, heterogeneous packed bed model to simulate the CL-ODH of ethane to ethylene with a Na 2 MoO 4 -promoted CaTi 0.1 Mn 0.9 O 3 redox catalyst. Here, the overall reaction kinetics was well-described by coupling the gas-phase steam cracking of ethane with the reduction kinetics of the redox catalyst by H 2 and C 2 H 4 . The impact of H 2 on the formation rate of CO 2 byproduct from C 2 H 4 conversion was also thoroughly investigated to validate the applicability of the kinetic model under operational environments. The temperature variation within the different CL-ODH steps and the temperature distribution along the bed were also carefully considered. The accuracy of the model was validated by experiments conducted in a large lab-scale packed bed reactor (200 g catalyst loading), with an average deviation of 2.8% in terms of ethane conversion and ethylene yield. The model was subsequently used to optimize the operating parameters of the CL-ODH reactor, indicating that up to 63.7% single-pass C 2 +olefin yield can be achieved with the current redox catalyst bed whereas further optimization of the redox catalyst to inhibit C 2 H 4 activation can result in 69.4% single-pass C 2 +yield while maintaining low CO 2 selectivity.

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

Automated descriptor selection, volcano curve generation, and active site determination using the DescMAP software

The material space for catalyst discovery is expansive. Volcano curves are traditionally employed to provide physical insights into optimal catalyst characteristics for new material selection. Their generation lies on a single descriptor picked using expert knowledge. Here we present DescMAP, a Python-based software, to automate the selection of descriptors, the generation of volcano maps, and the identification of active sites for structure-sensitive reactions. Here, we consider traditional energy-based and geometric descriptors for structure-sensitive reactions. DescMAP is integrated with the Virtual Kinetic Laboratory (VLab) to provide multiple functionalities. It inputs spreadsheets or template files for flexibility and outputs interactive graphs for post-processing. We demonstrate its features using the non-oxidative dehydrogenation of ethane to ethylene over (111) closed-packed surfaces and the methane total oxidation over various Pt facets. It can be easily applied to other complex chemistries and achieves quick screening of potential catalysts.

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

Corrosion Engineering of Part‐Per‐Million Single Atom Pt 1 /Ni(OH) 2 Electrocatalyst for PET Upcycling at Ampere‐Level Current Density

The plastic waste issue has posed a series of formidable challenges for the ecological environment and human health. While conventional recycling strategies often lead to plastic down-cycling, the electrochemical strategy of recovering valuable monomers enables an ideal, circular plastic economy. Here a corrosion synthesized single atom Pt 1 /Ni(OH) 2 electrocatalyst with part-per-million noble Pt loading for highly efficient and selective upcycling of polyethylene terephthalate (PET) into valuable chemicals (potassium diformate and terephthalic acid) and green hydrogen is reported. Electro-oxidation of PET hydrolysate, ethylene glycol (EG), to formate is processed with high Faraday efficiency (FE) and selectivity (>90%) at the current density close to 1000 mA cm −2 (1.444 V vs RHE). The in situ spectroscopy and density functional theory calculations provide insights into the mechanism and the understanding of the high efficiency. Remarkably, the electro-oxidation of EG at the ampere-level current density is also successfully illustrated by using a membrane-electrode assembly with high FEs to formate integrated with hydrogen production for 500 h of continuous operation. In conclusion, this process allows valuable chemical production at high space-time yield and is highly profitable (588–700 $\$$ ton −1 PET), showing an industrial perspective on single-atom catalysis of electrochemical plastic upcycling.

36 MATERIALS SCIENCE↗
DOE OSTI2025

CO Adsorbates Induced Framework-Associated Low-Valence Co δ+ Sites in Co-ZSM-5 for Ethane Dehydrogenation

The dynamic structural evolution of heterogeneous catalysts is a ubiquitous phenomenon that has attracted a lot of interest. Catalyst reconstruction can occur after appropriate pretreatment, resulting in more efficient active catalysts, which is an attractive but challenging issue. Here, we reveal a CO activation strategy that controls the microenvironment of the Co sites in the high-silica Co-ZSM-5 catalyst (denoted as 0.50Co-Z5(340)), resulting in three times higher initial conversion and superior regeneration durability in the ethane dehydrogenation reaction compared to the same catalyst without CO pretreatment. In situ spectroscopy and metadynamics simulations reveal that the Co 2+ sites in 0.50Co-Z5(340) dislodge from the framework and move toward the nearby Brønsted acid sites, forming framework-associated low-valence Co δ+ species. Mechanistic studies indicate that the Co δ+ species catalyze ethane C–H bond cleavage via an oxidative addition mechanism, and ethylene is produced simultaneously with H* coupling (direct pathway). The promoted C–H bond activation and facile ethylene desorption explain the superior ethane dehydrogenation performance of the herein CO preactivated 0.50Co-Z5(340) catalyst.

