Journal of Cleaner Production 296 (2021) 126589

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Journal of Cleaner Production

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

Review

A review on conventional and novel materials towards heavy metal

adsorption in wastewater treatment application
Wai Siong Chai a, b, Jie Ying Cheun b, P. Senthil Kumar c, Muhammad Mubashir d,
Zahid Majeed e, Fawzi Banat f, Shih-Hsin Ho a, **, Pau Loke Show b, *
a
State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin, 150090, PR China
b
Department of Chemical and Environmental Engineering, Faculty of Science and Engineering, University of Nottingham Malaysia, Jalan Broga, Semenyih,
43500, Selangor Darul Ehsan, Malaysia
c
Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Chennai, 603110, India
d
Department of Petroleum Engineering, School of Engineering, Asia Pacific University of Technology and Innovation, 57000, Kuala Lumpur, Malaysia
e
Environmental Biotechnology Laboratory, Department of Biotechnology, University of Azad Jammu and Kashmir, Chehla Campus, Muzaffarabad, Azad
Kashmir, Pakistan
f
Department of Chemical Engineering, Khalifa University, 127788, Abu Dhabi, United Arab Emirates

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

Article history: Wastewater treatment remains a critical issue globally till date despite various technological advance-
Received 26 November 2020 ments and breakthroughs. Heavy metal in wastewater poses a great threat to human health if untreated
Received in revised form properly, which makes its removal of utmost importance. Among various wastewater treatment tech-
26 February 2021
niques, adsorption is the most common technique to remove heavy metal in wastewater due to its
Accepted 28 February 2021
Available online 3 March 2021
flexible design, operation, and cost-effectiveness. Activated carbon being the most conventional adsor-
bent to remove heavy metal ion in wastewater owing to its microporous structure and ease of surface
Handling Editor. Bin Chen functionalization. However, the activated carbon separation from wastewater solution has been difficult
and its high cost have prohibited its wide usage. Recently, the emergence of different novel materials has
Keywords: also showed their competitiveness in heavy metal ion removal. These promising novel materials exhibit
Wastewater treatment several excellent attributes, for example large surface area, great mechanical strength, and high chemical
Heavy metal removal inertness. This paper presents a brief review on the use, theory and future perspectives of conventional,
Adsorption as well as novel materials towards heavy metal adsorption in wastewater treatment application.
Conventional materials
© 2021 Elsevier Ltd. All rights reserved.
Novel materials

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Conventional materials in heavy metal adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Activated carbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Biomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Novel materials in heavy metal adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1. Nanosized metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2. Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.3. Graphitic carbon nitride (g-C3N4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4. MXenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.5. Metal organic framework (MOF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4. Conclusions, challenges and future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.1. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

* Corresponding author.
** Corresponding author.
E-mail addresses: cloudcws@gmail.com (W.S. Chai), jycheun@gmail.com (J.Y. Cheun), senthilchem8582@gmail.com (P.S. Kumar), mubashir@apu.edu.my (M. Mubashir),
zahid.majeed@ajku.edu.pk (Z. Majeed), fawzi.banat@ku.ac.ae (F. Banat), stephen6949@hit.edu.cn (S.-H. Ho), PauLoke.Show@nottingham.edu.my (P.L. Show).

https://doi.org/10.1016/j.jclepro.2021.126589
0959-6526/© 2021 Elsevier Ltd. All rights reserved.
W.S. Chai, J.Y. Cheun, P.S. Kumar et al. Journal of Cleaner Production 296 (2021) 126589

4.2. Future outlook & challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

1. Introduction fuel combustion, landfills, metal finishing and electroplating,

extraction operations and street run-offs (Akpor, 2014).
Environmental contamination has always been public concern, Heavy metals cause adverse effects to both human health and
particularly water pollution. Metal contaminated wastewater that environment, for example copper ions can cause liver damage,
originates from anthropogenic activities in numerous sectors, for insomnia and inhibit soil enzymatic activities. Mercury causes
instance agricultural activities, industries (mining, battery, nuclear, rheumatoid arthritis, nervous and circulatory disorders on human
textile dyes, tannery, etc.), domestic sewage and others, has always health as well as affect aquatic system whereas chromium may
been a threat to human health and environment. The most im- cause headache, diarrhea and nausea. Copper may leads to liver
mediate impact towards environment is the destruction of marine illness and anemia while lead poisoning contributes to muscle
habitat, soil degradation that leads to lower yield of crops and often impair, kidney failure and damages infant brain (Cheng et al., 2019).
heavy metals present in contaminated water are taken up by plants, Detrimental effects of heavy metals on human health include
thereby entering food chains and cause adverse consequences to various organ damage and disease, skin irritation, anemia, impaired
human and animals (Sankaran et al., 2020). voluntary muscle function. Owing to the heavy metal characteris-
Though heavy metals e.g. Cd, Zn, Pb, Fe, Cu, Hg, Ni, Mn, Co, etc., tics which are highly soluble, stable, non-biodegradable nature and
are normally present in trace amounts, they are considered as the can migrate throughout aqueous medium, metal contaminated
most toxic and widespread components in wastewater effluent wastewater effluents negatively affect health and also cause
(Zhou et al., 2020). These heavy metals are not metabolized by the detrimental impacts on plants such as inhibition of photosynthesis,
body leading to accumulation in soft tissues which is hazardous to reduced seed germination, decreased enzyme activity and chloro-
human health (Sankaran et al., 2020). Besides, the United Nations phyll synthesis. The reactivity of these elements are determined by
has stated that 80% of the global wastewater are released to the the form and arrangement of atom electron shells which influence
ecosystem sometimes without or with some treatment. Fig. 1 their tendency to form complexes and, thus contribute to physio-
demonstrates the mean concentrations of heavy metals in water logical and biochemical activity (Burakov et al., 2018).
bodies from 1990s to 2010s in comparison with the US Environ- To remove heavy metal efficiently from aqueous media, a variety
mental Protection Agency (USEPA) standards. However, most of the of techniques have been proposed such as solvent extraction,
heavy metal concentrations are still offsetting the standards set. coagulation, ion exchange, chemical precipitation, membrane
Additionally, the rising demand for clean water in expanding cities, filtration and electrochemical technologies. Selection of the ap-
for sustainable agriculture purposes and to enhance energy gen- proaches used generally rely on: e.g. costs, efficiency, reliability,
eration in industrial development urge for high quality treated ef- feasibility, environmental impact, practicality and operation diffi-
fluents (UN-Water, n.d.). culties (Crini and Lichtfouse, 2019). Table 1 demonstrates the ad-
Trace elements with an atomic density higher than 4 ± 1 g/cm3 vantages and disadvantages of several conventional techniques
are known as heavy metals and persist in wastewater derived from used in wastewater treatment. However, these methods have some
natural and anthropogenic factors. The main natural sources of drawbacks including poor efficiency, inadequate removal, sensitive
heavy metal pollutants include soil erosion, urban runoffs, aerosol operating conditions, high energy requirements and costly disposal
particulate, volcanic activities whereas human factors comprise procedures.

Fig. 1. Heavy Metal Concentrations (mg/L) from global rivers and lake bodies at year 1990s and 2010s in comparison with the standards of USEPA. Reprinted from (Zhou et al., 2020)
with permission from Elsevier.

