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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Binding and Translocation of Substrate Allosterically Promotes Functional Interactions Within the AlkB–AlkG Electron Transfer Complex

The alkane monooxygenase AlkB and rubredoxin AlkG form an electron transfer complex that hydroxylates terminal alkanes to produce alcohols. The recent cryoEM study of Fontimonas thermophila AlkB-AlkG complex revealed its architecture, including a dodecane (D12) substrate at the active site. However, FtAlkBG molecular mechanism of action of remains unknown. Here, in this study, we examined its dynamics and interactions by multiscale computations, including molecular dynamics simulations, elastic network models, and QM/MM of the oxygen activation mechanism at the AlkB catalytic site. D12 maintained stable interactions within the catalytic site during two MD runs, coordinated by hydrophobic residues L263-L264, I267, I133. A third extended run revealed that D12 could translocate to a membrane-exposed site near S49/F46 along a hydrophobic channel gated by I54. During this translocation, D12 was temporarily stabilized at intermediate sites IS1 (lined by I27/L30-G31/G50/L53-I54/P59/S124/A127-V128) and IS2 (I33-G34/L37/L45-F46/S49) before nearly exiting the protein, and diffused back to the active site, assisted by L30. Substrate binding and translocation across those intermediate sites affects the coupling between the iron centers in AlkBG, and interfacial interactions between AlkB-AlkG. The channel was further connected to the cytosol, near two surface-exposed arginines, potentially allowing for O 2 passage. The allosteric effects between D12 putative entry site, catalytic site and AlkB-AlkG interface were analyzed by ENM-based methods which confirmed the cooperative perturbation-responses and strongly correlated movements of residues belonging to those distal regions. Our study provides new mechanistic insights into key sites and their interactions that could be targeted for developing AlkB-variants with desirable alkane conversion functions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

A Robust Methodology to Elucidate Kinetics of Room Temperature Electrochemical Propane Adsorption on Platinum

Electrocatalytic activation of alkanes can further decarbonize chemical manufacturing by leveraging affordable renewable electricity and readily available shale gas reserves in the United States. Earlier works have identified the unique role of Pt in adsorbing and activating alkanes, like propane, at room temperature in acidic, aqueous electrolytes, revealing spontaneous formation of deeply dehydrogenated propane-derived surface species with an intact C 3 - backbone. Although an adsorption mechanism was hypothesized, it has not been explicitly investigated to date, preventing the quantification of kinetic rate parameters. A robust methodology to investigate and benchmark propane adsorption kinetics on Pt is critical for the rational design of electrocatalysts that exhibit higher selectivity toward desired partially oxidized products. Herein, we analyze an oxidative current transience that appears during the adsorption of propane on Pt in aqueous electrochemical conditions and develop a methodology that elucidates the adsorption mechanism and enables quantification of rate parameters such as order dependences and apparent activation barriers. This method yields an expected first-order dependence with respect to propane concentration at low coverage and reveals a second-order dependence with respect to the concentration of surface active sites. Additionally, the apparent activation barrier for propane adsorption was calculated using an Arrhenius analysis of the current transience under temperature control. The experimentally measured activation barrier of 35 kJ mol –1 is in excellent agreement with the theoretical barrier calculated by density functional theory (DFT). The kinetic analysis was extended, via the use of transition state theory, to extract entropy and enthalpy of activation, yielding consistent results with the proposed two-step adsorption mechanism and DFT calculations. These results demonstrate reliable quantification of kinetic parameters for electrocatalytic activation of C–H bonds in alkanes that can be employed for rational catalyst development for a versatile range of electrocatalytic conditions.

alkane activation↗
DOE OSTI2025

Zero-Carbon Biofuels: An Optimized Two-Stage System for High Productivity Conversion of CO2 to Liquid Fuels

