Applied Catalysis B: Environmental 24 (2000) 243–253

AMnO3 (A=La, Nd, Sm) and Sm1−x Srx MnO3 perovskites as

combustion catalysts: structural, redox and catalytic properties
Paolo Ciambelli b , Stefano Cimino a , Sergio De Rossi c , Marco Faticanti c , Luciana Lisi d ,
Giuliano Minelli c , Ida Pettiti c , Piero Porta c,∗ , Gennaro Russo a , Maria Turco a
a Dipartimento di Ingegneria Chimica, Università ‘Federico II’, Napoli, Italy
b Dipartimento di Ingegneria Chimica e Alimentare, Università di Salerno, Salerno, Italy
c Centro di Studio del CNR su ‘Struttura e Attività Catalitica di Sistemi di Ossidi’ (SACSO), c/o Dipartimento di Chimica, Università La
Sapienza, Piazzale A. Moro 5, 00185 Rome, Italy
d Istituto di Ricerche sulla Combustione, CNR, c/o Dipartimento di Ingegneria Chimica, Piazzale V. Tecchio 80, 80125 Napoli, Italy

Received 13 June 1999; received in revised form 3 September 1999; accepted 3 September 1999

Abstract
Catalytic combustion of methane has been investigated over AMnO3 (A = La, Nd, Sm) and Sm1−x Srx MnO3 (x = 0.1,
0.3, 0.5) perovskites prepared by citrate method. The catalysts were characterized by chemical analysis, XRD and TPR
techniques. Catalytic activity measurements were carried out with a fixed bed reactor at T = 623–1023 K, space veloc-
ity = 40 000 N cm3 g−1 h−1 , CH4 concentration = 0.4% v/v, O2 concentration = 10% v/v.
Specific surface areas of perovskites were in the range 13–20 m2 g−1 . XRD analysis showed that LaMnO3 , NdMnO3 ,
SmMnO3 and Sm1−x Srx MnO3 (x = 0.1) are single phase perovskite type oxides. Traces of Sm2 O3 besides the perovskite phase
were detected in the Sm1−x Srx MnO3 catalysts for x = 0.3, 0.5. Chemical analysis gave evidence of the presence of a significant
fraction of Mn(IV) in AMnO3 . The fraction of Mn(IV) in the Sm1−x Srx MnO3 samples increased with x. TPR measurements
on AMnO3 showed that the perovskites were reduced in two steps at low and high temperature, related to Mn(IV) → Mn(III)
and Mn(III) → Mn(II) reductions, respectively. The onset temperatures were in the order LaMnO3 > NdMnO3 > SmMnO3 . In
Sm1−x Srx MnO3 the Sr substitution for Sm caused the formation of Mn(IV) easily reducible to Mn(II) even at low temperature.
Catalytic activity tests showed that all samples gave methane complete conversion with 100% selectivity to CO2 below 1023 K.
The activation energies of the AMnO3 perovskites varied in the same order as the onset temperatures in TPR experiments
suggesting that the catalytic activity is affected by the reducibility of manganese. Sr substitution for Sm in SmMnO3 perovskites
resulted in a reduction of activity with respect to the unsubstituted perovskite. This behaviour was related to the reduction
of Mn(IV) to Mn(II), occurring under reaction conditions, hindering the redox mechanism. ©2000 Elsevier Science B.V. All
rights reserved.
Keywords: Catalytic methane combustion; Perovskites; Redox properties

1. Introduction

Catalytic combustion has been proposed as a

∗Corresponding author. Fax: +39-3-6-490-324. method for promoting the effective oxidation of
E-mail address: porta@axrma.uniromal.it (P. Porta). fuel/air lean mixtures with low emissions of NOx , CO

