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Magnesium borohydride (Mg(BH4)2) is an attractive candidate as a hydrogen storage material due to its high hydrogen content and predicted favorable thermodynamics. In this work we demonstrate reversible hydrogen desorption in partially decomposed Mg(BH4)2 which was ball milled together with 2 mol% Co-based additives. Powder X-ray diffraction and infrared spectroscopy showed that after partial decomposition at 285 °C, amorphous boron-hydride compounds were formed. Rehydrogenation at equivalent temperatures and hydrogen pressures of 120 bar yielded the formation of crystalline Mg(BH4)2 in the first cycle, and amorphous Mg(BH4)2 with other boron–hydrogen compounds upon the third H2 absorption. Reversibility was observed in the samples with and without Co-based additives, although the additives enhanced hydrogen desorption kinetics in the first cycle. X-ray absorption spectroscopy at Co K-edge revealed that all the additives, apart from Co2B, reacted during the first desorption to form new stable species. [ABSTRACT FROM AUTHOR]

Hydrogen–fluorine exchange in the NaBH4–NaBF4 system is investigated using a range of experimental methods combined with DFT calculations and a possible mechanism for the reactions is proposed. Fluorine substitution is observed using in situ synchrotron radiation powder X-ray diffraction (SR-PXD) as a new Rock salt type compound with idealized composition NaBF2H2 in the temperature range T = 200 to 215 °C. Combined use of solid-state 19F MAS NMR, FT-IR and DFT calculations supports the formation of a BF2H2− complex ion, reproducing the observation of a 19F chemical shift at −144.2 ppm, which is different from that of NaBF4 at −159.2 ppm, along with the new absorption bands observed in the IR spectra. After further heating, the fluorine substituted compound becomes X-ray amorphous and decomposes to NaF at ∼310 °C. This work shows that fluorine-substituted borohydrides tend to decompose to more stable compounds, e.g. NaF and BF3 or amorphous products such as closo-boranes, e.g. Na2B12H12. The NaBH4–NaBF4 composite decomposes at lower temperatures (300 °C) compared to NaBH4 (476 °C), as observed by thermogravimetric analysis. NaBH4–NaBF4 (1 : 0.5) preserves 30% of the hydrogen storage capacity after three hydrogen release and uptake cycles compared to 8% for NaBH4 as measured using Sievert’s method under identical conditions, but more than 50% using prolonged hydrogen absorption time. The reversible hydrogen storage capacity tends to decrease possibly due to the formation of NaF and Na2B12H12. On the other hand, the additive sodium fluoride appears to facilitate hydrogen uptake, prevent foaming, phase segregation and loss of material from the sample container for samples of NaBH4–NaF. [ABSTRACT FROM AUTHOR]

Abstract: By means of in situ synchrotron radiation powder X-ray diffraction, powder neutron diffraction, attenuated total reflectance infrared spectroscopy, differential scanning calorimetry and the Sieverts techniques we have investigated how anion substitution in the LiBH4–LiBr system leads to changes in the structural, physical, chemical and hydrogen storage properties of this material. Mechano-chemical treatment facilitates formation of a hexagonal solid solution h-Li(BH4)1−xBrx whereas heating at elevated temperatures, i.e. T > 112 °C appears to allow full solubility in the system LiBH4−LiBr. The first step in the anion substitution process may be dissolution of small amounts of LiBH4 in α-LiBr deduced from observation of a hexagonal solid solution with unit cell volume similar to β-LiBr for a hand-mixed sample. The solid solution, Li(BH4)1−xBrx, is isostructural to the hexagonal high temperature polymorph of LiBH4. This solid solution melts at a significantly higher temperature depending on the composition as compared to h-LiBH4. Furthermore, a new hexalithium borate tribromide, Li6(BO3)Br3 was discovered and structurally characterized. [Copyright &y& Elsevier]

