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At least 271 records · Page 15

Mineralogical Trends Over the Clay-Sulfate Transition in Gale Crater from the Mars Science Laboratory CheMin Instrument

The Mars Science Laboratory Curiosity rover landed in Gale crater in 2012 to explore a sedimentary sequence in lower Aeolis Mons (informally known as Mount Sharp)that shows changes in mineralogy from orbital visible/near-infrared reflectance spectroscopy[1]. Sedimentary layers with spectral signatures of hydrated Mg sulfate overly layers with signatures of Fe/Mg smectite, a mineralogical stratigraphy that is seen in other ancient sedimentary rocks across Mars[e.g., 2-4]. Curiosity recently completed its campaign in a valley with a strong orbital signature of smectite, named Glen Torridon. Mineralogical measurements by the CheMin X-ray diffractometer(XRD), complemented by evolved gas analyses by the Sample Analysis at Mars (SAM) instrument suite, allowed the identification of abundant Fe3+-bearing dioctahedral smectite (i.e., nontronite) in Glen Torridon [5-6]. Curiosity left Glen Torridon in February 2021 and began traversing through a “clay-sulfate transition” zone on the way to the pediment and the sulfate unit[e.g., 7]. This clay-sulfate transition is defined in orbital reflectance spectroscopy as having a weak signature of hydrated Mg sulfate. Curiosity has drilled five outcrops over the traverse through the clay-sulfate transition and delivered the rock powders to CheMin for mineralogical analysis. Here, we report on the mineral assemblages of those five targets derived from CheMin XRD patterns and discuss mineralogical trends as the rover approaches the sulfate unit.

Mars↗

Mechanical Characterization of Low Modulus Polymer-Modified Calcium-Silicate-Hydrate (C-S-H) Binder

Calcium-silicate-hydrate (C-S-H) represents a key microstructural phase that governs the mechanical properties of concrete at a large scale. Defects in the C-S-H phase are also responsible for the poor ductility and low tensile strength of concrete. Manipulating the microstructure of C-S-H can lead to new cementitious materials with improved structural performance. This paper presents an experimental investigation aiming to characterize a new synthetic polymer-modified synthetic calcium-silicate-hydrate (C-S-H)/styrene-butadiene rubber (SBR) binder. The new C-S-H/SBR binder is produced by calcining calcium carbonate and mixing this with fumed silica (SiO 2 ), deionized water and SBR. Mechanical, physical, chemical and microstructural characterization was conducted to measure the properties of new hardened C-S-H binder. Results from the experimental investigation demonstrate the ability to engineer a new C-S-H binder with low elastic modulus and improved toughness and bond strength by controlling the SBR content and method of C-S-H synthesis. The new binder suggests the possible development of a new family of low-modulus silica-polymer binders that might fit many engineering applications such as cementing oil and gas wells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stratospheric aircraft exhaust plume and wake chemistry studies

This report documents progress to date in an ongoing study to analyze and model emissions leaving a proposed High Speed Civil Transport (HSCT) from when the exhaust gases leave the engine until they are deposited at atmospheric scales in the stratosphere. Estimates are given for the emissions, summarizing relevant earlier work (CIAP) and reviewing current propulsion research efforts. The chemical evolution and the mixing and vortical motion of the exhaust are analyzed to track the exhaust and its speciation as the emissions are mixed to atmospheric scales. The species tracked include those that could be heterogeneously reactive on the surfaces of the condensed solid water (ice) particles and on exhaust soot particle surfaces. Dispersion and reaction of chemical constituents in the far wake are studied with a Lagrangian air parcel model, in conjunction with a radiation code to calculate the net heating/cooling. Laboratory measurements of heterogeneous chemistry of aqueous sulfuric acid and nitric acid hydrates are also described. Results include the solubility of HCl in sulfuric acid which is a key parameter for modeling stratospheric processing. We also report initial results for condensation of nitric acid trihydrate from gas phase H2O and HNO3.

