Journal of Solid State Chemistry 203 (2013) 174–180

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Journal of Solid State Chemistry

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Intercalation and controlled release properties of vitamin C

intercalated layered double hydroxide
Xiaorui Gao a,b,c,n, Lixu Lei b, Dermot O'Hare c, Juan Xie a, Pengran Gao b, Tao Chang a
a
College of Science, Hebei University of Engineering, Handan 056038, China
b
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China
c
Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK

art ic l e i nf o a b s t r a c t

Article history: Two drug-inorganic composites involving vitamin C (VC) intercalated in Mg–Al and Mg–Fe layered double
Received 30 January 2013 hydroxides (LDHs) have been synthesized by the calcination–rehydration (reconstruction) method. Powder
Received in revised form X-ray diffraction (XRD), Fourier transform infrared (FTIR), and UV–vis absorption spectroscopy indicate a
4 April 2013
successful intercalation of VC into the interlayer galleries of the LDH host. Studies of VC release from the
Accepted 14 April 2013
LDHs in deionised water and in aqueous CO32− solutions imply that Mg3Al–VC LDH is a better controlled
Available online 22 April 2013
release system than Mg3Fe–VC LDH. Analysis of the release profiles using a number of kinetic models
Keywords: suggests a solution-dependent release mechanism, and a diffusion-controlled deintercalation mechanism
Layered double hydroxide in deionised water, but an ion exchange process in CO32− solution.
Controlled release
& 2013 Elsevier Inc. All rights reserved.
Vitamin C
Intercalation

1. Introduction such problems. These systems utilize carriers that slowly release
their contents in order to maintain drug concentrations at the
L-Ascorbic acid (vitamin C), a water soluble vitamin, has a desired levels for a longer period of time.
variety of biological, pharmaceutical and dermatological functions; Recently, biocompatible inorganic materials, such as layered
it promotes collagen biosynthesis, provides photoprotection, double hydroxides (LDHs), are being used in drug delivery and
causes melanin reduction, scavenges free radical, and enhances controlled release systems. These materials are more stable and less
the immunity (anti-viral effect) [1–6]. Moreover, vitamin C can toxic than conventional drug carriers [15,16]. LDH consists of
help to prevent scurvy, reduce the risk of cancers and cardiovas- positively charged hydrotalcite-like layer of metal hydroxide and
cular diseases [7,8], decrease low density lipoprotein (LDL) the interlayer region typically occupied by anionic species and water
cholesterol in the plasma of hyperlipidemia patients [9,10] and molecules. LDHs are a family of natural and synthetic compounds
enhance the absorption of iron to prevent anaemia [11]. having a general formula of [M1−xM′x(OH)2](An−)x/n·mH2O (abbre-
Vitamin C, however, is very unstable to air, moisture, light, heat, viated as M1−xM′x −A), where M and M′ represent divalent and
metal ions, and base, resulting in decomposition to biologically trivalent metal ions, respectively, and An− is the anion between the
inactive compounds [12,13]. To prevent the decomposition of vitamin layers. LDH can be prepared in laboratory using a range of different
C, delivering it to a specific location is very important. On the other techniques, for example coprecipitation [17–19], anion exchange
hand, human body requires only a very small amount of vitamin C [20,21] and reconstruction [22,23]. LDHs are well known for their
for physiological functions. Both insufficient and excessive supplies of anionic exchange properties and their stable structure, so have been
vitamin C cause harmful effects on human body [14]. Additionally, extensively studied, for instance as absorbents [24], photocatalysis
there are many cases where conventional drug administration [25], catalyst support [26], electrode materials [27], drug carriers [28–
methods do not provide satisfactory pharmacokinetic profiles 32], anion exchangers [33], optical materials [18,34].
because the drug concentration rapidly falls below desired levels. Several studies describing the intercalation and controlled
Therefore, a drug delivery and controlled release system is a more release of vitamin C in the layered double hydroxides have been
sophisticated drug administration method designed to overcome reported. For example, Kameshima et al. [35] synthesized Mg3Al–VC
LDHs by coprecipitation, anion exchange and reconstruction meth-
ods, respectively. The sample prepared using a reconstruction
n
Corresponding author at: College of Science, Hebei University of Engineering,
method shows the highest intercalation of vitamin C (30 wt%).
Handan 056038, China. Fax: +86 310 6022022. The deintercalation of vitamin C was carried out in HCl solution and
E-mail address: gxr_1320@sina.com (X. Gao). show that almost 40% of the intercalated vitamin C was released

