Hydrogen-Stabilized ScYNdGd Medium-Entropy Alloy for Hydrogen Storage.

The research on the functional properties of medium- and high-entropy alloys (MEAs and HEAs) has been in the spotlight recently. Many significant discoveries have been made lately in hydrogen-based economy-related research where these alloys may be utilized in all of its key sectors: water electrolysis, hydrogen storage, and fuel cell applications. Despite the rapid development of MEAs and HEAs with the ability to reversibly absorb hydrogen, the research is limited to transition-metal-based alloys that crystallize in body-centered cubic solid solution or Laves phase structures. To date, no study has been devoted to the hydrogenation of rare-earth-element (REE)-based MEAs or HEAs, as well as to the alloys crystallizing in face-centered-cubic (FCC) or hexagonal-close-packed structures. Here, we elucidate the formation and hydrogen storage properties of REE-based ScYNdGd MEA. More specifically, we present the astounding stabilization of the single-phase FCC structure induced by the hydrogen absorption process. Moreover, the measured unprecedented high storage capacity of 2.5 H/M has been observed after hydrogenation conducted under mild conditions that proceeded without any phase transformation in the material. The studied MEA can be facilely activated, even after a long passivation time. The results of complementary measurements showed that the hydrogen desorption process proceeds in two steps. In the first, hydrogen is released from octahedral interstitial sites at relatively low temperatures. In the second, high-temperature process, it is associated with the desorption of hydrogen atoms stored in tetrahedral sites. The presented results may impact future research of a novel group of REE-based MEAs and HEAs with adaptable hydrogen storage properties and a broad scope of possible applications.

Establishing ZIF-8 as a reference material for hydrogen cryoadsorption: An interlaboratory study.

Hydrogen storage by cryoadsorption on porous materials has the advantages of low material cost, safety, fast kinetics, and high cyclic stability. The further development of this technology requires reliable data on the H2 uptake of the adsorbents, however, even for activated carbons the values between different laboratories show sometimes large discrepancies. So far no reference material for hydrogen cryoadsorption is available. The metal-organic framework ZIF-8 is an ideal material possessing high thermal, chemical, and mechanical stability that reduces degradation during handling and activation. Here, we distributed ZIF-8 pellets synthesized by extrusion to 9 laboratories equipped with 15 different experimental setups including gravimetric and volumetric analyzers. The gravimetric H2 uptake of the pellets was measured at 77 K and up to 100 bar showing a high reproducibility between the different laboratories, with a small relative standard deviation of 3-4 % between pressures of 10-100 bar. The effect of operating variables like the amount of sample or analysis temperature was evaluated, remarking the calibration of devices and other correction procedures as the most significant deviation sources. Overall, the reproducible hydrogen cryoadsorption measurements indicate the robustness of the ZIF-8 pellets, which we want to propose as a reference material.

Chemical Affinity of Ag-Exchanged Zeolites for Efficient Hydrogen Isotope Separation.

We report an ion-exchanged zeolite as an excellent candidate for large-scale application in hydrogen isotope separation. Ag(I)-exchanged zeolite Y has been synthesized through a standard ion-exchange procedure. The D2/H2 separation performance has been systematically investigated via thermal desorption spectroscopy (TDS). Undercoordinated Ag+ in zeolite AgY acts as a strong adsorption site and adorbs preferentially the heavier isotopologue even above liquid nitrogen temperature. The highest D2/H2 selectivity of 10 is found at an exposure temperature of 90 K. Furthermore, the high Al content of the zeolite structure leads to a high density of Ag sites, resulting in a high gas uptake. In the framework, approximately one-third of the total physisorbed hydrogen isotopes are adsorbed on the Ag sites, corresponding to 3 mmol/g. A density functional theory (DFT) calculation reveals that the isotopologue-selective adsorption of hydrogen at Ag sites contributes to the outstanding hydrogen isotope separation, which has been directly observed through cryogenic thermal desorption spectroscopy. The overall performance of zeolite AgY, showing good selectivity combined with high gas uptake, is very promising for future technical applications.

Hydrogen Isotope Separation Using a Metal-Organic Cage Built from Macrocycles.

