Environmental Pollution 252 (2019) 352e365

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Recent advances for dyes removal using novel adsorbents: A review☆

Yanbo Zhou a, b, *, Jian Lu a, Yi Zhou a, c, Yongdi Liu a, c
a
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and
Technology, No. 130 Meilong Road, Shanghai, 200237, China
b
Key Laboratory of Coal Gasification and Energy Chemical Engineering of Ministry of Education, East China University of Science and Technology, No. 130
Meilong Road, Shanghai, 200237, China
c
Shanghai Institute of Pollution Control and Ecological Security, No. 1515 Zhongshan Second North Road, Shanghai, 200092, China

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

Article history: Dyeing wastewaters are toxic and carcinogenic to both aquatic life and human beings. Adsorption
Received 30 January 2019 technology, as a facile and effective method, has been extensively used for removing dyes from aqueous
Received in revised form solutions for decades. Numerous researchers have attempted to seek or design alternative materials for
13 May 2019
dye adsorption. However, using various novel adsorbents to remove dyes has not been extensively
Accepted 14 May 2019
Available online 16 May 2019
reviewed before. In this review, the key advancement on the preparation and modification of novel
adsorbents and their adsorption capacities for dyes removal under various conditions have been high-
lighted and discussed. Specific adsorption mechanisms and functionalization methods, particularly for
Keywords:
Dye
increasing adsorption capacities are discussed for each adsorbent. This review article mainly includes (1)
Adsorption the categorization, side effects and removal technologies of dyes; (2) the characteristics, advantages and
Adsorbent limitations of each sort of adsorbents; (3) the functionalization and modification methods and con-
Dyeing wastewater trolling mechanisms; and (4) discussion on the problems and future perspectives about adsorption
Treatment technology from adsorbents aspects and practical application aspects.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Water resource, as the most precious resource for human sur-
vival, is facing unprecedented challenges. Water pollution has
become one of the most serious global issues. However, this situ-
ation is still spreading; a large amount of wastewater is produced
and poured into the water environment every year. Among
different types of wastewaters, dyeing wastewater deserves sig-
nificant attention. Since the last century, with the continuous
development of printing and dyeing industrialization process, large
amounts of dyes are released into the environment. Dyes are basic
daily chemical compounds and being widely used in many fields to
color their products such as textile, leather, paper, rubber, printing,
plastics, etc (Rafatullah et al., 2010; Sivakumar and Rao, 2003;
Sokolowska-Gajda et al., 1996). It is approximated that over 10,000
different dyes and pigments are used industrially and
☆
This paper has been recommended for acceptance by Dr. Da Chen.
* Corresponding author. State Environmental Protection Key Laboratory of
Environmental Risk Assessment and Control on Chemical Process, East China Uni-
versity of Science and Technology, No. 130 Meilong Road, Shanghai, 200237, China.
E-mail address: zhouyanbo@ecust.edu.cn (Y. Zhou).
approximately 0.7 million tons of dyes are synthesized every year
worldwide (Ogugbue and Sawidis, 2011). About 200 l of water is
needed to produce 1 kg of textile and about 1.6 million liter water is
consumed for an average sized textile mill per day (Petcu et al.,
2016). The large amount of dye pollutants in the wastewater
brings a huge risk to the environment. For instance, the dye can
bring adverse impact to both aquatic organisms and human beings
because dyes can reduce sunlight transmission (Crini and Badot,
2008; Dincer et al., 2007) and normally contain toxic substances,
such as heavy metals (like lead, chromium, etc.) and aromatics
(Ramanath, 2005). Dyes molecules in wastewater lead to mutage-
nicity, carcinogenicity, and dysfunction of human beings’ kidney,
liver, brain, reproductive system and central nervous system.
In order to treat dyeing wastewater, a wide range of physical,
chemical and biological techniques are introduced to remove dyes
during the past years(Gupta and Suhas, 2009). However, dyes are
highly resistant to degradation because of their complex chemical
structures. Normally, they are stable under various conditions such
as aerobic digestion, light, heat and oxidizing agents(Crini, 2006).
Therefore, adsorption technology has been extensively used to treat
dyeing wastewater as it is cost-effective and highly efficient(Qa-
deer, 2007). In practical operation, activated carbon is one of the

https://doi.org/10.1016/j.envpol.2019.05.072
0269-7491/© 2019 Elsevier Ltd. All rights reserved.
 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365
most widely applied conventional adsorbent thanks to its excellent
adsorption performance(Gupta and Suhas, 2009). However, its
application has been limited by the high price and the complicated
regeneration processes (Deniz and Kepekci, 2016; Silva et al., 2016).
Besides, conventional activated carbon is ineffective and has low
selectivity towards dispersed vat dyes (Crini, 2006). In order to
reduce the cost and enhance the adsorption efficient, many novel
alternatives have been developed to replace conventional activated
carbon.
During the past decades, many novel adsorbents such as clays/
zeolites and their composites, biosorbents, agricultural solid
wastes, industrial by-products and their composites and miscella-
neous materials have been prepared and modified for dyes removal
from simulated wastewater by many researchers (Demirbas, 2009;
Rafatullah et al., 2010; Vakili et al., 2014; Yagub et al., 2014). In
recent years, a large amount of newly modified adsorbents, com-
posite adsorbents or multi-functional materials have been prepared
and used. However, there are few review articles concerned on the
dye adsorption by numerous adsorbents from a macro respective.
Therefore, a review focusing on the different kinds of novel ad-
sorbents and their adsorption performance of dyes is still needed.
So, in this review, categorization of dyes and their side effects, dyes
removal technologies and adsorption isotherm models are listed.
We summarize and reorganize the research results, and aim to
provide a summary of up-to-date progress of various alternative
materials used for dyes removal. The characteristics, advantages
and limitations of most adsorbents are provided. Moreover, this
review also presents the effectiveness of various adsorbents under
different environmental parameters. Though numerous materials
possess excellent adsorption ability, few of them have been pro-
gressed into industrial scale application. A comprehensive discus-
sion of the limitations and challenges of adsorption technology
used today from the adsorbents aspects and practical application
aspects is provided. In the end, prospective developments and their
associated challenges of novel adsorbents that must be overcome
are proposed and discussed.
2. Categorization of dyes and their side effects
Dyes could be classified according to chemical structure, color,
application and particle charge in solution. Normally, we can divide
dyes in to natural dyes and synthetic dyes. Natural dyes usually
extracted from animals and minerals. However, as the improve-
ment of industrial activities, natural dyes couldn't meet the needs
of people's demand. Therefore, synthetic dyes are developed and
have replaced natural dyes gradually particularly in fabrics and
textile industries. Normally, synthetic dyes including ionic dyes and
non-ionic dyes. Ionic dyes are further classified in to cationic dyes
and anionic dyes (acid, reactive and direct dyes), and non-ionic
dyes into vat and disperse dyes. In addition to above categoriza-
tion, dyes classified by chemical structure are also very common,
including azo, Anthraquinone, Indigoid, Nitroso, Nitro, Triaryl-
methane dyes(Ngulube et al., 2017; Yagub et al., 2014).
As we all know color is indispensable to modern life. While dyes
give us vivid colors, they are also discharged into the water body as
industrial waste and seriously threaten the safe of life. Most of the
dyes are the complex of organic compounds like aromatics, amines
and trace heavy metals like Cd, Cu, Pb, Zn and Co(Ramanath, 2005).
The component of dyes makes them are toxic. Normally, the pres-
ence of dyes in water body may affect the photosynthesis of aquatic
life due to it may block the transmission of sunlight. What is serious
is that most of dyes are carcinogenic, mutagenic, or teratogenic to
both animals and human beings. As far as we known, dyes mole-
cules in wastewater may lead to dysfunction of human beings’
multiple organs and reproductive system, central nervous system.
353
The cationic, acidic, direct and disperse dyes all may make benign
and malignant tumors and the direct dye may lead to bladder
cancer. The reactive dyes may cause dermatitis, allergic conjuncti-
vitis, rhinitis, occupational asthma(Tan et al., 2015). Additionally,
most of the dyes are chemically stable and resistant to degradation
and thus they remain in the effluents for a long time(Yagub et al.,
2014).
Due to their negative effects and long-time stay in water,
highlighting efficient treat methods and technologies of dye
wastewater is necessary.
3. Dyes removal technologies
Ever since the side effects of dyes were discovered by scientists,
almost all the physical, chemical and biological methods are
applied in dyeing wastewater treatment including coagulation,
flocculation, membrane separations, adsorption, ion-exchange,
oxidation, advanced oxidation process, electrochemical process,
photocatalysis, biodegradation and so on. Their main advantages
and disadvantages are shown in Table 1.
The strengths of biological treatment are common, simple and
ecological compared to physical and chemical methods. Normally,
numerous microorganisms are used for the decolouration of syn-
thetic dyes under aerobic or anaerobic. However, biological treat-
ment requires strict external environmental conditions such as
nutrition, temperature and pH. Additionally, the bioreactor needs a
certain amount of land, the process is generally more complex and
needs to consume a certain amount of time(Ngulube et al., 2017).
Even so, the efficiency of biological treatment is often not satisfying
due to most synthetic dyes usually have stable and complex
chemical structures and resist to biodegradation. The production
and disposition of excess sludge is also a question.
The advantage of chemical methods is that they are usually
effective. However, the production and deposition of the sludge
may add the cost of the process. Normally, the chemical technol-
ogies will consume large amounts of chemical reagents and elec-
trical energy(Jamal et al., 2015). Additionally, the chemical residue
may lead to secondary pollution. Recently, advanced oxidation
process is gained emerging concerns due to its powerful oxidizing
ability. Although these methods are efficient, they are costly and
more importantly the oxide intermediates may be toxic(Wang
et al., 2019b; Zhou et al., 2017a). All of above reasons makes the
methods are commercially unattractive.
The conventional physical methods including membrane-
separation and adsorption technologies. Membrane-separation is
an efficient technology including microfiltration, ultrafiltration,
nanofiltration and reverse osmosis(Shamraiz et al., 2016). The
application of membrane technology in dyeing wastewater is not
common because the service life of membrane is short and it is easy
to be polluted (Shamraiz et al., 2016). From the literature, adsorp-
tion is the most commonly used method to treat dyeing wastewater
due to its simple operation process, low cost and ideal effect(Mu
and Wang, 2016). Although there are still many issues need to be
settled, the adsorption process won't form any hazardous sub-
stances(Crini, 2006).
4. Adsorption isotherm models
Adsorption isothermal models are important tools for studying
adsorption behaviors and mechanisms, and they can reflect the
interaction between adsorbents and adsorbates(Huang et al., 2018).
Langmuir and Freundlich model are the most classical models of
adsorption, which are given by the following equations (Model 1
and Model 3).
Langmuir isotherm is an ideal monolayer adsorbed model, that
354 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365

