Regeneration of aluminium hydride using dimethylethylamine

Lacina, David; Wegrzyn, James; Reilly, J.J.; Celebi, Y.; Graetz, Jason

doi:10.1039/c002064h

Cited by 41 publications

(66 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Although the formation of bis(quinuclidine) alane occurs at low temperature, this complex is difficult to separate and decomposes at high temperatures where the AlH 3 is unstable. Although some amine alanes can be converted into less stable adducts by a transamination reaction (e.g., with triethylamine [19]) as previously demonstrated for DMEA [6] and trimethylamine [20]), stable adducts formed with solid amines, such as quinuclidine alane or TEDA alane, are unlikely to be effective for AlH 3 regeneration. However, bis(quinuclidine) alane may be useful for other applications, such as the reduction of organic functional groups [21].…”

Section: Discussionmentioning

confidence: 92%

“…This is part of a continuing effort to regenerate aluminum hydride using a simple regeneration procedure that involves the formation of a ligand-stabilized adduct followed by separation. This process was also used to regenerate LiAlH 4 from LiH, Al * , and H 2 using a THF ligand [10,11], and AlH 3 from dimethylethylamine alane [6]. Here we describe the synthe- * Corresponding author.…”

Section: Introductionmentioning

confidence: 98%

“…Following the pioneering work of Ashby [4], AlH 3 adducts of the tertiary amines were recently prepared using triethylenediamine (TEDA) [5] and dimethylethylamine (DMEA) [6] via direct reaction with catalyzed Al (hereafter written as Al*) in a THF slurry at room temperature under moderate hydrogen pressure. The direct synthesis of alanates and alane adducts from activated or catalyzed aluminum powder and hydrogen gas (under pressure) was originally performed by Ashby [4,7] and Clasen [8] and more recently by Bogdanovic and Schwickardi [9].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The reversible synthesis of bis(quinuclidine) alane

Lacina

Reilly

Johnson

et al. 2011

Journal of Alloys and Compounds

Self Cite

View full text Add to dashboard Cite

Section: Discussionmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The reversible synthesis of bis(quinuclidine) alane

Lacina

Reilly

Johnson

et al. 2011

Journal of Alloys and Compounds

Self Cite

View full text Add to dashboard Cite

“…This type of reaction places restrictions on the choice of amines, since the first amine must form a more stable adduct and should have a higher vapor pressure than the second amine or the adduct. It was recently demonstrated that the amines in DMEA-AlH 3 and TMA-AlH 3 could be exchanged with TEA to form TEAAlH 3 under mild conditions, as shown below [114,116]:…”

Section: Chemical Regenerationmentioning

confidence: 99%

“…• C) in the absence of a stabilizing amine [114][115][116][117][118]. Once the hydride is formed, the second step involves the removal of the stabilizing ligand and the recovery of the pure AlH 3 .…”

Section: Chemical Regenerationmentioning

confidence: 99%

Metastable Metal Hydrides for Hydrogen Storage

Graetz

2012

ISRN Materials Science

Self Cite

View full text Add to dashboard Cite

The possibility of using hydrogen as a reliable energy carrier for both stationary and mobile applications has gained renewed interest in recent years due to improvements in high temperature fuel cells and a reduction in hydrogen production costs. However, a number of challenges remain and new media are needed that are capable of safely storing hydrogen with high gravimetric and volumetric densities. Metal hydrides and complex metal hydrides offer some hope of overcoming these challenges; however, many of the high capacity "reversible" hydrides exhibit a large endothermic decomposition enthalpy making it difficult to release the hydrogen at low temperatures. On the other hand, the metastable hydrides are characterized by a low reaction enthalpy and a decomposition reaction that is thermodynamically favorable under ambient conditions. The rapid, low temperature hydrogen evolution rates that can be achieved with these materials offer much promise for mobile PEM fuel cell applications. However, a critical challenge exists to develop new methods to regenerate these hydrides directly from the reactants and hydrogen gas. This spotlight paper presents an overview of some of the metastable metal hydrides for hydrogen storage and a few new approaches being investigated to address the key challenges associated with these materials.

show abstract

Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage

Stavila

Dun

et al. 2021

Angewandte Chemie

View full text Add to dashboard Cite

Metastable metal hydrides have many attractive features as hydrogen storage media, but generally cannot be directly regenerated under hydrogen gas and require complex regeneration schemes. Here, we demonstrate nanoconfinement of metastable aluminum hydride inside pores of two Covalent Triazine Frameworks, CTF-bipyridine and CTF-biphenyl. The resulting nanoconfined materials exhibit rapid hydrogen release between 90 and 150 °C, with full desorption into metallic aluminum at 250 °C. Sieverts, 27 Al MAS NMR, 27 Al{ 1 H} REDOR experiments, coupled with computational spectroscopy, reveal that AlH 3 @CTF-bipyridine can be regenerated at 60 °C under 700 bar hydrogen, a pressure which is >10 times lower compared to the pressure required to rehydrogenate bulk metallic Al. In contrast, no reversibility is observed for the AlH 3 @CTF-biphenyl material. DFT calculations show that the presence of small AlH 3 clusters, coupled with the efficient charge redistribution between the hydride and bipyridine groups of CTFbipyridine, is critical to the observed reversibility.

show abstract

Regeneration of aluminium hydride using dimethylethylamine

Cited by 41 publications

References 30 publications

The reversible synthesis of bis(quinuclidine) alane

The reversible synthesis of bis(quinuclidine) alane

Metastable Metal Hydrides for Hydrogen Storage

Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage

Contact Info

Product

Resources

About