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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS1978

Catalytic decomposition of methanol for onboard hydrogen generation

The steam reformation of an equimolar mixture of methanol and water on a copper chromite catalyst was studied at three furnace temperatures and at feed space velocities from 800 to 2600 per hour. The hydrogen space velocity could be related to the reactor temperature by the equation Sv = A exp (-omega T), where A and omega are constants determined for each value of alpha and T is temperature. At a methanol conversion of 0.87 and a reactor temperature of 589 K, the extrapolated value of the hydrogen space velocity was 9400 per hour. This velocity was used to estimate the size of an onboard hydrogen reactor for automotive applications. Such a reactor would need only about 0.8 liter of catalyst to produce 7630 STP liters (1.5 lb) of hydrogen per hour. This quantity of catalyst would fit into nine tubes 17.8 centimeters along and 2.54 centimeters in inside diameter, which is smaller than most mufflers. The reactor products would contain 12 to 13 percent more chemical energy than the incoming methanol and water.

Brabbs, T.↗
DOE OSTI2023

Dual atom catalysts for rapid electrochemical reduction of CO to ethylene

Strong CO adsorption and facile CO dimerization are the key challenges in electrochemical CO2 reduction towards multi-carbon (C2+) products. We recently showed that CoPc immobilized on a single-walled carbon nanotube can selectively reduce CO2 to methanol. This is enabled through molecular strain, which dramatically improves the CO adsorption energy to CoPc, which in turn facilitates methanol formation. We now examine the extended Phthalocyanine (PcEx) dual atom catalyst (DAC), which is intrinsically strained and contains two catalyst centers, making it a candidate for reducing CO to C2+ products. Using Quantum Mechanics (QM), we screened 20 elements embedded in the PcEx, seeking catalysts with weak hydrogen binding, strong CO binding, and facile CO dimerization. We identi>ied Fe, Ru, Co, and Ir as the best performers and subsequently evaluated the entire CO to C2H4 mechanism (9 steps) using each of these elements as catalysts. In terms of limiting potential and overall exergonicity, we identi>ied CoPcEx as the best catalyst, followed by IrPcEx. We then examined the full CO to C2H4 mechanism on the bimetallic IrCoPcEx catalyst using grand canonical QM to obtain the reaction energetics as a function of applied potential. We conclude that the bimetallic IrCoPcEx is most promising for ef>iciently converting CO to ethylene.

Musgrave, Charles B.↗
DOE OSTI2023

Interaction of methanol with a layered α-Sn(IV) phosphate on its surface: A solid-state NMR study

Here, a layered crystalline phosphate, α-Sn(HPO 4 ) 2 ·H 2 O, treated with CD 3 OD was characterized by the 31 P, 119 Sn, 1 H and 2 H solid-state NMR techniques. The 2 H solid-echo MAS NMR spectra of the product have unexpectedly revealed deuterated hydronium ions on the surface of this material instead of intercalated methanol. According to the 13 C NMR and GC–MS studies, these ions are formed by water molecules following a dehydration of the methanol-d 4 to yield deuterated dimethyl ether.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Formation of oxides of nitrogen in monodisperse spray combustion of hydrocarbon fuels

Experimental results of exit plane NO/NO(x) emissions from atmospheric monodisperse fuel spray combustion are presented. Six different hydrocarbon fuels were studied: isopropanol, n-propanol, n-octane, iso-octane, n-heptane and methanol. The results indicate an optimum droplet size for minimizing NO/NO(x) production for all of the test fuels. At the optimum droplet diameter, reductions in NO/NO(x) relative to the NO(x) occurred at droplet diameters of 55 and 48 microns respectively, as compared to a 50-micron droplet size for isopropanol. The occurrence of the minimum NO(x) point at different droplet diameters for the different fuels appears to be governed by the extent of prevaporization of the fuel in the spray, and is consistent with theoretical calculations based on each fuel's physical properties. Estimates are also given for the behavior of heavy fuels and of polydisperse fuel sprays in shifting the minimum NO(x) point compared to a monodisperse situation.