Table 1
The advantages and disadvantages of different dyes removal technologies.

Technology Advantages Disadvantages

Membrane separation
Adsorption
Ion change
Coagulation/Flocculation
Advanced oxidation process
Electrochemical process
Photochemical process
Biodegradation
High efficiency, reuse salts Short lifetime, economically unfeasible
High efficiency, simple operation Ineffective to certain dyes, the regeneration is costly,
process, low cost, won't form hazardous substances the disposal of adsorbent residue is also an issue, loss of adsorbents
No loss of sorbents Economically unattractive, ineffective to certain dyes
Simple, economically attractive High sludge production and disposal issues
High efficiency, rapid Sludge production, economically unfeasible, high chemical
reagents and electricity consumption, formation of by-products
High efficiency, rapid High electricity consumption and economically unfeasible
No sludge production, rapid The formation of by-products and power consumption
Economically attractive and simple Require strict external environmental conditions, slow
process, occupy a certain area of land

assumed the molecules adsorbed on adsorbent surface can form a
monolayer, and each molecule adsorbed on the surface has the
same adsorption activation energy(Zhou et al., 2011; Zhou et al.,
2015b). The model has the following equation:
KL qm Ce
qe ¼
1 þ KL Ce
qe d equilibrium absorption capacity (mg/g)
qm dmaximum adsorption capacity(mg/g)
Ce d equilibrium concentration of adsorbate (mg/L)
KL d adsorption equilibrium constant (L/mg)
The hypothesis of Langmuir model ignores the interaction be-
tween adsorbed molecules, and each adsorption pore or active site
can only accept one molecule. Recently, another monolayer
adsorption model (Hill model, named Model 2) has been devel-
oped. Unlike Langmuir model, Hill model assumes that each
adsorption site can accept n molecules (Azha et al., 2019; Sellaoui
et al., 2017a). The model can be described by following form:
nNm
Q¼ C1=2 n
1þð C Þ
Using above adsorption models to describe the adsorption
performance and mechanisms of dyes onto different novel adsor-
bents has been widely studied. Wang et al. (2019a) studied the
adsorption performance of Methylene Blue by cellulose/montmo-
rillonite (MTM) hydrogels using Langmuir and Freundlich model.
According to the R2 value, the Freundlich model is more suitable
(Model1)
than Langmuir model which suggests that the adsorption is a
multilayer process. Chen et al. (2018) used Langmuir and Freund-
lich model to study the adsorption performance of beta-
cyclodextrin coated silica to bromophenol blue (BPB) and crystal
violet (CV). It was found that Freundlich model has a better fit to
BPB, but for CV the Langmuir model is more suitable. Sellaoui et al.
(Azha et al., 2019) used Model 2 to study the adsorption mechanism
between iron-modified composite adsorbent coating and Acid
Red1(AR1). The parameter n represents the number of dye mo-
lecular linked to each adsorption site. The parameter n varies from
1.13 to 3.88 as temperature increased which indicates the adsorp-
tion is a multi-molecular process and the AR1 molecules can
interact with an inclined position. Other adsorption isotherms
models such as two or three parameter isotherms, multilayer
physisorption isotherms and saturation multilayer model can refer
to Ref(Foo and Hameed, 2010), (Sellaoui et al., 2017b)and (Azha
et al., 2018).
(Model2)
5. Novel adsorbents

5.1. Clays/zeolites and their composites

Q dequilibrium absorption capacity (mg/g)
ndnumber of molecules connected at each adsorption site
C1=2 dadsorbate concentration at halfesaturation(mg/g)
Nm dnumber of occupied adsorption sites
Freundlich isotherm is a classic model for multilayer adsorption.
It is assumed that adsorbates are nonlinearly adsorbed by particles
in soil or water(Zhou et al., 2015c; Zhou et al., 2014). Generally,
Freundlich model is applied to describe the adsorption perfor-
mance for highly interactive species or organic component on those
materials with large specific surface area and developed pore
structure such as activated carbon(Foo and Hameed, 2010). The
model is given by:
qe ¼ KF ðCe Þ1 = n (Model3)
qe d equilibrium absorption capacity (mg/g)
Ce d equilibrium concentration of adsorbate (mg/L)
ndadsorption constant, represents the adsorption strength
KF dAdsorption capacity constant of adsorbent related to
adsorption capacity (mmol/g)
The clays and zeolites are hydrous aluminosilicates with layered
structure(Babel and Kurniawan, 2003). The adsorption mechanism
of clays and zeolites is that they contain exchangeable ions on the
surface, which can absorb cations and/or anions through ion ex-
change and/or adsorption(Rafatullah et al., 2010). Furthermore,
they are cheap, abundant in nature, low toxicity as well as have
high surface area. There are four main groups of clays: kaolinite,
illite, montmorilloniteesmectite and chlorite.
In recent years, excellent adsorption competence of clays and
their composites to remove dyes have been proved by many re-
searchers (Table 2). However, their practical application has been
limited by several shortcomings. Firstly, clays have a natural
negative charge which limited the adsorption capacities of acid
dye(Errais et al., 2012). Secondly, the low organic carbon content
and hydrophilic surfaces of clays have restricted the efficiency of
adsorbing nonionic organic dyes in water. Furthermore, it's difficult
to recycle and reuse waste clay particles from aqueous solution due
to their high dispersion(Xu et al., 2012). Hence, several modification
methods such as acid and alkali treatment, pillar support, ion ex-
change, grafting and cross-linking are developed to enhance its
adsorption performance (Ngulube et al., 2017). After modification,
the specific surface area of clays may be improved so that it can
 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365 355

Table 2
Recent reported adsorption capacities of clays, zeolites and their composites.