0022-4596/$ - see front matter & 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jssc.2013.04.028
 X. Gao et al. / Journal of Solid State Chemistry 203 (2013) 174–180 175

after 60 min. Choy et al. [36] intercalated 23.1% vitamin C in the 2.5. Characterization
ZnAl LDH. The deintercalation of the ZnAl–VC LDH hybrid in an
aqueous CO32− solution resulted in about 50% vitamin C release. Carbon, hydrogen and nitrogen (CHN) analyses were carried out
Gasser et al. [37] used anion exchange method to intercalate by a Carlo Erba EA1108 Elemental Analyser, and metals analysis by
vitamin C in ZnFe–VC and MgFe–VC LDHs. The maximum amounts Fisons Horizon Inductively Coupled Plasma Optical Emission Spec-
of VC released are almost 40% and 50% of the total for ZnFe–VC and troscopy (ICP-OES). X-ray powder diffraction (XRD) patterns were
MgFe–VC, respectively. There are also several reports describing the recorded using a PANalytical X’pert Pro diffractometer, fitted with a
structure of vitamin C intercalated LDHs [38,39]. solid state X’Celerator detector. The diffractometer was operated
In these studies, the structural stability of vitamin C is improved with CuKα radiation (α1 ¼1.5406 Ǻ, α2 ¼1.5433 Ǻ, weighted
by intercalating it in the LDHs, but the amounts of vitamin C average¼ 1.5418 Ǻ) in reflection mode, at 40 kV and 40 mA. All
intercalated and then subsequently released are still not very high. the FTIR spectra were recorded on a Bio-Rad FTS 6000 FTIR
In this paper, we report the synthesis of two layered double Spectrometer equipped with a DuraSamplIR II diamond accessory
hydroxide materials, namely MgAl–VC and MgFe–VC LDHs using in attenuated total reflectance (ATR) mode in the range of 700–
the reconstruction method. Furthermore, the quantity and the 4000 cm−1; 100 scans at 4 cm−1 resolution were collected. The
kinetics of vitamin C release from the host materials were absorption in the range 2500–1667 cm−1 is from the DuraSamplIR
investigated. II diamond surface. Thermogravimetric analysis data were collected
using a Rhoemetric Scientific STA-1500H: 20 mg of sample was
heated in a corundum crucible between room temperature and
2. Experimental 700 1C at a rate of 10 1C min−1 under a flowing stream of argon.
UV–vis absorption spectroscopy was used to determine the content
2.1. Materials of vitamin C on a T60U PG Instruments UV–vis spectrophotometer
using wavelength scan mode and quartz cuvettes. The wavelength
The ascorbic acid (vitamin C), sodium ascorbate and other range used was from 190 nm to 400 nm.
inorganic reagents were purchased from Sigma-Aldrich and used
without further purification.
3. Results and discussion

2.2. Preparation of LDH hosts 3.1. Powder X-ray diffraction and elemental analysis

The pristine CO3–LDHs were synthesized by a standard copre- The XRD patterns for the pristine and LDH hybrids exhibit a
cipitation method. A base solution was prepared by dissolving series of (0 0 l; l ¼3, 6) Bragg reflections as shown in Fig. 1. The
20 mmol of Na2CO3 in 40 mL of deionised water. This solution was basal spacing of Mg3Al LDH and Mg3Fe LDH containing CO32− is
then added dropwise to 80 mL of a mixed salt solution prepared 7.6 Å, which is in good agreement with that of hydrotalcite
by dissolving 30 mmol of Mg(NO3)2
6H2O and 10 mmol of Al [40–42]. After calcination at 500 1C for 5 h, the layered structure
(NO3)3
9H2O (or Fe(NO3)3
9H2O) under vigorous stirring. The of LDH has been destroyed and new reflections due to periclase
solution pH was adjusted to 10 by dropwise addition of 1 M NaOH (MgO) are observed (Fig. 1b and e).
solution into the mixed solution. A suspension was formed and
aged at 80 1C for 24 h. The products were filtered, washed with
deionised water to remove any precursor impurities and with a
small amount of acetone to facilitate drying, and then dried at
60 1C for 24 h.

