Journal of Molecular Structure 1241 (2021) 130596

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstr

Role of nanomaterial’s as adsorbent for heterogeneous reaction in

waste water treatment
M. Sridevi a,∗, C. Nirmala a, N. Jawahar a, G. Arthi b, Sugumari Vallinayagam c,
Vipin Kumar Sharma d
a
Department of Biotechnology, Vinayaka Mission’s Kirupananda Variyar Engineering College, Vinayaka Mission’s Research Foundation (Deemed to be
University), Salem, 636 308, Tamil Nadu, India
b
Department of Biotechnology, Karpaga Vinayaga College of Engineering and Technology, Chengalpattu, 603 308, Tamil Nadu, India
c
Department of Biotechnology, Mepco Schlenk Engineering College, Sivakasi, Tamilnadu, 626005, India
d
Department of Biochemistry, Central University of Haryana, Jant Pali, Mahendergarh, 123031, India

a r t i c l e i n f o a b s t r a c t

Article history: Industrial development takes part a vital part in the development of a country economy. On the other
Received 25 December 2020 hand, it is also one reason for the declining circumstance of our ecology. Water pollution is a worldwide
Revised 10 April 2021
challenge that distresses ecology and social healthiness with substantial economic and public expendi-
Accepted 27 April 2021
tures. The emergent shortage of portable water resources involves an efficient wastewater treatment sys-
Available online 11 May 2021
tem. One potential approach that numerous research has stated that success is nanomaterials in water
Keywords: and wastewater treatment. The rapid evolution of nanomaterial sciences research and its integrated tech-
Nanoparticles niques such as nanophotocatalyst has shown their emergent potential; conversely, there has not been a
Adsorption great extent of statistics available on their execution. Several nano-material based approaches employed
Heavy metal in wastewater treatment deliberated in this manuscript. This review emphasises advances in nanotech-
Heterogeneous reaction kinetics nology and their respective kinetics, different reaction-based models for wastewater treatment.
Waste water
© 2021 Elsevier B.V. All rights reserved.

1. Introduction
The freshwater is one of the very important requirements of
humankind on the earth. The availability of freshwater resources
is very less when compared to the total available quantity of water
around the world. Pollution of water leads to a serious problem
because 7.5 billion people are daily using clean water for various
purposes. Pollution due to various practices of humankind such
as industrial utilization, domestic and agricultural purposes leads
to waste water [1]. Though many conventional technologies are
available to overcome the problem, the economic value, require-
ment of more energy, generation of toxic sludge, limited removal
of contaminants poses limitations [2]. Adsorption, a low cost effec-
tive technique uses a varied range of adsorbents is recommended
for the effective removal of different types of pollutants from the
waste water. Though the process is well known for recovery for
industrial, potable, and other water resources, lack of suitable high
capacity adsorbents and limited use on commercial scale columns
∗
Corresponding author at: Department of Biotechnology, Vinayaka Mission’s
Kirupananda Variyar Engineering College, Vinayaka Mission’s Research Foundation
(Deemed to be University), Salem, 636308, Tamil Nadu, India.
E-mail address: drsridevimuruhan@gmail.com (M. Sridevi).
poses restrictions. Based on the pollutant type and their proper-
ties, the adsorbents can be selected for the removal process. Apart
from activated carbon, agricultural wastes and industrial byprod-
ucts have emerged widely as low-cost adsorbents for treatment
processes [3].
Recently nanomaterial’s synthesized from organic or inorganic
materials have gained attention as a promising alternative for the
treatment of waste water. They have high affinity and consider-
able binding capacities to adsorb pollutants based on hydropho-
bicity and speciation behavior from waste water. Nickel oxide, car-
bon, zinc, iron, titanium, nano clay, etc., are some of the materials
that are used to synthesize the nanomaterial’s which function as
an adsorbent in waste water treatment [4]. Their small size, large
surface area, large ‘surface area to volume’ ratio at the nano level
improved their adsorption capacity and makes them as better ad-
sorbing materials than conventional materials. Approaches like oxi-
dation, reduction, fenton process, ozonation, sonolysis are involved
for the synthesis of these nanocatalysts to degrade the contami-
nants [5]. Their small size, active surface with high porosity en-
ables them to adsorb, separate and remove contaminating mate-
rials from the water. These contaminants can be later degraded
by various chemical and biological methods [1,3]. After saturation,
the nanomaterial’s can also be chemically regenerated. Nanoparti-

https://doi.org/10.1016/j.molstruc.2021.130596
0022-2860/© 2021 Elsevier B.V. All rights reserved.
M. Sridevi, C. Nirmala, N. Jawahar et al. Journal of Molecular Structure 1241 (2021) 130596

Table 1
List of nanomaterials to treat waste water.

