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Thermal behaviour of CuMgMn and NiMgMn layered double

hydroxides and characterization of formed oxides


Frantisek Kovanda
a,
*
, Tomas Grygar
b
, V t Dornicak
a
, Tomas Rojka
a
,
Petr Bezdicka
b
, Kveta Jiratova
c
a
Department of Solid State Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague, Czech Republic
b
Institute of Inorganic Chemistry AS CR, 250 68 R

ez, Czech Republic


c
Institute of Chemical Process Fundamentals AS CR, Rozvojova 135, 165 02 Prague, Czech Republic
Received 8 September 2003; received in revised form 20 December 2003; accepted 28 January 2004
Available online 2 July 2004
Abstract
Thermal behaviour of synthetic CuMgMn and NiMgMn layered double hydroxides (LDHs) with M
II
/Mg/Mn molar ratio
of 1:1:1 was studied in the temperature range 2001100 8Cby thermal analysis (TG/DTA/EGA), powder X-ray diffraction (XRD),
Raman spectroscopy, and voltammetry of microparticles. Powder XRD patterns of prepared LDHs showed characteristic
hydrotalcite-like phases, but further phases were indirectly found as admixtures. The CuMgMn precipitate was decomposed at
temperatures up to ca. 200 8C to form an XRD-amorphous mixture of oxides. The crystallization of CuO (tenorite) and a spinel
type mixed oxide of varying composition Cu
x
Mg
y
Mn
z
O
4
with Mn
4+
was detected at 300500 8C. At high temperatures (9001000
8C), tenorite disappeared and a consecutive crystallization of 2CuO
d
MgO (gueggonite) was observed. The high-temperature
transformation of oxide phases led to a formation of Cu
I
oxides accompanied by oxygen evolution. The DTAcurve of NiMgMn
sample exhibited two endothermic effects characteristic for hydrotalcite-like compounds. The first one with minimum at 190 8C
can be ascribed to a loss of interlayer water, the second one with minimum at 305 8C to the sample decomposition. Heating of the
NiMgMn sample at 300 8C led to the onset of crystallization of oxide phases identified as Ni
x
Mg
y
Mn
z
O
4
spinel, (Ni,Mg)O
oxide containing Mn
4+
cations, and easily reducible XRD-amorphous species, probably free Mn
III,IV
oxides. At 600 8C (Raman
spectroscopy) and 700 8C (XRD), the (Ni,Mg)
6
MnO
8
oxide with murdochite structure together with spinel phase were detected.
Only spinel and (Ni,Mg)Owere found after heating at 900 8Cand higher temperatures. Temperature-programmed reduction (TPR)
profiles of calcined CuMgMn samples exhibited a single reduction peak with maximum around 250 8C. The highest H
2
consumption was observed for the sample calcined at 800 8C. The reduction of NiMgMn samples proceeded by a more complex
way and the TPR profiles reflected the phase composition changing depending on the calcination temperature.
D 2004 Elsevier B.V. All rights reserved.
Keywords: CuMgMn basic carbonates; NiMgMn hydrotalcite; Layered double hydroxides; Thermal decomposition; Mixed oxides
0169-1317/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2004.01.007
* Corresponding author. Tel.: +420 2 2435 4087; fax: +420 2 2431 1082.
E-mail address: Frantisek.Kovanda@vscht.cz (F. Kovanda).
Applied Clay Science 28 (2005) 121136
www.elsevier.com/locate/clay
1. Introduction
Acontrolled thermal decomposition of hydrotalcite-
like compounds (layered double hydroxides, LDHs),
represented by the general formula [M
I I
1 x
M
III
x
(OH)
2
]
x+
[A
n
x/nd
yH
2
O]
x
where M
II
and M
III
are
divalent and trivalent metal cations and A
n
is an n-
valent anion, gives finely dispersed mixed oxides of
M
II
and M
III
usable in various applications. For
example, many hydrotalcite-like compounds are used
in heterogeneous catalysis as precursors for preparation
of mixed oxide-based catalysts, whose catalytic per-
formance strongly depends on the way of their thermal
treatment (Cavani et al., 1991; Vaccari, 1998). There-
fore, the thermal behaviour of the hydrotalcite-like
compounds is studied in detail. In addition, the
precursors of more complex oxide mixtures may
essentially affect their final composition. For example,
calcination of mixture of Mn nitrates with other
transition metal salts yields primarily h-MnO
2
and
subsequently cubic Mn
2
O
3
, while homogeneous pre-
cursors of hydrotalcite-type yield preferentially mixed
oxides at relatively low temperatures.
A great number of studies on thermal decom-
position of layered double hydroxides was per-
formed with synthetic MgAl hydrotalcite (Reichle
et al., 1986; Hibino et al., 1995; Hudson et al.,
1995; Bellotto et al., 1996; Rives, 2001). Two
characteristic processes accompanied by a consid-
erable weight loss and an endothermic effect can be
observed during hydrotalcite heating: the release of
interlayer water at 150250 8C and the thermal
decomposition at 350600 8C, with a simultaneously
proceeding transformation of the hydroxyl and
carbonate groups into water and carbon dioxide,
respectively. A new MgO phase starts to form above
400 8C and MgAl
2
O
4
spinel crystallization is
detected at 900 8C and higher temperatures. Thermal
decomposition of the other hydrotalcite-like com-
pounds containing various M
II
and M
III
metal
cations can also be characterized by two endother-
mic transitions mentioned above. Both these tran-
sitions depend qualitatively and quantitatively on
many factors, especially on the chemical composi-
tion (the nature and relative amounts of the M
II
and
M
III
cations and the type of anions), the sample
crystallinity, and the atmosphere used during decom-
position. After dehydroxylation, the layered crystal
structure collapses and predominantly amorphous
mixed oxides are obtained. A gradual crystallization
of the oxides at higher temperatures can be observed
and a M
II
M
III
2
O
4
spinel-like phase and/or divalent
metal oxides M
II
O are usually detected in the
powder XRD patterns. The ill-organized mixed
oxides display generally three broad diffraction
maxima corresponding to the future strongest lines
of the spinel-like phase. Therefore, they are also
called pre-spinel oxides and it is possible that the
transformation from the layered structure to this
oxide phase is topotactic (De Roy et al., 2001). In
some cases, the transformation of primary oxides
and the formation of new oxide phases could be
observed at high temperatures. For example, the
heating of copper-containing hydrotalcite-like com-
pounds leads to the formation of CuO and/or Cu
II
containing spinel-like phase. At least partial decom-
position of Cu
II
oxides takes place at temperatures
above 900 8C and new Cu
I
-containing oxide phases
are formed (Kovanda et al., 2001). The trans-
formation of primarily formed oxides was also
observed during heating of the NiMn hydrotalcite-
like compounds (Barriga et al., 1996; Kovanda et
al., 2003).
A large number of various M
II
M
III
layered double
hydroxides was prepared and reported in the literature.
However, only a few papers reported on hydrotalcite-
like compounds containing manganese. The layered
double hydroxides occurring in nature, Mn
II
Al
(charmarite) and MgMn
III
(desautelsite), were
described by Chao and Gault (1997) and Dunn et al.
