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j.jssc.2004.07.010-ZnAL-hidrotermico-utilizado Nas Sinteses
j.jssc.2004.07.010-ZnAL-hidrotermico-utilizado Nas Sinteses
Abstract
Zn/Al hydrotalcites were synthesized by coprecipitation at increasing pH from 6.0 to 14.0, followed by hydrothermal treatment at
150 1C for 7 days. The materials were characterized by X-ray diffraction (XRD), STEM, inductively coupled plasma–atomic
emission spectroscopy (ICP–AES), thermal analysis, infrared spectroscopy and Raman spectroscopy. The XRD analysis for the
samples prepared between pH 9.0 and 12.0 showed a pattern typical of hydrotalcite, with a c-axis distance of 22.6 Å. STEM
showed that the pH of preparation affected the stability of the hydrotalcite and that instability, observed at pH 9.0, favored the
formation of mixed phases when treated hydrothermally. It was also shown that treatment of a stable starting material increased the
crystallinity and resulted in the formation of hexagonal plate-shaped particles. ICP–AES and thermal analysis showed that the Zn/
Al ratio and thermal stability increased with pH. Thermal analysis showed three major weight losses corresponding to the loss of
interparticle water, interlayer water and dehydroxylation of the hydroxide layers and decarbonization of the interlayer region.
r 2004 Elsevier Inc. All rights reserved.
0022-4596/$ - see front matter r 2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jssc.2004.07.010
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4048 J.T. Kloprogge et al. / Journal of Solid State Chemistry 177 (2004) 4047–4057
increase particle size, to improve their chemical and pH from 6.0 to 6.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, and
physical properties. 414, and labelled 3–10. In all experiments, solutions
A recent study has shown that the carbonate anion were added using a peristaltic pump at a rate of 40 mL/
concentration in the interlayer region of hydrotalcite min, under vigorous stirring. The pH was maintained
was affected by both temperature and aging [5]. It was constant by adding HNO3 when necessary. When the
shown that the best crystalline material was obtained at addition was complete, the mixture was stirred for a
25 1C, with at least 5 h of aging. Generally, it is accepted further 1.5 h, during which time the pH was still
that a basic pH is required for the preparation of maintained constant. Two samples were selected based
hydrotalcites. However, the optimal pH depends on on their purity, stability and crystallinity, and were
which cations are used and where their hydroxide treated hydrothermally at autogenous water vapor
precipitation curves cross. The crystallinity of the pressure at 150 1C, in Teflon-lined stainless steel Parr
precipitated hydrotalcite can be further increased by Bombs for 7 days (samples 11 and 12). All samples were
hydrothermal treatment [6,7]. In 1980, Miyata showed filtered, thoroughly washed several times, in approxi-
that using a higher temperature, 180 1C, for hydro- mately 500 mL of deionized water each time to remove
thermal treatment increased the crystallite size [8]. excess soluble ions, and finally the samples were oven
Several studies have reported on the influence of the dried at 60 1C for 1 h.
synthesis parameters and show that pH is the major
factor in the formation of Zn/Al hydrotalcite [9–13]. Zn/ 2.2. Characterization
Al hydrotalcites have been used for anion exchange
reactions, pillaring and absorption [14–24] and a 2.2.1. Powder X-ray diffraction (XRD)
number of catalytic applications, either with the Powder XRD (XRD) diagrams were recorded on a
hydrotalcite structure or after calcination as the mixed Phillips wide-angle PW 1050/25 vertical goniometer
metal oxide [25–32]. equipped with a graphic diffracted beam monochroma-
This study forms part of an ongoing investigation on tor. The d-values and intensity measurements were
the effects of reaction conditions during synthesis and improved by application of an in-house developed
hydrothermal treatment of the hydrotalcite minerals computer-aided divergence slit system enabling constant
with various cations and anions to improve their sampling area irradiation (20 mm long) at any angle of
physical and chemical properties. The aim of this study incidence. The radiation applied was CoKa from a long
is to obtain insight into the nature of the Zn/Al fine-focus Co tube operating at 40 kV and 40 mA. The
hydrotalcite-type materials when the experimental con- samples were measured in the step-scan mode from 5 to
ditions are varied. Samples were prepared over a wide 7512y, with steps of 0.0212y and a counting time of 2 s.