Nanomaterials Method of treatment Type of contaminant Reference

Carbon-based nanosorbents Adsorption Organic Compounds, Heavy metals [8]

Carbon nanotubes Photocatalytic degradation Reactive Black 5 dye [7]
Magnetite (Fe3 O4 ) Adsorption Organic Compounds, Heavy metals [9]
Nanoclay Adsorption Organic Compounds, Heavy metals [9]
Nanotube Adsorption Organic Compounds, Heavy metals [9]
Micelles Adsorption Organic pollutants [9]
Titanium dioxide (TiO2 ) Photocatalytic degradation Organic contaminants [9]
Copper oxide (CUO) - Titanium dioxide (TiO2 ) Photocatalytic degradation Methyl orange (Azo dyes) [10]
Tin disulphide (SnS2 ) / Reduced graphene oxide (rGO) Photocatalytic degradation Methyl orange (Azo dyes) [9]
Copper oxide (CuO) / Zinc oxide (ZnO) Photocatalytic degradation Rhodamine B and Congo red dyes [10]
Molybdenum disulfide (MoS2 )/ Magnetite (Fe3 O4 ) Photocatalytic degradation Rhodamine B dye [11]
Nickel oxide Adsorption Heavy metals [12]

cles act as catalysts in the removal of pollutants from waste wa-
ter. The catalytic action can be either a homogeneous or hetero-
geneous reaction. In the homogeneous reaction, the catalyst is di-
rectly introduced with the waste water that oxidises the effluent.
Whereas in the heterogeneous reaction the catalyst attaches with
a stable surface and carries out the catalytic oxidation [4,5]. In
past two decades hybrid nanomaterial’s as heterogeneous catalysts
combined with advanced oxidation processes (AOP) and advanced
hybrid oxidation processes are used with the increased focus on
research and development of waste water treatment. Nanoparti-
cles, compared to their consistent bulk material are studied to
have stronger heterogeneous reaction properties for most water
pollutants. High catalytic efficiency is ideal for prospective het-
erogeneous catalysts. A heterogeneous electrochemical waste wa-
ter treatment system based on Fenton’s chemistry is one of the
most exciting and efficient emerging technologies for waste water
treatment. Extensive research has been directed towards the devel-
opment of different synthetic heterogeneous metallic nanocatalyst
[6].
Based on all these aspects of water purification using nano-
materials, in this article we review the latest developments of
nanomaterials used in adsorption of waste water. The kinetics in-
volved in heterogeneous catalysis using these nanomaterials as ad-
sorbents, adsorption mechanisms and recent developments for re-
moval of heavy metals and ions from waste water treatment is
summarised and discussed from the up-to-date literature.
observable parameters on the overall rate. The reactivity of hetero-
geneous catalysts takes place at the surface atoms and depends on
size [15]. Subsequently, great effort is made to maximize the sur-
face area of a catalyst by distributing it over the support. Yet deter-
mination of rate equations via kinetic studies is mandatory. Several
adsorption kinetic models have been developed to understand the
adsorption kinetics and rate-limiting step but an applicable kinetic
model is necessary to analyze the rate and the mechanism of ad-
sorption processes Fig. 1.
The most renowned model to study the adsorption kinetics
of pollutants and quantify the extent of uptake in adsorption
kinetics is simple-first-order, pseudo-first-order, pseudo-second-
order and intra-particle diffusion models [16–19].The first-order
reversible reaction model, the external mass transfer model, the
first-order equation of Bhattacharya and Venkobachar, Elovich’s
model, and Ritchie’s equation, Weber and Morris sorption kinetic
model, Adam–Bohart–Thomas relation are also applied to unveil
the adsorbate-adsorption phenomenon [20].
Broadly the Sorption kinetic models can be divided into two
main types: reaction-based models and diffusion-based models
Fig. 2 [21].
3.1. Reaction-based models
3.1.1. Simple-first-order
The simple-first-order rate equations is given by Eq. (1)

2. Nanomaterials for waste water treatment ks

log qt = t + log qe (1)
2303
Nanomaterials having a size between 1-100 nanometer. Due The global kinetic of the reaction for Pseudo-zero order model
to its nanoscale size nanomaterials gains few advantages such as is as follows
Surface bulk volume ratio increase and surface area increase [7].
dC
This leads to the effective treatment of waste water. Some of the − = −r = kOH [HO·] = kms (2)
dt
nanomaterials that helps to treat the waste water are given below
(Table 1). Where “C” is the concentration of pollutant species, r is the reac-
tion rate, “kOH ” is reaction kinetic rate constant and “kms ” is the
3. Kinetics in heterogeneous catalysis apparent pseudo-zero order kinetic constant [22].