Porous materials that contain ultrafine pore apertures can separate hydrogen isotopes via kinetic quantum sieving (KQS). However, it is challenging to design materials with suitably narrow pores for KQS that also show good adsorption capacities and operate at practical temperatures. Here, we investigate a metal-organic cage (MOC) assembled from organic macrocycles and ZnII ions that exhibits narrow windows (<3.0 Å). Two polymorphs, referred to as 2α and 2ß, were observed. Both polymorphs exhibit D2 /H2 selectivity in the temperature range 30-100 K. At higher temperature (77 K), the D2 adsorption capacity of 2ß increases to about 2.7 times that of 2α, along with a reasonable D2 /H2 selectivity. Gas sorption analysis and thermal desorption spectroscopy suggest a gate-opening effect of the MOCs pore aperture. This promotes KQS at temperatures above liquid nitrogen temperature, indicating that MOCs hold promise for hydrogen isotope separation in real industrial environments.

Improving Reproducibility in Hydrogen Storage Material Research.

Research into new reversible hydrogen storage materials has the potential to help accelerate the transition to a hydrogen economy. The discovery of an efficient and cost-effective method of safely storing hydrogen would revolutionise its use as a sustainable energy carrier. Accurately measuring storage capacities - particularly of novel nanomaterials - has however proved challenging, and progress is being hindered by ongoing problems with reproducibility. Various metal and complex hydrides are being investigated, together with nanoporous adsorbents such as carbons, metal-organic frameworks and microporous organic polymers. The hydrogen storage properties of these materials are commonly determined using either the manometric (or Sieverts) technique or gravimetric methods, but both approaches are prone to significant error, if not performed with great care. Although commercial manometric and gravimetric instruments are widely available, they must be operated with an awareness of the limits of their applicability and the error sources inherent to the measurement techniques. This article therefore describes the measurement of hydrogen sorption and covers the required experimental procedures, aspects of troubleshooting and recommended reporting guidelines, with a view of helping improve reproducibility in experimental hydrogen storage material research.

Specific Isotope-Responsive Breathing Transition in Flexible Metal-Organic Frameworks.

An isotope-selective responsive system based on molecular recognition in porous materials has potential for the storage and purification of isotopic mixtures but is considered unachievable because of the almost identical physicochemical properties of the isotopes. Herein, a unique isotope-responsive breathing transition of the flexible metal-organic framework (MOF), MIL-53(Al), which can selectively recognize and respond to only D2 molecules through a secondary breathing transition, is reported. This novel phenomenon is examined using in situ neutron diffraction experiments under the same conditions for H2 and D2 sorption experiments. This work can guide the development of a novel isotope-selective recognition system and provide opportunities to fabricate flexible MOF systems for energy-efficient purification of the isotopic mixture.

Exploiting Dynamic Opening of Apertures in a Partially Fluorinated MOF for Enhancing H2 Desorption Temperature and Isotope Separation.

Deuterium has been recognized as an irreplaceable element in industrial and scientific research. However, hydrogen isotope separation still remains a huge challenge due to the identical physicochemical properties of the isotopes. In this paper, a partially fluorinated metal-organic framework (MOF) with copper, a so-called FMOFCu, was investigated to determine the separation efficiency and capacity of the framework for deuterium extraction from a hydrogen isotope mixture. The unique structure of this porous material consists of a trimodal pore system with large tubular cavities connected through a smaller cavity with bottleneck apertures with a size of 3.6 Å plus a third hidden cavity connected by an even smaller aperture of 2.5 Å. Depending on the temperature, these two apertures show a gate-opening effect and the cavities get successively accessible for hydrogen with increasing temperature. Thermal desorption spectroscopy (TDS) measurements indicate that the locally flexible MOF can separate D2 from anisotope mixture efficiently, with a selectivity of 14 at 25 K and 4 at 77 K.

Systematic Experimental Study on Quantum Sieving of Hydrogen Isotopes in Metal-Amide-Imidazolate Frameworks with narrow 1-D Channels.

