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Zeolite-Based Nanocomposites for Wastewater Treatment

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DOI: 10.1007/978-981-19-2572-6_23

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Zeolite-Based Nanocomposites
for Wastewater Treatment

Veena Sodha, Rama Gaur, Rajib Bandyopadhyay, and Syed Shahabuddin

1 Introduction

Water is essential for humans and the environment and is the basic need for all living
organisms on earth. The quality of water is deteriorating continuously due to growth
in population and industry [1]. Sources of wastewater include a variety of domestic
and industrial activities. Looking at the situation, there must be persistent efforts
in the field of water purification. Various methods including chemical, biological,
and physical have been reported for wastewater treatment [2]. Some of them include
adsorption [3], photocatalysis [4], ultrafiltration [5], biofiltration [6], etc. Zeolites
have been recognized as useful adsorbents for a variety of purposes [7]. Owing to
their intrinsic adsorption [8] and ion exchange [9] properties, zeolites have shown
good results for water purification. The studies on photocatalytic activity of zeolites
are scanty and this field has not been explored much. Photocatalysis is an efficient
method for the degradation of persistent organic pollutants (POPs) from water [10].
POPs are hydrophobic chemicals that usually exist as solids in soil and water. As
POPs interfere with the food chain, they primarily affect humans and other predators
[11]. As they are not easily degradable, there must be constant efforts in developing
and improving their degradation methods. As mentioned earlier, both photocatalysis
and adsorption have proved efficient and economical for wastewater treatment [3,
4]. With the combination of photocatalysis and adsorption properties together in one

V. Sodha · R. Gaur · R. Bandyopadhyay · S. Shahabuddin (B)

Department of Chemistry, School of Technology, Pandit Deendayal Energy University,
Knowledge Corridor, Raisan, Gandhinagar, Gujarat 382007, India
e-mail: [email protected]
R. Bandyopadhyay
e-mail: [email protected]
S. Shahabuddin
Faculty of Applied Science, Universiti Teknologi MARA, Cawangan Negeri Sembilan, Kampus
Kuala Pilah, 40450 Kuala Pilah, Shah Alam, Malaysia

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2022 295
K. Mukherjee et al. (eds.), Tailored Functional Materials, Springer Proceedings
in Materials 15, https://doi.org/10.1007/978-981-19-2572-6_23
296 V. Sodha et al.

material, it is expected to observe extraordinary behaviors that can be useful for the
treatment of wastewater, including POPs.

2 Zeolites

Zeolites are crystalline, micro/meso/macro porous, three-dimensional aluminosili-

cates with a systematized structure that is made up of tetrahedral units TO4, linked
by a shared O atom; where T is Al or Si [12]. Exchangeable cations and water are
located in the void between the large cavities in the zeolite structure [8]. The general
chemical formula of zeolites can be expressed as Ma/n[AlaSibO2 (a + b)]·qH2 O;
where M is {Na, Li, K} and/or {Ca, Sr, Ba, Mg}, and n denotes the charge of cation;
the value of b/a = 1–6 and q/a = 1–4 [8].

2.1 Classification of Zeolites

Zeolites can be classified on the basis of their occurrence, pore size, Si–Al ratio,
crystal structure, etc [13]. The general classification of zeolites is depicted in Fig. 1.
Tables 2 and 3 illustrate the classification of zeolites as per their pore size and Si to
Al ratio, respectively [13].

Fig. 1 General classification of zeolites

Zeolite-Based Nanocomposites for Wastewater Treatment 297

Table 1 Classification of
Type of zeolite Number of rings Free pore diameter
zeolites as per their pore size
(nm)
(a) Zeolites having 8-rings 0.3–0.45
small pores
(b) Zeolites having 10-rings 0.45–0.6
medium pores
(c) Zeolites having 12-rings 0.6–0.8
large pores
(d) Zeolites having 14-rings 0.8–1.0
extra-large pores

Table 2 Classification of
Type of zeolite Si–Al ratio range
zeolites as per Si to Al ratio
(e) Low Si:Al ratio 1.0–1.5
(f) Intermediate Si:Al ratio 2–5
(g) High Si:Al ratio 10 to several thousands