In an absorption system, the efficacy of an adsorbent is deter- 3.1.2. Pseudo-first-order

mined by the adsorption equilibrium and isotherm modeling stud-
ies. They provide the basic insight required for the design, opti-
mization and operation of efficient adsorption processes for waste
water treatment plants. In a given system the identification of the
adsorption mechanism and assessment of potential rate-controlling
steps by suitable kinetic models is essential [13]. In addition, the
kinetics of pollutant uptake, adsorbate residence time, rate of ad-
sorption, are the most important factors to choose the optimum
condition for full-scale batch removal processes [14]. Various fac-
tors like initial pollutant concentration, temperature, pH, adsorbent
particle size, pollutant’s nature, and contact time governs the ad-
sorption capacity. A kinetic model is concerned with the effect of
The pseudo-first-order kinetic model has been used extensively
to describe the sorption of metal ions onto a variety of adsorbents
and for pollutants adsorption from aqueous solutions [23].
The kinetic model is represented by the Eq. (2),
−k1
log(qe − qt ) = log qe t, (3)
2.303
Where qe and qt are the amounts of adsorbate (mg/g) at equilib-
rium and at time t, respectively. ks and k1 are the rate constants
(1/h) [24].
Usually, the equilibrium sorption capacity, qe , must be known
in experimental data, but in many cases qe is unknown and as

2
M. Sridevi, C. Nirmala, N. Jawahar et al. Journal of Molecular Structure 1241 (2021) 130596

Fig. 1. Schematic representation of photocatalyis.

3.2. Diffusion-based models

Simple-first-
order
3.2.1. Intraparticle diffusion model
Intraparticle diffusion model also known as the Weber and
Reaction-based Pseudo-first- Morris (1963) sorption kinetic model, in which the diffusion of pol-
models order
lutant inside the adsorbent is the rate-limiting step. The equation
can be expressed as [18,27].
Pseudo-second-
Sorption order qt = kp t1/2 + C; (5)
Kinetic models
where C is the intercept and kp is the Weber and Morris intra-
Intraparticle particle-diffusion rate constant (mg /g h1/2 ), which can be evalu-
diffusion model
Diffusion-based ated from the slope of the linear plot of qt versus t1/2
models
External 3.2.2. External diffusion model
diffusion model
If external diffusion of pollutant is the rate-limiting step, then
it has been shown that Eq. (5.8) can be fitted into sorption data
Fig. 2. Adsorption kinetic models for pollutant removal from waste water. with some success [28].
Ct A
ln = −kf t (6)
chemisorption tends to become unmeasurably slow. Hence qe can C0 V
be considered as an adjustable parameter and determined by trial where C0 , Ct , A/V, and t are the initial pollutant concentration, con-
and error to analyze the pseudo-first-order model kinetics. centration at time t, the external sorption area to the total solution
The disadvantages of this model are volume, and sorption time, respectively. The external diffusion co-
efficient kf (cm/s) can be calculated from the slope of the straight
1. The linear equation does not give theoretical qe values that line obtained from Eq. (5).
agree with experimental qe values
2. The plots are only linear for approximately first 30 min, beyond 3.3. Modeling of equilibrium adsorption processes
this time the experimental and theoretical data do not correlate
well. Adsorption system can be investigated by equilibrium batch
sorption experiments and dynamic continuous-flow sorption stud-
ies.
The experimental adsorption data in batch mode can be de-
3.1.3. Pseudo-second-order
termined by Equilibrium isotherm model equations like Langmuir,
Pseudo-second-order kinetics is considered more suitable and
Freundlich, Brunauer–Emmett–Teller, Halsey, Redlich–Peterson,
superior for representing the kinetic data in adsorption systems
Dubinin–Raduskevich, Smith, Elovich, Henderson and Lagergren
than pseudo-first-order kinetics The pseudo-second-order kinetic
[29]. The best-fitting isotherms have to be identified to evalu-
model has been most widely used to study the adsorption of metal
ate the efficacy of the adsorbent to develop suitable industrial
ions and dyes onto nanosorbents, like copper, nickel, lead, and
application designs. The Langmuir, Brunauer–Emmett–Teller and
methylene blue through their valence forces [14,25].
Freundlich are most widely used to describe adsorption data.
The rate formula is as follows:

1 1 1 3.3.1. Langmuir isotherms

= + t (4) Langmuir adsorption isotherms (Eq. (7)) describe the relation-
qt k2 q2 e qe
ship between the amount of adsorbate adsorbed on the solid sur-
where k2 is the equilibrium rate constant (g/mg/ h).The slopes and face of the adsorbent at a fixed temperature and its equilibrium
intercepts t/q versus t plot are used to calculate k2 [26]. concentration in aqueous solution. Langmuir isotherms are based