0926-3373/00/$ – see front matter ©2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 3 3 7 3 ( 9 9 ) 0 0 1 1 0 - 1
244 P. Ciambelli et al. / Applied Catalysis B: Environmental 24 (2000) 243–253
and unburnt hydrocarbons [1,2]. Therefore, by this
process neither potentially harmful emissions are pro-
duced nor expensive secondary treatments required
to meet the stringent demands on atmospheric pollu-
tion limitation [3]. Catalytic combustion operates at
low temperature compared to the conventional flame
combustion thus reducing the formation of thermal
NOx starting at about 1773 K [1,4].
Catalytic materials to be used in the combustor must
posses several properties such as high surface area,
thermal stability, high durability with respect to oxi-
dation activity and product selectivity. Noble metals
and metal oxides have been reported as active cat-
alysts for methane total oxidation [1]. Noble metals
based catalysts are the most active ones even at low
temperature, but they are expensive and their thermal
stability is poor, due to sintering and volatility. On
the other hand transition metal oxides are cheaper, but
less active and undergo sintering at moderate temper-
ature [1,2,5]. Much attention has been paid recently
to perovskite-type oxides, of general formula ABO3
(where A and B are usually rare earth and transition
metal cations, respectively), as catalysts for total oxi-
dation of hydrocarbons, due to their high activity and
thermal stability [1,2,6].
Many metallic elements are stable in the ABO3
perovskite structure provided that their cationic
radii fit well the sizes of the 12-coordinated A
and 6-coordinated B sites, e.g. rA > 0.90 Å, and
rB > 0.51 Å. Moreover, the high stability of the per-
ovskite structure allows the partial substitution of
either A and B cations by other metals with differ-
ent oxidation state and the consequent generation of
structural defects (e.g. anionic or cationic vacancies)
[7–9]. The effect of the nature of the B cation on
the physico-chemical and catalytic properties of lan-
thanum based perovskites has been widely studied,
perovskites containing manganese or cobalt having
been found the most active in methane combustion
[10]. It was reported that the substitution of B by lower
valence cations in LaMnO3 and LaCoO3 perovskites
generally promotes methane oxidation [1], whereas
the effect of rare earth has been less investigated, only
few studies concerning ACoO3 perovskites having
been reported [11,12].
Perovskite oxides are generally prepared by ceramic
methods that require very high temperature and pro-
duce materials with surface area lower than 1 m2 g−1 ,
limiting to some extent their application in catalysis.
In order to improve the catalytic activity it is thus nec-
essary to produce such materials with higher surface
areas using suitable precursors which may give, under
mild heat treatment, the desired catalysts. For this pur-
pose the citrate method was proposed by Zhang et al.
[13] to prepare high surface area perovskites. This
method involves addition of citric acid to the precursor
nitrate solution. From citrate complexes, through sev-
eral decomposition steps leading to the elimination of
the residual CO3 2− and NO3 − ions, perovskite struc-
ture is obtained. It was found that this method allows
to obtain more homogeneous dispersion of the pre-
cursor salts. Therefore, a lower calcination tempera-
ture than other methods is needed to obtain perovskite
structure, thus avoiding sintering phenomena.
This paper reports on the catalytic activity of
large surface area AMnO3 (A = La, Nd, Sm, Sr)
perovskites, prepared by citrate precursors, in the
combustion of methane, with the aim to understand
the effect of the rare earth A cation on their catalytic
behaviour. Structural and redox properties were also
investigated.
2. Experimental
LaMnO3 , NdMnO3 and Sm1−x Srx MnO3 (x = 0.0,
0.1, 0.3, 0.5) catalysts were prepared according to the
method described by Zhang et al. [13]. A concentrated
solution of metal nitrates was mixed with an aqueous
solution of citric acid. The molar ratio of citric acid
to total metal cations was fixed at unity. Water was
evaporated from the mixed solution at 343 K and the
sol was further dehydrated to yield a solid amorphous
citrate precursor. The product was ground and fired
at 573 K for 1 h, then reground and calcined for 5 h
at 823 K. The final calcination, after regrinding, was
performed for 5 h at 1073 K.
The content of all metals (Table 1) was determined
by inductively coupled plasma emission spectroscopy
(ICP). To determine the relative concentration of
Mn(III) and Mn(IV), part of the sample was dissolved
in a known excess of standard ammonium-ferrous
(Mohr’s salt) sulfate solution acidified with sulfuric
acid. The excess of Fe(II) was then titrated with stan-
dard potassium permanganate solution and the num-
ber of milliequivalents of iron oxidized by Mn(III)
 P. Ciambelli et al. / Applied Catalysis B: Environmental 24 (2000) 243–253 245

Table 1
Sm1−x Srx MnO3 , NdMnO3 and LaMnO3 perovskitesa
Sm1−x Srx MnO3 NdMnO3 LaMnO3