(1979), respectively. Hansen and Taylor (1991) pre-
pared the MgMn layered double hydroxide of
desautelsite type by air oxidation of MnCO
3
suspended
in Mg(NO
3
)
2
solution at constant pH ~9 and also by
coprecipitation of Mg
2+
and Mn
2+
containing solution
in strongly alkaline conditions. Fernandez et al. (1994)
studied the thermal stability of MgMn hydrotalcite-
like compound prepared by the coprecipitation of
Mg(NO
3
)
2
and MnCl
2
solution in alkaline NaOH/
Na
2
CO
3
solution. According to the temperature-pro-
grammed reduction (TPR), the main part of Mn
2+
(84%) was oxidized to Mn
3+
during the synthesis. The
calcination of the MgMn hydrotalcite-like compound
caused its thermal decomposition at 390 8C, which was
followed by the formation of an amorphous material.
Crystallization of MgO and Mg
2
MnO
4
spinel was
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 122
observed at higher temperatures. Partial oxidation of
Mn
2+
to Mn
3+
was also observed during precipitation
of MgMnAl layered double hydroxides at constant
pH (Velu et al., 1999). The Mn
2+
/Mn
3+
ions were
present in a distorted octahedral environment. Calci-
nation at 450 8C resulted in the formation of a poorly
crystalline MgO-like solid solution. At a higher Mn
content, Mn
3
O
4
(hausmannite) and spinel-like
MnAl
2
O
4
were also obtained together with the MgO-
like phase.
Barriga et al. (1996) reported the preparation and
characterization of NiMn hydrotalcite-like com-
pounds with Ni/Mn molar ratios close to 2 and 3.
Formation of NiO as the major product in both
samples was observed during thermal decomposition
in air at 450 8C. During calcination of Ni2Mn sample,
NiMnO
3
(ilmenite) was formed at 700 8C, while
NiMn
2
O
4
spinel was observed in Ni3Mn sample. At
1000 8C, NiO and NiMn
2
O
4
spinel occurred in both
samples. In our recent work (Kovanda et al., 2003),
we studied the thermal behaviour of similar NiMn
layered double hydroxide with Ni/Mn molar ratio of
2. Thermal decomposition of this LDH at ca. 265 8C
resulted in the formation of a predominantly amor-
phous mixture of oxides. A relatively high content of
amorphous part was observed in samples heated at
200500 8C. The onset of crystallization of mixed
oxide Ni
6
MnO
8
with murdochite structure was
detected by XRD in samples heated at 300 8C and
NiMnO
3
with ilmenite structure was detected in
samples heated at 500 8C. The further reconstruction
of oxides took place above 600 8C. NiMnO
3
and
Ni
6
MnO
8
were converted to spinel Ni
x
Mn
y
O
4
occur-
ring together with NiO. These oxides were observed
in diffraction patterns of samples heated at 800 8C and
higher temperatures.
In the present work, the thermal behaviour of M
II

MgMn layered double hydroxides (M


II
=Cu or Ni)
with M
II
/Mg/Mn molar ratio of 1:1:1 is studied. The
thermal decomposition of starting layered double
hydroxides and phase transitions taking place during
their heating are reported. Thermal analysis, powder
X-ray diffraction, Raman spectroscopy, voltammetry
of microparticles, chemical and elemental analysis,
surface area measurements, scanning electron micro-
scopy and temperature-programmed reduction were
used to describe the thermal stability of LDHs and
their conversion to crystalline oxides.
2. Experimental methods
2.1. Preparation of samples
CuMgMn and NiMgMn layered double hydroxides
were prepared by coprecipitation. An aqueous solution (450
ml ) of Cu( NO
3
)
2d
3H
2
O or Ni ( NO
3
)
2d
6H
2
O,
Mg(NO
3
)
2d
6H
2
O and Mn(NO
3
)
2d
4H
2
O with M
II
/Mg/Mn
molar ratio of 1:1:1 (M
II
=Cu or Ni) and total metal ion
concentration of 1.0 mol l
1
was added dropwise into 200
ml of 0.5M Na
2
CO
3
solution under vigorous stirring.
During the synthesis, the temperature was maintained at
25 8C and pH at about 10 by a simultaneous addition of 3M
NaOH. The addition of both solutions took about 1 h. The
resulting suspension was then maintained at 25 8C with
stirring for 2 h. The obtained product was filtered off,
washed several times with distilled water and dried at 60 8C
in air. The dried products were heated at the chosen
temperature in the range 2001100 8C in air for 2 h and then
cooled to room temperature. These heated samples were
used for the XRD, Raman, voltammetric, TPR and surface
area measurements.
Reference compounds were synthesized in the following
ways: CuO by precipitation of CuCl
2
solution by NaOH at
90 8C and calcination of the intermediate at 500 8C,
Ni
6
MnO
8
and Ni
1.2
Mn
1.8
O
4
by evaporation of metal nitrates
solution with citric acid, drying and calcination of the solid
residue at 650 and 800 8C, respectively, and Mg
0.3
Ni
0.7
O by
coprecipitation of metal sulfates by NaOH solution and
calcination of the dry product at 900 8C.
2.2. Characterization of the products
Powder X-ray diffraction patterns were recorded using
a Seifert XRD 3000P instrument with Co K
a
radiation
(k=1.79 2, graphite monochromator, goniometer with the
BraggBrentano geometry) in 2h range 12758, step size
0.058. Rayflex and PowderCell 2.4 were used for phase
identification and quantitative analysis, respectively. Pow-
derCell is based on fitting of the experimental diffracto-
grams to the patterns generated from the crystal structures
of the components by refining their scale factor (recalcu-
lated to the percentage by the program), lattice parame-
ters, and diffraction-line profile functions. For refinement
of lattice parameters, DiffracPlus Topas, release 2000
(Bruker AXS, Germany) was used. The structural models
were taken from the Inorganic Crystal Structure Database
ICSD/Retrieve 2.01 (FIZ Karlsruhe, Germany). Both
programs (i.e. PowderCell and DiffracPlus Topas) perform
full-profile fitting by refining lattice parameters and
profile functions. DiffracPlus Topas belongs to the so-
called Rietveld programs family. It integrates various
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 123
types of X-ray analyses by supporting full-profile fit
methods currently employed in powder diffractometry.
Thermal analyses, including thermogravimetry (TG),
differential thermal analysis (DTA) and evolved gas analysis
(EGA), were carried out using a Netzsch STA 409 instru-
ment equipped by the quadrupole mass spectrometer QMS
403/4 (Balzers) for analysis of gases evolved during sample
heating. The heating rate of 10 8C min
1
in air or argon with
flow rate of 75 ml min
1
and 50 mg of sample were used.
The furnace and mass spectrometer were connected by
stainless steel capillary of 0.1 mm i.d. heated to about 200
8C to prevent the condensation of evolved gases. Gaseous
products were continually monitored for chosen mass
numbers m/z (18H
2
O
+
, 44CO
2
+
, 16O
+
and 32O
2
+
).