3
M. Sridevi, C. Nirmala, N. Jawahar et al.
on following assumptions: (1) the surface of the adsorbent is in
contact with a solution containing an adsorbate, which is strongly
attracted to the surface; (2) the surface has a specific number of
sites where the solute molecules can be adsorbed; and (3) the ad-
sorption involves the attachment of only one layer of molecules to
the surface, that is, monolayer adsorption
m · KL · Ce
q= (7)
1 + KL · Ce
where q, adsorbent concentration (μg/kg); qm maximum sorption
capacity (μg/kg); K, Langmuir affinity constant (L/mol) and Ce,
aqueous concentration (mol/L).
The advantages of the isotherm has Henry law and finite satu-
ration limit so valid over a wide range of concentrations. The dis-
advantages of Langmuir isotherm is that, it is based on monolayer
assumption and the model do not consider multilayer adsorption
or lateral sorbate-sorbate surface interactions.
3.3.2. Freundlich isotherm
Herbert F. Freundlich described an alternate isotherm to de-
scribe the data at lower concentrations. The Freundlich isotherm
is an empirical equation for the explanation of adsorption equi-
librium. The Freundlich isotherm is capable of describing the ad-
sorption of pollutants on a wide variety of nanosorbents. On aver-
Table 2
Other commonly used isotherms for adsorption systems.
Model Equation
Boyd Kinetic Model F = 1 − −(6/π 2 ) exp(−Bt )
where Bt is the mathematical function of F
Bhattacharya and Log [1-U(T)]=-(k/2.303)t
Venkobachar Model where U(T ) = [(C0 − −Ct )/(C0 − −Ce )], and k is the
Bhattacharya and Venkobachar rate constant (min−1)
Elovich Kinetic Model qt=β ln(αβ )+ β lnt
where α and β , known as the Elovich coefficients,
represent the initial sorption rate [mg/(g min)] and the
desorption constant (g/mg), respectively.
Temkin Model qe = RT ln(bKT Ce )
where B is the Temkin constant related to the heat of
adsorption, A is the equilibrium binding constant
corresponding to the maximum binding
energy (L/mg), and R is the gas constant (8.314 J/mol/K).
KRP Ce
Redlich-Peterson Model qe = β The equation is widely used as a compromise between
1+aRP Ce
where KRP (l/g) and α (l/mg)β are Redlich–Peterson
isotherm constants and β is the exponent that lies
between 0 and 1.
Dubinin and Radushkevich ln(qe ) = ln(qm ) − β ε 2
Model where qe is the amount of adsorbate adsorbed per unit
dosage of the adsorbent
(mg/g), qm is the theoretical monolayer saturation
capacity (mg/g), β is
the activity coefficient (mol2/kJ2) related to the mean
sorption energy, and
ε is the Polanyi potential
Halsey Model qe = (1/nH) In KH - (1/nH)lnCqe where KH and n are Halsey
isotherm constant
Flory-Huggins Model ln(θ /Co ) = lnKFH + η ln(1 − θ )
Where θ is degree of surface coverage, η is number of
adsorbates occupying adsorption sites, and KF H is
Flory-Huggins equilibrium constant (Lmol−1)
Ks C e β s
Sips Model qe =
1−as Ce β s
where Ks is Sips isotherm model constant (Lg−1), βs is
Sips isotherm exponent, and αs is Sips isotherm model
constant (Lg−1)
4
Journal of Molecular Structure 1241 (2021) 130596
age, a favorable adsorption tends to have a Freundlich constant n
between 1 and 10. A larger value of n (smaller value of 1/n) im-
plies stronger interaction between adsorbent and pollutant, while
1/n equal to 1 indicates linear adsorption leading to identical ad-
sorption energies for all sites [14].
The Freundlich isotherm (Eq. (8)) also assumes monolayer ad-
sorption, but that is for multiple sorption sites with different bind-
ing energies.
qe = KF · Ce ·1/n (8)
where qe, the amount of adsorbate adsorbed per gram of the ad-
sorbent at equilibrium (mg/g); KF , Freundlich isotherm constant
(mg/g) related to adsorption capacity; Ce , the equilibrium con-
centration of adsorbate (mg/L); n, Freundlich exponent (unit less)
related to adsorption intensity. 1/n values indicate the isotherm
would be (1/n = 0), favorable (0 < 1), or unfavorable (1/n>1).
The Langmuir or Freundlich isotherm model fails to describe
the adsorption behavior of pollutants from aqueous solutions onto
the nanosorbent. More than one model has been applied to illus-
trate the adsorption mechanism in many cases. Few equations that
contain two fitting parameters are Temkin isotherm, Flory-Huggins,
and Dubinin- Raduskevich equations, whereas Redlich–Paterson
and Sips isotherms have more than two parameters Table 2 [29].
Comments Refs
Due to the double nature of intraparticle diffusion (both [30]
film and pore diffusion), and in order to determine the
actual rate-controlling step involved in the solute
adsorption, the kinetic data can be analysed by using the
Boyd model.
describe adsorption kinetics of pollutants in aqueous [20]
media
describe adsorption kinetics, [31]
assuming that the actual solid surfaces are energetically
heterogeneous
The equation is a Simple expression and is Same as [29]
Freundlick. It doesnot have correct Henry law limit and