2.3. Preparation of VC–LDH intercalation compounds

The vitamin C intercalation products (Mg3Al–VC and Mg3Fe–VC

LDHs) were prepared by a reconstruction method. First, the oxide
precursors were prepared by the thermal decomposition of the
CO3–LDHs at 500 1C for 5 h in a muffle furnace to give. Then, 1 g of
oxide precursor was added to an aqueous solution (100 mL)
containing a fivefold excess of the sodium ascorbate under flowing
N2 (to prevent the formation of the carbonate intercalation). The
solution was stirred vigorously at 15 1C for 120 h, then filtered,
washed and dried as described above. The products were pale
yellow solids.

2.4. In vitro release studies

The release of the VC anions from their hosts was determined

by UV–vis spectroscopy. An amount of 0.1 g the VC–LDH composite
was added to 50 mL of either deionised water, or the carbonate
solutions with different concentration (0.1 M and 0.01 M), and
stirred at 15 1C. After the appropriate time, the suspension was
filtered, and the concentration of released VC in the filtrate Fig. 1. XRD patterns of solid products. (a) Mg3Al–CO3 LDH, (b) Mg3Al oxide
quantified using the UV–vis spectrophotometer at 265 nm, corre- precursor, (c) Mg3Al–VC LDH, (d) Mg3Fe–CO3 LDH, (e) Mg3Fe oxide precursor,
sponding to the typical absorption peak of vitamin C. (f) Mg3Fe–VC LDH.
176 X. Gao et al. / Journal of Solid State Chemistry 203 (2013) 174–180

The XRD patterns of solid products obtained by reconstruction According to ICP and CHN analysis data, the chemical formulas
method are shown in Fig. 1c and f. It is found that the (0 0 3) and of two VC–LDH are obtained (shown in Table 2). Based on the
(0 0 6) Bragg reflection shift to lower angles and become broader, formulas, the loadings of VC in the two VC–LDH compounds are
implying that the intercalation of VC decreases the crystallinity of expressed as a percentage of their maximum ion-exchange capa-
LDHs. The basal spacings are, respectively, expanded to be 9.6 Å and city. They are 45% and 34% for Mg3Al–VC and Mg3Fe–VC, respec-
8.9 Å for Mg3Al LDH and Mg3Fe LDH accompanied with the disap- tively. The Mg/Fe system exhibits the lower percentage loading.
pearance of periclase reflections, meaning that the Mg–Al and Mg–Fe The reason is possible that decreased interlayer separation asso-
oxide precursors were reconstructed the LDH structure by the ciated with intercalation of the VC guest molecule may lead to
rehydration reaction. The VC–LDH interlayer distances were calcu- strong interlayer bonding and small VC loading [39].
lated by subtracting the inorganic layer thickness (4.8 Å) [43] from
the d0 0 3-spacing. The determined values are, respectively, 4.8 Å and 3.2. FTIR characterization
4.1 Å. The layer distance is determined by the size and type of anions
[44]. The length and cross-sectional area of the ascorbate anion have Fig. 3 shows the FTIR spectra used to verify the intercalation of
been determined to be 4.9 Å and 21.6 Å2, respectively [45]. We the VC anion into each of the LDH host. In each case, the VC–LDH
speculated that for Mg3Al–VC, an antiparallel monolayer of anions spectrum is compared with that of sodium ascorbate (NaVC). The
nearly perpendicular to the metal hydroxide layers is adopted, broad peak centered at about 3400 cm−1 is characteristic of all LDHs
however, for Mg3Fe–VC, the furan ring has an angle of about 571 and arises from the νOH absorptions of the co-intercalated water
with one basal layer, with the terminal hydroxyl group hydrogen molecules. Absorptions occurring below 1000 cm−1 are associated
bonded to another basal layer. The schemes are shown in Fig. 2. with metal–oxygen vibrations within the hydroxide layers. In the
The lattice parameters of the pristine and LDH hybrids are spectrum of solid NaVC (Fig. 3a), the peaks relating to O–H and C–O
calculated from the relations of c ¼3d0 0 3 and a ¼2d1 1 0 (Table 1). bonds stretches are found in the expected regions. The most
The a-lattice parameters are not observed to change substantially diagnostic absorptions are those occurring at 1362–1364 cm−1 and
upon intercalation, as it is independent of the interlayer separa- 1627–1630 cm−1 corresponding to vibrations within the lactone
tion. However, c-lattice parameters increase after the intercalation linkage (C–O–C) and of the carbonyl group (C¼O), respectively
of VC, which is related to the size of gallery species and their [35,46]. These absorptions, whilst shifted to slightly higher wave-
configuration between the layers [36]. So, it can be seen that the numbers possibly due to weakening of intramolecular H-bonds
calculated lattice parameters also confirm that intercalation leads upon intercalation, are present in Mg3Al–VC and Mg3Fe–VC. The
to a simple layer expansion almost without any effects on the characteristic VC peaks in the FTIR spectrum of Mg3Fe–VC are
hydroxide lattice. weaker than that of Mg3Al–VC. This is consistent with the elemental
analysis data that suggested a lower loading percentage. The FTIR
data likewise confirm the VC anions have been intercalated in the
interlayer.