Raman spectra were collected using the LabRam HR
system (Jobin Yvon). The 785.02 nm line of laser was used
for excitation. An objective (100) was used to focus the
laser beam on the sample placed on an XY motorized
sample stage. The scattered light was analyzed by spectro-
graph with holographic grating (600 gr/mm), slit width 150
Am and opened confocal hole (1000 Am). Adjustment of the
system was regularly checked using a silicon sample and by
measurement in the zero-order position of the grating. The
time of acquisition of a particular spectral window was
optimized for individual sample measurements (ca. 200
400 s). Three accumulations were co-added to obtain a
spectrum. The spectra were fitted by Gauss curves to
separate individual bands and find the band maxima using
OriginPro 7.0 (Origin Lab, USA).
For voltammetry of microparticles (Grygar et al., 2002;
Kovanda et al., 2003), the powdered samples were mechan-
ically deposited on the surface of paraffin-impregnated
graphite rod. Potentials were measured against saturated
calomel reference electrode (SCE). Voltammetric curves
were measured from the open circuit potential (i.e. equili-
brium potential) toward negative potentials at a scan rate of 3
mV s
1
using AAutolab (EcoChemie, the Netherlands).
The chemical composition of the samples was deter-
mined by AAS after sample dissolution in hydrochloric
acid. The average error of the determination was about 3%
rel. The metal ions redox state was determined by iodometry
or by permanganometric back-titration after sample dis-
solution in an acidified solution of (NH
4
)
2
Fe(SO
4
)
2
(Mohr
salt). Iodometry, i.e. dissolution in excess KI in cold diluted
HCl, is more convenient but it was only applicable in
samples obtained at lower calcination temperatures (b600
8C). The less reactive calcines obtained at higher temper-
atures had to be dissolved in diluted H
2
SO
4
and H
3
PO
4
under heating in nitrogen atmosphere with stirring and
ultrasonication. The methods yielded the same results within
a common error of estimation (35% rel.). In both these
redox analyses, Mn
3+
, Mn
4+
, Cu
2+
, and Ni
3+
ions could be
determined. The results were expressed as an average formal
Mn valence.
Surface area measurements were carried out by nitrogen
adsorption at 77 K and evaluated by one-point BET method.
Scanning electron micrographs (SEM) of the samples
were taken with a scanning electron microscope Hitachi S-
4700 at a magnification of about 50,000 times. No
conductive layer was applied for coating observed samples
in order to maintain all surface details at high resolution.
The very low accelerating voltage of 1.5 kV was applied to
avoid the surface charging.
Temperature-programmed reduction (TPR) measure-
ments were carried out with 50 mg sample weight in a
hydrogennitrogen mixture (10 mol% H
2
, flow rate of 40 ml
min
1
). The temperature was linearly raised at the rate of 20
8C min
1
up to 800 8C. After freezing of arising water at
76 8C, a composition of gases was analyzed by the
thermal-conductivity detector.
3. Results and discussion
3.1. Composition of prepared LDHs
The following results were obtained by the
chemical analysis of the dried products (in wt.%):
Cu 18.2, Mg 5.8, Mn 15.9, CO
3
2
9.6 for CuMgMn
sample, and Ni 18.8, Mg 7.5, Mn 19.6, CO
3
2
10.9 for
NiMgMn sample. The results corresponded approx-
imately to the molar ratio in the nitrate solutions used
for coprecipitation. In the powder XRD patterns of
both samples, only a hydrotalcite-like phase was
detected, the NiMgMn sample exhibiting a higher
crystallinity in comparison with the CuMgMn one.
According to the reports presented previously
(Fernandez et al., 1994; Barriga et al., 1996; Velu et
al., 1999), the main part of Mn
2+
is oxidized to Mn
3+
during coprecipitation but some Mn cations in
hydroxide layers may be present as divalent. The
theoretical value of Mn/CO
3
2
molar ratio equal to 2
should be expected if all manganese cations in
hydroxide layers were present as Mn
3+
. The Mn/
CO
3
2
molar ratio of 1.81 and 1.96 was determined by
chemical analysis of CuMgMn and NiMgMn
samples, respectively, and likely all Mn
2+
cations
were oxidized during LDHs preparation. This
assumption was also supported by the mean formal
Mn valences of 3.57 and 3.08 in CuMgMn and Ni
MgMn samples, respectively. The Mn formal
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 124
valence values indicated that some Mn, particularly in
the CuMgMn sample, had to be in the valence 4+
(e.g. a formation of amorphous Mn
IV
species such as
MnO
2
could be considered). A possible explanation is
that the CuMgMn sample contained another phase
beside the LDH component, while the Mn valence in
the NiMgMn sample was much closer to the value
expected for the LDH compound. In the case of Ni
Mn LDH studied recently (Kovanda et al., 2003),
indefiniteness in the valence of manganese cations
was observed. EPR spectroscopy results and the Mn/
CO
3
2
molar ratio of 2.36 indicated the presence of
Mn
2+
, but the Mn formal valence in the dried NiMn
LDH was of 3.22 according to the chemical analysis.
Thus, the non-integer Mn formal valence in the dried
samples may be a result of Mn
2+
, Mn
3+
and Mn
4+
combination and an evaluation of the LDH charge
density from Mn/CO
3
2
ratio seems to be uncertain. In
both prepared samples, the Mn/CO
3
2
molar ratio
lower than 2 was determined and the existence of
carbonate containing species, which were not detected
by XRD, may be expected. The composition of dried
products is probably more complex and cannot be
expressed by simple chemical formulae.
3.2. Powder X-ray diffraction and SEM imaging
Powder XRD patterns of CuMgMn samples
heated at different temperatures are presented in
Fig. 1. The CuMgMn precipitate was decomposed
at temperatures up to ca. 200 8C and the sample heated
at 200 8C was almost amorphous. Heating at 400 8C
resulted in a highly disordered periclase-type inter-
mediate with broad XRD lines at d~2.4 and 2.1 2. A
trace amount of CuO (tenorite) was also found in this
sample. Tenorite and spinel Cu
x
Mg
y
Mn
z
O
4
with
Mn
III,IV
were detected in the temperature range 500
900 8C. The tenorite lattice parameters remained
almost constant with heating and corresponded to a
stoichiometric CuO. The full-profile fitting XRD
patterns yielding CuO content hence enabled the
evaluation of the spinel elemental composition by
subtracting the Cu belonging to CuO from the total
elemental composition of the oxide mixture. Accord-
ing to such XRD data processing, the spinel had an
almost constant composition Cu
0.7
Mg
1.0
Mn
1.2
O
4
between 500 and 800 8C and an almost constant
lattice parameter (Table 3), which indicated rather
surprising thermal stability of the oxide mixture
formed. The crystallization of mixed oxide 2CuO
d
MgO (gueggonite) at the expense of CuO and spinel
started at 900 8C (Table 1). MgO (periclase) and Cu
2
O
(cuprite) together with spinel and an unidentified
(incompletely crystallized) phase with broad diffrac-
tion lines were detected at 1100 8C.
