CHEM. RES.

CHINESE UNIVERSITIES 2010, 26(4), 517521

Hydrothermal Synthesis and Characterization of Double

Perovskites RSrMnFeO6(R=La, Pr, Nd, Sm)
ZHANG Gang-hua, YUAN Hong-ming, CHEN Yan, LI Wei-juan, YANG Mei-qi and FENG Shou-hua*
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry,
Jilin University, Changchun 130012, P. R. China
Abstract A series of double perovskites RSrMnFeO6(R=La, Pr, Nd, Sm) was synthesized under mild hydrothermal
conditions. Crystal growths of the samples were sensitive to alkalinity, temperature, filling fraction, and composition
of initial reaction mixture. The desired series of compounds belongs to the class of AABBO6 perovskites with a
random distribution of Mn and Fe atoms over the B-cation sub-lattice. Their structures show the distorted orthorhombic symmetry with space group Pnma. The shapes and sizes of the crystals were analyzed on a Rigaku JSM-6700F by
scanning electron microscopy. Analysis done by XPS, Mssbauer spectroscopy and iodometric titration reveals that
Mn and Fe ions have +4 and +3 oxidation states, respectively.
Keywords Double perovskites; Orthorhombic; Hydrothermal synthesis
Article ID 1005-9040(2010)-04-517-05

Introduction

Double perovskite oxides with a general formula

A2BBO6 or AABBO6(where A and A are alkaline-earth and/or rare-earth metals and B and B are
transition metals) have been widely investigated for
their catalytic[1,2], magnetic[3], dielectric properties[4]
and colossal magnetoresistance(CMR). After the discovery of room temperature CMR and tunnelling
magnetoresistance(TMR) in the double perovskites
Sr2FeMoO6 and Sr2FeReO6, respectively[5,6], there
have been growing interests worldwide in researching
for effective methods to make double perovskite materials[79]. On the basis of B-cation arrangement,
double perovskite can be classified into three general
classes[10], namely, (1) the distorted or random perovskite[1114]; (2) the rock salt type[11,15]; and (3) the
layered type [16].
Ramesha et al.[13] reported cubic/pseudo-cubic
perovskite structure for ALaMnFeO6(A=Ca, Ba, Sr)
and were unable to find the doubling of the primitive
perovskite cell from their X-ray powder diffraction
analysis. Subsequently, Shaheen[14] confirmed the
structure of LaCaMnFeO6 by neutron powder diffraction method. They described that the crystal structure
of the former had a random distribution of Mn and Fe
atoms over the B-cation sub-lattice. However, besides
La ions, other rare earth cations substitutions at the

A-site of such Fe-doped manganites were rare reported.

The approaches conventionally used for fabricating double perovskites rely on high temperature
solid state reactions and sol-gel processes of oxides,
nitrates and/or carbonate precursors[14,17,18]. But these
need a much higher temperature, and usually have
inhomogeneous chemical components and such inhomogeneity cannot be avoided. The partial substitution of the divalent cation by the trivalent lanthanide
one at the A-site of the perovskite manganates under
hydrothermal conditions has been reported before[19,20].
To the best of our knowledge, there have been no previous reports on the hydrothermal synthesis of the
manganites with Fe doped at the Mn site. In this study
we employed hydrothermal technique for the first time
to prepare a family of double perovskites RSrMnFeO6
(R=La, Pr, Nd, Sm). The motivation of this study is to
develop new preparative methods by which chemical
operation could be readily conducted and perfect
crystals could be obtained.

Experimental

The synthesis was performed from the solutions

of metal salts in aqueous potassium hydroxide, and
carried out in an 80-mL Teflon-lined stainless steel
autoclave with a filling capacity of 80%. In order to

*Corresponding author. E-mail: shfeng@mail.jlu.edu.cn

Received May 20, 2009; accepted September 15, 2009.
Supported by the National Natural Science Foundation of China(Nos.20631010, 90922034 and 20771042).

