BRIEF COMMUNICATIONS
Chinese Science Bulletin 2005 Vol. 50 No. 7 707ü710
Mechanism of NO decompo-
sition on perovskite (-like)
catalysts
ZHU Junjiang1, 2, XIAO Dehai1, LI Jing1,
YANG Xiangguang1 & WU Yue1
1. Changchun Institute of Applied Chemistry, Chinese Academy of Sci-
ences, Changchun 130022, China;
2. Graduate School of Chinese Academy of Sciences, Beijing 100039,
China
Correspondence should be addressed to Yang Xiangguang (email: xgy-
ang@ciac.jl.cn)
DOI: 10.1360/982004-326
NOx emitting from industrial and mobile exhaust are
serious pollutant in air atmosphere, and the removal of
them is an urgent task of today in environment-protection
field[1,2]. Although the present three-way-catalyst (TWC)
can remove NOx from the mobile exhaust effectively, it
will be out of work as lean-burn strategies are used to in-
crease energy efficiency (for example, the diesel engine
operated in the lean-burn condition), hence, the technol-
ogy that can remove NOx in the presence of excess oxygen
is desired[3]. In addition, because the capability of noble-
metal catalyst for NOx removal is weak at high tempera-
tures (>873 K)[4], it is thus necessary to comprehend the
process of NOx decomposition, which would help to solve
the problem of NOx removal.
For NO decomposition reaction (2NO = N2 + O2), it is
generally accepted that N2 was formed through the de-
composition of N2O species, i.e. 2NOėN2O + Oads and
N2OadsėN2 + Oads[3,5ü7]. While the way of oxygen forma-
tion is still unclear at present[8]. According to the litera-
tures, there are two proposed ways for oxygen desorption,
that is, i) the direct desorption of two vicinal oxygen, Oads
+ OadsėO2[6]; and ii) the indirect desorption with NO as
an intermediate, NOads + Oads ėNO2, NO2 + OadsėNO3 ads,
NO3 adsėNO + O2[3,9]. Accordingly, there are two ways for
NO2 formation, that is, iii) reaction of gaseous NO and O2
occurring in the downstream, O2 + 2NOė2NO2; and iv)
reaction of adsorbed O atom and NO occurring on the
catalyst surface, Oads + NOadsėNO2. Recently, Iglesia et
al.[3] suggested that the O2 formation over Cu-ZSM-5
mainly occurred through the decomposition of NO3(a) spe-
cies, but there is still no literature discussing the way of O2
and NO2 formation over perovskite (-like) oxides. In this
work, by discussing the possible reaction steps occurring
in the process of NO decomposition, we proposed that the
way of NO decomposition over perovskite (-like) mixed
oxides occurred with NO2 as an intermediate, and NO2
Chinese Science Bulletin Vol. 50 No. 7 April 2005
was mainly formed on the catalyst surface in the way of
Oads + NOadsėNO2, while O2 was formed through the
dissociation of NO2 species in the way of 2NO2(g) =
2NO(g) + O2(g).
The samples, LaSrNiO4 and La0.4Sr0.6Mn0.8Ni0.2O3,
were prepared by the conventional citric combustion
method[10].
O2-TPD experiment was carried out on a homemade
apparatus equipped with a thermal conductivity detector
(TCD). The samples (0.2 g) were first treated in O2 at
1073 K for 1 h and cooled to room temperature in the
same atmosphere, then swept with pure He (or 0.5%
O2/He) at a rate of 11.8 mL/min until the base line on the
recorder remained unchanged. Finally, the sample was
heated at a rate of 20 K/min in He (or 0.5% O2/He) to re-
cord the TPD profile.
Steady-state activities of catalysts were evaluated using
a single-pass flow micro-reactor made of quartz, with an
internal diameter of 6 mm. The reactant gas (1% NO/He +
0%10% O2/He) was passed through 0.5 g (in the absence
of oxygen) or 1.0 g (in the presence of oxygen) catalysts
at a rate of 25 or 40 mL/min (in all, to keep W/F = 1.2
g·s·cm3). The gas composition was analyzed before and
after the reaction by an on-line gas chromatography, using
molecular sieve 5A column for separating NO, N2 and O2.
N2O was not analyzed here because it was difficult to
form between 773 and 1123 K as reported in ref. [9]. Be-
fore the data were obtained, reactions were maintained for
a period of ~2 h at each temperature to ensure the
steady-state conditions.
According to the literatures reported previously, the
possible reaction steps occurring in the process of NO
decomposition are summarized in Table 1.