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

Process for converting alkanes to olefins

A process and apparatus for converting an alkane to an olefin. In one embodiment, the process involves oxidative coupling of an alkane, e.g., methane, with an oxidant, such as air, to produce an olefin having twice the number of carbon atoms as the alkane, e.g., ethylene. In another embodiment, the process involves oxidative dehydrogenation of an alkane, e.g., ethane, with an oxidant to form an olefin having the same number of carbon atoms as the alkane, e.g., ethylene. The process involves passing a flow of the oxidant from a first flow passage through a porous medium; diffusing a flow of the alkane from a second flow passage into the porous medium; and contacting the reactant alkane and the oxidant in the presence of a catalyst within the porous medium to produce the olefin.

Weissman, Jeffrey G.↗
DOE OSTI2022

Process for converting alkanes to olefins

A process and apparatus for converting an alkane to an olefin. In one embodiment, the process involves oxidative coupling of an alkane, e.g., methane, with an oxidant, such as air, to produce an olefin having twice the number of carbon atoms as the alkane, e.g., ethylene. In another embodiment, the process involves oxidative dehydrogenation of an alkane, e.g., ethane, with an oxidant to form an olefin having the same number of carbon atoms as the alkane, e.g., ethylene. The process involves passing a flow of the oxidant from a first flow passage through a porous medium; diffusing a flow of the alkane from a second flow passage into the porous medium; and contacting the reactant alkane and the oxidant in the presence of a catalyst within the porous medium to produce the olefin.

Weissman, Jeffrey↗
DOE OSTI2025

Rhodium‐Catalyzed Oxidative Alkenylation of Naphthalene: Factors That Influence Reaction at the β‐ versus α‐Position

The catalyst precursor [(η 2 -C 2 H 4 ) 2 Rh(μ-OAc)] 2 and in situ oxidant Cu(OPiv) 2 (OPiv = t-BuCOO – ) convert naphthalene and olefins (i.e., ethylene and propylene) to alkenylnaphthalenes. Under all reaction conditions tested, the functionalization is selective for the β-position of naphthalene with the highest observed β:α ratio >20:1. The β-selectivity is catalyst controlled, but oxidant identity, ethylene pressure, and olefin identity influence the ratio of β-alkenylation to α-alkenylation. The concentration of HOPiv and naphthalene do not have an effect on the β:α ratio under the reaction conditions tested. Arenes similar to naphthalene (i.e., o-xylene and 1,2,3,4-tetrahydronaphthalene) give quantitative selectivity for alkenylation at the position β to the substituent. Using propylene as the olefin for naphthalene alkenylation, the β:α ratio is 32(7):1. and the anti-Markovnikov to Markovnikov ratio is 16(2):1.

Alkenes↗
DOE OSTI2022

CaMn 0.9 Ti 0.1 O 3 based redox catalysts for chemical looping – Oxidative dehydrogenation of ethane: Effects of Na 2 MoO 4 promoter and degree of reduction on the reaction kinetics

Reduction kinetics and stability of 20 wt% Na 2 MoO 4 -promoted CaMn 0.9 Ti 0.1 O 3 were investigated for its applications in Chemical Looping – Oxidative Dehydrogenation (CL-ODH) of ethane, a potential alternative for ethylene production with higher efficiency and lower emissions. Here, the present work reports a kinetics model and parameters for a Na 2 MoO 4 -promoted, Ti-doped CaMnO 3 (CaMn 0.9 Ti 0.1 O 3 ) redox catalyst under H 2 and C 2 H 4 . A first-order reaction model provides the best fit for the reduction of Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 under H 2 , while the C 2 H 4 reduction is well described by an Avrami–Erofe’ev model. The activation energy for C 2 H 4 oxidation is approximately three times higher than that for H 2 conversion, showing that the activation of C 2 H 4 is significantly more difficult on the surface of the redox catalyst. The reduction rate of Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 under H 2 at 750 °C is more than two orders of magnitude greater than that under C 2 H 4 , while the reduction rate of unpromoted CaMn 0.9 Ti 0.1 O 3 is comparable under H 2 and C 2 H 4 , showing that the addition of Na 2 MoO 4 effectively suppresses C 2 H 4 combustion relative to H 2 oxidation. The kinetics results for Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 confirm its excellent selectivity towards hydrogen combustion, making it a promising candidate under CL-ODH. Additionally, the stability of the CaMn 0.9 Ti 0.1 O 3 @ Na 2 MoO 4 core-shell structure, which was the underlying reason for the excellent selectivity, was examined under both shallow and deep reductions. It was determined that deep reduction of the redox catalyst, e.g. higher than 80% solid conversion, would lead to loss of sodium and hence to decreased selectivity for hydrogen combustion. In contrast, the core-shell structure was well-maintained, exhibiting excellent performance after 50 redox cycles when deep reduction of the redox catalyst was avoided. This study offers a basis for both the CL-ODH reactor design and redox catalyst optimizations.

