Applied Clay Science 65-66 (2012) 121–127

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Applied Clay Science

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Research paper

Efficient decarbonation of carbonate-type layered double hydroxide (CO32−LDH) by

ammonium salts in alcohol medium
Nobuo Iyi ⁎, Hirohisa Yamada
National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, Ibaraki 305-0044, Japan

a r t i c l e i n f o a b s t r a c t

Article history: The deintercalation of carbonate ion (decarbonation) from CO32−LDH (Mg/Al = 3) was conducted in alcohols
Received 28 February 2012 at room temperature (20–25 °C) under N2 flow using ammonium salts, such as the hydrochloride (HC) salts
Received in revised form 30 April 2012 of various amines, with pKa values between 0 and 14. These salts were expected to function as proton sources
Accepted 3 May 2012
in the conversion of CO32− into CO2 during decarbonation. When using equivalent amounts of HCs with
Available online 21 July 2012
pKa = 1–8 (medium acidity), CO32−LDH was successfully decarbonated in methanol after 2 h with the release
Keywords:
of CO2 to yield Cl −LDHs containing b5% residual CO32−. For HCs with higher pKa values (8–11; weak acidity),
LDH three times the amount of HCs were needed to obtain LDHs with b5% remaining CO32−. For a salt with
Layered double hydroxide pKa > 11, no appreciable CO2 evolution was observed and the remaining CO32− in the product was about
Deintercalation of carbonate 70% even when six equivalents of the HC were used. Thus, decarbonation behavior in alcohol depended on
Ammonium salt salt pKa values, and efficient decarbonation was observed for ammonium salts with pKa ≤ 11. Ammonium
pKa salts of organic acids were also useful for the incorporation of their conjugate bases into the LDHs. Increased
temperature was very effective in reducing the residual CO32−.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Layered double hydroxides (LDHs) are interesting inorganic layered
materials related to the mineral hydrotalcite (Mg3Al(OH)8(CO32−)1/2·
2H2O), composed of brucite-like metal hydroxide layers and interlayer
anions (Braterman et al., 2004; Cavani et al., 1991; Miyata, 1975). Re-
cently, attention has been focused on the application of LDHs to DDSs
(drug delivery systems) (Choy et al., 1999; Nakayama et al., 2003)
and nanolayered composites formed through layer-by-layer (LbL) stac-
king (Li et al., 2006; Liu et al., 2006). Among the LDHs containing various
anions, CO32−LDH is the most frequently prepared on an industrial basis,
and highly crystalline LDHs containing interlayer carbonate ions (CO32−)
can be easily prepared (Okamoto et al., 2007; Reichle, 1986). However,
because of the high affinity of CO32− for LDHs, it is very difficult to
deintercalate CO32− by conventional anion exchange (Miyata, 1983).
Considering that most prepared LDHs are of the CO32−-type, decarbon-
ation, i.e., conversion of CO32− LDHs into LDHs containing other anions
with the concomitant release of CO32− or CO2, is an important process
in LDH chemistry.
One of the promising decarbonation methods uses acids. Historically,
mineral acids such as HCl were used for the decarbonation of CO32−LDHs
as aqueous solutions (Bish, 1980; Bish and Brindley, 1977) or as gas
(Costantino et al., 1998). However, the LDH layer itself tended to dis-
solve in highly acidic environments and appreciable weight loss would
⁎ Corresponding author. Fax: + 81 298 52 7449.
E-mail address: iyi.nobuo@nims.go.jp (N. Iyi).
occur during complete decarbonation. It was reported that the addition
of Cl− anion to aqueous solution of the inorganic acid (HCl) enhanced
the decarbonation reaction (Hines et al., 2000; Iyi and Sasaki, 2008a;
Iyi et al., 2004) and resulted in optimum conditions for complete decar-
bonation without any weight loss or shape change (Iyi et al., 2004). Sub-
sequently, to control the acidity, we used an acetate buffer solution in
place of HCl (Iyi and Sasaki, 2008b). The acetate buffer, which is com-
posed of acetic acid and sodium acetate, was expected to supply protons
for conversion of CO32− into CO2. In fact, it was shown that decarbonation
was more efficiently conducted by using acetate-buffer under N2 flow
(Iyi and Yamada, 2010).
Recently, decarbonations in non-aqueous media have attracted at-
tention: anion-exchange in hot glycerol (Hansen and Taylor, 1991), de-
carbonation using a DMF–ethanol mixture (Gordijo et al., 2007), and
direct replacement of CO32−LDH carbonate ion by carboxylate in 1-
propanol/toluene mixed solvent containing a dicarboxylic acid under
solvothermal conditions (Lee et al., 2003) have been reported. Hayashi
and Nakayama (2011) published an important paper describing the
anion exchange of CO32−LDH in methanol solutions of NaCl and NaNO3
at 50 °C, and highlighted the importance of solvent in decarbonation re-
action. These results implied that alcohol acted as a proton source at
high temperature, as already suggested by Hansen and Taylor (1991).
Subsequently, for more effective decarbonation of CO32−LDHs in alcohol,
we used mineral acids as the proton sources and observed that decar-
bonation was completed at room temperature within 0.5–1 h (Iyi et
al., 2011b). We noted that quantitative reaction occurred in alcohol, un-
like the aqueous system. These results indicated that the use of alcohol
was advantageous for the decarbonation of LDHs, and the acidity of

