Aluminum hydride separation using N -Alkylmorpholine

Chengbao Ni, Liu Yang, James Muckerman, Jason Graetz

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

We describe experimental and theoretical studies of several amine·alane adducts for alane separation. First, N- alkylmorpholine·alane adducts (NMM·AlH3 and NEM·AlH3; NMM = N-methylmorpholine, NEM = N-ethylmorpholine) were synthesized and characterized by NMR, IR, and XRD studies. Because of the bifunctionality (or dual coordination mode) of N-alkylmorpholine, NMM·AlH3 and NEM·AlH3 exhibit significantly improved thermal stability compared with the related amine·alane adducts. In the solid state, both NMM·AlH3 and NEM·AlH 3 are polymers, which readily dissociate into monomers in donor solvents, as suggested by IR spectroscopy. In addition, the cost- and energy-effective transamination of (amine)2·AlH3 with NMM (or NEM) has been achieved. Because of the fast reaction kinetics, the transamination reaction could be combined with hydrogenation of Al metal to prepare NMM·AlH3 in a single step, further improving the efficiency of the process. Moreover, the thermal decomposition pathways of NMM·AlH3 and NEM·AlH3 have been elucidated. While NMM·AlH3 decomposes to Al metal directly, NEM·AlH3 can be selectively decomposed to give AlH3 under certain conditions. The dramatically different thermal properties of N-alkylmorpholine·AlH3 could be attributed to the different steric hindrance and basicity of N-alkylmorpholine compounds. Compared with the Et3N/Et3N·AlH3 process, our new approach using N-alkylmorpholine significantly improves the kinetics, selectivity, yields, and energy efficiency of AlH3 recovery. Lastly, theoretical calculations of molecular geometries, absolute free energies, Al-H vibrational frequencies, and thermodynamics of amine·alane adducts with different structures are in good agreement with experimental observations and provide further information for the interactions between amines and AlH3.

Original languageEnglish
Pages (from-to)14983-14991
Number of pages9
JournalJournal of Physical Chemistry C
Volume117
Issue number29
DOIs
Publication statusPublished - Jul 25 2013

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aluminum hydrides
Aluminum
Hydrides
adducts
Amines
Metals
Vibrational spectra
Alkalinity
Reaction kinetics
Free energy
Hydrogenation
Energy efficiency
Infrared spectroscopy
amines
Polymers
Pyrolysis
Thermodynamic stability
Thermodynamic properties
Monomers
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Aluminum hydride separation using N -Alkylmorpholine. / Ni, Chengbao; Yang, Liu; Muckerman, James; Graetz, Jason.

In: Journal of Physical Chemistry C, Vol. 117, No. 29, 25.07.2013, p. 14983-14991.

Research output: Contribution to journalArticle

Ni, Chengbao ; Yang, Liu ; Muckerman, James ; Graetz, Jason. / Aluminum hydride separation using N -Alkylmorpholine. In: Journal of Physical Chemistry C. 2013 ; Vol. 117, No. 29. pp. 14983-14991.
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abstract = "We describe experimental and theoretical studies of several amine·alane adducts for alane separation. First, N- alkylmorpholine·alane adducts (NMM·AlH3 and NEM·AlH3; NMM = N-methylmorpholine, NEM = N-ethylmorpholine) were synthesized and characterized by NMR, IR, and XRD studies. Because of the bifunctionality (or dual coordination mode) of N-alkylmorpholine, NMM·AlH3 and NEM·AlH3 exhibit significantly improved thermal stability compared with the related amine·alane adducts. In the solid state, both NMM·AlH3 and NEM·AlH 3 are polymers, which readily dissociate into monomers in donor solvents, as suggested by IR spectroscopy. In addition, the cost- and energy-effective transamination of (amine)2·AlH3 with NMM (or NEM) has been achieved. Because of the fast reaction kinetics, the transamination reaction could be combined with hydrogenation of Al metal to prepare NMM·AlH3 in a single step, further improving the efficiency of the process. Moreover, the thermal decomposition pathways of NMM·AlH3 and NEM·AlH3 have been elucidated. While NMM·AlH3 decomposes to Al metal directly, NEM·AlH3 can be selectively decomposed to give AlH3 under certain conditions. The dramatically different thermal properties of N-alkylmorpholine·AlH3 could be attributed to the different steric hindrance and basicity of N-alkylmorpholine compounds. Compared with the Et3N/Et3N·AlH3 process, our new approach using N-alkylmorpholine significantly improves the kinetics, selectivity, yields, and energy efficiency of AlH3 recovery. Lastly, theoretical calculations of molecular geometries, absolute free energies, Al-H vibrational frequencies, and thermodynamics of amine·alane adducts with different structures are in good agreement with experimental observations and provide further information for the interactions between amines and AlH3.",
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