x = 0.0 x = 0.1 x = 0.3 x = 0.5

Phases P P P + Sm P + Sm P P
a 5.39 5.36 5.45 5.43 5.44 5.52
b 5.71 5.74 5.49 5.43 5.79
c 7.68 7.56 7.52 7.50 7.55 13.33
V 236 233 225 221 238 351
Tc 0 +95 +90 +80 +100 +165
µ 5.14 5.07 5.90 5.33 5.90 5.72
SABET 19 20 14 13 20 20
SAcalc 29 26 36 36 33 13
H2 low T peak (T)max 0.20 (733) 0.20 (738) 0.47 (788) 0.47 (793) 0.17 (611) 0.21 (713)
H2 high T peak (T)max 0.44 (1023) 0.41 (1053) 0.27 (1056) 0.25 (1043) 0.50 (1063) 0.38 (1063)
Ea 17.1 20.8 18.6 18.4 19.3 23.3
Pre-exponential factor 0.21 1.30 0.65 0.63 0.35 8.1
D 290 330 240 250 260 730
Mnexp 22.2 21.1 21.6 22.0 21.5 20.0
Mnnom 21.5 22.1 23.1 24.6 22.0 22.4
Srexp 5.3 10.5 18.5
Srnom 3.7 10.9 19.6
Smexp 53.6 53.9 43.6 32.8
Smnom 58.9 54.1 44.7 33.7
Ndexp 53.4
Ndnom 57.9
Laexp 46.6
Lanom 56.7
Mn(IV)/Mntot 0.28 0.35 0.64 0.64 0.23 0.35
t 0.92 0.93 0.97
a Phases detected by XRD (P: perovskite, Sm: Sm O ). Lattice parameters: a/Å, b/Å, c/Å, V/Å3 . Curie temperature, T /K and magnetic
2 3 c
moment, µ/µB . Surface area (m2 g−1 ) determined by BET, SABET , and calculated (see text), SAcalc . Hydrogen uptake by TPR at low
T, H2 low T peak , (mol H2 mol−1 Mn), with T taken at the maximum of the peak, (T)max /K, in parentheses. Hydrogen uptake by TPR
at high T, H2 high T peak , (mol H2 mol−1 Mn), with T taken at the maximum of the peak, (T)max /K, in parentheses. Activation energy,
Ea (kcal mol−1 ). Pre-exponential factor (l m−2 h−1 ) × 106 . Crystallite size, D/Å. Experimental and nominal percentage for each element.
Fraction of Mn(IV)/Mn total. Tolerance factor, t.

and Mn(IV) was obtained by the difference between
the total milliequivalents of Fe(II) added and the mil-
liequivalents of excess iron determined by titration.
Phase analysis, lattice parameters and particle
sizes determination were performed by X-ray powder
diffraction (XRD) using a Philips PW 1029 diffrac-
tometer with Ni-filtered Cu K␣ radiation. Lattice
parameters were calculated by means of the UNIT-
CELL program. 1 Particle sizes were evaluated by
means of the Scherrer equation D = Kλ/β cos θ after
Warren’s correction for instrumental broadening [14].
1 T.J.B. Holland and S.A.T. Redfern, J. Appl. Crystallogr., 30
(1997) 84.
K is a constant equal to 0.9, λ the wavelength of the
X-ray used, β the effective line width of the X-ray
reflection under observation, calculated by the expres-
sion β 2 = B2 − b2 [where B is the full width at half
maximum (FWHM)], b the instrumental broadening
determined through the FWHM of the X-ray reflec-
tion at θ = 14◦ of SiO2 having particles larger than
1000 Å, θ the diffraction angle of the (1 1 1) X-ray
reflection (θ 1 1 1 = 12.8◦ ) for samarium and neodim-
ium compounds, and of the (1 0 2) X-ray reflection
(θ 1 0 2 = 11.5◦ ) for the lanthanum perovskite.
BET surface areas (SABET ) of the materials were
measured by N2 adsorption at 77 K using a volumetric
all glass apparatus.
246 P. Ciambelli et al. / Applied Catalysis B: Environmental 24 (2000) 243–253