0169-1317/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2012.05.001
122 N. Iyi, H. Yamada / Applied Clay Science 65-66 (2012) 121–127
the proton source is the key to control the decarbonation reaction
(Yamada et al., 2011).
In this study, the effect of the acidity of the proton source on the de-
carbonation of LDHs in alcohol medium was investigated using reagents
with varying acidities, with the aim of controlling the decarbonation be-
havior. As pKa is one of the indexes which represents the proton-
supplying ability, we have chosen acidic compounds which have pKa
values intermediate between the mineral acids (pKab 0) and alcohols
(pKa= 15–17). These are the salts derived from ammonia, amines,
and other organic nitrogen compounds, for which “ammonium salts”
is used as a general term in this paper. These ammonium salts contain
anions to be incorporated in the LDH interlayer as well as protonated ni-
trogen cations which act as the proton source. Although the pKa values
used in this study were for aqueous solutions, there were significant
relationships between decarbonation behavior and the pKa value of
the HC salt. In this paper, the decarbonation behavior of LDHs in alco-
hols in the presence of ammonium salts under various reaction condi-
tions – amount of salt, reaction temperature, reaction time, etc. – will
be presented.
2. Experimental
In this study, LDH with Mg/Al = 3 was used. The formula used for
calculating the molecular weight was Mg3Al(OH)8(Xn−)1/n·2H2O. Here,
Xn− = n-valent anions. In this formula, Al was fixed to unity. The expres-
sion Xn−LDH denotes an LDH containing the n-valent anion (Xn−) in the
interlayer space.
2.1. Materials and reagents
The initial CO32−LDH (Mg/Al = 3) was commercially available
(DHT-6, Kyowa Kagaku Kogyo Co., Ltd.). The ammonium salts, mostly
of the hydrochloride form (abbreviated as HC), used in this study as pro-
ton sources were: (1) diphenylamine HC, (2) methylsulfonylaniline HC,
(3) m-chloroaniline HC, (4) 1-naphthylamine HC, (5) aniline HC, (6)
methoxyamine HC, (7) N,O-dimethylhydroxylamine HC, (8) phenylhy-
drazine HC, (9) pyridine HC, (10) N-methylhydroxylamine HC, (11) hy-
droxylamine HC, (12) N,N-diethylaniline, (13) N-methylmorpholine HC,
(14) triethanolamine HC, (15) hydrazine HC, (16) morpholine HC, (17)
diethanolamine HC, (18) ammonium chloride, (19) benzylamine HC,
(20) ethanolamine HC, (21) trimethylamine HC, (22) methylamine HC,
(23) ethylamine HC, (24) dimethylamine HC, (25) triethylamine HC,
(26) diethylamine HC, and (27) guanidine HC. These 27 HC salts are
listed in Table S1 of the Supporting Information (SI) with the same num-
bering, which contains detailed information about pKa values (Albert et
al., 1948; Bissot et al., 1957; Braude and Nachod, 1955; Conant and
Bartlett, 1932; Eicher et al., 2003; Hall, 1957; Nihon-Kagakukai, 1993),
sourcing, and toxicity.
Other ammonium salts used were ammonium perchlorate (NH4ClO4)
and ammonium nitrate (NH4NO3) (Kanto Chemical Co. Ltd. (Cica)). The
salts used for comparative experiments were KCl, NaCl, LiCl, and
tetramethylammonium chloride (Cica). Ammonium salts of organic
acids were ammonium acetate (CH3COONH4, abbreviated as AcONH4)
and ammonium isethionate (HO(CH2)2SO3NH4, abbreviated as IseNH4).
Sodium acetate and sodium isethionate were also used for comparative
experiments. Methanol and ethanol were used as alcohol solvents.
Other reagents used were: acetone, HCl (0.1 M; in ethanol), HClO4
(60%; in water), and Na2CO3. These reagents were purchased from
Kanto Chemical Co., Ltd. (Cica), and used without further purification.
2.2. Decarbonation procedure
To express the amount of ammonium salts used for decarbonation,
the mole ratio (f) of the salt to the CO32− in the LDH was used (f=
[salt]/(2×[CO32−])). The ratio, f=1, indicates the amount of ammonium
salt which has the potential to release the equivalent amount of proton