518

CHEM. RES. CHINESE UNIVERSITIES

ensure intimate mixing of reagents, the solutions of

the metal salts were prepared prior to mixing form 0.4
mol/L MnCl2, 0.1 mol/L KMnO4, 0.2 mol/L Fe(NO3)2,
0.2 mol/L R(NO3)3(R=La, Pr, Nd, Sm) and 0.2 mol/L
Sr(NO3)2, respectively.
In a typical synthesis procedure for RSrMnFeO6
(R=La, Pr, Nd, Sm), 14 mL of KMnO4 and 10 g of
KOH were mixed by stirring to form a solution. To
this solution was added 9 mL of MnCl2 dropwise under constant stirring that was cooled in an ice bath to
form a k-birnessite gel precursor. This was followed
by an addition of 12.5 mL of Sr(NO3)3, 12.5 mL of
R(NO3)3(R=La, Pr, Nd, Sm), 12.5 mL of Fe(NO3)3
and 50 g of KOH. The reaction mixture was stirred
with a magnetic stirrer before being transferred into a
Teflon-lined stainless steel autoclave. The crystallization was carried out under autogenous pressure at
260 C for 23 d. After the autoclave was cooled and
depressurized, the product was washed with distilled
water and sonicated by a direct immersion of a titanium horn(Vibracell, 20 kHz, 200 W/cm2). Singlephase RSrFeMnO6 was obtained as dark crystalline
powder. Powder X-ray diffraction(XRD) data were
collected on a Rigaku D/Max 2500V/PC X-ray diffractometer with Cu K radiation(=0.15418 nm) at
50 kV and 250 mA. Scanning electron microscopy(SEM) was performed on a Rigaku JSM-6700F
microscope operated at 10 kV. Inductively couple
plasma(ICP) analysis was carried out on a Perkin-Elmer Optima 3300DV ICP instrument.
The average B-site oxidation state of the powder
was determined by iodometric titration as reported
previously in the literature[21,22]. The oxidation states
of Mn and Fe were further investigated by X-ray photoelectron spectroscopy(XPS) on a Thermo
ESCALAB 250 spectrometer with a monochromatic
aluminum X-ray source. The spectra collected for the
C1s, Mn2p, Fe2p, and O1s regions, and the Fe2p3/2,
Mn2p3/2 binding energies were corrected versus the C1s
reference of 284.6 eV. The 57Fe Mssbauer spectra
were recorded on a constant acceleration Mssbauer
spectrometer with a 57Co(Pd) source at room temperatures.

Results and Discussion

Compared to solid state reactions, hydrothermal

reactions may occur at relatively low temperature and
allow ready chemical operations[23,24]. We have used

Vol.26

MnO4

2+

and Mn ions
hydrothermal redox reactions of
to make CMR materials and disproportionation reactions to prepare three oxidation state manganese
oxides[25,26]. The factors that affect hydrothermal synthesis such as precursor, mineral reagent, alkaline
concentration, appropriate reaction temperature and
pressure play a significant role in the course of the
reaction. For instance, in our specific case when the
reaction temperature was lower than 260 C, we
obtained a mixture containing our title compounds and
an impurity of R(OH)3(R=La, Pr, Nd, Sm). The
amount of alkali is a key factor in producing the
perovskite in hydrothermal processing. KOH not only
maintains the alkalinity but also acts as mineralizing
agent. When the alkalinity was less than 15 mol/L in
our synthesis, the impurity mixture of R(OH)3,
KxMnO2(0.50.7)H2O and Fe(OH)3 was formed.
This indicates there is some competition between
thermodynamically and kinetically stabilized phases.
The high alkalinity of the reaction system is necessary
to obtain the desired ratios of n(R):n(Sr):n(Mn):n(Fe).
The optimal synthetic conditions for preparing the title
compounds are listed in Table 1. In the order of from
La to Sm, the needed alkalinity of the reactions decreased. We propose that the effect of alkalinity is due
to the fact that R3+ ions show a significant amphoteric
characteristic and the solubility of R(OH)3(from R=La
to R=Sm) increases in KOH.
Table 1

Optimal synthetic conditions for preparing

RSrMnFeO6(R=La, Pr, Nd, Sm)
c(KOH)/(molL1)

Reaction temperature/C

Time/h

LaSrMnFeO6
PrSrMnFeO6

19
18

260
260

48
72

NdSrMnFeO6

15

260

72

SmSrMnFeO6

15

260

72

Compound

EDX analysis of selected regions for the sample

shows the presence of all four metals in region analyzed with a constant ratio. The ICP composition
analysis indicates that the ratios of R:Sr:Mn:Fe were
in good agreement with the theoretical value, e.g.,
n(R):n(Sr):n(Mn):n(Fe)=1:1:1:1 for the perovskitetype oxides (Table 2). The oxygen contents in our
Table 2

Chemical compositions of RSrMnFeO6 (R=La,

Pr, Nd, Sm) obtained from ICP and iodometric
titration
n(Ln):n(Sr):n(Mn):
n(Fe)[Calculated
value (ICP)]

