Review Article

ISSN 1998-0124 CN 11-5974/O4

2019, 12(1): 000–000 https://doi.org/10.1007/s12274-019-2309-8

Nanomaterials for the abatement of cadmium (II) ions from water/

wastewater
Kumar Vikrant1, Vanish Kumar2, Kowsalya Vellingiri3, and Ki-Hyun Kim1 ()
1
Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-ro, Seoul 04763, Republic of Korea
2
National Agri-Food Biotechnology Institute (NABI), S.A.S. Nagar, Punjab 140306, India
3
Environmental and Water Resources Engineering Division, Department of Civil Engineering, IIT Madras, Chennai 600036, India

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019
Received: 20 October 2018 / Revised: 18 January 2019 / Accepted: 20 January 2019

ABSTRACT
The rapid rise of modern industry is the source of unchecked effluents containing many pernicious heavy metals (e.g., cadmium). To rehabilitate
the ecology, food resources, and health of humans and animals, various conventional methodologies are being used in wastewater treatment
facilities for the abatement of cadmium. Nonetheless, the development of advanced, economical, and efficient adsorbents is needed because
of the many shortcomings of conventional methods (e.g., high cost, intensive operation, and inefficiency). Recent advancements in materials
science and chemistry have introduced the use of nanomaterials, which possess very high specific surface areas and multiple functionalities,
for the removal of specific targets such as cadmium. This review explores the recent developments and trends in nanomaterial adsorption
technology for the mitigation of cadmium. The paper further surveys the present obstacles and future opportunities for the advancement of
nanomaterial-based technologies in the area of water treatment.

KEYWORDS
nanomaterials, cadmium, adsorption, pollution control, water purification, heavy metal

1 Introduction accumulate in the food chain [11].

The regulation and removal of cadmium from water is a high-
priority environmental control enterprise because of the deleterious
potential of cadmium species toward animal and human health and
overall ecosystems in both the short and long terms [1, 2]. Although
only a quarter of the Earth’s surface is covered by landmass [3],
about 97% of all water resources are stored in the oceans, making
them ill-suited for most purposes [4]. Moreover, of the remaining
3% of available water, about 2.4% is confined as ice, glaciers, and
atmospheric/soil moisture, remaining out of reach for normal,
everyday applications. Consequently, only 0.6% of the Earth’s total
water resources can be classified as drinkable freshwater (groundwater,
lakes, and rivers) [4] .
Recently, the research community has become markedly interested
in the abatement of heavy metals (e.g., cadmium, mercury, lead,
chromium, and arsenic) from water/wastewater because it has
recognized the environmental significance of their toxic effects. For
instance, taking in cadmium-laden water can damage the cardiovascular
and urinary systems and lead to diverse diseases, including skeletal
deformation, high blood pressure, infertility, and emphysema [5, 6].
Cadmium has also been recognized as a human carcinogen by the
United States Environmental Protection Agency (US EPA) [7].
Essentially, the presence of cadmium within living cells can lead
to the generation of H2O2 [8]. A rise in peroxide concentration
within a cell can induce lipid peroxidation (oxidative stress) and
glutathione and ascorbate depletion [9]. Moreover, H2O2 can cause
nuclear DNA to defunctionalize proteins through the conversion of
thiol groups into sulfones [10]. Cadmium has been recognized as a
high-priority target by the US EPA because of its tendency to
The prime sources of anthropogenic cadmium are ceramics,
electroplating, metallurgical plants, mining, paint and pigment
plants, plastic production facilities, and dry battery manufacturing
plants [12, 13]. Given the harm caused by cadmium species, a
permissible limitation of 0.003 mg·L−1 for Cd(II) ions was set for
drinking water by the World Health Organization [14]. To tackle the
pressing issue of cadmium pollution, various conventional methods
have been used in wastewater treatment facilities, as detailed in
section 2; however, most conventional methods cannot yet reduce
highly contaminated water to the permissible level [15, 16]. Also,
the conventional options are generally uneconomical because they
require secondary treatments before the discharge of effluents [17].
The adsorptive remediation of cadmium rich water has been
recommended as the most fitting and simple option [18]. Finding
an adequate sorbent for the effective removal of Cd(II) ions has thus
become a paramount issue [19]. To that end, many nanomaterials
(NMs) have been developed as highly efficient, economical, and
environmentally benign adsorbents for cadmium [20]. In comparison
to conventional sorbents (e.g., activated carbon and zeolite), NMs
have distinct physicochemical characteristics (e.g., high specific
surface area, short passage for diffusion, and tunable active surface
sites) that provide excellent sorption capacities [18, 21]. Although
many toxic heavy metals (e.g., cadmium, mercury, lead, chromium,
and arsenic) may occur together in wastewater, the sources of each
metal may vary greatly depending on conditions [20, 22–24]. Likewise,
as the concentration of particular metallic species might be
distinctively different from others in wastewater systems, it is often
desirable to adopt selective separation approaches to efficiently
treat them [20, 23]. Moreover, the extent of interactions between

Address correspondence to kkim61@hanyang.ac.kr

2 Nano Res.
NMs and individual heavy metallic species (e.g., surface complexation
and cation exchange) may vary significantly by their intrinsic chemical
properties [24–26]. Hence, it is imperative to properly evaluate the
performances of NMs for sorptive interactions with individual
heavy metallic species (e.g., Cd(II) ions).
For this review article, we have collected insights into various
topics and factors that affect the use of NMs for the removal of
cadmium (Cd(II)) ions from water. To do that, we initially analyzed
the feasibility of various NMs for their use in Cd(II) ion-rich water/
wastewater. A section has been devoted to assessing the performance
of the various conventional methods for comparison with NM
technology. Each section of the review describes a variety of NMs
to promote understanding of this subject. Moreover, we discuss
the underlying hindrances and barriers to current nanotechnology
to propel further advancement in this challenging area of research.
On the whole, we furnish a thorough account of the current
state-of-the-art in using nanotechnology for the abatement of Cd(II)
ions from wastewater/water, and we provide a detailed roadmap for
the further growth of this pollutant treatment technology.
2 Conventional approaches to the treatment of
Cd(II) ions
The presence of heavy metals in the water system exerts harmful
effects on both aquatic and terrestrial systems. To resolve those
problems, many approaches (e.g., chemical precipitation, ion exchange
filtration, chelation, electrochemical techniques, osmosis, coagulation,
adsorption, and electrodialysis) (Fig. 1) have been developed and
used.
The chemical precipitation method is often used to treat heavy
metal-contaminated water because of its simple operation and low
cost [27]. Insoluble precipitates of heavy metals are formed through
chemical reactions and then removed from the treated water through
filtration or sedimentation. Conventionally, two major approaches
have been used for heavy metal chemical precipitation, sulfide and
hydroxide precipitation [27–30]. Those approaches require iron
sulfide/sulfate reducing bacteria and Ca(OH)2/NaOH, respectively,
and both of them have important limitations. For instance, the
hydroxide precipitation method is limited by the generation of low
density sludge, precipitation at different pH for different metals,
and the inhibition of metal-oxide precipitation in the presence of
complexing agents. On the other hand, the precipitates formed
using the sulfide precipitation approach are less soluble than those
formed using the hydroxide precipitation method, and sulfide
precipitation can generate H2S gas and colloidal precipitates that are
difficult to separate. Chelating precipitation is another method used
for the chemical precipitation of metal ions [31–33]. A few chelating
 
Figure 1 List of methods explored for the removal of heavy metals.
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agents (e.g., trimercaptotriazine, sodium dimethyldithiocarbamate,
and potassium/sodium thiocarbonate) have been specifically prepared
for the treatment of heavy metal-rich water systems [31]. However,
these commercially available chelating agents are environmentally
risky and have limited binding sites for heavy metals. A few other
heavy metal chelating materials (e.g., 1,3-benzenediamidoethanethiol
dianion, 1,3,5-hexahydrotriazinedithiocarbamate, N,Nʹ-bis-
(dithiocarboxy)piperazine, potassium ethyl xanthate, and dipropyl
dithiophosphate) have also been tested [32, 34–36]. Although those
chelating agents exhibited good removal efficiency for heavy metals,
they still require further refinement in terms of environmental safety
and efficiency.
The ion exchange method for the treatment of water systems rich
in heavy metals, especially Cd(II) ions, has the advantages of rapid
kinetics, a large capacity for treatment, and great removal efficiency
[27, 37, 38]. Ion-exchange materials that have been explored for
the removal of heavy metal (e.g., Cd(II) ions) from water include
natural/synthetic resins, zeolites, and silicate minerals [37, 39–42].
Likewise, the membrane filtration approach to the removal of heavy
metals has also been explored. On the basis of the filtration
membrane used, membrane filtration is divided into four methods:
reverse osmosis, ultrafiltration, electrodialysis, and nanofiltration
[43–46]. The membrane used for ultrafiltration is suitable for the
removal of colloidal materials and metal complexes. However, the
pore size in ultrafiltration membranes is larger than metal ions, so
several modifications (e.g., polymer enhanced ultrafiltration and
micellar enhanced ultrafiltration) have been made to increase the
efficiency of ultrafiltration. Materials such as ceramics, cellulose,
polycarbonates, polysulfones, polyethersulfone, and their modifications
are widely used in ultrafiltration-based abatement of heavy metallic
ions from water systems [44, 47–52]. A semi-permeable membrane
has been used for the reverse osmosis approach. Reverse osmosis is
an efficient technique for the abatement of heavy metallic ions from
wastewater/water that has been widely used in water purification
systems [53, 54]. However, its limitations (e.g., large power
requirements to maintain the pumping pressure, cost, and need for
frequent membrane replacements due to its poisoning) have led
researchers to explore alternatives [27, 53]. The use of nanofiltration
decreases the energy required to use the membrane filtration
approach [27]. Another membrane filtration approach, electrodialysis,
uses ion-exchange membranes [55]. The coagulation and flocculation
approach has demonstrated good potential in the abatement of
heavy metallic ions from aqueous systems [56, 57]. However, all
those techniques require additional treatment, such as precipitation,
to remove heavy metallic ions from wastewater/water [27]. The
floatation and electrochemical approaches are also commonly used
for this purpose [58–63].
Adsorption is one of the most promising options for the abatement
of heavy metals from aqueous systems, with benefits such as low
cost and high efficiency, flexibility, and simplicity [64–66]. Many
conventional materials (e.g., activated carbon, amorphous silica,
clay minerals, diatomite, biomass, zeolites, and polymers) have been
tested for the adsorptive removal of heavy metals [38, 64, 67–72].
All the conventional techniques remove Cd(II) ions from water, but
they are subject to some specific limitations [27]. For instance,
chemical precipitation cannot remove low concentrations of heavy
metals, and it forms large amounts of sludge. Chemical regeneration
is required for ion exchange resins, and the high cost of activated
carbon (a commonly used adsorbent) limits the use of adsorption.
Likewise, the membrane filtration approach faces problems such as
membrane fouling, high cost, and process complexity. Economic
factors (e.g., the initial capital requirements and high operational
and maintenance costs) limit the applicability of floatation- and
electrochemical-based heavy metal removal systems. Advancements
in materials have produced dramatic progress in the development
Nano Res. 3