to convert all the CO32− in an LDH into CO2.
A typical decarbonation process was as follows.
To a suspension of CO32−LDH with Mg/Al = 3 (100 mg; 0.331 mmol
based on the formula; the amount of CO32− = 0.166 mmol) in 40 mL
alcohol, a solution of HC (f = 1; 0.331 mmol) in 10 mL alcohol was
added dropwise (≤1.0 min) with vigorous stirring under N2 flow
(0.5 L·min− 1). The mixed suspension was stirred at room temperature
(20–25 °C) under N2 flow for 2 h. The resulting suspension was filtered
through a membrane filter with a pore size of 0.2 μm (Millipore®),
washed with alcohol, and vacuum-dried. The filtration was conducted
under N2 flow. Depending on the solubility of the salts in alcohol, the
volume of alcohol used for preparing the HC solution was adjusted up
to 20 mL while the total volume of alcohol used was kept constant at
50 mL.
The CO2 concentration in the N2 outlet (Testo-535 CO2 meter, Testo
AG, Germany) was monitored after complete addition of the HC solution,
which allowed assessment of the reaction rate. The weight recovery was
measured in order to monitor the dissolution of the host LDHs.
2.3. Characterization techniques
For the determination of the carbonate content in the product, FT-IR
absorbance data were used to derive the CO32− content as previously
described (Iyi et al., 2004). For LDH containing NO3−, a C (carbon)
analysis was conducted using a LECO CS-444LS apparatus to determine
the remaining CO32− because of overlapping of characteristic absorption
bands of CO32− and NO3− in the FT-IR profile (Iyi et al., 2009). The CO32−
content in the product was expressed in % ratio relative to that of the
initial CO32−LDH. The FT-IR transmittance spectra were recorded using
a Perkin-Elmer 1600 FT-IR spectrometer at room temperature in the
wavenumber range from 4000 to 450 cm− 1 (KBr pellet).
Powder X-ray diffraction (PXRD) of the products was conducted at
a scanning speed of 2θ = 2°/min using a RINT 1200 (Rigaku Co., Ltd.) dif-
fractometer with Ni-filtered CuKα radiation (λ = 0.15418 nm). The
measurement was conducted at 25 °C in N2 atmosphere with control
of relative humidity (RH) by using an RH-controlled atmosphere suppli-
er (SHINYEI SRG-1R-1, Japan). The basal spacing corresponds to the d003
for the unit cell, which is the c-value of the subcell containing one inter-
layer space and one third of that of the hydrotalcite unit cell.
3. Results and discussion
3.1. Decarbonation of CO32−LDH
3.1.1. CO32−LDH/ammonium HCs
Decarbonation of CO32−LDH was conducted in alcohol at room tem-
perature (20–25 °C) for 2 h under N2 flow as described in Section 2.2.
Methanol was used as the solvent in this experiment because HCs gen-
erally show better solubility in methanol than in ethanol. The salts listed
in Table S1 of SI (Supplementary Information) were used in quantities
of f = 1 and 3. The obtained products were confirmed to be Cl−LDH
with different amounts of residual (or remaining) CO32− on the basis
of the FT-IR and XRD data. The completely decarbonated LDH showed
the d003 = 0.797 nm at 60% RH, which is consistent with the reported
value for Cl−LDH with Mg/Al= 3 (0.798 nm; Iyi et al., 2007). The con-
tent of CO32−, i.e. the amount of remaining CO32−, in the decarbonated
product is plotted against pKa values in Fig. 1.
For f = 1, the residual CO32− was less than 5% for the HCs with
pKa b 8. For HCs with pKa > 8, the amount of remaining CO32− increased
sharply up to 70% as the pKa value increased, though there was an ex-
ception with trimethylamine HC (pKa= 9.7), as indicated in the figure.
Guanidine HC (pKa= 13.71) resulted in 72% remaining CO32−.
When excess HC was used (f = 3), the residual CO32− decreased to
b5% for HCs with pKab 11. Since pKa values around 10.6–11.0 constitute
the border region, some anomalies were observed in this vicinity: For
 N. Iyi, H. Yamada / Applied Clay Science 65-66 (2012) 121–127 123

