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.

Producing Alkali Metal Hydrides from Hydroxides.

In this study, a novel method for producing different alkali metal hydrides (NaH, KH, RbH, and CsH) from their corresponding metal hydroxides (NaOH, KOH, RbOH, and CsOH) is presented. For the production of NaH from NaOH, a variety of metallic reducing agents (Mg, Al, Si, CaH2, Cr, Mn, and Sr) were investigated. The reactions took place in an autoclave reactor with paraffin oil at 250 °C and 14 bar of H2 pressure. Splitting the process into two steps (metal formation and hydrogenation) simplified the separation and purification for the produced metal hydride. Moreover, the study explores the potential for this method of NaH production to be used for NaBH4 production and regeneration for hydrogen export applications. This approach offers an alternative, cost-effective method for producing NaH.

Divalent closo-monocarborane solvates for solid-state ionic conductors.

Li-ion batteries have held the dominant position in battery research for the last 30+ years. However, due to inadequate resources and the cost of necessary elements (e.g., lithium ore) in addition to safety issues concerning the components and construction, it has become more important to look at alternative technologies. Multivalent metal batteries with solid-state electrolytes are a potential option for future battery applications. The synthesis and characterisation of divalent hydrated closo-monocarborane salts - Mg[CB11H12]2·xH2O, Ca[CB11H12]2·xH2O, and Zn[CB11H12]2·xH2O - have shown potential as solid-state electrolytes. The coordination of a solvent (e.g. H2O) to the cation in these complexes shows a significant improvement in ionic conductivity, i.e. for Zn[CB11H12]2·xH2O dried at 100 °C (10-3 S cm-1 at 170 °C) and dried at 150 °C (10-5 S cm-1 at 170 °C). Solvent choice also proved important with the ionic conductivity of Mg[CB11H12]2·3en (en = ethylenediamine) being higher than that of Mg[CB11H12]2·3.1H2O (2.6 × 10-5 S cm-1 and 1.7 × 10-8 S cm-1 at 100 °C, respectively), however, the oxidative stability was lower (<1 V (Mg2+/Mg) and 1.9 V (Mg2+/Mg), respectively). Thermal characterisation of the divalent closo-monocarborane salts showed melting and desolvation, prior to high temperature decomposition.

Thermochemical energy storage in barium carbonate enhanced by iron(III) oxide.

Renewable energy requires cost effective and reliable storage to compete with fossil fuels. This study introduces a new reactive carbonate composite (RCC) where Fe2O3 is used to thermodynamically destabilise BaCO3 and reduce its decomposition temperature from 1400 °C to 850 °C, which is more suitable for thermal energy storage applications. Fe2O3 is consumed on heating to form BaFe12O19, which is a stable Fe source for promoting reversible CO2 reactions. Two reversible reaction steps were observed that corresponded to, first, the reaction between ß-BaCO3 and BaFe12O19, and second, between γ-BaCO3 and BaFe12O19. The thermodynamic parameters were determined to be ΔH = 199 ± 6 kJ mol-1 of CO2, ΔS = 180 ± 6 J K-1 mol-1 of CO2 and ΔH = 212 ± 6 kJ mol-1 of CO2, ΔS = 185 ± 7 J K-1 mol-1 of CO2, respectively, for the two reactions. Due to the low-cost and high gravimetric and volumetric energy density, the RCC is demonstrated to be a promising candidate for next generation thermal energy storage.

Stannaborates: tuning the ion conductivity of dodecaborate salts with tin substitution.

Metal substituted dodecaborate anions can be coupled with alkali metal cations to have great potential as solid-state ion conductors for battery applications. A tin atom can replace a B-H unit within an unsubstituted dodecaborate cage to produce a stable, polar divalent anion. The chemical and structural change in forming a stannaborate results in a modified crystal structure of respective group 1 metal salts, and as a result, improves the material's ion conductivity. Li2B11H11Sn shows high ion conductivity of ∼8 mS cm-1 at 130 °C, similar to the state-of-the-art LiCB11H12 at these temperatures, however, obtaining high ion conductivity at room temperature is not possible with pristine alkali metal stannaborates.

Role of π-Radical Localization on Thermally Stable Cross-Links Between Polycyclic Aromatic Hydrocarbons.