Miake-Lye, R. C.↗

The H•/H– Redox Couple and Absolute Hydration Energy of H–

A supermolecule-continuum approach with water clusters up to n = 16 H2O molecules has been used to predict the absolute hydration free energies at 298 K ($\Delta$G hyd ) of both hydrogen (H•) and hydride (H - ) to be 4.6 and -78 ± 2 kcal/mol, respectively. These values are combined with a high accuracy prediction of the gas phase electron affinity ($\Delta$G gas,298K = -16.9 kcal/mol) to determine the aqueous electron affinity of H• of 99.5 ± 2 kcal/mol, which yields a reduction potential for H• vs SHE of -0.03 ± 0.15 V. This value is in agreement within 0.2 V with most estimates obtained using a wide variety of approaches. The results of this study can be used to improve the absolute hydricity scale in water which provides additional insights into how a putative hydride interacts with solvent, but do not change the ability to predict the relative reactivity of two species using relative hydricity scales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Demystifying the Diffuse Vibrational Spectrum of Aqueous Protons Through Cold Cluster Spectroscopy

The ease with which the pH is routinely determined for aqueous solutions masks the fact that the cationic product of Arrhenius acid dissolution, the hydrated proton, or H + (aq), is a remarkably complex species. Here, we review how results obtained over the past 30 years in the study of H + ·(H 2 O) n cluster ions isolated in the gas phase shed light on the chemical nature of H + (aq). This effort has also revealed molecular-level aspects of the Grotthuss relay mechanism for positive-charge translocation in water. Recently developed methods involving cryogenic cooling in radiofrequency ion traps and the application of two-color, infrared–infrared (IR–IR) double-resonance spectroscopy have established a clear picture of how local hydrogen-bond topology drives the diverse spectral signatures of the excess proton. This information now enables a new generation of cluster studies designed to unravel the microscopic mechanics underlying the ultrafast relaxation dynamics displayed by H + (aq).

Chemistry↗

Preliminary results of an experimental study of the interactions of basalt glass and a water vapor atmosphere: Implications for weathering on Mars

Models of weathering processes on the surface of Mars invoke hydrothermal alteration as the primary mechanism responsible for clay formation. Previous experimental studies of basalt glass interactions with water under hydrothermal conditions demonstrate that phyllosilicates and zeolites are the primary alteration minerals. Gas-solid weathering is thought to be less thermodynamically favorable and relatively unimportant, however, the experimental alteration of basalt glass under vapor ion conditions (large SA/V) can result in the formation of clay minerals, zeolites, and hydrated calcium silicates. We have undertaken a study of the reacted layers formed on basalt glasses experimentally altered under vapor hydration conditions to resolve this issue. High SA/V ratios promote reaction product buildup in solution and promote alteration mineral formation. It was previously shown that these reaction conditions promote weathering processes similar to those found in nature for tektite glasses, rhyolitic glasses, and basalt glasses. The hydration of basalt glass is described for 100 percent relative humidity experiments at temperatures of 150, 175, and 200 C for up to 400 days. Preliminary characterization of the alteration layers with analytical electron and scanning microscopy suggest that the reaction mechanism includes precipitation of a smectite clay on the outermost surface of the glass. Between the clay and the unreacted glass is an amorphous gel-like phase (palagonite). Our results provide an experimental basis for proposing that basalt glass interactions with vapor atmospheres can be an important source of clay minerals.

Mazer, J. J.↗

Microhydration of the metastable N -Protomer of 4-Aminobenzoic acid by condensation at 80 K: H/D exchange without conversion to the more stable O- protomer

4-Aminobenzoic acid (4ABA) is a model scaffold for studying solvent-mediated proton transfer. Although protonation at the carboxylic group (O-protomer) is energetically favored in the gas phase, the N-protomer, where the proton remains on the amino group, can be kinetically trapped by electrospray ionization of 4ABA in an aprotic solvent such as acetonitrile. Here we report the formation of the hydrated deuterium isotopologues of the N-protomers, RND 3 + ·(H 2 O) n=1-3 , (R=C 6 H 4 COOD), which are generated by condensing water molecules onto the bare N-protomers in a liquid nitrogen cooled, radiofrequency octopole ion trap at 80 K. The product clusters are then transferred to a 20 K cryogenic ion trap where they are tagged with weakly bound D 2 molecules. The structures of these clusters are determined by analysis of their vibrational patterns obtained by resonant IR photodissociation. The resulting patterns confirm that the metastable N-protomer configuration remains intact even when warmed by sequential condensation of water molecules. Attachment of H 2 O molecules onto the RND 3 + head group also affords the opportunity to explore the possibility of H/D exchange between the acid scaffold and the proximal water network. The spectroscopic results establish that although the RND 3 + ·(H 2 O) n=1,2 clusters are formed without H/D exchange, the n = 3 cluster exhibits about 10% H/D exchange as evidenced by the appearance of the telltale HOD bands. Furthermore, the site of exchange on the acid is determined to be the acidic OH by the emergence of the OH stretching fundamental in the -COOH motif.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterogeneous phase reactions of Martian volatiles with putative regolith minerals