applicable over wide range of concentrations
[29]
the Langmuir and Freundlich isotherm systems.
This model has three parameters and incorporates the
advantageous significance of both models. The equation
Approaches Freundlick at high concentration
The equation assumes that the characteristics of sorption [29]
curves are related to the porosity of the adsorbent
The Halsey isotherm is used to evaluate multilayer [29]
adsorption at a relatively large distance from the surface
Flory-Huggins isotherm describes the degree of surface [29]
coverage characteristics of the
adsorbate on the adsorbent
[29]
M. Sridevi, C. Nirmala, N. Jawahar et al.
Table 3
Kinetic models for heterogeneous catalysts using CWAO.
Model Equation Comment
M1 rH = k1 [A]p
[O2 ]q
(where rH, heterogeneous combinations
and k1, the surface reaction rate constant)
rH = k1 KA Ko2 [A][O2 ]
M2
(1 + KA [A] + Ko2 [O2 ])2
(KA and KO2 , the pollutant and O2
adsorption equilibrium constants on
catalyst surface, respectively)
rH = k1 KA Ko2 ·0.5 [A][O2 ]0.5
M3 0.5
(1 + KA [A] + Ko2
0.5
[A][O2 ] )
rH = k1 KA Ko2 ·0.5 [A][O2 ]0.5
M4 0.5
(1 + KA [A]) + (1 + Ko2
0.5
[A][O2 ] )
Power law or Langmuir-Hinshelwood-Hougen-Watson (LHHW)
are also used to describe the reaction kinetics of catalytic wet
air oxidation (CWAO), tyrosol conversion by wet peroxide photo-
oxidation (using an Al–Fe montmorillonite) [32]. For heterogeneous
catalysts using CWAO, novel or improved kinetic models (Table 3)
were developed that can be applied for many organic waste water
pollutants degradations [33].
General lumped kinetic model (GLKM), a triangular model for
non-catalytic WAO of acetic was developed. The performance of
GLKM model was improved based on LHHW called extended
lumped kinetic model (ELKM). The main difference between these
two models is GLKM could not express the adsorption/desorption
of reactants/product as compared with ELKM [36].
Based on the level of accuracy obtained from adsorption
processes, successful modeling and interpretation of adsorption
isotherms can be done. Therefore suitable linear and nonlinear re-
gression analysis has to be analysed for efficient adsorption sys-
tems.
4. Adsorption mechanism and recent developments in waste
water treatment
The heavy metals quantity in ecosystems increases with in-
crease in industrialization. Challenging task for scientists and re-
searchers is to remove these heavy metals. Various methods like
ion exchange, chemical precipitation, electrochemical processes, re-
verse osmosis, coagulation, solvent extraction and adsorption are
available for the removal of heavy metals. Though, many tech-
niques are available, adsorption technique offers low cost, re-
versibility, high efficiency and ease of operation [37] hence it is
widely used for the heavy metals removal from ecosystems.
4.1. Adsorption mechanism
The accumulation phenomenon of solute (adsorbate) molecules
at the solid adsorbent surface is known as adsorption. A solid ma-
terial is an adsorbent that has the ability to take out certain sub-
stances from a media by causing them to adhere to its surface
without altering the physical properties. Substance that adsorbed
on the surface of solid adsorbent is known as adsorbate. Adsorp-
tion process does not necessitate high energy, large water or addi-
tional chemicals. The smaller particle size, the greater will be the
reactivity [38].
Adsorption happens by two phenomena, ie chemisorption or
physisorption. Chemisorption involves same kind valence forces for
Journal of Molecular Structure 1241 (2021) 130596
Refs
• an empirical power-law kinetic model [32]
• useful for homogeneous or heterogeneous reactions depending on
catalyst concentration
• M2 is based on Langmuir-Hinshelwood-Hougen-Watson (LHHW)
[34]
model
• LHHW describes the equilibrium adsorption of pollutant and O2 into
different types of active sites, whereas M2
• M3 is quite similar to M2 in terms of same active site reaction of
[35]
pollutant and O2 molecule, but O2 molecule undergoes dissociation
• surface reaction occurs between the adsorbed pollutant and O2
• suitable for reaction when the dissociated O2 and pollutant adsorb
[35]
into distinctly different active sites of the catalyst
the formation of chemical compounds where as Physisorption oc-
curs when intermolecular forces, are used to append the absorbate
onto the absorbent [39]. Parameters such as the interaction be-
tween the adsorbent and adsorbate, pH, surface charge, adsorbate
area, and size of adsorbent and adsorbate will determine the ad-
sorption process. Isotherm and Kinetic studies evaluate the adsorp-
tion phenomena, rate and efficiency [40].
Nanomaterials have external dimensions in nanoscale (usually
1–100 nm) or those with nanoscale internal structure/surface. The
properties like small size effect, surface effect, macro quantum
