Article http://sciencetechindonesia.com

Article History
Received: 8 December 2016
Received in revised form: 15 February 2017
Accepted: 25 February 2017

DOI: 10.26554/sti.2017.2.2.45-49
©2017 Published under the term of  the CC BY NC SA license

Science & Technology Indonesia
p-ISSN: 2580-4405 e-ISSN: 2580-4391
Sci. Technol. Indonesia 2 (2017) 45-49

PILLARIZATION OF DOUBLE LAYER HYDROXIDES USING H3[α-PW12O40]·nH2O 
: EFFECT OF PILLARIZATION TIME

Muhammad Imron1*, Muhammad Said1

1Department of  Chemistry, Faculty of  Mathematics and Natural Sciences,  Sriwijaya University
*Corresponding Author E-mail : muhammadimron211195@gmail.com

ABSTRACT
The pillarization of  Mg/Al double layer hydroxides using polyoxometalate H

3
[α-PW

12
O

40
]·nH

2
O by comparing the pillarization time i.e. 3 

hours, 6 hours, 9 hours, 12 hours, 24 hours, 36 hours and 48 hours has been done. The product of  a pillarization was characterized using 
an FT-IR spectrophotometer and XRD analysis. The result characterization of  FT-IR spectrophotometer does not show the optimum 
of  pillarization each time condition. Characterization using XRD shows the optimum pillarization process at 36 hours by showing the 
existence of  double layer hydroxides material at diffraction angle 11.69o deg, 18.30o deg and 34.71o deg. Diffraction in the 60o-63o deg 
indicates the existence of  a pillarization double layer hydroxides. 

Keywords: Layered double hydroxides, pillarization, polyoxometalate H
3
[α-PW

12
O

40
]·nH

2
O.

INTRODUCTION
Inorganic materials can be classified into layered materials and 

porous materials. These materials have their respective advantag-
es as absorbents, catalysts, ion exchangers, and sensors (Lin et al, 
1997). The layered material is divided into two types: layered mate-
rials are in nature and coated materials are synthesized in the lab-
oratory (Han et al, 2017). The layered material in nature has many 
advantages such as kaolin, halloysite (halloysite), illite, vermiculite, 
bentonite and much more. The layered compounds that are in the 
interior have a deficiency that is still a lot of  impurities and is diffi-
cult to replace (Shimizu et al, 2006). 

Meanwhile, the synthetic-coated and modification materials in 
the laboratory have many advantages i.e. fewer impurities and the 
structure is easy to replace so it can be modified and widely applied 
as adsorbent or catalyst for example double layer hydroxides. Aside 
from being an absorbent and a catalyst, double layer hydroxides 
is usually applied as ion exchangers, catalyst carriers, in industry, 
and medicine (Delidovich & Palkovits, 1991). For example, a dou-
ble-layer hydroxides material commonly used as a catalyst for con-
densation reactions is Mg/Al hydrotalcite (Mg/Al mole ratio in the 
range of  2.1 to 3.6) with carbonate and nitrate anions in interlayer 
space (Hincapié et al, 2017). 

In the use of  layered materials still have weaknesses that are 
small surface area and the distance between the narrow layers due 
to the presence of  small exchange ions (Goodarzi et al, 2016). To 
overcome this problem, the double layer hydroxides is modified 
by means of  pillarization. The studies were undertaken by Zhang 
(2004) and Qin (2014) double layer hydroxides were inserted anion 
carboxylic and folic acid compounds and produced a surface area 
of    40-48 m2/g. This result is better than the undamaged double 
layer hydroxides surface area of    26 m2/g. When compared Kwon 
and Pinnavaia (1989) to Zhang (2012), He studied double layer 

hydroxides was inserted using two types of  α[SiV
3
W

9
O

40
]4- and 

H
3
PW

12
O

40
 compounds which comprised a Keggin-type polyox-

ometalate compound with 155 m2/g surface area Uncoated dou-
ble layer hydroxides surface area of    26 m2/g. This suggests that 
the polyoxometalate compound can produce a larger surface area 
compared to other anion compounds so that the polyoxometalate 
double layer hydroxides can be effectively used as an adsorbent. 