In MIT’s Zero-Carbon Biofuels work, under ARPAe’s EcoSynBio funding, we capitalized on our previously developed technology of the oleaginous yeast, Yarrowia lipolytica, engineered to produce high titer biodiesel-like lipids and alkanes, and set out to reduce or eliminate CO 2 generation during lipid production. We set out to do this by both engineering Y. lipolytica with the necessary enzymes to allow the generation of reducing equivalents from H 2 , formic acid, or methanol, and, in parallel, installing the non-oxidative glycolysis (NOG) pathway. The goal was that combination of these two would enable stoichiometric conversion of glucose and acetate to biodiesel products. Furthermore, our ARPAe Electrofuels funded research, yielded a very innovative two-stage system where gases comprising CO 2 and H 2 are used for the production of liquid fuels. Acetate is produced from CO 2 and H 2 , via acetogenic fermentation, in the first stage as the intermediary product, then fed to Y. lipolytica in the second stage, for conversion to lipids and alkanes. To increase the commercial competitiveness of the two-stage system, by improvement to the overall productivity, we recently showed that synergistic substrate co-feeding drastically enhances CO 2 fixation rates and set out to explore additional co-substrate pairs, including methanol and formic acid, in order to maximize acetate productivity. Finally, given the attractiveness as a biofuel, we also set out to attempt an important increase in the production of alkanes over lipids in Yarrowia.

10 SYNTHETIC FUELS↗
DOE OSTI2024

Air quality impacts from the development of unconventional oil and gas well pads: Air toxics and other volatile organic compounds

Unconventional oil and natural gas development (UOGD) has expanded rapidly across the United States in recent decades and raised concerns about associated air quality impacts. While significant effort has been made to quantify methane emissions, relatively few observations have been made of Volatile Organic Compounds (VOCs), especially during drilling and completion of new wells. Extensive air monitoring during development of several large, multi-well pads in Broomfield, Colorado, in the Denver-Julesburg Basin, provides a novel opportunity to examine changes in local air toxics and other VOC concentrations during well drilling and completions and production. These operations offer an especially useful case to study as several management practices were implemented to reduce emissions (e.g., electrified, grid-powered drill rigs and closed loop fluid handling systems to reduce truck traffic and limit fluid handling on the pad). With simultaneous measurements of methane and 50 VOCs from October 2018 to December 2022 at as many as 19 sites near well pads, in adjacent neighborhoods, and at a more distant reference location, we identify impacts from each phase of well development and production. Use of weekly, time-integrated canisters, a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous photoionization detectors (PID) to trigger canister collection upon detection of VOC-rich plumes, and an instrumented vehicle, provided a powerful suite of measurements to characterize both transient plumes and longer-term changes in air quality. Prior to the start of well development, VOC gradients were small across Broomfield. Once drilling commenced, concentrations of oil and gas (O&G) related VOCs, including alkanes and aromatics, increased around active well pads. Concentration increases were clearly apparent during certain operations, including drilling, coil tubing/millout operations, and production tubing installation. Emissions of C 8 –C 10 n-alkanes during drilling operations highlighted the importance of VOC emissions from synthetic drilling mud chosen to reduce odor impacts. More than 90 samples were collected of transient plumes. Using composition measurements, meteorological data, and information about well pad activities, these plumes were connected with specific UOGD operations including drilling, flowback, and production equipment maintenance. The chemical signatures of these plumes differed by operation type (e.g., C 8 –C 10 n-alkanes constituted a larger fraction of measured VOCs in drilling-related plumes). Concentrations of individual, oil and gas-related VOCs in these plumes were often several orders of magnitude higher than in background air, with maximum ethane and benzene concentrations of 79,600 and 819 ppbv, respectively. Because these plumes typically impact a monitoring site for just several minutes, they are easily missed by slower-responding instruments. Study measurements highlight future emission mitigation opportunities during UOGD operations, including better control of emissions from shakers that separate drill cuttings from drilling mud, production separator maintenance operations, and periodic emptying of sand cans during flowback operations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Novel, active, and uncultured hydrocarbon-degrading microbes in the ocean