The chemical reactivity of several minerals thought to be present in Martian fines is tested with respect to gases known in the Martian atmosphere. In these experiments, liquid water is excluded from the system, environmental temperatures are maintained below 0 C, and the solar illumination spectrum is stimulated in the visible and UV using a xenon arc lamp. Reactions are detected by mass spectrometric analysis of the gas phase over solid samples. No reactions were detected for Mars nominal gas over sulfates, nitrates, chloride, nontronite clay, or magnetite. Oxidation was not observed for basaltic glass, nontronite, and magnetite. However, experiments incorporating SO2 gas an expected product of volcanism and intrusive volatile release - gave positive results. Displacement of CO2 by SO2 occurred in all four carbonates tested. These reactions are catalyzed by irradiation with the solar simulator. A calcium nitrate hydrate released NO2 in the presence of SO2. These results have implications for the cycling of atmospheric CO2, H2O, and N2 through the regolith.

Clark, B. C.↗

Radiolytic Gas-Driven Cryovolcanism in the Outer Solar System

Water ices in surface crusts of Europa, Enceladus, Saturn's main rings, and Kuiper Belt Objects can become heavily oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. Oxidant accumulations and gas production are manifested in part through observed H2O2 on Europa. tentatively also on Enceladus, and found elsewhere in gaseous or condensed phases at moons and rings of Jupiter and Saturn. On subsequent chemical contact in sub-surface environments with significant concentrations of primordially abundant reductants such as NH3 and CH4, oxidants of radiolytic origin can react exothermically to power gas-driven cryovolcanism. The gas-piston effect enormously amplifies the mass flow output in the case of gas formation at basal thermal margins of incompressible fluid reservoirs. Surface irradiation, H2O2 production, NH3 oxidation, and resultant heat, gas, and gas-driven mass flow rates are computed in the fluid reservoir case for selected bodies. At Enceladus the oxidant power inputs are comparable to limits on nonthermal kinetic power for the south polar plumes. Total heat output and plume gas abundance may be accounted for at Enceladus if plume activity is cyclic in high and low "Old Faithful" phases, so that oxidants can accumulate during low activity phases. Interior upwelling of primordially abundant NH3 and CH4 hydrates is assumed to resupply the reductant fuels. Much lower irradiation fluxes on Kuiper Belt Objects require correspondingly larger times for accumulation of oxidants to produce comparable resurfacing, but brightness and surface composition of some objects suggest that such activity may be ongoing.

Cooper, John F.↗

Facile hermetic TEM grid preparation for molecular imaging of hydrated biological samples at room temperature

Abstract Although structures of vitrified supramolecular complexes have been determined at near-atomic resolution, elucidating in situ molecular structure in living cells remains a challenge. Here, we report a straightforward liquid cell technique, originally developed for real-time visualization of dynamics at a liquid-gas interface using transmission electron microscopy, to image wet biological samples. Due to the scattering effects from the liquid phase, the micrographs display an amplitude contrast comparable to that observed in negatively stained samples. We succeed in resolving subunits within the protein complex GroEL imaged in a buffer solution at room temperature. Additionally, we capture various stages of virus cell entry, a process for which only sparse structural data exists due to their transient nature. To scrutinize the morphological details further, we used individual particle electron tomography for 3D reconstruction of each virus. These findings showcase this approach potential as an efficient, cost-effective complement to other microscopy technique in addressing biological questions at the molecular level.