3.3. Thermogravimetric analysis

The intercalation products were analysed by TGA and DTG to

determine the intercalated water content and the decomposition
temperature of VC in VC–LDHs and NaVC. Three samples TGA straight
lines, for the Mg3Al–VC (a), Mg3Fe–VC (b), VC (c), Mg3Al–CO3 (d) and
Mg3Fe–CO3 (e) are shown in Fig. 4. These compounds decompose by
the well-established route observed for most LDHs intercalated with
organic molecules. In the first step, the co-intercalated water is lost at
temperatures up to 150 1C, leaving a dehydrated LDH (calculated loss
3.9%/8.7%, observed loss 4.0%/7.9% for Mg3Al–VC and Mg3Fe–VC,
respectively). This is then followed by the loss of water from the
hydroxide layers and interlayers, and the decomposition of the VC
anion in consecutive steps between 200 1C and 500 1C. The final
product is a mixture of magnesium and aluminium (or iron) oxides
[47], and carbon soot (calcd. 60.5%/61.2%, obsvd. 54.6%/59.2% for
Mg3Al–VC and Mg3Fe–VC, respectively).
For Mg3Al–CO3 and Mg3Fe–CO3, the first step, up to 200 1C,
corresponds to removal of water physisorbed on the external
surface of the crystallites as well as water intercalated in the
Fig. 2. Schematic illustrations of VC–LDHs. (a) Mg3Al–VC and (b) Mg3Fe–VC. interlayer galleries and corresponds to up to 15% of the total weight
of the samples. The corresponding strongest water loss peaks occur
at around 200 1C for Mg3Al–CO3 and 163 1C for Mg3Fe–CO3, respec-
Table 1 tively, which is higher than those of Mg3Al–VC and Mg3Fe–VC. This
The interlayer spacings, and lattice parameters of CO3–LDHs and VC–LDHs. implies that water molecules are more strongly hydrogen bonded to
carbonate anions in the interlayer region than it is to VC anions due
Sample d(0 0 3) (Å) d(1 1 0)(Å) Lattice parameter
to bigger interlayer spacing [48]. The second weight loss step for
a/Å c/Å Mg3Al–CO3 and Mg3Fe–CO3 is the dehydroxylation of layers and loss
of carbonate anions, corresponding endothermic event at around
Mg3Al–CO3 7.6 1.51 3.02 22.8 400 1C and 368 1C, respectively.
Mg3Al–VC 9.6 1.50 3.00 28.8 In addition, from the DTG data (dash lines in Fig. 4a–c), the
Mg3Fe–CO3 7.6 1.53 3.06 22.8
Mg3Fe–VC 8.9 1.50 3.00 26.7
decomposition of intercalated VC occurs at elevated temperatures,
423 1C and 400 1C for Mg3Al–VC and Mg3Fe–VC, respectively; however,
 X. Gao et al. / Journal of Solid State Chemistry 203 (2013) 174–180 177

Table 2
Chemical compositions of VC–LDH.

Sample Elemental contents/wt% obs. (Calc.) Chemical formula

Mg Fe Al C H

Mg3Al–VC 21.5 (21.4) 8.02 (8.03) 9.65 (9.64) 3.89 (3.91) Mg3Al(OH)8[(C6H7O6)0.45(OH)0.55]
0.73H2O
Mg3Fe–VC 19.7 (19.6) 15.4 (15.3) 6.66 (6.68) 3.97 (3.98) Mg3Fe(OH)8[(C6H7O6)0.34(OH)0.66]
1.77H2O

Fig. 3. FTIR spectra of NaVC (a), Mg3Al–VC (b) and Mg3Fe–VC (c).

for the VC sample, decomposition temperature is about 230 1C. It

implies that intercalating VC in the LDH can improve the thermal
stability of VC.

