116
7 The Reactions with Monoxides for Pollution Removal
Fig. 7.15 Comparison of the
reaction of a the nickel oxide
clusters and b the bare nickel
clusters with NO at 2 sccm.
The species Ni x O y (NO) z
+
are labeled as (x, y, z). These
spectra show the similarity in
reaction products formed.
Reproduced with permission
from Ref. [92]. Copyright
1999 American Chemical
Society
reaction mechanisms occur between NO and Ni x
+ /Ni x O y
+ . Together with an examination of pseudo-first-order bimolecular rate constants for these reactions, it was
demonstrated that competing processes such as oxidation and replacement of oxygen
with NO were involved. It was noted that the presence of a few magic peaks in the
distributions indicated unusual stability of the size-selected product cluster species,
such as Ni 3 O(NO) 3
+ and Ni 2 O(NO) 3
+ which were observed in the low-mass region
of the product distributions for the reactions of NO with both Ni x
+ and Ni x O y
+ [92].
Similarly, the fast flow reactor coupled with a quadrupole mass spectrometer was
also used to study the gas-phase reactions of anionic nickel and nickel oxide clusters
(Ni x O y
− , where x = 1–12 and y = 0–2) with nitric oxide, and the rate constants
were examined for the initial reaction occurring between the Ni x
− cluster anions and
NO [91]. The results throwed light on three processes: (i) nickel and nickel oxide
clusters are oxidized at the reaction with nitric oxide; (ii) addition products with
the oxides are also formed; (iii) nitrogen dioxide and nitrogen trioxide are formed
on nickel oxide clusters and subsequently released as anions (NO 2
− and NO 3
− ). In
comparison, N 2 O
− was not observed because of its low electron affinity compared
with NO 2 and nickel/nickel oxide clusters [93, 94].
References
1. M. Walter, J. Akola, O. Lopez-Acevedo, P.D. Jadzinsky, G. Calero, C.J. Ackerson, R.L.
Whetten, H. Grönbeck, H. Häkkinen, Proc. Natl. Acad. Sci. U. S. A. 105, 9157–9162 (2008)
2. M.B. Abreu, C. Powell, A.C. Reber, S.N. Khanna, J. Am. Chem. Soc. 134, 20507–20512 (2012)
7 The Reactions with Monoxides for Pollution Removal
Fig. 7.15 Comparison of the
reaction of a the nickel oxide
clusters and b the bare nickel
clusters with NO at 2 sccm.
The species Ni x O y (NO) z
+
are labeled as (x, y, z). These
spectra show the similarity in
reaction products formed.
Reproduced with permission
from Ref. [92]. Copyright
1999 American Chemical
Society
reaction mechanisms occur between NO and Ni x
+ /Ni x O y
+ . Together with an examination of pseudo-first-order bimolecular rate constants for these reactions, it was
demonstrated that competing processes such as oxidation and replacement of oxygen
with NO were involved. It was noted that the presence of a few magic peaks in the
distributions indicated unusual stability of the size-selected product cluster species,
such as Ni 3 O(NO) 3
+ and Ni 2 O(NO) 3
+ which were observed in the low-mass region
of the product distributions for the reactions of NO with both Ni x
+ and Ni x O y
+ [92].
Similarly, the fast flow reactor coupled with a quadrupole mass spectrometer was
also used to study the gas-phase reactions of anionic nickel and nickel oxide clusters
(Ni x O y
− , where x = 1–12 and y = 0–2) with nitric oxide, and the rate constants
were examined for the initial reaction occurring between the Ni x
− cluster anions and
NO [91]. The results throwed light on three processes: (i) nickel and nickel oxide
clusters are oxidized at the reaction with nitric oxide; (ii) addition products with
the oxides are also formed; (iii) nitrogen dioxide and nitrogen trioxide are formed
on nickel oxide clusters and subsequently released as anions (NO 2
− and NO 3
− ). In
comparison, N 2 O
− was not observed because of its low electron affinity compared
with NO 2 and nickel/nickel oxide clusters [93, 94].
References
1. M. Walter, J. Akola, O. Lopez-Acevedo, P.D. Jadzinsky, G. Calero, C.J. Ackerson, R.L.
Whetten, H. Grönbeck, H. Häkkinen, Proc. Natl. Acad. Sci. U. S. A. 105, 9157–9162 (2008)
2. M.B. Abreu, C. Powell, A.C. Reber, S.N. Khanna, J. Am. Chem. Soc. 134, 20507–20512 (2012)