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Cite This: ACS Omega 2019, 4, 3198−3204 http://pubs.acs.org/journal/acsodf

Interaction of Pristine Hydrocalumite-Like Layered Double

Hydroxides with Carbon Dioxide
Anand N. Narayanappa and P. Vishnu Kamath*
Department of Chemistry, Central College, Bangalore University, Bangalore 560 001, India
*
S Supporting Information

ABSTRACT: The layered double hydroxides (LDHs) of Ca2+ and

trivalent cations, Al3+ and Fe3+, are single-source precursors to
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generate supported CaO, which picks up CO2 from the gas phase in
the temperature range 350−550 °C. The supports are ternary oxides,
mayenite, and Ca2Fe2O5. The uptake capacity of the Fe3+-containing
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LDH at 1.9 mmol g−1 is two times the capacity of the Al3+-
containing LDH. The product of CO2 uptake is calcite CaCO3. It is
observed that the intercalated chloride ions reduce the thermal
penalty by inducing the early decomposition of CaCO3. In the case
of the chloride-intercalated LDHs of Ca2+ and Fe3+, the CaCO3
formed is completely decomposed at 900 °C. This is in contrast with
the CaCO3 formed from bare CaO, which shows no sign of
decomposition at 900 °C under similar conditions. This work shows
that the hydrocalumite-like LDHs are candidate materials for CO2 mineralization.

1. INTRODUCTION
The accumulation of anthropogenic CO2 in the atmosphere is
responsible for the rise in the temperature of the earth’s
atmosphere. There are major efforts underway to mineralize
CO2 and store it as a benign solid carbonate, an approach
known as carbon capture and storage.1,2 An alternative is to use
the mineralized form as a feedstock for pure CO2 for other
chemical processes.3,4 In the latter approach, the temperature
difference between CO2 uptake and its eventual regeneration
constitutes the thermal penalty.5,6 For purposes of energy
efficiency, materials with low thermal penalty are preferred.
A number of materials have been used as candidates for CO2
capture and are reviewed elsewhere.7 Among them, sintered
layered double hydroxides (LDHs) comprise a prominent
family of materials. LDHs decompose to yield mixed metal
oxides (MMOs).8 Metal oxides in general exhibit surface
acidity and are not expected to mineralize CO2, as the latter is
also acidic in nature. Nevertheless, a modest CO2 uptake
capacity of 0.3 mmol g−1 has been reported for the MMOs of
Mg2+ and Al3+ obtained by the thermal decomposition of
hydrotalcite-like LDHs.9 This capacity is attributed to the
adsorption of CO2 within the morphological pores of the
MMO. The same MMO is also reported to exhibit a CO2
uptake capacity of 0.53 mmol g−1.10 Modifications in the
morphology of the crystallites and amorphization led to only
modest gains in the CO2 uptake capacity.11,12 LDHs infused
with up to 30% by weight of K2CO3 were found to show CO2
uptake capacity of ∼1 mmol g−1 of LDH after calcination.13
From chemical, structural, and compositional criteria,
pristine LDHs offer themselves as superior candidate materials
for CO2 capture when compared to the sintered LDHs for the
following reasons.
(i) The LDHs comprise positively charged metal hydroxide
layers having the general formula [M-
(II)1−xM′(III)x(OH)2]x+ (x = 0.2−0.33), wherein,
M(II) is commonly Mg2+ and M′(III) is commonly
Al3+, Cr3+, and Fe3+. Anions are intercalated in the
interlayer region. The LDHs are structurally and
functionally the “inverse” of the cationic clays. While
the cationic clays exhibit surface acidity, the LDHs are
endowed with surface basicity.14 The interaction of
pristine LDHs with CO2 has the character of an acid−
base reaction whereby the LDHs are expected to have a
high affinity for CO2.
(ii) Structurally, the LDHs have interlayer galleries which
provide space for storage. The LDHs are also known to
swell and function as receptacles for increasing numbers
of intercalated species by means of a hydrogen-bonded
network.15
Despite these advantages, the pristine hydrotalcite-like
[Mg−Al] LDH did not gain any mass when exposed to CO2
(pressure 1 atm) over the temperature range 30−400 °C,16
although the [Mg−Al] LDHs sorb carbonate anions from
solution in quantities proportional to their layer charge.
