Hydrogen-rich Systems Research Articles

A systematic study on the phase diagram and superconductivity of ternary clathrate Ca-Sc-H at high pressures.

This work explores potential high-temperature superconductor materials in hydrogen-rich systems. Here, the crystal structure stabilities of ternary Ca-Sc-H systems under high-pressure (P = 100-250 GPa) and their superconductivities are investigated using the particle swarm optimization methodology combined with first-principles calculations. For the predicted candidate structures of Ca-Sc-H systems, the pressure-dependent phase diagram and thermodynamic convex hull were investigated across a wide range of compositions; the electronic properties of all the predicted phases were analyzed in detail to study the bonding behavior of these stable phases. We identified the crystal structures of four thermodynamically stable compounds: R3̄m-CaScH6, Immm-CaSc2H9,C2/m-Ca2ScH10, and R3̄m-CaScH12. Among them, R3̄m-CaScH12 was predicted to have the highest Tc value (i.e., 173 K) at 200 GPa. The discovery of this previously unreported pressure-induced decomposition of Ca-Sc-H systems will pave the way for investigations on the nature of hydrogen-metal interactions.

A 62-minute orbital period black widow binary in a wide hierarchical triple

Over a dozen millisecond pulsars are ablating low-mass companions in close binary systems. In the original 'black widow', the eight-hour orbital period eclipsing pulsar PSR J1959+2048 (PSR B1957+20)1, high-energy emission originating from the pulsar2 is irradiating and may eventually destroy3 a low-mass companion. These systems are not only physical laboratories that reveal the interesting results of exposing a close companion star to the relativistic energy output of a pulsar, but are also believed to harbour some of the most massive neutron stars4, allowing for robust tests of the neutron star equation of state. Here we report observations of ZTF J1406+1222, a wide hierarchical triple hosting a 62-minute orbital period black widow candidate, the optical flux of which varies by a factor of more than ten. ZTF J1406+1222 pushes the boundaries of evolutionary models5, falling below the 80-minute minimum orbital period of hydrogen-rich systems. The wide tertiary companion is a rare low-metallicity cool subdwarf star, and the system has a Galactic halo orbit consistent with passing near the Galactic Centre, making it a probe of formation channels, neutron star kick physics6 and binary evolution.

Structure and stability of possible new L i-Y-H ternary hydrides

The research on the superconductivity of hydrogen-rich compounds has become a hot research topic in the field of high-temperature superconductors in recent years and yttrium hydride YH<sub>9+x</sub> has been experimentally confirmed to have high temperature superconductivity (near room temperature (Tc = 262 K)), following behind the research of H<sub>3</sub>S (Tc = 200 K) and LaH<sub>10</sub> (Tc = 260 K). The theoretical study of binary hydrogen-rich systems is relatively mature, while the structural characteristics and superconductivity of ternary or quaternary hydrogen-rich compounds are still under exploration. In this paper, nLiH + YH<sub>3</sub>→Li<sub>n</sub>YH<sub>n+3</sub> (<i>n</i> = 1–3) is the synthesis way to explore the stable configuration of ternary hydride LinYH<sub>n+3</sub> in a pressure range of 0–300 GPa. The crystal structure, electronic structure, thermodynamic and kinetic stability of LiYH<sub>4</sub>, Li<sub>2</sub>YH<sub>5</sub> and Li<sub>3</sub>YH<sub>6</sub> in the pressure range of 0–300 GPa are studied based on the structure prediction by particle swarm optimization algorithm and first-principles calculation. The CALYPSO method is used to search for 1–4 times molecular formula structures for Li-Y-H ternary systems with different stoichiometric ratios in the pressure range of 0–300 GPa in steps of 50 GPa. The results show that LiYH<sub>4</sub>-<i>P</i>4/<i>nmm</i>, Li<sub>2</sub>YH<sub>5</sub>-<i>I</i>4/<i>mmm</i>, and Li<sub>3</sub>YH<sub>6</sub>-P4/nmm can be respectively synthesized with a certain ratio between LiH and YH<sub>3</sub> respectively in a pressure range of 169–221 GPa, 141–300 GPa and 166–300 GPa. The Li<sub>2</sub>YH<sub>5</sub> has the lowest stable pressure and widest range which can be the possible choice in experiment. The results can provide the data support for the superconductivity research and experimental synthesis of hydrides in Li-Y-H ternary system.