Nizami, A. A.↗
DOE OSTI2025

Low Temperature CO 2 Hydrogenation on Unsupported Mo 2 C Catalysts

CO 2 hydrogenation to methanol, a key reaction for decarbonizing the fuel and chemical industries, requires catalyst formulations that hydrogenate CO 2 selectively to methanol at temperatures where methanol conversion is not significantly equilibrium limited (<423 K). Herein we report continuous CO 2 hydrogenation at low temperatures (348-408 K, H 2 /CO 2 = 0.1-50, 5-35 bar) with high selectivity to methanol (up to ca. 80%) over unsupported β-Mo 2 C catalysts. Active site density quantification via titration with trifluoroacetic acid at reaction temperatures enables an assessment of site-specific rates. Methanation and reverse water gas shift (RWGS) occur concurrently with methanol synthesis during CO 2 hydrogenation over Mo 2 C. Reaction pathway analysis, product cofeeds, and reversibility formalisms show that all products form through primary reaction pathways from CO 2 , but secondary reactions of CO contribute significantly to rates of methanation. Dependences of forward rates on reactant and product concentration determined by independently varying the CO 2 , H 2 , CO, H 2 O, CH 3 OH, and CH 4 pressure in conjunction with reversibility formalisms reveal that all products form through H-assisted CO 2 activation and involve partially hydrogenated CO 2 -derived intermediates. Here, these inferences were verified by quantitative agreement between measured site-time yields and site-time yields predicted by closed form kinetic rate expressions in an integral reactor model over widely varying conditions (85-2000 kPa H 2 , 80-1500 kPa CO 2 , 0-45 kPa H 2 O, 0-21 kPa CO, 0-25 kPa CH 3 OH, 0-75 kPa CH 4 , 5-87 mol Mo s s mol CO 2 -1 ). Coverages calculated based on the kinetic model reveal that the Mo 2 C surface is covered with bidentate CO- and CO 2 -derived intermediates of the stoichiometry H 2 CO 2 and H 2 CO, indicating that H 2 and CO x do not compete for surface occupancy but instead adsorb cooperatively to form partially hydrogenated intermediates. Hydrogenation of the CO-derived H 2 CO** intermediate favors methanation, while hydrogenation of CO 2 -derived H 2 CO 2 ** favors methanol synthesis. Together, these findings demonstrate the ability of unsupported Mo 2 C to catalyze the hydrogenation of CO 2 to methanol at low temperatures and provide insight into the reaction network and mechanisms involved in its formation.

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

Reaction Pathways over ZnZrO 2 -Based Catalysts and Catalytic Sorbents

Reactive capture and conversion (RCC) is a process intensification approach that integrates CO 2 capture and hydrogenation within a single unit, removing the CO 2 purification and storage steps of traditional process flow schemes. This alters the catalytic step from a traditional steady-state (SS) flow process to a transient capture and conversion cycle, which could lead to product distributions distinct from those observed in conventional SS experiments. Such differences are investigated in the combined capture and hydrogenation of carbon dioxide to methanol over a ZnZrO 2 catalyst and a ZnZrO 2 + NaNO 3 /Mg 3 AlO x catalytic sorbent (CS) using fixed-bed kinetic measurements, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and steady-state isotopic transient kinetic analysis-DRIFTS (SSITKA-DRIFTS). Under SS conditions, ZnZrO 2 produced methanol through sequential hydrogenation of HCOO* and CH 3 O* intermediates. On the contrary, CO was attributed primarily to CO 2 dissociation at oxygen vacancies, as supported by isotopic shifts and measured reaction orders. For the CS, isotopic switching experiments suggested that monodentate carbonate species (CO 3 2− , abbreviated as m-CO 3 2− ) act as active intermediates that can be hydrogenated to HCOO* and subsequently to CH 3 O. Under RCC conditions, in situ DRIFTS and isotopic experiments reveal that m-CO 3 2− species formed during the CO 2 capture step follow two competing routes upon H 2 exposure: (i) direct hydrogenation to methane on the sorbent domain or (ii) migration of m-CO 3 2− to the ZnZrO 2 domain, where they are hydrogenated to methanol through the HCOO pathway. Overall, RCC enables carbonate hydrogenation routes not observed under SS cofeed conditions. Thus, the reaction pathways and rates during RCC can be different from operation under conventional SS conditions, and the product distribution is determined here by competition between carbonate hydrogenation on sorbent sites and migration to ZnZrO 2 for methanol synthesis.