Metal-organic frameworks (MOFs) with a Zr-oxo cluster [(Zr 6 O 4 (OH) 4 )] 12 - are exceptionally stable and offer vast potential for a wide range of applications. Synthesis parameters strongly affect the quality, stability, morphology, etc. , of the MOFs. In this study, we present an experimental set-up that allows following in situ element-specific chemical transformations during synthesis and the effect of various reaction parameters on the reaction products. Zr-fumarate formation was monitored using X-ray absorption spectroscopy (XAS) in ZrCl 4 -DMF-based solutions. We have studied (i) the local (∼2-5 Å) environment around Zr 4+ ions in the early stages of the Zr-oxo cluster formation and MOF-synthesis reaction, (ii) kinetics of the synthesis reaction and its dependence on water and modulator concentrations, and (iii) the effect of the reaction parameters on MOF product quality. XAS data have provided direct evidence that the increased amounts of water and modulator accelerate the reaction. It has also confirmed that water is essential for MOF formation in DMF. Zr-cluster formation and the synthesis reaction were not observed in the absence of water in ZrCl 4 -DMF and ZrCl 4 -DMF-linker-modulator solutions. According to the EXAFS data, Zr 4+ ions are octahedrally coordinated by chlorine atoms in anhydrous solutions with and without the linker. In contrast, the Zr-oxo clusters and MOFs were formed only in the presence of water. The results of the in situ experiments were correlated with post-synthetic characterization of the resultant MOF products.

The synthesis of Ce-fumarate and Zr-fumarate metal-organic framework (MOF) is monitored for the first time with in situ Raman spectroscopy in custom-built solvothermal reactors. Several synthesis conditions were explored for Ce-fumarate at room temperature. The use of the method for high-temperature synthesis of Zr-fumarate is also demonstrated. In situ Raman monitoring provided insights into both the solution and crystalline phases of the reaction medium, revealing the dynamic interplay among precursors, modulators, and the forming MOF structure. The reaction kinetics was determined by following the characteristic peak at 1666 cm -1 . The conversion was in good agreement with the reaction kinetics determined via in situ synchrotron powder diffraction. The resulting MOF products were further characterized using ex situ X-ray powder diffraction, scanning electron microscopy, thermogravimetry, and surface area measurements. This study demonstrates a simple and industrially scalable method for monitoring MOF synthesis in situ, which can provide insights into the stages and mechanisms of formation of MOFs and other compounds., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Metal hydroborates are versatile materials with interesting properties related to energy storage and cation conductivity. The hydrides containing B 3 H 8 - (triborane, or octahydrotriborate) ions have been at the center of attention for some time as reversible intermediates in the decomposition of BH 4 - (3BH 4 - ↔ B 3 H 8 - + 2H 2 ), and as conducting media in electrolytes based on boron-hydride cage clusters. We report here the first observation of two phase transitions in CsB 3 H 8 prior to its decomposition above 230 °C. The previously reported orthorhombic room temperature phase (here named α-CsB 3 H 8 ) with the space group Ama2 changes into a new phase with the space group Pnma at 73 °C (here named β-CsB 3 H 8 ), and then into a face-centered cubic phase, here named γ-CsB 3 H 8 , at 88 °C. These phases are not stable at room temperature thus requiring in situ measurements for their characterization. The phase transitions and decomposition pathway of CsB 3 H 8 were studied with in situ synchrotron powder X-ray diffraction (SR-PXD), in situ and ex situ vibrational spectroscopies (Raman and FTIR), and differential-scanning calorimetry combined with thermo-gravimetric analysis (DSC-TGA). The structure determination was validated by vibrational spectroscopy analysis and modeling of the periodic structures by density functional methods. In γ-CsB 3 H 8 , a significant disorder in B 3 H 8 - positions and orientations was found which can potentially benefit cation conducting properties through the paddle mechanism.

