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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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This study presents a comprehensive experimental dataset on the temperature-dependent diffusion of hydrogen (H 2 ) in reservoir rocks. The results demonstrate that H 2 diffuses through reservoir rocks up to 100 times faster than methane (CH 4 ).
Vascular plants require boron to cross-link the rhamnogalacturonan-II (RG-II) domain of pectin to form functional cell walls. Boronic acids, which form reversible esters with cis-diols like borate, have been proposed to influence RG-II cross-linking, though the mechanism remains unclear. We used suspension-cultured rose cells adapted to grow without boron to investigate the effect of boronic acids on RG-II dimerization. When grown with phenylboronic acid (PBA) as the sole boron source, nearly all RG-II was crosslinked, whereas methylboronic acid (MBA) only partially restored cross-linking. In contrast, in vitro assays showed that homogeneous RG-II monomers did not dimerize with alkyl or aryl boronic acids unless supplemented with hydrogen peroxide (H2O2), which oxidatively converts boronic acids to boric acid. Real-time NMR spectroscopy and density functional theory calculations provided insight into the reaction mechanism and energetics of oxidation respectively. Together, our data show that exogenous boronic acids are a source of boric acid for plants, and that the deboronation reaction generates aryl or alkyl alcohol byproducts that can undergo further chemical modification in planta. The fate and potential roles of these byproducts in planta remain to be determined.
Here, we ally steady-state kinetics, kinetic isotope effects, and density functional theory (DFT) calculations to illustrate that Cu-based catalysts remain saturated by H-adatoms (H*) and molecular formic acid (HCOOH**) during CO 2 hydrogenation. High H* coverage under methanol synthesis conditions is evidenced by reverse water-gas shift (RWGS) rates that exhibit positive H 2 reaction orders only at P H2 ≲ 0.5 bar, above which methanol synthesis and RWGS rates exhibit first and zeroth order dependence on P H2 , respectively. HCOOH** also accumulates on the surface with increasing P CO2 as informed by the Langmuir-type dependence on P CO2 (0.25-23 bar) for both methanol synthesis and RWGS. As both HCOOH** and H* have one H-atom per site occupied, the two species share the same P H2 dependence and give rise to CO 2 reaction orders that are independent of P H2 . Surface coverages determined based on kinetic analyses are further corroborated with DFT-derived adsorption energies that show favorable HCOOH** adsorbate-adsorbate interactions as well as repulsive interactions for bidentate formate (HCOO**) on H*-saturated surfaces. Methanol selectivity remains invariant with P CO2 and P CO despite CO inhibiting reaction rates, thereby demonstrating methanol synthesis and RWGS occur on the same active site. In contrast, water preferentially inhibits methanol synthesis rates, increases methanol synthesis H 2 reaction order from 1.0 to 1.5, and alters the methanol synthesis H 2 /D 2 kinetic isotope effect; the inhibitory effect of H 2 O thus cannot be attributed to competitive adsorption alone and instead reflects a change in the rate-determining step for methanol synthesis. The disparate kinetics of methanol synthesis and RWGS evince a branching pathway where methanol is formed from formates and CO is formed from carboxylates. The presented work thus identifies the relevant surface species, underscores the distinct catalytic role of water in branching methanol synthesis and RWGS pathways, and, in doing so, details a mechanistic picture that yields predictable rates and reaction orders for both methanol synthesis and RWGS on Cu-based CO 2 hydrogenation catalysts.
Producing enantioenriched molecules from racemic mixtures is essential for manufacturing. Traditional methods such as resolution, deracemization and enantioconvergent catalysis primarily involve separating or converting enantiomers without altering their structures, or functionalization of stereocentres at or proximal to functional groups. However, there are challenges in enantioselectively forging C–H bonds that are remote from functional groups via hydrogen atom transfer (HAT) with these methods. Here we introduce a strategy for the photoenzymatic stereoablative enantioconvergence of γ-chiral oximes using repurposed flavin-dependent ene-reductases. A photoinduced single-electron reduction of the γ-chiral oxime by an ene-reductase generates an iminyl radical, which then undergoes stereoablative 1,5-HAT at the γ-stereocentre. Subsequent chiral reconstruction through enzymatic HAT and spontaneous imine hydrolysis yields the γ-chiral ketone with high enantioselectivity. This work provides a robust method for remote stereoablative enantioconvergent HAT and broadens the synthetic utility of photobiocatalysis.