of systems for removing heavy metals, especially for adsorption.
The rest of this review provides detailed information about using
nanomaterials to remove Cd(II) ions from contaminated water.
3 Nanotechnological approaches
For the abatement of Cd(II) ions from wastewater, the use of NMs
composed of inorganic constituents has been recommended
preferably due to their faster uptake kinetics and resulting superior
performance [20] (Tables 1 and 2). As summarized in Table 1, the
inorganic NMs can be generally classified into three categories: (i)
transition metal oxides, (ii) transition metals, and (iii) carbon-
based materials. The recovery of spent nanoparticles (NPs) after
wastewater treatment poses a practical constraint to the application
of nanotechnology [73]. 
In this regard, NMs and their composites with magnetic

Table 1 Removal of Cd(II) ions from water through inorganic nanomaterials and their composites
Optimum Initial Cd Maximum Maximum Final Cd Distribution
Order Nanomaterial adsorption concentration removal adsorption capacity concentration coefficient Reference
−1
condition (°C, pH) (μM) efficiency (%) (mg·g ) (μM) (mg·g−1 ·μM−1)
[A] Transition
metal oxide
nanomaterials
1 Fe3O4 25, 6 88.96 90 9.68 8.896 1.09 [91]
2 Fe3O4 25, 4 117.92 88.7 10.9 13.325 0.82 [90]
3 Fe3O4 25, 5.5 1334.4 — 11 — — [215]
4 Fe3O4-SO3H 25, 7 88.96 94 80.9 5.338 15.16 [82]
5 CNSR-Fe3O4 30, 10 444.8 99.9 54.6 0.445 122.75 [92]
6 Ni-αFe2O3 55, 7 177.92 98 90.91 3.558 25.55 [93]
7 CoFe2O4/SiO2 25, 8 8.89 95 5 0.445 11.25 [94]
8 γ-Fe2O3/MgSNTs 25 444.8 — 200 — — [98]
9 NiO — 117.92 — 97 — — [102]
10 CuO nanoblades 25, 7 889.6 99.2 192.3 7.117 27.02 [105]
11 MNP-OPP 45, 7 142.33 96 76.92 5.693 13.51 [103]
12 ZrO2 20, 7 8.89 99.9 3.18 0.009 357.71 [104]
13 NZP 30, 6 500 — 214.7 — — [121]
14 SM-MNP 25, 5 8.89 92 5.18 0.711 7.28 [216]
15 ZnO nanorods 30, 8 889.6 91 147.25 80.064 1.84 [79]
16 PANI/CoHCF 25, 8 889.6 64.15 27.17 318.922 0.09 [108]
17 GAC-NSIO 25, 6 444.8 — 7.84 — — [217]
18 Ti-C 25, 7 444.8 — 31.7 — — [106]
19 HA-TiO2 25, 9 0.35 — 0.36 — — [116]
20 TiO2 dandelions 25, 5 1779.2 80 396 355.840 1.11 [80]
[B] Transition
metal nanoparticles
1 nZVI 25, 9 444.8 78 188 97.856 1.92 [129]
2 FeSSi 25, 6 600 — 105 — — [135]
3 MoS2/TMPyP — 2.49 91 — — — [139]
4 CdS Np 30, 6 444.8 — 141.5 — — [144]
5 Ag NP 25, 6.5 44.48 — 4.67 — — [218]
[C] Carbon based
nanomaterials
1 CNT 25, 7 8.89 27 0.65 6.490 0.10 [199]
2 MWCNT 25, 8 889.6 95.1 181.8 43.590 4.17 [148]
3 e-MWCNT 45 44.48 — 25.7 — — [219]
4 N-doped CNT 25, 7 600 — 7.86 — — [149]
5 Oxidized N-doped 25, 5 700 — 9.33 — — [152]
MWCNT
6 MWCNT-COOH 25, 7 444.8 96 16.34 17.792 0.92 [153]
7 CNT-PAC 26, 5.5 20.19 98.35 11.16 0.333 33.50 [154]
8 γ-Fe2O3/MWCNT 25, 8 133.44 97.2 78.81 3.736 21.09 [157]
9 PEG-MWCNT 25, 4 88.96 97 77.6 2.669 29.08 [155]
10 MGO 25, 6 1,779.2 85 91.29 266.880 0.34 [160]
11 Cys-MGO nanosheet 55, 9 133.44 — 30.3 — — [163]
12 aGO 20, 5 177.92 — 156 — — [166]
13 MDFGO 25, 6.2 444.8 99.4 — — — [164]

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4 Nano Res.

(Continued)
Optimum Initial Cd Maximum Maximum Final Cd Distribution
Order Nanomaterial adsorption concentration removal adsorption capacity concentration coefficient Reference
condition (°C, pH) (μM) efficiency (%) (mg·g−1) (μM) (mg·g−1 ·μM−1)
14 M-Fe3O4-GO 25, 5 222.4 — 125 — — [165]
15 SG-PySA-GO 22 1,067.52 — 10 — — [169]
16 TCAS-rGO 46, 7 88.96 90 128 8.896 14.39 [172]
17 nZVI/rGO 25.31, 6.48 179.34 76.11 25.37 42.844 0.59 [174]
18 3D-SRGO 55, 6 17.79 93 234.8 1.245 188.55 [177]
19 EDA-GCNP 35, 6 88.96 99 18.7 0.890 21.02 [220]
20 MT-CD/SiO2 25, 6 88.96 90 0.3 8.896 0.03 [203]

Table 2 Removal of Cd(II) ions from water through organic/miscellaneous nanomaterials and their composites
Optimum Initial Cd Maximum Maximum Final Cd Distribution
Order Nanomaterial adsorption concentration removal adsorption capacity concentration coefficient Reference
condition (°C, pH) (μM) efficiency (%) (mg·g−1) (μM) (mg·g−1·μM−1)
[A] Organic
nanocomposites
1 MECT 25, 5 889.6 82 209.2 160.13 1.31 [182]
2 P(MB-IA)-g-MNCC 50, 6 889.6 99 262.27 8.90 29.48 [178]
3 CTS-VMT 30, 4 444.8 97 58.48 13.34 4.38 [190]
4 Nanocellulose fibers 25, 6 222.4 90.7 9.7 20.68 0.47 [179]
5 nHApC 25, 5.6 889.6 92 122 71.17 1.71 [189]
6 carboxycellulose 25, 7 2,224 84 2,550 355.84 7.17 [180]
nanofibers
[B] Miscellaneous
nanomaterials
1 Polylysine-resorcinol 25, 8 88.96 98 220 1.78 123.65 [191]
alumina nanotube
2 TPDP/SiO2 25, 5.5 88.96 93 148.32 6.23 23.82 [192]
3 MgO NP 25, 7 889.6 — 1,500 — — [193]
4 MNCLAP 25, 5 2,000 — 123.89 — — [194]
5 nano γ-Al2O3 25, 5 444.8 87 17.22 57.82 0.30 [195]
6 nHAp 25, 5.5 224.82 — 64.07 — — [196]