Based on the Pinnavaia (1996), the double layer hydroxides 
Mg/Al intercalated with anionic polyoxometalate compound 
with Keggin (α-H

2
W

12
O

40
6-) has a height of  10, while the Daw-

son type (α-P
2
W

18
O

62
6-) has two altitudes of  14.5 and 12.8, Fin-

ke (Co
4
(H

2
0)

2
(PW

9
O

34
)

2
10-) The double layer hydroxy Mg

3
Al 

intercalated with anionic polyoxometalate compound with Keg-
gin (α-H

2
W

12
O40

6
-) has a height of  10, while the Dawson type 

(α-P
2
W

18
O

6
26-) has two altitudes of  14.5 and 12.8, Finke (Co

4
(H

2
O)

2
 

(PW
9
O

34
)

2
10-) also has two heights of  13.3 and 12.6. The also has 

two heights of  13.3 and 12.6. The differences in polyoxometalates 
orientation are rationalized in terms of  different electrostatic in-
teractions and hydrogen bonds between the polyoxometalate pillar 
and the double layer  hydroxide layer. In this study, a double layer 
hydroxides was pillarized with polyoxometalate H

3
[α-PW

12
O

40
]·n-

H
2
O. The pillarization time was studied in order to know the opti-

mal time for these process. 

EXPERIMENTAL SECTION
Equipments

Equipments used in this research are a set of  standard labo-
ratory, magnetic stirrer, thermometer, hot plate, oven, vacuum,  
desiccator,  X -Ray Diffraction (Rigaku Miniflex 600), and FT-IR 
spectrophotometer (Shimadzu prestige-21).

Materials
The materials used in this research are sodium phosphate 

(Na
3
PO

4
), sodium tungstate (Na

2
O

4
W), hydrochloric acid (HCl), 

potassium hydroxide (KOH), potassium chloride (KCl), diethyl 
ether ((C2H5)2O), sodium hydroxide (NaOH), sodium carbonate 
(Na

2
CO

3
), magnesium nitrate (Mg(NO

3
)
2
), aluminum nitrate (Al(-

NO
3
)

3
).

mailto:muhammadimron211195@gmail.com


Imron et al. 2017/Science & Technology Indonesia 2 (2) 2017:45-49

© 2017 Published under the term of  the CC BY NC SA 4.0 licence 46

Procedures
Synthesis of  Mg/Al Double Layer Hydroxides

The double layer hydroxy preparation was carried out by mixing 
as much as 64.01 g of  Mg(NO

3
)

3
.6H

2
O (2 mol) and 46.64 g  of  

Al(NO
3
)
3
.9H

2
O (1 mol) into 150 mL of  quads (solution A). A total 

of  NaOH with 26.62 g NaCO
3
 was dissolved in 150 mL aquades 

(solution B). Solution A is added to solution B and stirred slowly 
followed by the addition of  100 mL of  aquades and a pH ranging 
from 9 to 10 to form a precipitate. The obtained precipitate is dried 
in an oven at 80 °C and ready to be characterized using FT-IR 
spectroscopy, and XRD analysis.

Synthesis of  Polyoxometalate H3[α-PW12O40]·nH2O
A total of  125 g of  sodium tungstate and 20 g of  sodium phos-

phate were mixed with 187.5 ml of  boiling water in 500 mL of  a 
glass beaker. A total of  100 ml of  concentrated hydrochloric acid 
was added slowly to the mixture and stirred using a magnetic stir-
rer. The stirring process is continuous or continuous which causes 
the solid to dissolve. The phosphotungstate acid will begin to sep-
arate when half  of  the hydrochloric acid is added then the resulting 
solution becomes clear and cooled. A cold solution was added 75 
mL of  diethyl ether and extracted. After extraction process ob-
tained 3 layers which then separated and taken the bottom layer. 
The bottom layer obtained was evaporated using a rotary evapora-
tor to obtain a white solid H

3
[α-PW

12
O

40
]·nH

2
O. Characterization 

of  H
3
[α-PW

12
O

40
]·nH

2
O compounds was performed using FT-IR 

spectrophotometer and XRD analysis.