The NiMgMn LDH seems to be more thermally
stable than the CuMgMn precipitate, which may be
caused by lower stability of Cu-containing hydro-
talcite-like compounds. For example, CuAl LDH is
decomposed at temperature as low as about 200 8C
(Alejandre et al., 1999; Kovanda et al., 2001),
whereas much higher decomposition temperature of
365 8C was found for NiAl LDH (Jitianu et al.,
2000). The possible explanation is that the distortion
of octahedral environment at copper cations due to the
JahnTeller effect may decrease the stability of
hydroxide layers in favour of another structure of
CuO. The NiMgMn LDH heated at 200 8C was
Fig. 1. Powder XRD patterns of CuMgMn precipitate heated at
various temperatures. Hhydrotalcite-like phase, Ipericlase-
type intermediate, TCuO (tenorite), SCu
x
Mg
y
Mn
z
O
4
(spinel),
G2CuO
d
MgO (gueggonite), CCu
2
O (cuprite), PMgO
(periclase).
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 125
disordered but some broad and weak hydrotalcite
diffraction lines remained in powder XRD pattern
(Fig. 2). According to the DTA and EGA measure-
ments (see below), the thermal decomposition of Ni
MgMn LDH occurred at about 305 8C. Conse-
quently, the LDH was not detected in the sample
heated at 300 8C, but the onset of oxide phase
crystallization might be implied. The Ni
x
Mg
y
Mn
z
O
4
spinel and cubic bunsenite (NiO) related oxide were
detected in powder XRD pattern of the sample heated
at 400 8C. The assignment of the bunsenite-like oxide
in samples calcined at 400600 8C as disordered
murdochite, M
D
, is based on its too low lattice
parameter, resembling rather a/2 of Mg-doped mur-
dochite (Ni,Mg)
6
MnO
8
(Taguchi et al., 1995) than a
of Mg-doped bunsenite (Ni,Mg)O (Davies, 1982); the
term ddisorderedT refers to disordered cation position
in the parent bunsenite structure. Together with spinel,
the (Ni,Mg)
6
MnO
8
mixed oxide with regular murdo-
chite structure was found in the samples calcined at
700 and 800 8C. The subsequent transformation of
oxides took place at 900 8C. Only spinel and Mg-
containing bunsenite (Ni,Mg)O were detected in
powder XRD patterns of samples calcined at 900 8C
and higher temperatures. The changes in the phase
composition of the calcination products and the lattice
parameters of the formed cubic oxides are presented
in Tables 2 and 3, respectively.
In NiMn oxide mixtures (Kovanda et al., 2003) it
was possible to estimate the phase and elemental
composition of the mixture components because
relatively well-defined, stoichiometric oxides Ni
6
MnO
8
, NiMnO
3
, and NiO were present beside non-
stoichiometric spinel Ni
x
Mn
y
O
4
. In the ternary Ni
MgMn oxide mixtures formed during calcination of
NiMgMn LDH, further non-stoichiometric oxides
may be present: murdochite-like mixed oxide
Ni
6x
Mg
x
MnO
8
and Mg-doped bunsenite Mg
x
Table 1
Surface area, chemical, elemental and phase compositions of samples prepared by heating of CuMgMn precipitate at various temperatures
T (8C) S
BET
(m
2
g
1
)
Cu
(wt.%)
Mg
(wt.%)
Mn
(wt.%)
Mn
valence
CuO
(wt.%)
Cu
x
Mg
y
Mn
z
O
4
(wt.%)
2CuO
d
MgO
(wt.%)
60 110 18.2 5.8 15.9 3.57 0 0 0
200 155 27.8 8.9 22.6 3.58 0 0 0
300 128 29.9 9.4 25.0 3.70 0 0 0
400 98 30.0 9.5 25.8 3.74 7
a
61 0
500 62 31.1 9.9 26.6 3.70 17
a
76 0
600 34 31.6 10.0 25.9 3.71 17 83 0
700 11 31.8 10.2 26.8 3.61 19 81 0
800 2.2 31.6 10.1 26.4 3.62 20 80 0
900 0.4 32.0 10.1 27.8 3.39 14 70 16
Phase composition is expressed in percentage of crystalline fraction.
a
An amount of 32 and 7 wt.% of periclase-type intermediate was determined at 400 and 500 8C, respectively.
Fig. 2. Powder XRD patterns of NiMgMn LDH heated at various
temperatures. Hhydrotalcite-like phase, M
D
(Ni,Mg)O contain-
ing Mn
4+
(disordered murdochite), M(Ni,Mg)
6
MnO
8
(murdo-
chite), SNi
x
Mg
y
Mn
z
O
4
(spinel), B(Ni,Mg)O (Mg-containing
bunsenite).
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 126
Ni
1x
O. The value of x cannot be directly estimated by
full-profile fitting of XRD patterns because of a strong
overlap of the diffraction lines of these phases with
Ni
x
Mg
y
Mn
z
O
4
spinel. However, the lattice parameter
a of both murdochite (Taguchi et al., 1995) and
bunsenite (Davies, 1982) are known to depend linearly
on Mg content that was used for XRD phase analysis.
The spinel elemental composition was obtained by
subtracting the content of Mg and Ni in bunsenite or
murdochite and Mn in murdochite from the total
elemental composition of the oxide mixture deter-
mined by chemical analysis. The Ni
x
Mg
y
Mn
z
O
4
spinel
lattice parameters were compared with the results
published by Feltz and Niednicht (1991).
At 700 and 800 8C, the murdochite-like and spinel
oxides in NiMgMn calcines had approximate
formulae (Ni
0.7
Mg
0.3
)
6
MnO
8
and Ni
0.6
Mg
1.1
Mn
1.3
O
4
,
respectively. Above 800 8C, the spinel was enriched
in Mn and Ni having been evolved from the decayed
murdochite; this change together with decrease of
average formal valence of Mn caused the growth of
the spinel lattice parameter (Table 3).
The changes of the samples texture depending on
the calcination temperature can be seen in the SEM
images in Figs. 3 and 4. Although the powder XRD
pattern of the dried CuMgMn precipitate exhibited
hydrotalcite-type diffraction lines, no microcrystals
can be distinguished in the SEM image and the dried
sample seems to be amorphous in a morphological
sense (Fig. 3). The sample calcined at 400 8C is more
porous and remains apparently non-crystalline. A
growth of the oxide crystals can be seen in the sample
calcined at 800 8C. A recrystallization of the oxides
accompanied by some disorder and disruptions,
caused probably by at least partial decomposition of
Cu
II
oxides and formation of new phases, is docu-
mented in the SEM image of the sample calcined at
1000 8C. In contrast to the CuMgMn precipitate,
thin platy crystals characteristic for hydrotalcite-like
compounds can be distinguished in the dried NiMg
Mn LDH (Fig. 4). These crystals were destroyed
during thermal decomposition but a crystallization of
oxides still did not appear in the sample calcined at
400 8C. Avisible crystallization of the oxide phases is
documented in SEM images of the samples calcined at
800 and 1000 8C.
3.3. Thermal analysis and surface area measurements
During the heating of CuMgMn sample, a broad
endothermic effect with minimum at 140150 8C
accompanied by the release of water and CO
2
was
observed (Fig. 5). Therefore, the endothermic effect
was ascribed to the precipitate thermal decomposition.
