JOURNAL OF RARE EARTHS, Vol. 35, No. 5, May 2017, P.

474

Facile synthesis and characterization of acetate intercalated Co-La

layered double hydroxide
Meenakshi Pokhriyal, Sitharaman Uma, Rajamani Nagarajan*
(Materials Chemistry Group, Department of Chemistry, University of Delhi, Delhi 110007, India)

Received 26 July 2016; revised 25 November 2016

Abstract: Layered double hydroxide (LDH) comprising of Co2+ and La3+-ions with acetate counter anion was successfully synthe-
sized by hydrogen peroxide catalyzed hydrolysis reaction and characterized extensively. The observed reflections in the powder X-ray
diffraction pattern could be indexed in P 3 space group with a=0.316 nm and c=2.97 nm. Lattice fringes of distances corresponding to
the peaks observed in X-ray diffraction pattern were observed in high resolution transmission electron microscopic images.
UV-visible diffuse reflectance spectroscopy results confirmed the presence of Co(OH)6 along with the presence of charge-transfer
band due to the interlayer carboxylate anion. Magnetization measurements at room temperature indicated high spin configuration of
Co2+ -ion in the sample exhibiting paramagnetic behavior. The mixed metal oxide from calcination was used to reconstruct the parent
layered structure. Intercalation experiments with other organic anions in Co-La LDH proved be successful.

Keywords: layered double hydroxides; chemical synthesis; X-ray diffraction; intercalation; organic-inorganic hybrids; rare earths

Inorganic lamellar solids exist in many forms and are systems. Recently published work on the efficient cata-
widely investigated owing to superior application possi- lytic role of calcined oxides from multicationic Mg/Al/
bilities for the betterment of society in areas such as en- Me LDHs (Me=Y, Dy, Gd, Sm and La) for the highly
vironment, health, and information technologies[1–7]. Lay- demanding isomerization reaction of 2,3-dimethyl-1-
ered double hydroxides (LDHs) are a unique class of butene illustrates the need for the generation of lantha-
multifunctional materials and are extensively researched nide incorporated hydroxides[14]. Combined with the
due to their ease of synthesis and stability. They exhibit a electro active and magnetic cobalt ions being part of the
broad spectrum of applications originating mainly from lamellar structure, one can efficiently explore electro ca-
the flexibility of the choice of metal cations and rich in- talysis of many industrially important reactions with the
tercalation chemistry[1–9]. They are represented by the ease of removing the catalysts simply by the application
general formula [M2+1–xM3+x(OH)2][An–x/n]·mH2O where of magnetic field[15–17]. The significance of incorporating
M2+ and M3+ are divalent and trivalent cations, respec- cobalt ions in LDHs to act as cellular delivery carriers for
tively; x is equal to the ratio M3+/(M2++M3+), A is an an- the anionic drug molecules due to the overall negative
ion of valence n. The structure of LDHs can be described charge of plasma membrane has been elaborated very
starting with the brucite-like structure, M(OH)2, wherein recently[18]. With all these facts in mind, our aim was to
M2+-ions are surrounded by the hydroxide ions in an oc- explore a reliable method of holding these two techno-
tahedral fashion sharing edges to form infinite charge logically significant metal ions in a layered double hy-
neutral layers. Isomorphous replacement of fraction of droxide arrangement. Towards this objective, hydrogen
the divalent cations with a trivalent cation in such bru- peroxide catalyzed room temperature hydrolysis of ace-
cite-based LDHs creates excess positive charge on the tate salts of cobalt and lanthanum has been carried out
layers, counter balanced by the presence of inter layer, along with the characterization of product from it using
(exchangeable) anions. an array of analytical techniques. It is noteworthy that
Cobalt containing layered hydroxides and oxides has layered salts of zinc, nickel and cobalt have been re-
been used for several catalytic applications such as hy- ported earlier by the polyol hydrolysis process without
droxylation of phenol, Fischer-Tropsch catalysts and the requirement of any base as precipitating agent[19].
steam reform of methanol[10–13]. Additionally, when com- Acetate anion also preserves layered arrangements in
bined with the strong and intrinsically basic lanthanum rare earth hydroxide salts[20]. The intercalation ability of
ions, one can multiply the catalytic functions of such the acetate containing Co-La LDH with other organic