Adsorbents Dyes Adsorption capacity Sources

Magnesium phyllosilicates Yellow GR 1343 mg g1 Moscofian et al. (2012)

Magnesium phyllosilicates Blue RN 1286 mg g1 Moscofian et al. (2012)
Mesoporous zeolite Crystal violet 1217 mg g1 ~o et al. (2018)
Bria
Natural clay (Turkey) Acid Red 88 1133 mg g1 Akar and Uysal (2010)
Montmorillonite/graphene oxide composite Crystal violet 746 mg g1 Puri and Sumana (2018)
Montmorillonite/graphene oxide composite Methylene blue 641 mg g1 Yang et al. (2019)
Kaolin-based mesoporous silica Methylene blue 653 mg g1 Li et al. (2015)
Mesoporous zeolite Methylene blue 548 mg g1 ~o et al. (2018)
Bria
Activated organo-bentonite/sodium Alginate composite Methylene blue 414 mg g1 Belhouchat et al. (2017)
Magnesium phyllosilicates Red RB 344 mg g1 Moscofian et al. (2012)
Cellulose/clay composite hydrogel Methylene blue 277 mg g1 Wang et al. (2019a)
Porous Clay Heterostructures with Silica-zirconia (SiZrePCH) Acid Blue 25 266 mg g1 Aguiar et al. (2017)
Mesoporous zeolite Basic fuchsin 238 mg g1 ~o et al. (2018)
Bria
Zeolite/chitosan composite Methylene blue 199 mg g1 Khanday et al. (2017)
Smectite rich natural clays Basic yellow 28 77 mg g1 Chaari et al. (2019)