CCUS↗
DOE OSTI2025

Preliminary Kinetic Analysis of Non-Equilibrium Plasma- Assisted Methanol Pyrolysis and Oxidation Experiments

Efforts to enhance power generation efficiency and reduce emissions have driven interest in novel combustion techniques, including non-equilibrium plasma (NEP) ignitors. NEP ignitors show promise in improving energy conversion efficiency, fuel reforming, emission control, and lean-flammability limits. However, their adoption is hindered by a limited understanding of the interplay between plasma-enhanced combustion and thermal chemistry, particularly for complex fuels under engine-relevant conditions. Developing experimentally validated kinetic mechanisms is therefore critical. Additionally, the increasing interest in renewable biofuels like ethanol and methanol, coupled with the desirable qualities of NEP ignitors, presents a compelling opportunity for study. Therefore, this work acts as an extension of a previous work (Bopaiah et al., 2023) pertaining to the experimental results of NEP-assisted methanol pyrolysis and oxidation. Experiments were performed with a custom-built plasma flow reactor at 0.5 atm and temperatures from 523-1203 K. All reactive mixtures are extremely diluted to minimize exothermicity due to reactivity, allowing isothermal assumptions and the isolation of plasma chemistry from thermal chemistry. A dielectric barrier discharge plasma, at 14 kV and 15 ns full-width half maximum, was applied to the reactive mixture at varying frequencies to maintain the number of pulses with increasing temperature. Steady-state product speciation was performed downstream of the reactor with ex-situ GC/MS diagnostics. The attained experimental results were examined through in-depth analysis performed by means of an in-development plasma-coupled kinetic mechanism. As discussed in the previous work, the plasma significantly accelerates methanol pyrolysis, increasing stable intermediate production, including oxygenated and nitrile species. Plasma-assisted oxidation shows even faster fuel consumption compared to pyrolysis and a 200 K ignition shift compared to thermal oxidation. For plasma-assisted pyrolysis, the model demonstrates that accelerated fuel consumption stems from dissociative quenching of excited N2 states with fuel and H2, generating H radicals that react to rapidly form CH3 and CH2OH radicals. At low temperatures, these radicals recombine to produce oxygenates, while CH3 drives nitrile and hydrocarbon formation at higher temperatures. While the model captures pyrolysis trends well, discrepancies in methane, ethylene, and ethanol predictions are present. Similarly, the model faces challenges in accurately representing plasma-assisted oxidation, predicting a much steeper fuel gradient and ignition 100 K earlier than the experiment. While a similar scheme to pyrolysis is nested in the reaction pathway, the enhancement of the O and H radical fluxes and their initiation of the OH and HO2 radical pools dominate fuel and intermediate oxidation. The overestimation of these processes is shown to be responsible for the divergence of model from experiment. While the modelling predictions of this preliminary mechanism are not perfect, they serve as a valuable starting point. Primarily, they elicited new reaction pathways that are not otherwise possible in thermal chemistry induced reaction kinetics. The results also provide a basis for the future work that should be performed. For example, theoretical and experimental studies on excited nitrogen species and fuel/fuel radical interactions, quantification of the NOx production, and the kinetics behind the slow ignition observed in oxidation should be emphasized.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
NASA NTRS1974

New reactions of paraformaldehyde and formaldehyde with inorganic compounds

Both paraformaldehyde and formaldehyde undergo reactions in the presence of several inorganic compounds to generate a variety of interesting organic products that can be important in chemical evolutionary processes. Some examples are acrolein, acetaldehyde, methyl formate, methanol, glycolaldehyde and formic acid. The organic compounds are produced at temperatures as low as 56 C and in high yield (up to 75%). The quantity produced depends principally on the nature of the inorganic compound, the ratio of the inorganic compound to paraformaldehyde, temperature and reaction time. The percent distribution of product depends on some of the foregoing factors.

Becker, R. S.↗
DOE OSTI2023

Significant Roles of Surface Hydrides in Enhancing the Performance of Cu/BaTiO 2.8 H 0.2 Catalyst for CO 2 Hydrogenation to Methanol

A BaTiO 3 lattice is shown in the background of the cover picture, with the stack of orange balls symbolizing Cu nanoparticles. Pipes delivering the reactants and products have the shapes of H — and e — indicating they are involved in the catalytic hydrogenation of CO 2 . Lattice O is replaced with hydrides for the enhanced performance in CO 2 hydrogenation to methanol, as demonstrated by Zili Wu et al. in their Research Article (e202313389).