2
W.S. Chai, J.Y. Cheun, P.S. Kumar et al. Journal of Cleaner Production 296 (2021) 126589

Among the methods, adsorption technique emerges to the
forefront as a result of its flexibility in operation, design processes
and appears to have significant effect on toxicity, biological avail-
ability and transport of heavy metals in wastewater. The three main
steps of adsorption onto solid sorbent involve transport of
contaminant to sorbent surface from aqueous solution, adsorption
onto solid surface and transport within sorbent particle. The
charged contaminants tend to adsorb on oppositely charged ad-
sorbents via electrostatic force of attraction. Heavy metals show
strong affinity for surface hydroxyl or other functional groups. Since
adsorption is often reversible as it is accompanied with desorption
process (reverse process of adsorption in which adsorbate ions are
transferred from adsorbent surface), adsorbents can be regenerated
for multiple use, making it a cost-effective and high efficiency
process to produce high quality treated effluents. Langmuir
maximum adsorption capacity (qmax) and Freundlich adsorption
isotherm (KF) are parameters that are usually used for interpreting
the metal adsorption of various materials.
The two types of adsorption are physical and chemisorption
(also refer as activated adsorption) whereby physical adsorption is
the binding between adsorbent and adsorbate surface due to non-
specific van der Waals force whereas the latter forms ionic or co-
valent bonds by chemical reactions. Physical adsorption is revers-
ible, but less specific, on the other hand, chemisorption is more
specific and irreversible (Tripathi and Rawat Ranjan, 2015). There
are several factors which influence the adsorbent’s efficiency
including temperature, pH, stirring duration and initial concen-
tration. The rate of heavy metal adsorption typically rises with the
surge of the above mentioned factors (Burakov et al., 2018).
Moreover, adsorbents with high adsorption interaction the target
heavy metal ions should be used to remove the contaminants
effectively.
Some of the conventional adsorbent examples will be activated
carbon, nanosized metal oxides (NMOs), biomass, agricultural
waste and others. Among these adsorbents, activated carbon re-
ceives the most attention and is universally used as adsorbent in
water purification because it can be easily modified by chemical
process to improve adsorption capacity. Even so, powdered acti-
vated carbon is hard to be separated from the solution and is
expensive (Sankaran et al., 2020). There are also researches that
indicate the practical use of bioadsorbent for an economical and
environmentally friendly approach in wastewater treatment.

Table 1
Comparison of the advantages and disadvantages of contaminated water treatment methods.

Process Main Characteristics Advantages Disadvantages

Ion Exchange Use of resins or adsorbents
High regeneration as resins can
Large volumes require large columns
(O’Connell et al., Nondestructive process be regenerated
Beads fouling by organic matter and
2008)
Efficient and rapid process particulates (requires physiochemical

Suitable resins can be selective pretreatment)
towards pollutants
Sensitive to effluent pH

Applicable for continuous and
Selective resins have limited commercial
batch flow use
Chemical Precipitation Uptake of pollutants and separation of the solids formed
Cost-effective (e.g. uses simple
Large sludge production volume, create
(Hunsom et al., equipment) handling and disposal troubles
2005)
Efficient for fluoride and metals
Ineffective in removing low concentration
removal metal ions

Reduce chemical oxygen
Requires oxidation step if metals are
demand significantly complexed
Membrane filtration Nondestructive separation by using semipermeable barrier
Requires small space
High energy requirements
(Zhang et al., 2009)
Uncomplicated, efficient and
High operation and maintenance costs
rapid process
Rapid fouling on membrane

No chemicals needed
Limited flowrates

Generate relatively less solid
waste

Wide range of real applications
Coagulation/ Uptake of pollutants and separation of the products formed
Simple process
Requires adjunction of non-reusable co-
Flocculation (Aziz
Low capital cost agulants and flocculants
et al., 2018)
Highly efficient for suspended
Poor removal of Arsenic
solids and colloidal particles
Large generation of sludge volume

Bacterial inactivation capability
Solvent extraction Separation technology by adding solvent
Common for wastewater recycle
High capital cost (equipment)
(Crini and
Use for large scale operations
Entrainment of phases result in poor
Lichtfouse, 2019) with high loads of contaminants effluent quality

Relatively low operating costs
Possible cross contamination of aqueous

Simple monitoring and streams
controlling of process
Use of organic solvent may be highly toxic
Biological methods Application of either pure or mixed biological cultures
Efficient in eliminating
Necessary to create an optimally favorable
(Crini and biodegradable organic matter condition or environment
þ
Lichtfouse, 2019) (NH4 , NH3, iron)
Relatively slow process

High removal of biochemical
Might require pre-treatment of non-
oxygen demand and suspended biodegradable or toxic compounds
solids
Complexity of microbiological

Use of microorganisms (white- mechanisms
rot fungus) broadly accepted by
public
Adsorption (Bobade Mass transfer process involving atoms, ions or molecules from
High effective adsorption
The methods are non-selective
and Eshtiagi, 2015) liquid gripping on solid surface via chemical or physical process with fast kinetics
Relatively high cost of materials such as
interaction
Require simple equipment commercial activated carbon

Wide variety of target
Require several types of adsorbents
contaminants
Regeneration is expensive and may result