ABSTRACT Given the vast quantity of oil and gas input to the marine environment annually, hydrocarbon degradation by marine microorganisms is an essential ecosystem service. Linkages between taxonomy and hydrocarbon degradation capabilities are largely based on cultivation studies, leaving a knowledge gap regarding the intrinsic ability of uncultured marine microbes to degrade hydrocarbons. To address this knowledge gap, metagenomic sequence data from the Deepwater Horizon (DWH) oil spill deep-sea plume was assembled to which metagenomic and metatranscriptomic reads were mapped. Assembly and binning produced new DWH metagenome-assembled genomes that were evaluated along with their close relatives, all of which are from the marine environment (38 total). These analyses revealed globally distributed hydrocarbon-degrading microbes with clade-specific substrate degradation potentials that have not been reported previously. For example, methane oxidation capabilities were identified in all Cycloclasticus . Furthermore, all Bermanella encoded and expressed genes for non-gaseous n -alkane degradation; however, DWH Bermanella encoded alkane hydroxylase, not alkane 1-monooxygenase. All but one previously unrecognized DWH plume member in the SAR324 and UBA11654 have the capacity for aromatic hydrocarbon degradation. In contrast, Colwellia were diverse in the hydrocarbon substrates they could degrade. All clades encoded nutrient acquisition strategies and response to cold temperatures, while sensory and acquisition capabilities were clade specific. These novel insights regarding hydrocarbon degradation by uncultured planktonic microbes provides missing data, allowing for better prediction of the fate of oil and gas when hydrocarbons are input to the ocean, leading to a greater understanding of the ecological consequences to the marine environment. IMPORTANCE Microbial degradation of hydrocarbons is a critically important process promoting ecosystem health, yet much of what is known about this process is based on physiological experiments with a few hydrocarbon substrates and cultured microbes. Thus, the ability to degrade the diversity of hydrocarbons that comprise oil and gas by microbes in the environment, particularly in the ocean, is not well characterized. Therefore, this study aimed to utilize non-cultivation-based ‘omics data to explore novel genomes of uncultured marine microbes involved in degradation of oil and gas. Analyses of newly assembled metagenomic data and previously existing genomes from other marine data sets, with metagenomic and metatranscriptomic read recruitment, revealed globally distributed hydrocarbon-degrading marine microbes with clade-specific substrate degradation potentials that have not been previously reported. This new understanding of oil and gas degradation by uncultured marine microbes suggested that the global ocean harbors a diversity of hydrocarbon-degrading bacteria, which can act as primary agents regulating ecosystem health.

Howe, Kathryn L.↗
NASA NTRS1972

Origin of organic matter in early solar system. V - Further studies of meteoritic hydrocarbons and a discussion of their origin.

The Murchison meteorite contains aliphatic and aromatic hydrocarbons similar to those made in static Fischer-Tropsch-type syntheses. Principal compound classes above C8 are n-alkanes, mono- and dimethylalkanes, alkenes, alkylbenzenes and -naphthalenes. Below C8, n-alkanes are virtually absent; instead, benzene, toluene, branched alkanes dominate. The CH4/C2H6 ratio is greater than 30, possibly greater than 700. Isoprenoids from C17 to C20 occur in a surface rinse but not in subsequent extracts and appear to be terrestrial contaminants. Thiophenes, porphyrin-like pigments, and chlorobenzenes were also found; the latter appear to be contaminants. In the Allende meteorite, only methane, benzene, toluene and an aromatic polymer seem to be indigeneous. A comprehensive review of current evidence shows that Fischer-Tropsch-type reactions can account for most principal features of meteorite organic matter.

Studier, M. H.↗
NASA NTRS1978

Infrared band intensities of saturated hydrocarbons

Kramers-Kronig analysis is applied to measured values of spectral reflectance at near-normal incidence to determine the real and the imaginary parts of the complex index of refraction for methane, ethane, propane, n-butane, n-hexane, n-heptane, and n-decane in the liquid state. The results indicate that the strengths of the characteristic bands as measured by the integral of the imaginary part are roughly constant for all the liquid alkanes except for methane. The intensity of the CH valence vibration bands in the spectra of the alkanes except methane is directly proportional to the number of CH groups per unit volume. The relations for the intensity of the bands due to CH2 and CH3 deformations are examined. Characteristic band intensities of the type established for NH4(+) and SO4(2-) groups in solutions and crystals cannot be extended to the more closely coupled CH2 and CH3 groups in alkane molecules.

