Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Comparison

Knowledge of the relative stabilities of alane (AlH3) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for thirty-eight alane complexes with NH3-nRn (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH2-nRn (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine, and obtaining upper limits of delta G for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. Based on this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system.Comment: Accepted by the Journal of Physical Chemistry

Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Investigation.

Knowledge of the relative stabilities of alane (AlH(3)) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for 38 alane complexes with NH(3-n)R(n) (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH(2-n)R(n) (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine and obtaining upper limits of ΔG° for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. On the basis of this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system

Alane adsorption and dissociation on the Si(001) surface

We used DFT to study the energetics of the decomposition of alane, AlH3, on the Si(001) surface, as the acceptor complement to PH3. Alane forms a dative bond with the raised atoms of silicon surface dimers, via the Si atom lone pair. We calculated the energies of various structures along the pathway of successive dehydrogenation events following adsorption: AlH2, AlH and Al, finding a gradual, significant decrease in energy. For each stage, we analyse the structure and bonding, and present simulated STM images of the lowest energy structures. Finally, we find that the energy of Al atoms incorporated into the surface, ejecting a Si atom, is comparable to Al adatoms. These findings show that Al incorporation is likely to be as precisely controlled as P incorporation, if slightly less easy to achieve.Comment: Submitted to J. Phys.: Condens. Matte

Characterisation of mechanochemically synthesised alane (AlH3) nanoparticles

A mechanochemical synthesis process has been used to synthesise alane (AlH3) nanoparticles. The alane is synthesised via a chemical reaction between lithium alanate (LiAlH4) and aluminium chloride (AlCl3) at room temperature within a ball mill and at 77K within a cryogenic mill. The reaction product formed consists of alane nanoparticles embedded within a lithium chloride (LiCl) by-product phase. The LiCl is washed with a solvent resulting in alane nanoparticles which are separated from the by-product phase but are kinetically stabilised by an amorphous particle surface layer. The synthesis of a particular alane structural phase is largely dependent on the milling conditions and two major phases (α, α′) as well as two minor phases (β, γ) have been identified. Ball milling at room temperature can also provide enough energy to allow alane to release hydrogen gas and form aluminium metal nanoparticles. A comparison between XRD and hydrogen desorption results suggest a non-crystalline AlH3 phase is present in the synthesised samples

Presystemic influences on thirst, salt appetite, and vasopressin secretion in the hypovolemic rat

Recent studies have shown that when dehydrated rats are given access to water or various concentrations of saline solution, they consume the same volume of fluid in an initial drinking bout (Hoffmann et al., 2006). Furthermore, there was a close relation between fluid intake and distension of the stomach and small intestine when dehydrated rats drank water or saline (Hoffmann et al., 2006). These results are consistent with the hypothesis that fluid ingestion is constrained by a rapid inhibitory signal associated with GI fill. This volume-dependent early inhibition of thirst is reminiscent of the volume-dependent oropharyngeal reflex that Ramsay and colleagues described in dogs (Thrasher et al., 1981). Other studies (Huang et al., 2000) have shown that rats infused iv with hypertonic saline develop a strong motivation to consume water and show a marked increase in pVP. After water ingestion, pVP decreased rapidly before there was a change in systemic pOsm. Plasma VP remained elevated in rats that were given isotonic saline to drink. These results are consistent with the hypothesis that VP secretion is rapidly inhibited when dilute fluid enters the GI tract. The present studies sought to determine whether an early inhibition of fluid consumption by hypovolemic rats also was associated with GI fill. We imposed a 16-hr delay between the time that PEG solution was injected and the start of the drinking test. These animals have a substantial volume deficit (30-40%) as well as increased circulating levels of VP, OT, AngII, and aldosterone. Therefore, they have a pronounced thirst and salt appetite and will be eager to consume large volumes of fluid rapidly, thus allowing us to determine whether 1) distension of the stomach and small intestine provide a rapid inhibitory feedback signal for thirst and salt appetite, 2) gastric emptying of water or 0.30 M NaCl solution provide a presystemic signal that influences VP secretion, 3) changes in systemic pOsm influence ingestive behavior or VP secretion in rats with prolonged hypovolemia, and 4) GI fill continues to act as an inhibitory signal for fluid consumption after the first drinking bout