Broad range of commercial in loss of adsorbents
products

3
W.S. Chai, J.Y. Cheun, P.S. Kumar et al.
Nowadays, the great demand in highly porous nanostructures for
instance graphene, fullerenes, graphitic carbon nitride and metal
organic frameworks (MOFs) have also been discussed to use as an
alternative to eliminate heavy metals from the contaminated water,
taking the benefits of nanotechnology into account. For this reason,
such nanomodified adsorbents may introduce chances for offering
prospective solutions to tackle water pollution issue.
This review presents a brief view on the use and theory of
conventional as well as novel adsorbents for the purpose of heavy
metal adsorption in wastewater treatment process. In addition,
comparison between these materials with activated carbon as
benchmark regarding the adsorptive performance is prepared, with
a conclusion on the current technical challenges faced by novel
materials and the viewpoints of employing nanomaterials in the
future.
2. Conventional materials in heavy metal adsorption
There are a variety of adsorbents existing in different nature
which can either be utilized in pristine or modified structures to
remove harmful heavy metal ions from wastewater. The ones that
are described in the present review are activated carbon and
biomaterials.
2.1. Activated carbons
Activated carbons (ACs) are frequently used as adsorbents at
water treatment plants for adsorbing heavy metals owing to the
microporous structure, large surface area and chemical complexity.
Their external surface possesses variable functional groups for
example phenol, carbonyl, lactone, carboxyl, quinone and others. It
is proven that the adsorption performance of ACs is dependent on
surface functional groups and pore size distribution. However,
activated carbon may react with oxygen under moderate temper-
ature (300  C). Commercial ACs are present in granular, powder,
clothe and fibrous form (Ahmad and Azam, 2019).
Coal, coconut shell and wood are normally used as precursor for
the manufacture of ACs. As coal based ACs are expensive, it has
prompted further research onto inexpensive ACs, developed from
abundant and various agricultural waste materials. The effect of pH,
contact time, temperature and initial Cr6þ concentration on the
performance of rubber wood saw dust based adsorbent was
experimented (Akmar Zakaria et al., 2009). Cr6þ can be removed
spontaneously via direct reduction of oxidation number from þ6
to þ3 by contacting with the electron donor groups on adsorbent.
Another mechanism comprises of three steps starting with Cr6þ
bind to positively charged groups on activated carbon surface. The
next step takes place at the adjacent electron donor groups to
reduce to þ3 and lastly, Cr3þ ions are returned to the water because
of repulsion between the cations and the positively charged sites.
The optimum material was acquired under the following condi-
tions: optimum pH 2.0, complete removal of 100 mg/L initial Cr6þ
concentration with 1 h contact time and adsorbent dosage greater
than 1.5% (w/v).
Maximum Cr4þ adsorption of 95% was recorded with rice husk
carbon (Wong et al., 2003). Generally, the adsorption relied on
adsorbent concentration, temperature, time and pH of the solution
(optimum pH: 12.0) (Khan et al., 2004). Besides the conventional
rice husk adsorbents, modification was carried out on rice husk
based ACs by using tartaric acid in batch studies (Hsu and Pan,
2007)and was shown to be a potential material in the binary
component sorption of Cu2þ and Pb2þ from aqueous media (Hsu
and Pan, 2007; Wong et al., 2003).
Cd2þ and Zn2þ removal study was performed from contami-
nated water using AC generated from sugarcane bagasse (Mohan
4
Journal of Cleaner Production 296 (2021) 126589
and Singh, 2002). They achieved the maximum uptake (100%) at
pH 8.0, which was evident to have higher affinity than other ad-
sorbents. The elimination of Cr4þ from heavy metal contaminated
water based on bagasse and coconut jute was studied. The
maximum removal obtained 99.8% and was most effective at low
Cr4þ concentration and low pH (Sharma and Forster, 1995). The use
of AC prepared from coconut tree sawdust was explored in order to
remove Cr4þ from aqueous media (Selvi et al., 2001). Various
adsorption experiments revealed that the utmost withdrawal was
better acquired in the acidic pH range and the qmax calculated from
Langmuir isotherm was 3.46 mg/g at an initial pH 3.0 for particle
size of 125e250 mm.
Coconut shell to produce AC via chemical activation using ZnCl2
for adsorption of heavy metal ions from wastewater was investi-
gated (Bernard et al., 2013). They realized that as the percentage
metal ions removal rises, contact time also increases. The adsorp-
tion capacity for contaminant ions declined with the trend
Pb2þ>Fe2þ>Cu2þ>Zn2þ. The optimum adsorbent dosage was cho-
sen to be 1 g for removal of Cu2þ, Fe2þ and Zn2þ with percentage
removal 78.16, 84.1 and 34.77%, respectively. The experimented
withdrawal of Cu2þ from wastewater using hazelnut shell based AC
as adsorbent material and the maximum adsorption capacity of
58.0 mg/g (Demirbas et al., 2009), similar to palm shell AC
(Issabayeva et al., 2010). Both authors disclosed that the ions are
better eliminated at higher pH on the account of deprotonated and
negatively charged adsorbent surface at higher pH, thus metal
cations are attracted leading to more heavy metals adsorbed on the
surface of adsorbent. The poultry litter-based AC exhibits remark-
ably higher adsorption capacity (1.2 mmol/g for Cu2þ) and affinity
for dissolved heavy metal ions as compared to commercial AC
manufactured from coconut shells and bituminous coal (Guo et al.,
2010).
The adsorption performance of apricot stone-based AC was
investigated to withdraw trace metal ions from wastewater (Kobya
et al., 2005). Chemical activation employing concentrated H2SO4
was carried out on apricot stone with the weight ratio of 1:1 and
heated to 200  C for 24 h. The adsorption capacity of respective
metal ion was experimented to be notably affected by pH whereby
the maximum Cr6þ, Pb2þ, Cd2þ, Co2þ, Cr3þ, Ni2þ and Cu2þ ions
removal occurred at pH 1, 3, 5, 6, 4, 4 and 4 respectively. AC derived
from olive stone waste produced from olive oil manufacturing
resulted a similar adsorption capacity as apricot stone AC (Bohli
et al., 2015). pH ¼ 5.0 was the optimum pH and average contact
time was 200 min. The adsorption capacity declined in the
following sequence: Pb2þ(147.526 mg/g) > Cd2þ(57.08 mg/
g) > Cu2þ(17.665 mg/g). The authors concluded that AC derived
from olive stone, with very low economy value, are suitable to treat
metal contaminated water. It exhibited a higher affinity for copper
than nickel or lead. The same precursor was studied in which olive
stone AC was produced using microwave (Alslaibi et al., 2013).
Agitation speed was set at 200 rpm with 3 h contact time and at pH
5.0 to remove Cu2þ, Pb2þ, Cd2þ, Zn2þ, Fe2þ and Ni2þ from metal
contaminated water. The removal efficiency of these ions was re-
ported between 95.32 and 99.32%.
Other than the above-stated materials, AC from eucalyptus bark
(Kongsuwan et al., 2009), soybean hulls (Khan et al., 2004), bamboo
(Lo et al., 2012) and others could be a great choice for heavy metals
removal. To conclude, ACs are mostly used to remove undesirable
odors, color, taste and organic impurities from water in the treat-
ment of domestic and industrial wastewater, but the adsorption by
ACs have some restrictions such as loss of adsorption efficiency
after regeneration, the need for regeneration after exhausting and
may cause secondary pollution as the contaminants are separated
from the ACs but not destroyed. Therefore, the studies and appli-
cations of other adsorbents are necessary.
W.S. Chai, J.Y. Cheun, P.S. Kumar et al.
2.2. Biomaterials
Bioremediation or biosorption of heavy metals has gained
popularity in the wastewater treatment process as it possesses high
efficiency in adsorbing heavy metal ions from dilute water effluents
and has low operating cost. The removal of heavy metal using egg
shells was investigated in proving the use of an economical bio-
logical adsorbent (Lin et al., 2020; Sankaran et al., 2020) whereas
more than 95% of the heavy metal pollutants especially Cu2þ, Ni2þ,
were removed using hydroxyapatite from fishbone (Herna ndez-
Cocoletzi et al., 2020). The production of biomass such as fungi,
bacterial is cheaper than other conventional materials. It is un-
necessary to add any chemical reagents as the uptake and removal
of certain metals are highly specific. Moreover, there is a reduced
volume of toxic materials produced (Shamim, 2018). However, the
adsorption reaction involving these biosorbents are mostly
exothermic process. The biosorption capacity remain unaffected in
the temperature range 20e35  C. In some cases, high temperatures,
e.g. 50  C may improve adsorption rate but may cause permanent
damage to microbial living cells. Therefore, they are influenced by
the effects of temperature in which an increase in temperature lead
to decrease in adsorption capacity.
The adsorption process on biosorbents cell walls especially
bacteria can be dependent or independent of metabolism. Meta-
bolism dependent biosorption occurs on the surface via formation
of van der Waals forces, electrostatic attraction, covalent bond and
precipitation. Such adsorption mechanism involves generation of
energy from ATP in which the ligands on the biological material cell
wall immobilizes heavy metal and allow adsorption to take place.
Cell wall composition, medium conditions and nature of heavy
metals are among the factors that affect metal uptake by living
biomass. On the other hand, metabolism independent biosorption
happens in biomass comprising of dead cells. Ionic bonding or
physiochemical adsorption involves in this process. The bio-
sorbents that are discussed below are algae, bacteria, fungi and
biochar.
Among the biomaterials, algae, a renewable, non-toxic natural
biomass, are gaining rising attention particularly because they are
able to accumulate high metal contents and are relatively cheap to
process since it is a rich resource in oceanic environment. As such,
microalgae have been associated with wastewater bioremediation
by assimilating the nutrients (Chai et al., 2021; Leong et al., 2019;
Salam, 2019). Microalgal bacterial flocs have been a promising
means for wastewater treatment in terms of removing nutrients
from seafood wastewater, for instance Chlorella vulgaris produced
from bioflocculation removed 93.0% of total suspended solids and
88.0% of nutrients (Nguyen et al., 2019). Nevertheless, the protein
contents of algae such are high resulting in active growth and the
formation of protein-required functional groups (C. H. Tan et al.,
2020). Moreover, the surface of algae consists of diversified func-
tional groups including amino, hydroxyl, sulfate and carboxyl
which serve as potential binding sites for metals. Both adsorption
on the cell surfaces and internal diffusion encompass the uptake of
heavy metals by algae. Fig. 2 illustrates the biosorption mechanisms
of algae adsorbent. The adsorption capacity of a marine algae to
remove Cu2þ from water was found out to increase with rise in pH
(Vijayaraghavan et al., 2004). Efficient biosorption of Cd2þ ions was
demonstrated using marine algae Padina sp (Kaewsarn and Yu,
2001).
Biosorption for Zn2þ, Cu2þ and Pb2þ, Zn2þ, Cd2þ, Cu2þ was
investigated using marine macroalgae Chaetomorphalinum (Ajjabi
and Chouba, 2009) and dried marine algae Caulerpa lentillifera
(Pavasant et al., 2006), respectively. Also, microalgal biomass has
also been widely investigated as adsorbents as they are easy to
grow and produce in large quantities. Microalgae are efficient in
5
Journal of Cleaner Production 296 (2021) 126589
removing phosphorus and nitrogen organic pollutants to prevent
eutrophication. Microalgal cultures utilize inorganic phosphorus
and nitrogen for growth which provide an effective means for
tertiary and quinary treatments, not leading to secondary pollution.
In general, increase in algae cultural temperatures till optimum
temperatures (25e30  C) potentially increases metal ion bio-
sorption capacity (Sibi, 2019). The real life application of algae in
removing heavy metals from various metal ions remains as a
challenge as the selectivity of metal biosorption of algae is complex
regardless of the extensive studies carried out since most of them
focus on the capacity of algae to remove single heavy metal ion
under controlled-conditions (Cheng et al., 2019).
The biosorption of heavy metals by bacteria is an inexpensive
technology to remediate contaminants from polluted aqueous so-
lution. Bacteria have been used as biosorbents because of their
ability to grow under controlled conditions and resilience to a wide
range of environmental conditions. Bacteria is an ecofriendly and
cheap adsorbent. The metal ions are first bound to the reactive
functional groups on bacterial cell wall such as amine, carboxyl,
phosphate, sulfate and hydroxyl (Hassan et al., 2010). Gram positive
charged bacteria has higher affinity to uptake metal due to the
presence of more glycoproteins compare to Gram negative bacteria
with the presence of more phospholipids and lipopolysaccharides
on their cell walls. In general, the biosorption capacity of heavy
metal ions rises with increase in pH value because of the more
negatively charged binding sites on bacterial biomass surface
(Shamim, 2018). Other biosorption of bacteria that have maximum
adsorption capacity of approximately 70e123 mg/g (Pb2þ and Ni2þ)
and are found to rely on equilibrium time, pH, initial metal ion
concentration (Gabr et al., 2008; Pan et al., 2007; Souiri et al., 2009).
Generally, the temperature that suits most of the bacteria bio-
sorbents range from 25 to 35  C (Jin et al., 2018) but optimum
temperature varies for different heavy metals (Rodríguez-Tirado
et al., 2012). Fig. 3 illustrates the adsorption mechanisms of
bacteria.
Fungi are eukaryotic living organism and can be used as bio-
sorbents in living or biomass forms. The cell wall structure of fungi
that is made up of 90% polysaccharides, which offers good metal
binding properties with various functional groups such as proteins,
carboxyl, phosphate and uranic acids. They grow easily, yield large
amount of biomass as well as can be handled morphologically and
genetically. qmax for feasible and pre-treated biomass was reported
to be 19.4 and 43.7 mg/g respectively. Desirable biosorption process
for fungi takes place at room temperature. Fungal biosorption
provides an environmentally sound and economically feasible so-
lution for the removal of heavy metals from aqueous solutions
(Dhankhar and Hooda, 2011).
Biochar is a material that is rich in carbon, manufactured in the
absence of oxygen by heating the biomass through pyrolysis pro-
cess. As a result of its graphene-like carbon matrix, high porosity,
enhanced surface area, high cation and anion exchange capacity,
biochar is able to hinder contaminants and pollutants from water or
soil to organisms and further reduce the bioavailability of pollut-
ants by adsorption. Biochar have been extensively used during
anaerobic digestion and to eliminate the trace metals, pathogens
and suspended matter in wastewater treatment process (X. Tan
et al., 2020). Micropores are the most abundant pores found
within biochar contributing to the large surface area and high
adsorption capacity. The adsorption mechanism is depending on
the chemical properties of biochar surface and the nature of pol-
lutants. The major pathways of biochar adsorption are via physical
passage in which the contaminants subside on the adsorbent sur-
face, pore filling method occurs through the condensation of
adsorbate into the pores of biochar and precipitation route where
adsorbate form layers on adsorbent layers (Enaime et al., 2020).
W.S. Chai, J.Y. Cheun, P.S. Kumar et al. Journal of Cleaner Production 296 (2021) 126589