100 100 100

Carbonate content (%)

80 80 80

Carbonate content (%)

Weight (%)
60
(a) 60 60
f=1 (b)
40 f=3
40 40

20
*

0
0 2 4 6
pKa
Fig. 1. Carbonate (CO32−) content relative to that of the initial CO32−LDH. The content
(%) is plotted against the pKa values of the hydrochloride (HC) salts (Table S1 in SI)
for the salt quantities (a) f = [HC]/ (2× [CO32−])= 1 (filled circles), and (b) f = 3 (hollow
squares). The reaction was conducted in methanol at room temperature (20–25 °C)
under N2 flow. The quantity f = 1 indicates an equivalent amount. The asterisk (*) indi-
cates the point for trimethylamine HC.
diethylamine HC (pKa= 10.98), the residual CO32− was 8%. However, in
the cases of ethylamine HC (pKa = 10.63) and methylamine HC
(pKa= 10.62), which have lower pKa values than diethylamine HC,
the residual CO32− contents were found to be 33% and 32%, respectively.
For guanidine HC, which has a larger pKa value, the remaining CO32− was
observed to be about 74%, even if excess salt amounts (f = 3) were ap-
plied. In the case of guanidine HC, no CO2 evolution was detected, and
it was the same even if the salt amount was increased up to f = 6.
For further investigation into the effects of excess salt amounts on
the weight and remaining CO32−, the amount of salt was varied up to
f = 6. The weight and content of the remaining CO32− were plotted for
diphenylamine HC (pKa= 0.78) in Fig. 2, methoxyamine HC
(pKa= 4.60) in Fig. 3, dimethylamine HC (pKa= 10.64) in Fig. 4, and
guanidine HC (pKa= 13.71) in Fig. 5. By increasing the amount of the
salt, the weight decreased for diphenylamine HC: at f = 6, the weight
was 73% of the initial weight (Fig. 2). This behavior is similar to that ob-
served for the experiments using mineral acids in alcohols (Iyi et al.,
2011b). However, for the other HCs, no significant weight decreases
were detected (Figs. 3–5). For these HCs, the powder XRD profiles of
the products are shown in Fig. S2-1 (SI); the FT-IR spectra are in Figs.
S2-2 and S2-3 (SI). The XRD profiles indicate that the layered structure
was not changed by the decarbonation operation. The XRD and FT‐IR
profiles for the completely decarbonated products are similar to those
of Cl−LDH3. The carbonate contents expected from the FT‐IR profiles
are consistent with the basal spacings derived from the XRD profiles.
100
20 20
8 10 12 14
0 0
0 1 2 3 4 5 6
Amount of methoxyamine HC (f )
Fig. 3. The CO32− content (%) and weight of the product (%) relative to those of the ini-
tial CO32−LDH plotted against the amount of methoxyamine HC (pKa = 4.60).
The decarbonation behavior can be classified into four groups
according to the pKa value of the HC salt. The four salts mentioned
above are representative of the decarbonation behavior of each group:
[1] Group 1, pKa b 1: quantitative decarbonation occurred and ex-
cess salt caused weight loss due to dissolution of LDH layers.
[2] Group 2, pKa = 1–8: quantitative decarbonation occurred. Even
if excess salt was used, no significant weight loss was observed.
[3] Group 3, pKa = 8–11: decarbonation occurred, but excess salt
(f = 3–6) was needed. Excess salt did not cause any significant
weight loss.
[4] Group 4, pKa > 11: decarbonation was very limited, even if ex-
cess salt (f = 6) was used.
These behaviors were observed for reactions conducted at room
temperature. As will be mentioned, higher reaction temperatures
lead to decreases in the remaining CO32− in the products.
The change in the CO2 concentration in the outlet N2 gas is shown
in Fig. 6 for the reaction using methoxyamine HC (f = 1). Similar CO2-
evolution behavior was observed when other HCs with pKa ≤ 11 were
used.
Comparative experiments were conducted in which salts having
no proton-supplying ability, such as NaCl, KCl, LiCl, and (CH3)4NCl,
were used. The results showed that, even if the amount of salt was in-
creased up to f = 6, about 70–85% of the CO32− remained (see Fig. S3
in SI).
To explore the effect of the solvent, degassed water was used in place
of methanol, with methoxyamine HC (Group 2) and trimethylamine HC
(Group 3). The salt amount was f =8, and the reaction time was 3 h, at
100
100 100

80 80
Carbonate content (%)

Carbonate content (%)

