TY - JOUR
T1 - Catalytic Synthesis of Nitric Monoxide at the AlN(0001) Surface
T2 - Ab Initio Analysis
AU - Strak, Pawel
AU - Sakowski, Konrad
AU - Kempisty, Pawel
AU - Grzegory, Izabella
AU - Krukowski, Stanislaw
N1 - Funding Information:
The research was partially supported by Polish National Science Centre grants number DEC-2015/19/B/ST5/02136 and 2017/27/B/ST3/01899. This research was carried out with the support of the Interdisciplinary Centre for Mathematical and Computational Modelling at the University of Warsaw (ICM UW) under grant no. G15-9.
PY - 2019/5/2
Y1 - 2019/5/2
N2 - Molecular nitrogen and molecular oxygen adsorption at the Al-terminated AlN(0001) surface was investigated using ab initio simulations. It was shown that both species undergo barrierless dissociation during attachment to the surface. The H3 adsorption site was identified as the most favorable for both O and N adatoms. The adsorption energies for O2 and N2 were found to be 14.8 and 6.0 eV, respectively. At the clean surface, separate N and O adatoms have their energies 4.37 eV lower than the NO admolecule. At normal nitrogen pressures, the AlN(0001) surface is fully covered by nitrogen adatoms. It was shown for this coverage that adsorption of oxygen leads to creation of the NO admolecule which is a necessary step for nitric monoxide synthesis. The energetics of NO molecules is related to electronic charge transfer: from the two possible configurations, it is shown that T4 and H3 are donors and acceptors, respectively. The resulting coverage is the mixture of both configurations, controlled by electron charge balance. Thus, the ab initio modeling provides indication that AlN(0001) is the powerful catalyst for high pressure-high temperature synthesis of nitric monoxide (NO), indicating that AlN may be a candidate for applications in industrial mass synthesis of nitrogen-based materials such as fertilizers or explosives.
AB - Molecular nitrogen and molecular oxygen adsorption at the Al-terminated AlN(0001) surface was investigated using ab initio simulations. It was shown that both species undergo barrierless dissociation during attachment to the surface. The H3 adsorption site was identified as the most favorable for both O and N adatoms. The adsorption energies for O2 and N2 were found to be 14.8 and 6.0 eV, respectively. At the clean surface, separate N and O adatoms have their energies 4.37 eV lower than the NO admolecule. At normal nitrogen pressures, the AlN(0001) surface is fully covered by nitrogen adatoms. It was shown for this coverage that adsorption of oxygen leads to creation of the NO admolecule which is a necessary step for nitric monoxide synthesis. The energetics of NO molecules is related to electronic charge transfer: from the two possible configurations, it is shown that T4 and H3 are donors and acceptors, respectively. The resulting coverage is the mixture of both configurations, controlled by electron charge balance. Thus, the ab initio modeling provides indication that AlN(0001) is the powerful catalyst for high pressure-high temperature synthesis of nitric monoxide (NO), indicating that AlN may be a candidate for applications in industrial mass synthesis of nitrogen-based materials such as fertilizers or explosives.
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U2 - 10.1021/acs.jpcc.8b12472
DO - 10.1021/acs.jpcc.8b12472
M3 - Article
AN - SCOPUS:85065339924
VL - 123
SP - 10893
EP - 10906
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 17
ER -