Fig. 2. Biosorption mechanism of algae. Reprinted from (Salam, 2019) with permission from Green Wave Publishing of Canada.

Fig. 3. The different mechanisms of bacterial biosorption. Reprinted from (Etesami, 2018) with permission from Elsevier.

The dissociation of oxygen-containing functional groups leads
to negatively charged biochar surface which allow electrostatic
attraction between biochar and cations. The removal of Cu2þ was
examined using rice straw biochar and ion exchange of native
cations with Cu2þ was reported to be the presiding mechanism
controlling the adsorption (Kołodyn ska et al., 2017). Microalgae-
based biochar has an irregular porosity of 1 mm that allows it to
act as an adsorbent, however, biochar derived from microalgae has
a lower cation exchange capacity compared to lignocellulose bio-
char (Yu et al., 2017).
The adsorption system positively correlated with adsorbent
dosage, whereby the adsorbent dosage increases the sorption sites
and therefore increases the removal efficiency of inorganic
pollutants. However, an excess of dosage rate may lead to over-
lapping of adsorption layers, shielding the active sites on adsorbent
surface. Hence, the adsorbent dosage should be optimized to ach-
ieve utmost adsorption efficiency and cost-effective operation.
Most research showed that the adsorption efficiency escalated as
the temperature rose indicating an endothermic reaction of
adsorption process. Maximum removal efficiency is achieved at
temperature in between 30 and 45  C (Enaime et al., 2020). Biochar
comes to the forefront as the promising replacement for removal of
heavy metals when compared to conventional adsorbents like
activated carbon. A more efficient uptake of heavy metal ions was
reported using biochar (115.5 m2/g) compared to commercial
activated carbon (759.8 m2/g) owing to larger amount of oxygen