pH range, and the reagent addition was optimized. Jade software package (Materials Data, Inc.) was used
Samples were selected, based on their purity, stability to analyze the data; identification of the existing
and crystallinity, and treated hydrothermally to inves- crystalline phases was based on comparison with pre-
tigate (1) the effects of aging under the influence of existing JCPDS diffraction data files. Pattern manipula-
temperature, pressure and time, and (2) the effects of pH tion and interpretation were performed using TracesV4
of preparation on the crystallinity of the hydrothermally (Diffraction Technology Pty. Ltd.) and Microsoft
treated hydrotalcite. EXCEL.
prepared at 10, 50, 100, and 200 ppm. Small amounts of (003)
12, hydrothermally
the samples were accurately weighed and digested in treated
(1010)
(1011)
(110)
(113)
(015)
(018)
2.2.5. Fourier transform infrared (FTIR) and Raman to the variation in synthesis conditions, where based on
spectroscopy the Zn solubility curves precipitation of ZnO starts at
FTIR spectra were recorded using the KBr tablet pH 9 [35]. The addition of the hydroxide-containing
technique (2 wt% sample) on a Perkin-Elmer FT-IR solution to the cations-containing solution yielded a
1000 spectrometer; 64 scans were taken to improve the hydrotalcite-type material without the ZnO impurity.
signal-to-noise ratio in the range of 400–4000 cm1, the Proceeding via this pathway is therefore preferred as it
normal resolution was 4 cm1. The Raman spectra were progresses under acidic conditions that do not favor the
obtained using a Renishaw 1000 Raman microscope formation of ZnO [35]. Under strong alkaline condi-
system, which includes a monochromator, a filter system tions, ZnO species are not soluble and compete with the
and a charged-coupled device (CCD) as the detector. formation of Zn/Al hydrotalcite.
Raman spectra were excited on a Spectra-Physics model
127 He/Ne laser (633 nm), scanned for 15 s for 1000 3.2. The effect of pH of synthesis
scans and recorded in the range of 400–1800 and
2800–4000 cm1. Data manipulation, such as baseline The pH of preparation is important in the formation
adjustment, smoothing and normalizing as well as of all hydrotalcite-type materials and the optimum pH
interpretation, was performed using the Spectracalc depends on the cations used (Fig. 1). Sample 3 (pH
software package GRAMS (Galactic Industries Cor- 6.0–6.5) displays very weak, broad peaks at higher 2y
poration, NH, USA) and Microsoft EXCEL. Band values (14.91) compared to sample 2 (pH 12, 13.61). The
component analysis was undertaken using the Jandel XRD patterns of sample 3 (pH 6.0–6.5) show that no
‘‘Peakfit’’ software package, which enabled the type of hydrotalcite structure is formed under acidic synthesis
fitting function to be selected and allowed specific conditions. The broadness of the peaks indicates that
parameters to be fixed or varied accordingly. the sample is poorly crystalline, where the reflections
occur at similar 2y values as for brucite, indicating that a
low crystalline hydroxide similar to brucite is formed
3. Results and discussion instead of hydrotalcite. Samples prepared within the pH
range of 9.0–12.0 (samples 4–9 and 2) show patterns
3.1. Effect of reagent addition similar to that of natural hydrotalcite [7], with the (003)
reflection corresponding to a c-axis of 22.5 Å. The
The XRD patterns of all samples are shown in Fig. 1. difference between these samples is in the intensity of
The crystalline components in samples 1 and 2 (pH 12) the (00l) reflections. As pH increases, from 9.0 to 12.0,
show some significant differences. Both show a sharp the intensity of the reflections increases and the line
symmetric (003) reflection at low 2y angles correspond- width decreases, corresponding to an increase in crystal-
ing to a c-axis of 22.8 Å. Both spectra also show broad linity. Samples 2 and 9 at pH 12 and 11.5, respectively,
asymmetric peaks at higher angles, which are character- have the most intense and sharpest peaks, and thus are