characteristics (e.g., Fe3O4 and Fe3O4-SO3H; Table 1) have received
widespread attention. The magnetic NMs typically consist of a
core–shell structure. The inner layer is generally made up of
metals such as iron, nickel, and cobalt and their ferromagnetic/
superparamagnetic alloys/oxides, and the outer layer contains
polymers, organic compounds, silica, or alumina [20, 74] (Tables 1
and 2). The novelty of hybrid inorganic magnetic NMs lies in the
fact that they can selectively treat heavy metals (e.g., Cd(II) ions) in
wastewater, and their recovery upon treatment is made easy by the
application of an external magnetic field [75]. Selecting a suitable
support material during the synthesis of NMs is often crucial to the
stability and facile regeneration of the system [20]. Interestingly, a
wide variety of supports (inorganic, organic, and hybrids of transition
elements and carbon-based systems (e.g., carbon nanotubes (CNTs)
and graphene)) have been used in the fabrication of NMs [21].
3.1 Transition metal oxide-based nanomaterials
Metal oxides of transition elements have been actively used in
wastewater treatment because of their high surface area, great
adsorption capacity for heavy metals, and easy reuse upon recovery
from the treated aqueous systems [76, 77]. Moreover, transition
metal-oxides are particularly attractive for removing toxic metal
species such as Cd(II) ions due to their eco-friendliness, easy
availability, and low price [78]. According to the analysis of the data
summarized in Table 1, magnetite (Fe3O4) and other iron oxides
compose a large portion of the transition metal oxide-based NMs
that can be used for Cd(II) ion removal. In fact, they combine high
Cd(II) ion sorption capacity with great ion exchange capability and
the ability to be magnetically separated [20]. In addition to iron
oxide–based NMs, other transition metal oxides such as TiO2 and
ZnO have been used for the removal of Cd(II) ions from water [79,
80] (Table 1).
3.1.1 Iron oxide-based sorbents
The most commonly used transition metal oxide NM is magnetite
(Table 1). Magnetite allows easy functionalization for specific
interactions with Cd(II) ions due to its superb magnetic characteristics
and high specific surface area [81] (Table 1). The main advantage of
the magnetic NMs is their easy recovery by applying an external
magnetic field upon completion of the sorptive treatment [73]. The
recovered NMs can then be regenerated using a strong base or acid
(e.g., sodium hydroxide or hydrochloric acid) [82]. Nevertheless,
as Fe3O4 NMs are prone to corrosion and oxidation under very
low pH conditions, they may require suitable functionalization or
modification of the parent material (e.g., modification with amino-
methylene-phosphonic groups) to overcome the attack of strong
acids [83].
The conventional synthesis methods for Fe3O4 NMs (e.g., sol-gel
method, co-precipitation, and micro emulsion) require huge
amounts of expensive and toxic organic solvents (e.g., benzene and
hydrazine), making them highly unfavorable [84, 85]. In addition,
the commonly employed synthesis protocols are tedious and

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Nano Res.
arduous to downgrade the practicality [86]. Also, iron oxide NMs
succumb to agglomeration under van der Waals forces during
separation from the bulk phase, resulting in large particles [87]. To
overcome the latter limitation, organic or inorganic surfactants and
hydrophilic polymers are often used as capping or dispersion agents
[87]. However, most of those agents are also highly toxic. As a
consequence, green synthesis approaches for magnetic NMs have
been explored extensively [88, 89]. Tangerine peel extract effectively
induced co-precipitation for the synthesis of Fe3O4 NMs [90]. The
tangerine peel extract also effectively reduced NM agglomeration,
reducing the NM size from 200 to 50 nm as the concentration
of tangerine peel extract increased from 2% to 6%. Overall, the
performance of those green NMs was comparable with that of
other NMs (e.g., 88.7% removal efficiency and 10.9 mg·g−1 sorption
capacity) [90] (Table 1).
The functionalization of an NM plays a pivotal role in maximizing
its sorption capacity toward Cd(II) ions [20]. For instance, the
performance of pristine Fe3O4 NMs was moderately good (e.g., 90%
removal efficiency and 9.68 mg·g−1 sorption capacity) but poorer
than that of many functionalized transition metal oxide NMs [91]
(Table 1). Therefore, post-synthetic alterations (e.g., fixing specific
functional groups (such as thiols) on the residual functionalities
(such as hydroxyls) present on the iron oxide NM surface) have
been widely explored to enhance the affinity of iron-oxide NMs
toward Cd(II) ions [92, 93]. In principle, the presence of functional
groups such as –SO3H, –SH, and –OH on the adsorbent surface
may facilitate cation exchange and complexation reactions with
Cd(II) ions to promote their removal processes (Eqs. (1)–(3)). In
this regard, a free radical polymerization approach was reported to
anchor SO3H groups on magnetite NMs (Fe3O4-SO3H) [82] (Fig. 2(a)).
The Fe3O4-SO3H NMs demonstrated good performance toward
Cd(II) ion removal (94% removal efficiency, 80.9 mg·g−1 sorption
capacity with recyclability for up to 10 cycles), which was attributed
to complexation between the sulfo functionalities and cadmium
species [82] (Table 1).
Magnetite NMs functionalized with cashew nut shell resin (CNSR)
provided a cost effective option that simultaneously used waste
biomass (Fig. 3) [92]. The CNSR-Fe3O4 NMs had good performance
toward Cd(II) ions (99.9% removal efficiency and 54.6 mg·g−1
sorption capacity), which was attributed to enhancement of the
surface active sites for Cd(II) ion sorption [92] (Table 1). Hematite
(αFe2O3) was doped with 15 wt.% Ni to produce Ni-αFe2O3 NMs
that displayed good performance for the abatement of Cd(II) ions
(98% removal efficiency and 90.91 mg·g−1 sorption capacity) [93]
(Table 1).
Magnetic CoFe2O4 NMs were coated with SiO2 because silica is
widely known to be biocompatible and chemically inert, making it
a great support material [94]. The CoFe2O4/SiO2 NMs displayed a
moderate tendency for Cd(II) ion sorption compared with other
transition metal oxide NMs (95% removal efficiency and 5 mg·g−1
Figure 2 Adsorption of Cd(II) ions by Fe3O4-SO3H NMs. (a) Schematic preparation of Fe3O4-SO3H NMs. (b) Effect of pH on Cd(II) ion sorption. (Reproduced with
permission from [82], © Elsevier 2017).
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5
sorption capacity) [94] (Table 1). Interestingly, the CoFe2O4/SiO2
NMs were exceptionally reusable (up to 45 cycles) because the silica
coating protected the iron core from corrosive eluents [95]. Similar
to silica (SiO2, a non-negatively charged compound that requires no
coupling ions), silicates (SiO44−, compounds bearing an anion and at
least one cation with silicon as the central atom and electronegative
groups as the ligands) have attracted widespread attention in
wastewater treatment technologies because of their environmental
benignity, low cost, and high stability [96].
Mesoporous one-dimensional magnesium silica nanotubes
(MgSNTs) have shown good capacity for the adsorption of heavy
metallic ions due to their high mechanical sturdiness and short
diffusion pathway for the target analyte [97]. For instance,
ferromagnetic γ-Fe2O3/MgSNTs with a high specific surface area
and porous nanotube structure displayed a maximum sorption
capacity of 200 mg·g−1 for Cd(II) ions [98] (Fig. 4). The surface of
the synthesized γ-Fe2O3/MgSNTs was seen to bear a negative charge
density that electrostatically attracted the cationic Cd(II) ions [98].
Cation exchange between Mg2+ ions and Cd(II) ions present on the
surface of the γ-Fe2O3/MgSNTs was primarily responsible for the
abatement of Cd(II) ions [95].
The Cd(II) ions in aqueous systems can exist in diverse forms
(Cd(OH)+, Cd(OH)3–, Cd(OH)2, and Cd2+) depending on the
solution pH [91]. For the sorptive abatement of Cd(II) ions via iron
oxide NMs, the use of acidic conditions (pH below 2) should be
avoided. At such acidic pH, H+ cations might compete with the
positively charged Cd(II) ions to occupy functional sites on the NM
surface [21]. Likewise, basic conditions (pH > 8) are suspected to
hamper the sorption process through the formation of insoluble
cadmium hydroxides [82]. Fe3O4-SO3H NMs possessing –OH,
–SO3H, and –SH groups exhibit the best performance in neutral or
alkaline pH (Eqs. (1)–(3)) (Fig. 2(b)).
2 [Fe3O4-SO3H](s) + Cd2+(aq) → [(Fe3O4-SO3H)2Cd](s) + 2 H+ (aq)
(1)
2 [Fe3O4-OH](s) + Cd2+(aq) → [(Fe3O4-O)2Cd](s) + 2 H+(aq)
(2)
2 [Fe3O4-SH](s) + Cd2+(aq) → [(Fe3O4-S)2Cd](s) + 2 H+(aq)
(3)
3.1.2 Miscellaneous
Along with iron-oxide-based NMs, other transition metal oxide-
based NMs (e.g., TiO2, ZnO, CuO, and NiO) have also been explored
for the abatement of Cd(II) ions (Table 1). Diverse synthesis routes,
such as the sol-gel approach, homogeneous solution precipitation,
and reverse micellar routes, have been applied to the production
of transition metal oxide-based NMs [99, 100]. However, new and
advanced synthesis methods need to be developed to prevent the
Research
6 Nano Res.
Figure 3 Preparation of CNSR-functionalized Fe3O4 nanoparticles. (Reproduced
with permission from [92], © Elsevier 2017).
 