Another important candidate LDH for CO2 mineralization is
the hydrocalumite-like LDH, in which M(II) is the Ca2+ ion
and M′(III) is Al3+ or Fe3+.17 Although the conversion of
Received: January 10, 2019
Accepted: February 1, 2019
Published: February 13, 2019

© 2019 American Chemical Society 3198 DOI: 10.1021/acsomega.9b00083

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Table 1. Composition of the Hydrocalumite-Like LDHs
2+ 3+
Ca content M content anion content anion content
sample [wt. %]a [wt. %]a [wt. %]a [mol %]b
[Ca−Al−Cl] 26.2 (28.8) 9.9 (9.7) 7.5 (7.63) 0.6 (1.0)
[Ca−Fe−Cl] 27.1 (26.1) 19.8 (18.8) 5.1 (5.1) 0.43 (1.0)
[Ca−Al−NO3] 27.6 (27.4) 9.7 (9.2) 13.8 (12.7) 0.6 (1.0)
a
Values in parenthesis are calculated based on the approximate composition given in the last column. bValues given in parenthesis are expected to
be the nominal composition of the LDHs (x = 0.33).
Ca(OH)2/CaO to CaCO3 is widely studied in the context of
deep well disposal of CO2 under high pressure and its
subsequent mineralization to CaCO3,18 there is relatively less
work on the sorption and uptake of CO2 by the [Ca−M′] (M′
= Al3+ and Fe3+) LDHs. The [Ca−M′] LDHs are of interest
for many reasons in both the pristine and sintered forms.
(1) Given its high natural abundance, Ca2+ is ubiquitous in
soil and offers economic advantages over Mg2+.
(2) Ca(OH)2 is more basic than Mg(OH)2 and is expected
to take up CO2 quantitatively in a facile manner to yield
CaCO3 (expected uptake 13.5 mmol g−1).
(3) The LDH of Ca and Al crystallizes in a cation-ordered
structure (space group R3̅), in which the Ca2+ ion has a
seventh coordination with a water molecule in the
interlayer.17 In the hydrocalumite structure, the Ca2+ ion
is displaced away from the central plane of Al3+ ions.
This displacement facilitates coordination with a water
molecule in the interlayer. The puckered nature of the
metal hydroxide layer helps to trap the intercalated ion.
For instance, when the [Ca−Al−Cl] LDH is dehydrated,
the Cl− ion moves to the seventh coordination of Ca2+
and is efficiently grafted to the layer. A similar
phenomenon in the presence of CO32− could help
immobilize CO2 more effectively than otherwise.
Thereby, the [Ca−Al] LDH offers a different structure
model for the mineralization of CO2 and its confinement
in the interlayer gallery.
(4) The decomposition temperature of Ca-containing LDHs
is in the range of 300−400 °C. The flue gas temperature
is very close to the decomposition temperature of Ca-
containing LDHs facilitating the reaction between the
LDH and CO2.
(5) LDHs decompose with a mass loss of 30−40%. The
large mass loss results in the formation of a highly
porous MMO residue which is not only compositionally
metastable19 but also has a large reactive surface area.20
These conditions are ideally suited for the reconstruc-
tion of the LDH with the uptake of CO2 and water vapor
from the flue gas. This makes Ca-containing LDHs
interesting in CO2 sorption studies.
As a first step to examining the suitability of the [Ca−
M′(III)] LDHs as sorbents for CO2, this work reports the
uptake of CO2 by a cohort of [Ca−M′−X] LDHs (M′ = Al3+
and Fe3+; X = Cl− and NO3−).