59 BASIC BIOLOGICAL SCIENCES↗

Portable Apparatus for Electrochemical Sensing of Ethylene

A small, lightweight, portable apparatus based on an electrochemical sensing principle has been developed for monitoring low concentrations of ethylene in air. Ethylene has long been known to be produced by plants and to stimulate the growth and other aspects of the development of plants (including, notably, ripening of fruits and vegetables), even at concentrations as low as tens of parts per billion (ppb). The effects are magnified in plant-growth and -storage chambers wherein ethylene can accumulate. There is increasing recognition in agriculture and related industries that it is desirable to monitor and control ethylene concentrations in order to optimize the growth, storage, and ripening of plant products. Hence, there are numerous potential uses for the present apparatus in conjunction with equipment for controlling ethylene concentrations. The ethylene sensor is of a thick-film type with a design optimized for a low detection limit. The sensor includes a noble metal sensing electrode on a chip and a hydrated solid-electrolyte membrane that is held in contact with the chip. Also located on the sensor chip are a counter electrode and a reference electrode. The sensing electrode is held at a fixed potential versus the reference electrode. Detection takes place at active-triple-point areas where the sensing electrode, electrolyte, and sample gas meet. These areas are formed by cutting openings in the electrolyte membrane. The electrode current generated from electrochemical oxidation of ethylene at the active triple points is proportional to the concentration of ethylene. An additional film of the solid-electrolyte membrane material is deposited on the sensing electrode to increase the effective triple-point areas and thereby enhance the detection signal. The sensor chip is placed in a holder that is part of a polycarbonate housing. When fully assembled, the housing holds the solid-electrolyte membrane in contact with the chip (see figure). The housing includes a water reservoir for keeping the solid-electrolyte membrane hydrated. The housing also includes flow channels for circulating a sample stream of air over the chip: ethylene is brought to the sensing surface predominately by convection in this sample stream. The sample stream is generated by a built-in sampling pump. The forced circulation of sample air contributes to the attainment of a low detection limit.

Manoukian, Mourad↗

The Origin of Organic Matter in the Solar System: Evidence from Interplanetary Dust Particles

The origin of the organic matter in interplanetary materials has not been established. A variety of mechanisms have been proposed, with two extreme cases being a Fisher-Tropsch type process operating in the gas phase of the solar nebula or a Miller-Urey type process, which requires interaction with an aqueous fluid, presumably occurring on an asteroid. In the Fisher-Tropsch case, we might expect similar organic matter in hydrated and anhydrous interplanetary materials. However, aqueous alteration is required in the case of the Miller-Urey process, and we would expect to see organic matter preferentially in interplanetary materials that exhibit evidence of aqueous activity, such as the presence of hydrated silicates. The types and abundance of organic matter in meteorites have been used as an indicator of the origin of organic matter in the Solar System. Indigenous complex organic matter, including amino acids, has been found in hydrated carbonaceous chondrite meteorites, such as Murchison. Much lower amounts of complex organic matter, possibly only terrestrial contamination, have been found in anhydrous carbonaceous chondrite meteorites, such as Allende, that contain most of their carbon in elemental form. These results seem to favor production of the bulk of the organic matter in the Solar System by aqueous processing on parent bodies such as asteroids, a Miller-Urey process. However, the hydrated carbonaceous chondrite meteorites have approximately solar abundances of the moderately volatile elements, while all anhydrous carbonaceous chondrite meteorites have significantly lower contents of these moderately volatile elements. Two mechanisms, incomplete condensation or evaporation, both of which involve processing at approx. 1200 C, have been suggested to explain the lower content of the moderately volatile elements in all anhydrous meteorites. Additional information is contained in the original extended abstract.

Flynn, G. J.↗

Hydrolysis of Metal Dioxides Differentiates d-block from f-block Elements: Pa(V) as a 6d Transition Metal; Pr(V) as a 4f “Lanthanyl”