Table 1 The possible reaction steps occurring in the process of NO
decomposition
(i) Adsorption steps
NO(g) œ NO(a) (1)
(ii) Surface rearranged and desorption steps
NO(a)ėN(a)+O(a) (2) 2N(a)ėN2(g) (3)
2O(a) œ O2(g) (4) NO(a)+N(a)ėN2O(g) (5)
NO(a)+O(a)œNO2(a) œNO2(g) (6) NO2+O(a)œNO3(a)ėNO(g)+O2(g) (7)
2NO(a)ėN2(g)+2O(a) (8) 2NO(a)ėN2O(g)+O(a) (9)
(iii) Gas-phase reaction
2NO(g)+O2(g) œ2NO2(g) (10) 2NO2(g)œ2NO(g)+O2(g) (11)
(iv) N2O intermediate step (N2O was not observed in the present case)
N2O(g)œN2O(a) (12) N2O(a)ėN2(g)+O(a) (13)
From Table 1, it is known that there are two possible
reaction routes, reactions (6) and (10), corresponding to
NO2 formation. In reaction (10), NO2 is formed by the
reaction of gaseous NO and O2 in the cool region down-
707
BRIEF COMMUNICATIONS
stream[5,6], while in reaction (6), NO2 is formed by the should occur through reaction (10).
reaction of adsorbed NO and O atom on catalyst surface.
In order to investigate which one is the main route of NO2
formation, a blank experiment was carried out. In this ex-
periment, the two gases (1%NO/He and 0.5%O2/He) were
mixed before feeding to the reactor, which was filled with
quartz instead of catalyst; the reaction tube was kept at
1073 K. The conversion of O2 was taken as the parameter
to determine the degree of reaction carried out. The O2
conversion measured in this experiment was only 25%,
which is far lower than that calculated in thermodynamics
(~100%). This indicates that the oxidation of NO to NO2
is not easy to occur at low concentration. However, when
catalyst was loaded in the reactor, the O2 conversion
reached 80%, which is far higher than 25% (similar result
was also obtained in ref. [9]). This indicates that NO2 is
mainly formed on the catalyst surface through reaction (6).
Otherwise, the existence of catalyst will have no much
impact on O2 conversion, and the O2 conversion measured
with catalyst loading should be less than that measured in
the blank experiment, namely, below 25%. Hence, it can Fig. 1. O2-TPD profiles plotted with and without oxygen in helium.
Catalyst: LaSrNiO4.
be concluded that reaction (6) is the main route of NO2
formation. However, we cannot detect this reaction di-
rectly at present due to the participation of the atomic
oxygen species (O(a)).
There are three possible reaction routes, reactions (4),
(7) and (11), corresponding to O2 formation. Reaction (4)
assumed that O2 formation occurred through the simple
desorption of two vicinal adsorbed oxygen atoms[11]; reac-
tion (7) assumed that O2 formation occurred through the
decomposition of NO3(a) species, which was derived from
adsorbed NO and O atom; while the O2 in reaction (11)
was supposed to be formed through the direct dissociation
of NO2 species. In order to clarify the main route of O2
formation, two experiments were performed. One is
O2-TPD experiment, which was performed with and
without O2 in He; the result is shown in Fig. 1. The small Fig. 2. Activity of NO decomposition as a function of O2 partial pres-
difference of the two desorption temperatures (ǻTmaxİ10 sure. Catalyst: LaSrNiO4.
K) and the nearly same magnitude of the two desorption
peak areas (Ab/Aa = 1.04) indicated that these two profiles While for the two other ways (reactions (7) and (11)), it
were almost the same, namely, the impact of gaseous is difficult to distinguish which one is the main route of O2
oxygen on oxygen desorption can be neglected. The other formation on the above basis, since both of them involved
is the activity of NO decomposition, which was performed the NO2 species. Therefore, other criteria must be consid-
in different oxygen partial pressure. The results in Fig. 2 ered. From the stability of NO3(a) species and thermody-
indicated that the gaseous oxygen has great impact on the namic equilibrium of NO2 dissociation reaction, it might
activity and the degree of impact mitigated with the in- be deduced that at low temperatures (T<767 K), reaction
crease of oxygen partial pressures. These two experiments (7) is the main route of O2 formation, since NO2 cannot be
suggested that O2 formation, in NO decomposition reac- dissociated spontaneously at low temperatures. This route
tion, did not occur through reaction (4). Otherwise, the is mainly performed on these catalysts, of which the activ-
gaseous oxygen, as that in O2-TPD, should have no or ity could be exhibited below 767 K, for example,
minor impact on the activity, since the gaseous oxygen has M-ZSM5 (M: Cu, Fe, Co, etc.)[3,12ü14]. While at high tem-
no influence on O2 desorption (see O2-TPD). In fact, ac- peratures (T>873 K), because NO2 direct dissociation re-
cording to the way of NO2 formation (reaction (6)), it can action can occur and NO3(a) species is unstable and diffi-
also be deduced that the oxygen desorption did not occurr cult to form[9,15], it is unnecessary for NO2 to convert into
through reaction (4), otherwise, the way of NO2 formation NO3(a) species before dissociating into NO and O2. That is

708 Chinese Science Bulletin Vol. 50 No. 7 April 2005


to say, reaction (11) becomes the main route of O2 forma-
tion at high temperature range. This route is mainly per-
formed on these catalysts, of which the activity is exhib-
ited at high temperatures (T > 873 K), for example, the
perovskite (-like) mixed oxides[7,9].