Figure 4 The programmed synthesis of magnetic magnesium silicate nanotubes
(MgSNTs) from carbon nanotubes (CNTs). TREG = triethylene glycol, TEOS =
tetraethoxysilane. (Reproduced with permission from [98], © Wiley-VCH 2013).
agglomeration of the produced NMs and control their morphology
through simple reaction conditions such as temperature and reactant
concentrations [89].
Interestingly, metal oxalates have often been used for the synthesis
of complex and simple metal oxides because they have the tendency
to decompose at fairly low temperatures [101]. In this way, NiO
NPs were synthesized from nickel oxalates prepared via a single
stage solvothermal approach without toxic surfactants [102]. The
NiO NPs demonstrated good performance with a peak sorption
capacity of 97 mg·g−1 for Cd(II) ions [102] (Table 1). On a similar
note, orange peels (rich in pectin, hemi-cellulose, cellulose, carboxyls,
and hydroxyls) were powdered and synthesized into magnetic NPs
(MNP-OPP) using a co-precipitation approach with magnetite [103].
The MNP-OPP displayed good performance for Cd(II) ions (96%
removal efficiency and 76.92 mg·g−1 sorption capacity), which was
attributed to the involvement of ion-exchange and complexation
(Table 1) (Eq. (4)).
–Fe–O–(C=O) –(OH)n + Cd2+ → –Fe–O–(C=O)–(O–Cd)n+ + n H+
(4)
Biocompatible and chemically inert ZrO2 NPs rich in hydroxyl
functionalities exhibited average performance in the abatement of
Cd(II) ions from water (99.9% removal efficiency and 3.18 mg·g−1
sorption capacity), with regeneration for up to 3 cycles [104] (Table 1).
ZnO-based NMs possessed hydroxyl-rich functionalities for the
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efficient removal of heavy metal ions through ion exchange [95]. For
that reason, ZnO nanorods were synthesized via a hydrothermal
process, an ecofriendly, economical, catalyst-less growth process
that provided easy control over the NP morphology [79]. The high
removal capacity of the ZnO nanorods against Cd(II) ions (147.25 mg·g−1
and 91% removal efficiency) was attributed to complexation and
ion exchange [79] (Table 1). CuO nanoblades demonstrated good
performance for the removal of Cd(II) (99.2% removal efficiency
and 192.3 mg·g−1 sorption capacity), with lower viability than the
control (Fig. 5(a)) [105]. Titanium hybrid nanocomposites (Ti-C)
formed by functionalizing TiO2 NPs with 1,5 diphenyl-carbazone
exhibited a maximum sorption capacity of 31.7 mg·g−1 for Cd(II) ions
[106] (Table 1). Likewise, TiO2 dandelion NPs were synthesized by
critically managing reaction conditions such as pH, pressure, the
control agent for preventing aggregation, and the alcoholysis rate
[80]. The excellent sorption capacity (396 mg·g−1 and 80% removal
efficiency) of the TiO2 dandelion NPs was attributed to the presence of
rich hydroxyl functionalities on the surface, which provided a large
number of chelating sites to coordinate with Cd(II) ions [80, 95].
The past decade has produced prolific growth in the use of
adsorbents analogous to Prussian blue (CkM3[M(CN)6]2·nH2O, in
which M is a transition metal and C is an alkali ion) because of
their good sorption capabilities for wastewater treatment [66]. Also,
various chelating polymers such as polyaniline (PANI, rich in nitrogen
atoms bearing positive charges) are being increasingly applied
for sorptive removal due to their high selectivity toward heavy
metals, great reusability, and ease of handling [16, 107]. PANI was
synergistically combined with cobalt hexacyanoferrate (a Prussian
blue analogue) to form PANI-CoHCF nanocomposites that displayed
average sorption capacity (27.17 mg·g−1) for the sorptive removal of
Cd(II) ions (64.2% removal efficiency) (Fig. 6) [108].
For the proper application of NM technology, the cytotoxic
characteristics of a given NM need to be specified [109]. Because
the size of most NMs is comparable to that of biological cells, NMs
can penetrate biological systems and result in severe toxicity [110]. For
example, transition metal oxide-based NMs induce great oxidative
stress in biological cells (e.g., mitochondria) through the formation
of reactive oxygen species (e.g., OH and OOH free radicals) [111].
Such oxygen species can disrupt DNA, alter essential protein
molecules, and target the central nervous system [112]. As a con-
sequence, the optimum amounts of NMs recommended for wastewater
treatment applications boost their agglomeration, which reduces
Figure 5 Adsorption of Cd(II) ions by CuO nanoblades and multi-walled carbon
nanotubes. (a) Effect of adsorbent concentration on Cd removal by CuO nanoblades.
(b) Cytotoxicity analysis of synthesized CuO nanoblades. (c) Effect of solution pH
on percentage removal of cadmium by multi-walled carbon nanotubes. (Reproduced
with permission from [105, 148], © Elsevier 2017).
Nano Res.
 
Figure 6 Schematic of the formation of PANI-CoHCF nanocomposites.
(Reproduced with permission from [108], © Taylor & Francis, 2016).
their cytotoxicity but also deteriorates their performance [105]. For
example, high concentrations of CuO nanoblades (0.75–1.0 mg·mL−1)
were recommended for the abatement of Cd(II) ions from water-
based systems to conform with cytotoxicity standards (Fig. 5(b)).
The agglomerated NMs do not disperse easily in aqueous solutions,
but they also do no not penetrate biological cells [105].
From a practical perspective, it is essential to understand the
interactions between NMs and natural organic matter, such as
humic acid (HA), which is abundant in natural aquatic environments
[109]. Interactions between NMs and HA can involve cation bridging,
anion exchange, hydrophobic interactions, ligand exchange, hydrogen
bonding, and entropic effects [113]. Essentially, HA can reduce the
number of active sites present on the NM surface or increase the
affinity of NMs toward the heavy metals, increasing their dispersibility
by reducing the size of aggregate NM clusters [114, 115]. Nano-TiO2
particles were coated with HA via a solution precipitation-based
approach [116]. Interestingly, the HA-TiO2 NPs demonstrated a
maximum sorption capacity of only 0.36 mg·g−1, the smallest capacity
value reported for any NM examined for the abatement of Cd(II)
ions [116] (Tables 1 and 2).
The practical application of most transition metal oxide NMs is
limited in wastewater treatment because their ultrafine size causes
elevated pressure drops and poor mechanical sturdiness in fixed
beds and similar setups [20, 117]. However, this drawback can be
curbed by impregnating the NMs into materials with larger pores,
such as zeolites and activated carbon [118]. Such hybrid systems
provide better permeability and an easy separation of phases in
flow systems [20]. Polymer-based ion exchangers are also a great
possibility for hybrid systems because they possess both sufficient
rigidity (due to a polymeric backbone) and the Donnan membrane
effect (due to the presence of covalently bonded charged functionalities
on the polymer surface) [21, 119]. Such polymeric ion exchange
systems can provide effective preconcentration and elevated
permeation of Cd(II) ions prior to their removal by metal oxide
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7
NMs [120]. For that reason, a nanocomposite designated as NZP was
developed by impregnating ZrO2·nH2O into a commercial cation
exchanger (D-001) made up of a highly porous polystyrene framework
[121]. The maximum sorption capacity of NZP toward Cd(II) ions
(214.7 mg·g−1) was attributed to the efficient dispersion of the ZrO2 NPs
in the crosslinked and nanoporous framework of the polymeric
cation exchanger [121] (Table 1).
3.2 Transition metal-based nanomaterials
A major portion of inorganic NMs are transition metals used
for the treatment of wastewaters rich in heavy metals [20, 95].
Interestingly, transition metal–based NM composites are relatively
inert on the bulk scale (because of relativistic contractions, molecular
orbital theory, and the electrochemical potential on the nanoscale),
thus elevating their practical usability [21, 122]. The great specific
surface area of transition metal-based NPs can be effectively
exploited for the abatement of water pollutants by dispersing those
NPs in the treatment system (homogeneous chemical approach)
[123]. However, that approach is impractical because recovering the
spent NPs is difficult [124]. Therefore, a heterogeneous chemical
approach is often applied in which transition metal-based NPs are
synergistically coupled with suitable support materials such as oxides
and polymers [78]. Interestingly, such synergistic combinations
elevate the number of active surface functionalities on the NM
surface and strengthen the affinity of the NM toward the target
pollutants [125]. Also, the support material adds stability and prevents
NPs from leaching into the water system (nanoscale particles are
highly unstable because of their very high surface energy) [126].
Zerovalent iron (nZVI) NPs have often been used to remove
heavy metallic ions from aqueous solutions [127, 128]. nZVI NPs
typically consist of an Fe(0)-based core and an iron oxide-based outer
layer [74]. The performance of nZVI NPs was moderate for the
abatement of Cd(II) ions (78% removal efficiency and 188 mg·g−1
sorption capacity) [129] (Table 1). Interestingly, because cadmium
has more positive standard electrode potential (E0, E10 = −0.403 V)
than iron (E20 = −0.447 V), Cd(II) is readily reduced to Cd(0) upon
interaction with iron-based NPs [130]. A sharp elevation in the
abatement of Cd(II) ions by nZVI NPs was found at pH ≥ 8.5 (Fig. 7)
[129]. Essentially, at pH values higher than 8.0, the Cd(II) ions
precipitate out as Cd(OH)2 and are also hydrolyzed to form Cd2(OH)3+
and Cd(OH)+ ions [22]. The formation of those cadmium species
might imply a heightened deposition and electrostatic attraction
with nZVI NPs [131]. The isoelectric point of nZVI (around pH 8.1)
plays a vital role in the abatement of Cd(II) ions. As the nZVI
surface becomes negatively charged (above the isoelectric point),
electrostatic interactions with the Cd(II) ions increase (Fig. 7) [129].
The practicality of using pristine iron NPs for the abatement
of Cd(II) ions is largely limited by their chemical instability in the
presence of other commonly encountered ions in wastewater [126].
For example, Cl− ions severely inhibit the sorption of Cd(II) ions
onto nZVI [132]. Therefore, sulfidation of iron-based NPs by
synthesizing Fe(0)/FeS (S-nZVI) nanocomposites has been touted
as a good option to improve their stability and performance toward
heavy metal removal [133, 134]. In this regard, nano-SiO2-seeded
S-nZVI nanocomposites (FeSSi) showcased a peak adsorption capacity
of 105 mg·g−1 for Cd(II) ions, which was achieved through precipitation
and chemisorption [135] (Table 1).
In recent years, the great potential of transition metal dichalcogenides
(TMDs, e.g., MoSe2, WSe2, and WS2) has been recognized in various
environmental applications, such as the sensing and removal of
hazardous pollutants [118, 136]. With an MX2 stoichiometry and
two dimensional structure, TMDs are made up of hexagonal sheets
of transition metals (M) packed between two layers of chalcogen
species (X) [136]. Interestingly, nano MoS2 tends to exhibit very
high chemical versatility coupled with great dispersibility (no
Research
8 Nano Res.
 