LaSrMnFeO6
PrSrMnFeO6

n(Ln):n(Sr):n(Mn):
n(Fe):n(O)
(Theoretical value)
1:1:1:1:6
1:1:1:1:6

0.98:1.02:1.01:0.99
0.99:1.01:1.02:0.98

Oxygen
content
(%)
5.98
6.00

NdSrMnFeO6

1:1:1:1:6

0.97:1.03:1.02:0.98

5.99

SmSrMnFeO6

1:1:1:1:6

0.98:1.02:1.03:0.97

5.97

Compound

No.4

ZHANG Gang-hua et al.

samples were obtained from iodometric titration. Thus

the formula of our samples is RSrMnFeO6.
The powder XRD data as shown in Fig.1 could
be indexed on the basis of the known perovskite
GdFeO3 crystal structure[27] and refined by the Rietveld method. The products crystallized in the orthor-

519

hombic system with space group Pnma. The crystallographic parameters of the cells(Table 3) of
RSrMnFeO6(R= La, Pr, Nd, Sm) decrease in the order
of from La to Sm, correlating to their sizes. The selected interatomic distances and bond angles are
shown in Table 4.

Fig.1

Table 3

Experimental(dot), calculated(line) and difference(bottom line) X-ray diffraction profiles

for RSrMnFeO6[R=La(A), Pr(B), Nd(C), Sm(D)]
Unit cell, positional and reliability factors for the Rietveld refinements of RSrMnFeO6 (R=La, Pr, Nd, Sm), in
the orthorhombic Pnma space group from XRD data

Compound
La/Sr
Pr/Sr
a/nm
0.5479(3)
0.5464(4)
b/nm
0.7739(2)
0.7736(2)
c/nm
0.5478(3)
0.5469(3)
V/nm3
0.23227(8)
0.23117(2)
xa
0.0001(1)
0.0024(9)
ya
0.0006(2)
0.0003(1)
0.4144(3)
0.4294(1)
xb
0.0600(5)
0.0770(4)
yb
xc
0.2545(1)
0.2417(8)
yc
0.0010(6)
0.0002(5)
zc
0.7414(4)
0.7595(9)
Rwp(%)
9.67
10.54
Rp(%)
6.09
6.62
2
1.58
1.23
a. R/Sr 4c(x, 1/4, y); b. Mn/Fe 4b(0, 0, 1/2); O1 4c(x, 1/4, y); c. O2 8d(x, y, z).

Table 4

Nd/Sr
0.5454(2)
0.7693(2)
0.5463(2)
0.22921(4)
0.0067(7)
0.0030(2)
0.5849(2)
0.0613(1)
0.2348(9)
0.0123(8)
0.7660(2)
10.22
7.15
1.22

Sm/Sr
0.5443(1)
0.7690(2)
0.5465(1)
0.22874(7)
0.0075(3)
0.0014(2)
0.5300(4)
0.1001(5)
0.2808(1)
0.0166(2)
0.7240(3)
7.94
4.66
1.28

Selected interatomic distances and bond angles for RSrMnFeO6 (R=La, Pr, Nd, Sm) crystal structures

Compound
d[(Mn, Fe)O1]/nm
d[(Mn, Fe)O2]/nm
Average d[(Mn, Fe)O1]/nm
d[(Sr, R)O1]/nm
d[(Sr, R)O2]/nm

(Mn, Fe)O1(Mn, Fe)/()

(Mn, Fe)O2(Mn, Fe)/()

La/Sr
0.201(7)2
0.192(2)2
0.195(3)2
0.195(3)
0.245(2)1
0.229(4)1
0.276(9)2
0.270(6)2
0.269(7)2
147.0(1)
176.9(7)

Pr/Sr
0.201(6)2
0.192(8)2
0.193(9)2
0.195(1)
0.239(7)1
0.234(2)1
0.277(4)2
0.269(1)2
0.268(2)2
147.0(8)
175.9 (2)

Nd/Sr
0.200(6)2
0.193(2)2
0.193(9)2
0.195(1)
0.243(2)1
0.224(9)1
0.277(5)2
0.272(1)2
0.256(2)2
146.8(9)
170.9(1)

Sm/Sr
0.200(5)2
0.192(7)2
0.196(2)2
0.195(6)
0.265(8)1
0.219(6)1
0.277(2)2
0.265(5)2
0.249(5)2
146.9(1)
165.0(2)