istic of clay minerals possessing a layered structure and the most crystalline samples. Sample 10 (pH414) shows
are similar to the pattern of natural hydrotalcite [7,34]. a structure different from the previous samples; it is
Sample 1 (pH 12), however, shows additional peaks that composed of one major crystalline phase being ZnO and
are associated with the second major phase zincite a minor phase, sodium nitrate. Based on solubility
(ZnO) and sodium nitrate (NaNO3) as a minor phase. curves and predominance diagrams for Zn2+, at this
The difference in the crystalline products formed is due strong alkaline pH, zinc-hydroxy complexes, such as
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4050 J.T. Kloprogge et al. / Journal of Solid State Chemistry 177 (2004) 4047–4057
12, hydrothermally
treated
11, hydrothermally
5,5pH 9.5
treated
10, pH > 14
1, pH 12
9, pH
9 11.5
Relative Intensity
Weight Loss (mg)
2, pH 12
dW/dT
9, pH 11.5
11, hydrothermal
8, pH 11
7, pH 10.5
6, pH 10
5, pH 9.5
DTA 4, pH 9
TGA
3, pH 6-6.5
12, hydrothermal
400 800 1200 1600 2000 2400 2800 3200 3600 4000
100 150 200 250 300 350
Wavenumber/cm-1
Temperature (˚C)
Fig. 4. FT-IR spectra of all synthetically prepared samples (1–12),
Fig. 3. Thermal analysis of Zn/Al hydrotalcite of samples 5, 9, 11, and showing the effects of pH and hydrothermal treatment.
12: (a) TGA, (b) DTA.
the removal of the interlayer water is finished at hydrotalcites (Zn, Al) are distributed at random, it is
190 1C. TGA-MS study of Mg/Al-hydrotalcite has unlikely than an OH group is surrounded by three metal
shown that up to 200 1C water is lost in several steps, cations of the same kind, especially Al3OH. In most
accumulating in a major loss around 195 1C [44]. The cases, one OH group will be coordinated by the two
decomposition step, starting at 200 1C, is due to different metal cations. In the following sections, the
the decomposition (dehydroxylation) of the hydroxide vibrations will be assigned to the coordination which it
layers and the removal of interlayer anions (carbonate) most likely resembles, e.g. ‘‘Al-OH’’. All spectra show a
[44]. The end products of the thermal decomposition very broadband between 2700 and 3750 cm1. Band
have been shown to be metal oxides as well as mixed- component analysis (Fig. 5) reveals three superimposed
oxide spinel-type phases [43,45]. The patterns of various peaks at 3025, 3348, and 3468 cm1. The 3025 cm1
samples differ with respect to the temperature at which band is generally interpreted as the CO3–H2O bridging
the weight losses occur, such that sample 5 (pH 9.5) mode [7,47]. The 3348 cm1 band is ascribed to the H-
occurs at a lower temperature than for sample 9 (pH bonded interlayer H2O surrounding the anions. The
11.5). Since stability is dependant on temperature, strong band at 3468 cm1 is assigned to the metal-OH-
sample 9 appears to be the most stable sample from stretching mode. However, the various metals (Zn, Al)
this series [46]. It is concluded, in comparison with the bonded to the OH group cannot be distinguished
XRD and TEM results, that the more crystalline between themselves [48].
samples have the highest thermal stability. Within the range of pH synthesis conditions, the
The FT-IR spectra for samples synthesized at various positions of the infrared bands change up to 50 cm1
pH conditions are shown in Fig. 4, and their assignment and generally the intensity increases with increasing pH.
in Table 2. With the infrared assignment, it has to be In addition, peaks become sharper with increasing pH.
kept in mind that most of the OH groups are (when not Since increasing intensity corresponds to an increase in
at the edges of the crystals) triply coordinated to the di- the order, the samples prepared at pH 11.5 and 12 are
and trivalent cations [33]. If the various metals in the the most crystalline and the sample prepared at pH 6.5
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(a) (b)
-1
1361 cm
-1
1384 cm
Relative Intensity (a.u.)