Table 3 Summary of water treatment methods used by early of twentieth century

Treatment methods Objectives
Mechanical separation By gravity—sedimentation
By screening—screen, scrubbers, and filters
By adhesion—scrubbers, filters
Coagulation Chemical process of drawing matter together
thereby making them easier to remove by
mechanical separation
Chemical purification Iron removal, softening by use of lime,
neutralization of suspected acids
Disinfection processes (Previously known as Objective of these processes is to poison and
poisoning processes) kill objectionable organisms without adding
poisonous substances. For example, ozonation
Biological processes Oxidation of organic matter by using them as
food organisms thereby destructing them.
Destruction of objectionable organism by
creating unfavorable conditions such as
removing their food by purification process
Aeration Evaporation of objectionable gases and
carbonic acid
Boiling Best household method

2.2 Physicochemical Properties of Zeolites

Zeolites have the ability to act as adsorbent and molecular scale sieves [7, 14]. They
are good ion exchangers and can easily catalyze reactions as they have fixed pore sizes
298 V. Sodha et al.

and active sites in their crystal lattice [15]. Adsorption of methylene blue dye on a
Chinese natural zeolite was studied with varying flow rates and initial concentrations,
followed by estimation of kinetic parameters by Han et al. [16]. The results showed
good adsorption results, thereby removing methylene blue from the experimental
solution. Figure 2 shows the resulting dye degradation at different parameters; where
v = flow rate; t = time; c0 = initial concentration of MB; and ct = concentration of
MB at time t.
The ammonium removal performance of Yemeni natural zeolite was successfully
investigated by Alshameri et al. [17]. Aguiñaga et al. successfully performed photo-
catalytic decomposition of caffeine by natural zeolite (clinoptilolite–mordenite).
When the results were compared to the TiO2 particles, it was observed that TiO2
needed the same time as the zeolites for the complete breakdown of caffeine under
similar conditions. Figure 3 shows the graph of the photocatalytic degradation of
caffeine as a function of time; where NH is a hydrogenated form of natural zeolite
(NZ); NFe is obtained by ion exchange of NZ; and SH is synthetic clinoptilolite-
mordenite zeolite. The diffuse reflectance spectra of natural and synthetic zeolites

Fig. 2 Effect of flow rate

and initial concentration of
MB on the surface of zeolite
[16]

Fig. 3 Photocatalytic
degradation of caffeine in
aqueous solution by NH,
NFe, and SH [18]
Zeolite-Based Nanocomposites for Wastewater Treatment 299

are obtained. Applying Kubelka–Munk function to these spectra, adsorption edge

of natural zeolites (NH, NFe) and synthetic zeolites (C, M) were obtained. Spec-
troscopic analysis of the zeolite ZSM-5 shows that bands developed in the 200–
500 nm range are due to iron species in their different states and that iron is common
in synthetic zeolites [18]. The typical structure of aluminosilicate zeolite holds a
bandgap around 7 eV [18]. The estimated bandgap of natural mordenite was 2.63 eV.
With the help of experimental data, band gap energies were analyzed using a Tauc
plot [18]. For synthetic clinoptilolite C, band gap energies were analyzed at 4.26
and 4.46 eV for direct and indirect transitions, respectively. Likewise, 3.26 and 3.45
for synthetic mordenite. From the data given above, we may conclude that zeolites
can have a bandgap similar to that of semiconductors. Therefore, they are able to
exhibit the photocatalytic property which in turn is helpful for degradation of POPs
in wastewater.