80 80
Weight (%)

60 60
Weight (%)

60 60

40 40
40 40

20 20
20 20

0 0
0 1 2 3 4 5 6 0 0
Amount of diphenylamine HC (f ) 0 1 2 3 4 5 6
Amount of dimethylamine HC (f )
Fig. 2. The CO32− content (%) and weight of the product (%) relative to those of the ini-
tial CO32−LDH plotted against the amount of diphenylamine HC (pKa = 0.78) for the de- Fig. 4. The CO32− content (%) and weight of the product (%) relative to those of the ini-
carbonation reaction in methanol at room temperature. tial CO32−LDH plotted against the amount of dimethylamine HC (pKa = 10.64).
124 N. Iyi, H. Yamada / Applied Clay Science 65-66 (2012) 121–127
100
80
Carbonate content (%)
60
40
20
0 0
0 1 2 3 4 5
Amount of guanidine HC (f )
Fig. 5. The CO32− content (%) and weight of the product (%) relative to those of the ini-
tial CO32−LDH plotted against the amount of guanidine HC (pKa = 13.71).
room temperature under N2 flow. For methoxyamine HC in water, in-
deed, no remaining CO32− was observed in the LDH; however, the weight
of the product decreased to 67%. On the other hand, for trimethylamine
HC in water, the residual CO32− content was as much as 78%, though no
weight loss was observed. When methanol was used under the same
conditions, complete decarbonation without any weight loss occurred
in both cases. Thus, in alcohol, LDH dissolution is suppressed and decar-
bonation is enhanced compared with an aqueous medium.
3.1.2. CO32−LDH/NH4+ salts
NH4+ salts with various counter ions (NH4Cl, NH4ClO4, and NH4NO3)
were used to investigate the incorporation of ClO4− and NO3− anions as
well as Cl−. The pKa value of NH4+ is 9.24, which corresponds to
Group 3 (vide ante).
The experiments were conducted as described in Section 2.2. The
CO2 concentration of the outlet gas reached a peak 2–5 min after addi-
tion of the methanolic NH4+ salt; however, the decrease in the concen-
tration was rather slow and 1.5 h was required until no significant
CO2 evolution was detected.
As for the amount of the salt, f = 1 was not enough for full decar-
bonation in the case of NH4+ salts as already mentioned. Therefore,
the amount of added NH4+ salt was varied up to f = 6, and the
remaining CO32− was determined. Fig. 7 shows the content of residual
CO32− (%) plotted against the amount of ammonium salt (f), together
with the weight (%). The remaining CO32− decreased as the amount of
the salt increased, and at f = 2–3, the remaining amount was 3–5% for
both NH4Cl and NH4ClO4, and about 12% for NH4NO3. However,
CO2 concentration
200 ppm
0 10 20 30 40 50
Time (min)
Fig. 6. Time-dependent change in the CO2 concentration of the outlet N2 gas for the de-
carbonation reaction in methanol at RT under N2 flow using methoxyamine HC (f = 1).
100
NH4ClO4 120
Carbonate content (%)
80 100 100
NH4NO3
Weight (%)
Weight (%)
NH4Cl
80 80
60
60 60
40 NH4Cl
40 40
NH4ClO4
20 20 20
NH4NO3
0 0
0 1 2 3 4 5 6
6
Amount of ammonium salt (f )
Fig. 7. The CO32− content (%) and weight of the product (%) relative to those of the ini-
tial CO32−LDH plotted against the amount (f) of the ammonium salts NH4Cl, NH4ClO4,
and NH4NO3 (pKa value for NH4+ = 9.24).
adding salt up to f = 6 caused no change in the remaining CO32−
amount. The powder XRD profiles and FT-IR spectra of the products
after treated with NH4Cl, NH4ClO4, and NH4NO3 (f = 4) are shown in
Figs.S4-1 and S4-2 (SI), respectively. These XRD profiles and FT-IR
spectra were consistent with the reported ones for Cl −LDH, ClO4−LDH,
and NO3−LDH (Iyi et al., 2007, 2009; Kloprogge et al., 2002), respective-
ly. As also shown in Fig. 7, the weight changed up to f = 2–3 because of
the change of molecular weight due to the exchange of anions, and for
salt amounts of up to f = 6, any weight change attributable to dissolu-
tion of the LDH layer was not observed.
To check the weight change after extended reaction times for
NH4Cl, NH4ClO4, and NH4NO3, the following two parallel experiments
at the loading of f = 5 were conducted. One experiment was terminated
after 1.5 h and the other experiment was continued for 5 d. The differ-
ence in weight between the 1.5 h and 5 d samples was b0.5% on average,
which was comparable to measurement error. This implies that even if
excess ammonium salt and prolonged reaction times were applied, sig-
nificant weight changes due to the dissolution of the LDH layer would
not occur because of the low acidity (pKa = 9.24).