Ethylene is recognized as one of the most significant chemicals globally. The projected ethylene production for 2023 stands at 227.6 million tonnes, with expectations of continued demand growth. The primary use of ethylene, accounting for over 76%, lies in the production of plastics such as polyethylene, polyvinyl chloride, and polystyrene. Despite the enduring carbon retention potential of plastics themselves, traditional ethylene feedstock production from fossil resources contributes substantially to greenhouse gas emissions, ranging from 0.29 to 2.29 kg CO2 /kg Ethylene depending on various factors like feedstock and process design. Various decarbonization strategies, including the utilization of hydrogen as a primary heat source, have been proposed to reduce the carbon footprint of ethylene production, but their efficacy remains limited, offering at best a 0–30% reduction in on-site CO 2 emissions.
Due to the detection of phosphine (PH 3 ) in the solar system gas giants Jupiter and Saturn, PH 3 has long been suggested to be detectable in exosolar substellar atmospheres too. However, to date, direct detection of phosphine has proven to be elusive in exoplanet atmosphere surveys. We construct an updated phosphorus-hydrogen-oxygen (PHO) photochemical network suitable for the simulation of gas giant hydrogen-dominated atmospheres. Using this network, we examine PHO photochemistry in hot Jupiter and warm Neptune exoplanet atmospheres at solar and enriched metallicities. Our results show for HD 189733b-like hot Jupiters that HOPO, PO, and P 2 are typically the dominant P carriers at pressures important for transit and emission spectra, rather than PH 3 . For GJ1214b-like warm Neptune atmospheres our results suggest that at solar metallicity PH 3 is dominant in the absence of photochemistry, but is generally not in high abundance for all other chemical environments. At 10 and 100 times solar, small oxygenated phosphorus molecules such as HOPO and PO dominate for both thermochemical and photochemical simulations. The network is able to reproduce well the observed PH 3 abundances on Jupiter and Saturn. Despite progress in improving the accuracy of the PHO network, large portions of the reaction rate data remain with approximate, uncertain, or missing values, which could change the conclusions of the current study significantly. Improving understanding of the kinetics of phosphorus-bearing chemical reactions will be a key undertaking for astronomers aiming to detect phosphine and other phosphorus species in both rocky and gaseous exoplanetary atmospheres in the near future.
Blending natural gas (NG) with hydrogen (H₂) can improve combustion and engine performance while potentially facilitating the catalytic conversion of methane and other pollutants, resulting in cleaner tailpipe emissions. This study evaluates the impact of H2 on the conversion of methane, CO, and NOx emissions on a commercial three-way catalyst (TWC) in a flow reactor using synthetic gas mixtures that simulate stoichiometric engine exhausts with NG or NG+H₂ combustion. The work examines whether, and how, the additional amount of H₂ in the exhaust stream affects the conversion efficiency of methane and other pollutants. Experiments were conducted with both degreened and aged catalysts under controlled conditions, systematically varying temperature, the air-to-fuel equivalence ratio (λ), and λ modulation. Test conditions covered λ values from 0.996 to 1.000 to represent nominally stoichiometric engine operation with different λ modulation amplitudes, as well as a range of temperatures to inform control strategies for effective CH₄, CO, and NOₓ reduction. Overall, the results show that hydrogen addition significantly improves the conversion efficiency of CH₄ and NOₓ, particularly at temperatures below 500 °C. More significantly, this study highlights that exhaust gas composition, operating temperature, λ management, and the oxygen storage capacity of the TWC all play major roles in affecting the tailpipe emissions from NG and NG+H₂ combustion.
Vacuum test facilities are required for high speed cryopumping of gaseous hydrogen at low pressures. One method involves the catalytic oxidation of hydrogen and condensation of the resulting water on a liquid nitrogen-cooled surface.
Dynamics of water rejection from hydrogen-oxygen fuel cell to hydrogen stream
Determining fugacities of hydrogen in hydrogen and propane mixtures using semipermeable membrane
Simulated hydrogen leakage in electrolytic hydrogen-oxygen fuel cells
Hydrogen gas pressure requirements during pressurization and transfer of liquid hydrogen from spherical tanks
Absorption of hydrogen by palladium and electrical resistivity of hydrogen-palladium system
Multiple velocity dispersion in normal hydrogen and normal hydrogen-helium mixtures at room temperature using ultrasonic interferometer
Hydrogen-hydrogen excitation collisions by impact parameter treatment, investigating rotation coupling influence in four state cross sections approximation
Hydrogen-hydrogen double excitation collision cross sections computed by impact parameter method, using Born and two state approximations
Quadrupole coupling between single and double excitation channels in hydrogen-hydrogen collisions found ineffective due to energy defect between channels
Flux, energy spectra, and pitch angle distributions of precipitated low energy hydrogen and electrons from Nike-Tomahawk auroral hydrogen experiment