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Spectrochimica Acta Part A 64 (2006) 273–278

Determination of structural modification in acid activated


montmorillonite clay by FT-IR spectroscopy
Beena Tyagi ∗ , Chintan D. Chudasama, Raksh V. Jasra
Department of Silicates and Catalysis Discipline, Central Salt and Marine Chemicals Research Institute (CSMCRI),
G.B. Marg, 364 002 Bhavnagar, Gujarat, India

Received 18 May 2005; accepted 5 July 2005

Abstract

The structural modifications and the Bronsted acid sites generated during the acid treatment of montmorillonite clay with varied concentration
of sulphuric acid was determined using FT-IR spectroscopy. Octahedral sheet is affected at low acid concentration resulting into the dissolution
of cations; among them Mg2+ cations are prone to dissolve than Fe2+/3+ and Al3+ . Tetrahedral sheet is affected at higher acid concentration.
The partial substitution of octahedral Al3+ by Mg2+ or Fe2+/3+ cations and the presence of other non-smectite minerals such as kaolinites was
also been clearly identified, thus making FT-IR spectroscopy as a rapid technique for monitoring the structural features of montmorillonite
clay.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Acid activation; Montmorillonite; FT-IR spectroscopy; Structural modification

1. Introduction thus making the composition of T-O-T (Fig. 1). Invariably a


partial substitution of Al3+ in octahedral sites by Mg2+ and
Acid-activated montmorillonite clays find wide applica- Fe2+ /Fe3+ and to a lesser degree, a partial substitution of
tions in chemical, foodstuff, beverage, and paper industry as Si4+ in tetrahedral sites by Al3+ is observed in the natural
well as for cleaning and detergents usage [1]. They are also clay samples. Due to this substitution, T-O-T layers are neg-
used as catalysts [2–4] and catalyst support [5,6]. In fact, acid- atively charged and interlayer space between T-O-T layers is
treated montmorillonite clay is one of the widely studied solid occupied by exchangeable cations such as Na+ , K+ , Ca2+ to
acid catalysts for many organic transformations such as iso- neutralize the charge. During acid treatment of the clay, ini-
merisation [7], alkylation [5,6,8] and acylation [9] reactions. tially interlayer cations are replaced with H+ ions followed by
The treatment of natural purified montmorillonite clay with dissolution of aluminium octahedral and silicon tetrahedral
hot mineral acid is known to impart surface acidity to the clay, sheets with subsequent dissolution of structural cations. The
which results into its improved adsorption and catalytic prop- structural changes occurring in the clay depend on both the
erties. Montmorillonite is dioctahedral clay of smectite group clay type and acid treatment conditions such as acid concen-
and is composed of stacked alumino-silicate layers. The silica tration time and temperature. For example, Hectorite, a trioc-
tetrahedra (T) (Si4+ in tetrahedral coordination with O2− ) and tahedral smectite clay dissolves faster than montmorillonite,
alumina octahedra (O) (Al3+ in octahedral coordination with a dioctahedral clay. Further, increased Mg or Fe cations in
O2− ) are interconnected (by the sharing of O2− at polyhedral the clay structure also increase the dissolution rate. The final
corners and edges) in such a way that a sheet of alumina octa- reaction product of acid treated smectite is similar, the amor-
hedral is sandwiched between two sheets of silica tetrahedral, phous silica with a three dimentional cross-linked structure.
However, for catalytic applications the complete dissolution
∗ Corresponding author. Tel.: +91 278 2471793; fax: +91 278 2567 562.
of parent clay mineral is not desirable. Komadel et al. [10]
E-mail addresses: btyagi@csmcri.org (B. Tyagi), rvjasra@csmcri.org found mildly acid treated Mg-rich montmorillonite and hec-
(R.V. Jasra). torite to be catalytic active; treatment for a prolonged time

1386-1425/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2005.07.018
274 B. Tyagi et al. / Spectrochimica Acta Part A 64 (2006) 273–278

Fig. 1. Structure of montmorillonite clay.