Pillarization Double-layer hydroxides with Polyoxometalate 
H3[α-PW12O40]•nH2O

Two grams of  double layer hydroxy were dissolved 25 NaOH 
and 1 g of  polyoxometalate compound with 50 ml of  aquades then 
heated to 70 oC (using a hot plate) under N

2
 gas. After 1 hour of  

reaction, the temperature is lowered to 30 °C. Then the suspension 
is cooled and the product is washed with water and dried at room 
temperature. Characterization of  pillarization compounds was 
done using XRD, and FT-IR spectrophotometer.

RESULTS AND DISCUSSION
Preparation and Characterization of  Double Layer Hy-
droxides, Polyoxometalate H3[α-PW12O40]·nH2O and Dou-
ble Layer Hydroxy Pillarization with Polyoxometalate 
H3[α-PW12O40]·nH2O  Using FT-IR Spectrophotometer.

Synthesis of  double layer hydroxides compound using magne-
sium nitrate and aluminum nitrate to form Mg/Al double layer 
hydroxides. M2+ charged metal cations represent magnesium and 
aluminum represented by M3+ each of  which is bound to an OH- 
anion. The results of  the process of  synthesis this double layer 

hydroxides are white solid, which is further characterized by using 
FT-IR spectrophotometer (Hanifah & Palapa, 2016).

The FT-IR spectra of  the double layer hydroxides material is 
presented in Figure 1. The widespread vibration peak between the 
3800-300 cm-1 wave numbers is the vibration of  the OH strain 
within the structure of  the double layer hydroxides. The presence 
of  a peak detected at the wave number 1635.54 cm-1 is the bend vi-
bration of  OH. In the region of  wavenumber 1381.03 cm-1, there is 
a vibration which is symmetrical stretching of  nitrate and     671.23 
cm-1 is nitrate bending vibration. In the wave number 408.91 cm-1 
is the vibration of  Mg-O (Swenson et al, 2016).

Synthesis of  polyoxometalate H
3
[α-PW

12
O

40
]·nH

2
O compound 

using concentrated hydrochloric acid which aims to form phos-
photungstate acid so as to cause the acidity of  the polyoxometalate 
compound to increase. The result of  the synthesis of  polyoxome-
talate compound of    H

3
[α-PW

12
O

40
].nH

2
O is in the form of  white 

solid.
After the formation of  the H

3
[α-PW

12
O

40
]·nH

2
O, the com-

pound was then characterized using an FT-IR spectrophotometer 
which serves to identify functional compound groups formed on 
the H

3
[α-PW

12
O

40
]·nH

2
O. The FT-IR spectrum of  the polyoxome-

talate H
3
[α-PW

12
O

40
]·nH

2
O compound of  the result of  the mea-

surement is shown in Figure 2.
Figure 2 shows the peaks of  the functional groups of  the poly-

oxometalate H
3
[α-PW

12
O

40
].nH

2
O  compound appear at about 

4000-400 cm-1 wavenumbers. The wave number 1081 cm-1 is a P-O 
vibration. The wave number 987 cm-1 denotes the vibration W = 
O. At the 802 cm-1 wavenumber is a W-Oc-W vibration (Kim et 
al.2009).

The double layer hydroxides pillilization process with the poly-
oxometalate H

3
[α-PW

12
O

40
].nH

2
O compound was conducted to 

increase the distance between the double layer hydroxides layer to 
wider by replacing the OH-anion present in the double layer hy-
droxides using a larger anion of  the polyoxometalate-type keggin 
[α-PW

12
O

40
]3-.

The double layerhydroxides pillar by using anion [α-PW
12

O
40

]3- 
was carried out with aquades augmentation of  the polyoxometa-
late H

3
[α-PW

12
O

40
].nH

2
O compound and the addition of  sodium 

hydroxide to the double layer hydroxides material to form a sus-
pension aimed at facilitating the process of  anion exchange in the 
process the pillarization. To find out that there are other anions 
involved in the process of  pillarization such as carbonate, the pro-
cess of  pillarization is done by using inert gas nitrogen. This ni-
trogen gas can drive and remove carbonate ions and be released 
as CO

2
.