Magnesium borohydride (Mg(BH 4 ) 2 ) is a promising material for solid state hydrogen storage. However, the predicted reversible hydrogen sorption properties at moderate temperatures have not been reached due to sluggish hydrogen sorption kinetics. Hydrogen (H) → deuterium (D) exchange experiments can contribute to the understanding of the stability of the BH 4 - anion. Pure γ-Mg(BH 4 ) 2 , ball milled Mg(BH 4 ) 2 and composites with the additives nickel triboride (Ni 3 O 2 O 5 ) have been investigated. In situ Raman analysis demonstrated that in pure γ-Mg(BH 4 ) 2 the isotopic exchange reaction during continuous heating started at ∼80 °C, while the ball milled sample did not show any exchange at 3 bar D 2 . However, during ex situ exchange reactions investigated by infrared (IR) and thermogravimetric (TG) analyses a comparable H → D exchange during long exposures (23 h) to deuterium atmosphere was observed for as received, ball milled and γ-Mg(BH 4 ) 2 O 2 O 5 , while the Ni 3 B additive hindered isotopic exchange. The specific surface areas (SSA) were shown to be very different for as received γ-Mg(BH 4 ) 2 , BET area = 900 m 2 g -1 , and ball milled Mg(BH 4 ) 2 , BET area = 30 m 2 g -1 , respectively, and this explains why no gas-solid H(D) diffusion was observed for the ball milled (amorphous) Mg(BH 4 ) 2 during the short time frames of in situ Raman measurements. The heat treated ball milled sample partially regained the porous γ-Mg(BH 4 ) 2 structure (BET area = 560 m 2 g -1 ). This in combination with the long reaction times allowing for the reaction to approach equilibrium explains the observed gas-solid H(D) diffusion during long exposure. We have also demonstrated that a small amount of D can be substituted in both high surface area and low surface area samples at room temperature proving that the B-H bonds in Mg(BH 4 ) 2 can be challenged at these mild conditions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Magnesium borohydride (Mg(BH4)2) is one of the most promising complex hydrides presently studied for energy-related applications. Many of its properties depend on the stability of the BH4(-) anion. The BH4(-) stability was investigated with respect to H→D exchange. In situ Raman measurements on high-surface-area porous Mg(BH4 )2 in 0.3 MPa D2 have shown that the isotopic exchange at appreciable rates occurs already at 373 K. This is the lowest exchange temperature observed in stable borohydrides. Gas-solid isotopic exchange follows the BH4(-) +D˙ →BH3D(-) +H˙ mechanism at least at the initial reaction steps. Ex situ deuteration of porous Mg(BH4)2 and its dense-phase polymorph indicates that the intrinsic porosity of the hydride is the key behind the high isotopic exchange rates. It implies that the solid-state H(D) diffusion is considerably slower than the gas-solid H→D exchange reaction at the surface and it is a rate-limiting steps for hydrogen desorption and absorption in Mg(BH4)2., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Systematic studies of H2 adsorption by variable temperature infrared (VTIR) spectroscopy have added value in the characterization of hydrogen storage materials. As a key study to describe the potential of the method, here we report VTIR spectroscopy results of H2 adsorption at isostructural MOFs CPO-27-M (M = Mg, Mn, Co, Ni, Zn). The strongest perturbation of H2 vibrational frequency is due to the interaction with an open metal site. Although ionic radius is an empirical value, the direct correlation between ionic radii of the metal cation and H2 interaction energy is found in MOFs of the same topology. The highest enthalpy of hydrogen adsorption 15 ± 1 kJ mol(-1) was found for Ni(2+). VTIR results of H2 adsorption at isostructural MOFs CPO-27-M (M = Mg, Mn, Co, Ni, Zn) were compared with data obtained from analogous studies performed on a large variety of microporous materials (MOFs and zeolites), underlining the relevance of the approach to get reliable energetic and entropic (ΔH(0) and ΔS(0)) values to be compared with computational data and isosteric heats.