adsorb nonionic dyes or after ion-exchanging and grafting posi-
tively charged groups, the modified clays maybe could absorb acid
dyes. Li et al. proposed a novel method to change kaolin into
mesoporous silica through facile strategies which efficiently
improved the specific surface area and the adsorption capac-
ity(652.9 mg g1 for Methylene Blue)(Li et al., 2015). Inorganic/
inorganic composites magnetic MnFe2O4/bentonite was synthe-
sized by Saeedeh Hashemian et al.(Hashemian, 2010) to overcome
the high dispersion of bentonite in aqueous solution. Chen et al.
(Wang et al., 2019a) developed a novel and green organic/inorganic
composite. They used wood cellulose to modify montmorillonite to
overcome the high dispersion of montmorillonite. Furthermore, the
adsorption capacity to Methylene Blue of this novel material ob-
tained great improvement compared to montmorillonite alone.
In general, zeolites are naturally occurring highly porous crys-
talline aluminosilicates. The adsorption capacity of zeolites for dyes
is mainly due to their ion exchange capacity, which is the same as
clay(Crini, 2006). Apart from high ion-exchange capacity, zeolites
materials also have relatively high specific surface areas and cheap
prices. Therefore, zeolites have been widely applied as adsorbents
for dyeing wastewater treatment(Wang and Peng, 2010). There are
many types of natural zeolites such as clinoptilolite, mordenite,
chabazite, analcime and laumontite.
Though natural zeolites have many essential physical and
chemical properties, they have some limitations. The adsorption
performance of anions and organics by these materials is not
satisfying. Therefore, modification methods are necessary such as
acid/base treatment and surfactant impregnation are commonly
adopted to alter the hydrophilic/hydrophobic nature to improve the
adsorption capacity. Although the adsorption capacity for dyes of
zeolites may not be as good as that of clays, they are abundant in
nature and relatively low price which can compensate for the
associated drawbacks. And zeolites exhibit different ion adsorption
selectivity and competitive adsorption in multi-component
systems.
5.2. Biosorbents
5.2.1. Chitosan and its composites
Chitosan is mainly extracted from shellfish, shrimps, crabs and
insects with low cost, high reaction activity, good biocompatibility
and non-toxicity. Chitosan exhibits the great potential for adsorp-
tion of dyes due to their high contents of amino and hydroxy
functional groups. The adsorption mechanism of chitosan to dyes is
mainly through the protonation of the amino group on the surface
and then it can absorb cationic dyes through electrostatic interac-
tion. Using chitosan composites to adsorb dyes has aroused great
interest recently, which has been reviewed by Crini et al.(Crini and
Badot, 2008) and Rafatullah et al.(Mohammadtaghi Vakili, 2014).
However, the practical application of chitosan has been limited
by the solubility in acidic solution, low mechanical strength and
deformation after drying(Crini, 2006). Therefore, several modifi-
cation methods such as cross-linking, impregnation and grafting
are induced to overcome those limitations. In general, cross-linking
agents include glutaraldehyde (GLA), epichlorohydrin (ECH),
ethylene glycol diglycidyl ether (EDGE) and tripolyphosphate (TPP),
etc. As for surface impregnation, surfactants such as sodium
dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB)
or Triton X-100 (TX-100) are widely used(Mohammadtaghi Vakili,
2014). Some functional groups such as amino group, carboxyl
group, sulfur group and alkyl group can also be grafted to chitosan.
The controlling mechanism after modification is mainly through
increasing the specific surface area or adding new functional
groups. As for as we know, the maximum adsorption amount could
reach 2352.99 mg g-1 for acid orange 7 using Dodecyl Trimethyl
Ammonium Chloride(DTAC)/chitosan organic/organic composite
(Zhang et al., 2014). To overcome the solubility of chitosan in acidic
solution, Lipatova et al. recently developed a novel, sample and
non-toxicity organic/organic material which immobilized the chi-
tosan nanoparticles on fibrous carrier. This adsorbent is not only
stable in acidic media, recyclable but also showed satisfying
adsorption capacity to number of anionic dyes(Lipatova et al.,
2018a; Lipatova et al., 2018b).
Seung H. Woo et al.(Chatterjee et al., 2011) generated a kind of
chitosan hydrogel beads modified by alkali (CB) and sodium
dodecyl sulphate (CSB) gelation to absorb Reactive Black 5 (RB5)
from simulated wastewater. The maximum adsorption amount of
PEI-CB and PEI-CSB are 709.27 mg g1 and 413.23 mg g1,
respectively.
In order to promote the separation and recovery of chitosan, a
magnetically separable organic/inorganic composite of chitosan
and graphene oxide (MCGO) was developed for the removal of MB
from wastewater(Fan et al., 2012a). The adsorption was sponta-
neous and the maximum adsorption amount of grafted magnetic
chitosan for MB was 95.16 mg g1. In addition, the MCGO has good
mechanical strength and are easy to recycle. The material also has
good reusability.
The synthesis process of chitosan aerogels (CAs) and the
removal mechanism of various dyes by chitosan-based adsorbents
is shown in Fig. 1. More information could be obtained in Table 3.
5.2.2. Cyclodextrin and its composites
Cyclodextrins (CDs) are natural, green and nontoxic material
extracted from starch(Brusseau, 1997). CDs contain 6, 7 or 8 D-
356 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365
Fig. 1. (a1) The synthesis process of chitosan aerogels (CAs) and (a2) adsorption
mechanism of methyl orange (MO) onto CAs (Zhang et al., 2017). (b) Adsorption of dyes
using magnetic chitosan-Fe(III) hydrogel (Shen et al., 2011). (For interpretation of the
references to color in this figure legend, the reader is referred to the Web version of
this article.)
glucopyranose-based polymers linked by a-D-(1 / 4) bonds and
have an internal hydrophobic cavity and an external hydrophilic
surface(Crini, 2014). The hydrophobic cavity could trap numerous
molecules with matched size and polarity(Zhou et al., 2019). The
interaction mechanisms between cyclodextrin and guest molecule
mainly include van der Waals force, hydrogen bond, coulomb force
and hydrophilic/hydrophobic force. The cyclodextrin can be
modified through the hydroxyl groups on CD surface(Zhou et al.,
2014). It not only can cross-link surface hydroxyl groups onto
polymers by cross-linking agents but also can be loaded on the
surfaces of other materials (Li et al., 2018a,b). Therefore, many
cyclodextrin derivatives, cyclodextrin-based composites and CD
polymers are prepared to remove dyes by adsorption.
Crini et al.(Crini and Peindy, 2006) prepared cyclodextrin-based
materials with carboxylic groups to adsorb C.I. Basic Blue 9 (BB 9)
from simulated wastewater. It was calculated that the monolayer
adsorption amount could reach up to 56.5 mg g1. And the
adsorption competence increased with the increasing dosage of the
adsorbent.
More interestingly, CDs also exhibit a certain photocatalytic
activity. Whether CDs monomers or CDs immobilized on sawdust,
they have certain photocatalytic activity and can enhance the
photo-degradation of organic compounds such as BPA(Zhou et al.,
2015a; Zhou et al., 2017b). Many dyes are photosensitive or hav-
ing photosensitization activity. From this point of view, this char-
acteristic of cyclodextrin can be further studied in the future.
Cyclodextrin-based composites have also been widely studied.
Chen et al.(Wang et al., 2015) prepared a magnetic b-cyclodextrin-
graphene oxide organic/inorganic nanocomposites (Fe3O4/b-CD/
GO) for Malachite Green removal from simulated wastewater. The
as prepared nanocomposites had excellent adsorption competence
which could reach 990.10 mg g1 at pH 7. Also, the nanomaterial
had satisfying regeneration performance. The removal rate almost
had no decrease after three times circulation.
Zhao et al. (2015a) reported an EDTA-cross-linked b-cyclodex-
trin (EDTA-b-CD) bifunctional organic/organic composite adsor-
bent for simultaneous adsorption of heavy metals and dyes, as
shown in Fig. 2(b). The adsorption capacity of EDTA-b-CD for
Methylene Blue, Safranin O, and Crystal Violet were 0.262, 0.169,
and 0.280 mmol g1, respectively. The cavities of CDs can trap dye
molecules and the EDTA groups act not only as cross-linkers but
also as chelating sites for metal ions. This material has potential
application in removing coexisted toxic pollutants.
Though cyclodextrin-based adsorbents have satisfying adsorp-
tion effect, their practical application in wastewater treatment are
limited by many reasons. Firstly, the cyclodextrin monomer can't be
used directly in solution due to its solubility. Secondly,
cyclodextrin-based composites and cyclodextrin polymers are
usually synthesized through complicated processes which also add
the cost(Zhou et al., 2018).
In the next stage, we need to make progress in greener and more
economical synthetic methods, and consider the use of cyclodex-
trin to enhance photodegradation performance to achieve
adsorption and in situ regeneration. In this way, the feasibility of
the application of cyclodextrin adsorbents in dye wastewater
treatment will be accelerated(Zhou et al., 2017b).
The adsorption of dyes by some cyclodextrin-based materials is
shown in Fig. 2. Table 3 shows some of the adsorption capacity
reported in the literature.
5.2.3. Biomass
Using biomass to remove dyes by adsorption have been widely
studied. The controlling mechanisms of biomass and modified
biomass mainly include ion exchange, surface adsorption,
complexation, chelation, etc (Crini, 2006; Sadhasivam et al., 2007;
Wang and Hu, 2007). Biosorption is a useful method for removing
trace amount of pollutants from wastewater. Algae, fungi and
bacteria are examples of biomass used for dye adsorption. Microbial
biomass is produced in fermentation processes and a lot of by-
products are generated during these processes, which can be
used in biosorption of pollutants(Crini, 2006). Table S1 shows some
of the adsorption capacities reported in the recent literature. Pinto
et al. investigated the adsorption capacity of Spirulina platensis for
the first time, a cheap and easily available biomass, to adsorb food
dyes and the biosorption capacity was very satisfying
(1653.0 mg g1 for acid blue 9)(Dotto et al., 2012).
However, some shortcomings have limited the practical appli-
cation of biomass. Normally, biomass has low adsorption rate
because the adsorption process is strongly influenced by the pH.
Also, some other environmental factors like salts or ions can also
influence the adsorption performance.
 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365
Table 3
Recent reported adsorption capacities of chitosan, cyclodextrin and their composites.