Quantum sieving of hydrogen isotopes is experimentally studied in isostructural hexagonal metal-organic frameworks having 1-D channels, named IFP-1, -3, -4 and -7. Inside the channels, different molecules or atoms restrict the channel diameter periodically with apertures larger (4.2 Šfor IFP-1, 3.1 Šfor IFP-3) and smaller (2.1 Šfor IFP-7, 1.7 Šfor IFP-4) than the kinetic diameter of hydrogen isotopes. From a geometrical point of view, no gas should penetrate into IFP-7 and IFP-4, but due to the thermally induced flexibility, so-called gate-opening effect of the apertures, penetration becomes possible with increasing temperature. Thermal desorption spectroscopy (TDS) measurements with pure H2 or D2 have been applied to study isotope adsorption. Further TDS experiments after exposure to an equimolar H2 /D2 mixture allow to determine directly the selectivity of isotope separation by quantum sieving. IFP-7 shows a very low selectivity not higher than S=2. The selectivity of the materials with the smallest pore aperture IFP-4 has a constant value of S≈2 for different exposure times and pressures, which can be explained by the 1-D channel structure. Due to the relatively small cavities between the apertures of IFP-4 and IFP-7, molecules in the channels cannot pass each other, which leads to a single-file filling. Therefore, no time dependence is observed, since the quantum sieving effect occurs only at the outermost pore aperture, resulting in a low separation selectivity.

An International Laboratory Comparison Study of Volumetric and Gravimetric Hydrogen Adsorption Measurements.

In order to determine a material's hydrogen storage potential, capacity measurements must be robust, reproducible, and accurate. Commonly, research reports focus on the gravimetric capacity, and often times the volumetric capacity is not reported. Determining volumetric capacities is not as straight-forward, especially for amorphous materials. This is the first study to compare measurement reproducibility across laboratories for excess and total volumetric hydrogen sorption capacities based on the packing volume. The use of consistent measurement protocols, common analysis, and figure of merits for reporting data in this study, enable the comparison of the results for two different materials. Importantly, the results show good agreement for excess gravimetric capacities amongst the laboratories. Irreproducibility for excess and total volumetric capacities is attributed to real differences in the measured packing volume of the material.

Dynamic Janus Metasurfaces in the Visible Spectral Region.

Janus monolayers have long been captivated as a popular notion for breaking in-plane and out-of-plane structural symmetry. Originated from chemistry and materials science, the concept of Janus functions have been recently extended to ultrathin metasurfaces by arranging meta-atoms asymmetrically with respect to the propagation or polarization direction of the incident light. However, such metasurfaces are intrinsically static and the information they carry can be straightforwardly decrypted by scanning the incident light directions and polarization states once the devices are fabricated. In this Letter, we present a dynamic Janus metasurface scheme in the visible spectral region. In each super unit cell, three plasmonic pixels are categorized into two sets. One set contains a magnesium nanorod and a gold nanorod that are orthogonally oriented with respect to each other, working as counter pixels. The other set only contains a magnesium nanorod. The effective pixels on the Janus metasurface can be reversibly regulated by hydrogenation/dehydrogenation of the magnesium nanorods. Such dynamic controllability at visible frequencies allows for flat optical elements with novel functionalities including beam steering, bifocal lensing, holographic encryption, and dual optical function switching.

Selective Hydrogen Isotope Separation via Breathing Transition in MIL-53(Al).

Breathing of MIL-53(Al), a flexible metal-organic framework (MOF), leads to dynamic changes as narrow pore (np) transitions to large pore (lp). During the flexible and reversible transition, the pore apertures are continuously adjusted, thus providing the tremendous opportunity to separate mixtures of similar-sized and similar-shaped molecules that require precise pore tuning. Herein, for the first time, we report a strategy for effectively separating hydrogen isotopes through the dynamic pore change during the breathing of MIL-53(Al), a representative of flexible MOFs. The experiment shows that the selectivity for D2 over H2 is strongly related to the state of the pore structure of MIL-53(Al). The highest selectivity (SD2/H2 = 13.6 at 40 K) was obtained by optimizing the exposure temperature, pressure, and time to systematically tune the pore state of MIL-53(Al).

Exploiting Diffusion Barrier and Chemical Affinity of Metal-Organic Frameworks for Efficient Hydrogen Isotope Separation.

