CHAPTER 7

Synthesis of Bentonite ZnO nanocomposites and applications.

7.1. Introduction

Bentonite is a natural clay powder, comprising of finely grained particles.

Bentonite word was proposed by Knight (1989) and in 1926 by Ross & Shannon.
Bentonite has smectite and montmorillimate minerals, and it is a deposit of clay
elements. It has applications in various fields of environmental application, like
protection of land erosion, soil pollution protection, purification of drinking and
wastewater. Major types of bentonite powder are Na- Bentonite (swelling bentonite)
and Ca – Bentonite (Non- swelling type).

Bentonite and zeolites are aluminosilicates. The essential component of bentonite

is montmorilonate, it is the finest crystals of clay, zeolites have three-dimensional
crystalline structure with the channels of molecular dimensions, both bentonite and
zeolites have adsorption capacity, bentonite powder consists of ash made of
volcanoes. Bentonites can be used as such or after the activation of bentonites by
several physico-chemical treatments like acid activation, ion exchange process and
heating techniques. Acid-activated bentonite has diverse applications as an adsorbent,
catalyst, bleaching earth and nanocomposites. (Kodi 1997: 633-643). Acid activation
process brings some physicochemical changes in bentonite powder, like the change
in crystallinity, swelling, pore structure, surface area, catalytic activity, strength,
surface acidity and also the chemical and mineral composition (Banat 2000: 391-
398, Onal 2002: 409-416, Park S.J. 2002: 160-165).

In this work, clintoptile bentonite powder has been activated with hydrochloric
acid. Clintoptile is a South African natural zeolite, and it is a good choice material
because it has high cation exchange capacity, mechanical and chemical stability, low
cost and easy availability. ZnO is the most effective nano metal oxide with a band
gap of 3.37 eV, and high surface area. ZnO nanocatalyst has materialized as more
efficient photocatalyst for the detoxification of water, because it generates hydrogen
peroxide more efficiently, and it has more active sites (Nazar Elamin 2013: 32-35).

BP-3 and caffeine are the emerging contaminants and being recognised as
emerging pollutants to aquatic organisms in water. Humans and domestic animals

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release large quantitiesof PPCPS into the environment through excretion, disposal of
unused pharmaceutical products and agricultural wastes (Polynton and Vulpe, 2009:
83-95) a wide range of pharmaceutical products have been detected in surface and
groundwater. Caffeine, nicotine and nicotine metabolite like cotinine, are widely
detected in groundwater, personal care products are transmitted into aquatic system.
Sewage treatment plants do not have PPCPs removal equipment, the majority of
compounds used as sunscreens are lipophilic, conjugated aromatic compounds, but
these are found in the aqueous environment (Jeon 2006: 192-202). PPCP`s act as
endocrine disruptors interfering with hormone production and aquatic life is at risk.

Yusan S. 2016: 2158–2163, synthesized ZnO, and diatomite-supported ZnO

nanostructures, and it was prepared using a direct precipitation and co-precipitation
method, respectively. The surface charge of the samples was assessed by zeta
potential measurements. Characterization exhibited that the ZnO particles were
efficaciously distributed in the diatomite support. Synthesised nanoparticles have the
potential for different applications.

Bel Hadjltaief H. 2016, ZnO–TiO2/ clay photocatalyst was prepared using a

natural Tunisian clay as support. Its efficiency was assayed in the photocatalytic
degradation of methyl green in aqueous solutions, in the presence of UVA
irradiation. The photocatalyst was synthesised using a metal organic chemical vapour
deposition (MOCVD) with Ti (OPri)4 deposed on the natural Na+ clay, followed by a
modified sol-gel synthesis method. The activity tests showed that the
photodegradation efficiency for ZnO–TiO2/ clay is higher than for the TiO2/ clay
catalyst. Almost complete mineralisation was obtained upon 30 min of light
irradiation in the presence of the ZnO–TiO2/ clay catalyst.

The experimental results indicate that this ZnO–TiO2/ clay catalyst shows high
photocatalytic activity, higher than the Na+ exchanged clay and TiO2/ clay, pointing
to a positive effect of the presence of ZnO in the catalytic composition, due to the
suitable arrangement of their respective valence and conduction bands, favoring both
electron and hole transfer and delaying their recombination.