According to the evolved gas analysis, the release of
interlayer water and the dehydroxylation of hydroxide
layers occurred simultaneously, the maximum water
release taking place at 160 8C. As it was mentioned
above, the Mn/CO
3
2
molar ratio of 1.81 was
determined by chemical analysis of CuMgMn
sample dried at 60 8C, which indicated an excess of
carbonate in comparison with apparent LDH compo-
sition. This excess may be explained by presence of
carbonate-containing species in the sample not detect-
Table 2
Surface area, chemical, elemental and phase compositions of samples prepared by heating of NiMgMn LDH at various temperatures
T (8C) S
BET
(m
2
g
1
)
Ni
(wt.%)
Mg
(wt.%)
Mn
(wt.%)
Mn
valence
(Ni,Mg,Mn
IV
)O
(M
D
) (wt.%)
(Ni,Mg)
6
MnO
8
(wt.%)
Ni
x
Mg
y
Mn
z
O
4
(wt.%)
(Ni,Mg)O
(wt.%)
60 97 18.8 7.5 19.6 3.08 0 0 0 0
200 143 21.0 8.1 21.7 3.46 0 0 0 0
300 151 24.1 9.4 24.9 3.93 45 0 55 0
400 93 23.2 9.3 25.6 4.04 53 0 47 0
500 74 25.7 10.1 26.3 4.04 35 0 65 0
600 31 27.0 10.6 27.5 3.94 37 0 63 0
700 22 26.8 10.6 28.1 3.62 0 45 55 0
800 10 27.4 10.7 28.6 3.52 0 45 55 0
900 2.4 27.5 11.0 27.8 3.49 0 0 80 20
1000 0.8 26.1 11.1 27.9 3.36 0 0 74 26
1100 0.1 27.2 10.7 28.4 3.16 0 0 70 30
Phase composition is expressed in percentage of crystalline fraction.
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 127
able by XRD. A part of carbonate determined may
also be ascribed to the carbon dioxide adsorbed on the
basic sample surface. A slight carbon dioxide evolu-
tion was detected around 120 8C and it may be
connected with a release of surface adsorbed CO
2
.
The maximum CO
2
evolution was observed at ca. 220
8C and attributed to the LDH decomposition. A
decomposition of the residual carbonate accompanied
by CO
2
release was observed at 540 and 610 8C,
respectively. Thermal decomposition of Cu-contain-
ing hydrotalcite-like compounds (CuMgAl and Cu
Al) with a subsequent release of residual carbonate at
higher temperatures has recently been reported (Velu
and Swamy, 1996; Alejandre et al., 1999). An
interaction between hydroxide layers and interlayer
carbonate was considered, which may lead to a
Fig. 3. SEM images of CuMgMn precipitate: adried at 60 8C, b, c, dcalcined at 400, 800 and 1000 8C, respectively.
Table 3
Lattice parameters a of cubic oxides (in angstrom) in the heated samples (crystal type is given in parentheses)
T (8C) Cu
x
Mg
y
Mn
z
O
4
(spinel)
(Ni,Mg,Mn
IV
)O
(disordered murdochite, M
D
)
(Ni,Mg)
6
MnO
8
(murdochite)
Ni
x
Mg
y
Mn
z
O
4
(spinel)
(Ni,Mg)O
(bunsenite/periclase)
300 4.14 8.30
400 8.27 4.15 8.30
500 8.312 4.160 8.305
600 8.324 4.165 8.317
700 8.317 8.344 8.330
800 8.324 8.344 8.335
900 8.339 4.189
1000 8.360 4.193
1100 8.361 4.189
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 128
formation of copper-containing metastable phase such
as oxocarbonate. A similar effect was observed also
for MgAl hydrotalcite (Hibino et al., 1995).
The total weight loss of about 31% up to 700 8C
corresponded to the loss of entire amount of water
(including both the dehydration of the LDH interlayer
space and dehydroxylation of the hydroxide layers)
and carbon dioxide release. Thermal decomposition of
the CuMgMn precipitate caused a considerable
increase of its surface area (from 110 m
2
g
1
measured for the dried sample to 155 m
2
g
1
measured for the sample heated at 200 8C). After
reaching the maximum value at 200 8C, the surface
area gradually decreased with increasing calcination
temperature (Table 1).
Two slight endothermic effects on the DTA curve
were detected at 910 and 1020 8C, respectively; the
latter was accompanied by the weight loss of about
1.5%. These effects were ascribed to a transformation
of oxide phases at high temperatures, namely to a
decomposition of CuO and formation of Cu
I
-contain-
ing oxides. An analogous endothermic effect and an
oxygen evolution were observed during thermal
analysis performed in argon. In contrast to the
measurements performed in air, only one weak and
broad endothermic effect shifted to lower temper-
atures (with minimum detected at ca. 840 8C) was
observed. A very slight oxygen evolution was also
observed at 1080 8C. The results of thermal analyses
both in air and argon were similar but the release of
the residual carbonate detected in argon was also
shifted to lower temperatures (445 and 570 8C,
respectively).
The thermal analysis results of NiMgMn LDH
are presented in Fig. 6. Two endothermic effects
characteristic for hydrotalcite-like compounds were
observed in the DTA curve. The first one with a
minimum at 190 8C accompanied by the release of
water was ascribed to the loss of interlayer water.
The presence of CO
2
in gases evolved at low
temperature, i.e. a slight CO
2
evolution at 155160
8C, might be explained by the release of surface-
Fig. 4. SEM images of NiMgMn LDH: adried at 60 8C, b, c, dcalcined at 400, 800 and 1000 8C, respectively.
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 129
adsorbed CO
2
, analogously to the CuMgMn
sample discussed above. The second endothermic
DTA effect measured at 305 8C was attributed to
the complete LDH decomposition. The simultaneous
water and CO
2
release at this temperature was also
confirmed by the analysis of evolved gases. The
total weight loss of about 32% up to 700 8C was
observed. The same endothermic effects were
observed in argon.
A slight endothermic effect accompanied by a
weight loss of 1.3% was detected at 840 8C in air,
which is probably connected with a conversion of
oxide phases at high temperatures. In argon, a broad
endothermic effect accompanied by oxygen evolution
at 840 8C was also detected. An additional CO
2
evolution at 415 8C was observed in argon. This CO
2
evolution was not detected in air. The surface area of
NiMgMn sample increased from 97 m
2
g
1
(the
dried sample) to 151 m
2
g
1
(the 300 8C calcine) and
then gradually decreased with increasing calcination
temperature similarly as it was observed for CuMg
Mn sample (Table 2).
3.4. Raman spectroscopy
The Raman spectra of CuMgMn and NiMg
Mn precipitates and calcines are shown in Figs. 7 and
8, respectively. The Raman spectrum of the dried Cu
MgMn precipitate exhibited two distinct bands, one
at about 490 cm
1
and the stronger one at about 610
cm
1
, while NiMgMn at about 470, 540 and 610
cm
1
. Similar bands were found in the spectra of Mg
Al hydrotalcite at 476 and 552 cm
1
(Kloprogge and
Frost, 1999) and also in the spectra of CoAl and Ni
Al hydrotalcite-like compounds at 462 and 521 cm
1
,
and at 482 and 545 cm
1
, respectively (Perez-
Fig. 5. Thermogravimetry (TG), derivative thermogravimetry (DTG), differential thermal analysis (DTA) and evolved gas analysis results (H
2
O,
CO
2
, O
2
) of CuMgMn precipitate in air and argon.