In all, it was suggested that in NO decomposition reac-
tion, the formation of N2 and O2 mainly occurred through
the way of 4NOėN2 + 2NO2 and 2NO2ė2NO + O2, re-
spectively. Based on these routes, the decrease of NO de-
composition activity in the presence of gaseous oxygen,
then, is ascribed to the suppression of gaseous oxygen on
NO2 dissociation reaction (2NO2(g) œ 2NO(g) + O2(g)).
In order to check the fact that NO2 is an important in-
termediate in NO decomposition, an additional experiment
(ratio of [O2]/[N2] as a function of contact time (W/F))
was performed, in which the sample was chosen to be a
highly active catalyst La0.4Sr0.6Mn0.8Ni0.2O3 and some of
results are discussed below.
From Fig. 3, it is seen that the ratio of [O2]/[N2] in
creased with the increase of contact time (W/F) at the be-
ginning, then kept constant (95%) at higher values (W/F
ı4 g·s·cm3), this indicates that the amount of O2 pro-
duced in NO decomposition is always lower than that of
N2. The reason might be that there exists a thermodynamic
equilibrium among O2, NO and NO2 (2NO2 = 2NO + O2)
and NO2 cannot be dissociated into NO and O2 completely
due to the restriction of thermodynamics. At low contact
time (or high flow rate), the time for NO2 staying on the
catalyst is shorter and the recycle frequency of NO2 is less,
and as a result, the amount of O2 produced is little, result-
ing in the lower [O2]/[N2] ratio. With the increase of con-
tact time, the recycle frequency of NO2 increased and
more amount of O2 was produced, consequently, the ratio
of [O2]/[N2] increased. When the recycle frequency of
NO2 reached a certain value that could make the NO2 dis-
sociation reaction reach the thermodynamic equilibrium
(here, W/Fı4 g·s·cm3), NO2 cannot be dissociated fur-
Fig. 3. Ratio of [O2]/[N2] obtained in NO decomposition as a function of
contact time (W/F). Catalyst: La0.4Sr0.6Mn0.8Ni0.2O3.
Chinese Science Bulletin Vol. 50 No. 7 April 2005
BRIEF COMMUNICATIONS
ther and the ratio of [O2]/[N2] keeps constant. The con-
stant of [O2]/[N2] measured in our experiment was ~95%
(1073 K), which was in compliance with the thermody-
namic calculation of the reaction NO2 = NO + 1/2O2
(1100 K, 96%). The so accordant values supported the fact
that the formation of O2 occurred through the NO2 disso-
ciation reaction.
Similar to what is expatiated in refs. [69, 11], that the
oxygen vacancy is an important factor for NO decomposi-
tion reaction, in this work, it was also considered that the
active site of NO decomposition over perovskite (-like)
mixed oxides was composed of the oxygen vacancy and
the transition metal with lower oxidative state. Generally,
in the structure of perovskite (-like) mixed oxides there
existed a lot of oxygen vacancies, which offered the space
and facilitated the adsorption of NO. The adsorbed NO
then received one electron from the transition metal with
lower oxidative state and was activated to participate in
the reaction. However, it should be noted that the oxygen
vacancies participating in the reaction must be in disorder
status and is adjacent to the transition metal with low oxi-
dative state; otherwise, they will have no contribution to
the reaction[16].