For comparison, experiments using degassed water in place of
methanol were conducted. The amount of NH4Cl was f = 8 and the re-
action was conducted at room temperature under N2 flow for 3 h. No
CO2 was detected in the outlet gas, and the CO32− content of the product
was about 90% (see FT-IR profile in Fig. S5 of SI). Thus, only slight CO32−
exchange was observed in the case of water in contrast to the reaction
in methanol. This is in accordance with the result for trimethylamine
HC belonging to the same group as NH4Cl (Group 3) described in the
preceding section.
3.2. Effect of reaction temperature
The effect of the reaction temperature on the decarbonation rate
was investigated because pKa values are known to change according
to temperature. Ammonium chloride (NH4Cl, Group 3) was selected
for this experiment, which was conducted in methanol for 2 h at various
reaction temperatures (20, 30, and 40 °C) as described in Section 2.2.
The amount of the salt was f = 1. The amount of remaining CO32− was
8% for the product obtained at 30 °C and 2% for that obtained at 40 °C.
Since the remaining CO32− for NH4Cl at 20 °C was about 50% (Fig. 7),
the effect of temperature was apparent. The change in the intensity of
60
the characteristic CO32− band (νC–O) in the FT-IR profile is shown in
Fig. 8. To check the weight loss at higher temperature, the experiment
was conducted with excess salt (f = 3) at 50 °C for 2 h. No significant
weight loss was observed, and the remaining CO32− in the product
was about 1%.
 N. Iyi, H. Yamada / Applied Clay Science 65-66 (2012) 121–127
νC-O
Absorbance (a.u.)
o which sometimes required repeated anion exchange. The detailed
(a) 20 C
o
(b) 30 C
o ture for 2 h, and product with no remaining CO32− and no significant
(c) 40 C
2000 1500 1000
-1
Wavenumber (cm )
Fig. 8. FT-IR spectra for specimens decarbonated in methanol using NH4Cl (f = 1) at
(a) 20 °C, (b) 30 °C, and (c) 40 °C. The characteristic absorption band of CO32− (νC–O)
is indicated by the dotted rectangle in the figure.
These results indicated that an increase in reaction temperature
was very effective for reducing the remaining CO32− in LDHs when
using HCs with pKa = 8–11 (Group 3). High reaction temperature
could be also applied to accelerate the reaction when using HCs
with pKa b 8; however, the salt amount should be kept at f = 1 to
avoid LDH dissolution.
Comparative experiments using the neutral salts NaCl and NaClO4
were conducted in methanol. For the decarbonation experiment with
NaCl (f = 1) at 50 °C for 2 h, the remaining CO32− was 75%, and for the
experiment with NaCl (f = 1) at 60 °C for 2 h, the remaining CO32− was
64%. Indeed, partial anion-exchange occurred, but the decarbonation
rate was far lower than the experiments using ammonium salts. Only
when the reaction was conducted at 60 °C for 3 h with a very large ex-
cess of NaCl (f = 49), the residual CO32 − was reduced to 12%. These re-
sults are consistent with the observation by Hayashi and Nakayama
(2011) that high temperature showed a significant effect on decarbon-
ation. For the experiment at 60 °C for 3 h using NaClO4 (f = 75.5), the
remaining CO32− was about 20%. In these cases, CO2 was detected in
the outlet gas, which means that the alcohol acted as the proton source
at high temperature. Thus, indeed the remaining CO32− was reduced to a
large extent by using large excess quantities of neutral salts; however,
remaining CO32− of b5% was not attained under these conditions, in con-
trast to the experiments using ammonium salts with pKa ≤ 11.
3.3. Effect of atmosphere
The decarbonation experiments so far described were conducted
under N2 flow. To examine the effect of the atmosphere, comparative
experiments were conducted by using ambient air instead of N2 and de-
carbonation operation was carried out under air flow (0.5 L/min). Am-
bient air, which contains normally ca. 450 ppm CO2, was supplied by
an air pump. The filtration was conducted under N2 flow to avoid the
change in carbonate content of the products during the filtration
operation.
When decarbonation was carried out under air flow as described
above, the remaining CO32− was about 20% for NH4Cl (f = 3) in methanol
(Fig. S6(a) in SI). The remaining CO32− was significantly large consider-
ing that only a slight amount of CO32− remained in the parallel experi-
ment conducted under N2 flow (Fig. S6(b) in SI). In contrast, even