The surface area values were also calculated mixed at atmospheric pressure to obtain inlet concen-
starting from particle sizes using the expression trations of 0.4% methane, 10% O2 , N2 as balance.
SAcalc = 30 000/rd, where r is the radius of crystal- The feed and product streams were analyzed by on
lites (supposed spherical) deduced from the crystallite line HP 6890 gaschromatograph equipped with ther-
sizes (D) measured by means of X-ray line broaden- mal conductivity and flame ionization detectors and
ing (r = D/2), and d is the bulk density derived from with Porapak Q and molecular sieve 5A columns. A
the formula: d = (MZ)/(VN), where M is the molar silica gel water trap placed before the gaschromato-
mass of the formula unit, Z the number of formula graph allowed to dry the product stream. For each test
units per unit cell, V the measured unit cell volume, the methane conversion was calculated as the average
N the Avogadro’s constant. of at least three measurements. Carbon balance was
Magnetic susceptibilities were measured by the closed to within ±5% in all catalytic tests.
Gouy method over the temperature range 100–300 K
and at different magnetic-field strengths. Correction
was made for the diamagnetism of the samples. 3. Results and discussion
Temperature-programmed desorption (TPD) of O2
and temperature-programmed reduction (TPR) with 3.1. Oxides
H2 were performed using a Micromeritics TPD/TPR
2900 analyser equipped with a TC detector and cou- Table 1 reports the main features of the perovskite
pled with a Hiden HPR 20 mass spectrometer. The samples in terms of phases present, chemical composi-
sample (30 mg) was preheated in flowing air at 1073 K tion, surface area, structural and magnetic properties.
for 2 h before each TPD or TPR test. In TPR analyses a Fig. 1 shows that LaMnO3 , NdMnO3 , SmMnO3
2% H2 /Ar mixture (25 cm3 min−1 ) was used to reduce and Sm0.9 Sr0.1 MnO3 samples are single phase
the sample by heating 10 K min−1 up to 1073 K. Wa-
ter produced by the sample reduction was condensed
in a cold trap before reaching the detectors. Only H2
was detected in the outlet gas confirming the effective-
ness of the cold trap. In O2 TPD analyses the sample
was heated 10 K min−1 up to 1073 K in flowing He
(25 cm3 min−1 ). Only O2 was detected in the outlet
gas of TPD measurements.
Catalytic combustion experiments were carried out
with a downflow quartz annular reactor electrically
heated in a three zone tube furnace. The annular
cross-section was chosen to obtain a small equiv-
alent diameter that enables to control the catalyst
temperature and to reduce the temperature gradients
within the bed. Catalyst particles in the range of
180–250 ␮m were diluted 1 : 10 in quartz powder of
the same dimension and placed on a porous quartz
disk. The narrowing of the reactor diameter both
in the pre- and in the post-catalytic zone and the
presence of ␣-Al2 O3 pellets upside the catalytic bed
limited the occurrence of homogeneous reactions.
The temperature of the catalytic bed was measured
by a K-type thermocouple. The space velocity was
Fig. 1. XRD spectra for all samples. (a) LaMnO3 , (b) NdMnO3 ,
40 000 N cm3 g−1 h−1 in all tests, the temperature was (c) SmMnO3 , (d) Sm0.9 Sr0.1 MnO3 , (e) Sm0.7 Sr0.3 MnO3 , (f)
in the range 623–1023 K. The gaseous flow rates were Sm0.5 Sr0.5 MnO3 . Asterisks indicate the most intense lines of
measured by Brooks 5850 mass flow controllers and Sm2 O3 .
 P. Ciambelli et al. / Applied Catalysis B: Environmental 24 (2000) 243–253 247