Samira Bendou 2014: 404-413, studied the effect of acid treatment (HCl) for the
activation of bentonite using diluted hydrochloric acid at room temperature, it was
found that bentonite sample activated at lower acid concentration 0.4 M HCl showed

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 maximum efficienc, having more surface area and active sites, and bentonite
activation with higher acid concentration (0.6 M) caused the decrease in the surface
area.

The above-referred literature survey provides the clear evidence for the
preparation of bentonite supported ZnO nanoparticles. Acid-activated bentonite
powder shows more efficiency as compared to commercial plane bentonite powder.

The aim of the study is the activation of bentonite powder, and synthesis of bentonite
supported ZnO nanoparticles, characterisation of synthesised nanoparticles by
XRD, SEM-EDS, ATR-IR and ICP-OES. It's application as photocatalyst for the
elimination of caffeine in water and elimination of BP-3 in water. Meanwhile,
bentonite ZnO Cellulose acetate composite membranes were prepared and used for
BP-3 removal in water.

7.1.1. Experimental details

7.1.1.2. Materials
Cellulose acetate (CAc, molecular weight =25,000 Da) was purchased from
Aldrich, Dimethylformamide (DMF) and acetone were purchased from Merck
(India) Ltd. ZnO nanoparticle (product code: 677450) was purchased from Sigma, 2-
hydroxy4-methoxybenzophenone (C14H12O3), caffeine (C8H10N4O2), APS
((NH4)2S2O8), HCl (36 %) were purchased from Arva synthesis, Merck and Fischer
scientific respectively and were used without further purification. Bentonite
(clintoptile) was purchased from local vender and ground to a fine powder sieved
and used for the studies. Double distilled water, generated from the double distilled
water plant in the lab was used for preparation feed, membrane preparation.

7.1.1.3. Activation of Bentonite/ clintoptile powder.

Bentonite powder finely grounded and sieved was activated explained below,
experiments were conducted in a 500 mL clean beaker, 3 g of clay was added to
100 mL of 0.4 M HCl solution, and the solution was heated up to 80 ○C. Solution
was stirring continuously for 10 h at a speed of 400 rpm. After the stirring solution
was centrifuged for 15 min at 4000 rpm, the supernatant acid solution was drained,
and the bentonite paste was washed with distilled water to remove the traces of
chloride and finally dried in a hot air oven at 105 ○C for 5 h, to get a constant

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weight. The activated sample was stored in closed plastic bottles and then used for
further studies.

7.1.1.4. Synthesis of Bentonite supported ZnO composite material

The solid-state dispersion technique was used for the preparation of composite
material. The ZnO nanoparticles were purchased from Sigma. The bentonite
supported ZnO (10 %), ZnO (20 %) catalyst was prepared. ZnO (1 g) and
clintoptile/ bentonite natural and activated (9 g) weighed in a clean beaker of 10
mL, and ethanol was added. A slurry of the mixture was prepared, agitated by the
use of pestle and mortar and stirred for 40 min at ambient condition After the
evaporation of the solvent in a hot air oven at 90 °C, the dried solid powder was
crushed by grinding in mortar and pestle for the formation of homogeneous solid-
state mixture. The powdered mixture was then calcined at 480 °C for 4 h, to get the
bentonite supported ZnO catalyst (Durga Kumari 2002: 155-165). The bentonite
supported ZnO was characterised by XRD, ICP-OES, ATR-IR, EDS, SEM, and
then used for the photocatalytic degradation studies.

7.1.1.5. Preparation of Cellulose Acetate, Bentonite supported ZnO composite

membranes:
Bentonite/ clintoptile supported ZnO nanoparticle was prepared by solid state
dispersion technique, composite membrane was prepared by DIPS method ( Mulder
M. 2000: 331-334). The different concentration of bentonite supported 10 % ZnO
was used for the preparation of composite membranes. Table 7.1 displays the
concentration of nanoparticles and cellulose acetate in the membranes. The
composite membrane with different concentration of zeolite supported ZnO
nanoparticle was labeled as CAM, CABe-1, CABe-2 and CABe-3.

