In situ solid state 11B MAS-NMR studies of the thermal decomposition of ammonia borane

Mechanistic studies of the hydrogen release pathways from a solid state hydrogen storage material

Ashley C. Stowe, Wendy J. Shaw, John Linehan, Benjamin Schmid, Tom Autrey

Research output: Contribution to journalArticle

297 Citations (Scopus)

Abstract

The mechanism of hydrogen release from solid state ammonia borane (AB) has been investigated via in situ solid state 11B and 11B{1H} MAS-NMR techniques in external fields of 7.1 T and 18.8 T at a decomposition temperature of 88°C, well below the reported melting point. The decomposition of AB is well described by an induction, nucleation and growth mechanistic pathway. During the induction period, little hydrogen is released from AB; however, a new species identified as a mobile phase of AB is observed in the 11B NMR spectra. Subsequent to induction, at reaction times when hydrogen is initially being released, three additional species are observed: the diammoniate of diborane (DADB), [(NH 3)2BH2]+[BH4] -, and two BH2N2 species believed to be the linear (NH3BH2NH2BH3) and cyclic dimer (NH2BH2)2 of aminoborane. At longer reaction times the sharper features are replaced by broad, structureless peaks of a complex polymeric aminoborane (PAB) containing both BH2N 2 and BHN3 species. The following mechanistic model for the induction, nucleation and growth for AB decomposition leading to formation of hydrogen is proposed: (i) an induction period that yields a mobile phase of AB caused by disruption of the dihydrogen bonds; (ii) nucleation that yields reactive DADB from the mobile AB; and (iii) growth that includes a bimolecular reaction between DADB and AB to release the stored hydrogen.

Original languageEnglish
Pages (from-to)1831-1836
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume9
Issue number15
DOIs
Publication statusPublished - 2007

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Boranes
boranes
Hydrogen storage
Ammonia
thermal decomposition
ammonia
Hydrogen
Pyrolysis
Nuclear magnetic resonance
solid state
nuclear magnetic resonance
hydrogen
induction
diborane
Nucleation
nucleation
Decomposition
decomposition
reaction time
Dimers

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

In situ solid state 11B MAS-NMR studies of the thermal decomposition of ammonia borane : Mechanistic studies of the hydrogen release pathways from a solid state hydrogen storage material. / Stowe, Ashley C.; Shaw, Wendy J.; Linehan, John; Schmid, Benjamin; Autrey, Tom.

In: Physical Chemistry Chemical Physics, Vol. 9, No. 15, 2007, p. 1831-1836.

Research output: Contribution to journalArticle

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