tunnel effect and quantum effect, add to their extraordinary ad-
sorption reactivity and capacity for heavy metal adsorption [41].
Few researchers have demonstrated the chemical adsorption mech-
anism through combined ion exchange−surface complexation for
metal ions removal [42]. Adsorption and its applications of carbon
nanotubes, nanosized metal oxides, novel organic–inorganic hy-
brids and metal/metal oxides nanoparticles and polymer-supported
adsorbents well summarised [43,44].
Enormous adsorbents such as nanosized metal oxides (NMOs),
including nanosized ferric oxides, manganese oxides, aluminum
oxides, titanium oxides, magnesium oxides, and cerium oxides;
chitosan, graphene oxide (GO), modified iron oxide, complexing
membranes have been reported for heavy metal removal Table 4
[45,46].
5. Removal of heavy metals and ions
A big concern is to remove the heavy metals ions from the en-
vironment due to its toxicity and non-biodegradable nature and its
health hazards for all living organisms. The industrial and munic-
ipal solid wastes are important source of pollution. They are con-
taminated with heavy metals like mercury, Cadmium, iron, Man-
ganese, lead and the treatment of these wastes with the environ-
mental standard is needed [47]. To limit the spread of the heavy
metals within water sources, nowadays nanomaterials were syn-
thesised and utilised Fig. 3.
5.1. Waste water treatment with metal/metal oxide containing
nanoparticles
Nano Metal Oxides (NMOs) such as manganese oxides, nano-
sized ferric oxides, magnesium oxides aluminum oxides, titanium
oxides, and cerium oxides, shows potential adsorbents for heavy
metal elimination from aqueous systems. The size and shape of
NMOs are considered as the most influential factors with regard
5
M. Sridevi, C. Nirmala, N. Jawahar et al.
Table 4
Nanomaterials types for heavy metal removal in waste water treatment – an overview.
Nanoadsorbents Example
Nanometals and Nickel oxide NP, Silver NP and Titanium dioxide,
nanometal oxides Magnetic NP, copper, etc
Carbon nanomaterials Graphene oxide, graphene, fullerenes, carbon nanotubes,
and activated carbons, etc.
Nanofiber Membranes Polyacrylonitrile/polyaniline, Polypyrrole/ polyacrylonitrile
and Polypyrrole-polyaniline nanofiber, etc
Nano photocatalyst cerium oxide, Tatanium oxide, Bismuh nanoparticle, etc
Fig. 3. The impact of heavy metal and its removal techniques.
to their adsorption performance. The adsorption process is a func-
tion of concentrations of adsorbent and adsorbate and with contact
time.
5.1.1. Nickel oxide nanoparticles
The adsorption of Nickel (II) ions [Ni (II)] by a Nano adsorbent
- Hydrous Manganese Oxides Nanopowders (MONs) from aqueous
solution at pH 6, contact time 90 min was onto 35 mg/g MONs.
The pseudo-second-order model and Freundlish isotherm was ob-
served in adsorption behavior of Ni (II) onto MONs. The adsorp-
tion type involved is physiosorption (physical sorption) took place
at low temperature. Synthesised nanoparticles of iron and nickel
composite reduce Pb and Cr (VI) concentration [48].
5.1.2. Silica-based nanomaterials
Nanostructured silica/graphite oxide composites, graphite oxide
and silica nanoparticles were synthesised for the heavy metal ions
removal from aqueous solutions by a batch adsorption method and
have been modelled using classical Langmuir and Freundlich ad-
sorption isotherms [49]. Silica-based nanomaterials are also capa-
ble of removing heavy metals due to their properties, like excellent
surface characteristics and non-toxicity. The nanosilica can remove
Cd (II), Ni (II), and Pb (II), and Cu (II) [50].
5.1.3. Iron oxide nano-particles
Adsorption of metals from waste water by Iron oxide nano-
particles (Fe2 O3 ) depend on the pH, adsorbent dose, temperature
6
Journal of Molecular Structure 1241 (2021) 130596
Heavy metals removed predominantly
Ni (II), Cd (II), Pb (II), Cu (II), Cr (III), Co(II), Pb(II), As(III),
Hg (II) etc
Zn (II), Pb(II), Cd (II), Cu(II), Ni(II)
Pb(II), Cd(II), Hg(II), Cu(II),Cr (VI)
Cr(VI), Hg (II), Cu (II), As(III), Zn (II), Pb(II) and Ni(II)
and incubation time. Fe2 O3 surface modification study has been
carried by many researchers. Surface modifications of Fe2 O3 nano-
particles with 3-aminopropyltrimethoxysilane, 1,6-hexadiamine,
iron oxide magnetic NMs, carbon-encapsulated magnetic nanopar-
ticles [51,52], effectively removed different pollutants such as Ni
(II), Cu (II), Cr (III), Co (II), Pb (II), Cd (II), and As(III) simultane-
ously from waste water. For removal of copper ions carboxymethyl-
β -cyclodextrin modified Fe3 O4 nanoparticles (CMCD-MNPs) were
fabricated and γ - Fe2 O3 (maghemite) nanoparticles employed for
removal of toxic metal ions such as Pb(II), Zn(II) and Cd(II). Fe/Ni
reinforced by kaolinite (K-Fe/Ni) made from bimetallic nanopar-
ticles removed Cu(II) and nitrate ions. Graphene magnetic mate-