-1
1359 cm
-1
1399 cm -1
1397 cm
1250 1300 1350 1400 1450 1500 1250 1300 1350 1400 1450 1500
-1 -1
Wavelength (cm ) Wavelength (cm )
(c)
-1
1423 cm
Relative Intensity (a.u.)
-1
1510 cm
-1
1384 cm
-1
1359 cm
exhibited similar carbonate infrared active stretching 3.3. The effect of hydrothermal treatment of Zn/Al–Ht
modes (samples 1, 2, 4–9, 12) also have comparable
bands in the Raman spectra. The samples show a peak at Two samples from the previous pH series were treated
553 cm1 assigned to the ‘‘Al-OH’’ translation mode as hydrothermally; one synthesized at the high pH with
well as a peak 500 cm1 that can be assigned to ‘‘Zn- good crystallinity (sample 9, pH 11.5) and the other
OH’’ or ‘‘Al-OH’’ translation modes, but is probably a at lower pH with poor crystallinity (sample 5, pH 9.5).
combination of both. Both these peaks have shoulders Fig. 1 shows that the two hydrothermally treated
that are too weak to accurately assign. Sample 3 shows samples (11 and 12) have different structures. Sample
no assignable peaks, consistent with XRD and IR, in this 11 appears to have lost all of the hydrotalcite structure
region. Sample 10 (pH414) shows the same peak at and is composed of one major crystalline phase, ZnO,
439 cm1 and is more intense and sharper that the former and two or even three other minor crystalline phases,
sample. Furthermore, this sample contains no peaks at containing various amounts of Zn2+, Al3+, CO2 3 , and
555 cm1 assigned to ‘‘Al-OH’’ as expected. OH. The minor phases are associated with the
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4054 J.T. Kloprogge et al. / Journal of Solid State Chemistry 177 (2004) 4047–4057
Table 2
Infrared frequencies and assignments of the various modes of vibrations between 1000 and 400 cm1 [48,49,51]
1 2 10 11 12 NO
3 CO2
3 Natural Gibbsite Hydrozincite Zincite Suggested
(pH 12) (pH 12) (pH 414) (HT) (HT) HT (Al(OH)3) (Zn5(CO3)2(OH)6) (ZnO) assignment
430 cm-1
785 cm-1
Relative Intensity (a.u.)
552 cm-1
12,hydrothermal
Relative Intensity (a.u.)
400 450 500 550 600 650 700 750 800 850 900 950 1000
Wavenumber (cm -1)
Fig. 7. Band component analysis of the lower frequency region, 10, pH > 14
between 1000 and 400 cm1, of the infrared spectrum of synthetic Zn/
Al hydrotalcite sample 2.
1, pH 12
electron diffraction pattern, and according to the STEM a ratio of 1:1. It is concluded that these particles grew as
is primarily composed of Zn and O. This phase is a result of the dissolution of the larger hexagonal-
assigned to the hydrozincite, even though carbon could shaped, crystalline phases. However, the contribution
not be observed, but the structure is different from the from this phase to the total sample is small as only a few
ZnO phase of sample 10 (pH 14). The next phase is crystals were observed.
structurally similar to the other ZnO phase observed The TGA/DTA of sample 12 is shown in Fig. 3. This
with elongated crystals that are rounded at the top. This sample exhibits similar thermal properties as the two
phase differs from the first phase in terms of the starting samples previously discussed. The primary
morphology; it is thinner and edges are rounded, and is difference between all these samples is the thermal
composed of Zn and O in a different ratio. This phase is stability. Sample 12 is the most thermally stable, where
assigned to ZnO. The third phase has a hexagonal shape all decomposition steps occur at higher temperatures
with a particle size of 77 nm across. The diffraction than for the other samples. Furthermore, this sample
pattern is strong and the STEM analysis revealed a confirms that the more crystalline samples are the most
ratio of Zn/Al of 2. The fourth phase is also highly thermally stable.
crystalline according to the diffraction pattern, The infrared spectrum of sample 11 is eminently
and particles have cubic-type morphology. The particle different from the hydrotalcite samples (Fig. 4, Table 2).