 Therefore, the process of  pillarization of   double-layer hydroxy 
material with polyoxometalate  H

3
[α-PW

12
O

40
].nH

2
O compounds 

in this study was conducted by varying the time of  pillarization 

Figure 1 FT-IR spectra of  Mg/Al double layer hydroxides com-
pound

Figure 2. FT-IR spectra of  the polyoxometalate H
3
[α-PW

12
O

40
].

nH
2
O



Imron et al. 2017/Science & Technology Indonesia 2 (2) 2017:45-49

© 2017 Published under the term of  the CC BY NC SA 4.0 licence 47

for 3 hours, 6 hours, 9 hours, 12 hours, 24 hours, 36 hours, and 48 
hours for the purpose of  determining the double layer hydroxides 
material which is the most optimized pillarization of  the polyoxo-
metalate H

3
[α-PW

12
O

40
] compound. At the end of  the process of  

pillarization of  polyoxometalate compounds H
3
[α-PW

12
O

40
].nH

2
O 

obtained white solids. 
The result of  pillarization process of  Mg-Al double-layer hy-

droxides material with H
3
[α-PW

12
O

40
].nH

2
O was characterized 

using FT-IR spectrophotometer to see functional group formed. 
FT-IR spectrum resulted from the pillaration of  double layer hy-
droxides material with H

3
[α-PW

12
O

40
].nH

2
O of  the measurements 

shown in Figure 3.
The presence of  functional groups seen in the 3-hours time 

frame in Figure 3a indicates the presence of  vibration 3463.15 
cm-1 represents O-H stretching. At the 1635.54 cm-1 wavenumber 

is the vibration of  the O-H bond. At the wavenumber 1373.32 
cm-1 showing the symmetric nitrate of  the synthesis product of  the 
double layer hydroxides Mg-Al. In the wavenumber 447.49 cm-1 
shows the presence of  Mg-O. These four peaks are also seen in the 
FT-IR spectra in Figure 3b, 3c, 3d, 3e, 3f, and 3g. These four peaks 
indicate the presence of  a Mg-Al double-layer hydroxides material.
Figure 3a shows the presence of  a vibration peak for a polyox-
ometalate compound at an 856.39 cm-1 wavenumber indicating a 
W-Oc-W vibration. In Figure 3b shows that a vibration peak of  
a polyoxometalate compound appearing at 1056.99 cm-1 indicates 
the presence of  P-O vibration and 771.53 cm-1 indicating the vibra-
tion of  W-Oc-W. Figure 3c shows the presence of  W-Oc-W vibra-
tion at the wave number 786.9 cm-1. Figure 3d shows the presence 
of  W-Oc-W vibration at the wave number 763.61 cm-1. Figure 3e 
shows the presence of  W-Oc-W vibration at wavenumber 671.23 
cm-1. Figure 3f  shows the existence of  P-O vibration at wavenum-
ber 1049.28 cm-1 and vibration of  W-Oc-W at wavenumber 779.24 
cm-1. Figure 3g shows the presence of  W-Oc-W vibration at the 
wavenumber 786.96 cm-1. From the results of  measurements with 
FT-IR spectrophotometers, FTIR spectrum have not been able to 
show optimal pillarization results between the comparison of  the 
time of  pillarization of  3 hours, 6 hours, 9 hours, 12 hours, 24 
hours, 36 hours and 48 hours. Next, is measured by X-ray powder 
diffraction to determine the optimal time of  pillarization.

Characterization of  Double Layer Hydroxides, Polyoxome-
talate H3[α-PW12O40]·nH2O and Double Layer Hydroxides 
Pillared with Polyoxometalate H3[α-PW12O40]·nH2O  Using 
X-Ray Analysis

The double layer hydroxides material characterized using XRD 
is presented in Figure 4. Double layer hydroxy has a strong dif-
fraction peak at 2θ value i.e. 11.70 with basal spacing 7.5 . The 
diffraction angles at 29 deg, 27deg and 28deg are typical of  the 
Mg-Al double layer hydroxides. According to Hurma and Kose 
(2016), the X-ray diffraction pattern showing the layered structure 
is in the 2θ diffraction of  10deg and 60deg. The layered structure 
allows the anion to reside on the interlayer of  the double layer 
hydroxides material, according to Brandl et al (2017) the peak in 
the 2θ diffraction pattern of  60o deg indicates that the presence 
of  anions on interlayers may be anion nitrate, carbonate, hydroxy 
or other anions.