rial (Fe3 O4 -GS) combinations removed heavy metals Pb(II)), Cd(II),
Hg(II), Cr(VI) and Ni(II). Review on iron oxide nanoparticle elabo-
rates about the synthesis and its application [53–55].
5.1.4. Silver nanoparticle and titanium dioxide nanoparticles
Silver nanoparticles are derived from its salts like silver nitrate
and silver chloride. Ag nanoparticles doping with other metallic
nanoparticles or its composites could be used for waste water re-
moval. Nanometer titanium dioxide (193 m2 /g and the average
pore width was 7.2 nm) used as adsorbent to remove heavy met-
als such as mercury, lead and cadmium from industrial waste wa-
ter. Under the optimised operating conditions of pH 7.0, 0.5 mol
L − 1 HCl, a sample flow rate of 10 mL min−1 for complete elution,
the removal of heavy metals 5 was 2.4, 48.7 and 23.5 mg g − 1
respectively in industrial waste water [56].
M. Sridevi, C. Nirmala, N. Jawahar et al.
5.1.5. Magnetic nanoadsorbents
Magnetic nanoparticles have paying attention in the heavy met-
als removal from waste water. Amino-functionalized Fe3 O4 nano-
particles, anisotropic hexagonal ferrite Magnetic nanoadsorbents
like hematite (α -Fe2 O3), maghemite (γ -Fe2 O3), and spinel
ferrites remove toxic elements from contaminated water [57].
Abundant reports supports that MNPs remove arsenic, chromium,
cobalt, copper, lead, and nickel in their ionic forms [55]. Magnetic
iron oxide nanoparticles synthesised from tea waste template re-
moved As (III). Poly vinyl pyrrolidone-coated magnetic nanoparti-
cles were used to remove metals (Cd, Cr, Ni, and Pb) [58].
5.1.6. Gold nanoparticle
Aluminum supported Gold nanoparticles and citrate-coated
Gold nanoparticles effectively removed Hg (II) metal ion. Colloidal
gold is formed by reducing Au3+ to Au0 using reducing agents
like alcohols, ascorbic and citric acid, amines, citrate, hydrazines
and toluene [59]. The solution becomes saturated, the metal gets
precipitated gradually and gold nanoparticles are formed with in-
crease in concentration. Au NP–aluminum oxide adsorbents, Tween
20-stabilized gold nanoparticles and Citrate-coated Au nanoparti-
cles removes Hg (II) from aqueous solution [60].
5.1.7. Zeolite
Zeolite nanoparticles have been produced by pulsed laser intro-
duction to the zeolite Linde Type A (LTA) microparticles or with
fly ash by hydrothermal activation. Zeolites employed widely for
the removal of Ni(II), Cr(III), Cu(II), Zn(II) and Cd(II) heavy metals
from the waste water sources of electroplating industry and acid
mines [61].
5.1.8. Nanoscale zero-valent
Nanoscale zero-valent iron (nZVI) is a Fe (0) and ferric oxide
coating consisting composite, used for treating waste water pol-
luted with heavy metals like chromium, cadmium, copper, silver
and zinc. Nano-zero valent iron can be used along with chlori-
nated hydrocarbon fluids and perchlorates for groundwater con-
tamination remediation. It has specific surface, high reactivity, and
has very low life time. It has received increased attention to treat
heavy metals, such as Ni (II), Cr (VI), Hg (II), Cd (II), Cu (II), etc.
[62].
5.1.9. Magnesium oxide nanoparticle
MgO nanoparticle efficiency and mechanism to remove lead
from aqueous media and a novel dumbbell-like manganese diox-
ide/gelatin has been investigated for its adsorption performances
towards Pb (II) and Cd (II) [63].
5.2. Carbon nanomaterials
Copper nanoparticles have surprising optical, catalytic and
electrical conducting properties. Carbon nanomaterials such as
graphene oxide, graphene, fullerenes, carbon nanotubes, and acti-
vated carbons are used in sensors, energy storage, water purifica-
tion, electronics, disease diagnosis, drug delivery, etc. due to their
excellent mechanical, chemical, electrical and thermal characteris-
tics. The removal of heavy metal ions, e.g. Zinc, lead, cadmium,
copper, nickel with multipore activated carbon (MPAC) using the
agricultural waste of long-root Eichhornia crassipes has been stud-
ied. Sulfonated Activated Carbon prepared from sewage sludge of
waste water treatment removed Pb(II), Cd(II), Cu(II), and Ni(II) ions
from water efficiently [64]. Activated carbon prepared from the
agricultural waste of eucalyptus bark, wood saw dust of rubber
plant, Moso and Ma bamboo, Palm shell, olive stone etc., also effi-
ciently removed heavy metals from the waste water [65,66].
7
Journal of Molecular Structure 1241 (2021) 130596
5.2.1. Carbon nanotubes
Carbon nanotubes (CNTs) as new adsorbents, proved to own
enormous potential for removing heavy metal ions such as cad-
mium, lead, copper, chromium, nickel, manganese, thallium. Fur-
ther, nickel oxide/carbon nanotube nanocomposite removes lead
[43,67].
5.2.2. Graphene oxide
Graphene Oxide (GO) is important carbon-based nanomaterial
that also adsorbs pollutants like heavy metals and synthetic dyes.
GO has properties, like elasticity and stiffness, electrical and ther-