2. RESULTS
A majority of the naturally occurring as well as laboratory-
synthesized LDHs have CO32− ions intercalated in the
interlayer region. CO32−-intercalated [Ca−M′] LDHs are less
known owing to the fact that the single cation CaCO3 forms in
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mass loss from TGA [%]
loss of H2O total loss
N2 CO2 N2 CO2 approximate composition
14.7 13.4 41.1 37.7 [Ca2Al(OH)6]Cl0.60(OH)0.40·2.3H2O
14.4 14.1 35.8 35.8 [Ca2Fe(OH)6]Cl0.43(OH)0.57·2.45H2O
13.3 11.1 47.3 30 [Ca2Al(OH)6](NO3)0.60(OH)0.40·2.2H2O
preference to the LDH during coprecipitation.21 The [Ca−M′]
LDHs are generally obtained with intercalated Cl− ions.22 The
most common of these having the formula Ca2Al(OH)6Cl·
2H2O is called Friedel’s salt.17 The as-prepared [Ca−M′−Cl]
(M′ = Al and Fe) LDHs are highly crystalline, and the powder
X-ray diffraction (PXRD) patterns (Figure S1 in the
Supporting Information) exhibit sharp 00l (l = 3n) reflections
in the low-angle region (5−25° 2θ) typical of layered materials
followed by hkl reflections which obey the reflection
conditions −h + k + l = 3n (Table S1) in the high-angle
regions (2θ > 25°), indicative of rhombohedral symmetry. The
refined cell parameters are in agreement with earlier reports on
these LDHs.17,22 The [Ca−Al−NO3] LDH crystallizes in the
hexagonal symmetry (Figure S2, Table S2). Given the large
difference in the ionic radii of Ca2+ (114 pm) and the trivalent
cations (Al3+ 67.5 pm and Fe3+ 78.5 pm), the [Ca−M′] LDHs
crystallize in cation-ordered structures. The a-parameter (a ≈
5.74 Å) is a measure of the M′···M′ distance within the metal
hydroxide layer and is typical of the composition x = 0.33
([Ca2+]/[M′] = 2).
The approximate formulae of the LDHs (Table 1) were
arrived at by a combination of different independent
estimations. As an illustration, the methodology is described
in detail for [Ca−Al−Cl]. The metal contents determined
independently by a combination of AAS and gravimetry
correspond to the nominal composition [Ca2M′(OH)2]+. The
Cl− content estimated independently by ion chromatography
was found to be substoichiometric. The shortfall of negative
charge required to neutralize the positive charge on the metal
hydroxide layer was made up by the inclusion of hydroxyl ions
in the interlayer to yield the LDH composition [Ca2Al-
(OH)6]Cl0.6(OH)0.4. Such an assumption is reasonable as the
precipitation is carried out at high pH (11.5−12). There is
evidence to suggest that LDHs comprising univalent anions are
rarely single anion materials and generally contain more than
one anion.23,24 The intercalated water content was estimated
by thermogravimetric analysis (TGA).
The TGA of the as-prepared [Ca−Al−Cl] LDH (Figure 1a)
carried out in flowing N2 matches with similar data published
by other authors.17 The mass loss occurs in three well-defined
sigmoidal steps, the inflection temperatures being 146 °C (step
I), 343 °C (step II), and 682 °C (step III) (Table 2).
Assuming step I to correspond to dehydration yields a water
content corresponding to 2.3 water molecules per formula unit.
The total mass loss (observed 41.1%; expected 41.4%)
corresponds to the complete decomposition reaction
[Ca 2Al(OH)6 ]Cl 0.6(OH)0.4 ·2.3H 2O → 2CaO + 0.5Al 2O3
The mass loss associated with step II corresponds to
dehydration and dehydroxylation (observed 16.2%; expected
20.6%). The third mass loss (step III) corresponds to anion
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Table 3. Mass Change in TGA under Flowing CO2

step Ia step IIa step IIIb step IVa% step Vc
LDH % (°C) % (°C) % (°C) (°C) % (°C)
[Ca−Al−Cl] 13.4 14.8 4.6 14.5 8.7
(132) (380) (497) (800−869) (810)
[Ca−Al−NO3] 11.1 12.5 4.6 11.1
(123) (351) (467.5) (511−900)
[Ca−Fe−Cl] 13.9 12.1 8.5 18.3 (774)
(147) (322) (497)
a
Mass loss. bMass gain in heating cycle. cMass gain in cooling cycle.

are comparable to those obtained in the control under

flowing N2. However, following these two steps, unlike
in the control experiment, a plateau is established from
394 to 460 °C (plateau-I).