3.4. Controlled release data

The solid state UV–vis absorption spectrum of VC exhibits a

characteristic absorption band in the range of 235–300 nm (Fig. 5).
This band is attributed to the π-π* (enone) transition for VC. The
absorption maximum of VC at 265 nm in water arises from depro-
tonation of ascorbic acid to ascorbate at pH 7 [49]. No significant
differences are found between vitamin C and the VC–LDH hybrids.
Deintercalation of the VC–LDH hybrids were carried out in
deionised water and Na2CO3 aqueous solutions at two different
concentrations (0.1 M and 0.01 M) for time intervals of up to
420 min. After the required time interval, the product was filtered,
and the UV–vis absorption spectra of the filtrate collected were
tested. The concentrations (wt%) of deintercalated VC were esti-
mated by the characteristic absorption peaks at 265 in the UV–vis
spectra of VC, respectively. The amount of deintercalated VC
plotted with reaction time is depicted in Fig. 6.
All the VC release curves (Fig. 6a–c) show the broadly similar
features. Mg3Al–VC and Mg3Fe–VC have high initial VC release
rates. For the different LDH system and deintercalation medium,
the amounts of VC release are different. The release processes in
CO32− solutions are uniformly found to lead to greater release after
420 min than the corresponding reactions in deionised water,
which is consistent with previously observed data on the release
of some drugs from a hydrotalcite-like compound [20].
Similar to the release of other drugs from pillared LDH [50], the
rapid release of the intercalated material during the initial stage is Fig. 4. TGA and DTG plots of (a) Mg3Al–VC, (b) Mg3Fe–VC, (c) ascorbic acid (VC),
followed by a slow release of some or all of remaining drug. (d) Mg3Al–CO3 and (e) Mg3Fe–CO3.
The release profile of Mg3Al–VC and MgFe–VC show a high initial
VC release rate in the initial 30 min or 35 min, and reaches an 300 min in deionized water. The maximum amount of VC released
almost constant level after 120 min or 180 min in 0.1 M and 0.01 M is almost 68%, 60% and 36% of the total for Mg3Al–VC, and 58%, 50%
Na2CO3 solutions, respectively, and very slow release rate after and 22% of the total for MgFe–VC, in 0.1 M, 0.01 M Na2CO3
178 X. Gao et al. / Journal of Solid State Chemistry 203 (2013) 174–180

studies [36], for Mg3Al and Mg3Fe LDHs system, the amounts of VC
released in the Na2CO3 medium are higher, and can improve the
availability of VC as a drug.
The rate of drug diffusion out of the matrix is controlled by the
rigidity of the layers and the diffusion path length [50]. In contrast
to the release of other drugs from intercalated LDH materials
reported in the literature [51], the release of VC from intercalated
LDH materials prepared in this work is not complete. The cause of
the partial release may be attributed to the possibility that the
drug molecules are deeply embedded in the LDH host and
complete release is very slow, especially for Mg3Fe–VC, the smaller
interlayer space may lead to stronger interaction between the VC
anions and the host layers, then affect the diffusion of VC anions
from the interlayer of LDH. On the other hand, this reason could be
also explained by its rapid degradation into 2,3-diketo-L-gulonic
acid, oxalic acid, L-threonic acid, CO2, L-xylonic acid and L-lyxonic
acid in the presence of dissolved O2 [52,53].
Fig. 5. UV–vis absorption spectra of sodium ascorbate (NaVC), Mg3Al–VC and
Mg3Fe–VC. 3.5. Kinetic analysis

In order to gain more insight into the kinetics of the release, we

applied five commonly used models to the release curves. Models
used are the Avrami–Erofe’ev Eq. (i), the Elovich model (ii), first-
order rate model (iii), the modified Freundlich Eq. (iv) and a
parabolic diffusion model (v) [54–58]:
lnð–lnð1–αÞÞ ¼ nlnðkd Þ þ nlnðtÞ ðiÞ