Adsorbent Dye
Magnetic b-cyclodextrinechitosan nanoparticles Methylene blue
Chitosan/surfactant composite Acid orange 7
HP-CD/PEG400 modified Fe3O4 nanoparticles Congo red
Chitosan/surfactant composite Orange G
Magnetic b-cyclodextrin-graphene oxide Malachite green
b-cyclodextrin-based fibers Methylene blue
Grafted chitosan beads Reactive Black 5
Chitosan sponge Rose Bengal
Electrospun composite chitosan aerogel Indigo carmine
Chitosan/b-cyclodextrin composite Methyl orange
Chitosan/graphene oxide composite hydrogel Methylene blue
Polyurethane/chitosan foam Food Red 17
Sericin/b-cyclodextrin/PVA composite Methylene blue
Halloysite-Cyclodextrin Nanosponges Methylene blue
Chitosan/polyvinyl alcohol/zeolite Methyl orange
Chitosan/hyper-crosslinked polymer composite Indigo carmine
5.3. Agricultural solid wastes
The usage of waste materials as adsorbents, such as forestry and
agricultural waste materials, is attractive for water purification.
Agricultural solid wastes are abundant and cheap. The feasibility of
using sawdust and bark has been widely studied. Agricultural and
forestry wastes are generally rich in cellulose, hemicellulose and
lignin. Its surface contains a large number of active groups such as
hydroxyl, carbonyl, amino, carboxyl, methyl and so on. The
adsorption mechanism of agricultural solid wastes and their com-
posites is that these functional groups can adsorb organic com-
pounds and heavy metals through hydrogen bonding,
complexation, ion exchange, etc.
5.3.1. Sawdust and its composites
Sawdust is an abundant by-product of the wood industry with
very low price. Normally sawdust contains numerous functional
groups which may be favorable for absorbing dye molecules by
different ways. Usually sawdust can be modified by acid and alkali
to increase the content of pectin and cellulose on its surface.
Furthermore, the rich hydroxyl, carboxyl groups on its surface
provides the possibility for further modification. The adsorption
competence of sawdust has been demonstrated by many re-
searchers. The reported adsorption capacities for sawdust, bark and
other agricultural solid wastes are shown in Table 3.
Garg et al.(Garg, 2004) used formaldehyde and sulphuric acid
pretreated Indian Rosewood (Dalbergia sissoo) sawdust to absorb
Methylene Blue in dyeing effluent. It was found that adsorption
process was very quick which smaller than 30 min. Malik(Malik,
2004) investigated the potential of mahogany sawdust as adsor-
bent for direct dye (Direct Blue 2B, Direct Green B) removal. The
equilibrium adsorption capacity was found to be larger than
300 mg g1 from Langmuir equation. Sawdust can be modified as a
base material and combined with other materials. Nazir et al. (Khan
and Nazir, 2015) used bamboo sawdust as a base to synthesis an
organic/inorganic composite Fe2O3/chitosan/bamboo sawdust to
solve the problem of solubility of chitosan. And this material good
adsorption capacity toward model dye Bromothymol Blue
(217.39 mg g1).
5.3.2. Bark
Bark is the by-product of the timber industry with abundant
polyphenol. Bark, like sawdust, is an interesting adsorbent for dyes
removal thanks to its low cost and high availability. The modifica-
tion methods of bark are the same as sawdust.
Rais Ahmad(Ahmad, 2009) investigated the potential of
357
Adsorption capacity Sources
2.78 g g1 Fan et al. (2012b)
2353 mg g1 Zhang et al. (2014)
1895 mg g1 Yu et al. (2014b)
1452 mg g1 Zhang et al. (2014)
990 mg g1 Wang et al. (2015)
826 mg g1 Zhao et al. (2015c)
709 mg g1 Chatterjee et al. (2011)
602 mg g1 Wang et al. (2017b)
565 mg g1 Salzano de Luna et al. (2019)
392 mg g1 Jiang et al. (2018)
350 mg g1 Chen et al. (2013)
267 mg g1 da Rosa Schio et al. (2019)
261 mg g1 Zhao et al. (2015b)
226 mg g1 Massaro et al. (2017)
153 mg g1 Habiba et al. (2018)
118 mg g1 Salzano de Luna et al. (2017)
coniferous pinus bark powder (CPBP) as adsorbent for Crystal Violet
removal from wastewater. According to the author, the amount of
dye uptake increased from 6.3 to 8.9 mg g1 in concentration range
of 10e50 mg L1. Also, the adsorption is endothermic indicated by
thermodynamic parameters. Rodrigues et al. studied the potential
application of a certain bark from a medicinal plant to absorb
cationic dyes (Methylene Blue(MB), Crystal Violet(CV) and Rhoda-
mine B(Rh.B)) from simulated water(Demarchi et al., 2012). The
maximum adsorption amount were calculated to be 211.5, 89.5 and
69.4 mg g1 for Rh.B, MB and CV at room temperature, respectively.
Also, the adsorption process was spontaneous and endothermic.
Other agricultural solid materials from abundance and cheap
resources such as cotton fiber(Xiong et al., 2014), sawdust(Zhang
et al., 2015), coffee residues(Kyzas et al., 2012), rice husk(Sharma
et al., 2010) and orange peel(Khaled et al., 2009) have also been
successfully employed for dyes adsorption (Table 4).
5.4. Industrial by-products and their composites
Industrial wastes such as metal hydroxide sludge, fly ash and red
mud may be potential substitutes to replace the more costly con-
ventional adsorbents due to their low price and abundance.
5.4.1. Metal hydroxide sludge
Metal hydroxide sludge is one of the industrial by-products
which contains insoluble metal hydroxides and other salts and
can be used to adsorb the dyes. The main controlling mechanism of
metal hydroxide sludge is ion-exchange. Boaventura et al. (Santos
et al., 2008) used metal hydroxides from an industrial waste
sludge as adsorbent to remove Remazol Brilliant Blue dye in
simulated wastewater. The maximum adsorption amount was
91.0 mg g1 obtained from Langmuir model. Also, the adsorption
process is mainly through ion-exchange. Attallah et al. (2013)
investigated the potential use of metal hydroxides sludge (MHS)
for the adsorption of Congo Red (CR) and Naphthol Green B (NGB)
dyes from simulated water. The maximum capacities of CR and NGB
were 40 and 10 mg g1 at pH 6, respectively. Kaygusuz et al.
investigated a material including Al(III) hydroxides to absorb
reactive dye Reactive Blue 222 (RB 222) (Gunes and Kaygusuz,
2015). According to the authors, the maximum adsorption
amount was 18.38 mg g1. The use of metal hydroxide sludge as
adsorbents is not only effective and economic but also contributing
to the effective and useful disposal of industrial sludge waste.
5.4.2. Fly ash
Fly ash is the by-product of coal-based thermal power plants.
358 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365
Fig. 2. (a) Synthesis process of b-cyclodextrin functionalized Fe3O4 magnetic nano-
particles (Zhou et al., 2016); (b) Synthesis process and structure of EDTA-cross-linked
b-cyclodextrin (Zhao et al., 2015a); (c) Synthesis process and structure of a novel
amphoteric b-cyclodextrin-based adsorbent CD/CA-PDMAEMA (Zhou et al., 2018).
Owing to its low cost and abundance in nature, a large amount of
researchers have tested the potential of fly ash to absorb dyes.
However, fly ash itself is hazardous because it may contain heavy
metals(Janos et al., 2003). The adsorption mechanism of fly ash and
its composites includes the molecular attraction, which mainly
depends on the pore size characteristics and specific area of fly ash.
And a large amount of aluminum salt and iron salt in fly ash are
formed into A1(H2O)3þ and Fe(H2O)3þ after being mixed with
water to produce flocculation. Ghosh et al.(Ghosh and
Bandyopadhyay, 2016) used a type of fly ash collected from a
local industry to adsorb Crystal Violet (CV) in aqueous solution. The
pHpzc and BET surface area were reported as 3.30 and 8.57 m2 g1,
respectively. Also, 98.33% removal efficiency could be reached in
90 min at the optimum condition. However, the adsorption capac-
ity is not so ideal and it's hard to recycle the adsorbents after usage.
Therefore, physical and chemical methods are necessary to modify
the fly ash. Mao et al.(Zhang et al., 2016) synthesized a fly ash/
CoFe2O4(CFA/CFO) magnetic inorganic/inorganic composite to
absorb Malachite Green from simulated wastewater. The maximum
adsorption capacity of CFA/CFO could reach 89.3 mg g1 at the
optimal pH and temperature. The authors conclude that the large
surface area of CFA promotes the adsorption capacity.
5.4.3. Red mud
Waste red mud is a bauxite processing residue discarded in
Alumina production. The main adsorption mechanism of red mud
to dyes is ion-exchange. Gupta et al. (2004) used red mud to remove
Rhodamine B (RB), Fast Green (FG) and Methylene Blue (MB) from
simulated wastewater. It was reported that the removal efficiency
of RB, FG and MB on this adsorbent were 92.5, 94.0, and 75.0%,
respectively. Fu et al.(Coruh et al., 2011) studied the potential of
microwave activated red mud for Disperse Blue 2BLN dye removal
from simulated wastewater. It was reported that the maximum
adsorption amount of Disperse Blue 2BLN was 45 mg g1 obtained
from Langmuir equation. Furthermore, the removal of color,
chemical oxygen demand (COD) and total organic carbon (TOC)
could reach 99%, 64% and 50% under the optimal condition,
respectively. More adsorption capacity information about red mud
can be got from Table S2.
5.5. Miscellaneous adsorbents
From the past decades, some emerging and promising adsor-
bents such as nanomaterials and Metal organic frameworks (MOFs)
are widely studied for dyes adsorption due to their porous struc-
ture, high surface area and adjustable functional groups. In this
part, we mainly introduce the recent studies on nanomaterials and
MOFs. Fig. 3 shows the dyes adsorption by nanomaterials and
MOFs.
5.5.1. Nanomaterials and their composites
Nanotechnology has been applied in almost all scientific and
technological fields during the past years(Santhosh et al., 2016). In
fact, a large amount of nanomaterials have been synthesized and
applied in the pollutants removal from wastewater including
carbonaceous nanomaterials (carbon nanotubes, graphene, etc.),
metallic nanomaterials (nano-TiO2, nano-ZnO, etc.), bio-
nanomaterials (nanochitosan, etc.). Here, we mainly introduce the
carbon nanotubes (CNTs) by reason of their large surface area, pore
volume and proper functionalities.
Basically, CNTs are tube-like in shape (Santhosh et al., 2016).
There are two types of CNTS: single walled carbon nanotubes
(SWCNTs) and multiwalled carbon nanotubes (MWCNTs). The us-
age of CNTs for dyes containing wastewater treatment began in
2004. With their high active site, relatively large surface area and
controlled pore structure, CNTs exhibits better sorption perfor-
mance compared to the conventional adsorbents. Using MWCNTs
to adsorb Methyl Orange (MO) from simulated wastewater was
studied by Yao et al. (2011). The adsorption capacity for MO could
range from 35.4 to 64.7 mg g1. The adsorption of MO onto
MWCNTs was a physisorption, endothermic and spontaneous
process predicted by thermodynamic analysis.
 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365 359