under air flow, no remaining CO32− was observed for experiments
using HCl (f = 1.25, Fig. S6(c) in SI) and HClO4 (f = 1.25). These results
indicate that CO32− incorporation from CO2 in the air increases as the
acidity becomes weaker.
125
3.4. Ammonium salts of organic acids
We applied the “ammonium-salt decarbonation method” to a one-
step synthesis of water-swellable LDH hybrids – AcO −LDH (Iyi et al.,
2008) and Ise −LDH (Iyi et al., 2011a) – directly from CO32−LDH. Pre-
viously, these organo-LDHs, which contain acetate (AcO −) and
isethionate (Ise −), respectively, were prepared by two-step processes
procedure and results are described in S-7 in SI.
For the preparation of AcO −LDH, ammonium acetate (AcONH4)
was used. The reaction was conducted in methanol at room tempera-
weight loss was observed for f = 8 and 10. At higher reaction temper-
atures, full decarbonation with quantitative yield was attained. At the
loading of f = 1, the reaction temperature should be higher than
45 °C. When using AcONa, which does not supply protons, instead
of AcONH4, even with salt amounts up to f = 8 at room temperature,
the resulting product was basically CO32−LDH (remaining CO32− ~ 74%)
with some incorporation of AcO− (Fig. S7-1(b) in SI).
For the preparation of Ise−LDH, ammonium isethionate (IseNH4)
was used. When the reaction was conducted in methanol at 60 °C for
2 h with an IseNH4 amount of f = 2, no remaining CO32− was observed
(Fig. S7-2(a) in SI), and the obtained product showed the same FT-IR
profile as previously reported (Iyi et al., 2011a). When using IseNa,
which does not supply protons, instead of IseNH4, the experiment
yielded LDH only partially exchanged by Ise− with the remaining CO32−
of 33% (Fig. S7-2(b) in SI). Considering that the concentration in the out-
let gas was very low in the case of IseNa, anion-exchange of CO32− with
Ise− occurred in alcohol to some extent.
Thus, the use of ammonium salts of organic acids in alcohol also
significantly enhanced the incorporation of the conjugate-base anions
of those organic acids, and increased temperature was shown to be
very effective in reducing the residual CO32−. Hayashi and Nakayama
(2011) reported that, by treatment with medicinal drugs containing
carboxyl group in methanol at 60 °C, CO32−LDH was decarbonated to
yield the LDHs intercalated with the corresponding carboxylates. In
this case, the carboxyl groups of the drugs would have supplied protons
for decarbonation. We could show that ammonium salts of organic
acids can be also useful for this reaction.
3.5. Reactions constituting decarbonation in alcohol
Partial exchange of CO32− by Cl− occurred even if there was no pro-
ton source in the reaction system. This was a normal anion-exchange
reaction without CO2 evolution. The equilibrium equation could be
expressed as follows:
n o
– 2– 2– –
2Cl ðsolnÞ þ CO3 ðLDHÞ⇌CO3 ðsolnÞ þ f2Cl gðLDHÞ: ð1Þ
Here, (soln) indicates the alcoholic solution phase, and { }(LDH), the
interlayer space of the LDH.
Eq. (1) is applicable to the experiments which used neutral salts
such as NaCl at room temperature as already described, for which the
remaining CO32− was 70–90%. The degree of CO32− replacement reflects
the selectivity of anions. This type of anion-exchange occurs also in
aqueous system; for example about 50% of carbonate was replaced by
Cl− if nearly saturated NaCl aqueous solution (~25 wt.%) was used
(see Fig. 5 in Iyi et al., 2004).
In the presence of a proton source, conversion of CO32− into CO2
occurs by neutralization as shown in Eq. (2).
2– þ
CO3 ðsolnÞ þ 2H ðsolnÞ⇌H2 OðsolnÞ þ CO2 : ð2Þ
This is also an equilibrium reaction; however, if the evolved CO2 is
expelled from the reaction system as a gas, a shift of the equilibrium
126 N. Iyi, H. Yamada / Applied Clay Science 65-66 (2012) 121–127
to the right occurs for a higher decarbonation rate (see Eq. (3)). Con-
sequently, the equilibrium reaction (Eq. (1)) also shifts to the right,
causing a decrease in the carbonate content of the LDH interlayer as
a whole.
2– þ 0 and 14. The decarbonation behavior depended on pKa values of the
CO3 ðsolnÞ þ 2H ðsolnÞ→H2 OðsolnÞ þ CO2 ↑ ð3Þ
Thus, with a proton source, the decarbonation reaction proceeds re-
gardless of the anion selectivity, consequently, much more efficiently
than the normal anion exchange. In this study, we revealed that ammo-
nium salts with medium pKa values in the range 0–11, also worked as