Deuterium plays a pivotal role in industrial and scientific research, and is irreplaceable for various applications such as isotope tracing, neutron moderation, and neutron scattering. In addition, deuterium is a key energy source for fusion reactions. Thus, the isolation of deuterium from a physico-chemically almost identical isotopic mixture is a seminal challenge in modern separation technology. However, current commercial approaches suffer from extremely low separation efficiency (i.e., cryogenic distillation, selectivity of 1.5 at 24 K), requiring a cost-effective and large-scale separation technique. Herein, we report a highly effective hydrogen isotope separation system based on metal-organic frameworks (MOFs) having the highest reported separation factor as high as ∼26 at 77 K by maximizing synergistic effects of the chemical affinity quantum sieving (CAQS) and kinetic quantum sieving (KQS). For this purpose, the MOF-74 system having high hydrogen adsorption enthalpies due to strong open metal sites is chosen for CAQS functionality, and imidazole molecules (IM) are employed to the system for enhancing the KQS effect. To the best of our knowledge, this work is not only the first attempt to implement two quantum sieving effects, KQS and CAQS, in one system, but also provides experimental validation of the utility of this system for practical industrial usage by isolating high-purity D2 through direct selective separation studies using 1:1 D2/H2 mixtures.

Direct patterning of vortex generators on a fiber tip using a focused ion beam.

The realization of spiral phase optical elements on the cleaved end of an optical fiber by focused ion beam milling is presented. A focused Ga+ ion beam with an acceleration voltage of 30 keV is used to etch continuous spiral phase plates and fork gratings directly on the tip of the fiber. The phase characteristics of the output beam generated by the fabricated structures measured via an interference experiment confirmed the presence of phase singularity in the output beam. The devices are expected to be promising candidates for all-fiber beam shaping and optical trapping applications.

"Job-Sharing" Storage of Hydrogen in Ru/Li2O Nanocomposites.

A "job-sharing" hydrogen storage mechanism is proposed and experimentally investigated in Ru/Li2O nanocomposites in which H(+) is accommodated on the Li2O side, while H(-) or e(-) is stored on the side of Ru. Thermal desorption-mass spectroscopy results show that after loading with D2, Ru/Li2O exhibits an extra desorption peak, which is in contrast to Ru nanoparticles or ball-milled Li2O alone, indicating a synergistic hydrogen storage effect due to the presence of both phases. By varying the ratio of the two phases, it is shown that the effect increases monotonically with the area of the heterojunctions, indicating interface related hydrogen storage. X-ray diffraction, Fourier transform infrared spectroscopy, and nuclear magnetic resonance results show that a weak LiO···D bond is formed after loading in Ru/Li2O nanocomposites with D2. The storage-pressure curve seems to favor H(+)/H(-) over H(+)/e(-) mechanism.

Small-pore hydridic frameworks store densely packed hydrogen.

Nanoporous materials have attracted great attention for gas storage, but achieving high volumetric storage capacity remains a challenge. Here, by using neutron powder diffraction, volumetric gas adsorption, inelastic neutron scattering and first-principles calculations, we investigate a magnesium borohydride framework that has small pores and a partially negatively charged non-flat interior for hydrogen and nitrogen uptake. Hydrogen and nitrogen occupy distinctly different adsorption sites in the pores, with very different limiting capacities of 2.33 H2 and 0.66 N2 per Mg(BH4)2. Molecular hydrogen is packed extremely densely, with about twice the density of liquid hydrogen (144 g H2 per litre of pore volume). We found a penta-dihydrogen cluster where H2 molecules in one position have rotational freedom, whereas H2 molecules in another position have a well-defined orientation and a directional interaction with the framework. This study reveals that densely packed hydrogen can be stabilized in small-pore materials at ambient pressures.

ZIF-8 Pellets as a Robust Material for Hydrogen Cryo-Adsorption Tanks.

Cryoadsorption on the inner surface of porous materials is a promising solution for safe, fast, and reversible hydrogen storage. Within the class of highly porous metal-organic frameworks, zeolitic imidazolate frameworks (ZIFs) show high thermal, chemical, and mechanical stability. In this study, we selected ZIF-8 synthesized mechanochemically by twin-screw extrusion as powder and pellets. The hydrogen storage capacity at 77 K and up to 100 bar has been analyzed in two laboratories applying three different measurement setups showing a high reproducibility. Pelletizing ZIF-8 increases the packing density close to the corresponding value for a single crystal without loss of porosity, resulting in an improved volumetric hydrogen storage capacity close to the upper limit for a single crystal. The high volumetric uptake combined with a low and constant heat of adsorption provides ca. 31 g of usable hydrogen per liter of pellet assuming a temperature-pressure swing adsorption process between 77 K - 100 bar and 117 K - 5 bar. Cycling experiments do not indicate any degradation in storage capacity. The excellent stability during preparation, handling, and operation of ZIF-8 pellets demonstrates its potential as a robust adsorbent material for technical application in pilot- and full-scale adsorption vessel prototypes.