or with higher acid concentration resulted in the decrease of determine the isomorphic substitution in octahedral layer, as
activity or completely catalytic inactive clay to yield tetrahy- well as identifying the presence of non-smectite phases as the
dropyranyl ether from 2,3-dihydropyran with methanol. The impurities in the clay.
surface acidity and textural properties like surface area and
pore volume, which determine the catalytic and adsorption
behaviour of the clay largely depend on the structural modifi- 2. Experimental
cations resulting on acid treatment. Therefore, it is imperative
to monitor the structural and textural modification occurring 2.1. Materials and methods
during the acid treatment. Various analytic methods such
as X-ray diffraction, cation exchange capacity, and surface Natural montmorillonite clay was procured from Barmer
area, besides chemical composition, are employed to study district of Rajasthan, India. Concentrated H2 SO4 (98% assay)
the effect of acid-activation on the clay structure. Infra red was purchased from s. d. Fine Chemicals, India.
spectroscopy, a relatively simpler and sensitive technique is Natural clay was up-graded by sedimentation to remove
used to study the mineralogical and chemical structure of clay impurities like grit before use. Typically, 10 g of natural clay
minerals [11,12] and has emerged as a powerful tool to study was vigorously stirred in 1 l of distilled water and then kept for
the structural modification of clays during the acid treatment sedimentation for 24 h. The fraction corresponding to 2/3rd
[13–16]. Effect of HCl and H2 SO4 acid concentration and of the uppermost portion of the supernatant was separated
time of acid treatment on the acidity and catalytic activity of and dried in atmosphere for 2 days; dried residue was pow-
clays was studied by Komadel et al. [10]. FT-IR spectroscopy dered and sieved to150 mesh particle size. The up-graded
has also been used for investigating the nature of acid sites clay (1 g) was refluxed with H2 SO4 (5 ml) of various con-
present on solid acids [17–20]. In the present work, we report centrations (1–10 N) at 80 ◦ C for 4 h. The slurry was cooled,
the use of FT-IR spectroscopy technique to study the struc- filtered and washed thoroughly with hot distilled water, till
tural modifications occurring in montmorillonite clay during the filtrate was free from sulphate ions (checked by BaCl2
its acid activation with varied concentration of sulphuric acid. solution). It was dried initially at room temperature followed
It has been shown that this technique can also be used to at 120 ◦ C for 6 h. The lumps of dried clay were powdered and
B. Tyagi et al. / Spectrochimica Acta Part A 64 (2006) 273–278 275

Table 1 Table 2
Chemical analysis (wt.%) of untreated and treated montmorillonite clay Dissolution (wt.%) of cations and increase (wt.%) of SiO2 in montmoril-
Sample SiO2 Al2 O3 Fe2 O3 MgO CaO Na2 O K2 O TiO2 lonite clay after acid treatments
Sample SiO2 Al2 O3 Fe2 O3 MgO CaO Na2 O K2 O
N0 56 23.3 7.6 3.0 6.0 2.1 1.08 0.058
N-1 60 20.8 8.1 3.2 4.7 1.94 0.98 0.063 N-1 7.1 10.7 – – 21.7 7.6 9.3
N-2 62 20.6 7.1 3.0 4.5 1.90 0.90 0.064 N-2 10.7 11.6 6.6 – 25.0 9.5 16.7
N-3 65 19.0 7.0 2.8 4.0 1.86 0.89 0.050 N-3 16.1 18.0 7.9 6.7 33.3 11.4 17.6
N-4 66 19.1 6.9 1.9 3.8 1.82 0.82 0.054 N-4 17.8 18.4 9.2 36.7 36.7 13.3 24.0
N-5 68 18.3 6.6 1.8 3.5 1.80 0.64 0.059 N-5 21.4 21.4 13.1 40.0 41.7 14.3 40.7
N-6 69 17.5 6.4 1.6 3.2 1.60 0.50 0.054 N-6 23.2 24.9 15.8 46.7 46.7 23.8 53.7
N-7 70 16.5 6.3 1.4 2.9 1.20 0.44 0.058 N-7 25.0 29.1 17.1 53.3 51.7 42.8 59.2
N-8 71 16.6 6.1 1.0 2.1 1.10 0.32 0.048 N-8 26.8 28.7 19.7 66.7 65.0 47.6 70.4
N-9 73 16.2 5.9 0.82 1.7 0.84 – 0.056 N-9 30.3 30.5 22.4 72.7 71.7 60.0 –
N-10 74 12.4 5.7 0.70 1.4 0.70 – 0.057 N-10 32.1 46.8 25.0 76.7 77.0 66.7 –