Reaction paths of alane dissociation on the Si(001) surface

Building on our earlier study, we examine the kinetic barriers to decomposition of alane, AlH$_3$, on the Si(001) surface, using the nudged elastic band (NEB) approach within DFT. We find that the initial decomposition to AlH with two H atoms on the surface proceeds without a significant barrier. There are several pathways available to lose the final hydrogen, though these present barriers of up to 1 eV. Incorporation is more challenging, with the initial structures less stable in several cases than the starting structures, just as was found for phosphorus. We identify a stable route for Al incorporation following selective surface hydrogen desorption (e.g. by STM tip). The overall process parallels PH$_3$, and indicates that atomically precise acceptor doping should be possible.Comment: 19 pages, 8 figures, submitted to J. Physics.: Condens. Matte

Multiscale modeling of interaction of alane clusters on Al(111) surfaces: A reactive force field and infrared absorption spectroscopy approach

We have used reactive force field (ReaxFF) to investigate the mechanism of interaction of alanes on Al(111) surface. Our simulations show that, on the Al(111) surface, alanes oligomerize into larger alanes. In addition, from our simulations, adsorption of atomic hydrogen on Al(111) surface leads to the formation of alanes via H-induced etching of aluminum atoms from the surface. The alanes then agglomerate at the step edges forming stringlike conformations. The identification of these stringlike intermediates as a precursor to the bulk hydride phase allows us to explain the loss of resolution in surface IR experiments with increasing hydrogen coverage on single crystal Al(111) surface. This is in excellent agreement with the experimental works of Go et al. [ E. Go, K. Thuermer, and J. E. Reutt-Robey, Surf. Sci. 437, 377 (1999) ]. The mobility of alanes molecules has been studied using molecular dynamics and it is found that the migration energy barrier of Al_(2)H_6 is 2.99 kcal/mol while the prefactor is D_0 = 2.82 × 10^(−3) cm^2/s. We further investigated the interaction between an alane and an aluminum vacancy using classical molecular dynamics simulations. We found that a vacancy acts as a trap for alane, and eventually fractionates/annihilates it. These results show that ReaxFF can be used, in conjunction with ab initio methods, to study complex reactions on surfaces at both ambient and elevated temperature conditions

Parametrization of a reactive force field for aluminum hydride

A reactive force field, REAXFF, for aluminum hydride has been developed based on density functional theory (DFT) derived data. REAXFF_(AlH_3) is used to study the dynamics governing hydrogen desorption in AlH_3. During the abstraction process of surface molecular hydrogen charge transfer is found to be well described by REAXFF_(AlH_3). Results on heat of desorption versus cluster size show that there is a strong dependence of the heat of desorption on the particle size, which implies that nanostructuring enhances desorption process. In the gas phase, it was observed that small alane clusters agglomerated into a bigger cluster. After agglomeration molecular hydrogen was desorbed from the structure. This thermodynamically driven spontaneous agglomeration followed by desorption of molecular hydrogen provides a mechanism on how mobile alane clusters can facilitate the mass transport of aluminum atoms during the thermal decomposition of NaAlH_4

Towards Direct Synthesis of Alane: A Predicted Defect-Mediated Pathway Confirmed Experimentally

Alane (AlH3) is a unique energetic material that has not found a broad practical use for over 70 years because it is difficult to synthesize directly from its elements. Using density functional theory, we examine the defect-mediated formation of alane monomers on Al(111) in a two-step process: (1) dissociative adsorption of H2 and (2) alane formation, which are both endothermic on a clean surface. Only with Ti dopant to facilitate H2 dissociation and vacancies to provide Al adatoms, both processes become exothermic. In agreement, in situ scanning tunneling microscopy showed that during H2 exposure, alane monomers and clusters form primarily in the vicinity of Al vacancies and Ti atoms. Moreover, ball milling of the Al samples with Ti (providing necessary defects) showed a 10 % conversion of Al into AlH3 or closely related species at 344 bar H2, indicating that the predicted pathway may lead to the direct synthesis of alane from elements at pressures much lower than the 104 bar expected from bulk thermodynamics

A comprehensive insight in the MOCVD of aluminum through interaction between reactive transport modeling and targeted growth experiments

Growth experiments and reactive transport modeling were combined to formulate a comprehensive predictive model for aluminum growth from dimethylethylamine alane. The growth-rate profile was experimentally investigated as a function of substrate temperature. The reactive transport model, built under the computational fluid dynamics software PHOENICS, was used to reproduce the experimental measurements and to contribute to the understanding of the aluminum growth process, under sub-atmospheric pressure conditions. The growth mechanism of aluminum films was based on well established in literature reaction order and activation energy of homogeneous and heterogeneous chemical reactions. The reactive transport model was used further to investigate the effect of some key operating parameters on the process output. Simulation results are suggestive of modifications in the operating parameters that could enhance the growth rate and the spatial uniformity of the film thickness