A squarate-pillared titanium oxide quantum sieve towards practical hydrogen isotope separation.

Separating deuterium from hydrogen isotope mixtures is of vital importance to develop nuclear energy industry, as well as other isotope-related advanced technologies. As one of the most promising alternatives to conventional techniques for deuterium purification, kinetic quantum sieving using porous materials has shown a great potential to address this challenging objective. From the knowledge gained in this field; it becomes clear that a quantum sieve encompassing a wide range of practical features in addition to its separation performance is highly demanded to approach the industrial level. Here, the rational design of an ultra-microporous squarate pillared titanium oxide hybrid framework has been achieved, of which we report the comprehensive assessment towards practical deuterium separation. The material not only displays a good performance combining high selectivity and volumetric uptake, reversible adsorption-desorption cycles, and facile regeneration in adsorptive sieving of deuterium, but also features a cost-effective green scalable synthesis using chemical feedstock, and a good stability (thermal, chemical, mechanical and radiolytic) under various working conditions. Our findings provide an overall assessment of the material for hydrogen isotope purification and the results represent a step forward towards next generation practical materials for quantum sieving of important gas isotopes.

Metal@COFs: covalent organic frameworks as templates for Pd nanoparticles and hydrogen storage properties of Pd@COF-102 hybrid material.

Three-dimensional covalent organic frameworks (COFs) have been demonstrated as a new class of templates for nanoparticles. Photodecomposition of the [Pd(η(3)-C(3) H(5))(η(5)-C(5)H(5))]@COF-102 inclusion compound (synthesized by a gas-phase infiltration method) led to the formation of the Pd@COF-102 hybrid material. Advanced electron microscopy techniques (including high-angle annular dark-field scanning transmission electron microscopy and electron tomography) along with other conventional characterization techniques unambiguously showed that highly monodisperse Pd nanoparticles ((2.4±0.5) nm) were evenly distributed inside the COF-102 framework. The Pd@COF-102 hybrid material is a rare example of a metal-nanoparticle-loaded porous crystalline material with a very narrow size distribution without any larger agglomerates even at high loadings (30 wt %). Two samples with moderate Pd content (3.5 and 9.5 wt %) were used to study the hydrogen storage properties of the metal-decorated COF surface. The uptakes at room temperature from these samples were higher than those of similar systems such as Pd@metal-organic frameworks (MOFs). The studies show that the H(2) capacities were enhanced by a factor of 2-3 through Pd impregnation on COF-102 at room temperature and 20 bar. This remarkable enhancement is not just due to Pd hydride formation and can be mainly ascribed to hydrogenation of residual organic compounds, such as bicyclopentadiene. The significantly higher reversible hydrogen storage capacity that comes from decomposed products of the employed organometallic Pd precursor suggests that this discovery may be relevant to the discussion of the spillover phenomenon in metal/MOFs and related systems.

Novel characterization of the adsorption sites in large pore metal-organic frameworks: combination of X-ray powder diffraction and thermal desorption spectroscopy.

The preferred adsorption sites of xenon in the recently synthesized metal-organic framework MFU-4l(arge) possessing a bimodal pore structure (with pore sizes of 12 Å and 18.6 Å) were studied via the combination of low temperature thermal desorption spectroscopy and in situ X-ray powder diffraction. The diffraction patterns were collected at 110 K and 150 K according to the temperature of the desorption maxima. The maximum entropy method was used to reconstruct the electron density distribution of the structure and to localize the adsorbed xenon using refined data of the Xe-filled and empty sample. First principles calculations revealed that Xe atoms exclusively occupy the Wyckoff 32f position at approximately 2/3 2/3 2/3 along the body diagonal of the cubic crystal structure. At 110 K, Xe atoms occupy all 32 f positions (8 atoms per pore) while at 150 K the occupancy descends to 25% (2 atoms per pore). No Xe occupation of the small pores is observed by neither experimental measurements nor theoretical studies.