Table 3
sieved to150 mesh particle size. The clay samples thus pre- FT-IR band assignments for montmorillonite clay
pared are designated as N-1 to N-10 with the suffix indicating Maxima (cm−1 ) Assignments
the concentration of H2 SO4 used during the digestion. The 3697 OH stretching
untreated clay is designated as N0 . The chemical analysis of 3623 OH stretching
untreated and treated clay samples were done using the meth- 3440 OH stretching, hydration
ods described by Vogel [21] and Oulton [22] and the data are 1639 OH bending, hydration
1113 Si O stretching, out-of-plane
summarized in Table 1. In general, SiO2, Al2 O3 , CaO and
1035 Si O stretching, in-plane
MgO contents were determined gravimetrically; Fe2 O3 and 915 AlAlOH bending
TiO2 by UV spectroscopy and Na2 O and K2 O were deter- 875 AlFeOH bending
mined by flame photometery. 836 AlMgOH bending
793 Platy form of tridymite
692 Quartz
2.2. FT-IR spectroscopy 529 Si O bending

FT-IR study was carried out using Perkin-Elmer Spec-


trum GX having a standard mid-IR DTGS detector. FT-IR 3.1. Partial substitution in octahedral layer
spectra were recorded, in the range of 400–4000 cm−1 at a
resolution of 4 cm−1 with KBr pellets technique. The KBr The partial substitution of Al3+ in octahedral layer by
pellets were prepared by mixing the clay sample with KBr Mg2+ and Fe2+ can be clearly seen by FT-IR spectra as
powder (around 1:100) and using a Hydraulic press at the the vibrations involving the protons, especially OH vibra-
pressure of 10 tonnes. All the clay samples were dried at tions are directly affected by the nearest cationic environ-
120 ◦ C for 6 h and cooled under vacuum before recording the ment and provide information about the nature and content
spectra. of the cations. FT-IR spectrum of untreated clay (Fig. 2)
shows the bands at 3697 and 3623 cm−1 in OH stretching
region, which are assigned to hydroxyl groups coordinated
3. Results and discussion to octahedral cations [14], among which 3623 cm−1 is due to
hydroxyl group bonded with Al3+ cations [16]. The broad-
The studied montmorillonite clay contains mainly Al3+
with some Fe2+/3+ and Mg2+ as octahedral cations and Na+ ,
K+ and Ca2+ as exchangeable interlayer cations (Table 1).
Dissolution (%) of cations after acid treatment is calculated
and given in Table 2. The characterized vibrations of var-
ious hydroxyl groups associated with octahedral cations,
silicates, quartz and water present in the clay are listed in
Table 3. The most intensive band at 1035 cm−1 is attributed
to Si O in-plane stretching and 529 cm−1 is due to Si O
bending vibrations. The shoulder at 1113 cm−1 shows Si O
out-of-plane stretching vibration. The broad bands at 3440
and 1639 cm−1 are the stretching and bending vibrations for
the hydroxyl groups of water molecules present in the clay.
The other specific spectral features observed are discussed
below. Fig. 2. FT-IR spectra of untreated montmorillonite clay.
276 B. Tyagi et al. / Spectrochimica Acta Part A 64 (2006) 273–278

Fig. 3. FT-IR spectra of untreated (N0 ) and treated (N-1 and N-10) mont-
morillonite clay.

ness of 3623 cm−1 band shows the substitution of octahedral


Al3+ by Fe2+ or Mg2+ cations. Three bending vibrations of
hydroxyl groups associated with these cations, i.e., 915 cm−1
(AlAlOH), 875 cm−1 (AlFeOH) and 836 cm−1 (AlMgOH)
confirm the substitution in octahedral layer [1,12,14]. The
inflexion at 875 cm−1 and less intensive band at 836 cm−1
Fig. 4. FT-IR spectra of treated, N-1, N-4, N-7 and N-10 montmorillonite
indicates low content of Mg and Fe in the clay sample, which clay.
is in agreement with the chemical analysis data (Table 1).
treated with 10 N acid concentration. It clearly shows that
3.2. Presence of non-smectite phases Mg2+ ions are more prone to acid attack.
The shape of Si O stretching band at 1035 cm−1 shows the
The spectrum of untreated clay (Fig. 2) shows the pres- changes in Si environment after 6 N acid treatment (Fig. 5).
ence of non-smectite phases in the sample. The well resolved,
sharp and intense band at 3697 cm−1 in OH stretching
region along with the band at 915 cm−1 in OH bending
region indicates the presence of crystalline kaolinite in the
sample [11,12,14]. Thus the band at 915 cm−1 is associated
not only with AlAlOH vibration of montmorillonite but also
with the vibrations of kolinite. Madejova et al. [14] identi-
fied the variable amount of kaolinite in different samples of
montmorillonite and found IR spectroscopy more sensitive
than XRD, as out of 11 samples of montmorillonite studied,
presence of kaolinites was identified in 5 samples by IR spec-
troscopy, whereas XRD showed the presence of kaolinites
only in 3 samples. Furthermore, bands at 793 and 692 cm−1
show the presence of quartz admixtures present in the sam-
ple; the strong band at 793 cm−1 is assigned to platy form of
disordered tridymite and 692 cm−1 for quartz content [12].

