Towards direct synthesis of alane: A predicted defect-mediated pathway confirmed experimentally
Abstract
Abstract Alane (AlH 3 ) 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 H 2 and (2) alane formation, which are both endothermic on a clean surface. Only with Ti dopant to facilitate H 2 dissociation and vacancies to provide Al adatoms, both processes become exothermic. In agreement, in situ scanning tunneling microscopy showed that during H 2 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 AlH 3 or closely related species at 344 bar H 2 , indicating that the predicted pathway may lead to the direct synthesis of alane from elements at pressures much lower than the 10 4 bar expected from bulk thermodynamics.
- Authors:
-
[1];
[3];
[4];
[6];
[7]
- Ames Lab., Ames, IA (United States)
- Ames Lab., Ames, IA (United States); Univ. of Illinois Urbana-Champaign, Urbana, IL (United States)
- Univ. of Illinois Urbana-Champaign, Urbana, IL (United States); Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Univ. of Illinois Urbana-Champaign, Urbana, IL (United States); Univ. of Pittsburgh, Pittsburgh, PA (United States)
- Univ. of Illinois Urbana-Champaign, Urbana, IL (United States)
- Univ. of Illinois Urbana-Champaign, Urbana, IL (United States); Univ. of Wisconsin, Madison, WI (United States)
- Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Laboratory (AMES), Ames, IA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1321966
- Alternate Identifier(s):
- OSTI ID: 1786411
- Report Number(s):
- IS-J-025
Journal ID: ISSN 1864-5631
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemSusChem
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 17; Journal ID: ISSN 1864-5631
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Wang, Lin -Lin, Herwadkar, Aditi, Reich, Jason M., Johnson, Duane D., House, Stephen D., Pena-Martin, Pamela, Rockett, Angus A., Robertson, Ian M., Gupta, Shalabh, and Pecharsky, Vitalij K. Towards direct synthesis of alane: A predicted defect-mediated pathway confirmed experimentally. United States: N. p., 2016.
Web. doi:10.1002/cssc.201600338.
Wang, Lin -Lin, Herwadkar, Aditi, Reich, Jason M., Johnson, Duane D., House, Stephen D., Pena-Martin, Pamela, Rockett, Angus A., Robertson, Ian M., Gupta, Shalabh, & Pecharsky, Vitalij K. Towards direct synthesis of alane: A predicted defect-mediated pathway confirmed experimentally. United States. https://doi.org/10.1002/cssc.201600338
Wang, Lin -Lin, Herwadkar, Aditi, Reich, Jason M., Johnson, Duane D., House, Stephen D., Pena-Martin, Pamela, Rockett, Angus A., Robertson, Ian M., Gupta, Shalabh, and Pecharsky, Vitalij K. Thu .
"Towards direct synthesis of alane: A predicted defect-mediated pathway confirmed experimentally". United States. https://doi.org/10.1002/cssc.201600338. https://www.osti.gov/servlets/purl/1321966.
@article{osti_1321966,
title = {Towards direct synthesis of alane: A predicted defect-mediated pathway confirmed experimentally},
author = {Wang, Lin -Lin and Herwadkar, Aditi and Reich, Jason M. and Johnson, Duane D. and House, Stephen D. and Pena-Martin, Pamela and Rockett, Angus A. and Robertson, Ian M. and Gupta, Shalabh and Pecharsky, Vitalij K.},
abstractNote = {Abstract Alane (AlH 3 ) 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 H 2 and (2) alane formation, which are both endothermic on a clean surface. Only with Ti dopant to facilitate H 2 dissociation and vacancies to provide Al adatoms, both processes become exothermic. In agreement, in situ scanning tunneling microscopy showed that during H 2 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 AlH 3 or closely related species at 344 bar H 2 , indicating that the predicted pathway may lead to the direct synthesis of alane from elements at pressures much lower than the 10 4 bar expected from bulk thermodynamics.},
doi = {10.1002/cssc.201600338},
journal = {ChemSusChem},
number = 17,
volume = 9,
place = {United States},
year = {Thu Aug 18 00:00:00 EDT 2016},
month = {Thu Aug 18 00:00:00 EDT 2016}
}
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