6
W.S. Chai, J.Y. Cheun, P.S. Kumar et al.
functional groups on biochar surface (Kołodyn ska et al., 2017).
Overall, biomaterials have been proven effective in removing
heavy metals from wastewater with their economical feedstock and
ease in preparation process. Modification via physical and chemical
activation are suggested to enhance the surface area and porous
structure of biomaterials. However, more in situ experiments
should be carried out to examine its efficiency and effects on
environment prior to its widescale application. The biosorbents
may be utilized by developing countries to reduce impacts of in-
dustrial water pollution.
3. Novel materials in heavy metal adsorption
The costly production and regeneration of activated carbon
result in finding for other alternatives. Furthermore, conventional
materials normally cannot offer the preferred removal efficiency for
the heavy metals in wastewater treatment because of low metal
adsorption capacity. In recent years, researchers carry out studies
on developing novel adsorbents particularly nanostructured ma-
terials such as carbon nanotubes, graphene, fullerene, MXene and
others. The current materials used for heavy metal adsorption from
wastewater have high specific surface areas and large pore volumes
combined with the various types of intermolecular interactions,
allowing adsorption to occur effectively. Besides, they exhibit non-
corrosive property, superior mechanical strength, thermal stability
and electrical conductivity. The adsorption performance is gener-
ally better than other conventional adsorbents for example, iron
oxide, titanium dioxide, activated carbon and others. However,
novel materials possess some limitations whereby scientific and
technological research confront functionality and durability chal-
lenges that are important in environmental applications. The novel
materials that are discussed in this present review are nanosized
metal oxides, graphene, graphitic carbon nitride, MXene and metal
organic framework (MOF).
3.1. Nanosized metal oxides
Metal oxides have been considered as one of the promising
groups of adsorbent materials as a result of their outstanding
adsorption performance, ease in modification and generation,
inexpensive economic value and mass-produced features. Zinc
oxide nanoparticles synthesized from Phoenix dactylifera waste
shows competent inhibition towards bacteria in wastewater
treatment (Rambabu et al., 2021). In many cases, nanosized metal
oxides (NMOs) show great potential to remove most of the pol-
lutants to trace amount even the contaminants are present in low
concentrations, which is a vital benefit of adsorption over other
technologies. Furthermore, NMOs show higher adsorption rate
constant generally 10e200 times greater than activated carbon,
this is because of their particularly reactive surface which allow
adsorption to happen faster towards targeted contaminants (L.
Wang et al., 2020). Metal oxides have plenty of surface-active
sites which allow them to interact with various contaminants.
Fig. 4 illustrates the adsorption process starting with bulk
diffusion then film diffusion followed by pore diffusion and finally
the adsorption of adsorbate and active sites of adsorbent via
chemical or/and physical reaction. The most common adsorption
mechanism of metal oxides, particularly those composites and
amorphous structure is pore filling. Mesopores normally become
saturated at the initial phase whereas micropores consume longer
period to be filled due to stronger diffusion resistance. Owing to the
structural factors and adsorption of water molecules, metal oxide
surfaces are often coated with plenty hydroxyl groups. Hence,
electrostatic attraction is present between metal oxides and heavy
metal ions. Ion exchange process may also occur between the metal
7
Journal of Cleaner Production 296 (2021) 126589
oxides and the heavy metal cations such as cation exchange be-
tween MgO and Pb2þ or Cd2þ shown in the equation below.
MgO þ Pb2þ / PbO þ Mg2þ
MgO þ Cd2þ / CdO þ Mg2þ
Reduction or oxidation has been suggested to occur between
metal oxides and some specific multivalent heavy metal ions, for
example Cr3þ, Cr6þ, As3þ, As5þ, Sb3þ, Sb5þ, etc. as they have low
affinity towards adsorption sites. Metal oxides that are involved in
redox reactions include Fe3O4, MnO2, TiO2 and CeO2. The process
begins with the formation of an outer-sphere complex via elec-
trostatic attraction. Next, oxidation or reduction occurs between
adsorbate and adsorbent. Another mechanism involves the
adsorption of heavy metals using metal oxides is surface precipi-
tation. The adsorption of Cd2þ and Pb2þ ions on to MgO nano-
particles was outlined by causing surface precipitation (Xiong et al.,
2015), due to some of the unmodified metal oxides such as MgO
and ZnO which are readily hydrated by water molecules to produce
metal hydroxides that generate OH ions that can interact with
heavy metal cations to form insoluble matter. The precipitate will
form surface precipitation on the adsorbent surface.
Desorption and regenerability are vital to avoid secondary
pollution problems as well as to reuse the expensive adsorbents
which could save expenses. Metal oxides are generally recycled
through chemical regeneration strategy by leaching in chemical
solvents to desorb various organic and inorganic contaminants. The
chemical solvents used for desorption of metal oxides are acids,
chelating agents and organic solvents. In general, heavy metal
cations can be desorbed with acidic solution via electrostatic
repulsion for pH dependent adsorption process. For example, Cd2þ
cations are desorbed from Fe3O4 in HCl solution. For desorption
process that is sensitive to ionic strength, ion exchange process
takes place by using NaCl and KCl salt. Heavy metal cations such as
Pb2þ, Cu2þ, Cd2þ, etc., are desorbed from the adsorbent as metal
cations repel with protonated adsorbent surface by using HCl so-
lution. Arsenic and chromium ions mostly present in water as
oxyacid anions, thus, alkaline solutions can be utilized as effective
effluents. Alternatively, metal cations chelating agents (thiourea,
EDTA, etc.) are used for desorbing heavy metals from metal oxides
without corrosion. This was evident by (Hussain and Ahmed, 2019)
in which mercury was completely desorbed from Fe3O4@SiO2
adsorbent in a mixed solution of thiourea and HCl due to the strong
affinity between mercury and thiourea.
Nanosized metal oxides can strongly adsorb heavy metal ions
from aqueous media resulting from their large surface area and
large adsorption capacity. Besides, smaller particles exhibit faster
adsorption kinetics as they have lower diffusion resistance. How-
ever, nanoparticles tend to aggregate easily. Surface modification of
metal oxides is believed to be able to improvise the adsorption
performance, for instance the introduction of amine groups to
Fe3O4 increases the adsorption capacity of Cr6þ. In Table 2, the usual
metal oxides adsorbents available today and their features are
discussed.
3.2. Graphene
Graphene is a two-dimensional (2D), single atomic thick layer of
sp2 hybridized carbon atoms arranged in hexagonal lattice through
sigma and pi bonds. It is accessible in numerous forms including
original graphene, graphene oxide (GO) and reduced GO (rGO)
(Low et al, 2016, 2020). Fig. 5 shows the chemical structures of
graphene, GO and rGO. Graphene exhibits unique mechanical,
chemical and physical properties that makes it applicable in heavy
W.S. Chai, J.Y. Cheun, P.S. Kumar et al. Journal of Cleaner Production 296 (2021) 126589

Fig. 4. General Process of Adsorption. Reprinted from (L. Wang et al., 2020) with permission from the Royal Society of Chemistry.

Table 2
Various nanometal oxides and their respective features.

Metal Oxides Features

Nanosized Iron Oxides - Widely applied owing to its abundancy and low toxicity
- Ease and facileness in synthesis
- Environmentally friendly to be discharged straight to the contaminated sites with minute likelihood of secondary contamination
- Hematite commonly used in adsorption of heavy metals (Cu2þ) and organic pollutants
- Nanosized magnetite appears to show strong affinity to various trace metal ions for example Cu2þ, Pb2þ, Cd2þ, etc. Adsorption capacity of
nano-maghemite for Cr(VI) to be 19.2 mg/g which is higher than commercial activated carbon (15.47 mg/g) (Babel and Kurniawan, 2004)
Nanosized Aluminum - Large pore volume, large specific surface area and high porosity
Oxides - qmax for As (V) at 121 mg/g. It has been revealed that the electron deficiency on the positively charged surface of nanosized Al2O3 can be used
for adsorption of arsenic oxyanions (Jadhav et al., 2015)
- Excellent arsenic removal ability even at low initial concentrations (Li et al., 2011)
Nanosized Manganese - High redox potential, possible layer structures and negatively charged surface in neutral pH
Oxides - An efficient adsorbent for toxic metal ions (include Pb2þ, Cu2þ, Ni2þ, Cd2þ, etc.) by not only adsorbing on its surface but also intercalate the
interlayers of MnO2 (Islam et al., 2018)
Nanosized Titanium - Capable of removing various heavy metals (Cd, Pb, Ni, Cu, Zn)
Oxides - By comparing the distribution coefficient (Kd), nanosized TiO2 performed better than activated carbon and other metal oxide nanoparticles
which was experimented with a solution of pH ¼ 8 and San Antonio tap water (Engates and Shipley, 2011)
 10-50 nm diameter nano-TiO2 at pH ¼ 9.0 displayed adsorptive capacity to Cd and Zn as 7.9 mg/g and 15.3 mg/g respectively (Liang et al.,
2004)

metal adsorption from water. Its outstanding properties include
large specific surface area, great chemical stability, enhanced
functional sites and active sites found on its surface. The largely
delocalized p electrons and adjustable chemical properties of gra-
phene make it a more promising adsorbent in wastewater treat-
ment than activated carbon. GO is the oxidized form of graphene
derived from the chemical oxidation of graphite. It has high nega-
tive charge density and hydrophilicity contributed by the oxygen
functional groups present (Ramesha et al., 2011).
The functionalized graphene prepared from electrolysis method
was investigated as an adsorbent to remove Pb2þ and Cd2þ from
wastewater (Deng et al., 2010). The maximum uptake capacities
were 406.6 mg/g for Pb2þ at pH 5.1 and 73.42 mg/g for Cd2þ at pH
6.2 achieved within an equilibrium time of 40 min. Lignosulfonate-
modified graphene hydrogel was considered as an adsorbent owing
to its high porosity, high specific surface area and activity of
adsorption sites on the surface (G. Liao et al., 2018). The authors
reported the Pb2þ maximum adsorption capacity as 1308 mg/g and
that the sorbent is environmentally friendly as well as can be
recycled and reused making it suitable to engage for water treat-
ment on a widescale.
The adsorption of Pb2þ from wastewater was tested using few
layers of GO from graphite through the modified Hummer’s
method (Zhao et al., 2011). The oxygen-containing functional
groups found on the adsorbent improves the adsorption capacity to
1850 mg/g. L-cystine functionalized exfoliated GO (EGO) possess