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 Table 7.1. Membrane code and their composition

10 %
Membr CA ZnO Acetone DMF
Membrane descriptions
code (g) Bentonite (ml) (ml)
(g)
CAM 15.00 0 60 25 Neat CA
CA+ 0.25, wt % bentonite- ZnO
CABe – 1 14.75 0.25 60 25
(10 %)
CA+ 0.50 ,wt % bentonite- ZnO
CABe – 2 14.50 0.5 60 25
(10 %)
CA+ 0.75, wt % bentonite- ZnO
CABe -3 14.25 0.75 60 25
(10 %)

7.2. Results and discussions

Bentonites are aluminosilicates, the pore size distribution is very uniform and
sharp due to the fact that the pores form the part of the crystal structure itself. Na -
bentonites clayparticles tends to swell during operation, the ion exchange capacity is
inversely proportional to the Si/ Al ratio. Based on the previous studies, the specific
ion exchange capacity depends on the structure of the zeolite. However the
impregnation of ZnO in bentonite matrix increases the hydrophilicity as well as
charge due to the metal oxide and bentonite composites.

7. 2.1. X-ray diffraction analysis

The XRD studies of ZnO nanoparticle, bentonite supported 10 % ZnO
nanoparticles and pure bentonite powders were conducted. XRD pattern of the same
are shown in figure 7.1 XRD pattern of ZnO nanoparticles exhibited the peaks at 2θ
equal to 31.67°, 34.31°, 36.14°, 47.40°, 56.52°, 62.73°, 66.28°, 67.91° and 69.03°
which corresponded to a typical diffraction of zincite with hexagonal symmetry.
These peaks perfectly matched with the reference to JCPDS card no 36-1451 and the
lattice parameters are a = 3.24982 Å, c = 5.20661 Å.
Hosseinifard M.2013: 396-399. Synthesisesd pure ZnO nanoparticles, as no
impurity peaks were detected. From the XRD analysis of bentonite powder, it was
found that the peaks are at 7°, 12°, 19°, 21°, 23°, 29.05° and 40.9° are equal to,
characteristic peaks of bentonite (Leite 2008: 303, Leite 2010: 596). Peaks at 12°,
29.05° and 40.9° are conforms kaolinite form of bentonite and peaks at 21°, 23°,
42.08° are due to the presence of montmoillonite in bentonite powder. XRD

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Intensity of characteristic peaks of bentonite material is not high because of non-
crystallinity form (Kumar 1995: 1440-1448). From the XRD pattern of bentonite
supported 10 % ZnO, it is found that there is an increase in intensity of peaks at 2θ
equals to 7°, 16°, 19°, 21°, 23°, 29°, 31.67°, 34.31°, 36.14°, 47.40°, 56.52°, 62.73°,
66.28°, 67.91° and 69.03° confirms the impregnation of ZnO on the bentonite
powder (10 % ZnO benonite powder).

Figure 7.1. XRD Images of bentonite powder, ZnO pure and 10 % ZnO
bentonite powder.

7.2.2. SEM and EDS analysis of ZnO, bentonite supported ZnO NPs

Figure 7.2. SEM Images of a) ZnO pure b) Bentonite pure (10 KX),
c) Bentonite supported 5 % ZnO d) Bentonite supported 10% ZnO powder.

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 Figure 7.2 presents the SEM micrographs of ZnO, bentonite, and bentonite
supported 10 % ZnO samples. SEM analysis examines the distribution of ZnO species
over the bentonite. It is seen that the clean surface of bentonite powder is covered by
the ZnO particles, and there is no noticeable change in the typical morphology of the
support after the loading of ZnO. As can be seen from the SEM images, ZnO
nanoparticles are like clusters attaching to the bentonite surface. The EDS spectra of
ZnO nanoparticles confirms the presence of pure oxygen and zinc without impurities.
It is evidenced from the EDS spectra and elemental compositions in tables the
presence of Si, Al constituent of bentonite and also the presence of Zn conforms the
impregnation of ZnO on bentonite composite powder.

7.2.3. ICP studies of bentonite supported ZnO nanoparticles

ICP –OES elemental analysis of bentonite supported ZnO powder was carried out
after sample digestion in order to determine the concentration of aluminum, silica
and zinc. It is found that the silica and aluminum content in zeolite powder is 24.14
% and 12.15 % respectively and the zinc content was found to be 9.8 % W/V basis.
This summarizes the ZnO loading state dispersion technique. Activated bentonite
was also tested for silica and aluminium content and it was found to be 28.12 and
13.41 % respectively. Si/ Al ratio is 1.98 and after activation of bentonite the Si/ Al
ratio is found to be 2.09.

Table 7.2 Elemental composition of the samples obtained by EDS.

