Il sistema mg-ti nanostrutturato per lo stoccaggio d'idrogeno allo stato solido

Nella presente tesi ci si pone lo scopo di studiare stabilità, ciclabilità e cinetica di campioni composti da magnesio e titanio (Mg-Ti) prodotti con la tecnica della condensazione in gas inerte (IGC) per lo di stoccaggio di idrogeno. Il sistema Mg-Ti sembra essere un buon candidato per poter costruire serbatoi di idrogeno allo stato solido sia per applicazioni fisse che mobili. La ricerca di tecnologie efficaci per immagazzinare idrogeno è fondamentale per poter affermare un ciclo energetico sostenibile, svincolato dai combustibili fossili. Sia il lavoro di crescita dei campioni all'Università di Bologna, sia la caratterizzazione di questi nei laboratori dell' Institut de Chimie et des Materiaux Paris-Est (ICMPE) si collocano all'interno del progetto europeo COST per la ricerca di materiali nanostrutturati destinati ad applicazioni nel campo dello stoccaggio dell'energia in forma di idrogeno allo stato solido

Advances in Nanoparticle Condensation from the Gas Phase: MG-Based and TiO2-Based Materials for Energy Applications

This Thesis aims to study nanoparticles (NPs) synthesised via condensation from the gas phase. The advances achieved with this technique, first of all the development of a controlled reactive atmosphere and in situ capabilities, are presented. With the set-up developed, it is possible to synthesise NPs of a variety of compounds: alloys, oxides, hydrides, and also complex morphologies like nanocomposites and core-shell structures. Mg-based NPs are studied for their interest in hydrogen storage applications. Firstly, the problem of severe crystal growth in metallic Mg NPs is addressed. The dynamics of the self-assembly process is studied and the synthesis of Mg metal-oxide core-shell NPs is proved as a way to stabilise small size (in the 20-30 nm range) NPs. Addition of Ti is known to improve the hydrogen storage properties of Mg. Mg-Ti NPs in the form of air-stable pellets or nanopowders, are synthesised via condensation from inert or hydrogen rich atmosphere. The resulting MgH2-TiH2 nanocomposites show excellent hydrogen sorption kinetic properties with fast hydrogen absorptions as well as desorptions observed at temperatures as low as 343 K. Slight to no thermodynamics changes compared to the bulk Mg-H system are retrieved over a wide, low temperature range. Finally, the addition of V is studied as a method to improve light absorption in the visible range and photocatalytic efficiency of TiO2 NPs. A deep characterisation of the overall V-TiO2 NPs structure, morphology and optical properties is carried out along with the characterisation of the local chemical environment of the V ions, proving that V is always substitutional of the cation in TiO2, irrespective of the TiO2 polymorph present

Mg–Ti nanoparticles with superior kinetics for hydrogen storage

open5siAcknowledgements The assistance of F. Corticelli and V. Morandi (IMM-CNR, Bologna) during FE-SEM observations is gratefully acknowledged. Part of this work was supported by the COST Action MP1103 “Nanostructured materials for solid-state hydrogen storage”. We are grateful to the beamline I711 at MAXlab, Lund, Sweden for the provision of beamtime.Mg nanoparticles (NPs) with addition of Ti catalysts were synthesised by inert gas condensation and in situ hydrogenation at 150 °C. The NPs size and composition were systematically investigated by scanning electron microscopy, energy dispersive X-ray spectroscopy and powder X-ray diffraction (PXD), while time resolved in situ synchrotron radiation-PXD was used to monitor the mechanism for hydrogen uptake and release at 280 °C. The Mg–Ti NPs reveal activation energies of 68 kJ mol−1 for absorption and 78 kJ mol−1 for desorption by isothermal kinetics analysis, similar to the lowest values reported in the literature for MgH2 using Nb2O5 as a catalyst. Hence, hydrogen desorption (pdes = 8 mbar) and absorption (pabs = 260 mbar) is achieved at 200 °C in ∼2000 s, while keeping 5.3 wt% storage capacity. Thermodynamic data extracted from van ’t Hoff plots reveal unchanged values compared to bulk MgH2. Therefore, the improved hydrogen storage performances are assigned to the enhanced kinetics only.openCalizzi, Marco; Chericoni, Domizia; Jepsen, Lars H.; Jensen, Torben R.; Pasquini, LucaCalizzi, Marco; Chericoni, Domizia; Jepsen, Lars H.; Jensen, Torben R.; Pasquini, Luc