(ii) At the end of plateau-I, the LDH gains ∼4.5% mass (∼1
mmol g−1) in the temperature range 460−555 °C.
Thereafter, the mass is nearly constant with a downward
bias up to 750 °C (plateau-II). It is important to note
that the mass gain in flowing CO2 begins after the
dehydroxylation step. A prolonged stay at the plateau
temperature (T = 550 °C) in a separate experiment did
not lead to further mass gain (Figure S3).
(iii) A mass loss of ∼4.6% is observed at 788 °C.
(iv) On staying at 900 °C for up to 30 min, 37.7% total mass
loss is observed. This is less than the loss expected
(41.8%) for the complete decomposition of the LDH.
On cooling, the residue instantaneously regains some of
the mass earlier lost at T > 800 °C and reaches a
constant value at 700 °C (plateau-III). However,
plateau-III is nearly 5.5% mass lower than plateau-II
Figure 1. TGA and DTG curves of [Ca−Al−Cl] LDH in (a) flowing and ∼1% mass lower than plateau-I showing consid-
N2 and (b) flowing CO2.
erable hysteresis.
Table 2. Mass Loss Steps in TGA under Flowing N2 In separate experiments, the LDH was decomposed at the
temperatures corresponding to the three plateaus and
step II % step III % step IV % characterized by PXRD. The phase obtained at plateau-I
LDH step I % (°C) (°C) (°C) (°C)
(460 °C) has a reflection at ∼29.4° 2θ characteristic of 104
[Ca−Al−Cl] 14.7 (146) 16.2 (343) 10.2 (682) reflection of calcite CaCO3. The poor signal-to-noise ratio and
[Ca−Al−NO3] 13.3 13.2 (307) 12.5 (570) 8.3 (715) background are indicative of a significant volume fraction of X-
(118, 161)
[Ca−Fe−Cl] 14.4 (161) 12.1 (278) 9.4 (672)
ray amorphous content. The absence of the intense basal
reflections shows that the layered structure has collapsed. On
cooling back to the ambient, this phase does not regain mass,
expulsion (observed 10.2%; expected 6%). The difference in showing that dehydroxylation is not reversible. However, on
expected and observed values at the end of the steps II and III further heating in flowing CO2 to the temperature of plateau-II
arises because of overlapping of steps but the expected and (640 °C), CaCO3 formation is evident from the PXRD
observed total mass loss are in very good agreement. The step- pattern. The IR spectrum of the residue at plateau-II shows an
wise decomposition is enhancement of the absorption at 1409 cm−1 because of calcite
formation (see Figure S4 and the accompanying discussion of
[Ca 2Al(OH)6 ]Cl 0.6(OH)0.4 the IR spectra). At plateau-III, a mixture of CaCO3 and the
→ 2CaO + 0.6AlOCl + 0.2Al 2O3 ternary oxide mineral mayenite, Ca12Al14O33, is observed
(Figure 2). The thermodynamically stable ternary oxide is
→ 2CaO + 0.5Al 2O3 obtained at 900 °C and does not react with CO2. Only a part
A similar approach was used to arrive at the approximate of the CaO formed in excess over the ternary oxide at 900 °C
formulae of the other LDHs (Table 1). It is noteworthy that in gains CO2 on cooling to the temperature of plateau-III
the cooling cycle, the mass of the residue is unchanged, accounting for the hysteresis in the TGA.
showing that the decomposition is irreversible. Similar observations are made in the case of the [Ca−Fe−
The TGA measurement was repeated in flowing CO2 to Cl] LDH (Figure 3). The total mass loss (observed 35.8%;
examine the interaction of the LDH with CO2 in the gas phase expected 36.5%) in flowing N2 corresponds to the decom-
(Figure 1b, Table 3). The following observations were made: position reaction
(i) During the heating cycle, the LDH loses 28% of its mass [Ca 2Fe(OH)6 ]Cl 0.43(OH)0.57 ·2.45H 2O
up to 394 °C in two sigmoidal steps with inflection at
132 °C (step I) and 380 °C (step II). These two steps → 2CaO + 0.5Fe2O3

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Figure 2. PXRD patterns of the residues obtained from the
decomposition of [Ca−Al−Cl] LDH at plateaus (a) P-I, (b) P-II,
and (c) P-III. Reflections marked with asterisks are due to calcite
CaCO3. Unmarked reflections are due to mayenite.