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

Fluoride-Rich, Organic–Inorganic Gradient Interphase Enabled by Sacrificial Solvation Shells for Reversible Zinc Metal Batteries

Zinc metal batteries are strongly hindered by water corrosion, as solvated zinc ions would bring the active water molecules to the electrode/electrolyte interface constantly. Herein, we report a sacrificial solvation shell to repel active water molecules from the electrode/electrolyte interface and assist in forming a fluoride-rich, organic-inorganic gradient solid electrolyte interface (SEI) layer. Additionally, the simultaneous sacrificial process of methanol and Zn(CF 3 SO 3 ) 2 results in the gradient SEI layer with an organic-rich surface (CH 2 OC- and C 5 product) and an inorganic-rich (ZnF 2 ) bottom, which combines the merits of fast ion diffusion and high flexibility. As a result, the methanol additive enables corrosion-free zinc stripping/plating on copper foils for 300 cycles with an average coulombic efficiency of 99.5%, a record high cumulative plating capacity of 10 A h/cm 2 at 40 mA/cm 2 in Zn/Zn symmetrical batteries. More importantly, at an ultralow N/P ratio of 2, the practical VO 2 //20 mu m thick Zn plate full batteries with a high areal capacity of 4.7 mAh/cm 2 stably operate for over 250 cycles, establishing their promising application for grid-scale energy storage devices. Furthermore, directly utilizing the 20 μm thick Zn for the commercial-level areal capacity (4.7 mAh/cm 2 ) full zinc battery in our work would simplify the manufacturing process and boost the development of the commercial zinc battery for stationary storage.

25 ENERGY STORAGE↗
NASA NTRS1991

A tentative identification of methanol as the progenitor of the 3.52-micron emission feature in several comets

Continuum emission has been detected during 3.44-3.64 micron spectral region observations of Comets P/Brorsen-Metcalf, Okazaki-Levy-Rudenko, and Levy. The spatial brightness profile of the 3.52-micron emission feature was measured and found to be consistent with uniform outflow from a central, unresolved source; the molecule generating the emission is either directly sublimated from the cometary surface or is a short-lived parent specie's dissociation product. The modeled IR spectrum of CH3OH implies the consistency of the observed spectra with a methanol origin for the 3.52 emission.

Hoban, Susan↗
DOE OSTI2020

Near-Surface Imaging of the Multicomponent Gas Phase above a Silver Catalyst during Partial Oxidation of Methanol

Fundamental chemistry in heterogeneous catalysis is increasingly explored using operando techniques in order to address the pressure gap between ultrahigh vacuum studies and practical operating pressures. Because most operando experiments focus on the surface and surface-bound species, there is a knowledge gap of the near-surface gas phase and the fundamental information the properties of this region convey about catalytic mechanisms. In this work, we demonstrate in situ visualization and measurement of gas-phase species and temperature distributions in operando catalysis experiments using complementary near-surface optical and mass spectrometry techniques. The partial oxidation of methanol over a silver catalyst demonstrates the value of these diagnostic techniques at 600 Torr (800 mbar) pressure and temperatures from 150 to 410 °C. Planar laser-induced fluorescence provides two-dimensional images of the formaldehyde product distribution that show the development of the boundary layer above the catalyst under different flow conditions. Raman scattering imaging provides measurements of a wide range of major species, such as methanol, oxygen, nitrogen, formaldehyde, and water vapor. Near-surface molecular beam mass spectrometry enables simultaneous detection of all species using a gas sampling probe. Detection of gas-phase free radicals, such as CH 3 and CH 3 O, and of minor products, such as acetaldehyde, dimethyl ether, and methyl formate, provides insights into catalytic mechanisms of the partial oxidation of methanol. The combination of these techniques provides a detailed picture of the coupling between the gas phase and surface in heterogeneous catalysis and enables parametric studies under different operating conditions, which will enhance our ability to constrain microkinetic models of heterogeneous catalysis.

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

Contra-Thermodynamic Positional Isomerization of Olefins

A light-driven method for the contra-thermodynamic positional isomerization of olefins is described. In this work, stepwise PCET activation of a more substituted and more thermodynamically stable olefin substrate is mediated by an excited-state oxidant and a Brønsted base to afford an allylic radical that is captured by a Cr(II) cocatalyst to furnish an allylchromium- (III) intermediate. In situ protodemetalation of this allylchromium complex by methanol is highly regioselective and affords an isomerized and less thermodynamically stable alkene product. The higher oxidation potential of the less substituted olefin isomer renders it inert to further oxidation by the excited-state oxidant, enabling it to accumulate in solution over the course of the reaction. A broad range of isopropylidene substrates are accommodated, including enol ethers, enamides, styrenes, 1,3-dienes, and tetrasubstituted alkyl olefins. Mechanistic investigations of the protodemetalation step are also presented.