Hydrogen Desorption below 150 °c in MgH2-TiH2 Composite Nanoparticles: Equilibrium and Kinetic Properties

Reversible hydrogen sorption coupled with the MgH2 <-> Mg phase transformation was achieved in the remarkably low 340-425 K temperature range using MgH2-TiH2 composite nanoparticles obtained by reactive gas-phase condensation of Mg Ti vapors under He/H-2 atmosphere. The equilibrium pressures determined by in situ measurements at low temperature were slightly above those predicted using enthalpy Delta H and entropy Delta S of bulk magnesium. A single van't Hoff fit over a range extended up to 550 K yields the thermodynamic parameters Delta H = 68.1 0.9 kJ/molH(2) and Delta S = 119 2 J/(Kmo1H2) for hydride decomposition. A desorption rate of 0.18 wt % H-2/min was measured at T = 423 K and p(H-2) approximate to 1 mbar, i.e., close to equilibrium, without using a Pd catalysts. The nanoparticles displayed a small absorption desorption pressure hysteresis even at low temperatures. We critically discuss the influence exerted by nanostructural features such as interface free energy, elastic clamping, and phase mixing at the single nanopartide level on equilibrium and kinetic properties of hydrogen sorption

In situ Control of the Adsorption Species in CO2 Hydrogenation: Determination of Intermediates and Byproducts

CO2 hydrogenation over catalysts is a potentially exciting method to produce fuels while closing the CO2 cycle and mitigating global warming. The mechanism of this process has been controversial due to the difficulty in clearly identifying the species present and distinguishing which are reaction intermediates and which are byproducts. We in situ manipulated the independent formation and hydrogenation of each adsorption species produced in CO2 hydrogenation reaction over Ru/Al2O3 using operando diffuse reflectance infrared Fourier transformation spectroscopy (DRIFTS) and executed a novel iterative Gaussian fitting procedure. The adsorption species and their role in the CO2 hydrogenation reaction have been clearly identified. The adsorbed carbon monoxide (CO*) of four reactive structures was the key intermediate of methane (CH4) production. Bicarbonate (HCO3–*), formed on the metal–support interface, appeared to be not only the primary product of CO2 chemisorption but also a reservoir of CO* and consisted of the dominate reaction steps of CO2 methanation from the interface to the metal surface. Bidentate formate (Bi-HCOO–*) formed on Ru under a certain condition, consecutively converting to CO* to merge into the subsequent methanation process. Nonreactive byproducts of the reaction were also identified. The evolution of the surface species revealed the essential steps of the CO2 activation and hydrogenation reactions which were inevitably initiated from HCO3–* to CO* and finally from CO* to CH4

Identifying Reaction Species by Evolutionary Fitting and Kinetic Analysis: An Example of CO2 Hydrogenation in DRIFTS

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) investigations of molecules at the surface of catalysts exhibit a strong overlap of the adsorption peaks. Therefore, the investigation of the CO2 hydrogenation on a highly active catalyst surface requires a deconvolution of the adsorption spectra to clearly assign the signal to the chemical species. We developed an autonomous and efficient bi-level evolutionary Gaussian fitting (BEGF) procedure with a genetic algorithm at the upper level and a multipeak Gaussian fitting algorithm at the lower level to analyze self-consistently the set of spectra of an entire experiment. We show two examples of the application of BEGF procedure by analyzing the DRIFTS spectral sets of ex situ HCOO–* and CO2 hydrogenation on Ru/Al2O3. The fitting procedure deconvoluted the overlapped peaks and identified the bond vibrations of carbon monoxide, formate, bicarbonate, and carbonate through the developing trends of the peak intensities along the reaction. These revealed the progression of those species over the reaction timeline