Based on the above discussion for NO decomposition
reaction, that the NO2 formation occurred on the catalyst
surface in the way of Oads + NOadsėNO2 and the O2 for-
mation occurred through the dissociation of NO2 species
in the way of 2NO2 (g)ė2NO (g) + O2 (g). It is therefore de-
duced that NO decomposition reaction over perovskite
(-like) mixed oxides occurred through a recycle way, in
which NO2 is an intermediate and plays an important role
in the reaction, as described in Fig. 4.
Fig. 4. The recycle mechanism of NO decomposition over the
perovskite(-like) mixed oxides.
Acknowledgements This work was supported by the Ministry of Sci-
ence and Technology of China (Grant No. 2001AA324060) and the
National Natural Science Foundation of China (Grant No. 20177022).
References
1. Li, Y., Armor, J. N., Catalytic decomposition of nitrous oxide on
metal exchanged zeolites, Appl. Catal. B, 1992, 1(3): L21L29.
2. Voorhoeve, R. J. H., Advanced Materials in Catalysis, New York:
Academic Press, 1977, 129.
709
BRIEF COMMUNICATIONS
3. Moden, B., Costa, P. D., Iglesia, E. et al., Kinetics and mechanism
of steady-state catalytic NO decomposition reactions on Cu-ZSM5,
J. Catal., 2002, 209(1): 7586.
4. Hecker, W. C., Bell, A. T., Infrared observations of RhNCO and
Si—NCO species formed during the reduction of NO by CO over
silica-supported rhodium, J. Catal., 1984, 85(2): 389397.
5. Xie, S., Rosynek, M. P., Lunsford, J. H., Catalytic reactions of NO
over 07 mol% Ba/MgO catalysts: I. The direct decomposition of
NO, J. Catal., 1999, 188(1): 2431.
6. Teraoka, Y., Harada, T., Kagawa, S., Reaction mechanism of direct
decomposition of nitric oxide over Co- and Mn-based perovskite-
type oxides, J. Chem. Soc., Faraday Trans., 1998, 94(13): 1887
892.
7. Zhao, Z., Yang, X. G., Wu, Y., Comparative study of Nickel-based
perovskite-like mixed oxide catalysts for direct decomposition of
NO, Appl. Catal. B, 1996, 8(3): 281297.
8. Yokoi, Y., Uchida, H., Catalytic activity of perovskite-type oxide
catalysts for direct decomposition of NO: Correlation between
cluster model calculations and temperature-programmed desorption
experiments, Catal. Today, 1998, 42(1~2): 167174.
9. Ishihara, T., Ando, M., Sada, K. et al., Direct decomposition of NO
into N2 and O2 over La(Ba)Mn(In)O3 perovskite oxide, J. Catal.,
2003, 220 (1): 104114.
10. Yu, Z. L., Yuan, S. Y., Wu, Y. et al., Solid defect structure and cata-
710
lytic activity of perovskite-type catalysts La1–xSrxNiO3–Ȝ and
La1–1.333xThxNiO3–Ȝ, J. Chem. Soc., Faraday Trans., 1992, 88(21):
32453249.
11. Shin, S., Arakawa, H., Shimomura, K. et al., Absorption of NO in
the lattice of an oxygen deficient perovskite SrFeO3-x and the infra-
red spectroscopic study of the system NO-SrFeO3-x, Mat. Res. Bull.,
1979, 14(2): 633639.
12. Adelman, B. J., Lei, G. D., Sachtler, W. M. H., Co-adsorption of ni-
trogen monoxide and nitrogen dioxide in zeolitic de-NOx catalysts,
Catal. Lett., 1994, 28(1): 119130.
13. Chang, Y., McCarty, J. G., Decomposition of NO over [Co]-ZSM-5
zeolite: effect of co-adsorbed O2, J. Catal., 1998, 178(2): 408413.
14. Sierraalta, A., Anez, R., Brussin, M. R., Theoretical study of NO2
adsorption on a transition metal zeolite model, J. Catal., 2002,
205(1): 107114.
15. Rodriguez, J. A., Jirsak, T., Maiti, A. et al., Chemistry of NO2 on
CeO2 and MgO: Experimental and theoretical studies on the forma-
tion of NO3, J. Chem. Phys., 2000, 112(22): 99299939.
16. Shin, S., Hatakeyama, Y., Ogawa, K. et al., Catalytic decomposi-
tion of NO over brownmillerite-like compounds, Ca2Fe2O5 and
Sr2Fe2O5, Mat. Res. Bull., 1979, 14(1): 133136.
(Received September 15, 2004; accepted November 16, 2004)
Chinese Science Bulletin Vol. 50 No. 7 April 2005