Abstract
Alanes are believed to be the mass transport intermediate in many hydrogen storage reactions and thus important for understanding rehydrogenation kinetics for alanates and AIH3. Combining density functional theory (DFT) and surface infrared (IR) spectroscopy, we provide atomistic details about the formation of alanes on the Al(111) surface, a model environment for the rehydrogenation reactions. At low coverage, DFT predicts a 2-fold bridge site adsorption for atomic hydrogen at 1150 cm-1, which is too weak to be detected by IR but was previously observed in electron energy loss spectroscopy. At higher coverage, steps are the most favorable adsorption sites for atomic H adsorption, and it is likely that the AIH3 molecules form (initially strongly bound to steps) at saturation. With increasing exposures AIH 3 is extracted from the step edge and becomes highly mobile on the terraces in a weakly bound state, accounting for step etching observed in previous STM studies. The mobility of these weakly bound AIH3 molecules is the key factor leading to the growth of larger alanes through AIH3 oligomerization. The subsequent decomposition and desorption of alanes is also investigated and compared to previous temperature programmed desorption studies.
| Original language | English |
|---|---|
| Pages (from-to) | 10576-10587 |
| Number of pages | 12 |
| Journal | Journal of the American Chemical Society |
| Volume | 130 |
| Issue number | 32 |
| DOIs | |
| Publication status | Published - Aug 13 2008 |
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Formation and bonding of alane clusters on Al(111) surfaces studied by infrared absorption spectroscopy and theoretical modeling. / Chaudhuri, Santanu; Rangan, Sylvie; Veyan, Jean Francois; Muckerman, James; Chabal, Yves J.
In: Journal of the American Chemical Society, Vol. 130, No. 32, 13.08.2008, p. 10576-10587.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Formation and bonding of alane clusters on Al(111) surfaces studied by infrared absorption spectroscopy and theoretical modeling
AU - Chaudhuri, Santanu
AU - Rangan, Sylvie
AU - Veyan, Jean Francois
AU - Muckerman, James
AU - Chabal, Yves J.
PY - 2008/8/13
Y1 - 2008/8/13
N2 - Alanes are believed to be the mass transport intermediate in many hydrogen storage reactions and thus important for understanding rehydrogenation kinetics for alanates and AIH3. Combining density functional theory (DFT) and surface infrared (IR) spectroscopy, we provide atomistic details about the formation of alanes on the Al(111) surface, a model environment for the rehydrogenation reactions. At low coverage, DFT predicts a 2-fold bridge site adsorption for atomic hydrogen at 1150 cm-1, which is too weak to be detected by IR but was previously observed in electron energy loss spectroscopy. At higher coverage, steps are the most favorable adsorption sites for atomic H adsorption, and it is likely that the AIH3 molecules form (initially strongly bound to steps) at saturation. With increasing exposures AIH 3 is extracted from the step edge and becomes highly mobile on the terraces in a weakly bound state, accounting for step etching observed in previous STM studies. The mobility of these weakly bound AIH3 molecules is the key factor leading to the growth of larger alanes through AIH3 oligomerization. The subsequent decomposition and desorption of alanes is also investigated and compared to previous temperature programmed desorption studies.
AB - Alanes are believed to be the mass transport intermediate in many hydrogen storage reactions and thus important for understanding rehydrogenation kinetics for alanates and AIH3. Combining density functional theory (DFT) and surface infrared (IR) spectroscopy, we provide atomistic details about the formation of alanes on the Al(111) surface, a model environment for the rehydrogenation reactions. At low coverage, DFT predicts a 2-fold bridge site adsorption for atomic hydrogen at 1150 cm-1, which is too weak to be detected by IR but was previously observed in electron energy loss spectroscopy. At higher coverage, steps are the most favorable adsorption sites for atomic H adsorption, and it is likely that the AIH3 molecules form (initially strongly bound to steps) at saturation. With increasing exposures AIH 3 is extracted from the step edge and becomes highly mobile on the terraces in a weakly bound state, accounting for step etching observed in previous STM studies. The mobility of these weakly bound AIH3 molecules is the key factor leading to the growth of larger alanes through AIH3 oligomerization. The subsequent decomposition and desorption of alanes is also investigated and compared to previous temperature programmed desorption studies.
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UR - http://www.scopus.com/inward/citedby.url?scp=49449112329&partnerID=8YFLogxK
U2 - 10.1021/ja800136k
DO - 10.1021/ja800136k
M3 - Article
C2 - 18636724
AN - SCOPUS:49449112329
VL - 130
SP - 10576
EP - 10587
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 32
ER -