the proton sources for the decarbonation reaction in alcohol. If there is
no other proton source, alcohols used as solvents must be heated to sup-
ply protons due to their low acidities (pKa = 15–17; Nihon-Kagakukai,
1993). By heating under N2 flow, both reactions – Eqs. (1) and (3) –
occurred. These equations indicate that both proton source and anion
supplier are necessary for efficient decarbonation. When using NaCl in
methanol, NaCl acts as the anion supplier and heated methanol as the
proton source; on the other hand, when using ammonium salt in metha-
nol, the ammonium salts act as both proton- and anion-suppliers. Total
equation for the decarbonation using an ammonium salt, e.g.NH4Cl,
would be:
n o
2– –
2NH4 Cl þ CO3 ðLDHÞ→f2Cl gðLDHÞ þ H2 O þ 2NH3 þ CO2 ↑: ð4Þ
This equation indicates that elimination of CO2, H2O, and NH3 is
also important for decarbonation.
Such decarbonation reaction is not specific to CO32−LDH: a high
concentration of CO2 was observed in the outlet N2 gas after addition
of NH4Cl (f = 3) to Na2CO3 in methanol at room temperature. Without
addition of NH4Cl, it was necessary to heat up to 60 °C for CO2 to be
detected in the outlet gas, though the CO2 concentration is far less
than the experiment using NH4Cl (for detailed experimental condi-
tions and results using Na2CO3 instead of CO32−LDH, see S-8 of SI).
In this study, methanol and ethanol were used as solvents. The ad-
vantage of alcohols over water as the solvent for decarbonation was
first noticed by Hayashi and Nakayama (2011). We confirmed their
findings, and furthermore, we could show that ammonium salts,
which are both proton- and anion-suppliers, significantly enhanced
decarbonation reaction in alcohols.
3.6. Decarbonation in other polar organic solvents
It was already pointed out that polar organic solvents such as acetone
and tetrahydrofuran could also be used as the solvent for decarbonation
when using mineral acids (Iyi et al., 2011b). For decarbonation by am-
monium salts, preliminary experiments were conducted by using ace-
tone as the solvent in place of methanol (for details, see S-9 of SI).
Acetone is a polar solvent, however it is an aprotic one unlike alcohols.
For this experiment, NH4ClO4 was used at a loading of f = 3, at room
temperature under N2 flow for 2 h. Evolved CO2 was detected in the out-
let gas, but the reaction rate was sluggish, requiring 45 min to reach the
maximum CO2 concentration. The CO32− content in the product was 30%,
which was higher than that (~3%) when using methanol as the solvent.
However, the reaction conducted at 55 °C at the same loading (f = 3)
for 2 h yielded ClO4−LDH with the remaining CO32− b 2% (Fig. S9(d) in
SI).
Thus, slightly more severe conditions were required for decarbon-
ation in acetone, and, considering the solubility of the salts, alcohols
would be more versatile; however, decarbonation reaction occurred
even in acetone yielding completely decarbonated LDHs. Other polar
organic solvents would be usable for decarbonation if pertinent ammo-
nium salts will be used.
4. Conclusion
Decarbonation behavior was investigated for CO32−LDH (Mg/Al = 3)
in alcohols at room temperature under N2 flow in the presence of am-
monium salts (HC salts of various amines) with pKa values between
ammonium salts. Ammonium salts with pKa ≤ 11 acted as effective pro-
ton sources for decarbonation in alcohol at room temperature, and the
decarbonation reaction was significantly enhanced. When neutral
salts such as NaCl, which cannot supply protons, were used, the suspen-
sion required heating to make the alcohol solvent act as a proton source,
and large excess salts were needed. Ammonium salts of organic acids
were also shown to be useful for the incorporation of the conjugate
base of the acid into the LDHs. In all cases, increasing the reaction tem-
perature was very effective for accelerating the reaction and for reducing
the remaining CO32− in the LDHs.
Acknowledgments
We thank Mr. Y. Yajima (NIMS) for the elemental analysis of carbon.
This study was partly supported by a Grant-in-Aid for Scientific Re-
search (no. c-20550142) of the Ministry of Education, Culture, Sports,
Science and Technology (MEXT) of Japan, for which we are deeply
indebted.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://
dx.doi.org/10.1016/j.clay.2012.05.001.
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