Figure 7 Cd(II) removal rate of nZVI at different pH values with and without the
addition of nitrate. (Reproduced with permission from [129], © Elsevier 2014).
requirement for an assisting surfactant) [137]. Unique conjugated
systems with cyclic structures have allowed porphyrin derivatives
to be used in the synthesis of nanocomposites, improving their
removal characteristics for heavy metals [16, 138]. For example,
MoS2 was synergistically combined with 5, 10, 15, and 20-tetrakis
(1-methyl-4-pyridinio) porphyrin tetra (p-toluenesulfonate) (TMPyP)
to form MoS2/TMPyP nanocomposites that displayed a maximum
removal efficiency of 91% for Cd(II) ions [139] (Table 1). As
electrostatic interactions between the TMPyP on the MoS2 surface
and Cd(II) ions increased, cadmium removal proceeded efficiently
through complexation [138].
Templates are widely used in the synthesis of NPs [140]. Interestingly,
NPs synthesized via templates showed excellent dispersibility in
aqueous solutions, which systematically increased the accessibility
of the NPs to Cd(II) ions [141]. Among the many templates available
for NP synthesis, biological ones have attracted great attention because
they can allow the resulting NPs to specifically recognize molecules
by imparting certain favorable spatial organizations during growth
(distinct binding interactions, nucleation, and assembly) [142, 143].
Also, the biological templates provide good control over the size and
shape of NPs and increase the number of favorable functionalities
[142]. For example, Aspergillus versicolor mycelia, an inexpensive
fungus with easy handling and a rapid growth rate, was functionalized
with xanthate, which has low solubility and high stability with heavy
metal complexes, in the synthesis of CdS NPs that demonstrated
a maximum Cd (II) ion sorption capacity of 141.5 mg·g−1 [144]
(Table 1).
3.3 Carbon-based nanomaterials
NMs based on carbon have garnered widespread attention in recent
years as prospective platforms for the abatement of heavy metals
from water-based systems [145, 146]. Graphene and CNTs are two
major components of carbon-based NMs for the abatement of Cd(II)
ions because of their great surface area, tunable functional sites,
many inherent oxygen functionalities, and resistance toward corrosion
[26, 128]. However, advanced carbon-based nanocomposites work
better for the abatement of Cd(II) ions than their pristine forms
primarily due to synergistic effects and the presence of highly
favorable surface functionalities [20, 24, 147].
3.3.1 Carbon nanotube-based sorbents
CNTs are essentially graphene sheets rolled up in a tube-like
structure [147] and can be formed from a single layer of graphene
(single-walled, SWCNTs) or multiple layers of graphene (multi-
walled, MWCNTs) [26]. CNTs display great mechanical sturdiness,
primarily through the presence of sp2 hybridization carbons, as
compared to the sp3 bonds prevalent in other carbonaceous substances
[128]. MWCNTs have received more attention than SWCNTs for
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the sorptive abatement of Cd(II) ions because of their high surface
area, chemical inertness, high porosity framework with many voids,
π-π electrostatic interactions, light mass density, and strong binding
tendency toward Cd and other heavy metal ions due to their rich
surface functionalities with great hydrophobicity [20, 145]. Pristine
MWCNTs exhibited good performance toward Cd(II) ions (181.8 mg·g−1
and 95.1% removal efficiency) [148] (Table 1). The removal efficiency
for MWCNTs increased as the solution became more alkaline
(Fig. 5(c)). As explained above, under acidic conditions, H+ ions
compete with the Cd(II) ions for the active surface sites. Also, at
low pH, CNTs exist in carboxylated or hydroxylated forms that are
unfavorable for cadmium abatement [147, 148].
To improve the removal characteristics of CNTs, the pristine
forms are often doped with specific functionalities that favorably
attract the target pollutant(s) [147]. For example, nitrogen-doped
CNTs (CNx) obtain structural defects (heptagons and pentagons) in
the structural framework or vacancies pertaining to the hexagonal
network of carbon when they undergo oxidative treatments with
nitrogen oxide, ozone, or oxygen at temperatures ≤ 400 °C during their
synthesis [149, 150]. Those defects then favorably accommodate
surface functionalities and provide reactive anchoring sites for
Cd(II) ions [131, 151]. Because the presence of localized electrons
from nitrogen atoms in the CNT framework helps distorts its π
cloud, its chemical reactivity can be greatly improved [134].
To increase the dispersibility of CNTs in aqueous solutions,
various oxidative treatments can reduce their hydrophobicity, which
originates from intermolecular van der Waals attractions, while
purifying and chemically altering their structural framework by
introducing lactone, hydroxyls, carboxyls, carbonyls, pyrones, and
chromenes [26, 128]. CNx demonstrated a peak adsorption capacity
of 7.86 mg·g−1, which was attributed to the conjugation of cadmium
species with oxygen functionalities on the CNx surface [149] (Table 1).
In a similar study, CNx oxidized with nitric acid demonstrated a
peak sorption capacity of 9.33 mg·g−1 for Cd(II) ions because of
abundant carboxylic functional groups on the CNT surface [152]
(Table 1). In a similar way, MWCNTs were treated with nitric acid
to yield MWCNT-COOH, which showed an average performance
in the removal of Cd(II) ions (16.34 mg·g−1 and 96% removal
efficiency) [153] (Table 1). The sorptive removal of cadmium by
MWCNT-COOH was explained as the chelation between cadmium
species and the hydroxyl/carboxyl functionalities in MWCNT-
COOH [153].
CNT structures were also grown on powdered activated carbon
via a fixed catalyst chemical vapor deposition approach to yield
a synergistic hybrid material (CNT-PAC) [154]. The CNT-PAC
displayed an average performance in the removal of Cd(II) ions
(11.16 mg·g−1 with 98.35% removal efficiency) [154] (Table 1). Amino
groups are often incorporated into the CNT structure to boost its
affinity toward specific target pollutants [128] and have demonstrated
great reactivity with heavy metals such as Cd(II) ions for effective
removal. The amino molecules were synergistically combined with
the oxygen functionalities of CNTs to form active electrostatic and
chelation sites on the CNT surface [15, 147]. For example, amino
polyethylene glycol (PEG) was anchored on MWCNTs via oxidation
followed by SOCl2 treatment and amination to yield hybrid
nanocomposite PEG-MWCNTs (Fig. 8) [155]. The PEG-MWCNTs
efficiently removed Cd(II) ions (97 mg·g−1 with 77.6% removal
efficiency) from an aqueous solution [155] (Table 1).
Along with oxidative strategies, the introduction of specific
functionalities has been touted as a good strategy for increasing the
dispersibility of CNTs [156]. Also, the recovery of spent CNTs is a
major issue that can be effectively addressed by designing magnetic
CNT composites. The recovery of such composites can be carried out
efficiently by applying an external magnetic field [26]. For example,
maghemite NPs were fixed on the surface of MWCNTs treated with
nitric acid via coprecipitation [157]. The γ-Fe2O3/MWCNT composites
Nano Res.
Figure 8 Reaction pathways applied to obtain PEG-MWCNTs. (Reproduced with permission from [155] , © Forum of Chalcogeniders, 2013).
demonstrated good performance toward Cd(II) ions (78.81 mg·g−1
and 97.2% removal efficiency), with easy recovery and regeneration
capability for up to 5 cycles [157] (Table 1). Essentially, as soon as
the Fe2O3 NPs came in contact with water molecules, they used
hydroxyl groups to complete their shells (strong dependency on
the solution pH). The surface of the maghemite thus became rich
in O−, OH2, and OH functionalities that acted synergistically with
the inherent carboxyl groups of the MWCNTs to efficiently adsorb
Cd(II) ions [20, 145].
3.3.2 Graphene-based sorbents
Graphite oxide (GrO) organized in a monolayered fashion is known
as graphene oxide (GO) [158]. GO is typically synthesized via
sonication or mechanical stirring of exfoliated GrO [140]. The GO
surface is rich in oxygen functionalities such as epoxies, hydroxyls,
carbonyls, and carboxyls [158]. Interestingly, the GO surface
acquires a negative surface-charge density in aqueous solutions due
to deprotonation of the –COOH and –OH functionalities on its edge
[95]. Essentially, the negative surface-charge density of GO NPs
enables them to be dispersed homogenously in aqueous solutions
due to electrostatic repulsions between them [21]. Moreover,
the negative charge on the GO surface makes GO NPs excellent
candidates for the sorptive removal of positively charged pollutants
(e.g., Cd(II) ions) through electrostatic attraction [26].
The excellent potential of GO in the removal of various water
pollutants, including Cd(II) ions, has been recognized, along with
its numerous other merits (e.g., eco-friendliness, high specific
surface area (≥ 1,000 m2·g−1), and easily tailorable functionalities)
[128]. However, like several NMs discussed above, GO suffers from
a serious shortcoming in terms of recovering spent NPs [159].
Therefore, magnetic GO (MGO) was proposed and synthesized via
coprecipitation with iron oxides [160]. MGO efficiently removed
Cd(II) ions from water systems (91.29 mg·g−1 and 85% removal
efficiency) while maintaining regenerative capabilities for up to 3 cycles
[160] (Table 1).
Interestingly, various amino acids have been extensively incorporated
as ligands in the preparation of advanced materials for the abatement
of pollutants because of their strong affinity toward heavy metal