perovskite-type oxides. For the Sm1−x Srx MnO3 cat- Note that the elemental contents (reported in Table
alysts with x = 0.3 and x = 0.5 the XRD pattern re- 1) expected for the given formulae are in reasonable
veals, in addition to perovskite, the presence of two agreement with the experimental ones. Some more sig-
peaks at 2θ = 28.8◦ (d = 3.10 Å) and at 2θ = 30.6◦ nificant difference between nominal and experimental
(d = 2.92 Å) which correspond to the two strongest values is indeed found for the rare-earth elements in
lines of hexagonal Sm2 O3 (d = 3.09 Å, intensity the bicomponent oxides, and this may indicate that the
70; d = 2.94 Å, intensity 100) (a). NdMnO3 (b) and A-sublattice could be more cation defective than the
Sm1−x Srx MnO3 (c) oxides exhibit the orthorhombic B-sublattice for (Sm,Nd,La)MnO3 .
perovskite Pbnm structure, whereas LaMnO3 crys- The evaluation of the unit cell volume (reported in
tallizes in a primitive rhombohedral (non-primitive Table 1 and in Fig. 2) shows that the Sm1−x Srx MnO3
hexagonal) lattice (d) 2 . solid solution system presents a lattice contraction
Redox titration showed that in all AMnO3 samples at the increase of x, which is the result of the com-
there is a substantial fraction of manganese as Mn(IV) bined effect of the substitution of bigger Sr(II) ions
(35% for LaMnO3 , 23% for NdMnO3 and 28% for for Sm(III) in the 12-coordinated A sites and of
SmMnO3 , see Table 1). Thus, in agreement with the smaller Mn(IV) for Mn(III) in the 6-coordinated
results found by other authors for LaMnO3 [15–17], B sites {rSr(II) = 1.44 Å and rSm(III) = 1.24 Å,
also in our case the (La,Nd,Sm)-Mn perovskites can rMn(IV) = 0.53 Å and rMn(III) = 0.645 Å, for dodec-
be regarded as nonstoichiometric oxidized AMnO3+δ ahedral and octahedral coordination, respectively
materials. [18]}. Note also that NdMnO3 shows higher lat-
By taking into account the observed Mn(IV) con- tice volume than SmMnO3 , in agreement with the
tent and the concentration of each other element with relative rare-earth cation sizes [rSm(III) = 1.24 Å,
its corresponding charge, the following formulae rNd(III) = 1.27 Å].
have been derived for each LaMnO3 , NdMnO3 and
Sm1−x Srx MnO3 (x = 0.0, 0.1, 0.3, 0.5) catalyst:
LaMn(III)0.65 Mn(IV)0.35 O3.18
NdMn(III)0.77 Mn(IV)0.23 O3.12
SmMn(III)0.72 Mn(IV)0.28 O3.14
Sm0.9 Sr0.1 Mn(III)0.65 Mn(IV)0.35 O3.13
Sm0.7 Sr0.3 Mn(III)0.36 Mn(IV)0.64 O3.17
Sm0.5 Sr0.5 Mn(III)0.36 Mn(IV)0.64 O3.07
By normalizing to the three oxygens formula and
supposing, as found by Van Roosmalen et al. [16], the
presence of an equal amount of cation vacancies in
the A and B sites, the following cation defective per-
ovskites may be obtained (the corresponding formula
weight, FW, is given in parenthesis for each sample):
Nd0.96 Mn(III)0.74 Mn(IV)0.22 O3 (FW = 239.2)
La0.94 Mn(III)0.61 Mn(IV)0.33 O3 (FW = 230.2)
Sm0.96 Mn(III)0.69 Mn(IV)0.27 O3 (FW = 245.2)
Sm0.86 Sr0.1 Mn(III)0.62 Mn(IV)0.34 O3 (FW = 238.8)
Sm0.67 Sr0.28 Mn(III)0.34 Mn(IV)0.61 O3 (FW = 225.5)
Sm0.49 Sr0.49 Mn(III)0.35 Mn(IV)0.63 O3 (FW = 218.5)