Figure 3. TGA and DTG curves of [Ca−Fe−Cl] LDH in (a) flowing
N2 and (b) flowing CO2.
This mass loss is realized over three steps at 161 °C
(14.4%), 278 °C (12.1%), and 672 °C (9.4%). In flowing CO2,
a behavior similar to that seen in [Ca−Al−Cl] is observed. At
the end of the second step of the mass loss (26.1%, 400 °C,
plateau-I), the dehydroxylated residue is X-ray amorphous
(Figure 4). This residue does not gain mass on cooling, but on
heating in CO2, a mass gain corresponding to 8.5% of the
original LDH is observed at plateau-II (680 °C) to yield
CaCO3. The absence of any CaCO3 at plateau-I is responsible
for the higher uptake when compared to the [Ca−Al] LDH.
This mass gain corresponds to the uptake of 1.93 mmol g−1 of
the original LDH. Above 700 °C, there is a steep mass loss
(18.3%) until 900 °C because of the decomposition of the
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Figure 4. PXRD patterns of the residues obtained from the
decomposition of [Ca−Fe−Cl] LDH at (a) P-I, (b) P-II, and (c)
P-III. Reflections marked with asterisk correspond to CaCO3.
Unmarked reflections correspond to Ca2Fe2O5.
CaCO3 formed at plateau-II. The total mass loss corresponds
to a mixed oxide residue. On cooling, this oxide residue regains
mass in two minor steps (850 and 650 °C) to yield plateau-III
at which the residue corresponds to a mixture of CaCO3 and
Ca2Fe2O5. Evidently, the ternary oxide phase formed at 900 °C
does not pick up CO2 on cooling, resulting in a much greater
hysteresis between plateaus-I and III than that in the case of
the [Ca−Al] LDH.
As the Cl− ion is nonvolatile at moderate temperatures (T <
500 °C), similar experiments were performed on the NO3−-
intercalated LDH to see if the nitrate-LDH shows a higher
CO2 uptake than the chloride-LDH. Under flowing N2, the
[Ca−Al−NO3] LDH undergoes complete decomposition
(Figure S5, observed mass loss 47.3%; expected 44.8%).
Under flowing CO2, an uptake of 4.6% (∼1 mmol g−1 original
LDH) is observed (Figure 5) at plateau-II (500 °C). In this
Figure 5. TGA and DTG curves of [Ca−Al−NO3] LDH in flowing
CO2.
case, the decomposition is incomplete at 900 °C (observed
mass loss 30%) and correspondingly, there is no mass gain in
the cooling cycle. The residue obtained at 900 °C was
dissolved in dilute HCl and analyzed by ion chromatography.
Residual NO3− ion was observed to the extent of 0.07 mol %
(4.5 wt %) with respect to LDH and 0.10 mol % (6.3 wt %)
with respect to residue, showing that the decomposition of the
LDH is incomplete under flowing CO2 and the nitrate is
retained in the residue. The nitrate-containing phase could not
be identified. The phase obtained isothermally at plateau-I was
a mixture of CaCO3 and Ca(OH)2 (Figure S6). The phase
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obtained at plateau-II was CaCO3. At plateau-III, a mix of
CaCO3, mayenite, and another ternary oxide Ca5(Al3O7)2 was
observed.