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 130
Ram rez et al., 2001). The Raman bands of reference
compounds and measured samples are given in Table
4; the band positions were obtained by the spectra
decomposition to Gaussian curves.
In CuMgMn calcines up to 400 8Cthe appearance
of Raman spectra of the starting LDH precursor was
preserved, but a band at about 460 cm
1
and a shoulder
at about 670 cm
1
typical for spinel oxides appeared at
500 8C. Simultaneously, easily recognizable tenorite
bands at about 300 and 1110 cm
1
arose. A complete
change of the spectra occurred at 1000 and 1100 8C.
The spectra of NiMgMn samples calcined up to
500 8C consisted of a broad band very similar to those
of low temperature CuMgMn calcines, probably
indicating a similar structure of the LDH primary
decomposition products. Some of the band compo-
nents closely resembled those of MnO
2
(Table 4). The
characteristic double-maximum absorption feature of
the spinel was formed at 600 8C and at higher
temperatures together with two sharp and well
recognizable murdochite bands at 470 and 590
cm
1
. Above 800 8C, the murdochite bands disap-
peared and the spectrum became closely resembling
the spectrum of Ni
1.2
Mn
1.8
O
4
spinel; however, Mg-
bunsenite bands were completely overlapped by
spinel and cannot be identified by Raman spectro-
scopy. The spinel component is responsible for broad
overlapped bands (centred at 600 cm
1
) in both
calcined NiMgMn and CuMgMn samples (500
800 8C), which corresponds to a spinel with disor-
dered cationic occupation (Malavasi et al., 2002).
3.5. Voltammetry of microparticles
The voltammetry of microparticles is an electro-
chemical method, which can be applied in the analysis
Fig. 6. Thermogravimetry (TG), derivative thermogravimetry (DTG), differential thermal analysis (DTA) and evolved gas analysis results (H
2
O,
CO
2
, O
2
) of NiMgMn LDH in air and argon.
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 131
of both crystalline and amorphous solid mixtures,
determination of metal components in catalysts,
microanalysis of solid solutions, etc. (Grygar et al.,
2002; Kovanda et al., 2003). During the reductive
dissolution of CuMgMn samples, four different
responses depending on potential could be seen in
Fig. 9. These reductive dissolution cathodic peaks
were signed as C1, C2, C3, and C4, respectively. The
more detailed discussion of the cathodic peaks was
published elsewhere (Grygar et al., 2004).
The C1 peak was related to Mn
IV
(s)YMn
III
(s)
reduction in the solid and it indicated a presence of
Mn
IV
in the spinel structure. The C2 peak was
connected with the reductive dissolution of trivalent
manganese Mn
III
(s)YMn
2+
(aq) and also with the
copper reduction Cu
II
(s)YCu
0
(s) from solids quickly
dissolving to Cu
2+
(hydroxides, carbonates). At the
same potential, the reduction in solution Cu
2+
(aq)Y
Cu
0
(s) occurs. Therefore, the C2 peak was ascribed
to the spinel dissolution and to the reduction of
labile Cu
II
solids to Cu
0
. The C3 peak was detected
in all samples containing tenorite, both crystalline
and XRD amorphous. It was attributed to the CuO
reduction according to the equation: Cu
II
O(s)+
2H
+
+2e

YCu
0
(s)+H
2
O; this reaction was also con-
firmed by analysis of reference CuO. The subsequent
anodic peak, corresponding to the Cu
0
oxidation
Cu
0
(s)YCu
2+
(aq)+2e

, was observed in an anodic


scan in cyclic voltammetry (not shown in Fig. 9).
The other cathodic peak C4 was detected in
voltammograms of samples calcined above 900 8C.
It was attributed to reduction of gueggonite (i.e.
2Cu
II
O
d
MgO(s)+6H
+
+4e

Y2Cu
0
(s)+Mg
2+
(aq)+
3H
2
O). A cuprite reduction Cu
I
2
O(s)+2H
+
+2e

Y
2Cu
0
(s)+H
2
O may also take place in the samples
calcined at high temperatures.
According to the voltammetry of microparticles,
the onset of CuO formation was at 300 8C. C1 peak
indicating spinel dissolution was detected in sam-
ples calcined at 400 8C and higher temperatures,
and the crystallization of CuO and spinel was
Fig. 7. Raman spectra of CuMgMn precipitate heated at various
temperatures. TCuO (tenorite), SCu
x
Mg
y
Mn
z
O
4
(spinel).
Fig. 8. Raman spectra of NiMgMn LDH heated at various
temperatures. M(Ni,Mg)
6
MnO
8
(murdochite), SNi
x
Mg
y
Mn
z
O
4
(spinel), B(Ni,Mg)O (Mg-containing bunsenite).
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 132
complete at about 500 8C. Temperatures of the
onset of oxide phases formation found by voltam-
metry were by about 100 8C lower than those
indicated by XRD and Raman spectroscopy.
The reductive dissolution of NiMgMn LDH
occurred at approximately three potentials (Fig. 10).
The positive reduction peaks C1+C2 were related to
the dissolution of very reactive Mn
III,IV
oxides,
probably with a low degree of substitution. Ni
x
Mn
y
O
4
and Ni
x
Mg
y
Mn
z
O
4
spinels are much less reactive than
Cu
x
Mn
y
O
4
and Cu
x
Mg
y
Mn
z
O
4
spinel oxides. The
C3+C4 peaks close to 0 V and the negative C5 peak
were probably related to the dissolution of NiMg
Mn
III,IV
oxides with a substantial Ni content. A highly
reactive, probably amorphous Mn
III,IV
species, which
was responsible for sharp C1 peak found in the dried
NiMgMn LDH and in the sample heated at 200 8C,
was gradually consumed due to the incorporation into
NiMgMn oxides as the calcination temperature
increased. No such signal was observed in well-
crystalline reference NiMn oxides, but it was
obvious in calcines of NiMn LDH and attributed to
amorphous MnO
2
(Kovanda et al., 2003). The species
responsible for the C2 peak could be present either on
the surface of the particles of the major components or
Table 4
Raman bands of reference compounds and studied samples obtained
by decomposition of spectra to Gauss curves
Sample Raman bands (cm
1
) Phases
Ni
1.2
Mn
1.8
O
4
283 w, 457 w, 514 m, 559 m, 631 w,
643 m
Ni
6
MnO
8
294 m, 359 m, 465 w, 472 s, 519 w,
539 s, 570 m, 581 s, 629 w, 644 m
MnO
2
532, 588, 650 cm
1
(Ferrandon et al., 1999)
Mg
0.3
Ni
0.7
O 208 w, 422 w, 519 w, 569 w, 726 w,
1104 w
CuO 288 m, 336 m, 624 m, 1111 w
Cu
1.5
Mn
1.5
O
4
200 m, 432 w, 481 m, 546 w, 576 m,
634 w, 1026 w
Disordered
MgMn
2
O
4
~650 w (Malavasi et al., 2002)
CuMgMn 60 405 w, 491 w, 609 w
CuMgMn 200 Coalesced bands 426 w, 493 w,
614 w
CuMgMn 300 Coalesced bands 381 w, 513 w,
605 w, 653 w
CuMgMn 400 Coalesced bands 357 w, 509 w, 607 w,
672 w
CuMgMn 500 299 m, 397 w, 462 w, 537 w, 596 w,
670 w, 1117 w
T, S
CuMgMn 600 300 m, 367 w, 453 w, 537 w, 589 w,
655 w, 1090 w
T, S
CuMgMn 900 300 m, 344 m, 379 m, 439 w, 549 w,
588 m, 634 w, 1126 w
T, S
NiMgMn 60 Weak bands 311 w, 466 w, 547 m,
612 w
NiMgMn 200 Coalesced bands 354 w, 485 w,
538 w, 584 w, 631 w
NiMgMn 300 Coalesced bands 402 w, 485 w,
540 w, 591 w, 654 w
NiMgMn 500 Coalesced bands 365 w, 485 w,
548 w, 590 m, 625 m, 662 w
NiMgMn 600 360 w, 457 w, 472 s, 532 w, 540 m,
593 s, 635 w, 674 m, 729 s
M
NiMgMn 700 355 w, 455 w, 471 s, 523 m, 540 w,
589 s, 639 w, 671 m, 728 s
M
NiMgMn 900 353 w, 436 m, 523 m, 564 m, 632 m,
666 m
Underlined bands are responsible for clear local maxima. Peak width:
wwide (N50 cm
1
), mmedium (1550 cm
1
), ssharp (b15
cm
1
). Phase denotation: Ttenorite, Sspinel, Mmurdochite.