size is approximately the same as the hexagonal-shaped At high frequency (3000–4000 cm1), a broad feature
phase but smaller than the first two phases. This phase exists that is assigned to OH-stretching modes. At mid-
is quite common and appears to make up the bulk frequency, several bands are prominent that are assigned
of the sample, and is primarily composed of Al/Zn with to the presence of carbonate. Band component analysis
a ratio of 5/4. This was not expected since the XRD of this region shows the CO2 3 antisymmetric stretching
showed that no crystalline Al phase was likely to be modes are less superimposed, occurring at frequencies of
present. Although this cubic phase makes up the bulk of 1423 and 1510 cm1. These bands occur at different
the sample, the initial two ZnO phases are highly frequencies as they are not residing in the interlayer, as
crystalline and exhibit very strong diffraction patterns, with the hydrotalcites. Instead, it is assumed that
which probably suppress the diffraction of the smaller carbonate is present in a covalent metal-to-anion bond,
less crystalline phases. The final identifiable phase Zn–CO3, where the individual sites occupied by Zn, C
is a flat flaky structure, which exhibits a diffraction and O have symmetries C3I=S6, D3, and C2, respec-
pattern and is also a crystalline phase. The STEM tively [20,24]. It is also noticed that they occur at higher
reveals that this phase is composed of Zn, Al, C and frequencies; thus the carbonate species present in this
O in varying compositions, indicating a hydrotalcite-like sample is symmetric than those in the hydrotalcites. The
phase. band at 1384 cm1 is associated with the presence of
The TEM of sample 12 (Fig. 2d) showed large, flat nitrate. Furthermore, this sample shows another weak,
particles (260 nm) similar to those of the untreated broad, shoulder peak at 1359 cm1, which can be
samples. Although the morphology of most particles is assigned to a vibrational mode of hydrozincite, usually
fairly regular, there does appear to be another phase. found at 1340 cm1, which is consistent with previous
The predominant phase has a distorted hexagonal shape studies [51]. At lower frequency, sample 11 shows a
where some of the edges are rounded, similar to sample different pattern compared to all other samples. Band
9, indicating signs of dissolution during the hydrother- component analysis reveals numerous overlapping
mal treatment. The electron diffraction pattern shows a bands, where the predominant bands are associated
pattern stronger than sample 9. The STEM analysis with ‘‘ZnOH’’ translational modes (Table 2). Unlike
found a ratio of Zn/Al ratio of 2.5–3.2, compared to an sample 10 (pH414), also primarily composed of ZnO,
initial ratio of 2.6 in sample 9. The TEM also showed this sample shows CO2
3 and NO3 in-plane and out-of-
smaller crystals with a cubic morphology, on the plane bends (n4 and n2 ), that are associated with the
rounded surfaces of larger hexagonal-like crystals, hydrozincite phase, which lie at higher wavenumbers
which were too small for microanalyses. Thus, hydro- than for the hydrotalcites.
thermal treatment increases the crystallinity and allows The infrared spectrum of samples 12 (Fig. 4) is very
time for the classical hexagonal shape of the hydrotalcite similar to those of the other hydrotalcites, although
to form [2,54]. The presence of the smaller cubic-shaped there are several weak bands at low frequency that the
particles indicates that with aging predominant crystal other hydrotalcites do not show; these bands lie at a
growth occurs on the edges, resulting in relatively thin frequency associated with nitrate, 834 and 690 cm1.
hexagonal plate-shaped crystals with rounded edges. The primary difference between the spectra of these
These smaller particles are believed to be the initial hydrothermal samples and the untreated samples is in
stages of growth of a second phase that was found to be the intensity; such that sample 12 has more intense,
present. This second phase consisted of rounded sharper and better-resolved peaks than the starting
elongated crystals that are composed of Zn and O, in material, sample 9 (pH 11.5), and all other untreated
ARTICLE IN PRESS
4056 J.T. Kloprogge et al. / Journal of Solid State Chemistry 177 (2004) 4047–4057
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