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

Modified Energy Span Analysis of Catalytic Parallel Pathways and Selectivity

Mechanistic modeling provides vital insights into catalytic reactions. To analyze complex reaction networks with parallel pathways, we leverage the graph theory approach of the Energy Span Model (ESM) to develop a modified energy span analysis (MESA). A new method of cycle plots is proposed to perform reaction pathways analysis visually. We demonstrate this method on two published models: one describing carbon monoxide oxidation and the other simulating ethylene conversion to propanal via hydroformylation or ethane via hydrogenation. Fundamental insights explain kinetic observables, such as a reactant’s negative reaction order. General principles are revealed, such as rate-determining surface species being outside the primary reaction flux cycle and pathway selectivity being a purely kinetic property when reaction conditions are not near equilibrium. Lastly, we demonstrate MESA’s consistency with published microkinetic modeling results, highlighting this technique’s extension of the ESM to heterogeneous catalysts using collision theory to describe adsorption steps and concentration effects.

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

Synthesis of Pt 3 Zn 1 and Pt 1 Zn 1 intermetallic nanocatalysts for dehydrogenation of ethane

Pt 3 Zn 1 and Pt 1 Zn 1 intermetallic nanoparticles supported on SiO 2 were synthesized by combining atomic layer deposition (ALD) of ZnO, incipient wetness impregnation (IWI) of Pt, and appropriate hydrogen reduction. Here, the formation of Pt 1 Zn 1 and Pt 3 Zn 1 intermetallic nanoparticles was observed by both X-ray diffraction (XRD) and synchrotron X-ray absorption spectroscopy (XAS). STEM images showed that the 2–3 nm Pt-based intermetallic nanoparticles were uniformly dispersed on a SiO 2 support. The relationships between Pt–Zn intermetallic phases and synthesis conditions were established. In situ XAS measurements at Pt L 3 and Zn K edges during hydrogen reduction provided a detailed image of surface species evolution. Owing to a combined electronic and geometric effect, Pt 1 Zn 1 exhibited much higher reactivity and stability than Pt 3 Zn 1 and Pt in both the direct dehydrogenation and oxidative dehydrogenation of ethane to ethylene reactions.

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

Effects of film thickness on electrochemical properties of nanoscale polyethylenedioxythiophene (PEDOT) thin films grown by oxidative molecular layer deposition (oMLD)

Poly(3,4-ethylene dioxythiophene) (PEDOT) has a high theoretical charge storage capacity, making it of interest for electrochemical applications including energy storage and water desalination. Nanoscale thin films of PEDOT are particularly attractive for these applications to enable faster charging. Recent work has demonstrated that nanoscale thin films of PEDOT can be formed using sequential gas-phase exposures via oxidative molecular layer deposition, or oMLD, which provides advantages in conformality and uniformity on high aspect ratio substrates over other deposition techniques. But to date, the electrochemical properties of these oMLD PEDOT thin films have not been well-characterized. In this work, we examine the electrochemical properties of 5–100 nm thick PEDOT films formed using 20–175 oMLD deposition cycles. We find that film thickness of oMLD PEDOT films affects the orientation of ordered domains leading to a substantial change in charge storage capacity. Interestingly, we observe a minimum in charge storage capacity for an oMLD PEDOT film thickness of ~30 nm (60 oMLD cycles at 150 °C), coinciding with the highest degree of face-on oriented PEDOT domains as measured using grazing incidence wide angle X-ray scattering (GIWAXS). Thinner and thicker oMLD PEDOT films exhibit higher fractions of oblique (off-angle) orientations and corresponding increases in charge capacity of up to 120 mA h g -1 . Electrochemical measurements suggest that higher charge capacity in films with mixed domain orientation arise from the facile transport of ions from the liquid electrolyte into the PEDOT layer. Greater exposure of the electrolyte to PEDOT domain edges is posited to facilitate faster ion transport in these mixed domain films. In conclusion, these insights will inform future design of PEDOT coated high-aspect ratio structures for electrochemical energy storage and water treatment.