Sample Name Elements Weight % Atomic %

ZnO pure Zinc 86.47 38.99
Oxygen 13.53 61.01
Aluminium 15.47 11.57
Silica 32.58 23.41
Bentonite powder
Oxygen 51.25 64.65
Potassium 0.70 0.36
Aluminium 13.88 11.27
Bentonite supported 10% ZnO Silica 21.01 16.38
powder Oxygen 51.12 63.87
Potassium 3.52 1.97
Zinc 10.47 6.51

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7.2.4. Morphology studiesof CAc and CAc /ZnO/ bentonite composite
membrane:
The surface morphology of the membrane as illustrated in figure 7.3 (a), (c) and
(e). The cross section images are depicted in figure 7.3 (b), (d) and (f). Clearly, it is
noted that the dispersion of ZnO/ bentonite NPs on the membrane surfaces was
varied according to the concentration of NPs. The membranes prepared with less
amount of NPs exhibited more dispersion of NPs in figure 7.3 (a), as compared to
membranes of higher amount of NPs (i.e. figures 7.3 (c) and (e). The higher amount
of NPs agglomerates and forms clusters in figure 7.3 c and e. The cross-sectional
images give fine information on the incorporation of NPs embedded in the polymer
matrix layers as well as productivity of the membranes. {figure 7.3 (b), (d) and
figure 7.3 (f)}. Also, the structure of membrane layers has been changed accordingly
with ZnO/ bentonite content increases, the viscosity of the casting solution will also
increase which will disturb or troubles the penetration of NPs deeper into the
polymer matrix during phase inversion.

Figure 7.3. SEM images of the membrane surface (a) CABe-1 (c) CABe-2
and (e) CABe-3 Cross sectional images (b) CABe-1 (d) CABe-2and (f) CABe-3
of CA/ZnO bentonite composite membranes

It is found that increasing the NPs could intensify the formation of crosslinking
structure between NPs and polymeric chains, inhibiting the growth of finger-like
projections, as can be seen in figure 7.3 (a), (b), (c), (d), (e) and (f). The main factor

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 contributing to the formation of macro voids is the liquid-liquid demixing behaviour
during phase inversion process. Since ZnO/ bentonite has more affinity towards
water than the polymer chains, the penetration velocity of NPs into the polymer
matrix and the increase of solvent-diffusion velocity of the membrane to water are
higher during phase inversion.

7.2.5. Effect of bentonite activation rejection of BP-3, 3 ppm solution.

Figure 7.4. BP- 3 rejection studies with and without activation of bentonite.

Bentonites can be activated by acid or hot mineral solutions treatment; hydrogen

ions attack the aluminosilicate layers through the interlayer regions as a result of this
attack, there is a change in the structure, chemical composition and physical
properties of clay. The structure of raw clay is opened and becomes porous, acid
activated clay exhibit significantly different physical, chemical properties than non-
activated bentonite. The surface area and porosity structure of bentonite can be
changed to the desired extent by acid treatment. (Jacobs 1984 and Persquera 1992)
The mechanism of acid activation involves ion exchange process or replacement of
metallic ions by H+ ions, giving clay a highly active structure, which is acidic in
nature. As depicted in the figure 7.4 the rejection of BP-3 with the non-activated
bentonite membrane was 73 % and with the use of activated bentonite powder
rejection was found to be 86 %, there is an increase in the rejection of 3 ppm BP-3
solution with the use of activated bentonite powder for the preparation of CAc, ZnO
bentonite mixed matrix membrane.

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7. 2.6 Rejection with different concentration
The membrane flux was influenced by the composition of the membrane
material. Figure 7.5 shows the BP-3 and caffeine permeation results. It is evident
from the figure 7.5 that there is an increase in flux with an increase in the pressure
and the composition of membrane material. Flux increased with an increase in the
composition of bentonite supported ZnO nanoparticles. CABe-3 membrane showed
highest water flux because bentonite powder is hydrophilic in nature.

7.2.7. Rejection of BP-3 with activated and natural Bentonite.

Figure 7.5. Permeate flux studies with different pressure 3 ppm BP-3
solution withand without the activation of Bentonite powder.

Figure 7.6. Rejection studies of 3 ppm BP-3 solution versus pressure.

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 Figure 7.7. Rejection studies of caffeine 1 ppm solution versus pressure.

The rejection of BP-3 and caffeine experiments were conducted. The experiments
were repeated three times and mean results were reported. The effect of pressure and
feed concentration on performance were studied. The figure 7.6 shows permeate
flux and figure 7.7 show rejection of feed sample. The rejection rate of CAZe-3
membrane is higher when compared with all membranes, it showed 82 % of
rejection of BP-3 and almost negligible rejection of caffeine at 200 kpa pressure.