Table 4
Recent reported adsorption capacities of agricultural solid wastes.

Adsorbent Dye Adsorption capacity Sources

Rice husk ash Methylene blue 1456 mg g1 Sharma et al. (2010)
Pretreated rice husk Methylene blue 1348 mg g1 Sharma et al. (2010)
Sugarcane bagasse soot Methylene Blue 331 mg g1 Giusto et al. (2017)
Araucaria angustifolia bark Gentian violet 305 mg g1 Georgin et al. (2018)
Untreated coffee residues Basic Blue 3G 295 mg g1 Kyzas et al. (2012)
Untreated coffee residues Remazol Blue RN 179 mg g1 Kyzas et al. (2012)
Cotton fiber Congo red 175 mg g1 Xiong et al. (2014)
Cotton fiber Methylene blue 113 mg g1 Xiong et al. (2014)
Pistachio shell Reactive Red 238 110 mg g1 Deniz and Kepekci (2016)
Orange peel Direct Navy Blue 106 108 mg g1 Khaled et al. (2009)
Pine needles Malachite Green 97 mg g1 Hammud et al. (2015)
Bamboo sawdust Congo red 91 mg g1 Li et al. (2018)
Modified pine sawdust Methylene Blue 84 mg g1 Zhang et al. (2015)
Coir Pith Crystal Violet 66 mg g1 Parab et al. (2009)
Coir Pith Rhodamine B 56 mg g1 Parab et al. (2009)

Fig. 3. (a)Adsorption mechanism of MO and MB onto Alkali-Activated Multiwalled Carbon Nanotubes (Ma et al., 2012); (b) Adsorption mechanism of different azo dyes on CNTs
(Ferreira et al., 2017). (c) Plausible mechanisms of adsorption MO on cationic PED-MIL-101-Cr (Haque et al., 2010).