Pinkley, L. W.↗
NASA NTRS1980

The carbon isotope biogeochemistry of the individual hydrocarbons in bat guano and the ecology of insectivorous bats in the region of Carlsbad, New Mexico

The structures and C-13 contents of individual alkanes extracted from bat guano found in the Carlsbad region of New Mexico can be related to both the photosynthetic pathways of the local plants and the feeding habits of the insects that support the bats. Carbon isotopic analyses of the 62 most important plant species in the Pecos River Valley, the most significant feeding area for the Carlsbad bats, reveal the presence of 29 species with C3 photosynthesis and 33 species, mostly grasses, with C4 photosynthesis. Although the abundances of nonagricultural C3 and C4 plants are similar, alfalfa and cotton, both C3 plants, constitute over 95 per cent of the crop biomass. The molecular composition of the bat guano hydrocarbons is fully consistent with an insect origin. Two isotopically distinct groups of insect branched alkanes were discerned. These two groups of alkanes derived from two chemotaxonomically distinct populations of insects possessing distinctly different feeding habits. It is likely that one population grazes predominantly on crops whereas the other population prefers native vegetation. This and other isotopic evidence supports the notion that crop pests constitute a major percentage of the bats' diet.

Desmarais, D. J.↗
NASA NTRS1981

Development of urethane coating and potting material with improved hydrolytic and oxidative stability

A series of saturated hydrocarbon based urethanes was prepared and characterized for hydrolytic and oxidative stability. A series of ether based urethanes was used as a basis for comparison. The alkane base urethanes were found to be hydrolytically and oxidatively stable and had excellent electrical properties. The alkane based materials absorbed little or no water and were reversion resistant. There was little loss in hardness or weight when exposed to high temperature and humidity. Dielectric properties were excellent and suffered little adverse effects from the high temperature/humidity conditions. The alkane based urethanes were not degraded by ozone exposure.

Morris, D. E.↗
NASA NTRS1992

Indications of photochemical histories of Pacific air masses from measurements of atmospheric trace species at Point Arena, California

Measurements were made of a suite of photochemically active trace species (including light hydrocarbons, ozone, peroxyacetyl nitrate, HNO3, NO3(-), NO(x), and NO(y)) in marine air collected during a 10-day period in April and May 1985 at Point Arena (California), a coastal inflow site. It was found that the mixing ratios of the alkanes, ozone, peroxyacetyl nitrate, and HNO3 correlated with variations in the origins of calculated air parcel trajectories and with variations in the ratios of the light alkanes. The highest levels of alkanes and the photochemical products were found in parcels that had been rapidly transported across the North Pacific Ocean from near the 600-mbar level above the east Asian coast. It is suggested that production over the continents, transport to the marine areas, and parallel removal processes account for much of the observed correlation.

Parrish, D. D.↗
NASA NTRS1998

Fiber Supported Droplet Combustion-2 (FSDC-2)