14 SOLAR ENERGY↗
DOE OSTI2020

Probing the low-temperature chemistry of methyl hexanoate: Insights from oxygenate intermediates

Understanding the combustion of methyl esters is crucial to elucidate kinetic pathways and predict combustion parameters, soot yields, and fuel performance of biodiesel, however most kinetic studies of methyl esters have focused on smaller, surrogate model esters. Methyl hexanoate is a larger methyl ester approaching the chain length of methyl esters found in biodiesel and has not received as much research attention as other smaller esters. The purpose of this work is to present the first atmospheric pressure combustion data of methyl hexanoate, CH 3 CH 2 CH 2 CH 2 CH 2 COOCH 3 . Mixtures of 2% methyl hexanoate in O 2 and N 2 are studied using a plug flow reactor at atmospheric pressure, wall temperatures from 573 to 973 K, residence times from roughly 1-2 s., and fuel equivalence ratios of 1, 1.5, and 2. Exhaust gases are analyzed by a gas chromatograph-mass spectrometer system and species mole fractions are presented. Here, the literature model shows satisfactory agreement with the experimental species profiles and improvements for future mechanistic studies are suggested. In particular, this work proposes new unimolecular decomposition pathways of methyl hexanoate to form methanol or methyl acetate. Furthermore, the experiment detected three unsaturated esters that are direct products of the low temperature oxidation chemistry and it provides more insight into branching ratios for the formation of methyl hexanoate radicals and for the decomposition of hydroperoxyalkyl radicals.

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

Catalytic conversion of high S-lignin to a sustainable tri-epoxide polymer precursor

More than 40 million tons of thermosetting plastics are produced annually and 70% of those are epoxy polymers. The synthesis of bio-based epoxide provides a pathway for making renewable thermoset plastics. We describe in this study the use of a genetically modified high-S poplar lignin to produce 4-propyl-2,6-dimethoxyphenol (DMPP), which is converted to the tri-functional compound propylpyrogallol (DMPPO) by a reaction catalysed by N 2 O 5 in the green solvent water. The resulting DMPPO can be converted to a novel tri-epoxide by reaction with epichlorohydrin. Native high-S lignin as well as several organosolv lignins extracted from this poplar biomass were investigated as feedstocks. Notably, direct reductive catalytic fractionation (RCF) of the high-S poplar wood over Pd–Zn/C catalyst with Pd : Zn ratio 1 : 10 at 225 °C under 35 bar H 2 in methanol gave the highest yield of biophenol monomers from the lignin present, the major product being DMPP. Under optimized conditions, conversion of DMPP to DMPPO over the Nb 2 O 5 was nearly quantitative (96% yield), and this conversion could be made without extensive prior purification of the DMPP. The Nb 2 O 5 catalyst could be recycled several times before significant deactivation. This sequence of two catalytic reactions demonstrates that the production of epoxides from lignin-derived DMPPO is a realistic strategy for making renewable polymer building blocks from biomass.

09 BIOMASS FUELS↗
DOE OSTI2022

Ultrafast disruptive probing: Simultaneously keeping track of tens of reaction pathways

Ultrafast science depends on different implementations of the well-known pump–probe method. Here, we provide a formal description of ultrafast disruptive probing, a method in which the probe pulse disrupts a transient species that may be a metastable ion or a transient state of matter. Disruptive probing has the advantage of allowing for simultaneous tracking of the yield of tens of different processes. Our presentation includes a numerical model and experimental data on multiple products resulting from the strong-field ionization of two different molecules, partially deuterated methanol and norbornene. The correlated enhancement and depletion signals between all the different fragmentation channels offer comprehensive information on photochemical reaction pathways. In combination with ion imaging and/or coincidence momentum imaging or as complementary to atom-specific probing or ultrafast diffraction methods, disruptive probing is a particularly powerful tool for the study of strong-field laser–matter interactions.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Editorial: Synthetic metabolism for the third-generation (3G) biorefineries

The demand for energy has increased significantly to meet the development of the economy and the increasing population. With the continuous consumption of energy, the shortage of non-renewable resources and the greenhouse effect have aroused worldwide attention. Therefore, the conversion of one-carbon substrates such as formate, methanol, and carbon dioxide (CO 2 ) as sustainable feedstocks into high-value-added products is a potential way to address such concerns. Although one-carbon substrates can be converted into organics by natural pathways, these pathways may not be optimal due to the multiple enzymes involved and remarkable amounts of energy consumption. Thus, synthetic biology, as an emerging field, offers a new approach to boost one-carbon bioconversion.

09 BIOMASS FUELS↗