Foundation item: Project supported by DST (SB/S1/PC-08/2012), Govt. of India and University of Delhi under the “Scheme to Strengthen R&D
Doctoral Research Program” and DU-DST PURSE Grant
* Corresponding author: Rajamani Nagarajan (E-mail: [email protected]; Tel.: +91-11-27662650)
DOI: 10.1016/S1002-0721(17)60936-0
Meenakshi Pokhriyal et al., Facile synthesis and characterization of acetate intercalated Co-La layered double hydroxide 475

anions such as benzoate and malonate anions was exam- of alcohol and water in a ratio of 1:1 by volume followed
ined to illustrate the anion exchange ability as well as to by drying at 60 ºC.
prove the versatility of this system capable to generate
organic derivative of inorganics. From these experiments, 1.3 Characterization
one can understand the influence of larger ion lanthanum Powder X-ray diffraction (PXRD) patterns of the sam-
present as part of layered arrangement on the orientation ples were recorded using a high resolution PANanalyti-
of the intercalants. cal empyrean diffractometer, equipped with PIXcel3D
detector employing Cu Kα radiation (λ=0.15418 nm)
1 Experimental with a scan rate of 110 s/step and step size of 0.01313º at
25 ºC over the 2θ range of 5º–70º. FTIR spectra of the
1.1 Synthesis details samples were recorded using a Perkin Elmer 2000 Fou-
rier-transform infrared spectrometer using KBr disks.
0.4072 g of La2O3 (1.25 mmol, Sigma Aldrich, 99.9%)
Raman spectra of the samples in compressed form were
was dissolved in 100 mL of acetic acid (1.75 g/mol
collected using a Renishaw spectrometer via microscope
Merck, GR grade) and the resultant solution was concen-
system equipped with an Ar+ laser (λ=785 nm). The
trated to 10 mL by heating over a hot plate. In a separate
photoluminescence (PL) spectroscopy measurements in
beaker, 1.2454 g of Co(CH3COOH)2·4H2O (5 mmol,
solid form were performed using a Horiba Jobin Yvon
Sigma Aldrich, >98.0%) was dissolved in 10 mL of dou-
Fluorolog 3 spectrofluorometer at room temperature.
ble distilled water. Both these solutions were poured si-
UV-visible diffuse reflectance spectra were recorded
multaneously into a solution containing 5 mL of H2O2 in
over the range of 200–900 nm using a Perkin-Elmer
30 mL of double distilled water. This mixture was stirred
Lambda 35 spectrophotometer equipped with a 50 mm
for 24 h at room temperature and further dried at 60 ºC
integrating sphere. BaSO4 was used as the reference.
over a period of 48–72 h.
Thermogravimetric experiments were carried out using a
Regeneration experiment was performed by soaking
NETZSCH STA 449F3 instrument at a heating rate of 10
0.1062 g of calcined oxide (obtained by heating Co-La
ºC/min over the temperature range of 50–1000 ºC. Con-
LDH at 400 ºC for 6 h in air) in 50 mL of acetic acid
centrations of cobalt and lanthanum in the samples were
which was concentrated by heating to approximately 10
determined from ICP analysis employing a Vista MPX
mL of volume, followed by the addition of 2 mL of 30%
Varian ICP-AES. Elemental analysis of the samples was
H2O2 and 40 mL of double distilled water. The solution
carried out using an Elementar Analysenysteme GMBH
was stirred for 24 h at room temperature to yield a sus-
Varian EL III by the combustion method. Scanning elec-
pension. The solid was recovered by slow evaporation at
tron microscopy (SEM) micrograph of the sample was
60 ºC.
captured using an FESEM (FEI Quanta 200 F) micro-
1.2 Intercalation experiments scope. Transmission electron microscopy (TEM) images
and SAED patterns were obtained using an FEI Technai
For the intercalation of benzoate ion, 0.3 g of calcined
G2 20 electron microscope operating at 200 kV. Mag-
oxide was suspended in 10 mL of double distilled water.
netic measurements were performed using a vibrating
In a separate beaker, 0.8 g of benzoic acid (Thomas
sample magnetometer (Microsence EV9) at room tem-
Baker, AR Grade, 99.9%) was dissolved in 20 mL of
perature.
double distilled water, to which the suspension contain-
ing the calcined oxide was added together with 2 mL of
30% H2O2. The whole suspension was then stirred at
room temperature for 24 h and finally dried at 60 ºC for
over a period of 48–72 h.
For the malonate ion intercalation, 0.4072 g La2O3
(1.25 mmol) dissolved in excess (100 mL) of acetic acid
was concentrated to 10 mL by heating over a hot plate.
Separately, 1.2454 g of Co(CH3COOH)2·4H2O (5.0
mmol, Sigma Aldrich>98.0%) was dissolved in 10 mL of
double distilled water. Both these solutions were poured
simultaneously into a solution containing 0.7 g of malo-
nic acid (Spectrochem, 99% in 30 mL distilled water)
and 5 mL H2O2. The resultant pink colored mixture was
Fig. 1 PXRD pattern of the product from the hydrolysis of co-
stirred for 24 h at room temperature, after which the
balt and lanthanum acetates (Peaks marked with “*” be-
product was dried at 60 ºC. The excess malonic acid in
long to Co(CH3COO)2·4H2O)
the samples was removed by washing it with a mixture
476 JOURNAL OF RARE EARTHS, Vol. 35, No. 5, May 2017