Experimental results for the burning characteristics of fiber supported, liquid droplets in ambient Shuttle cabin air (21% oxygen, 1 bar pressure) were obtained from the Glove Box Facility aboard the STS-94/MSL-1 mission using the Fiber Supported Droplet Combustion - 2 (FSDC-2) apparatus. The combustion of individual droplets of methanol/water mixtures, ethanol, ethanol/water azeotrope, n-heptane, n-decane, and n-heptane/n-hexadecane mixtures were studied in quiescent air. The effects of low velocity, laminar gas phase forced convection on the combustion of individual droplets of n-heptane and n-decane were investigated and interactions of two droplet-arrays of n-heptane and n-decane droplets were also studied with and without gas phase convective flow. Initial diameters ranging from about 2mm to over 6mm were burned on 80-100 micron silicon fibers. In addition to phenomenological observations, quantitative data were obtained in the form of backlit images of the burning droplets, overall flame images, and radiometric combustion emission measurements as a function of the burning time in each experiment. In all, 124 of the 129 attempted experiments (or about twice the number of experiments originally planned for the STS-94/MSL-1 mission) were conducted successfully. The experimental results contribute new observations on the combustion properties of pure alkanes, binary alkane mixtures, and simple alcohols for droplet sizes not studied previously, including measurements on individual droplets and two-droplet arrays, inclusive of the effects of forced gas phase convection. New phenomena characterized experimentally for the first time include radiative extinction of droplet burning for alkanes and the "twin effect" which occurs as a result of interactions during the combustion of two-droplet arrays. Numerical modeling of isolated droplet combustion phenomenon has been conducted for methanol/water mixtures, n-heptane, and n-heptane/n-hexadecane mixtures, and results compare quantitatively with those found experimentally for methanol/water mixtures. Initial computational results qualitatively predict experimental results obtained for isolated n-heptane and n-heptane/n-hexadecane droplet combustion, although the effects of sooting are not yet included in the modeling work. Numerical modeling of ethanol and ethanol/water droplet burning is under development. Considerable data remain to be fully analyzed and will provide a large database for comparisons with further numerical and analytical modeling and development of future free droplet experiments aboard space platforms.

Colantonio, Renato↗
NASA NTRS1999

Pressure Effects on Combustion of Methanol and Methanol-Docecanol Droplets

The objective of this research is to improve understanding of the combustion of binary fuel mixtures in the vicinity of the critical point. Fiber-supported single droplets and two-droplet arrays of methanol and of mixtures of methanol and 1-dodecanol, initially 0.9 mm in diameter, were burned in room-temperature air at pressures from 0.1 MPa to 9.0 MPa in the NASA Lewis 2.2-second drop tower. The work is a continuation of a collaborative Japan-US research effort designed to increase knowledge of high-pressure combustion of fuel sprays, relevant to application in propulsive and power-production devices such as Diesel engines. Some previous publications from this cooperative program may be cited. All of the previous experiments concerned alkanes and alkane mixtures. The new research reported here addresses alcohols and alcohol mixtures, to ascertain the degree to which previous results for alkanes extend to alcohols. There have been many previous experimental studies of methanol droplet combustion and a few of alcohol mixtures, but not at the high pressures of interest here. There is some experimental information on methanol droplet combustion at elevated pressure but none on the alcohol mixtures extending to critical pressures, as in the present study.

Okai, K.↗
NASA NTRS2000

Experimental and Modeling Study of the Burning of an Ethanol Droplet in Microgravity

The microgravity ethanol droplet combustion experiments were performed aboard the STS-94/MSL-1 Shuttle mission within the Fiber-Supported Droplet Combustion-2 (FSDC-2) program. The burning histories and flame standoffs for pure ethanol and ethanol/water droplets were obtained from the images recorded with two 8 mm videocameras. The obtained results show that average gasification rate is related to the initial droplet size in a manner similar to n-alkanes and methanol and consistent with the results of Hara and Kumagai and the data taken recently in the NASA-Lewis 2.2 s droptower. A transient, moving finite-element chemically reacting flow model applied previously to sphero-symmetric combustion of methanol, methanol/water, n-alkane, and n-alkane binary mixture droplets was adopted for the problem of ethanol droplet combustion. The model includes detailed description of gas-phase reaction chemistry and transport, a simplified description of liquid phase transport, and non-luminous radiative heat transfer. Gas-phase chemistry was described with the detailed reaction mechanism of Norton and Dryer, which consists of 142 reversible elementary reactions of 33 species. Another recently published reaction mechanism of high-temperature ethanol oxidation was also considered. The model predictions were found to compare favorably with the experimental data. The model analysis also indicates that water condensation in the case of ethanol has smaller effect on average droplet gasification rate as compared with previously studied methanol cases. This effect is explained by non-ideal (azeotropic) behavior of binary ethanol-water mixtures. Further analysis of computational results and ethanol droplet radiative extinction behavior will be discussed.