Microporous metal-organic frameworks are a class of materials being vigorously investigated for mobile hydrogen storage applications. For high-pressure storage at ambient temperatures, the M(3)[(M(4)Cl)(3)(BTT)(8)](2) (M-BTT; BTT(3-) = 1,3,5-benzenetristetrazolate) series of frameworks are of particular interest due to the high density of exposed metal cation sites on the pore surface. These sites give enhanced zero-coverage isosteric heats of adsorption (Q(st)) approaching the optimal value for ambient storage applications. However, the Q(st) parameter provides only a limited insight into the thermodynamics of the individual adsorption sites, the tuning of which is paramount for optimizing the storage performance. Here, we begin by performing variable-temperature infrared spectroscopy studies of Mn-, Fe-, and Cu-BTT, allowing the thermodynamics of H(2) adsorption to be probed experimentally. This is complemented by a detailed DFT study, in which molecular fragments representing the metal clusters within the extended solid are simulated to obtain a more thorough description of the structural and thermodynamic aspects of H(2) adsorption at the strongest binding sites. Then, the effect of substitutions at the metal cluster (metal ion and anion within the tetranuclear cluster) is discussed, showing that the configuration of this unit indeed plays an important role in determining the affinity of the framework toward H(2). Interestingly, the theoretical study has identified that the Zn-based analogs would be expected to facilitate enhanced adsorption profiles over the compounds synthesized experimentally, highlighting the importance of a combined experimental and theoretical approach to the design and synthesis of new frameworks for H(2) storage applications.

The recently discovered UiO-66/67/68 class of isostructural metallorganic frameworks (MOFs) [J. H. Cavka et al. J. Am. Chem. Soc., 2008, 130, 13850] has attracted great interest because of its remarkable stability at high temperatures, high pressures and in the presence of different solvents, acids and bases [L. Valenzano et al. Chem. Mater., 2011, 23, 1700]. UiO-66 is obtained by connecting Zr(6)O(4)(OH)(4) inorganic cornerstones with 1,4-benzene-dicarboxylate (BDC) as linker resulting in a cubic MOF, which has already been successfully reproduced in several laboratories. Here we report the first complete structural, vibrational and electronic characterization of the isostructural UiO-67 material, obtained using the longer 4,4'-biphenyl-dicarboxylate (BPDC) linker, by combining laboratory XRPD, Zr K-edge EXAFS, TGA, FTIR, and UV-Vis studies. Comparison between experimental and periodic calculations performed at the B3LYP level of theory allows a full understanding of the structural, vibrational and electronic properties of the material. Both materials have been tested for molecular hydrogen storage at high pressures and at liquid nitrogen temperature. In this regard, the use of a longer ligand has a double benefit: (i) it reduces the density of the material and (ii) it increases the Langmuir surface area from 1281 to 2483 m(2) g(-1) and the micropore volume from 0.43 to 0.85 cm(3) g(-1). As a consequence, the H(2) uptake at 38 bar and 77 K increases from 2.4 mass% for UiO-66 up to 4.6 mass% for the new UiO-67 material. This value is among the highest values reported so far but is lower than those reported for MIL-101, IRMOF-20 and MOF-177 under similar pressure and temperature conditions (6.1, 6.2 and 7.0 mass%, respectively) [A. G. Wong-Foy et al. J. Am. Chem. Soc., 2006, 128, 3494; M. Dinca and J. R. Long. Angew. Chem., Int. Ed., 2008, 47, 6766]. Nevertheless the remarkable chemical and thermal stability of UiO-67 and the absence of Cr in its structure would make this material competitive.

The adsorption of CO and H(2) at the surface of transitional (gamma and delta) and corundum (alpha) phases of Al(2)O(3) is studied by means of FTIR spectroscopy at temperature variable in the 293-60 K (CO) and 293-20 K (H(2)) intervals with the aims of better clarifying the nature of the surface Lewis centres and evaluate the thermodynamics of the adsorption process.