Fig. 9. Voltammetry curves of CuMgMn precipitate heated at
various temperatures. Supporting electrolyte: acetic acid/sodium
acetate 1:1 (total concentration 0.2 M).
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 133
as separate particles; this cannot be distinguished by
voltammetry. The shape of the voltammetric curves
measured for samples calcined at 400 8C and higher
temperatures was similar to that obtained for reference
(Ni,Mn)
3
O
4
spinels (Kovanda et al., 2003). Bunsenite,
NiO, and periclase, MgO, do not yield voltammetric
peaks under the chosen conditions. Murdochite-type
oxides M
D
and (Ni,Mg)
6
MnO
8
are also electrochemi-
cally inactive, probably due to a too low content of
electrochemically active Mn
4+
cations in the oxide
lattice.
3.6. Temperature-programmed reduction
TPR experiments with CuMgMn precipitate
calcined at different temperatures (60, 400, 800, and
1000 8C, respectively) showed a single reduction peak
(Fig. 11) located at around 250 8C, although at least
two reducible phases (Cu and Mn oxides) are present
in the samples. The temperature of the peak maximum
increased slightly with increasing calcination temper-
ature. According to the results reported by Ferrandon
et al. (1999), CuO
x
exhibited a single, well-defined
TPR peak with maximum at 207 8C. Perhaps the
easily reducible CuO positively affects reduction of
Mg and Mn containing calcination products, as the
MgMn LDH calcined up to 400 8C showed a broad
peak with maximum at the temperature as high as
about 350 8C (Fernandez et al., 1994). Similar results
were obtained during our own TPR measurements
with MgMn hydrotalcite-like compound calcined at
400 8C. The highest amount of hydrogen consumed
was observed with the sample calcined at 800 8C.
Further increase in calcination temperature led to a
decrease in hydrogen consumption, due to a partial
Cu
II
to Cu
I
oxide transformation and decrease of Mn
valence.
Reduction of NiMgMn LDH calcined at differ-
ent temperatures in the range 601000 8C proceeded
in a more complicated manner (Fig. 12). The sample
dried at 60 8C showed some changes in four temper-
ature regions during TPR measurements. The slight
peak observed at ca. 120 8C cannot be connected with
the sample reduction but gases evolved during sample
heating might affect the detector response. The first
reduction peak appeared at 300 8C, the second at 380
8C, and the third at about 525 8C, respectively. The
peak around 300 8C can be ascribed to the reduction
Fig. 10. Voltammetry curves of NiMgMn LDH heated at various
temperatures. Supporting electrolyte: 0.2 M H
2
SO
4
.
Fig. 11. TPR profiles of CuMgMn precipitate heated at various
temperatures.
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 134
of an easily reducible Mn
IV
phase, probably the
MnO
2
-like species responsible for C1 peak in
voltammetry. During the reduction of free MnO
x
,
the peaks with maxima at 328 and 424 8C were
reported (Ferrandon et al., 1999). High-temperature
TPR peaks of the samples calcined at 400, 800, and
1000 8C shifted continuously to higher temperatures,
which may be explained by a continuous change of
the spinel composition and decreasing mean Mn
valence.
4. Conclusions
The new CuMgMn and NiMgMn layered
double hydroxides were prepared and their thermal
behaviour was studied using various techniques. The
presence of Mg in CuMgMn and NiMgMn
hydrotalcite-like precursors enhanced the formation
of spinel-like oxides in the calcines with respect to
Mg-free LDH. In NiMgMn samples, NiMnO
3
formation reported in calcined NiMn LDH (Kovanda
et al., 2003), was completely suppressed. Mg replaced
about 30 mol% of Ni in nickel oxides with murdochite
or bunsenite structure that introduced another variable
to both phase and elemental composition of the
calcines.
The heating of the CuMgMn precipitate resulted
in its thermal decomposition at temperatures up to
about 200 8C. The release of interlayer water and
dehydroxylation of hydroxide layers occurred simul-
taneously, the main part of carbonate was also
decomposed at this temperature. The residual carbo-
nate was released up to ca. 610 8C. According to the
voltammetry of microparticles, XRD, and Raman
spectroscopy, the crystallization of oxide phases, i.e.
CuO and Cu
x
Mg
y
Mn
z
O
4
spinel, occurred at 300500
8C with the onset of CuO formation at 300 8C. The
tenorite-spinel oxide mixture was very stable in the
temperature range of 500800 8C. The crystallization
of 2CuO
d
MgO was observed at 900 8C and a
substantial phase transformation to phases like Cu
2
O
and MgO was detected at 1100 8C. The high-temper-
ature transformation of the oxide phases was accom-
panied by the endothermic DTA effect and oxygen
evolution.
During the heating of NiMgMn LDH, the
release of interlayer water at 190 8C and the thermal
decomposition at about 300 8C were observed. TPR
and voltammetry indicated a certain segregation of
MnO
2
at initial stages of LDH decomposition at
200400 8C. The onset of crystallization of the
primary oxide phases, i.e. (Ni,Mg)O containing
Mn
4+
(with disordered murdochite structure), and
Ni
x
Mg
y
Mn
z
O
4
spinel, was detected at 300 8C.
According to XRD, disordered murdochite was
converted to cation-ordered murdochite at 700 8C,
and its subsequent transformation to Mg-containing
bunsenite (Ni,Mg)O and spinel took place at 900 8C.
Between 500 and 1000 8C, the oxides lattice
parameters changed considerably. The phase recon-
struction at high temperatures was accompanied by
oxygen evolution due to the Mn valence decrease,
not due to phase decomposition as in CuMgMn
oxide mixture.