Analysis of  the polyoxometalate H
3
[α-PW

12
O

40
].nH

2
O com-

pound was followed by characterization using X-ray diffraction. 
This characterization is aimed at determining the optimal pillar-
ization time obtained from the crystallinity of  the compound and 
determining the height of  the gallery in the layered structure. The 
XRD pawder pattern of   H

3
[α-PW

12
O

40
].nH

2
O is shown in Figure 

5.
Figure 5 shows the X-ray diffraction patterns H

3
[α-PW

12
O

40
].

nH
2
O compounds with the 2θ main regions of   15-20o deg, 24-31o 

deg, and 40-45o deg wherein those diffraction are characteristic for 
crystalline polyoxometalate compounds H

3
[α-PW

12
O

40
].nH

2
O. The 

result of  the measurement analysis is known that the highest peak 
occurs in the 25-31o deg and 45o deg.  Further, the polyoxometalate 
compound is pillared with a double layer hydroxides material at 
various times of  pillarization which aims to increase the distance 
between layers in a double layer hydroxy material. The polyoxome-
talate H

3
[α-PW

12
O

40
].nH

2
O compound obtained from the prepara-

tion results is further pillarized by double layer hydroxides material. 
The pillarized material is further characterized by X-ray power dif-
fraction as in Figure 6. 

Figure 6a shows the highest peak of  11.50, 23.110, dan 34.520. 

Figure 3. The FT-IR spectrum of  double layer hydroxides was 
pillarized by polyoxometalate with a various times of  pillarization 
(a) 3 hours, (b) 6 hours, (c) 9 hours, (d) 12 hours, (e) 24 hours, (f) 

36 hours, (g) 48 hours.

Figure 4. X-ray diffraction pattern of  double layer hydroxides



Imron et al. 2017/Science & Technology Indonesia 2 (2) 2017:45-49

© 2017 Published under the term of  the CC BY NC SA 4.0 licence 48

Figure 5b shows areas comprising regions of  11.560, 23.230, and 
34.600 having relatively high crystallinity (Matsunaga et al, 2017). 
These three diffractions denotes the properties of  double layer hy-
droxide materials having a plated structure with a basal spacing of  
7.64Å, 3.82 Å, and 2.59 Å, The area that emerged in 600-630 shows 
an anion adhesion on the interlayer of  double layer hydroxide ma-
terial.

Figure 6c shows an angular difference of  the diffraction form 
showing the presence of  a Mg-Al double layer hydroxides material 

in region 2θ having a peak of  11.470 23.220, and 34.630 indicated 
the successfully of  anions present in a double layer hydroxides ma-
terial. Diffraction at 62.020 with a basal value the largest spacing 
compared to the 3 hours and 6 hours pillarization times. Figure 6d 
has the same diffraction pattern as Figure 6a.

Figure 6e shows a diffraction angle of  11.120, 22.850, and  34.50. 
Figure 5f  shows also the presence of  a double layer hydroxides 
pillared material at 11.6910 diffraction angle with a larger basal 
spacing compared to a double layer hydroxy material of  0.00644 
Å.  Diffraction at 18.300 with a larger basal spacing compared to a 
double layer hydroxides material 0.06 Å. As well as the diffraction 
angle of   18. 330 has a difference of  0.03 Å, and the diffraction 
angle of   4.710  deg has a difference of  0.00466 Å. While in Figure 
6g has a diffraction angle of  11.980, and 35.110 with basal spacing 
7.38 Å and 2.55 Å. Therefore, the most success of  pillarization is 
36 hour time comparison of  the other times.

CONCLUSION
Pillarization of  Mg/Al double layer hydroxides with polyoxo-

metalate H
3
[α-PW

12
O

40
].nH

2
O at various times showed that pillar-

ization at 36 hours can optimal pillar double layer hydroxides. 

ACKNOWLEDGEMENT
The author would like to thank Prof. Aldes Lesbani, Ph.D for 

fruitful discussion of  this research.

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