New candidates for AM Canum Venaticorum stars among ASAS-SN transients

Abstract We studied Zwicky Transient Facility (ZTF) light curves of 34 dwarf nova candidates discovered by the All-Sky Automated Survey for Supernovae (ASAS-SN) between 2020 May 12 and September 9 and found six AM CVn-type candidates. All objects showed short outbursts (post-superoutburst rebrightenings) on the fading tail. Two objects (ASASSN-20eq, ASASSN-20la) showed double superoutbursts. Three objects (ASASSN-20jt, ASASSN-20ke, and ASASSN-20lr) showed short superoutbursts (5–6 d). These features in the light curve can be used in discriminating AM CVn-type candidates from hydrogen-rich systems. In contrast to hydrogen-rich systems, some object did not show red color excess during the rebrightening or fading tail phase. We interpret that this is due to the higher ionization temperature in helium disks. Two objects had long (likely) supercycles: ASASSN-20gx (8.5 yr) and ASASSN-20lr (7 yr). We provide a scheme for identifying AM CVn-type candidates based on the light curve characteristics.

Investigation of Superconductivity in Hydrogen-rich Systems

At pressures above one million atmospheres (100 GPa), oxygen becomes a shining metal, and moreover, it exhibits superconductivity. In this study, we have investigated the material properties at hig...

Benzyltoluene/dibenzyltoluene-based mixtures as suitable liquid organic hydrogen carrier systems for low temperature applications

In this contribution we propose mixtures of the two LOHC systems benzyltoluene (H0-BT)/perhydro benzyltoluene (H12-BT) and dibenzyltoluene (H0-DBT)/perhydro dibenzyltoluene (H18-DBT) as promising hydrogen storage media for technical applications at temperatures below ambient. The mixing of the two LOHC systems provides the advantage of a reduced viscosity of the hydrogen-rich system, for example a 20 wt% addition of H12-BT to H18-DBT reduces the viscosity at 10 °C by 80%. Interestingly, it is also found that the dehydrogenation of such mixture provides a hydrogen release productivity that is 12–16% higher compared to pure H18-DBT dehydrogenation under otherwise identical conditions. This enhanced rate is attributed to a combination of reduced hydrogen partial pressure in the reactor (due to the higher H12-BT vapor pressure), preferred H12-BT dehydrogenation (due to faster H12-BT diffusion) and effective transfer hydrogenation between the two LOHC systems.

Superconducting thorium hydrides under high pressure

There are lots of efforts on the investigate for high-temperature superconductors in hydrogen-rich system, since the LaH10 (250–260 K) and SH3 (203 K) compounds smashed the record for superconducting temperatures above 200 K. In this study, as a result of extensive simulations, we propose several unreported thorium hydrides under pressures, using our in-house developed CALYPSO structure searching method in combination with density functional theory. New ThH3 and Th2H7 structures are found as thermodynamically stable phases at atmospheric pressure. As a result of the analysis of the electronic properties in those predicted structures, it is found that the f electrons of Th and the s electrons of H mainly contribute to the fermi level, thus leading to the superconductivity. Our results enrich the knowledge in the Th–H system and provide insights into designing superconducting hydrides under high pressure.

Crystal structure prediction of uranium hydrides at high pressure: A new hydrogen-rich phase

Uranium hydride is a novel hydrogen-rich system which contains 5f electrons. Uranium hydride can not only be used in the nuclear fuel industry, but also be a candidate of high superconducting-temperature materials. In this paper, we have searched the stable uranium hydride structures by using particle swarm optimization method and first-principles calculations. Besides UH8 and UH9, we find that UH17, which contains larger hydrogen content than most hydride materials reported before, is also stable at high pressure. The atomic structures, electronic structures and phase diagram of uranium hydrides are provided, and we find that all of the discovered uranium hydrides are metals with negligible magnetic moments.