Kazakov, Andrei↗
NASA NTRS2000

An abiotic origin for hydrocarbons in the Allan Hills 84001 martian meteorite through cooling of magmatic and impact-generated gases

Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO2, and H2 below approximately 250-300 degrees C during rapid cooling of trapped magmatic or impact-generated gases. Depending on temperature, bulk composition, and oxidation-reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO2 ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01-0.001 together with high CO/CO2 ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO2 ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine-grain magnetite, formation of a CO-rich local gas phase, reduction of water vapor to H2, reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high-temperature quenching of CO-, H2-rich impact gases could have led to magnetite-catalyzed hydrocarbon synthesis.

Non-NASA Center↗
NASA NTRS2017

Analysis of Mixed Aryl/Alkyl Esters by Pyrolysis Gas Chromatography-Mass Spectrometry in the Presence of Perchlorate

Mars is an important target for Astrobiology. A key goal of the MSL mission was to determine whether Mars was habitable in the past, a que-tion that has now been definitely determined to be yes. Another key goal for Mars exploration is to understand the origin and distribution of organic material on Mars; this question is being addressed by the SAM instrument on MSL, and will also be informed by two upcoming Mars exploration missions, ExoMars and Mars 2020. These latter two missions have instrumentation capable of detecting and characterize organic molecules. Over the next decade, these missions will analyze organics in surface, near-surface and sub-surface samples. Each mission has the capability to analyze organics by different methods (pyrolysis gas chromatography-mass spectrometry [py-GC-MS]; laser desorption and thermal volatilization GC-MS; and Raman spectroscopy). Plausibly extraterrestrial organics were recently discovered by the Mars Science Laboratory (MSL), providing an important first step towards understanding the organic inventory on Mars [1]. The compounds detected were chlorobenzenes and chloroalkanes, but it was argued that chlorination of these compounds occurred during pyrolysis of samples containing unchlorinated organics in the presence of perchlorate. A recent report analyzed a suite of aromatic (benzene, toluene, benzoic acid, phthalic acid, and mellitic acid) and aliphatic (acetic acid, propane, propanol, and hexane) by pyrolysis under SAM-like conditions in the presence of perchlorate to attempt to constrain possible precursor molecules for the organic molecules detected on Mars. For aromatic compounds, the aromatic acids all readily produced SAM-relevant chlorobenzes, whereas benzene and toluene did not. This observation suggests that the chlorobenzene detected on Mars could have derived from compounds like mellitic acid, consistent with the previous hypothesis by Benner et al. [3]. Among the aliphatic molecules, it was shown that pyrolysis of alkanes and alcohols in the presence of perchlorates produced polychlorine containing chloro-alkanes similar to what was observed on Mars. Surpris-ingly, however, similar treatment of acetic acid pro-duced chloroketones, instead, and no chloroalkanes were reported. This suggests that the chloroalkanes detected in the Sheepbed mudstone were not derived from aliphatic carboxylic acids, but instead were from more reduced alcohols or even alkanes, or perhaps were degradation products of more complicated organic material. Because organics analyses on mars will rely heavily on py-GC-MS of perchlorate-containing samples over the next decade, it is important to understand the fate of organic molecules of biotic and abiotic origin under such conditions. In this work we begin a series of experiments to improve our understanding of products generated during py-GC-MS of increasingly complex organic molecules (esters, amides, peptides, nucleic acids, fatty acids) in the presence of perchlorate.