The thermal stability of cross-links between polycyclic aromatic hydrocarbons (PAHs) is critical for understanding the formation of soot pollutants, graphite, and carbon blacks. Recently, a variety of different π-radicals have been directly imaged and suggested to enable thermally stable bonding; however, a systematic study of reactivity has been lacking. In this work, we use density functional theory to study the reactivity of PAH π-radicals. The Mulliken spin densities are initially used to categorize the different classes of localization, and the bond energy is computed to determine the degree of localization required for thermal stability. The results showed that the bond energies of PAHs are strongly correlated with the calculated spin densities, but bond energies do not exist with the bond lengths due to significant rearrangement and steric effects during bond formation. A threshold for π-radical localization is suggested that will be stable in combustion and pyrolysis environments of ρMα ≥ 0.5. Finally, the formation of multicenter bonds between localized and delocalized π-radicals was investigated using the nudge elastic band (NEB) scan, and it was found that only delocalized π-radicals provided local energy minima. These results show that the localization of π-radicals is critical for the formation of thermally stable single-center bonds between aromatic radicals.

Sources of systematic error in DCE-MRI estimation of low-level blood-brain barrier leakage.

PURPOSE: Dynamic contrast-enhanced (DCE) -MRI with Patlak model analysis is increasingly used to quantify low-level blood-brain barrier (BBB) leakage in studies of pathophysiology. We aimed to investigate systematic errors due to physiological, experimental, and modeling factors influencing quantification of the permeability-surface area product PS and blood plasma volume vp , and to propose modifications to reduce the errors so that subtle differences in BBB permeability can be accurately measured. METHODS: Simulations were performed to predict the effects of potential sources of systematic error on conventional PS and vp quantification: restricted BBB water exchange, reduced cerebral blood flow, arterial input function (AIF) delay and B1+ error. The impact of targeted modifications to the acquisition and processing were evaluated, including: assumption of fast versus no BBB water exchange, bolus versus slow injection of contrast agent, exclusion of early data from model fitting and B1+ correction. The optimal protocol was applied in a cohort of recent mild ischaemic stroke patients. RESULTS: Simulation results demonstrated substantial systematic errors due to the factors investigated (absolute PS error ≤ 4.48 × 10-4 min-1 ). However, these were reduced (≤0.56 × 10-4 min-1 ) by applying modifications to the acquisition and processing pipeline. Processing modifications also had substantial effects on in-vivo normal-appearing white matter PS estimation (absolute change ≤ 0.45 × 10-4 min-1 ). CONCLUSION: Measuring subtle BBB leakage with DCE-MRI presents unique challenges and is affected by several confounds that should be considered when acquiring or interpreting such data. The evaluated modifications should improve accuracy in studies of neurodegenerative diseases involving subtle BBB breakdown.

Synthesis of closo-CB11H12- Salts Using Common Laboratory Reagents.

Lithium and sodium salts of the closo-carbadodecaborate anion [CB11H12]- have been shown to form stable solid-state electrolytes with excellent ionic conductivity for all-solid-state batteries (ASSB). However, potential commercial application is currently hindered by the difficult, low-yielding, and expensive synthetic pathways. We report a novel and cost-effective method to synthesize the [CB11H12]- anion in a 40% yield from [B11H14]-, which can be synthesized using common laboratory reagents. The method avoids the use of expensive and dangerous reagents such as NaH, decaborane, and CF3SiMe3 and shows excellent reproducibility in product yield and purity.

Thermochemical energy storage performance of zinc destabilized calcium hydride at high-temperatures.

CaH2 has 20 times the energy density of molten salts and was patented in 2010 as a potential solar thermal energy storage material. Unfortunately, its high operating temperature (>1000 °C) and corrosivity at that temperature make it challenging to use as a thermal energy storage (TES) material in concentrating solar power (CSP) plants. To overcome these practical limitations, here we propose the thermodynamic destabilization of CaH2 with Zn metal. It is a unique approach that reduces the decomposition temperature of pure CaH2 (1100 °C at 1 bar of H2 pressure) to 597 °C at 1 bar of H2 pressure. Its new decomposition temperature is closer to the required target temperature range for TES materials used in proposed third-generation high-temperature CSP plants. A three-step dehydrogenation reaction between CaH2 and Zn (1 : 3 molar ratio) was identified from mass spectrometry, temperature-programmed desorption and in situ X-ray diffraction studies. Three reaction products, CaZn13, CaZn11 and CaZn5, were confirmed from in situ X-ray diffraction studies at 190 °C, 390 °C and 590 °C, respectively. The experimental enthalpy and entropy of the second hydrogen release reaction were determined by pressure composition isotherm measurements, conducted between 565 and 614 °C, as ΔHdes = 131 ± 4 kJ mol-1 H2 and ΔSdes = 151 ± 4 J K-1 mol-1 H2. Hydrogen cycling studies of CaZn11 at 580 °C showed sufficient cycling capacity with no significant sintering occurring during heating, as confirmed by scanning electron microscopy, demonstrating its great potential as a TES material for CSP applications. Finally, a cost comparison study of known destabilized CaH2 systems was carried out to assess the commercial potential.