Acknowledgements
This work was supported by the Czech Ministry of
Education, Youth and Sports (research projects No.
CEZ:MSM 223/10/0002 and LN00A028) and by the
Grant Agency of Czech Republic (projects No. 106/
02/0523 and 104/04/2116). The authors thank Vladi-
m r Machovic (Laboratory of Molecular Spectro-
scopy, Institute of Chemical Technology, Prague) for
performing Raman spectroscopy measurements.
Fig. 12. TPR profiles of NiMgMn LDH heated at various
temperatures.
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 135
References
Alejandre, A., Medina, F., Salagre, P., Correig, X., Suerias, J.E.,
1999. Preparation and study of CuAl mixed oxides via
hydrotalcite-like precursors. Chem. Mater. 11, 939948.
Barriga, C., Fernandez, J.M., Ulibarri, M.A., Labajos, F.M., Rives,
V., 1996. Synthesis and characterization of new hydrotalcite-like
compounds containing Ni(II) and Mn(III) in the hydroxide
layers and of their calcination products. J. Solid State Chem.
124, 205213.
Bellotto, M., Rebours, B., Clause, O., Lynch, J., Bazin, D., Elkaim,
E., 1996. Hydrotalcite decomposition mechanism: a clue to the
structure and reactivity of spinel-like mixed oxides. J. Phys.
Chem. 100, 85358542.
Cavani, F., Trifiro, F., Vaccari, A., 1991. Hydrotalcite type anionic
clays: preparation, properties, and applications. Catal. Today 11,
173301.
Chao, G.Y., Gault, R.A., 1997. Quintinite-2H, quintinite-3T,
charmarite-2H, charmarite-3T and caresite-3T, a new group of
carbonate minerals related to the hydrotalcite-manasseite group.
Can. Mineral. 35, 15411549.
Davies, P.K., 1982. An X-ray diffraction study of phases in the
system CuONiOMgO at 1000 8C. J. Electrochem. Soc. 129,
31C35C.
De Roy, A., Forano, C., Besse, J.P., 2001. Layered double
hydroxides: synthesis and post-synthesis modification. In:
Rives, V. (Ed.), Layered Double Hydroxides: Present and
Future. Nova Science Publishers, New York, pp. 137.
Dunn, P.J., Peacor, D.R., Palmer, T.D., 1979. Desautelsite, a
new mineral of the pyroaurite group. Am. Mineral. 64,
127130.
Feltz, A., Niednicht, B., 1991. Investigation of electronically
conducting oxide systems: XX. MgNiMnO
4
and properties of
Mg
z
NiMn
2z
O
4
. J. Alloys Compd. 177, 149158.
Fernandez, J.M., Barriga, C., Ulibarri, M.-A., Labajos, F.M.,
Rives, V., 1994. Preparation and thermal stability of manga-
nese-containing hydrotalcite, [Mg
0.75
Mn
0.04
II
Mn
0.21
III
(OH)
2
]
(CO
3
)
0.11d
nH
2
O. J. Mater. Chem. 4, 11171121.
Ferrandon, M., Carnf, J., J7ras, S., Bjfrnbom, E., 1999. Total
oxidation catalysts based on manganese or copper oxides and
platinum or palladium: I. Characterization. Appl. Catal., A 180,
141151.
Grygar, T., Marken, F., Schrfder, U., Scholz, F., 2002. Electro-
chemical analysis of solids. A review. Collect. Czech. Chem.
Commun. 67, 163208.
Grygar, T., Rojka, T., Bezdicka, P., Vecern kova, E., Kovanda, F.,
2004. Voltammetric and X-ray diffraction analysis of early
stages of thermal crystallization of mixed Cu,Mn-oxides.
J. Solid State Electrochem. 8, 252259.
Hansen, H.C.B., Taylor, R.M., 1991. Formation of synthetic
analogues of double metal-hydroxy carbonate minerals under
controlled pH conditions: II. The synthesis of desautelsite. Clay
Miner. 26, 507525.
Hibino, T., Yamashita, Y., Kosuge, K., Tsunashima, A., 1995.
Decarbonation behavior of MgAlCO
3
hydrotalcite-like com-
pounds during heat treatment. Clays Clay Miner. 43, 427432.
Hudson, M.J., Carlino, S., Apperley, D.C., 1995. Thermal
conversion of a layered (Mg/Al) double hydroxide to the oxide.
J. Mater. Chem. 5, 323329.
Jitianu, M., Balasoiu, M., Marchidan, R., Zaharescu, M., Crisan, D.,
Craiu, M., 2000. Thermal behaviour of hydrotalcite-like
compounds: study of the resulting oxidic forms. Int. J. Inorg.
Mater. 2, 287300.
Kloprogge, J.T., Frost, R.L., 1999. Fourier transform infrared and
Raman spectroscopic study of the local structure of Mg-, Ni-,
and Co-hydrotalcites. J. Solid State Chem. 146, 506515.
Kovanda, F., Jiratova, K., Rymes, J., Kolousek, D., 2001. Character-
ization of activated Cu/Mg/Al hydrotalcites and their catalytic
activity in toluene combustion. Appl. Clay Sci. 18, 7180.
Kovanda, F., Grygar, T., Dornicak, V., 2003. Thermal behaviour of
NiMn layered double hydroxide and characterization of formed
oxides. Solid State Sci. 5, 10191026.
Malavasi, L., Galinetto, P., Mozzati, M.C., Azzoni, C.B., Flor, G.,
2002. Raman spectroscopy of AMn
2
O
4
(A=Mn, Mg, and Zn)
spinels. Phys. Chem. Chem. Phys. 4, 38763880.
Perez-Ram rez, J., Mul, G., Moulijn, J.A., 2001. In situ Fourier
transform infrared and laser Raman spectroscopic study of the
thermal decomposition of CoAl and NiAl hydrotalcites. Vibr.
Spectrosc. 27, 7588.
Reichle, W.T., Kang, S.Y., Everhardt, D.S., 1986. The nature of the
thermal decomposition of a catalytically active anionic clay
mineral. J. Catal. 101, 352359.
Rives, V., 2001. Study of layered double hydroxides by
thermal methods. In: Rives, V. (Ed.), Layered Double
Hydroxides: Present and Future. Nova Science Publishers,
New York, pp. 115137.
Taguchi, H., Omori, S., Magao, M., Kido, H., Shimada, M., 1995.
Crystal structure and magnetic properties of (Ni
1x
Mg
x
)
6
MnO
8
.
J. Solid State Chem. 118, 112116.
Vaccari, A., 1998. Preparation and catalytic properties of cationic
and anionic clays. Catal. Today 41, 5371.
Velu, S., Swamy, C.S., 1996. Synthesis and physicochemical
properties of a new coppermanganesealuminium ternary
hydrotalcite-like compound. J. Mater. Sci. Lett. 15, 16741677.
Velu, S., Shah, N., Jyothi, T.M., Sivasanker, S., 1999. Effect of
manganese substitution on the physicochemical properties and
catalytic toluene oxidation activities of MgAl layered double
hydroxides. Microporous Mesoporous Mater. 33, 6175.
F. Kovanda et al. / Applied Clay Science 28 (2005) 121136 136