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

Iridium pair sites anchored to Zr 6 O 8 nodes of the metal–organic framework UiO-66 catalyze ethylene hydrogenation

Isolated metal pair sites on metal oxide and zeolite supports are drawing attention as catalysts, because—in contrast to single atomically dispersed metals—they provide neighboring metal centers that can act cooperatively. We now report pairs of iridium atoms anchored to the Zr 6 O 8 nodes of the metal–organic framework (MOF) UiO-66, synthesized by chemisorption of Ir 2 (μ-OCH 3 ) 2 (COD) 2 (COD is cyclooctadienyl) followed by removal of the COD ligands. The supported species were characterized with infrared spectra of adsorbed CO combined with iridium LIII-edge extended X-ray absorption fine structure and high-energy-resolution fluorescence detection X-ray absorption near edge (HERFD XANES) spectra. The HERFD XANES spectra were recorded with the sample in a variety of atmospheres in which the iridium pair sites were stable, including CO, H 2 , and C 2 H 4 + H 2 at temperatures in the range of 35–80 °C. The data provide sensitive measures of the electronic structure of the iridium in the pair sites. The samples were evaluated as catalysts for ethylene hydrogenation, with the pair-sites being more selective for hydrogenation than analogous isolated atomically dispersed iridium, which catalyzes both hydrogenation and isomerization. Metal pair sites on MOFs offer uncharted opportunities for catalysts having reactivities associated with neighboring metal centers.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Reduced Graphene Oxide Aerogels with Functionalization-Mediated Disordered Stacking for Sodium-Ion Batteries

Surface modified reduced graphene oxide (rGO) aerogels were synthesized using the hydrothermal method. Ethylene diamine (EDA) and α-cyclodextrin (CD) were used to functionalize the surface of the graphene oxide layers. The oxygen reduction and surface modification occurred in-situ during the hydrothermal self-assembly process. The chemical functionality and structure of the resulting ethylene diamine modified (rGO-EDA) and cyclodextrin modified (rGO-CD) aerogels as well as of the pristine unmodified rGO aerogel were studied using XPS, SEM, XRD, and SANS techniques. The overall surface composition showed a significant decrease in the oxygen content for all synthesized aerogels. The surface modified aerogels were characterized by a disordered stacking of the assembled rGO layers. The surface functionalities resulted in a broad distribution of the interlayer spacing and introduced structural heterogeneities. Such disordered structures can enable a better adsorption mechanism of the sodium ions. Coin cells based on the synthesized aerogels and sodium metal were assembled and tested at several charge and discharge rates. The correlation between the surface functionality of the rGO, the induced structural heterogeneities due to the disordered stacking, and the electrochemical performance of sodium-ion batteries were investigated. Operando XRD measurements were carried out during the battery cycling to investigate the adsorption or intercalation nature of the sodiation mechanism.

25 ENERGY STORAGE↗
DOE OSTI2023

First-Principles Examination of Multiple Criteria of Organic Solvent Oxidative Stability in Batteries

Oxidative instability of the liquid electrolyte at or near battery cathode oxide surfaces has significant detrimental effects on batteries. Organic solvent molecules are often the fuel and precursors of such degradation processes, releasing electrons and protons that react with cathode oxides and electrolyte anions. These reactions contribute to cathode–electrolyte interphase (CEI) film formation, transition-metal ion dissolution, and phase transformation of the surface regions of the cathode. Here we apply density functional theory calculations to examine four criteria of oxidative stability (oxidation potential, hydrogen removal energies, and initial reactivity on two types of oxide facets) using four different solvent/additive molecules (ethylene carbonate, fluoroethylene carbonate, 1,3-dioxolane, and dimethyl ether). The ranking of molecular stability differs with each criterion. Surprisingly, the all-oxygen-terminated basal planes of layered oxides exhibit lower reaction barriers than spinel surface facets with exposed transition-metal cations, especially for ether solvents; the calculations also suggest basal planes contribute to the dissolution of transition-metal ions. Further, the structure–degradation relation complexity underscores the challenge of understanding the function of the CEI but also offers a guide to future degradation-mitigation strategies including facet engineering. Our predictions and models help establish a framework for future studies relevant to high-voltage conditions.

25 ENERGY STORAGE↗