Sebastiano Garroni

Melt-driven mechanochemical phase transformations in moderately exothermic powder mixtures

Usually, mechanochemical reactions between solid phases are either gradual (by deformation-induced mixing), or self-propagating (by exothermic chemical reaction). Here, by means of a systematic kinetic analysis of the Bi-Te system reacting to Bi2Te3, we establish a third possibility: if one or more of the powder reactants has a low melting point and low thermal effusivity, it is possible that local melting can occur from deformation-induced heating. The presence of hot liquid then triggers chemical mixing locally. The molten events are constrained to individual particles, making them distinct from self-propagating reactions, and occur much faster than conventional gradual reactions. We show that the mechanism is applicable to a broad variety of materials systems, many of which have important functional properties. This mechanistic picture offers a new perspective as compared to conventional, gradual mechanochemical synthesis, where thermal effects are generally ignored.

Mesoporous Titania Powders: The Role of Precursors, Ligand Addition and Calcination Rate on Their Morphology, Crystalline Structure and Photocatalytic Activity

We evaluate the influence of the use of different titania precursors, calcination rate, and ligand addition on the morphology, texture and phase content of synthesized mesoporous titania samples, parameters which, in turn, can play a key role in titania photocatalytic performances. The powders, obtained through the evaporation-induced self-assembly method, are characterized by means of ex situ X-Ray Powder Diffraction (XRPD) measurements, N₂ physisorption isotherms and transmission electron microscopy. The precursors are selected basing on two different approaches: the acid-base pair, using TiCl₄ and Ti(OBu)₄, and a more classic route with Ti(OiPr)₄ and HCl. For both precursors, different specimens were prepared by resorting to different calcination rates and with and without the addition of acetylacetone, that creates coordinated species with lower hydrolysis rates, and with different calcination rates. Each sample was employed as photoanode and tested in the water splitting reaction by recording I-V curves and comparing the results with commercial P25 powders. The complex data framework suggests that a narrow pore size distribution, due to the use of acetylacetone, plays a major role in the photoactivity, leading to a current density value higher than that of P25.

Mechanically activated metathesis reaction in NaNH2–MgH2 powder mixtures

The present work addresses the kinetics of chemical transformations activated by the mechanical processing of powder by ball milling. In particular, attention focuses on the reaction between NaNH2 and MgH2, specific case studies suitably chosen to throw light on the kinetic features emerging in connection with the exchange of anionic ligands induced by mechanical activation. Experimental findings indicate that the mechanical treatment of NaNH2–MgH2 powder mixtures induces a simple metathetic reaction with formation of NaH and Mg(NH2)2 phases. Chemical conversion data obtained by X-ray diffraction analysis have been interpreted using a kinetic model incorporating the statistical character of the mechanical processing by ball milling. The apparent rate constant measuring the reaction rate is related to the volume of powder effectively processed during individual collisions, and tentatively connected with the transfer of mechanical energy across the network formed by the points of contact between the powder particles trapped during collisions.

New amide-chloride phases in the Li-Al-N-H-Cl system: Formation and hydrogen storage behaviour

New amide-chloride phases were successfully synthesized by mechanical milling of the LiNH2-AlCl3 mixture at a molar ratio of 1 : 0.11 and further heating at 150 °C under argon (0.1 MPa) or under hydrogen pressure (0.7 MPa). Powder X-ray diffraction measurements as a function of milling time increase revealed that the milling of the LiNH2-0.11AlCl3 mixture results in the formation of a FCC solid solution with an excess of LiNH2. Subsequent heating of the LiNH2-0.11AlCl3 sample ball milled for 5 hours at 150 °C under argon or under hydrogen induces the appearance of an amide-chloride phase isostructural with cubic Li4(NH2)3Cl. This Li-Al-N-H-Cl phase transforms progressively into the trigonal phase after prolonged heating at 300 °C under hydrogen pressure. The thermal behaviour of the amide-chloride without and with LiH addition displays dissimilar decomposition pathways. The decomposition of amide-chloride alone involves the formation of ammonia and hydrogen from 120 to 300 °C. Conversely, the amide-chloride material in the presence of LiH only releases hydrogen avoiding the emission of ammonia. The resultant material is able to be rehydrogenated under moderate conditions (300 °C, 0.7 MPa H2), providing a new reversible hydrogen storage system.

KNH2–KH: a metal amide–hydride solid solution

We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2- ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.

A new potassium-based intermediate and its role in the desorption properties of the K–Mg–N–H system

New insights into the reaction pathways of different potassium/magnesium amide-hydride based systems are discussed. In situ SR-PXD experiments were for the first time performed in order to reveal the evolution of the phases connected with the hydrogen releasing processes. Evidence of a new K-N-H intermediate is shown and discussed with particular focus on structural modification. Based on these results, a new reaction mechanism of amide-hydride anionic exchange is proposed.