Gas-phase reactions of pentavalent metal dioxide cations M V O 2 + with water were studied experimentally for M = V, Nb, Ta, Pr, Pa, U, Pu, and Am. Addition of two H 2 O can occur by adsorption to yield hydrate (H 2 O) 2 M V O 2 + or by hydrolysis to yield hydroxide M V (OH) 4 + . Displacement of H 2 O by acetone indicates hydrates for Pr V , U V , Pu V , and Am V , whereas nondisplacement indicates hydroxides for Nb V , Ta V , and Pa V . Computed potential energy profiles agree with the experimental results and furthermore indicate that acetone unexpectedly induces dehydrolysis and displaces two H 2 O from (H 2 O)VO(OH) 2 + to yield (acetone) 2 VO 2 + . Structures and energies for several M V , as well as for Th IV and U VI , indicate that hydrolysis is governed by the involvement of valence f versus d orbitals in bonding: linear f-element dioxides are more resistant to hydrolysis than bent d-element dioxides. Accordingly, for early actinides, hydrolysis of Th IV is characteristic of a 6d-block transition metal; hydration of U V and U VI is characteristic of 5f actinyls; and Pa V is intermediate between 6d and 5f. The praseodymium oxide cation Pr V O 2 + is assigned as an actinyl-like lanthanyl with properties governed by 4f bonding.

36 MATERIALS SCIENCE↗

Extraction of Water from Martian Regolith Simulant via Open Reactor Concept

To demonstrate proof of concept water extraction from simulated Martian regolith, an open reactor design is presented along with experimental results. The open reactor concept avoids sealing surfaces and complex moving parts. In an abrasive environment like the Martian surface, those reactor elements would be difficult to maintain and present a high probability of failure. A general lunar geotechnical simulant was modified by adding borax decahydrate (Na2B4O7·10H2O) (BDH) to mimic the ~ 3 percent water content of hydrated salts in near surface soils on Mars. A rotating bucket wheel excavated the regolith from a source bin and deposited the material onto an inclined copper tray, which was fitted with heaters and a simple vibration system. The combination of vibration, tilt angle and heat was used to separate and expose as much regolith surface area as possible to liberate the water contained in the hydrated minerals, thereby increasing the efficiency of the system. The experiment was conducted in a vacuum system capable of maintaining a Martian like atmosphere. Evolved water vapor was directed to a condensing system using the ambient atmosphere as a sweep gas. The water vapor was condensed and measured. Processed simulant was captured in a collection bin and weighed in real time. The efficiency of the system was determined by comparing pre- and post-processing soil mass along with the volume of water captured.

Trunek, Andrew J.↗

Laboratory studies of refractory metal oxide smokes

Studies of the properties of refractory metal oxide smokes condensed from a gas containing various combinations of SiH4, Fe(CO)5, Al(CH3)3, TiCl4, O2 and N2O in a hydrogen carrier stream at 500 K greater than T greater than 1500 K were performed. Ultraviolet, visible and infrared spectra of pure, amorphous SiO(x), FeO(x), AlO(x) and TiO(x) smokes are discussed, as well as the spectra of various co-condensed amorphous oxides, such as FE(x)SiO(y) or Fe(x)AlO(y). Preliminary studies of the changes induced in the infrared spectra of iron-containing oxide smokes by vacuum thermal annealing suggest that such materials become increasingly opaque in the near infrared with increased processing: hydration may have the opposite effect. More work on the processing of these materials is required to confirm such a trend: this work is currently in progress. Preliminary studies of the ultraviolet spectra of amorphous Si2O3 and MgSiO(x) smokes revealed no interesting features in the region from 200 to 300 nm. Studies of the ultraviolet spectra of both amorphous, hydrated and annealed SiO(x), TiO(x), AlO(x) and FeO(x) smokes are currently in progress. Finally, data on the oxygen isotopic composition of the smokes produced in the experiments are presented, which indicate that the oxygen becomes isotopically fractionated during grain condensation. Oxygen in the grains is as much as 3 percent per amu lighter than the oxygen in the original gas stream. The authors are currently conducting experiments to understand the mechanism by which fractionation occurs.