Stability of Ar(H2)2 to 358 GPa

"Chemical precompression" through introducing impurity atoms into hydrogen has been proposed as a method to facilitate metallization of hydrogen under external pressure. Here we selected Ar(H2)2, a hydrogen-rich compound with molecular hydrogen, to explore the effect of "doping" on the intermolecular interaction of H2 molecules and metallization at ultrahigh pressure. Ar(H2)2 was studied experimentally by synchrotron X-ray diffraction to 265 GPa, by Raman and optical absorption spectroscopy to 358 GPa, and theoretically using the density-functional theory. Our measurements of the optical bandgap and the vibron frequency show that Ar(H2)2 retains 2-eV bandgap and H2 molecular units up to 358 GPa. This is attributed to reduced intermolecular interactions between H2 molecules in Ar(H2)2 compared with that in solid H2 A splitting of the molecular vibron mode above 216 GPa suggests an orientational ordering transition, which is not accompanied by a change in lattice symmetry. The experimental and theoretical equations of state of Ar(H2)2 provide direct insight into the structure and bonding of this hydrogen-rich system, suggesting a negative chemical pressure on H2 molecules brought about by doping of Ar.

Facile Preparation of Nanoporous PtCu Alloys for Preferential Oxidation of CO in Hydrogen-Rich System

Facile Preparation of Nanoporous PtCu Alloys for Preferential Oxidation of CO in Hydrogen-Rich System

New chemistry of hydrogen-rich systems uncovered with the help of extreme conditions

New chemistry of hydrogen-rich systems uncovered with the help of extreme conditions

Superconductivity well above room temperature in compressed MgH6

It has been suggested that hydrogen-rich systems at high pressure may exhibit notably high super-conducting transition temperatures. One of the more interesting theoretical predictions was that hydrogen sulfide can be metallized and the high-temperature superconducting state can be induced. A record critical temperature (203 K) was later confirmed for H3S in an experiment. In this paper, we investigated, within the framework of the Eliashberg formalism, the properties of compressed MgH6, which is expected to be a very good candidate for room-temperature superconductivity. This applies particularly to the pressure range from 300 to 400 GPa, where the transition temperature is close to 400 K. Moreover, the estimated thermodynamic properties and the resulting dimensionless ratios exceed the predictions of the Bardeen–Cooper–Schrieffer theory. This behavior is attributed to the strong electron–phonon coupling and retardation effects existing in hydrogen-dominated materials under high pressure.

Electrode Properties for Water Electrolysis of Hydrophilic Carbon Paper with Thermal Anneal

Hydrogen is considered a potential future energy source. Among other applications of hydrogen, hydrogen-rich water is emerging as a new health care product in industrial areas. Water electrolysis is typically used to generate a hydrogen rich water system. We annealed 10AA carbon paper in air to use it as an electrode of a hydrogen rich water generator. Driven by annealing, structural changes of the carbon paper were identified by secondary electron microscope analysis. Depending on the various annealing temperatures, changes of the hydrophilic characteristics were demonstrated. The crystal structures of pristine and heat-treated carbon paper were characterized by X-ray diffraction. Improvement of the efficiency of the electrochemical oxygen evolution reaction was measured via linear voltammetry. The optimized annealing temperature of 10AA carbon paper showed the possibility of using this material as an effective hydrogen rich water generator.

THE EVOLVED MAIN-SEQUENCE CHANNEL: HST AND LBT OBSERVATIONS OF CSS 120422:111127+571239

The "evolved main-sequence (EMS)" channel is thought to contribute significantly to the population of AM CVn-type systems in the Galaxy, and also to the number of cataclysmic variables (CVs) detected below the period minimum for hydrogen rich systems. CSS 120422:J111127+571239 was discovered by the Catalina Sky Survey in 2012 April. Its period was found to be 56 minutes, well below the minimum, and the optical spectrum is clearly depleted in hydrogen relative to helium, but still has two orders of magnitude more hydrogen than AM CVn stars. Doppler tomography of the Hα line hinted at a spiral structure existing in the disk. Here we present spectroscopy of CSS 120422:J111127+571239 using the Cosmic Origins Spectrograph FUV instrument on the Hubble Space Telescope and using the MODS spectrograph on the Large Binocular Telescope. The UV spectrum shows Si iv, N v, and He ii, but no detectable C iv. The anomalous nitrogen/carbon ratio is seen in a small number of other CVs and confirms a unique binary evolution. We also present and compare the optical spectrum of V418 Ser and advocate that it is also an EMS system.