Thermal properties of thermochemical heat storage materials.

The thermal conductivity, thermal diffusivity and heat capacity of materials are all vital properties in the determination of the efficiency of a thermal system. However, the thermal transport properties of heat storage materials are not consistent across previous studies, and are strongly dependent on the sample composition and measurement method. A comprehensive analysis of thermal transport properties using a consistent preparation and measurement method is lacking. This study aims to provide the foundation for a detailed insight into thermochemical heat storage material properties with consistent measurement methods. The thermal transport properties of pelletised metal hydrides, carbonates and oxides were measured using the transient plane source method to provide the thermal conductivity, thermal diffusivity and heat capacity. This information is valuable in the development of energy storage and chemical processing systems that are highly dependent on the thermal conductivity of materials.

Interrogation of the Effect of Polymorphism of a Metal-Organic Framework Host on the Structure of Embedded Pd Guest Nanoparticles.

Metal-organic frameworks (MOFs) are very promising host materials for nanoscale guest materials. However, some MOFs such as MIL-53 are known to undergo phase transitions which can complicate the guest particle size control. In this study, Pd nanoparticles embedded in Al-MIL-53 were synthesised via (a) electrodeposition and (b) gas-phase reduction. A thorough structural investigation revealed that each synthesis method most likely favoured a different phase of Al-MIL-53, presenting the possibility of MOF phase selection as a technique for size control of embedded nanoparticles. For the first time, we hereby report the use of pair distribution function analysis to successfully investigate the structure and morphology of guest particles embedded in a MOF host.

Thermodynamics and performance of the Mg-H-F system for thermochemical energy storage applications.

Magnesium hydride (MgH2) is a hydrogen storage material that operates at temperatures above 300 °C. Unfortunately, magnesium sintering occurs above 420 °C, inhibiting its application as a thermal energy storage material. In this study, the substitution of fluorine for hydrogen in MgH2 to form a range of Mg(HxF1-x)2 (x = 1, 0.95, 0.85, 0.70, 0.50, 0) composites has been utilised to thermodynamically stabilise the material, so it can be used as a thermochemical energy storage material that can replace molten salts in concentrating solar thermal plants. These materials have been studied by in situ synchrotron X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, temperature-programmed-desorption mass spectrometry and Pressure-Composition-Isothermal (PCI) analysis. Thermal analysis has determined that the thermal stability of Mg-H-F solid solutions increases proportionally with fluorine content, with Mg(H0.85F0.15)2 having a maximum rate of H2 desorption at 434 °C, with a practical hydrogen capacity of 4.6 ± 0.2 wt% H2 (theoretical 5.4 wt% H2). An extremely stable Mg(H0.43F0.57)2 phase is formed upon the decomposition of each Mg-H-F composition of which the remaining H2 is not released until above 505 °C. PCI measurements of Mg(H0.85F0.15)2 have determined the enthalpy (ΔHdes) to be 73.6 ± 0.2 kJ mol-1 H2 and entropy (ΔSdes) to be 131.2 ± 0.2 J K-1 mol-1 H2, which is slightly lower than MgH2 with ΔHdes of 74.06 kJ mol-1 H2 and ΔSdes = 133.4 J K-1 mol-1 H2. Cycling studies of Mg(H0.85F0.15)2 over six absorption/desorption cycles between 425 and 480 °C show an increased usable cycling temperature of ∼80 °C compared to bulk MgH2, increasing the thermal operating temperatures for technological applications.

Correction of inter-scan motion artifacts in quantitative R1 mapping by accounting for receive coil sensitivity effects.

PURPOSE: Inter-scan motion causes differential receive field modulation between scans, leading to errors when they are combined to quantify MRI parameters. We present a robust and efficient method that accounts for inter-scan motion by removing this modulation before parameter quantification. THEORY AND METHODS: Five participants moved between two high-resolution structural scans acquired with different flip angles. Before each high-resolution scan, the effective relative sensitivity of the receive head coil was estimated by combining two rapid low-resolution scans acquired receiving on each of the body and head coils. All data were co-registered and sensitivity variations were removed from the high-resolution scans by division with the effective relative sensitivity. R1 maps with and without this correction were calculated and compared against reference maps unaffected by inter-scan motion. RESULTS: Even after coregistration, inter-scan motion significantly biased the R1 maps, leading to spurious variation in R1 in brain tissue and deviations with respect to a no-motion reference. The proposed correction scheme reduced the error to within the typical scan-rescan error observed in datasets unaffected by motion. CONCLUSION: Inter-scan motion negatively impacts the accuracy and precision of R1 mapping. We present a validated correction method that accounts for position-specific receive field modulation. Magn Reson Med 76:1478-1485, 2016. © 2015 The Authors. Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

A force balance can explain local and global cell movements during early zebrafish development.