7.2.8. Photocatalytic Experiment

Photocatalytic activity of bentonite supported 10 % ZnO nanoparticles were
evaluated on the degradation of caffeine in UV light illumination. A known weight
of the catalyst was dispersed in a known volume of the caffeine along with an
electron scavenger ammonium persulphate, and the resultant mixture was stirred
throughout the experiment for uniform exposure of the catalyst to light. 5 mL
aliquots were withdrawn every 20 min, filtered through Millipore syringe filter (0.45
µm pore size). The degradation of the caffeine was monitored after removal of
photocatalyst by centrifugation at 4000 rpm and measured the decrease in the
absorption maxima at 270 nm caffeine.

7.2.9. Photocatalytic degradation of caffeine

Synthesised bentonite supported 10 % ZnO nanomaterial is tested as a
photocatalyst for degradation of caffeine under UV light. The effect of different
parameters such as photodegradation efficiency of ZnO, and 10 % ZnO bentonite

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powder with and without APS was evaluated. Effect of catalyst load of 10 % ZnO
bentonite powder on photodegradation was also evaluated. ZnO only showed only
39 % degradation whereas 10 % ZnO bentonite powder showed 79 % degradation of
caffeine. Bentonite supported 10% ZnO with 0.015 M APS showed almost
complete degradation (91 %) whereas ZnO with APS showed 63 % rejection.
Degradation efficiency of ZnO is increased by 1.5 times with the support of
Bentonite on 10 % ZnO, as depicted in figure 7.8. The synthesised catalyst is very
reactive in UV light.

Figure 7.8. Caffeine photodegradation with ZnO and 10% ZnO bentonite
powder

7.2.10. Effect of catalyst load on degradation of caffeine.

Figure 7.9. Effect of catalyst load on the photodegradation of caffeine.

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 Figure 7.9 shows the effect of catalyst load on the photo degradation efficiency of
caffeine. The results showed that photodegradation efficiency is increased with an
increase in catalyst loading and an optimum loading, and after which it is decreased.
The set of experiments were conducted by changing the catalytic load from 0.50 to
1.0 g/L, using 1 ppm caffeine solution by maintaining the constant concentration of
pollutant constant. The degradation of caffeine was increased, when the catalytic
load was increased of 0.50, 0.75 g to 1.0 g (52 %, 83 % and 73 % degradation were
observed respectively, this is because of the increase of active sites on ZnO surface.
Maximum degradation of caffeine was found to be at 0.75 g/L, and beyond this
catalyst load, the photo catalytic activity is decreased, because of the formation of
turbidity which reduces the light penetration into the solution and increased light
scattering (Chakrabarti 2004). This observation can be explained regarding the
availability of active sites on the surface of the catalyst and the penetration of solar
radiation into the suspension. An increase in catalyst dosage results in an increase in
the total active surface area of a catalyst which in turn increases the photo
degradation efficiency (Jang 2006). However, this effect is counteracted at high
catalyst dosages due to increased turbidity of the suspension. This is also due to
aggregation of catalyst particles, which reduced the interfacial area between the
reaction solution & the photocatalyst. The increased turbidity reduces penetration of
the much-needed light due to scattering, hence a decrease in photodegradation
efficiency at high catalyst dosage. With the help of above results, it was concluded
that 0.75 g/L ZnO catalyst could be used as an optimum catalytic amount for the
degradation reactions.

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7.3. Conclusion
10 % ZnO supported bentonite nanoparticles were synthesied by solid state
dispersion technique, and characteried by XRD, SEM and EDS. From the above
observation, it can be concluded synthesied 10 % ZnO supported bentonite is a very
good photocatalyst, and experimental results deplete that photodegradation of
caffeine was enhanced when bentonite supported 10 % ZnO was used as a catalyst,
which suggests that it has a great potential in the removal of emerging contaminants
from wastewater. The mixed matrix membrane cellulose acetate with bentonite
supported ZnO composite membrane were prepared by DIPS method. The
membrane was also characterized by XRD, SEM, and ICP studies. The membrane
with 0.75 g ZnO: Bentonite content (CABe-3) shows the maximum BP-3 rejection
of 81 % which was in good agreement with log Kow of feed and hydrophilicity of the
membrane. Increasing in the concentration of Benzophenone-3 increases the
rejection efficiency. However the rejection decrease with applying higher pressure.

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