Interface Enthalpy-Entropy Competition in Nanoscale Metal Hydrides

We analyzed the effect of the interfacial free energy on the thermodynamics of hydrogen sorption in nano-scaled materials. When the enthalpy and entropy terms are the same for all interfaces, as in an isotropic bi-phasic system, one obtains a compensation temperature, which does not depend on the system size nor on the relative phase abundance. The situation is different and more complex in a system with three or more phases, where the interfaces have different enthalpy and entropy. We also consider the possible effect of elastic strains on the stability of the hydride phase and on hysteresis. We compare a simple model with experimental data obtained on two different systems: (1) bi-phasic nanocomposites where ultrafine TiH2 crystallite are dispersed within a Mg nanoparticle and (2) Mg nanodots encapsulated by different phases

Interface Enthalpy-Entropy Competition in Nanoscale Metal Hydrides

We analyzed the effect of the interfacial free energy on the thermodynamics of hydrogen sorption in nano-scaled materials. When the enthalpy and entropy terms are the same for all interfaces, as in an isotropic bi-phasic system, one obtains a compensation temperature, which does not depend on the system size nor on the relative phase abundance. The situation is different and more complex in a system with three or more phases, where the interfaces have different enthalpy and entropy. We also consider the possible effect of elastic strains on the stability of the hydride phase and on hysteresis. We compare a simple model with experimental data obtained on two different systems: (1) bi-phasic nanocomposites where ultrafine TiH2 crystallite are dispersed within a Mg nanoparticle and (2) Mg nanodots encapsulated by different phases

Dehydrogenation-hydrogenation characteristics of nanocrystalline Mg2Ni powders compacted by high-pressure torsion

High-pressure torsion technique was applied on nanocrystalline Mg2Ni powders to produce bulk disks by simultaneous uniaxial compression and severe shear deformation. The hydrogen absorption and desorption behavior of the disks has been characterized by high-pressure calorimetry. During desorption, the decomposition of the Mg2NiH4 phase takes place, which is followed by the dehydrogenation of Mg2NiH0.3 solid solution. In order to monitor the sorption properties in details, partially dehydrogenated states of the fully absorbed disk have been performed by interrupting the desorption process at 75%, 50% and 25% hydrogen contents in a Sieverts’ type apparatus. Microstructural evolution during dehydrogenation has been investigated by X-ray diffraction. The variation of average crystallite size, lattice parameters and unit cell of the competing phases has been determined by the Rietveld refinement method of X-ray diffractograms. The unit cell volume of the Mg2NiH0.3 hydride solid solution decreases with decreasing hydrogen content. Coupled differential scanning calorimetry and thermogravimetry measurements were also taken on the partially desorbed states in order to determine the activation energy of hydrogen release

Synthesis of grid compliant substitute natural gas from a representative biogas mixture in a hybrid Ni/Ru catalysed reactor

We demonstrate biogas upgrading towards full CO2 conversion in mild conditions in a three-step reactor system using Ru- and Ni-based catalysts. In each of the three reactor stages, the temperature is carefully controlled, thus optimizing the reaction thermodynamics and kinetics, resulting in a maximized global CO2 conversion. At ambient pressure, 92% conversion can be achieved over a commercial Ru/Al2O3 catalyst at a space velocity of 2 L/h/gcat in every stage. At 2 bar conversion is enhanced to above 99%. It is possible to substitute the Ru-based catalyst in the first stage with a cheaper Ni-based catalyst, shifting the first-stage temperature to higher values forming also CO. CO has a positive effect on the following step since CO is converted to CH4 in the CO methanation reaction. In this way, it is possible to achieve the same final conversion compared to the Ru-operated reactor system using Ni in the first reactor stage