2 X-Ray Powder Data File, ASTM cards: (a) 19-1114 for Sm O ;

2 3
(b) 25-565 for NdMnO3 ; (c) 25-747 for SmMnO3 ; (d) 32-484 for Fig. 2. Cell volume as a function of the substitutional parameter
LaMnO3 ; (e) 39-1190 for La0.8 Sr1.2 CuO3.4 . x. 䊊 Sm1−x Srx MnO3 , 䊐 NdMnO3 .
248 P. Ciambelli et al. / Applied Catalysis B: Environmental 24 (2000) 243–253
Fig. 3. Inverse magnetic susceptibility as a function of temperature.
䊉 LaMnO3 , 䊊 NdMnO3 , 䊐 SmMnO3 , 4 Sm0.9 Sr0.1 MnO3 , N
Sm0.7 Sr0.3 MnO3 , 䉬 Sm0.5 Sr0.5 MnO3 .
The crystallite sizes (D1 0 2 for the hexagonal
LaMnO3 material, and D1 1 1 for the samarium and
neodimium orthorhombic perovskites) are reported in
Table 1. Their values are 730 Å for LaMnO3 , and in
the range 220–330 Å for all others catalysts.
Surface areas (SABET ), reported in Table 1, are
in the range 13–20 m2 g−1 . Also the surface areas
(SAcalc ) estimated on the basis of the radius of crys-
tallite sizes and of the X-ray density (d ≈ 7 g cm−3 )
are reported in Table 1. Note that the values of SABET
and SAcalc are of the same order of magnitude. The
difference between SABET and SAcalc may be due to
the fact that, in the calculation of the surface area, all
particles were supposed to have a spherical shape, and
this could not be true in our samples.
Fig. 3 shows the inverse atomic susceptibility,
1/χ at versus T. Note that only LaMnO3 does not
show a linear behavior of 1/χ at for the whole range
of temperatures. All samples but SmMnO3 exhibit
a ferromagnetic behavior. The extrapolated Curie
points, TC , and the effective
√ magnetic moments per
formula unit, µ = 2.83 χat T , are reported in Table
1.The ferromagnetic behavior of AMnO3 perovskites
is indeed predicted by theory and is caused by the
so-called ‘double-exchange’ interaction between near-
est Mn(III) and M(IV) paramagnetic cations [19].
The effective magnetic moment for all samples (µ
in the range 5.2–5.9 ␮B ) is higher than that expected
from the spin-only values of the paramagnetic species
present in the sample [Mn(III), Mn(IV)]. Note that
for LaMnO3 a rather high value (µ = 5.4 ␮B ) has also
been observed by Jonker [20].
3.2. TPR and O2 TPD measurements
No other reactions except the reduction of the
catalysts occur during the TPR experiments, only
H2 consumption having been detected both by TCD
and mass spectrometer. TPR profiles of NdMnO3 ,
LaMnO3 , SmMnO3 and Sm1−x Srx MnO3 perovskites
are shown in Fig. 4. The overall signal is made of two
main contributions for all catalysts. Furthermore, the
complexity of the low temperature peak in the TPR
curves of Sm1−x Srx MnO3 samples with 0.0 ≤ x ≤ 0.3
suggests the contribution of at least two signals also in
this temperature region. Both SmMnO3 and NdMnO3
samples show very sharp signals at high temperature
with maximum at 1023 and 1063 K, respectively. On
the contrary, LaMnO3 sample shows a broad signal
at high temperature occurring under isothermal con-
ditions, suggesting a slower reduction process. The
onset temperature of the reduction (Table 1) is in the
order LaMnO3 > NdMnO3 > SmMnO3 .
XRD analysis performed at the end of TPR exper-
iments showed the formation of MnO, A2 O3 and/or
A(OH)3 (A = La, Sm, Nd) for LaMnO3 , NdMnO3 ,
SmMnO3 and Sm0.9 Sr0.1 MnO3 catalysts, in agree-
ment with results reported in [21,22] for La–Mn
based perovskites. The X-ray spectra of the re-
duced Sm1−x Srx MnO3 samples with x = 0.3 and 0.5,
apart from the X-ray lines correspondent to MnO,
matched the pattern of a compound described by
N. Nguyen et al. as La0.8 Sr1.2 CuO3.4 [23]. It was
not surprising to find that, considering the analogy
among Cu(II)–Mn(II) and La(III)–Sm(III) species,
the product of complete reduction of our samples
at higher strontium content is similar to the parent
La0.8 Sr1.2 CuO3.4 compound. Fig. 5 reports, as exam-
ple, the XRD patterns of Sm0.5 Sr0.5 MnO3 (original,
after the first reduction step and after complete reduc-
tion).
 P. Ciambelli et al. / Applied Catalysis B: Environmental 24 (2000) 243–253
Fig. 4. (a) TPR profiles of LaMnO3 (full line), NdMnO3 (line with circles) and SmMnO3 (dotted line) perovskites. (b) TPR profiles of
Sm1−x Srx MnO3 perovskites. x = 0.1 (full line), x = 0.3 (dotted line), x = 0.5 (line with circles).
Fig. 5. XRD spectra of Sm0.5 Sr0.5 MnO3 . (a) sample calcined at
1073 K, (b) after TPR first peak, (c) after TPR up to 1073 K. As-
terisks and circles indicate the strongest X-ray lines corresponding
to Sm2 O3 and MnO, respectively. X-ray lines for SmMnO3 (c)
and for La0.8 Sr1.2 CuO34 (e) reference compounds are given at the
bottom and at the top, respectively.
In Table 1 the evaluated H2 uptakes, relevant to
the low and high temperature peaks, are reported. The
minimum value reached by the signal between the two
249
main peaks was chosen to separate them. The values
of the total H2 /Mn ratio, higher than 0.5 for all cat-
alysts, confirm the presence of a fraction of Mn(IV)
in the samples, as detected by the chemical analy-
sis. According to literature data [21,22], the reduction
steps Mn(IV) → Mn(III) → Mn(II) occur in LaMnO3
perovskite, the former at low temperature and the lat-
ter at high temperature. The same sequence could be