Although pure CNTs have good adsorption capacity, it's a
complicated procedure to separate CNTs from dyeing wastewater
after adsorption. Therefore, they are composited or grafted with
other materials such as magnetic nanoparticle (Fe3O4, Fe3C), gra-
phene oxide, chitosan, cyclodextrin, etc(Kyzas and Matis, 2015).
Ao et al.(Wang et al., 2014) prepared a magnetic composite
adsorbent using graphene, multi-walled carbon nanotubes
(MWCNTs) and Fe3O4 nanoparticles. The maximum adsorption
capacity of this composite adsorbent for Methylene Blue was
65.79 mg g1. Furthermore, the as-prepared material has good
regeneration performance. Ma et al.(Cheng et al., 2014) synthesized
a magnetic composite adsorbents using b-Cyclodextrin and carbon
nanotube (M-RCNT-CD) for Methylene Blue removal. The
maximum adsorption amount was 196.5 mg g1. The adsorption
process was spontaneous and endothermic demonstrated by
thermodynamic study.
Though nanomaterials have gained great interest, it's worth to
highlight and pay more attention to the toxicity of nanomaterials.
The toxicity of CNTs to human dermal fibroblast cells has been
demonstrated and widely recognized(Patlolla et al., 2010). Further
studies are required to reduce the impact to human beings and
extend the application of those nanomaterials.
360 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365
5.5.2. MOFs
Metal organic frameworks (MOFs) are a new class of crystalline
organic-inorganic hybrid solids (Ayati et al., 2016) which have been
used to remove numerous hazardous pollutants from wastewater
due to their porous structure and high surface area(Khan et al.,
2013; Zhao et al., 2011). MOF-type materials are recognized as
promising materials. However, so far, there have been few reports
on the use of MOFs in absorbing dyes. The main types of MOFs
reported for dye adsorption are MOF-235, MIL-100 and MIL-
101(Samokhvalov, 2015).The major adsorption mechanism is the
electrostatic interaction between the ionic dyes and the charged
sites of MOFs, but it's difficult to identify the adsorption sites.
Haque was the first researcher to adsorb use azo dyes with MOFs
in 2010(Haque et al., 2010). They used MIL-53-Cr and MIL-101-Cr to
absorb Methyl Orange in simulated wastewater, as shown in Fig. 3
(b). They concluded that MOFs could be potential adsorbents for
dyes treatment because of their high porosity, easy to modify and
regenerate.
Sung Hwa Jhung et al.(Haque et al., 2011) studied the feasibility
of MOF-235 for the removal of harmful dyes (Methyl Orange (MO)
and Methylene Blue (MB)) from simulated wastewater by adsorp-
tion. The maximum adsorption capacities were 501 and 252 mg g1
for MO and MB, respectively, which were much higher than those
of activated carbons. Also, the adsorption process was spontaneous
and endothermic.
Unfortunately, the MOFs are expensive and the synthesis pro-
cess is complicated. Therefore, scientists are encouraged to seek
alternative methods to reduce the cost and synthesis time for
producing MOFs in large scales.
6. Factors affecting adsorption of dye
There are many factors may affect dye adsorption performance
including solution pH, temperature, initial dye concentration,
dosage of adsorbents, etc. The optimal operation conditions of each
adsorbent for certain dye adsorption are different. However, opti-
mizing such conditions will be greatly beneficial to the large scale
application and the understanding of adsorption mechanism.
6.1. PH
The solution pH is one of the most important factors, which
influence the adsorption behavior. The variation in pH can influ-
ence the surface charge and the degree of ionization of the adsor-
bents (Nandi et al., 2009). Generally, at low pH, the removal
efficiency for cationic dye will decrease, while the removal per-
centage for anionic dyes will increase. In contrast, at high pH, the
removal percentage for anionic dyes will decrease and increase for
cation dyes (Mohamad Amran Mohd Salleh, 2011).
The point of zero charge (pHpzc) is an essential parameter for
understanding the mechanism and the favourability of the
adsorption process. The pHpzc value indicates the type of active
sites and the adsorption ability of adsorbents. When pH˃pHpzc, it's
favorable for cationic dye adsorption due to the existence of func-
tional groups such as OH-, COO-. Whereas anionic dye adsorption is
favorable at pH < pHpzc because the surfaces of adsorbents become
positively charged(Savova et al., 2003).
Aliakbar Dehghan et al.(Dehghani et al., 2017) investigated the
effect of pH on adsorption of Reactive Red 120 (RR120) and Reactive
Red 196 (RR196) by chitosan/zeolite composite. They noticed that
the removal efficiency of RR120 and RR196 decreased respectively
as pH increased. Brice Takam et al. (2017) used natural cocoa shell
husk (CPHN) and gliding arc plasma treated cocoa shell husk
(CPHP) to remove cationic dye Azur II, and anionic dye Reactive Red
2 (RR2) by adsorption. This observation could be attributed to our
above theories. Table S3 shows the effect of solution pH on dye
adsorption by different adsorbents.
6.2. Initial concentration
The removal efficiency usually depends on the relationship be-
tween the initial dye concentration and the available sites on an
adsorbent surface. In general, if the adsorption sites on the adsor-
bent's surface is saturate, the removal percentage decreases with an
increase of the initial dye concentration; if the adsorption sites on
the adsorbent's surface is unsaturated, the removal percentage
increases with the increase of the initial dye concentration because
the high initial dye concentration provides high mass transfer
driving force for adsorption (Eren and Acar, 2006).
Yang et al.(Jiang et al., 2018) investigated the effect of initial dye
concentration on Methyl Orange (MO) adsorption by a complex of
chitosan/b-cyclodextrin polymer and they found that the amount of
MO adsorption increased with the increase of initial dye concen-
tration. Ahmed G. Hassabo et al.(El-Zawahry et al., 2016) investi-
gated the effect of initial dye concentration on the adsorption of
Reactive Black 5 by Eichhornia crassipes/chitosan composite (EC/Cs).
They noticed that the adsorption capacity increased with the in-
crease of initial dye concentration while the removal efficiency
decreased as the initial dye concentration increased.
Table S4 presents the results of various reported studies on the
effect of initial dye concentration on adsorption.
6.3. Temperature
Temperature is another significant factor which can reveal the
adsorption is exothermic or endothermic(Argun et al., 2008). If the
adsorption capacity increases with increasing temperature, the
adsorption is an endothermic process. This may be due to the in-
crease of the mobility of the dye molecules and the number of
active sites of adsorbents (Senthilkumaar et al., 2006). On the
contrary, the adsorption is an exothermic process. The possible
reason is that the adsorptive interactions between the dye mole-
cules and the active sites of the adsorbents may be decreased with
the increasing temperature(Ofomaja and Ho, 2007).
Table S5 shows the compilation of results of various studies on
the effect of temperature on the dye adsorption by various
adsorbents.
6.4. Amount of adsorbent
In general, the removal efficiency increases with increasing
amount of adsorbent because the quantity of sorption sites will
increase by increasing adsorbent dosage(Ofomaja, 2008). The
relationship between adsorption capacity and adsorbent dosage
gives information for removal of certain amount of dye with the
smallest amount of adsorbent, which evaluate the practical appli-
cation of a adsorbent from an economic perspective(Mohamad
Amran Mohd Salleh, 2011).
Table S6 shows some studies on the effect of adsorbent dosage
on the adsorption of dyes by various adsorbents.
7. Discussions and remarks
To be an excellent adsorbent, it must meet several prerequisites:
1) enough mechanical strength and can tolerate various conditions
of wastewater; 2) high adsorption amount and rapid adsorption
rate; 3) effective to a wide range of dyes or have selectivity for
certain pollutant; and 4) easy to be regenerated and reused(Crini,
2006). Here, we mainly discuss and remark the shortcomings and
challenges that adsorption technology is facing from adsorbents
 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365
aspects and practical aspects.
7.1. Adsorbents aspects
7.1.1. Adsorption ability
The novel adsorbents compiled above exhibit different adsorp-
tion performances. It's a tough work to evaluate and compare the
adsorption abilities of different adsorbents. Firstly, performance is
directly affected by the properties of the adsorbent and adsorbate;
Secondly, the effectiveness of treatment depends on experimental
conditions such as pH, ionic strength, temperature and adsorbent
concentration, etc.
The synthesis of novel adsorbents that have high adsorption
capacity, be efficient for a wide range of dyes or selective removal of
certain highly toxic dyes and capable of withstanding various
environmental parameters has always been the subject of the
development of adsorbents and is also difficult. In recent years,
many emerging composites and modified adsorbents have been
synthesized to improve the adsorption performance and practical
application, which has become a new trend of adsorbents
developing.
Table S7 shows the summary of the maximum adsorption
amounts of different raw, modified and composite adsorbents for
dyes removal. From the recent literature reviewed, some adsor-
bents have excellent adsorption capacities such as chitosan/sur-
factant composite (1452.07 mg g1 for Orange G, 2352.99 mg g1
for Acid Orange 7), magnetic b-cyclodextrinechitosan nano-
particles (2780 mg g1 for Methylene Blue), Spirulina platensis
nanoparticles (1619.4 mg g1 for Acid Blue 9), rice husk ash
(1455.6 mg g1 for Methylene Blue), kaolin-based mesoporous sil-
ica (652.9 mg g1 for Methylene Blue), etc. These adsorbents have
significant adsorption amounts and can be used efficiently to
remove dyes from aqueous solution. In particular, chitosan, cyclo-
dextrin and their composites have gained great attention due to
their special characteristics and outstanding adsorption capacities.
For example, Zhang et al. (2014) used different surfactants (Octa-
decyl Trimethyl Ammonium Chloride, Dioctadecyl Dimethyl
Ammonium Chloride, Benzyl Hexadecyl Dimethyl Ammonium
Chloride, Dodecyl Trimethyl Ammonium Chloride) to modify chi-
tosan to enhance the adsorption capacity for Orange G and Acid
Orange 7. The modified chitosan gained satisfactory adsorption
capacity. Magnetic b-cyclodextrinechitosan nanoparticles were
synthesized and used to remove Methylene blue(Fan et al., 2012b).
The optimal adsorption amount can reach 2780 mg g1 which is the
highest up to now. This material is a typical composite adsorbent
which enhances the adsorption capacity by combining the hydroxyl
and amino groups of chitosan with the cavity of cyclodextrin. The
magnetic particle Fe3O4 was induced in the material for easy sep-
aration and reuse. It is worthwhile to note that chitosan, cyclo-