3 Wastewater

Each community generates all three types of wastes, i.e., liquid, solid, and gaseous.
Wastewater, which falls in the category of liquid waste, is the water that has been
used in a wide area of applications. In general, wastewater is a combination of
the liquid or waterborne wastes removed from the residence, institution, and the
commercial and industrial establishment [19]. When untreated wastewater is released
into sewers and water bodies, it can pose a risk to humans and the environment [19].
Due to rapid industrialization, the generation of synthetic chemicals has increased.
These synthetic chemicals are mostly organic in nature. Their occurrence in the
environment can expose them to human, aquatic life, and wildlife, via food chain or
drinking water [20]. These organic compounds are water-hating, are fat-soluble, and
are susceptible to bioaccumulation and long-range transport [21]. POPs discharged
locally disseminated pollution far from their source [21]. POPs consist of compounds
of several industries and synthetic chemicals and pesticides [21]. If POPs are not
treated properly, they can easily involve in the food chain. Refer Fig. 4 [21].
Hence, degradation of POPs at their earliest is required. Not only they are POPs
and heavy metals, but there are many other contaminants in the water that require
special attention. For years, a lot of effort has been made to innovate and develop

Fig. 4 Flowchart showing the transport of POPs in the environment and food chain
300 V. Sodha et al.

wastewater treatment technologies. Table 3 provides information on conventional

wastewater treatment techniques [22].
Subsequently, several new treatment technologies were introduced such as adsorp-
tion, membrane filtration, ion exchange, reverse osmosis, and photocatalysis [22].
We will discuss photocatalysis and adsorption in more detail.

4 Photocatalysis

If a photon catalyzes a reaction, the system is said to be photocatalytic. Semicon-

ductors are materials that exhibit photocatalytic properties [23]. Semiconductors
have two distinct energy bands, namely the valance band and the conduction band.
The energy gap between these two bands is the bandgap. When the photon of light
bombards the semiconductor material and when a photon of light bombards the
semiconducting material, electrons (e− ) excite from low-energy valance band to
high-energy conduction band leaving empty space behind, referred to as holes (h+ )
as depicted in Fig. 5. These electron–hole pairs are responsible for the formation of
active oxidizing species, which are further responsible for the degradation of organic
pollutants in wastewater [21].
Mechanism of heterogeneous photocatalysis involves following steps.

hv≥E g
Semiconductor photocatalyst → e− + h+

e− + O2 → O•−
2

Fig. 5 Schematic diagram of photocatalysis

Zeolite-Based Nanocomposites for Wastewater Treatment 301

O•− +
2 + H → OOH
•

2OOH• → H2 O2 + O2

H2 O2 + O•− − •
2 → OH + OH + O2

h+ + H2 O → OH• + H+

h+ + OH− → OH•

 
POPs + h+ , OH• , O•− •
2 , OOH or H2 O2 → Degraded products

M. N. Rashed et al. performed the methyl orange dye degradation in TiO2 suspen-
sion at different MO concentrations using three different light sources [24]. The elec-
tron–hole recombination in semiconducting materials limits its efficiency, which we
can overcome via making binary or trinary composites of semiconducting materials
[21].

5 Adsorption

Adsorption is a surface process in which molecules are transferred from a fluid mass
to a solid surface through physical forces or chemical interactions. It is generally
reversible, and the reversible of adsorption is desorption [25]. The adsorption process
falls under two categories, i.e., physical adsorption and chemical adsorption [26].
The properties of two different adsorption processes are illustrated in Table 4.

Table 4 Comparison between physical and chemical adsorption [26]

Physical adsorption Chemical adsorption References
Attraction forces Intermolecular forces such as Chemical bond forces such as
van der Waals force valance forces
Adsorption layer Single or multilayer Single layer
Adsorption heat Low High
Adsorption rate Fast Slow
Stability Instable Stable
Example Adsorption of alkyl and alkyl Chemisorption of oxygen on [27–29]
benzene sulfate on alumina aluminum surface
302 V. Sodha et al.