mal conductivity, mechanical strength, and many more. Adsorption
of Cr (VI) by reduced graphene oxide-cobalt oxide nano-particles,
adsorption of cadmium ions by the development of nanoscale ze-
rovalent iron particles supported on reduced graphene oxide has
been reported. Graphene-based nanocomposites are used to re-
move heavy metals such as Pb, Cd, Cr, Cu, As, Hg, Zn, Co etc.
[10,25,41,46,47].
5.3. Nano photocatalyst
Most common photocatalysts isTiO2, utilised for its high effi-
ciency properties, low cost and chemical stabliity. Illuminated TiO2
under ultraviolet light degraded the pollutants like Cr(VI), Hg (II),
Cu (II) and Ni(II). Nanoscale goethites serve as adsorbent and pho-
tocatalyst, goethite and hematite nano-photocatalysts removes Cu
(II) ion. photocatalyst ZnO nanopowder utilised for Hg(II) adsorp-
tion. Bismuth (Bi) nanomaterials photocatalyst, has chemical sta-
bility, suitable energy-band composition and it is nontoxic. Synthe-
sized Bi composites with TiO2 and showed improved photodegra-
dation effectiveness together than used individually [68].
Nanosized cerium oxide - CeO (II), a rare-earth oxide reported
for removal of Cr (VI) [133], As (V) and As (III) [178], Cu (II), Zn (II)
and Pb (II). Gadolinia-modified ceria photocatalyst adsorbed Pb (II)
ion [180]. Graphene material photocatalyst properties and its ap-
plication on heavy metals removal has been reviewed extensively
[69].
5.4. Nanomembrane
Synthesized carboxylated graphene oxide-incorporated
polyphenyl sulfone nano filtration membrane and Modified
PAN/PANI-Nylon Core Shell Nanofibers membrane removes
heavymetals [70]. Electrospun nanofiber membrane coordi-
nated with a zeolitic imidazolate framework (ZIF-8) was tested
with heavy metal removal. Cr (II) is removed by Aerogels which
was formed by a quaternary ammonium-functionalised cellulose
nanofiber [71].
Even though nano materials removing heavy metals are ad-
vantageous, it still has some shortcomings. For example the high
costs of nano materials obstruct their commercial usage, as it
is difficult to separate CNTs from waste water after the adsorp-
tion and may increase the secondary pollution threat. In addition,
nano material toxicity studies towards living organisms, its stabil-
ity; market readiness for heavy material removal is still a long way
to go [72]. Studies on nanoparticle green synthesis (with plants
and microbes) will decrease the toxicity of nanoadsorbents and
can increase its application in combating environmental pollution.
Nanoparticle synthesis utilizing wood, agricultural wastes, medic-
inal plants, clay materials etc. are to be extensively carried out
along with the effectiveness for field application.
6. Conclusions and outlook
Nanomaterials in nano photocatalyst establish extraordinary ef-
ficacy due to having a high rate of reaction. Conversely, there is
M. Sridevi, C. Nirmala, N. Jawahar et al.
still some insignificance that necessity discussed. To date, no oper-
ative digital checking practices occur that deal with reliable real-
time evaluation details on the supremacy of nanoparticles that are
remaining in minor quantities in treated water. Furthermore, spe-
cific research organizations and global research societies must or-
ganize precise strategies to overwhelm this dispute to reduce the
health risk. Additionally, advanced mechanical constraint of nano-
engineered water system is intermittently flexible to bulk develop-
ments, and at current, they are not self-effacing with conventional
treatment procedures in numerous cases. Nanophotocatalysis cycle
may happen in two states heterogeneously or homogeneously. The
most seriously considered state is heterogeneous nanophotocataly-
sis in the current period because of its wide degree in water dis-
infecting and related biological applications. Nano-engineered ma-
terials afford the excessive potential for water revolutions, specif-
ically decentralized wastewater treatment machinery, point-of-use
approaches, and highly degradable pollutants. Furthermore, there
is a great necessity to synthesize specifically improved nanomate-
rials that must be operative, have great productivity, and are easy
to manage and eco-friendly. It is also essential to take the price
into account and commercialization these approaches for wastew-
ater treatment. The different nanomaterial uses can offer a tremen-
dous deal to supply portable water to the entire ecosphere.
Declaration of Competing Interest
None.
CRediT authorship contribution statement
M. Sridevi: Conceptualization, Methodology. C. Nirmala: Data
curation, Formal analysis. N. Jawahar: Writing - original draft. G.
Arthi: Visualization, Investigation. Sugumari Vallinayagam: Super-
vision. Vipin Kumar Sharma: Writing - review & editing.
Acknowledgements
No funding to declare.
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