520

CHEM. RES. CHINESE UNIVERSITIES

The decreasing values of the (Mn, Fe)O(Mn,

Fe) bond angles on going from R=La to R=Sm indicate the increasing tilting distortion of the octahedral
framework. The average BO bond lengths were
found to be a constant value(ca. 0.195 nm). So the
effects of the different rare earth elements on BO
bond lengths were slight. Fig.2 shows the polyhedral
view of double perovskite structure of RSrMnFeO6
which clearly indicates the tilting of (Mn/Fe)O6 octahedra. The Mn and Fe atoms are randomly distributed
at B-cation sublattice. Since Fe is one of the nearest
neighbors of Mn and the small size of the R3+ and Sr2+
cations, the given cell and tilt system are not compatible with an ordering of either B- or A-cations. Similar
results have also been reported by other researchers[14,17]. Ordering is favored by large differences in
ionic radius and formal charges between B and B cations[28,29]. The crystal morphology and purity were
confirmed by SEM images as shown in Fig.3. They
have the sizes ranging from 5 to 10 m, each in a narrow size distribution. The cubic-shaped crystallites are
clearly shown, but the behavior of crystal growth may

Fig.2

Vol.26

be different from each other.

The iodometry measurements for Mn and Fe of
all the samples gave an average valence state of +3.48,
very close to its theoretical value of 3.50 calculated
from the neutrality for the title compound where Sr2+
on the A-site must compensate for the octahedral Mn4+
on the B-site and R3+ for Fe3+. X-Ray photoelectron
spectroscopy(XPS) was used to determine the oxidation states of Mn and Fe in our products. Fe2p3/2 and
Mn2p3/2 binding energies were corrected versus the C1s
reference of 284.6 eV. The binding energies of Mn in
MnO2(642.2 eV)[30] and Fe in Fe2O3(711.1 eV)[31]
were taken as the references. The Mn2p and Fe2p XPS
spectra are shown in Fig.4(A) and (B), respectively,
for a representative SmSrMnFeO6 sample.

Crystal structure of RSrMnFeO6(R=La, Pr, Nd,

Sm) double perovskites
Mn, Fe atoms are situated at the octahedra,
Sr and R atoms are shown as spheres.

Fig.4 XPS spectra of SmSrMnFeO6

(A) Fe2p; (B) Mn2p.

Fig.3

SEM images of crystalline samples

(A) LaSrMnFeO6; (B) PrSrMnFeO6;
(C) NdSrMnFeO6; (D) SmSrMnFeO6.

The measured binding energies of Mn(642.2 eV)

and Fe(710.7 eV) ions of the samples clearly correspond to those of MnO2 and Fe2O3, respectively. The
oxidation state of Fe in the different samples was also
identified by Mssbauer spectra. Fig.5 shows the
57
Fe Mssbauer spectra at room temperature for
RSrMnFeO6(R=La, Pr, Nd). In all the cases, each
spectrum exhibits a doublet pattern, indicating the
paramagnetic state of the samples at room temperature.
Hyperfine parameters such as isomer shift(IS), quadrupole splitting(QS) and the width at half
height(HWHM) for all the studied samples are listed
in Table 5. The isomer shifts for La/Sr, Pr/Sr and
Nd/Sr are found to be 0.36, 0.36 and 0.35 mm/s,

No.4

ZHANG Gang-hua et al.

3+

respectively. These values are typical of Fe ions in

octahedral coordination, being in accordance with
previous work[32,33]. Therefore, the oxidation states of
Mn and Fe in our samples were +4 and +3, respectively.

521

1967
[5] Kobayashi K. L., Kimura T., Sawada H., Terakura K., Tokura Y.,
Nature, 1998, 395, 677
[6] Kobayashi K. I., Kimura T., Tomioka Y., Sawada H., Terakura K.,
Tokura Y., Phys. Rev. B, 1999, 59, 11159
[7] Garcia-Landa B., Ritter C., Ibarra M. R., Blasco J., Algarabel P. A.,
Mahendiran R., Garcia J., Solid State Commun., 1999, 110, 435
[8] Zeng Z., Fawcett I. D., Greenblatt M., Croft M., Mater. Res. Bull.,
2001, 36, 705
[9] Han H., Kim C. S., Lee B. W., J. Magn. Magn. Mater., 2003, 254/255,
574
[10] Anderson M. T., Greenwood K. B., Taylor G. A., Poeppelmeier K. R.,
Prog. Solid State Chem., 1993, 22, 197
[11] Attfield M. P., Battle P. D., Bollen S. K., Gibb T. C., Whitehead R. J.,
J. Solid State Chem., 1992, 100, 37
[12] Attfield M. P., Battle P. D., Bollen S. K., Kim S. H., Powell A. V.,
Workman M., J Solid State Chem., 1992, 96, 344

Fig.5 Mssbauer spectra of RSrMnFeO6 at room

temperature
a. La/Sr; b. Pr/Sr; c. Nd/Sr.