species, inexpensive availability, biocompatibility, and highly durable/
flexible structure [161, 162]. Therefore, MGO nanosheets were
Figure 9 Proposed adsorption mechanism of Cd(II) adsorption on alkaline deoxygenated GO (aGO). (Reproduced with permission from [166], © IWA Pub. 2015).
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9
functionalized with cysteine, a water soluble, non-essential amino
acid bearing –COOH, –NH2, and –SH functionalities, to boost the
affinity of MGO for Cd(II) ions [163]. The Cys-MGO nanosheets
demonstrated a peak sorption capacity of 30.3 mg·g−1 for Cd(II)
ions with easy regeneration for up to 10 cycles [163] (Table 1).
Interestingly, the cys-MGO nanosheets displayed great selectivity
for Cd(II) ions in the presence of potentially interfering ions
commonly encountered in wastewater (e.g., Pb2+, Zn2+, Ni2+, Cu2+,
Cr3+, Fe3+, Ca2+, Mg2+, Na+, and K+), supporting their enhanced
practical applicability [163]. In a similar approach, MGO NPs
were functionalized with ethylene diamine to yield hybrid nano-
composites (MDFGO) that displayed a maximum removal efficiency
of 99.4% for Cd(II) ions [164] (Table 1). Similarly, MGO NPs were
functionalized with 3-mercaptopropyl trimethoxysilane to yield hybrid
nanocomposites (M-Fe3O4-GO) with a peak sorption capacity of
125 mg·g−1 for Cd(II) ions [165] (Table 1). The excellent removal
performance of M-Fe3O4-GO was attributed to complexation between
the GO surface and the Cd(II) ions due to strong Lewis acid-base
interactions along with ion-exchange due to the presence of thiol
groups in the nanocomposite structure [128, 165].
An alkaline hydrothermal approach was used to synthesize alkaline
deoxygenated GO (aGO) that had a peak adsorption capacity
of 156 mg·g−1 for Cd(II) ions [166] (Table 1). The electrostatic
attraction between Cd(II) ions and the negatively charged aGO
surface (containing –CO− due to deprotonation in the aqueous
solution) was described as the primary abatement mechanism, with
cationic π interactions between the Cd(II) ions and benzene rings/
phenolic hydroxyls also playing a major role (Fig. 9) [166]. Note that
various porous carbonaceous materials are used for the removal of
heavy metals. Among them, biochar (produced by the pyrolysis
of waste biomass) has attracted widespread attention as a cheap
adsorbent [161, 167]. Because NPs are often combined with support
materials to prevent their elution from the treatment system [95],
biochar has been used to stabilize GO NPs [168]. The GO-biochar
nanocomposite (SG-PySA-GO) was synthesized by the pyrolysis
of sweetgum (Liquidambar styraciflua) pretreated with GO [169].
However, the SG-PySA-GO nanocomposite demonstrated only a
moderate peak sorption capacity of 10 mg·g−1 for Cd(II) ions. The
observed affinity was ascribed to complexation, cation exchange,
electrostatic attraction, and π interactions in the GO basal plane
Research
10
[169] (Table 1).
Calixarenes are third-generation supramolecular compounds
that have been widely used as building blocks and host molecular
platforms for carriers of various metal ions as well as receptor
compounds for heavy metals [170, 171]. A wet chemical approach
was used to functionalize thiacalix[4]arenetetrasulfonate (TCAS)
on reduced graphene oxide (rGO) to yield the nanocomposite
TCAS-rGO, which demonstrated good performance for the
abatement of Cd(II) ions (128 mg·g−1 and 90% removal efficiency)
[172] (Table 1) (Fig. 10). The Pearson acid-base concept was used
to explain the sorptive removal of Cd(II) ions by TCAS-rGO [172].
Essentially, the TCAS structure consisted of bridging sulfur atoms,
which are regarded as soft bases with great affinity for Cd(II)
ions [173].
As elucidated in section 3.2, nZVI has been extensively used for
the sorptive abatement of heavy metals due to its great reactivity
and large surface area [20]. However, nZVI NPs suffer from many
shortcomings, such as frequent agglomeration, poor stability, poor
durability, and poor mechanical sturdiness [145]. To correct those
shortcomings, nZVI was functionalized with rGO to form a
nanocomposite (nZVI/rGO) with average performance for the
removal of Cd(II) ions (25.37 mg·g−1 and 76.11% removal efficiency)
[174] (Table 1).
Three-dimensional (3D) graphene-based aerogels have attracted
great attention for the abatement of heavy metals from water systems
[175]. These 3D aerogels possess a high specific surface area, high
strength-to-weight ratio, great mechanicalsturdiness, highly porous
structure, and easily accessible active surface sites for the target
pollutant [175, 176]. Therefore, a low-temperature gel, freeze-dried
approach was used to covalently anchor sulfonic acid bearing aryl
radicals onto rGO [177]. The synthesized hybrid nanocomposite
(3D-SRGO) demonstrated good performance for the removal of Cd(II)
ions (234.8 mg·g−1 and 93% removal efficiency) [177] (Table 1).
3.4 Organic polymeric nanomaterials/supported nano-
composites
Many nanostructures have been tested for the abatement of Cd(II)
ions from aquatic systems. The use of a biocompatible material such as
cellulose or chitosan is considered beneficial in the development of
heavy-metal removal systems because the raw materials are highly
abundant and inexpensive. Organic materials such as cellulose fit
those criteria [178–180]. In general, nanoscale cellulose, termed
Figure 10 Schematic of synthesis procedures for the TCAS-rGO nanocomposites. (Reproduced with permission from [172]. © Royal Society of Chemistry 2016).
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Nano Res.
nanocellulose (NC), exhibits enhanced functional properties (especially
hydrophilicity, biodegradability, regenerability, mechanical charac-
teristics, and specific surface area) compared to normal cellulose.
NC can be prepared from a variety of raw materials (rice straw,
spinifex grass, poplar alkaline peroxide mechanical pulp, lignocellulosic
fibers, and so on) [86, 179–181]. Rice straw nanofibers were prepared
using a physical-chemical treatment [179]. The NC fibers prepared
from rice straw demonstrated better removal efficiency for Cd(II)
than bulk cellulose and unprocessed rice straw. Their increased
adsorption of Cd(II) was ascribed to two major factors: (1) the removal
of non-cellulosic amorphous constituents during preparation of the
NC fibers, which increased the availability of hydroxyl groups on
the cellulose chains, and (2) increasing the negative charge on the
surface of the NC fibers through acid hydrolysis, which enhanced
the electrostatic interactions with cationic metals ions. The maximum
removal efficiency for the NC fibers was 90.7% (adsorption capacity
of 9.7 mg·g−1) [179]. On the other hand, NC synthesized form
Australian spinifex grass exhibited a maximum removal efficiency
of 84%, with a significantly high peak sorption capacity of 2,550 mg·g−1
for Cd(II) ions [180]. On the basis of Cd(II) ion concentrations,
Sharma, Chattopadhyay, Sharma, Geng, Amiralian, Martin and Hsiao
[180] proposed two types of removal mechanisms for Cd(II) by NC.
At lower levels of Cd(II) ions (below 500 ppm), the interaction
between the metal ions and the carboxylic acid present on NC
dominated, whereas at higher levels of Cd(II) ions (above 1000 ppm),
mineralization (i.e., forming Cd(OH)2 nanocrystals) predominated.
The change in the surface morphology of the NC is shown via
scanning electron microscope (SEM) images in Fig. 11.
The effectiveness of NC in removing Cd(II) ions could be upgraded
further by the addition of support materials that can be easily
functionalized with suitable ligands, e.g., sulfhydryl and carboxyl
groups [178]. The functionalities could be incorporated into the NC
structure by modification with 2-mercaptobenzamide. Moreover,
the structural properties, reusability, and functionality of NC
were improved by adding iron nanoparticles to form magnetite
nanocellulose (MNCC). Further improvements in the structure
of MNCC were achieved by grafting itaconic acid (IA) with a
crosslinking agent, e.g., ethylene glycol dimethacrylate. The final
structure is called 2-mercaptobenzamide modified IA-grafted-magnetite
nanocellulose composite (P(MB-IA)-g-MNCC). The interaction
between the carboxyl and hydroxyl groups of the nanocomposite
and Cd(II) was assumed to cause the removal of Cd(II) from the
water system via ion exchange and complexation.
Nano Res.
Figure 11 Scanning electron microscope images of nanocellulose after exposure to (a) 500 ppm and (b) 1,000 ppm cadmium nitrate solution. At the higher concentration
of Cd ions, the nanocrystals of Cd were observed in the form of aggregates on the fibers due to mineralization. (Reproduced with permission from [180], © American
Chemical Society 2018).
The MNCC-based organic adsorption system demonstrated a
peak sorption capacity of 262.3 mg·g−1 for Cd(II) ions. The P(MB-
IA)-g-MNCC followed pseudo-second-order kinetics for the sorption
of Cd(II) and fitted the Sips model well. The P(MB-IA)-g-MNCC
sorption system displayed good performance during multiple uses,
decreasing from 97.2% to 86.3% after five cycles. The used adsorbents
were regenerated using 0.1 M HCl.
Chitosan is another biopolymer found abundantly in nature.
This organic structure exhibited several advantages, such as
biocompatibility, biodegradability, and chelation properties with
metal ions via functional groups, e.g., amino and hydroxyl groups
[182]. However, a few modifications are suggested to improve
the adsorption properties, stability, and reusability of chitosan as an
effective adsorbent for metal ions. In general, adding magnetic
materials to chitosan would be a good option to enhance the