8
W.S. Chai, J.Y. Cheun, P.S. Kumar et al.
Fig. 5. (a) Chemical structure of graphene, GO and rGO and (b) route of graphite to rGO. Reprinted from (Abu-Nada et al., 2020) with permission from MDPI.
nitrogen, sulfur and oxygen-containing groups allowing it to bind
to Hg2þ ions effectively reaching a greater adsorption
capacity(79.36 mg/g) than the unmodified graphite (12.4 mg/g)
(Patel et al., 2017). Magnetic GO was synthesized using ultrasonic
treatment of graphite oxide and Fe3O4 (Zhang et al., 2014). The
adsorption mechanism of some trace metal ions including Cd2þ,
Pb2þ and Cu2þ is via exchange of metal cations and negatively
charged adsorption sites on adsorbent surface.
The production of graphene is relatively cheaper since there are
various methods to synthesize it chemically (chemical vapor
deposition, chemical exfoliation, mechanical cleavage, etc.). Among
the graphene-based materials, graphene oxide with pore size of
about 0.9 nm emerges to be highly cost effective. GO is non-
conductive making it highly durable. The prospect of producing
large amount of graphene nanomaterials have been performed via
an economical approach in water purification (Sreeprasad et al.,
2013). A significant key aspect for commercial application of the
adsorption process is the regeneration and reusability of adsorbent.
Several studies showed the desorption step to regenerate graphene
adsorbents using either strong acid (HCl) or strong alkali (NaOH).
After 5 cycles of regeneration, magnetite/non-oxidative graphene
composites (M-nOG) retained more than 92% of the first cycle
arsenic ions, As(V), implying that it is an economic and efficient
adsorbent (Abu-Nada et al., 2020).
In short, the modification of graphene adsorbent is important to
prevent aggregation between layers which in turn allow accessi-
bility of adsorption site for contaminants. In this case, the added
magnetic particles and oxygen groups play an important role to
improve removal ability of graphene. The novel technique to syn-
thesize graphene on large scale is the Hummer’s method, however,
the drawbacks are the production of large quantity of acidic wastes
leading to costly treatment and disposal issues. Therefore, explo-
ration of other methodologies is urgent to tackle this matter.
Nevertheless, graphene materials still exhibit a great potential in
heavy metal adsorption (Theron et al., 2008).
3.3. Graphitic carbon nitride (g-C3N4)
Graphitic carbon nitride (g-C3N4) is a 2D nano-adsorbent which
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Journal of Cleaner Production 296 (2021) 126589
has been identified as the most stable allotrope of carbon nitride. It
has stacked layer structures and exhibits outstanding chemical and
thermal stability under ambient circumstances.
g-C3N4 comprises of distinctly ordered tri-s-triazine (C6N7) units
arranged via hydrophobic effect and p-p interaction. The nega-
tively charged functionalities are due to lone pair electrons on ni-
trogen. Those negatively charged functional groups are relatively
capable for reaction with metal cations. Moreover, the surface
amino groups of g-C3N4 are also involved actively in adsorption for
heavy metals (Chen et al., 2017). g-C3N4 is anticipated to be a cost-
effective adsorbent for pollutants. Nonetheless, graphitic carbon
nitride is barely reported till now for the realistic application for the
adsorption of heavy metals. Fig. 6 illustrates the molecular struc-
ture of g-C3N4.
The adsorption performance of guanidine hydrochloride syn-
thesized g-C3N4 was evaluated to remove Cd(II), Pb(II) and Cr(VI)
from water (Xiao et al., 2019). Higher uptake capacities are achieved
at higher temperatures which reveal the endothermic nature of g-
C3N4. The adsorption of Pb(II) and Cd(II) mostly takes place through
electrostatic interaction on the tri-s-triazine units whereas anionic
Cr(VI) are mostly adsorbed on g-C3N4 outer surface. 80% of g-C3N4
adsorption ability is still retained after 10 successive cycles of
regeneration.
The salt method was employed to synthesize g-C3N4 in order to
remove Cu2þ, Cd2þ, Pb2þand Ni2þ (Shen et al., 2015). The adsorption
capacities of these ions exceeded than those of activated carbon.
The inner sphere surface complexation mechanism explained the
interaction between the carbon- and nitrogen-containing func-
tional groups of adsorbents and heavy metals. Both graphene ox-
ides and g-C3N4 displayed high sorption capacity and outstanding
regeneration ability that lower the cost of the materials to be
applied effectively in the withdrawal of heavy metals from waste-
water (Akbari Dehkharghani, 2019).
g-C3N4 nanosheets prepared from thermal and ultrasonic
method was reported to exhibit excellent adsorption performance
and capacity of metal ions (Q. Liao et al., 2018). The average pore
size for g-C3N4 is 9.762 nm with a specific surface area of 418.28 m2/
g. The adsorption process was strongly influenced by pH and
temperature but independent of ionic strength.
W.S. Chai, J.Y. Cheun, P.S. Kumar et al.
Fig. 6. Molecular structure of g-C3N4 and its adsorbed form. Reproduced from (Shen et al., 2015) with permission from Elsevier.
Nevertheless, few of the precursors used during synthesis of g-
C3N4 are harmful and the widescale production remain as chal-
lenge. Even though there are some limitations encountered during
the synthesis and application of g-C3N4 in the environmental
pollution management, it still emerges as a promising adsorbent in
the removal of heavy metal cations and anions from wastewater. To
attain the practical application in wastewater treatment, devel-
oping proper reactors should be addressed in the future.
3.4. MXenes
MXenes are ceramics that are one of the largest families of 2D
materials comprise of transition metal carbide/nitride materials.
They feature high chemical stability, excellent electrical conduc-
tivity and environment friendly feature. 2D nanomaterial has large
lateral size and nanometer thickness resulting in large specific
surface area that is desirable for wastewater treatment application.
In addition, the abundance of highly active functional groups (hy-
droxyl, oxygen, fluorine, etc.) on MXene surface and hydrophilic
property offer it as an effective adsorbent for many molecular and
ionic species.
The structure of MXene can be described as nþ1 layers of
transition metal elements M covering n layers of X (X is C or N
element). 3 different formulae of MXenes that have been confirmed
are M2X, M3X2 and M4X3 (Zhang et al., 2018). The term “MAX”
depicts the chemical composition of the parent compound
whereby “A” stands for IIIA or IVA element such as Pb, Al, Si, Sn, As,
etc. They were synthesized by exfoliating the “A” laminar compo-
nent in the mixture of hydrofluoric acid, hydrochloric acid,
ammonium bifluoride and lithium fluoride shown in Fig. 7.
Ti3C2(OH/ONa)xF2x MXene material was produced in 2014
through chemical exfoliation amid by alkalization intercalation.
The MXene showed high Pb2þ adsorption with a capacity of
140 mg/g in which Pb2þ ions form strong bonds with oxygen atoms
within hydroxyl potential traps. The intercalation of cations tend to
improve the distance between MXene’s interlayers by which the
interaction between MXene layers and surface functional groups
are enhanced (Peng et al., 2014). Ti3C2Tc MXene shows 250 mg/g
Cr(VI) adsorption capacity under room temperature and pH ¼ 5
(Ying et al., 2015). The adsorbent reduces Cr(VI) anion to Cr(III) and
subsequently adsorbs the reduced Cr(III) simultaneously. Cr(VI) is
first adsorbed on the protonated hydroxyl groups at low pH on
MXene via electrostatic attraction. After adsorption, the anions are
reduced to Cr(III) ions producing TiO2 simultaneously. Cr(III) then
react with the TieO bond on the MXene forming TieOeCr(III)
structure. Ti3C2Tc MXene is also an effective adsorbent for Cu2þ
ions with 78.45 mg/g maximum experimental removal capacity
and has 2.7 times higher reusability than of commercial activated
10
Journal of Cleaner Production 296 (2021) 126589
carbon (Shahzad et al., 2017). The adsorption mechanism is
revealed to be ion exchange between Cu2þ and negatively charged
terminal groups on Ti3C2Tc MXene surface followed by a further
oxidation-reduction reaction.
The formation of BaeF and BaeO bonds was reported to have
resulted from adsorption process using MXene as adsorbent to
withdraw barium ions (Fard et al., 2017). The maximum adsorption
capacity is higher than ACs and carbon nanotubes. Hydrothermal
synthesized Fe2O3/Ti3C2Tc nanocomposite demonstrated great
Hg(II) removal performance of 1128.41 mg/g (Zhang et al., 2016).
Both pristine and functionalized MXenes exhibit effective
removal of heavy metal ions by adsorption attributed to their
abundancy of functional groups, adjustable surface chemistry and
the capacity to respond to local chemical and electrical perturba-
tions. However, the number of experimentally synthesized MXenes
is limited which has become an important research direction.
Nevertheless, considering their effectiveness and highly selective
adsorption capacity, it is expected that MXene adsorbents cost is
rather competitive compare to other high-performance adsorbent
materials to address the issue related with wastewater treatment.
3.5. Metal organic framework (MOF)
Metal organic frameworks (MOFs) are crystalline porous solids
comprise of three-dimensional (3D) network of positively charged
metal ions (metal nodes) held in place by multidentate organic
molecules via coordination bonds forming a cage-like structure
(Wang et al., 2019). Owing to this hollow and highly ordered
structure, MOFs have a remarkably large internal surface area
ranging from 1000 to 10000 m2/g exceeding activated carbons.
Most of the MOFs exhibit superb chemical stability under harsh
conditions (Wang et al., 2016). In addition, they can be synthesized
via low cost and simple methods on a large scale. The adjustable
MOF’s physiochemical features together with the highly ordered
porous structure make MOF a promising next generation adsorbent
material that is effective in heavy metal ions elimination (Kobielska
et al., 2018). Recent studies shown that bimetallic MOFs exhibit
strong iodine adsorption (Wu et al., 2020).
CrO2
4 was the first anion to be studied using heterometallic 3D
framework 1-ClO4 as adsorbent. 85% of the ions were removed via
ion exchange mechanism (Shi et al., 2012). Higher adsorption ca-
pacity of 207 mg/g achieved using a new 3D MOF (Li et al., 2017).
However, its single crystallinity was demolished in the recycling
processes where the chromate ions were desorbed.
The two layered MOFs (FIR-53) showed rapid adsorption ki-
netics with 74 mg/g CrO2 4 . The reused FIR-53 was able to retain its
initial adsorption capacity after five cycles. Highest adsorption ca-
pacity (1709.2 mg/g) was achieved by Fe-gallic acid MOF. The
W.S. Chai, J.Y. Cheun, P.S. Kumar et al.
Fig. 7. (a) The 3 different structures of MXenes: M2X, M3X3 and M4X3, (b) Images of Ta4AlC3, Ti3AlC2 and Ti2AlC (from left to right), (c) Synthesis of MXenes from MAX. Reproduced
from (Zhang et al., 2018) with permission from the Royal Society of Chemistry.
adsorption mechanism happens through coordination at hydroxyl
groups on Zr nodes or by substituting the benzenedicarboxylic
(BDC) ligands in the framework (Wang et al., 2015). Fig. 8 displays
UiO-66 molecular structure and its adsorption mechanism.
MOF-based material, ZIF-8 showed effective removal of arsenic
ions As(V) with adsorption capacity of 90.92 mg/g as a result of its
developed porosity easing mass transfer within pore structure
(Sikora et al., 2020). The presence of amine and hydroxyl groups
allow the withdrawal of As(V) and As(III) to occur simultaneously
(Jian et al., 2015). MOF-based composites (140.27 mg/g), exhibited
1.6 times higher qmax than pristine ZIF-8 nanoparticles (90.8 mg/g)
for As(III). The information about their regeneration are still limited
(Jian et al., 2016). MOFs have also been widely investigated for Hg2þ
adsorption due to sulfur strong binding ability(Luo et al., 2015).
The high selectivity towards Pb2þ of MOF is attributed by the
fitting of metal ion radius to the pore size of MIL-101 (Li et al., 2018).
Among the MOFs, ZIF-8 displayed the highest Cu2þ adsorption ca-
pacity (800 mg/g) which is superior to AC and GO based adsorbent
(18 mg/g for GO/Fe3O4). Ion exchange process occurred at low
initial metal concentration while Cu2þ coordinate with nitrogen
groups at high Cu2þ concentrations (C. Wang et al., 2020).
In general, MOFs and MOF-based materials exhibited superb
adsorption capacity, fast adsorption kinetics and high selectivity.
However, less detailed information is reported regarding their
reusability, stabilization of MOFs over wider pH range and more
economical alternatives than expensive ligands.
Table 3 demonstrates the adsorption capacities of the novel
materials as well as the activated carbon whereas Table 4 analyzes
the cost effectiveness of each material as adsorbent.
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Journal of Cleaner Production 296 (2021) 126589
4. Conclusions, challenges and future outlook
4.1. Conclusions
A compilation of the conventional and potential novel materials
as adsorbent is presented in this current review. Among the novel
materials used, we are mainly focusing on promising nano-
adsorbents including graphene, graphitic carbon nitride (g-C3N4),
MXenes and metal organic framework (MOF). In this regard, the
modified novel materials having unique physical properties,
chemical stabilities and reusability make them possible to become
a promising alternative to conventional adsorbents for more effi-
cient removal of heavy metal ions from wastewater effluent.
From Table 3, it is evident that commercial activated carbon has
high adsorption capacity for Ni2þ due to the abundance of oxygen
functional groups for ion adsorption (Kuroki et al., 2019) whereas
Pb2þ adsorption peaks when using graphene oxide as adsorbent.
The chemisorption of graphene oxide adsorbent involves superfi-
cial complexation of heavy metal ions with oxygen containing
groups and due to hydrophilic properties of GO. GO shows a high
adsorption affinity for Pb2þ by forming a metal complex as they
share an electron pair. Moreover, Gibbs free energy suggest the
adsorption of Pb2þ on GO adsorbent to be thermodynamically
feasible and spontaneous (Guerrero-Fajardo et al., 2020). Graphitic
carbon nitride (g-C3N4) displays a remarkable adsorption capacity
for Zn2þ as there are 2 possible interactions: one is heavy metal ions
can form complexes with C^N another is that sp2 CeN can be
regarded as Lewis base whereas heavy metals are considered as
Lewis acid leading to complexation (Guo et al., 2018).
MXene, particularly Ti3C2Tc achieves highest adsorption
W.S. Chai, J.Y. Cheun, P.S. Kumar et al. Journal of Cleaner Production 296 (2021) 126589