3. DISCUSSION
The LDH crystallizes in a rhombohedral structure. CaO
crystallizes in the cubic rock salt structure. There is a well-
established topotactic relationship between the precursor and
product phases, which can be described as [00l]H/R∥[111]C (l
= 1 for H: hexagonal; l = 3 for R: rhombohedral; C: cubic).25
The decomposition of the LDH takes place by the
condensation of the metal hydroxide layers brought about by
dehydration and dehydroxylation. This occurs just below 400
°C. CaO is therefore expected to form throughout the bulk of
the LDH. The uptake of CO2 takes place thereafter at T > 460
°C. The uptake of CO2 is an addition reaction of the type CaO
+ CO2 → CaCO3. However, all of the Ca are not utilized in
the first cycle. If indeed all of the free CaO were to be utilized,
plateau-II would correspond to 86% of the mass of the [Ca−
Fe] LDH (91% in the case of [Ca−Al] LDH). The observed
mass gain at plateau-II corresponds to ∼26% Ca utilization
(∼11% in the case of the [Ca−Al] LDH). CaCO3 formation
evidently takes place on the exposed surface of the CaO
crystallites. Because continued stay (up to 2 h) at various
temperatures spanned by plateau-II did not lead to further
mass gain (Figure S3), it is our conclusion that CaO utilization
is not limited by the kinetics of CO2 uptake, but by the uptake
of CO2 at the surface of the CaO crystallites. The CaCO3
formed on the surface prevents a more complete material
utilization.
The residue obtained at plateau-II was calcined in flowing
nitrogen at 900 °C and reheated in flowing CO2. The oxide
residue gained nearly 30% mass by aggressive uptake of CO2 in
the temperature range of 434−685 °C (Figure S7). We
conclude that intermediate calcination at high temperature
exposes fresh CaO surface, facilitating increased material
utilization. This is in direct contrast to silica removal by
hydrotalcite-like LDHs.26,27 Silicates being nonvolatile ions
accumulate in the solid phase on repeated cycling, leading to
decreased efficiency. Carbonates are volatile ions and behave
differently.
Pure CaO is used for high-temperature CO2 cycling.
However, there are two major drawbacks of CaO: (i) the
thermal penalty is high.28,29 The CO2 uptake temperature is
close to 650 °C for CaO and 450 °C for Ca(OH)2, whereas no
decomposition of the formed CaCO3 is observed up to 900 °C
(Figure 6) in both cases. (ii) The CO2 uptake falls sharply by
80% during thermal cycling;30 the fall is attributed to high-
temperature sintering of the CaO crystallites.30,31
There have been major technological and scientific efforts to
alleviate these problems by (i) appropriate engineering to
utilize the heat generated by the exothermicity of the
carbonation cycle and reduce the thermal penalty32,33 and
(ii) by dispersing CaO on an inert oxide support such as
mineral mayenite to prevent agglomeration and sintering of the
active CaO crystallites.34,35
The use of hydrocalumite-based Ca-rich LDH as a precursor
has the potential to generate in single step, active CaO, as well
as mayenite (Ca2Fe2O5 in the [Ca−Fe] LDH) for effective
CO2 uptake. Further, the use of the intercalated Cl− ion
induces the decomposition of the formed CaCO3 at 900 °C in
the case of [Ca−Al−Cl] LDH. In contrast with this, the
CaCO3 formed by the uptake of CO2 by pure CaO (Figure 6)
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Figure 6. TGA and DTG curves of CaO in flowing CO2.
shows no signs of decomposition at 900 °C. In the case of
[Ca−Fe−Cl] LDH, the formed CaCO3 decomposes at 800 °C
itself bringing about a 100 °C reduction in the thermal penalty
compared to the [Ca−Al−Cl] LDH. The combined/
synergistic effect of Fe and Cl makes the [Ca−Fe−Cl] LDH
interesting for practical use. In all cases isothermal treatment of
the LDH at temperatures of the three plateaus did not enhance
the mass gain, showing that the mass gain in the TGA is not
limited by kinetics.
4. CONCLUSIONS
Hydrocalumite-like LDHs are superior to the hydrotalcite-like
compounds for applications related to mineralization of CO2.
These Ca-containing phases are single-source precursors for
both CaO and the ternary oxide supports. Among the
hydrocalumites, the [Ca−Fe−Cl] phase shows the highest
uptake of CO2. The product of CO2 uptake is the calcite form
of CaCO3. The presence of intercalated chloride ions appears
to reduce the thermal penalty when compared to CaO,
whereas intercalated nitrate ions fail to induce the decom-
position of the CaCO3 formed as a result of CO2 uptake.