reusability of the adsorption system [182, 183]. On the other hand,
the adsorption characteristics of chitosan could be enhanced by
modifications with thiourea, isatin, and xanthate groups as well
as chelating agents such as diethylenetriaminepentaacetic acid,
ethylenediaminetetraacetic acid (EDTA), and ethylene glycol
tetraacetic acid [182, 184–188].
A removal system for Cd(II) ions was developed using cross-
linked magnetic EDTA/chitosan/TiO2 (MECT) [182]. The MECT
nanocomposite followed the Langmuir model for the sorption of
Cd(II) ions, exhibiting a peak adsorption capacity of 209.2 mg·g−1.
The sorption capacity of this nanocomposite-based system dropped
to 90% after five cycles of regeneration. Likewise, hydroxyapatite/
chitosan nanorods (nHApC) were also proposed and used for the
sorption of Cd(II) ions [189]. The nHApC composite exhibited a
peak sorption capacity of 122 mg·g−1 for Cd(II) ions. The formation
of a biocomposite between chitosan and clay materials not only
increased the adsorption characteristics but also lowered the overall
cost [190]. Therefore, the excellent ion exchange property of
vermiculite (VMT), a phyllosilicate, was explored by forming a
composite with chitosan. The chitosan/vermiculite biocomposite
(CTS-VMT) was synthesized using epichlorohydrin as the cross-
linking agent. The composite demonstrated a peak sorption capacity
of 58.5 mg·g−1 for Cu(II) ions at pH 4. This chitosan-based biocomposite
followed the chelation mechanism for the sorption of heavy metallic
ions. The biocomposite displayed excellent performance in terms of
reusability, maintaining > 90% of its adsorption efficiency after four
uses, with HCl used for regeneration. The Cd(II) ion adsorption
parameters for the organic nanocomposites are given in Table 2.
3.5 Other nanomaterials
Nanomaterials are an efficient way to remove Cd(II) from polluted
water. In addition to the nanomaterials described above, a few other
nanomaterials, such as alumina NPs, magnesium oxide, meso-
porous silica, hydroxyapatite (HAp)-based nanostructures, and
their composites have also been used to remove Cd(II) ions from
water-based systems [191–196]. The exploration of the HAp-based
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11
material is special because it exhibited four routes of heavy
metal immobilization: 1) surface complexation, 2) ion exchange,
3) dissolution, and 4) precipitation and co-precipitation [196]. The
adsorption properties of HAp could be enhanced by using a nanoform
of hydroxyapatite (nHAp). The higher surface area of nHAp caused
greater Cd(II) ion immobilization compared with normal HAp.
The maximum sorption amount of Cd by nHAp was 1.41 mmol·g−1
(~ 158.5 mg·g−1), which is far higher than that from HAp (0.63 mmol·g−1
(~ 70.8 mg·g−1)) [196, 197]. Apatite materials, especially chlorapatite
(Ca10(PO4)6Cl2 (CLAP)), are very difficult to remove from water
after treatment [194]. Therefore, the use of magnetic chlorapatite
(MNCLAP) NPs could be beneficial. The MNCLAP system was
successfully tested on the abatement of Cd(II) ions from wastewater,
and the spent structures were easily recovered from the water system
with an external magnetic field [194].
Alumina NPs are another promising nanostructure explored for
the removal of Cd(II) ions from water [191, 195]. These structures
were explored as both NPs and nanotubes. The alumina NPs
synthesized using the sol-gel approach demonstrated a peak sorption
capacity of 17.22 mg·g−1 [195]. The surface modification of those
structures is critical for maximizing Cd(II) ion adsorption [191].
Alumina nanotubes were modified with polylysine and resorcinol
to achieve a peak sorption capacity of 220 mg·g−1 for Cd(II) ions.
Likewise, the modification of mesoporous silica with a ligand
(4-tert-octyl-4-((phenyl)diazenyl) phenol (TPDP)) enhanced the
Cd(II) ion sorption capacity from 3.62 to 148.3 mg·g−1 [192]. The
excellent removal capacity of magnesium oxide (MgO) nanostructures
was also tested for Cd(II) [193]. Those structures adsorbed Cd(II)
ions via electrostatic and ion exchange mechanisms. The MgO
nanostructures demonstrated a peak sorption capacity of 1,500 mg·g−1
for Cd(II) ions.
A wide range of nanomaterials has been tested for the abatement
of Cd(II) ions from aqueous systems (Tables 1 and 2). Those materials
have demonstrated promising sorption capacity for the development
of future heavy metal removal systems. Nevertheless, the final
performance cannot be assessed by simply considering adsorption
capacity. Therefore, in addition to adsorption capacity, we also analyzed
the distribution (or partition) coefficient of the Cd removal systems
summarized in this review to reduce bias stemming
4 Comparison between nanomaterials and com-
mercial adsorbents
According to kinetics studies, the adsorption capacity of a given
sorbent is directly and sensitively affected by the concentration (or
amount) of pollutant loaded onto the system. Loading higher
concentrations of pollutants on a sorption system will cause the
sorbates to occupy more sorption sites and yield a higher sorption
capacity per given mass than loading lower concentrations. In this
respect, the selection of an equilibrium sorption capacity is not a
useful tool for comparing sorption capacities determined at varying
Research
12
levels of pollutant concentration. To fairly evaluate the sorption
strengths of different sorbents, we use the distribution coefficient (Kp).
The formula for Kp is the sorption capacity divided by the final
concentration of sorbate remaining at the equilibrium (or maximal)
removal condition [198]. Because this procedure can reduce the
bias of the concentration effect just described, an evaluation based
on Kp values is meaningful irrespective of the diverse experimental
conditions used across many different studies. For example, according
to the data summarized in Table 1, the maximum sorption capacity
for Cd(II) ions (396 mg·g−1) was found when TiO2 dandelions were
used as the sorbent [80]. However, when the relative patterns for each
sorbent were compared based on Kp, ZrO2 exhibited the maximum
capability of all the materials listed in Table 1. The calculated Kp values
thus contrast sharply with those based on adsorption capacity. The
Kp value of ZrO2 was 358 mg·g−1·μM−1, whereas that for the TiO2
dandelions was only 1.11 mg·g−1·μM−1. As shown by this comparison,
ZrO2 is the best sorbent material for Cd(II) ions listed in Table 1.
Interestingly, the transmission electron microscopy (TEM) image of
ZrO2 confirmed that they are agglomerated with an irregular shape
(~ 13 nm diameter) (Fig. 12(a)). Likewise, their SEM image also
supported such observations (Fig. 12(b)) [104]. Apart from ZrO2, the
best adsorbents for the capture of Cd(II) ions in the aqueous phase
were 3D-SRGO (189 mg·g−1·μM−1) [177], CNSR-Fe3O4 (123 mg·g−1·μM−1)
[92], and polylysine-resorcinol alumina nanotubes (124 mg·g−1·μM−1)
[191]. Several sorbents have moderately strong adsorption capacities
for the removal of Cd(II) ions. Although their synthesis procedures
and structural properties differ, the performance of many NMs (e.g.,
Ni-αFe2O3, CNT, and-PAC) appears to be highly comparable to one
another. For example, we calculated Kp values in the range of <
34–21 mg·g−1·μM−1 for Ni-αFe2O3 (25.6 mg·g−1·μM−1) [93], CuO
nanoblades (27 mg·g−1·μM−1) [105], CNT-PAC (33.5 mg·g−1·μM−1) [154],
PEG-MWCNT (29.1 mg·g−1·μM−1) [155], and γ-Fe2O3/MWCNT
(21.1 mg·g−1·μM−1) [98] (Table 1). All those sorbents had Kp values
that exceeded those of the traditional adsorbents: activated carbon
(0.15 mg·g−1·μM−1) [199], activated clay (0.04 mg·g−1·μM−1) [200],
perlite (0.16 mg·g−1·μM−1) [201], and zeolite (10.4 mg·g−1·μM−1) [202].
Thus, the Kp values confirm the limited efficacy of the traditional
sorbents. Only a few NMs recorded such low Kp values: MT-CD/
SiO2 (0.03 mg·g−1·μM−1) [203] was even lower than activated clay
(0.04 mg·g−1·μM−1), and CNTs (0.10 mg·g−1·μM−1) [199], PANI/CoHCF
(0.09 mg·g−1·μM−1) [108], nZVI/rGO (0.59 mg·g−1·μM−1) [174], Fe3O4
(0.82 mg·g−1·μM−1) [90], and MWCNT-COOH (0.92 mg·g−1·μM−1)
Table 3 Removal of Cd(II) ions from water through commercial adsorbents
Initial Cd
Optimum adsorption
Order Adsorbent concentration
condition (°C, pH)
(μM)
1 Activated carbon 25, 7 8.89
2 Zeolite 25, 6 62.27
3 Activated clay 30, 6 889.6
4 Perlite 22, 6 8.89
Figure 12 Microscopic images of ZrO2. Panel (a) and (b) correspond to transmission electron microscopy (TEM) image and scanning electron microscopy (SEM)
image, respectively. (Reproduced with permission from [104]. © Elsevier 2016).
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Nano Res.
also reported low Kp values. Overall, our literature survey indicated
that NMs demonstrate better performance in capturing Cd2+ ions
than traditional materials because of their fascinating structures
and associated advantageous properties.
ZrO2 performed almost 35.7 times better than zeolite for cadmium
removal. The cost-effectiveness of sorbents used to remove Cd(II)
ions is also important and does not necessarily trend with Kp values.
For instance, although the sorption capabilities of CuO nanoblades
and PEG-MWCNT are comparable, the former has much smaller
synthesis costs than the latter [105, 155], making it a better option
for Cd(II) removal.
5 Challenges in nanotechnology for Cd(II) ion
removal
A brief self-explanatory description is provided for the practical
and/or proven advantages of NM-based technologies towards diverse
fields of environmental applications with the emphasis on water/
wastewater treatment in Fig. 13. As such, nanotechnology has
received great attention from the research and industrial community