roughly hypothesized also for Nd and Sm containing
perovskites. XRD patterns of the samples taken after
the first reduction step show the signals of a less crys-
talline perovskite phase (Fig. 5 for Sm0.5 Sr0.5 MnO3 ,
as example), but with increased cell parameters. The
lattice expansion can be explained by the reduction
of the Mn(IV) fraction to Mn(III) which has a larger
ionic radius than Mn(IV), thus confirming the above
interpretation of TPR curves. According to the above
hypothesis, the first TPR signal should correspond to
the reduction Mn(IV) → Mn(III) and the second to
the reduction Mn(III) → Mn(II). Therefore, a value of
H2 /Mn ratio of 0.5 should be expected for the sec-
ond peak. However, except for NdMnO3 , lower val-
ues were evaluated for the other samples. Thus, some
reduction to Mn(II) can likely occur even at low tem-
perature.
All Sr substituted perovskites show (Fig. 4) com-
plex TPR profiles due to the contribution of several
signals, with shape and intensity influenced by the ex-
tension of Sm substitution by Sr. Indeed, the signal at
low temperature increases while that at high temper-
250 P. Ciambelli et al. / Applied Catalysis B: Environmental 24 (2000) 243–253
ature decreases with the Sr content. A similar effect
due to Sr substitution was observed for LaMnO3 per-
ovskites by Irutsa et al. [24]. In the low temperature
signal (T < 833 K) at least two components can be ob-
served, whose intensity is strongly affected by Sr con-
tent. A signal at about 623 K, well evident for x = 0.1,
decreases with increasing Sr and, at the same time,
the intensity of the signal at about 773 K markedly in-
creases with Sr substitution.
The fraction of Mn(IV), evaluated from the total H2
uptake, increases with Sr substitution, in agreement
with the results of chemical analysis. Some reduction
of manganese to Mn(II) likely occurs in the low tem-
perature region also for the Sr substituted samples as
shown by the very high value of the H2 uptake cor-
responding to the first peak, increasing with the Sr
fraction. These results suggest that the addition of Sr
enhances the formation of Mn(IV) easily reducible to
Mn(II) which is already present, in lower amount, in
the SmMnO3 perovskite. The Sr substitution promotes
the reducibility of Mn(IV) probably because it causes
a lower crystallinity of the perovskite, as suggested
by Irutsa et al. [24] for La1−x Srx MnO3 perovskites,
and/or because it causes the formation of small crys-
tallites of manganese oxides not detectable by XRD.
Manganese oxides were reported by Arnone et al. [25]
to be easier reducible than manganese-containing per-
ovskites. As a consequence, the complexity of the low
temperature signal could be related either to the oc-
currence of two mono-electronic steps by reduction of
Mn(IV) within the perovskite first to Mn(III) and then
to Mn(II), or to the contribution of some manganese
oxides. However, we are well aware that the prepara-
tion conditions used for this work (previous prolonged
calcinations at lower temperatures and then final cal-
cination at 1073 K for 5 h) should provide a good crys-
tallization of possible manganese oxides (as it occurs
for the perovskite phase), thus easily detectable by
XRD. We are thus more inclined to suggest the two
mono-electronic reduction steps of Mn(IV) in the per-
ovskite phase.
After TPR experiments all samples were treated in
air flow at 1073 K and reduced again under the same
conditions of the first experiments obtaining very sim-
ilar results. This indicates that the catalysts undergo a
reversible reduction process. This behavior was also
confirmed by XRD analysis performed on a sample
re-oxidized in air at 1273 K after TPR experiments
showing that the perovskite phase was restored after
re-oxidation in air.
O2 TPD spectra (not reported) show two peaks for
all catalysts, the former with the maximum in the tem-
perature range 513–733 K and the latter with the max-
imum in the range 916–1073 K. The amount of oxy-
gen related to the low temperature peak is very small
for all catalysts while that evolved at high tempera-
ture ranges from 0.024 to 0.20 mol O2 per total mol
of transition metal cation, the maximum value being
given by LaMnO3 . The first peak, referred to as ␣
peak, was attributed to oxygen species weakly bound
to the surface while the second peak (β peak) was re-
lated to the reduction of B cations to lower oxidation
state [8] in the ABO3 structure. The values of O2 re-
leased both at low and at high temperature suggest
that the oxygen evolution must be related only to the
catalyst surface since larger amounts of O2 should be
expected for a phenomenon involving the bulk of the
sample. XRD analysis performed on the samples after
the TPD experiments revealed that no phase transfor-
mation occurs confirming the previous hypothesis.
The reversibility of the O2 release process was ver-
ified by performing a second TPD experiment after a
further treatment of the sample 2 h in flowing air at
1073 K. The complete superimposition of the first and
the second TPD profile for all catalysts confirms the
reversibility of the process. XRD spectra performed