Nuth, Joseph A.↗

Investigations Using Laboratory Testbeds to Interpret Flight Instrument Datasets from Mars Robotic Missions

The Astromaterials Research and Exploration Science Directorate at the NASA Johnson Space Center (JSC) has laboratory instrumentation that mimic the capabilities of corresponding flight instruments to enable interpretation of datasets returned from Mars robotic missions. The lab instruments have been and continue to be applied to datasets for the Moessbauer Spectrometer (MB) on the Mars Exploration Rovers (MER), the Thermal & Evolved Gas Analyzer (TEGA) on the Mars Phoenix Scout, the CRISM instrument on the Mars Reconnaissance Orbiter Missions and will be applied to datasets for the Sample Analysis at Mars (SAM), Chemistry and Mineralogy (CheMin) and Chemistry & Camera (ChemCam) instruments onboard the Mars Science Laboratory (MSL). The laboratory instruments can analyze analog samples at costs that are substantially lower than engineering models of flight instruments, but their success to enable interpretation of flight data depends on how closely their capabilities mimic those of the flight instrument. The JSC lab MB instruments are equivalent to the MER instruments except without flight qualified components and no reference channel Co-57 source. Data from analog samples were critical for identification of Mg-Fe carbonate at Gusev crater. Fiber-optic VNIR spectrometers are used to obtain CRISM-like spectral data over the range 350-2500 nm, and data for Fephyllosilicates show irreversible behavior in the electronic transition region upon dessication. The MB and VNIR instruments can be operated within chambers where, for example, the absolute H2O concentration can be measured and controlled. Phoenix's TEGA consisted of a calorimeter coupled to a mass spectrometer (MS). The JSC laboratory testbed instrument consisted of a differential scanning calorimeter (DSC) coupled to a MS configured to operate under total pressure (12 mbar), heating rate (20 C/min), and purge gas composition (N2) analogous to the flight TEGA. TEGA detected CO2 release at both low (400-680 C) and high (725-820 C) temperature and an endothermic reaction in concert with the high temperature release. The high-temperature thermal decomposition is consistent with calcite, dolomite, or ankerite, (3-6 wt.%) or any combination of these phase based upon laboratory testbed experiments. Recent laboratory experiments suggest that the low temperature CO2 release was caused by a reaction between calcium carbonate and hydrated magnesium perchlorate; although, CO2 release by the oxidation of organic materials and Fe-/Mg-rich carbonates cannot be ruled out. MSL landed in Gale crater on August 5, 2012. Although numerous analog samples have been analyzed on the JSC laboratory testbeds, no SAM, CheMin, or ChemCam analyses have been acquired by MSL to date. The JSC SAM laboratory testbed consists of a thermal analyzer coupled with a MS configured to operate under total pressure (30 mbar), heating rate (35 C/min), and purge gas composition (He) analogous to the flight SAM. The CheMin and ChemCam laboratory testbeds were developed and built by inXitu, Inc. and Los Alamos National Laboratory, respectively, to acquire datasets relevant to the MSL CheMin and ChemCam flight instruments.

Ming, D. W.↗

Bismuth-Functionalized Silica Aerogels for Iodine Capture

The U.S. Department of Energy is looking into alternative sorbents for the removal of radioiodine from off-gas streams in a used nuclear fuel reprocessing plant. One class of sorbents considered are bismuth-functionalized silica aerogels which offer an efficient capture of iodine from off-gas streams and are environmentally friendly and lower cost when compared to silver-functionalized sorbents. Two types of bismuth-functionalized silica aerogels were successfully manufactured using a hierarchical synthesis approach:1) The Bi 3+ -aerogel with bismuth oxide nitrate hydroxide hydrate particles and 2) Bi-aerogel with bismuth metal and bismuth sulfide nanoparticles. Both sorbents exhibited high sorption capacity for iodine. However, presence of particles of different composition, size, and distribution on aerogel support resulted in different iodine loadings. The Bi 3+ -aerogel exhibited sorption capacity of 289 mg/g. In contrast, Bi-aerogel exhibited more that 20% higher sorption capacity. The heat-treatment of Bi 3+ -aerogel at 225? under hydrogen atmosphere increased iodine loading capacity to 351 mg/g.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Composition and method for hydrogen storage

A method for hydrogen storage includes providing water and hydrogen gas to a containment volume, reducing the temperature of the water and hydrogen gas to form a hydrogen clathrate at a first cryogenic temperature and a first pressure and maintaining the hydrogen clathrate at second cryogenic temperature within a temperature range of up to 250 K to effect hydrogen storage. The low-pressure hydrogen hydrate includes H.sub.2 O molecules, H.sub.2 molecules and a unit cell including polyhedron cages of hydrogen-bonded frameworks of the H.sub.2 O molecules built around the H.sub.2 molecules.

Mao, Wendy L.↗