3.3. Structural modification due to acid treatment

FT-IR spectra (Fig. 3) of untreated (N0 ) and treated (N-1


and N-10) clay samples show the effect of acid concentration
on overall clay structure. The intensity of hydroxyl bending
vibration at 836 cm−1 (AlMgOH) and 875 cm−1 (AlFeOH)
reduces with increasing acid concentration (N-1 to N-10)
(Fig. 4), indicating the leaching of substituted Mg and Fe
cations with increasing acid concentration. The decrease in
the intensities of the bands indicates more decrease for Mg2+
than Fe2+ cations. The chemical analysis data (Table 2) also
shows higher leaching (77%) of MgO than Fe2 O3 ( 25%) after Fig. 5. FT-IR spectra of N-6 and N-7 montmorillonite clay.
B. Tyagi et al. / Spectrochimica Acta Part A 64 (2006) 273–278 277

Fig. 6. FT-IR spectra of N0 and N-1 montmorillonite clay.


Fig. 7. FT-IR spectra of N0 , N-2, N-7 and N-10 montmorillonite clay.

The Si O bending vibration at 529 cm−1 shifted towards with 2 N acid concentration, the intensity of which increases
higher frequency at 534 cm−1 and its intensity increases with with increasing acid concentration (Fig. 7). This band at
increasing acid treatment. It shows the effect on tetrahedral 3655 cm−1 , which was absent in the untreated clay sample, is
sheet at higher acid concentration (>6 N). assigned to the hydroxyl groups coordinated to Bronsted acid
The band at 793 cm−1 (tridymite) shifts at 796 cm−1 sites in clays [24] and zeolites [18]. These acid treated mont-
and the intensity of the band significantly increases even morillonite clay samples were also studied for the Bronsted
after 1 N acid treatment (Fig. 6), which further increases acid catalyzed isomerisation of ␣-pinene [7], wherein more
with increasing intensity of acid treatment. The band at than 96% ␣-pinene conversion was observed. Our resent FT-
692 cm−1 (quartz) also shows the increase in intensity after IR spectroscopic study using pyridine adsorption on the same
1 N acid treatment. The chemical analysis data (Table 2) also acid treated montmorillonite [25] also showed the formation
shows 32% total increase of SiO2 , out of which 7% increase of strong Bpy acid sites after the acid treatment. Thus, the
occurs only after the treatment with 1 N acid concentration. treatment of montmorillonite clay used with varied concen-
Dissolution of tetrahedral silica from the clay structure is tration (1–10 N) of H2 SO4 resulted into catalytic active clay
not likely to occur with lower acid concentration (1 N) as having Bronsted acid sites.
tetrahedral layer is relatively stable and is only affected at
higher acid concentration. On the other hand, octahedral
layer is affected at lower acid concentration [23]. There- 4. Conclusions
fore, the observed increase in silica at lower acid treatment is
due to the leaching of octahedral and exchangeable cations FT-IR spectroscopy is a sensitive and powerful technique
resulting the increase in the percentage of silica in total per- for characterization of the starting minerals and identifica-
centage of all minerals present in a given amount of clay tion of other minerals such as kaolinite or quartz, as the
sample. impurities in the montmorillonite clay sample and thus for
The bands at 3440 and 1639 cm−1 for water of hydration monitoring the purity of the clay. To understand the mod-
show significant decrease with increasing acid concentra- ification in chemical structure of clay on acid treatment,
tion (Fig. 3). The intensity of hydroxyl stretching bands at FT-IR study clearly demonstrates that sulphuric acid affects
3697 and 3623 cm−1 also reduces with increasing acid con- first the octahedral sheet of montmorillonite clay resulting
centration. It is due to the removal of octahedral cations into the dissolution of octahedral cations. Higher acid con-
causing the loss of water and hydroxyl groups coordinated to centration attacks the tetrahedral layer. Bronsted acid sites
them [16]. Furthermore, an important observation was noted generated during the acid treatment can be detected by FT-IR
that a shoulder at 3655 cm−1 starts to develop after treated spectroscopy.
278 B. Tyagi et al. / Spectrochimica Acta Part A 64 (2006) 273–278

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