Embryonic morphogenesis takes place via a series of dramatic collective cell movements. The mechanisms that coordinate these intricate structural transformations across an entire organism are not well understood. In this study, we used gentle mechanical deformation of developing zebrafish embryos to probe the role of physical forces in generating long-range intercellular coordination during epiboly, the process in which the blastoderm spreads over the yolk cell. Geometric distortion of the embryo resulted in nonuniform blastoderm migration and realignment of the anterior-posterior (AP) axis, as defined by the locations at which the head and tail form, toward the new long axis of the embryo and away from the initial animal-vegetal axis defined by the starting location of the blastoderm. We found that local alterations in the rate of blastoderm migration correlated with the local geometry of the embryo. Chemical disruption of the contractile ring of actin and myosin immediately vegetal to the blastoderm margin via Ca(2+) reduction or treatment with blebbistatin restored uniform migration and eliminated AP axis reorientation in mechanically deformed embryos; it also resulted in cellular disorganization at the blastoderm margin. Our results support a model in which tension generated by the contractile actomyosin ring coordinates epiboly on both the organismal and cellular scales. Our observations likewise suggest that the AP axis is distinct from the initial animal-vegetal axis in zebrafish.

Structural and kinetic investigation of the hydride composite Ca(BH4)2 + MgH2 system doped with NbF5 for solid-state hydrogen storage.

Designing safe, compact and high capacity hydrogen storage systems is the key step towards introducing a pollutant free hydrogen technology into a broad field of applications. Due to the chemical bonds of hydrogen-metal atoms, metal hydrides provide high energy density in safe hydrogen storage media. Reactive hydride composites (RHCs) are a promising class of high capacity solid state hydrogen storage systems. Ca(BH4)2 + MgH2 with a hydrogen content of 8.4 wt% is one of the most promising members of the RHCs. However, its relatively high desorption temperature of ∼350 °C is a major drawback to meeting the requirements for practical application. In this work, by using NbF5 as an additive, the dehydrogenation temperature of this RHC was significantly decreased. To elucidate the role of NbF5 in enhancing the desorption properties of the Ca(BH4)2 + MgH2 (Ca-RHC), a comprehensive investigation was carried out via manometric measurements, mass spectrometry, Differential Scanning Calorimetry (DSC), in situ Synchrotron Radiation-Powder X-ray Diffraction (SR-PXD), X-ray Absorption Spectroscopy (XAS), Anomalous Small-Angle X-ray Scattering (ASAXS), Scanning and Transmission Electron Microscopy (SEM, TEM) and Nuclear Magnetic Resonance (NMR) techniques.

Alkali metal alkoxyborate ester salts; a contemporary look at old compounds.

Research into the use of sodium tetraalkoxyborate salts for different chemical applications including synthetic catalysis, hydrogen storage, or battery applications has been investigated, however, understanding of the structural, thermal and electrochemical properties of these salts has been lacking since the 1950s and 1960s. A review of the synthesis, as well as a thorough characterization using 1H NMR, 11B NMR, 13C{1H} NMR, FTIR, XRD, in situ XRD, DSC-TGA, RGA-MS, TPPA, and EIS has newly identified polymorphic phase changes for Na[B(OMe)4], K[B(OMe)4], Li[B(OMe)4], Na[B(OEt)4], Na[B(OBu)4], and Na[B(OiBu)4]. The crystal structure of K[B(OMe)4] was also solved in I41/a (a = 22.337(2) Å, c = 7.648(3) Å, V = 3815.6(4) Å3, ρ = 1.128(1) g cm-3). Ionic conductivity of the different salts was analyzed, however it was found that the compounds with longer alkyl chains had no measurable ionic conductivity compared to the shorter chained samples, Na[B(OMe)4] and K[B(OMe)4] with 9.6 × 10-8 S cm-1 and 1.6 × 10-7 S cm-1, at 114 °C respectively.

Ionic conduction in ammonia functionalised closo-dodecaborates MB12H11NH3 (M = Li and Na).