2 Results and discussion

In Fig. 1, PXRD pattern of the product from the si-
multaneous hydrolysis of cobalt and lanthanum acetates
in the presence of hydrogen peroxide is presented. Ex-
cept the less intense reflection at 2θ=13.48º (possibly due
to cobaltous acetate), all other reflections were related to
each other. The intensity profiling of the observed reflec-
tions strongly suggested a layered arrangement of the
product. Attempts to index the PXRD pattern in hexago-
nal lattice ( R 3 space group) with cell dimensions of
0.316 and 2.97 nm were not successful as it generated
lesser number of reflections than observed. However, on Fig. 3 TG/DTG traces of the product from the hydrolysis of
lowering the symmetry by choosing P 3 space group, all cobalt and lanthanum acetates
the observed reflections could be accounted with the
same unit cell dimensions. It has been reported that when was observed at 1426 cm–1 [27]. Cation contents of the
acetate ions were present in the interlayer between the sample determined by ICP analysis indicated the pres-
metal hydroxide layers, the basal spacing of LDHs varied ence of 30% and 16% of cobalt and lanthanum (in the
depending on the hydration levels[21–25]. In most of the molar ratio of 2:1), respectively. Fig. 3 shows the ther-
cases, acetate ions orient themselves in monolayer fash- mogravimetric trace of the sample. The weight of the
ion[22–25]. Considering the ionic radius of acetate anion as sample was decreasing continuously till 710 ºC after it
0.60 nm[22], the observed basal spacing of 0.977 nm cor- remained constant. The mass loss pattern was a complex
responded to the existence of acetate ion in the interlayer one consisting of seven steps. Till 250 ºC two distinct
as monolayer. steps were noticed and they could arise from the removal
Signature band due to the stretching vibrations of hy- of surface-adsorbed and interlayer water molecules, re-
droxide was noticed as a broad band at 3399 cm–1 in the spectively. From the mass loss, the presence of 0.88
FTIR spectrum of the sample (Fig. 2). Additionally, moles of interlayer water was estimated. The major mass
bands at 1423 and 1565 cm–1 were present corresponding loss beyond 300 ºC, indicated the simultaneous dehy-
to the symmetric and asymmetric stretching modes of the droxylation and decomposition of acetate[28]. Combining
COO– group, respectively. Finger print bands of the ace- the results from ICP, elemental and mass loss experi-
tate ion were observed at 1333, 1027, 946, 675 and 620 ments, a final formula of Co0.64La0.36(OH)2
cm–1 [19]. The presence of metal-oxygen and interlayer (CH3COO)0.36·0.88H2O could be arrived for our sample.
acetate anion was further confirmed from the observation The formation of metal hydroxide under the present
of Raman bands at 512, 621, 668, 939, 1350 and 1426 experimental conditions without the addition of any
cm–1 (Fig. 2)[26]. Peaks at 621 and 668 cm–1 represented strong base can possibly be due to the intrinsically weak
the rocking (out of plane) and deformation (symmetric) basicity of acetate anion. As compared with other salts of
modes of COO–, respectively. Raman peak at 939 cm–1 cobalt such as cobalt chloride, the cobalt ion derived
signified C-C stretching (symmetric) mode. The band at from cobalt acetate has been reported to form complex of
1350 cm–1 corresponded to the CH3 deformation (sym- the type Co(OH)2(OAc)2 very easily and rapidly[29]. The
metric) mode. Band due to C–O symmetric stretching precise mechanism of formation of this layered arrange-
ment is not presently clear, but perhaps may be related to
the generation of appropriate precursor species by the hy-
drolysis of the cations. The hydrolysis constants of various
metal ions are presently unknown with high precision so
as to propose an insight into the nature of precursor spe-
cies[30]. With all these limitations, the following mecha-
nism may be operative in the current set of reactions.
M(OOCCH3)x M(H2O)n+
x +CH3COOH

CH3COOH CH3CO3H

Fig. 2 FTIR spectrum of the product from the hydrolysis of co- Hydrogen peroxide may be oxidizing the acetic acid to
balt and lanthanum acetates with the inset showing its per acetic acid as it is a well known epoxide forming re-
Raman spectrum agent. The epoxide connecting cobalt and the lanthanum
Meenakshi Pokhriyal et al., Facile synthesis and characterization of acetate intercalated Co-La layered double hydroxide 477