Effects of Stoichiometry on the H2‐Storage Properties of Mg(NH2)2–LiH–LiBH4 Tri‐Component Systems

The hydrogen desorption pathways and storage properties of 2 Mg(NH2 )2 -3 LiH-xLiBH4 samples (x=0, 1, 2, and 4) were investigated systematically by a combination of pressure composition isotherm (PCI), differential scanning calorimetric (DSC), and volumetric release methods. Experimental results showed that the desorption peak temperatures of 2 Mg(NH2 )2 -3 LiH-xLiBH4 samples were approximately 10-15 °C lower than that of 2 Mg(NH2 )2 -3 LiH. The 2 Mg(NH2 )2 -3 LiH-4 LiBH4 composite in particular began to release hydrogen at 90 °C, thereby exhibiting superior dehydrogenation performance. All of the LiBH4 -doped samples could be fully dehydrogenated and re-hydrogenated at a temperature of 143 °C. The high hydrogen pressure region (above 50 bar) of PCI curves for the LiBH4 -doped samples rose as the amount of LiBH4 increased. LiBH4 changed the desorption pathway of the 2 Mg(NH2 )2 -3 LiH sample under a hydrogen pressure of 50 bar, thereby resulting in the formation of MgNH and molten [LiNH2 -2 LiBH4 ]. That is different from the dehydrogenation pathway of 2 Mg(NH2 )2 -3 LiH sample without LiBH4 , which formed Li2 Mg2 N3 H3 and LiNH2 , as reported previously. In addition, the results of DSC analyses showed that the doped samples exhibited two independent endothermic events, which might be related to two different desorption pathways.

Highly ordered mesoporous magnesium niobate high-κ dielectric ceramic: synthesis, structural/mechanical characterization and thermal stability

The synthesis of a highly ordered mesoporous ternary Mg–Nb oxide by the Evaporation Induced Self-Assembly (EISA) method is presented for the first time. The as-prepared material shows 2D-hexagonal pore periodicity, with unimodal pore size distribution centered at 5.5 nm, and a large surface area (169 m2 g−1). The mechanical properties, determined by means of nanoindentation, are consistent with the presence of ordered domains of honeycomb-like hexagonal pore arrangements, in agreement with electron microscopy observations and N2 sorption isotherm analyses. The dielectric constant of the mesoporous sample, measured at room temperature in the frequency range 1 kHz to 1 MHz, is rather high (κ ∼ 25 at 1 MHz) and correlates well with the κ value of the bulk and the porosity level of this material. Moreover, the thermal stability of the mesoporous magnesium niobate is investigated after air-annealing treatments at different temperatures. While a significant decrease of the surface area is observed for TANN = 650 °C, the mesostructure fully collapses after annealing at 800 °C.

Insights into the Rb–Mg–N–H System: an Ordered Mixed Amide/Imide Phase and a Disordered Amide/Hydride Solid Solution

The crystal structure of a mixed amide-imide phase, RbMgND2ND, has been solved in the orthorhombic space group Pnma ( a = 9.55256(31), b = 3.70772(11) and c = 10.08308(32) Å). A new metal amide-hydride solid solution, Rb(NH2) xH(1- x), has been isolated and characterized in the entire compositional range. The profound analogies, as well as the subtle differences, with the crystal chemistry of KMgND2ND and K(NH2) xH1- x are thoroughly discussed. This approach suggests that the comparable performances obtained using K- and Rb-based additives for the Mg(NH2)2- 2LiH and 2LiN H2-MgH2 hydrogen storage systems are likely to depend on the structural similarities of possible reaction products and intermediates.

2Mg-Fe Alloy Processed by Hot Extrusion: Influence of Particle Size and Extrusion Reduction Ratio on Hydrogenation Properties

Samples of a 2Mg-Fe (at.%) mixture were produced by high energy ball-milling (HEBM) with ball to powder ratio = 20:1, in an argon gas atmosphere, in 190 ml vials (sample-1) to produce powders and in 300 ml vials (sample-2) to produce plates. Both samples were cold-pressed into preforms. The preforms were then extruded at 300°C at a ram speed of 1mm/min., with the following extrusion ratios: sample-1 at 3/1 to ensure porosity and sample-2 at 5/1 to increase the adhesion of the plates. The resulting bulks from samples 1 and 2 were hydrogenated for 24h in a reactor under 15 bar of H2 to produce the Mg2FeH6 complex hydride, and at 11 bar of H2 to produce both the complex hydride and MgH2 hydride. In addition, sample-1 was severely temperature-hydrogen cycled to verify its microstructural stability and the influence of grain size on the sorption properties. XRD patterns showed Mg(hc), Fe(ccc) and Mg2FeH6 in both samples, and sample-2 also contained MgH2 and MgO (attributed to processing contamination). DSC results demonstrated that the initial desorption temperature of sample-1 was lower than that of sample-2. However, sample-2 showed faster desorption kinetics, presenting a desorption peak about 73°C below that of sample-1. This could be attributed to the activation/catalyst effect of the MgH2 hydride. The improvement in sorption properties was attributed mainly to porosity and to the type of employed catalysts.