Metal hydroborates and their derivatives have been receiving attention as potential solid-state ion conductors for battery applications owing to their impressive electrochemical and mechanical characteristics. However, to date only a fraction of these compounds has been investigated as solid-state electrolytes. Here, MB12H11NH3 (M = Li and Na) hydroborates are synthesized and investigated as electrolyte materials for all-solid-state batteries. The room temperature α-NaB12H11NH3 was structurally solved in P212121 (a = 7.1972(3) Å, b = 9.9225(4) Å, and c = 14.5556(5) Å). It shows a polymorphic structural transition near 140 °C to cubic Fm3̄m. LiB12H11NH3 and NaB12H11NH3 exhibit cationic conductivities of σ(Li+) = 3.0 × 10-4 S cm-1 and σ(Na+) = 1.2 × 10-4 S cm-1 at 200 °C. Hydration is found to improve ionic conductivity of the hydroborates. It is presumed that modest ionic conductivities could be due to a lack of significant re-orientational dynamics in the crystal structure resulting from the presence of the bulky -NH3 group in the anion.

Thermal stability of Li2B12H12 and its role in the decomposition of LiBH4.

The purpose of this study is to compare the thermal and structural stability of single phase Li2B12H12 with the decomposition process of LiBH4. We have utilized differential thermal analysis/thermogravimetry (DTA/TGA) and temperature programmed desorption-mass spectroscopy (TPD-MS) in combination with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy to study the decomposition products of both LiBH4 and Li2B12H12 up to 600 °C, under both vacuum and hydrogen (H2) backpressure. We have synthesized highly pure single phase crystalline anhydrous Li2B12H12 (Pa-3 structure type) and studied its sensitivity to water and the process of deliquescence. Under either vacuum or H2 backpressure, after 250 °C, anhydrous Li2B12H12 begins to decompose to a substoichiometric Li2B12H12-x composition, which displays a very broad diffraction halo in the d-spacing range 5.85-7.00 Å, dependent on the amount of H released. Aging Pa-3 Li2B12H12 under 450 °C/125 bar H2 pressure for 24 h produces a previously unobserved well-crystallized ß-Li2B12H12 polymorph, and a nanocrystalline γ-Li2B12H12 polymorph. The isothermal release of hydrogen pressure from LiBH4 along the plateau and above the melting point (Tm = 280 °C) initially results in the formation of LiH and γ-Li2B12H12. The γ-Li2B12H12 polymorph then decomposes to a substoichiometric Li2B12H(12-x) composition. The Pa-3 Li2B12H12 phase is not observed during LiBH4 decomposition. Decomposition of LiBH4 under vacuum to 600 °C produces LiH and amorphous B with some Li dissolved within it. The lack of an obvious B-Li-B or B-H-B bridging band in the FTIR data for Li2B12H(12-x) suggests the H poor B12H(12-x) pseudo-icosahedra remain isolated and are not polymerized. Li2B12H(12-x) is persistent to at least 600 °C under vacuum, with no LiH formation observable and only a ca. d = 7.00 Å halo remaining. By 650 °C, Li2B12H(12-x) is finally decomposed, and amorphous B can be observed, with no LiH reflections. Further studies are required to clarify the structural symmetry of the ß- and γ-Li2B12H12 polymorphs and substoichiometric Li2B12H(12-x).

Eutectic melting in metal borohydrides.

A series of monometallic borohydrides and borohydride eutectic mixtures have been investigated during thermal ramping by mass spectroscopy, differential scanning calorimetry, and photography. Mixtures of LiBH4-NaBH4, LiBH4-KBH4, LiBH4-Mg(BH4)2, LiBH4-Ca(BH4)2, LiBH4-Mn(BH4)2, NaBH4-KBH4, and LiBH4-NaBH4-KBH4 all displayed melting behaviour below that of the monometallic phases (up to 167 °C lower). Generally, each system behaves differently with respect to their physical behaviour upon melting. The molten phases can exhibit colour changes, bubbling and in some cases frothing, or even liquid-solid phase transitions during hydrogen release. Remarkably, the eutectic melt can also allow for hydrogen release at temperatures lower than that of the individual components. Some systems display decomposition of the borohydride in the solid-state before melting and certain hydrogen release events have also been linked to the adverse reaction of samples with impurities, usually within the starting reagents, and these may also be coupled with bubbling or frothing of the ionic melt.

First-order phase transition in the Li2B12H12 system.

The thermal decomposition of anhydrous Pa3[combining macron] Li2B12H12 was studied in situ by high resolution synchrotron X-ray diffraction. A first-order phase transition can be observed at 355 °C where the unit cell volume expands by ca. 8.7%. The expanded ß-Li2B12H12 polymorph simultaneously decomposes to a hydrogen poor γ-Li2B12H12-x phase. Expansion of the unit cell across the discontinuity is consistent with reorientational motion of B12H12(2-) anions, and the presence of a frustrated Li(+) lattice indicating Li ion conduction.