because of the infinite merits of NMs based on significantly
enhanced porosity and surface flexibility that offer multifunctional
properties unavailable with conventional adsorbents (e.g., activated
carbons, polymeric organic resins, silica gel, zeolites, molecular sieves,
and alumina). However, because of low cost and facile production,
traditional sorbent materials continue to be used (with or without
modification) for the removal of diverse pollutants. Despite their
limited efficacy, conventional adsorbents (e.g., activated carbons,
polymeric organic resins, silica gel, zeolites, molecular sieves, and
alumina) are still commonly used for several reasons: (a) cost-
effectiveness, (b) easy availability, (c) no need for particular synthesis
or activation, (d) recyclability, (e) easy disposability, (f) relatively low
toxicity, and (g) no harmful end-product caused by sorbent–sorbate
interactions. Among those factors, cost-related issues (e.g., the
expense of synthesis and regeneration) remain the main limitation
for NMs. Additionally, concern remains that some NMs could
generate toxicity either through sorbent–sorbate interactions or at
the disposal stage.
To date, a few types of NMs have been synthesized in large
enough quantities to lower the market price. For instance, the price
of 1 kg of MWCNTs (> 90% carbon, dimension × length: 110–
170 nm × 5–9 μm) is 40,317 USD [204], whereas the price of 1 kg of
Maximum Maximum Final Cd Distribution
removal adsorption capacity concentration coefficient Reference
efficiency (%) (mg·g−1) (μM) (mg·g−1·μM−1)
38 0.8 5.51 0.15 [199]
96 25.9 2.49 10.40 [202]
75.2 8.71 220.62 0.04 [200]
55 0.64 4.00 0.16 [201]
Nano Res.
zeolite is 478 USD [205]. Although MWCNTs cost almost 100 times
more than zeolite, the performance of some functionalized MWCNTs
(e.g., MWCNT-COOH) is found to be even less effective than that
of zeolite (Table 1). The abnormally high cost of CNTs arises from
the usage of standard catalytic chemical vapor deposition-based
techniques which involve the breakdown of hydrocarbons (chemically
induced) onto a substrate [24]. In addition to the high cost and
energy intensive production procedure, the catalysts used during
their synthesis often deposit on the CNT surface to leave potential
risk to the environment (e.g., due to their toxicity) [23, 206]. Also,
because of the high van der Waals attraction, pristine CNTs have
low solubility in water to undergo eventual agglomeration which may
lower their performance with uneasy handling [23, 207]. In this
respect, the use of suitable modification (e.g., functionalization)
may offer a solution to the problems associated with CNTs or other
NMs [207, 208]. Therefore, despite the excellent performance of
certain NMs, they are not yet ready to meet the practical needs in
the field. Energy intensive production procedure, the catalysts used
during their synthesis often deposit on the CNT surface to leave
potential risk to the environment (e.g., due to their toxicity) [23, 206].
Also, because of the high van der Waals attraction, pristine CNTs
have low solubility in water to undergo eventual agglomeration
which may lower their performance with uneasy handling [23, 207]. In
this respect, the use of suitable modification (e.g., functionalization)
may offer a solution to the problems associated with CNTs or other
NMs [207, 208]. Therefore, despite the excellent performance of
certain NMs, they are not yet ready to meet the practical needs in
the field. In recent years, the utilization of organic polymeric NMs
has received numerous attention in the domain of water purification
owing to their distinct advantages of biodegradability, biocompatibility,
and eco-friendliness [209]. Nonetheless, the performance of most
organic polymeric NMs is generally observed to be inferior to that
of inorganic NMs (Tables 1 and 2).
Figure 13 A list of proven nanomaterial-based technologies towards environ-
mental applications [221–223].
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13
Further, as the organic NMs tend to be subject to relatively slow
uptake kinetics (e.g., requirement of a longer operation to achieve
the desired level of removal relative to other NMs), it makes them
less favorable for practical applications [20, 209]. In addition, as some
organic polymers (e.g., chitosan) may dissolve under highly acidic
conditions, the structural breakdown of the composite material can
be accompanied with the reduction of their performance [24, 210].
For the optimal use of NMs, an accurate assessment of their
life-cycle, from synthesis to regeneration and disposal, should be
done. Unlike catalytic degradation, adsorption transfers a pollutant
from one phase (pollutant contaminating a substance) to another
phase (pollutant loaded onto a sorbent). Thus, adsorption cannot
provide complete mineralization of the pollutant, as catalytic
degradation does. Only a few studies have considered the safe
disposal or regeneration of adsorbents loaded with Cd(II) [211].
Among them, phytoremediation was one of the options considered;
the Cd(II)-loaded adsorbent was used as a fertilizer for plant growth
[211]. The Cd(II) enriched plants/trees were then used as fuel/bio-ore
in an industrial mining process. But phytoremediation and similar
options apply mainly to traditional adsorbents (zeolite, activated
carbon, and bio-char) [212]. The toxicity of the functional moieties
on modern adsorbents has not yet been fully investigated. Incineration
or pyrolysis of the spent sorbent might be required. For instance,
using pyrolysis researchers recovered > 95% of the Cd(II) from a
spent bio-sorbent [213]. This high recovery rate arose from the low
melting point (321 °C) of Cd(II), which propelled the conversion
rate of Cd(II) into its gas and liquid forms [214]. However, only a
small amount of information is available about the use of pyrolysis
to treat spent bio-sorbents [211]. Likewise, recycling strategies for
NMs used to treat Cd(II) are still in their infancy. Consequently, the
two main challenges to using NMs for the capture of Cd(II) are (a)
the high cost of nanomaterials and (b) a lack of recycling or disposal
technologies for spent sorbents.
6 Conclusions and future prospects
We organized this review article to accentuate the practical
application of NMs to remove Cd(II) ions from water. Recent years
have witnessed a prolific rise in attempts to apply nanotechnology
to water management because of the unique advantages of NMs
(e.g., tailorable functionalities, great porosity, and high specific surface
area). To this end, we described the application of both organic and
inorganic NMs to the sorptive removal of Cd(II) ions. Essentially,
the efficiency of such abatement was sensitively affected by the
combined effects of the types of functional groups present on the
NM surface and the structural characteristics of nanocomposites
(e.g., short paths for the diffusion of the pollutant). Extensive
investigations have been made to functionalize NM surfaces with
target-specific functional groups to improve the affinity of NMs for
the target pollutant and boost the sorption capacity. The specific
functional groups immobilized on the NM surface should facilitate
the abatement of Cd(II) ions, primarily through ion-exchange and
complexation reactions involving soft–soft interactions.
The synthesis of nanocomposites has been regarded as an effective
and practical strategy for boosting the regenerative and sorptive
capabilities of NMs. The use of support materials such as silica is
a highly efficient option for stabilizing NPs in the aqueous phase
by distributing the excess surface energy. Also, many support
materials (e.g., GO, which bears oxygen-rich surface functional
sites) synergistically combine with the primary NM, introducing
new functionalities and upgrading the sorption performance. Most
reported NMs outperform traditional adsorbents (e.g., zeolites
and activated clay) for the abatement of Cd(II) ions. The excellent
performance of NMs in removing Cd(II) ions from water justifies
the further research needed to enable their real-world application.
Research
14
Despite their excellent performance, NMs suffer from some
significant limitations: extremely high synthesis/operating costs,
challenges with recyclability/disposability, and the need for toxic
substances during their preparation. Most of those challenges can
be resolved through the development of advanced and economic
synthesis routes using green synthesis approaches and the
functionalization/modification of pure NMs. The technical hindrances
to the practical application of NMs for water treatment can be
overcome through active collaborations among environmental
scientists, material engineers, and chemists. Interdisciplinary research
efforts are expected to propel nanotechnology toward real-world
applications.
Acknowledgements
The authors acknowledge the support made by the R&D Center
for Green Patrol Technologies through the R&D for Global Top
Environmental Technologies funded by the Ministry of Environment
(MOE 2018001850001) as well as a grant from the National Research
Foundation of Korea (NRF) funded by the Ministry of Science, ICT
& Future Planning (No. 2016R1E1A1A01940995). This work was
also supported by “Cooperative Research Program for Agriculture
Science & Technology Development (Project No. PJ014297)” Rural
Development Administration, Republic of Korea. V. K. acknowledges
the support from the Department of Science and Technology, New
Delhi, India, in the form of an INSPIRE Faculty Award.
Notes
There are no conflicts to declare.
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