1–C t =C 0 ¼ alnðtÞ þ b ðiiÞ

lnðC t =C 0 Þ ¼ –kd t ðiiiÞ

lnð1–C t =C 0 Þ ¼ lnðkd Þ þ alnðtÞ ðivÞ

ð1–C t =C 0 Þ=t ¼ kd t ð–0:5Þ þ a ðvÞ

In each model, C0 is the amount of guest VC in the VC–LDH at
t¼0, Ct is the amount of guest VC in the VC–LDH at time t, and kd is
the rate of release. a, b, and n are constants. α is the extent of
reaction. Fits of the models to the experimental release data in
initial release stage (within 30 min in sodium carbonate and
180 min in deionised water, respectively) are shown in Fig. 7.
It can be seen from Fig. 7 that all models can be used to describe
the kinetic of release of VC except for the parabolic diffusion model.
The parameters extracted from the four effective fitting of the
kinetic models are show in Table 3. In these models, according to
the R2 values and visual inspection of these “linear” plots, it appears
that the Avrami-Erofe’ev model is the most appropriate for describ-
ing release of VC. The Avrami-Erofe’ev model considers the release
as a sequence of nucleation and growth steps, in which α is the
extent of reaction (α¼0 at initiation and α¼1 at completion of the
reaction, namely, α¼1−Ct/C0). This mathematical model has been
applied to a number of intercalation and deintercalation reactions
[59,60]. The values of n may be determined from the slope of the
fitted plots. Usually, n is close to zero or one, with zero representing
instantaneous nucleation. However, the final value may also repre-
sent more than one possible mechanism, the identity of which may
not be easily determined.
The values of n in deionised water for Mg3Al–VC and Mg3Fe–VC
are 0.7 and 0.6, respectively, which corresponds to the mainly
diffusion control. The deintercalation processes of VC from Mg3Al–
VC and Mg3Fe–VC could include ion exchange with residual CO32−
Fig. 6. Release profiles between 0 min and 420 min of Mg3Al–VC and Mg3Fe–VC in ions in the water, or simultaneous leaching of the guest anions and
(a) 0.1 M CO32− solution (b) 0.01 M CO32− solution (c) deionised water. cations from the LDH matrix [20]. In contrast, the process in
sodium carbonate seems to be dominated by a direct ion-exchange
solutions and deionized water, respectively. These indicate that route because the values of n tend to be closer to 1.0. Moreover, as
Mg3Al LDH is a better system than Mg3Fe–VC with higher release the concentration of CO32− ions is higher; the release of VC is
amount and release rate. Moreover, compared with the previous quicker than in deionised water.
 X. Gao et al. / Journal of Solid State Chemistry 203 (2013) 174–180 179

Fig. 7. Linear fitting of various models to the release of VC from Mg3Al–VC and Mg3Fe–VC in (a) 0.1 M sodium carbonate, (b) 0.01 M sodium carbonate and (c) deionised
water. Fits for (i) the Avrami-Erofe’ev model, (ii) the Elovich model, (iii) the First-Order model, (iv) the Freundlich model, and (v) the parabolic diffusion model, are shown.

4. Conclusions characterized by powder XRD, FTIR, elemental analysis, thermogravi-

metric analysis and UV–vis spectra. They release the intercalated VC
Two vitamin C intercalated LDH hybrids (Mg3Al–VC and Mg3 gradually upon stirring in either deionised water or 0.1 M and 0.01 M
Fe–VC LDHs) have been synthesized by a reconstruction method and aqueous CO32− solutions. In the three release media, Mg3Al–VC LDH
180 X. Gao et al. / Journal of Solid State Chemistry 203 (2013) 174–180

Table 3
Parameters extracted from the four fitting of the kinetic models.

Release medium Fitted model Parameters

kd (  10−3) n a b

Mg/Al Mg/Fe Mg/Al Mg/Fe Mg/Al Mg/Fe Mg/Al Mg/Fe

0.1 M Na2CO3 Avrami 14.0 7.0 1.2 1.3

Elovich 0.19 0.15 −0.18 −0.16
First-order 26.2 17.9
Freundlich 15.9 7.7 1.1 1.2
0.01 M Na2CO3 Avrami 8.7 5.4 1.2 1.2
Elovich 0.13 0.09 −0.10 −0.09
First-order 14.5 10.3
Freundlich 9.3 5.7 1.1 1.2
Deionized water Avrami 9.1 7.9 0.7 0.6
Elovich 0.10 0.05 −0.24 −0.11
First-order 1.8 0.8
Freundlich 10.5 8.4 0.67 0.59

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