Fig. 8. (a) Molecular structure (b) 3D unit cell of UiO-66 framework; (c) Coordination of hydroxyl groups on Zr nodes, (d) Substitution of BDC ligands. Reproduced from (Wang et al.,
2015) with permission from Springer Nature.

Table 3
The adsorption capacities of activated carbon and novel materials.

Adsorbent materials Adsorption capacity(mg/g) Reusability Selectivity Challenges Source

Pb2þ Cu2þ Hg2þ Ni2þ Zn2þ Cd2þ Cr3þ

Activated carbon 294.1 58.0 126 400 344.8 178.5 60.9 Limited Low - Relatively high operating cost (Karnib et al., 2014; Zabihi et al.,
- Low selectivity 2010)
- Regeneration issues
- May cause secondary pollution
Graphene oxide 673 50.7 290 122 246 69.9 5.5 Reusable High - Expensive production (Bao et al., 2013; Burakov et al., 2018;
(GO) - Lack of studies on the recycling Galunin et al., 2018)
Graphitic carbon 189.4 N/A N/A 168 281.3 168.9 N/A Limited High - Finding of cheaper raw materials Guo et al. (2018)
nitride (g-C3N4) - Development of suitable reactor
MXene 36.6 78.5 1128 N/A N/A N/A N/A Limited High - Improper reusability Abu-Nada et al. (2020)
*Based on Ti3C2Tc - Demand for rational synthesis
- Inferior durability
Metal Organic 232 N/A 769 207 287 225 117 N/A N/A - Poor stability in water (Efome et al., 2018; Saleem et al.,
Framework (MOF) - Lack of information about reusability and 2016; Xiao et al., 2020)
*Based on UiO-66 regeneration
and 808 - Competitive adsorption of coexisting
heavy metals is not provided