The UV-visible diffuse reflectance spectrum of Co-La

LDH is reproduced in Fig. 6(a). Intense bands in the UV
and visible region was observed. While the absorption in
the UV region signified the LMCT arising due to bridged
carboxylate ligand[31], broad absorbance spanning from
400 to 670 nm confirmed the presence of octahedrally
coordinated Co2+ ions. Three spin-allowed d-d transitions
are possible for the octahedral Co2+ ions viz., ν1 (4T1g
(F)→4T2g (F)), ν2 (4T1g (F)→4A2g (F)) and ν3 (4T1g (F)→
4
T1g (P))[18,32]. Among these, ν1 and ν3 are of higher
probability, ν2 arising from two electron transition is of
low probability. A small hump observed at around 670
nm in our sample may correspond to ν2. The presence of
octahedrally coordinated Co2+ ion was further verified
from photoluminescence emission spectrum in which
bands at 413, 432 nm indicating the transitions of Co2+
Fig. 4 FESEM image (a), TEM (b), HR-TEM image (c) and ions are present (Fig. 6(b))[33]. Co-La LDH showed para-
SAED (d) pattern of product from the hydrolysis of co- magnetic behavior at room temperature (Fig. 7). The ef-
balt and lanthanum acetates fective magnetic moment (μeff) of this sample was calcu-
lated to be 3.19 μB, closer to the theoretical spin-only
ions may be the active precursor species which under- value for three unpaired electrons, 3.87 BM (high spin
goes further hydrolysis to result in Co-La LDH. Co2+; d7 system, S=3/2).
Lamellar morphology was quite evident in the SEM In Fig. 8, the PXRD patterns of the products from the
image of the sample (Fig. 4(a)). TEM, HR-TEM image
and SAED pattern of the sample are presented in Fig.
4(b–d), respectively. Hexagonal facets of the crystallites
were observed in the TEM image. The apparent lattice
fringes are presented in Fig. 4(c). Two interplanar dis-
tances of 0.201 and 0.251 nm between the adjacent
fringes could be calculated and they were in conformity
with the (0014) and (104) planar spacing observed in the
PXRD pattern of the sample. A ring pattern was ob-
served in SAED pattern and it could possibly be due to
the diffused spots. Highly crystalline sample by this pro-
cedure may not be viable as it is synthesized without the
use of any precipitating agent and/or ageing of precipi-
tates. On calcining Co-La LDH at 400 ºC in air, a mix- Fig. 5 PXRD pattern of Co-La LDH calcined at 400 °C (1) and
ture of Co3O4 and La2O3 formed (Fig. 5). When this was PXRD pattern of the regenerated product from the cal-
subjected to reconstruction experimental conditions, the cined oxide (2) (Reflections marked with “•” and “*” are
sample showed the formation of the parent layered dou- due to Co3O4 and La2O3, respectively)
ble hydroxide as evidenced by its PXRD pattern (Fig. 5).

Fig. 6 UV-visible diffuse reflectance spectrum (a) and photoluminescence emission spectrum (b) of Co-La LDH (λex=380 nm)
478 JOURNAL OF RARE EARTHS, Vol. 35, No. 5, May 2017

3 Conclusions
In summary, layered double hydroxide consisting of
Co2+ and La3+ -ions was successfully synthesized by the
room temperature hydrolysis of their acetates catalyzed
by hydrogen peroxide. The observed reflections in the
PXRD pattern could be indexed in hexagonal symmetry
(space group P 3 ). A plausible mechanism has been
proposed for the generation of such layered hydroxides
without the addition of a strong base. The presence of
octahedral Co2+ ion has been evidenced from UV-visible,
PL spectra and magnetization studies. Additionally, ace-
tate groups in the interlayer region promoted the charge
Fig. 7 Plot of magnetic susceptibility versus the magnetic field
transfer from the ligand to metal centers. The interlayer
of Co-La LDH at room temperature
acetate ion was exchanged with other organic anions
(both aliphatic and aromatic) paving way for the genera-
tion of organic derivative of inorganics. We believe that
results, described in present study will facilitate to gener-
ate other layered systems consisting of first row transi-
tion metal ions and other f-block ions and to study the
interplay between them.

Acknowledgements: Authors thank DST (SB/S1/PC-08/2012),

Govt. of India and University of Delhi under the “Scheme to
Strengthen R&D Doctoral Research Program” and DU-DST
PURSE Grant for funding the research. Meenakshi Pokhriyal
thanks CSIR for scholarship support. The authors wish to re-
cord their sincere thanks to USIC for instrumentation support.
Fig. 8 PXRD pattern of benzoate (1) and malonate (2) interca-
lated Co-La LDH (Reflections marked with “•” corre-
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