The Wade–Mingos rules in seven-vertex dimetallaborane chemistry: Hydrogen-rich Cp2M2B5H9 systems of the second and third row transition metals

The complete series of hydrogen-rich seven-vertex cyclopentadienyl dimetallaboranes Cp2M2B5H9 (Cp = η5-C5H5; M = Ir, Ru/Os, Re, Mo/W, Ta), including the experimentally known Mo and W derivatives, have been examined by density functional theory. The central M2B5 polyhedra depend on the skeletal electron count and, in most cases, can be related to the Wade–Mingos rules. Thus the six lowest-energy Cp2Ir2B5H9 structures with 18 Wadean skeletal electrons are all based on the expected nido polyhedron obtained by removal of a degree 5 vertex from a D2d bisdisphenoid. Similar geometries are also found for most of the lowest energy Cp2M2B5H9 structures (M = Ru, Os). The three lowest-energy Cp2Re2B5H9 structures all have central Re2B5 capped octahedra in accord with their 14 Wadean skeletal electrons. The low energy structures of the more hypoelectronic Cp2M2B5H9 (M = Mo, W, Ta) systems have bicapped trigonal bipyramid geometries in which the two MB2 faces of a central trigonal bipyramid are each capped by BH vertices. For Cp2M2B5H9 (M = Mo, W) the experimentally realized symmetrical D2h bicapped trigonal bipyramid structure of this type is obviously very favorable since it lies more than 23 kcal/mol in energy below the next lowest energy structure.

Percy W. Bridgman's second century

Percy Williams Bridgman's impact on science began in 1909 with his first three experimental papers. These publications on high pressure calibration, techniques, and compressibility, together with the many articles that followed, established his influence on the course of modern high pressure research. Grounded in classical thermodynamics and practical mechanics, his developments showed how the variable of pressure leads to myriad transformations in materials. Studies carried out under a broader range of conditions now provide unprecedented insights into chemical and physical properties at multimegabar pressures and temperatures from millikelvins to thousands of degrees, where novel electronic, magnetic, and superconducting phases are now being discovered. With careful attention to experimental techniques and material performance, Bridgman extended the available pressure range that could be achieved in the laboratory with the development of new devices. We are now witness to continued refinement of static and dynamic compression methods and in situ measurement techniques, including the marriage of high pressure methods with large facilities such as synchrotron, neutron, and laser sources. Bridgman showed the broad range of implications of this work; the modern field of high pressure research now spans physics and chemistry, geosciences and planetary science, materials science and technology, and biology. Selected examples illustrate Bridgman's impact and legacy in this, his second century. For dense hydrogen, new insights have been obtained from high P–T measurements as well as studies of alloys and compounds of hydrogen, leading to the creation of new metallic and superconducting phases. Studies of other hydrogen-rich systems provide both tests of fundamental theory and potentially useful materials for hydrogen storage. High pressure studies of oxides have led to new ferroelectric and multiferroic materials and phases with remarkable properties that guide the design and fabrication of new devices. With the discovery of super-Earths outside our solar system, the high pressure properties of silicates, oxides, volatiles, and the full complement of planetary materials are now problems of cosmic importance well beyond the conditions found on and within the Earth. Developments in high pressure biology are addressing the question of the depth of the biosphere, the processes and reservoirs of carbon in our planet, and new insights into the origins of life as we know it, as well as the possibility of extraterrestrial life. Improved materials that can withstand high P–T conditions and other extreme environments include new forms of diamond, which are advancing experimental methods and finding numerous applications in advanced technology. These developments dovetail with synergetic advances in a broad spectrum of radiation techniques including coherent X-ray, intense neutron, and ultrabright laser sources.