12
W.S. Chai, J.Y. Cheun, P.S. Kumar et al.
Table 4
The cost effectiveness of commercial activated carbon and novel materials.
Adsorbent materials Price (USD $/kg)
Activated Carbon 4.23 (Alibaba, n.d.)
Graphene oxide (GO) 10 (Alibaba, n.d.)
Graphitic carbon nitride (g-C3N4) 5 (CIMM Group, n.d.)
MXene *Based on Ti3C2Tc 7100 (Alibaba, n.d.)
Metal Organic Framework (MOF) 3349 (Sigma Aldrich, 2020)
*Based on UiO-66 and 808
capacity for Hg2þ among Mg2þ, Ca2þ, Naþ and Kþ as mercury ion
has high selectivity towards oxygenated and hydroxyl moieties on
MXene sheets (Ibrahim et al., 2020). In addition, MXene sphere,
acting like a cage, to entrap mercury ions exhibits excellent Hg2þ
adsorption ability attribute to several mechanisms including elec-
trostatic interaction of the porous surface, forming complexes and
ion exchange process. Similarly, UiO-66-NHC(S)NHMe MOF adsor-
bent shows outstanding adsorption affinity for Hg2þ. This might be
explained by the high conversion rate (73%) in the amine to methyl
thiourea post-synthetic modification step used to prepare this MOF,
combined with the low steric demands of the methyl thiourea
group (Saleem et al., 2016). Taking environmental considerations
into account, novel materials which may reduce secondary pollu-
tion are to be considered to be more environmental-friendly.
4.2. Future outlook & challenges
There are certain limitations in terms of cost effectiveness and
efficiency of the above-mentioned materials. Minimization of cost
and environmental impacts from waste products will be a vital
aspect to be studied for widescale usage of novel materials in
wastewater treatment. Although most of the novel materials show
excellent adsorption performance through theoretical simulations,
the number of experimentally synthesized novel materials, for
example MXenes are still limited. Therefore, the synthesis of large
scale of MXenes becomes a significant research direction. More-
over, there are often large inconsistencies between the experi-
mental and theoretical uptake capacities leading to non-ideal
surface conditions which appear to be a challenge for the widescale
usage of novel materials in wastewater treatment. In some studies,
the removal efficiency of adsorbents for heavy metal increased after
modification. Hence, it is believed that there are still many func-
tionalized or modified novel materials that are worth investigating
for future perspectives. The comparative studies between the fea-
tures and properties of readily available and newly derived adsor-
bent materials should be conducted.
Another challenge faced would be the further modifications
required to improve the adsorption of novel materials for example,
UiO-66 that is introduced with N-oxide functional group tends to
have improved adsorption performance (Shokouhfar et al., 2018).
However, the application of MOFs in practical industry still requires
further research as they are relatively expensive and cannot be
produced quickly in large scale (Chen et al., 2020). More research
on introducing simple synthesis methods to minimize cost and the
investigation of structural adaptations by ligands in ligands should
be carried out. The cost-effective recycling procedures, sustainable
disposable choices and durability are also inevitable for the appli-
cation of widescale usage of novel materials in practical. Clarifica-
tion of the exact mechanism contributing to the decline in
performance after recycled use is of great importance.
Activated carbon emerges to be the most mature materials used
as adsorbents in the wastewater treatment process. In 1930s,
granular activated carbon adsorption tank was first set up in
Journal of Cleaner Production 296 (2021) 126589
Cost effectiveness (mg/$) ¼ adsorption capacity (mg/kg)/price ($/kg)
Pb2þ Cu2þ Hg2þ Ni2þ Zn2þ Cd2þ Cr3þ
69,530 13,712 29,787 94,563 81,518 42,199 14,397
67,300 5070 29,000 1224 24,600 8720 550
37,880 N/A N/A 33,640 56,256 33,780 N/A
5.15 11.05 159 N/A N/A N/A N/A
69.27 N/A 229.62 62 86 67 34.94
Philadelphia, United States. After that, activated carbon technology
was continued to be utilized in developed western countries in
potable water treatment. The activated carbon, particularly bio-
logical activated carbon is mainly used in advanced water treat-
ment in countries such as Holland, Japan, America, Switzerland, etc
and industrial wastewater treatment (Jin et al., 2013). Adsorption
and separation nanotechnology were closest to commercial
maturity at present including the use of graphene and nanosized
metal oxides. There are only very few studies that conducted
adsorption experiments under real conditions which make metal
oxides less practical as adsorbents. Moreover, these nanomaterials
are facing challenges such as leakage into contact with water,
strenuous separation, easy to aggregate and potential to cause
adverse consequences on human health and ecosystem which
obstruct them to be successfully applied on large scale water
treatment facilities.
The current trends are to develop adsorbents from waste such as
biochar. At present, biochar adsorption is gradually applied in small
scale wastewater treatment field as it shows a good adsorption
effect on the removal of heavy metals. However, the quantitative
analysis of biochar heavy metal adsorption mechanism and
disposal of biochar after adsorption to avoid environmental risks
still require further studies prior to upscaling. In addition, graphene
oxide (GO) exhibits an outstanding adsorption capacity towards
Pb2þ than Ni2þ and Cd2þ as Pb2þ ion is more likely to bind -C-OH
and eC]O due to the lower energy barrier and relatively stable
structure of GO resulting in binding energy of 1.3 and 3.9 kcal/mol
for Pb2þ and Ni2þ respectively. Not only that, the bond length of
GO-Pb2þ is shorter suggesting a higher binding ability of GO to-
wards Pb2þ. Therefore, the ion characteristics of adsorbed metals
need to be determined in detailed prior to realistic application in
water treatment. The mutual affinity properties of both adsorbent
and adsorbate influence the adsorption capacity of GO towards
heavy metals.
Graphitic carbon nitride (g-C3N4) has yet to achieve the realistic
application in wastewater treatment due to the expensive raw
materials for g-C3N4. Nevertheless, low cost g-C3N4 are believed to
be a promising adsorbent which will certainly find applications in
wastewater treatment. The use of MOFs is limited in practical water
treatment applications due to their water stability, thus, there is
more attention being focused now on the synthesis of water stable
MOFs to be used as remediation of contaminants in aqueous me-
dium. Furthermore, the properties and features of MOFs especially
their high adsorption capacity outstand the traditional adsorbent in
terms of performance. An example of MOF that shows potential
application in large scale wastewater treatment is 3D UiO-66, even
so not many large-scale applications of heavy metals removal is
reported. Therefore, there is a need for viable transformation from
the MOFs production of laboratory scale to commercial level. Some
of the challenges that are faced during scale up of MOFs production
include decrease in reaction kinetics due to the scale-up of pro-
duction vessels, demand for large volume of chemicals, investiga-
tion for continuous process instead of batch production to reduce
13
W.S. Chai, J.Y. Cheun, P.S. Kumar et al.
labor costs and downtimes as well as the examination on the
feasibility of synthesis process for commercial application
(Ramanayaka et al., 2019).
From Table 4, it seems that activated carbon shows higher cost
effectiveness for most of the heavy metals and the application of
activated carbon to adsorb simultaneous heavy metals has been
applied in practical. Nevertheless, novel materials still exhibit po-
tential as prospective adsorbents owing to their unique physical
and chemical features achieving a higher adsorption capacity. More
research studies shall be carried out for the widescale usage of
novel materials in wastewater treatment. They are believed to be
the alternative for the conventional adsorbents. Furthermore,
covalently linked porous polymers, as a novel kind of porous ma-
terial, should also be further studied as they show huge potentials
in water treatment, with silsequioxanes-based hybrid porous
polymers exhibiting high adsorption capacity for metal ions (Du
and Liu, 2020; Soldatov and Liu, 2019).
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by the Fundamental Research Grant
Scheme, Malaysia [FRGS/1/2019/STG05/UNIM/02/2] and MyPAIR-
PHC-Hibiscus Grant [MyPAIR/1/2020/STG05/UNIM//1].
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