dextrin and their composites can remove not only dyes but also
other organic and inorganic pollutants. Zhou et al.(Huang et al.,
2018) successfully synthesized a novel multi-functional adsorbent
based on b-cyclodextrin for simultaneous removal of bisphenol A,
methylene blue (MB) and Cu2þ. The adsorption amount was found
to be 0.3636 mmol g1 for BPA, 0.9229 and 0.9155 mmol g1 for MB
and Cu2þ, respectively. The carboxyl group of citric acid can chelate
copper ions and electrostatically adsorb MB, while the cavity of
cyclodextrin can form inclusion complex with BPA. Interestingly,
they clearly clarified that MB molecular won't enter the cavity of
cyclodextrin.
7.1.2. Stability
The stability of various adsorbents is of utmost importance.
Normally, the stability of adsorbents not only means the degree of
mechanical strength but also means the adsorbents can be stable
361
under different environment conditions such as strong acid, strong
alkali, high temperature and high pressure. However, the literature
provides very little information about this aspect in recent pub-
lications(Crini and Peindy, 2006; Wang et al., 2017a).
Zhang et al. (2011) synthesized modified zirconium phosphate
nanoparticles for lead removal. They used a particle crack device to
examine the mechanical strength of the nanocomposites and used
a ball-milling instrument to evaluate the wear resistance. Some
biosorbents are biodegradable such as chitosan and cyclodextrin.
This property may limit the long-term applications of those ma-
terials, in particular in dynamic systems. For example, chitosan has
low thermal stability and is soluble in acidic solution which are
important factors we need to consider. Generally, we enhance the
stability of adsorbents by grafting, immobilization, crosslinking, etc.
It is reported that silica coated by PEI and crosslinked with gluta-
raldehyde(GA) can improve the physicochemical stability during
adsorption/desorption cycles (Ghoul et al., 2003). Khoobi
et al.(Vahedi et al., 2017) used a mixture of methanol/acetic acid to
regenerate the adsorbent. The authors concluded that their adsor-
bent was chemically stable since the reduction of adsorption ca-
pacity was less than 10% after five cycles.
The stability of adsorbents is an essential parameter. However,
we have no uniform standards or methods to measure the degree of
stability. Hence, more efforts are necessary to investigate and
evaluate the stability of different adsorbents.
7.2. Practical application aspects
7.2.1. Economic aspects
The cost of adsorbents is an essential factor that must be
considered for practical application. However, the cost estimation is
seldom reported in the literature. Most of the studies reported in
literature are limited to laboratory evaluations of adsorption ca-
pacity, while the costs are neglected. It was observed that the price
of zeolites was about US＄0.03e0.12/kg(Babel and Kurniawan,
2003), the average price of Fuller's earth was US＄0.04/kg(Sha-
wabkeh and Tutunji, 2003), the price of commercial activated car-
bon was about US＄2.0e2.2/kg(Xu et al., 2015). The direct
comparison of the cost of adsorbents is difficult and meaningless
without considering the properties and adsorption capacities of
different adsorbents.
Those so-called low-cost adsorbents actually only indicate their
original prices. When low-cost adsorbents are used, the processes
of regeneration and treatment are not usually economic. In our
opinion, all factors are needed to be considered such as the local
availability, transportation, treatment process and both recycle and
lifetime issues(Gupta and Suhas, 2009; Mohan and Pittman, 2006).
Generally, in order to improve the sorption capacity and the
selectivity, some treatment such as drying, autoclaving, cross-
linking of organic or inorganic chemicals are proposed. In addition
to the cost of modification, transportation costs should also be
considered. The regeneration process may consume a large amount
of solvent or power like heat. Moreover, the treatment of exhausted
adsorbents is another tough and important issue and has not been
considered seriously. As far as we know, there are few papers focus
on the subsequent cost we mentioned above. If the original price of
a specific adsorbent is relatively higher but this adsorbent can be
reused multiple times and the regeneration process is very facile
and inexpensive, then this adsorbent is still an economical and
promising material. Therefore, measuring the cost of adsorbents
from the entire life cycle may be helpful to the actual applica-
tion(Devi and Saroha, 2017). Though chitosan, cyclodextrin and
their composites have outstanding performance, their practical
application are limited by high original price and complicated
synthesis process. However, no critical assessment measuring
362 Y. Zhou et al. / Environmental Pollution 252 (2019) 352e365
those materials from the entire life cycles.
7.2.2. Desorption
Desorption process is of great importance to regenerate and
reuse those used adsorbents. Moreover, desorption study is also
essential to keep the process price down, recover the adsorbed
compounds and minimize the amount of waste. Furthermore,
desorption studies may help to understand the adsorption mech-
anism. Generally, desorption methods include thermal treatment,
acid (H2SO4, HNO3, HCl, H3PO4) and base (NaOH) treatment.
Moreover, organic solvents like methanol and ethanol can also be
used to regenerate adsorbents since organic pollutants may be
soluble in these solvents.
The desorption process is typically performed by mixing the
dye-saturated substrate with appropriate solvent to extract the dye
and then separate the adsorbent by filtration. The dye-solvent
mixture is dried at high temperature to evaporate the solvent.
The desorbed dye is measured on a spectrophotometer(Robinson
et al., 2002). Patel et al.(Sahu and Patel, 2015) reported the use of
four kinds of solvents (water, H2SO4 (0.1 M), HCl (0.1 M) and acetic
acid (0.1 M)) for desorption of safranin-O dye from the modified red
mud adsorbent and the maximum desorption efficiency (91%) was
achieved using 0.1 M H2SO4 elute. In the meantime, the desorption
efficiency by distilled water was only 6% indicating that physical
adsorption is not the dominate factor. Khoobi et al.(Vahedi et al.,
2017) used different elutes including ethanol, methanol, acetic
acid and a mixture of methanol/acetic acid to desorb Rhodamine B
(RhB) and Methylene Blue (MB) from their b-cyclodextrin-anhy-
dride polymer nano-adsorbents. It was observed that the mixture
of methanol and acetic acid (9:1 v/v) had the maximum desorption
efficiency, 99.5 and 98.0% for RhB and MB dyes, respectively. The
author used the acidic solvents because the adsorption capacity for
dyes decreased at low pH values. Recently, using photocatalytic
technology to regenerate and reuse the adsorbents has gained great
attention. Ma et al.(Yu et al., 2014a) combined the adsorption and
photocatalytic technologies together to realize the in-situ self-
regeneration of saturated adsorbents. They successfully synthe-
sized a self-regeneration adsorbent through combining the TiO2
and crosslinked chitosan together. This adsorbent can be regener-
ated under UV irradiation without any decrease in the adsorption
capacity after 8 cycles. More importantly, the pollutants can be
degraded and mineralized through photocatalysis.
The conventional desorption methods usually need to consume
large amounts of water and power, so there is an urgent need to
find cost-effective and feasible methods for the regeneration of
these adsorbents(Adeyemo et al., 2015).
7.2.3. Mixed pollutants
Numerous papers are concentrated on removal of single model
pollutant by adsorption. However, in real dye containing waste-
water, like textile industries, the effluents normally contains the
mixture of many dyes rather than a single one(Mavinkattimath
et al., 2017). Other than the mixture of many dyes, it was also re-
ported that heavy metals and endocrine disrupting chemicals
(EDCs) commonly coexist in textile industrial effluents(Albadarin
et al., 2014; Zhou et al., 2018). The presence of other pollutants in
the real wastewater may affect the adsorption efficiency of the
targeted dye on the adsorbent. The interactions between com-
pounds may mutually enhance (synergetic effect) or inhibit
(antagonistic effect) the adsorption(Turabik, 2008). Therefore, it's
complicated to predict the multi-component equilibrium perfor-
mance. The models for multi-component adsorption of dyes are
deeply needed(Noroozi and Sorial, 2013). In recent years, there is
limited data on multi-component dye adsorption. It's very impor-
tant to study the interference in terms of antagonistic and
synergetic effect of other pollutants on the adsorption of a target
dye.
8. Conclusion
This review provides a general overview of the removal of
different dyes from simulated wastewater by adsorption technol-
ogy with particular emphasis on the various novel adsorbents such
as clays/zeolites and their composites, biosorbents, agricultural
solid wastes, industrial by-products and their composites and
miscellaneous adsorbents. The review reveals that the composites
and modified adsorbents with well-distributed pores and large
surface area have better adsorption capacity compared to raw
materials. Among them, chitosan, cyclodextrin and their compos-
ites exhibit excellent adsorption performance toward certain dyes
and gained extensive attention. The green and controllable syn-
thesis of materials will be an important mission. Besides that, the
environmental parameters such as pH, initial dye concentration,
temperature and absorbent dose are critical factors which show
significant effects on dyes adsorption. For real application, more
work should be carried out in mixed pollutants system to meet the
actual wastewater treatment requirement. A better regeneration
method is a major challenge for low-cost long term running. The
stability of adsorbents is an essential parameter which can deter-
mine whether the adsorbent is suitable for practice application or
not, but insufficient attention has been paid to formally evaluate
the adsorbents stability in this field. Moreover, the cost analysis is
also of utmost importance but there are few articles provide cost
information. To better evaluate the cost, measuring the cost of
various adsorbents form the entire life cycle (especially during the
sorption/regeneration progress) should be established. In the
future, the researchers should pay more attention to turn more
novel adsorbents into conventional adsorbents, which means some
promising materials can be used more frequently and more widely
with an affordable cost in dyeing wastewater treatment.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (51778230), Shanghai Rising-Star Program
(17QA1401000) and the Fundamental Research Funds for the
Central Universities for their financial support (222201718003).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.envpol.2019.05.072.
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