Burton, A. S.↗
DOE OSTI2024

On the prediction of pressure effects for the combination kinetics of two alkyl radicals with the geometric mean rule

Here, alkyl combination reactions, along with their reverse alkane unimolecular decomposition reactions, are widely present in pyrolysis and combustion systems. These reactions occur mainly at temperatures at which their rate coefficients depend on pressure, and only a few studies have explored this dependence for large size alkyls. The accurate calculation of these kinetic data is limited by the size of the alkyl fragments involved, since the theoretical methods used are computationally expensive. Therefore, little reliable data is available for the modeling of real fuels alkane decomposition kinetics. In this paper, we propose an alternative approach that allows an accurate estimation of pressure-dependent kinetic rates for the combination of long-chain alkyl radicals, based on tabulated reaction models. The rates of combination of linear alkyls radicals forming ethane to pentane were calculated using the CASPT2-F12/cc-pVDZ-F12 level within VRC-TST theory combined with master-equation simulations. The computed high-pressure limit rate coefficients showed that n-propyl could be a minimum-size representative structure for larger n-alkyl chain, but this approach fails to capture the pressure dependence of the reaction that remains size-dependent for larger alkyls. The Geometric Mean Rule (GMR), a simple rule that links the self and cross-reactions of three alkyl radicals, is used to address this issue. Our theoretical calculations show for the first time that the GMR applies not only at the high-pressure limit, but also for every pressure explored. The GMR is shown to be accurate, with a maximum 22 % deviation in the falloff region for the estimation of rates for small alkyl combinations. Using this method, we propose a tabulated reaction rate rule for the combination of alkyl radicals up to C5+C5. The use of computed rate coefficients with the GMR approximation opens ways to develop pressure-dependent reaction rate rules for large n-alkyl combinations, based on accurate and computationally expensive theoretical calculations on smaller alkyl fragments.

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

Propane Activation on Pt Electrodes at Room Temperature: Quantification of Adsorbate Identity and Coverage

Abstract C−H bond activation is the first step in manufacturing chemical products from readily available light alkane feedstock and typically proceeds via carbon‐intensive thermal processes. The ongoing emphasis on decarbonization via electrification motivates low‐temperature electrochemical alternatives that could lead to sustainable chemicals production. Platinum (Pt) electrocatalysts have shown activity towards reacting alkanes; however, little is known about propane electrocatalytic activation and conditions suitable for enabling selective oxidation to valuable products. Herein, we utilize a combination of electrochemical mass spectrometry (ECMS) and density functional theory (DFT) calculations to elucidate the potential dependence of propane activation on Pt electrocatalysts. Results show a strong dependence of adsorption on the applied potential in room‐temperature aqueous acidic electrolyte, with a maximum coverage of propane‐derived adsorbates at 0.30 V vs RHE. Using charge deconvolution and deuterated experiments, the mechanism of adsorption was elucidated, and C 3 H 2 * was determined as the average dehydrogenated propane‐derived adsorbate species. DFT calculations further corroborate these results, showing that the formation of deeply dehydrogenated species is energetically accessible at room temperature. The combined theoretical and experimental findings yield insights for selective activation of paraffinic C−H bonds at room temperature, aqueous conditions—a critical step towards decarbonized chemical manufacturing.

Chemistry↗
DOE OSTI2025

Low temperature polyolefin deconstruction via tandem cracking-hydrogenation

The use of aluminum chloride in dichloromethane to crack polyolefin chains in tandem with alkylation of the resulting products has been previously reported as an efficient polyolefin recycling route. Building off this work, we report that a tandem cracking-hydrogenation system also efficiently converts polyolefins into gasoline-range light alkanes at mild temperatures without needing a hydrocarbon co-reactant. This Lewis acid and hydrogenation bifunctional system uses anhydrous aluminum chloride as the acid catalyst and Pd/C as a hydrogenation catalyst to achieve nearly 80 % conversion of low-density polyethylene (LDPE) at 70 °C in three hours, with 90+% selectivity towards gasoline-range (C 4 -C 12 ) branched alkanes. By combining the endothermic cracking reaction with the exothermic hydrogenation reaction, the thermodynamic limitations to low-temperature polyolefin deconstruction can be overcome. In using hydrogenation instead of alkylation, the system’s carbon efficiency is greatly improved, the cost of the reactants is reduced and the overall mass of both reactants and products reduced as well.

Alkylation↗