Table 5

banna G. N., Gopalakrishnan, Mater. Res. Bull., 2000, 35, 559

[14] Shaheen R., Bashir J., Rundlf H., Rennie A. R., Mater. Lett., 2005,

Fitting parameters of Mssbauer spectra

IS/(mms1)

QS/(mms1)

HWHM/(mms1)

LaSrMnFeO6
PrSrMnFeO6

0.36(0)
0.36(1)

0.66(0)
0.67(0)

0.23(1)
0.24(0)

NdSrMnFeO6

0.35(1)

0.72(1)

0.27(0)

Compound

[13] Ramesha K., Thangadurai V., Sutar D., Subramanyam S. V., Sub-

59, 2296
[15] Battle P. D., Jones C. W., J. Solid State Chem., 1989, 18, 108
[16] Anderson M. T., Poeppelmeier K. R., Chem. Mater., 1991, 3, 476
[17] Abakumov A. M., Rossell M. D., Seryakov S. A., Antipov E. V.,
J. Mater. Chem., 2005, 15, 4899
[18] Tian S. Z., Zhao J. C., Qiao C. D., Ji X. L., Jiang B. Z., Mater. Lett.,

Conclusions

A series of double perovskites RSrMnFeO6(R=La,

Pr, Nd, Sm) was synthesized under hydrothermal conditions, in which the crystals had a uniform size of
about 510 m. The compounds belong to the class
of AABBO6 type perovskites. The Rietveld refinement of powder X-ray diffraction data shows that the
crystal structures of RSrMnFeO6(R=La, Pr, Nd, Sm)
were distorted orthorhombic symmetry with a space
group Pnma, Mn and Fe oxidation states equal to +4
and +3, respectively, as determined by XPS and
iodometric titration. Mssbauer study indicated that
Fe in these compounds was in the trivalent high-spin
state. Our results indicate that the hydrothermal method is a promising route to even more complicated
double perovskite materials.

2006, 60, 2747

[19] Chen Y., Yuan H., Tian G., Zhang G., Feng S., J. Solid State Chem.,
2007, 180, 167
[20] Wang D., Yu R. B., Feng S. H., Zheng W. J., Pang G. S., Zhao H.,
Chem. J. Chinese Universities, 1998, 19(1), 165
[21] Li B., Hakuta Y., Hayashi H., Chem. Commun., 2005, 1732
[22] Mao Y. C., Li G. S., Xu W., Feng S. H., J. Mater. Chem., 2000, 10,
479
[23] Song Z., Li G. H., Yu Y., Shi Z., Feng S. H., Chem. Res. Chinese
Universities, 2009, 25(1), 1
[24] Wang L., Zhang H., Dong W., Shi Z., Feng S. H., Chem. Res. Chinese Universities, 2008, 24(4), 389
[25] Feng S., Xu R., Acc. Chem. Res., 2001, 34, 239
[26] Feng S., Yuan H., Shi Z., Chen Y., Wang Y., Huang K., Hou C., Li J.,
Pang G., Hou Y., J. Mater. Sci., 2008, 43, 2131
[27] Marezio M., Remeika J. P., Dernier P. D., Acta Crystallogr., Sect. B,
1970, B26, 2008
[28] Nakamura T., Choy J. H., J. Solid State Chem., 1977, 20, 233
[29] Galasso F., Pyle J., Inorg. Chem., 1963, 2, 482
[30] Bernal S., Botana F. J., Laachir A., Moral P., Martin G. A., Perrichon
V., Eur. J. Solid State Inorg. Chem., 1991, 28, 421

References
[1] Yamazoe N., Teraoka Y., Catal. Today, 1990, 8, 175
[2] Tejuca L. G., Fierro J. L. G., Properties and Applications of
Perovskite Type Oxides, Marcel Dekker, NewYork, 1993
[3] Hong K. P., Choi Y. H., Kwon Y. U., Jung D. Y., Lee J. S., Lee C. H.,
J. Solid State Chem., 2000, 150, 383
[4] Ganguli A. K., Grover V., Thirumal M., Mater. Res. Bull., 2001, 36,

[31] Seyama H., Soma M., J. Electron Spectrosc. Relat. Phemon., 1987,
42, 97
[32] Da Costa F. M. A., Dos Santos A. J. C., Inorg. Chim. Acta, 1987, 140,
105
[33] Hernandez T., Plazaola F., Rojo T., Barandiaran H. M., J. Alloys
Compd., 2001, 323/324, 440