5. EXPERIMENTAL SECTION
The [Ca−M−X] LDHs (M = Al and Fe; X = Cl− and NO3−)
were synthesized by coprecipitation. In separate experiments,
the [Ca−Al−Cl] and [Ca−Fe−Cl] LDHs were prepared by
dropwise addition of a mixed metal chloride solution in the
stoichiometric ratio ([Ca]/[M] = 2, dropping rate 0.3 mL
min−1) to a NaCl solution (100 mL; 0.4 mol L−1) containing
five times excess Cl− ions. The pH of 11.5 was maintained for
all of the syntheses by dispensing NaOH solution (0.5 mol
L−1) at 60 °C using a Metrohm model 836 Titrando, operating
in the pH STAT mode. N2 gas was bubbled during
precipitation and ageing to avoid carbonate contamination.
Once the precipitation was complete, the samples were aged in
mother liquor under a N2 blanket for 18 h under vigorous
stirring.
In the case of [Ca−Al−NO3] LDH, rapid coprecipitation
was carried out by mixing the mixed metal nitrate solution and
NaOH (50 mL, 2 mol L−1) in single step in a screw cap bottle.
NaNO3 (15 times in excess) was added to the NaOH solution
prior to mixing. The pH of the final mixture was >12. The
coprecipitated slurries were aged in mother liquor (48 h, T 85
°C).
All of the precipitates were centrifuged, washed with boiled
type II water (specific resistance 15 MΩ cm, Millipore
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Academic water purification system), and dried in a hot air
oven at 60 °C.
5.1. Wet Chemical Analysis. The compositions of the
LDH were determined by a combination of techniques. The
Ca and Fe contents were determined by atomic absorption
spectroscopy using a Shimadzu model AA-6650 atomic
absorption spectrometer. The Al content was estimated
gravimetrically by dissolving a preweighed amount of the
LDH in a mineral acid and precipitating Al3+ in an ammoniacal
buffer. The resulting gelatinous precipitate was calcined (T ≈
900 °C) and weighed as Al2O3. The anion contents were
determined by dissolving an accurately weighed amount of the
LDH in a suitable mineral acid. The anions released were
estimated by ion chromatography (Metrohm model 861
advanced compact ion chromatograph with Metrosep SUP5
150 column).
5.2. Characterization. All samples were characterized by
PXRD using a Bruker D8 ADVANCE powder diffractometer
(source Cu Kα radiation, Ni filter, λ = 1.5418 Å) operating in
reflection geometry. The PXRD patterns of the LDHs were
indexed by using APPLEMAN program, part of the code
PROSZKI suite of programs. The PXRD patterns of the oxide
residues were indexed by “finger printing” by comparing the
observed 2θ values with those reported in the powder
diffraction files. TGAs were carried out using a Mettler Toledo
TGA/SDTA 851e system (25−900 °C, heating rate 5 °C
min−1) driven by STARe 7.01 software. The analyses were
carried out in flowing N2 (control) and flowing CO2 (test) to
measure the mass gain if any, as a result of CO2 uptake. In
separate experiments, the LDHs were heated in the TGA
balance at different temperatures determined by the appear-
ance of plateaus in the TGA profile. The phases obtained were
analyzed by PXRD. TGA measurements were also carried out
on CaO and Ca(OH)2 used as controls. IR spectra were
recorded by using a Bruker model Alpha-P IR spectrometer
(Diamond ATR cell, 400−4000 cm−1, 4 cm−1 resolution).
■
ASSOCIATED CONTENT
* Supporting Information
S J. Enhancement of CO2 Sorption Uptake on Hydrotalcite by
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsome-
ga.9b00083.
PXRD patterns of the pristine hydrocalumite-like LDHs;
tables of 2θ values and indexing of the reflections of the
hydrocalumite-like LDHs; infrared spectra and TGA
profiles of phases obtained at the different plateau
temperatures; and TGA data of the nitrate-intercalated
LDH (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: vishnukamath8@hotmail.com.
ORCID
P. Vishnu Kamath: 0000-0002-3549-7024
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Authors thank the Department of Science and Technology,
Government of India, for financial support. Authors also thank
the Reviewers for their useful comments.
3203
■
Article
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3204 DOI: 10.1021/acsomega.9b00083

ACS Omega 2019, 4, 3198−3204