Fig. 6 Schematic of
adsorption

The adsorbates are transferred from the bulk of the solution to be treated to specific
sites on the adsorbent’s surface, causing an adsorption reaction on the adsorbent’s
surface, as shown in Fig. 6 [30].
Among the number of water purification techniques, adsorption is simple yet
effective [31]. Generally, materials used as an adsorbent in wastewater treatment are
activated carbon [32], clay minerals [33], biomaterials [34], industrial solid wastes
[35], and zeolites [8]. Lowitz discovered adsorption in 1785, and it was later employed
to remove colors from sugar during the refining process [36]. Subsequently, inacti-
vated charcoal filters were utilized to purify water in American water treatment plants
[36]. In Hamm, Germany, in 1929, and Bay City, Michigan, in 1930, adsorption on
the first granular-activated carbon (GAC) systems for water treatment was employed
[36]. Synthetic, modified, and natural zeolites were studied, and synthetic and modi-
fied zeolites were found to have higher adsorption and ion exchange properties [37].
Armagan et al. examined a Turkey clinoptilolite for adsorption of three azo dyes
(Everzol Black, Everzol Red, and Everzol Yellow) and observed limited adsorption
capacities. They noticed a significant improvement in adsorption after modification
with quaternary amines [38].

6 Synthesis and Characterization of Zeolite-Based

Nanocomposites

Using a quick green precipitation approach, Jahangirian et al. were able to synthesis
Zeolite/Fe2 O3 –NCs. The surface of zeolite was coated with Fe2 O3 –NPs [39]. SEM
images of zeolite (A) and zeolite/Fe2 O3 –NCs (B–F) are shown in Fig. 7. The parti-
cles’ cubic shape is due to the zeolite structure, which did not alter during the oper-
ation. It is obvious from the SEM images that ferric oxide aggregation occurs on the
surface of zeolite/Fe2 O3 –NCs [39].
There are four different paths of synthesizing Conductive polymers/zeolite-based
(nano-)composites [40]: (i) encapsulating the organic solvent dissolved monomer
Zeolite-Based Nanocomposites for Wastewater Treatment 303

Fig. 7 SEM images of a zeolite and zeolite/Fe2 O3 –NCs in b 1%, c 4%, d 7%, e 12%, and f 17%
of Fe2 O3 –NP [39]

within the zeolite cavities by a diffusion process, followed by oxidative polymeriza-

tion to form polymeric chains into zeolite cavities [41]; (ii) exposing the zeolite with
oxidant ions like Fe(III) and Cu(II) to monomer and acid vapors [42]; (iii) performing
in situ polymerization of the monomer with zeolite, and the polymer may form inside
and outside the zeolite channels [43, 44]; and (iv) by simply mixing zeolite powder
and conductive polymer [45]. Among the above discussed methods, methods (i) and
(ii) are of more interest as the nano-scale polymeric chains are formed into cavities
of zeolite. Hence, the electronic, mechanical, chemical, and optical properties may
be improved as the polymeric chains are organized in the nanometer scale [40]. Ivan
et al. [46] reported the synthesis of polyaniline/zeolite 5A composite. Synthesis path
comprised in situ oxidative polymerization of aniline in synthetic zeolite pattern.
After that, the constructed membrane was tested to see whether it could remove
cobalt ions from wastewater in the ultrafiltration process. SEM images of zeolite 5A
and polyaniline/zeolite 5A composite are shown in Fig. 8 [40, 46].
Synthesis of polyaniline/ZSM-5 zeolite composites was reported by Milojevic-
Rakic et al. [47]. Oxidative polymerization of aniline was performed by adding an
aqueous solution of APS in the zeolite ZSM-5 and aniline water dispersion, which
was prepared by previously reported weight ratios [48]. The material was synthesized
304 V. Sodha et al.

Fig. 8 SEM images at different magnifications of zeolite 5A (a, c) and polyaniline/zeolite 5A

composites (b, d) [46]

with and without acid medium. The synthesized composites were labeled as PZ1/1,
PZ1/5, and PZ1/10 for weight ratios ZSM-5/aniline of 1, 5, and 10, respectively,
and were evaluated as adsorbent for the organic herbicide in an aqueous solution.
Adsorption study was done using Freundlich, Langmuir, and Langmuir–Freundlich
isotherm models. Among all the PANI, pure ZSM-5, and PANI/ZSM-5 samples
tested, the deprotonated granular PANI synthesized in sulfuric acid medium had
the maximum glyphosate adsorption. The protonated nanostructured PANI and the
deprotonated PANI/ZSM-5 composite with 50% zeolite both have a high adsorption
capacity. Both materials were made using water and no acid [47].

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