Escolar Documentos
Profissional Documentos
Cultura Documentos
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
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