Atomistic Insights into the Running-in, Lubrication, and Failure of Hydrogenated Diamond-Like Carbon Coatings

The tribological performance of hydrogenated diamond-like carbon (DLC) coatings is studied by molecular dynamics simulations employing a screened reactive bond-order potential that has been adjusted to reliably describe bond-breaking under shear. Two types of DLC films are grown by CH2 deposition on an amorphous substrate with 45 and 60 eV impact energy resulting in 45 and 30% H content as well as 50 and 30% sp3 hybridization of the final films, respectively. By combining two equivalent realizations for both impact energies, a hydrogen-depleted and a hydrogen-rich tribo-contact is formed and studied for a realistic sliding speed of 20 m s−1 and loads of 1 and 5 GPa. While the hydrogen-rich system shows a pronounced drop of the friction coefficient for both loads, the hydrogen-depleted system exhibits such kind of running-in for 1 GPa, only. Chemical passivation of the DLC/DLC interface explains this running-in behavior. Fluctuations in the friction coefficient occurring at the higher load can be traced back to a cold welding of the DLC/DLC tribo-surfaces, leading to the formation of a transfer film (transferred from one DLC partner to the other) and the establishment of a new tribo-interface with a low friction coefficient. The presence of a hexadecane lubricant leads to low friction coefficients without any running-in for low loads. At 10 GPa load, the lubricant starts to degenerate resulting in enhanced friction.

High pressure chemistry in the H 2 -SiH 4 system

Understanding the behavior of hydrogen-rich systems at extreme conditions has significance to both condensed matter physics, where it may provide insight into the metallization and superconductivity of element one, and also to applied research areas, where it can provide guidance for designing improved hydrogen storage materials for transportation applications. Here we report the high-pressure study of the SiH4-H2 binary system up to 6.5 GPa at 300 K in a diamond anvil cell. Raman measurements indicate significant intermolecular interactions between H2 and SiH4. We found that the H2 vibron frequency is softened by the presence of SiH4 by as much as 40 cm(-1) for the fluid with 50 mol% H2 compared with pure H2 fluid at the same pressures. In contrast, the Si-H stretching modes of SiH4 shift to higher frequency in the mixed fluid compared with pure SiH4. Pressure-induced solidification of the H2-SiH4 fluid shows a binary eutectic point at 72(+/-2) mol% H2 and 6.1(+/-0.1) GPa, above which the fluid crystallizes into a mixture of two nearly end-member solids. Neither solid has a pure end-member composition, with the silane-rich solid containing 0.5-1.5 mol% H2 and the hydrogen-rich solid containing 0.5-1 mol% SiH4. These two crystalline phases can be regarded as doped hydrogen-dominant compounds. We were able to superpressurize the sample by 0.2-0.4 GPa above the eutectic before complete crystallization, indicating extended metastability.

No evidence of metallic methane at high pressure

Recently reported superconductivity in lithium under pressure has renewed the interest in hydrogen and hydrogen-rich systems in the long standing quest for room temperature superconductivity. As the required metallization of pure hydrogen cannot be achieved within current experimental capabilities, it has been suggested that the chemical precompression exerted by heavier atoms in compounds with a large hydrogen content should lower the required pressures to attain the metallic transition in these alloys. Following the trend of analyzing group IVa hydrides, we present an ab initio analysis of pressure-induced metallization of methane. According to our calculations, the metallization of methane is not predicted to occur below 520 GPa, which corresponds to a compression factor of 7.5.

Pressure induced metallization of Germane

Abstract Recently reported superconductivity in lithium under pressure has renewed the interest on hydrogen and hydrogen-rich systems in the long standing quest for room temperature superconductivity. Although the required metallization of pure hydrogen cannot be achieved within correct experimental capabilities, chemical precompression exerted by heavier atoms in compounds with a large hydrogen content is expected to imply that lower pressures might be required to attain the metallic transition in these alloys. In this article, we present an ab initio analysis of pressure induced metallization of germane, as a particular case between group IVa hydrides. According to our calculations, metallization of germane is predicted to occur at an experimentally accessible pressure of around 70 GPa, which corresponds to a compression factor of 3.4.