after O2 TPD cycles accordingly showed that the struc-
ture of catalysts was unchanged.
3.3. Catalytic activity measurements
Preliminary tests performed in the absence of cata-
lyst showed that homogeneous reactions are negligible
under the experimental conditions investigated.
The results of catalytic activity measurements are
reported in Figs. 6 and 7. All catalysts give complete
conversion of methane below 1023 K with 100% se-
lectivity to CO2 . After the first testing cycle, all cat-
alysts were cooled down to room temperature and a
second cycle was performed. The results of the sec-
ond cycle were the same of the first one, suggesting
that the catalysts do not undergo modification nor de-
activation in the reaction conditions investigated.
NdMnO3 is the less active catalyst in the whole
temperature range. LaMnO3 is less active than
 P. Ciambelli et al. / Applied Catalysis B: Environmental 24 (2000) 243–253
Fig. 6. CH4 conversion as a function of temperature. 䊉 LaMnO3 ,
N NdMnO3 and 䊏 SmMnO3 perovskites.
Fig. 7. CH4 conversion as a function of temperature for
Sm1−x Srx MnO3 perovskites. 䊏 x = 0,0, 䊐 x = 0,1 䊊 x = 0.3, 4
x = 0.5.
SmMnO3 up to 773 K, the reverse at higher temper-
ature. Sm1−x Srx MnO3 perovskites show comparable
catalytic activities, slightly increasing with Sr con-
tent, but they are less active than the unsubstituted
perovskite.
251
Fig. 8. Arrhenius plots for LaMnO3 , NdMnO3 and SmMnO3
perovskites. Symbols as in Fig. 6.
Fig. 9. Arrhenius plots for Sm1−x Srx MnO3 perovskites. Symbols
as in Fig. 7.
The values of the apparent activation energy and
of the pre-exponential factor, estimated from the Ar-
rhenius plots (Figs. 8 and 9) on the base of a CH4
first-order rate equation and on the hypothesis of
isothermal PFR behavior are reported in Table 1 for
252 P. Ciambelli et al. / Applied Catalysis B: Environmental 24 (2000) 243–253
all catalysts. The curves reported in Figs. 6 and 7, cal-
culated with the estimated kinetic parameters, show
a satisfactory agreement with the experimental data.
The highest value of apparent activation energy was
found for LaMnO3 , while lower values were estimated
for Nd and Sm containing perovskites. Comparable
values of apparent activation energy were reported in
[26] for ACoO3 catalysts, lanthanum based perovskite
showing the highest one.
As reported in [27] two different mechanisms can be
hypothesized for methane oxidation: the first, involv-
ing chemisorbed oxygen, is controlling at low tem-
perature, whereas the second, involving lattice oxy-
gen, occurs at high temperature. TPR experiments
showed that the reduction of manganese starts at lower
temperature for NdMnO3 and SmMnO3 with respect
to LaMnO3 . The easier reducibility of NdMnO3 and
SmMnO3 could be related to the low value of activa-
tion energy for these two samples. This agrees with
the results reported by Futai et al. [12] who associ-
ated the easy reducibility of ACoO3 perovskites to the
high activity in CO oxidation and reported the same
order of activation energy for La, Sm and Nd per-
ovskites. However, LaMnO3 perovskite, where man-
ganese is more stable towards reduction, is capable
to desorb larger quantities of lattice oxygen as shown
by TPD, thus being the most active sample at high
temperature.
As concerns Sr substituted samples, the perovskite
with the lowest Sr content (x = 0.1) shows an ap-
parent activation energy larger than that obtained for
SmMnO3 , whereas a further increase of Sr content
(samples with x = 0.3 and 0.5) leads to a decrease of
the activation energy values. The same trend of the
activation energy values was observed for the onset
temperature of the reduction in the TPR experiments
thus confirming that an easy reducibility of manganese
is correlated to the ability to activate methane at low
temperature. On the other hand, if manganese oxides,
in addition to the perovskite phase, were formed in
the samples with higher level of Sr substitution, a de-
crease in the apparent activation energy was to be ex-
pected since manganese oxides are known to activate
methane oxidation at lower temperature as compared
to corresponding perovskites [25].
Note that a promoting effect of Sr on the catalytic
activity was related by other authors to the presence of
Mn(IV) and Co(IV) in perovskite structures [6,12,27].
We did not find a similar effect for the Sm1−x Srx MnO3
system.
4. Conclusions
The main points put forward in this paper can be
summarized as follows: (i) all examined samples, but
Sm0.7 Sr0.3 MnO3 and Sm0.5 Sr0.5 MnO3 , were found to
be single perovskite phases; (ii) Mn(IV) in addition to
Mn(III) was found in all catalysts, the Mn(IV) frac-
tion increasing with x in the Sm1−x Srx MnO3 cata-
lysts; (iii) all samples gave complete methane con-
version with 100% selectivity to CO2 below 1023 K;
(iv) the catalytic activity paralleled the reducibility of
Mn(IV) in the various catalysts; (v) the substitution
of Sr for Sm resulted in a reduction of activity, this
behaviour could tentatively be related to reduction of
Mn(IV) to Mn(II) under reaction, hindering the redox
mechanism.
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