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Review
Recent progress and future challenges on the use of high performance magnetic
nano-adsorbents in environmental applications
Jenifer Gmez-Pastora, Eugenio Bringas, Inmaculada Ortiz
PII:
DOI:
Reference:
S1385-8947(14)00881-X
http://dx.doi.org/10.1016/j.cej.2014.06.119
CEJ 12376
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Accepted Date:
25 April 2014
27 June 2014
28 June 2014
Please cite this article as: J. Gmez-Pastora, E. Bringas, I. Ortiz, Recent progress and future challenges on the use
of high performance magnetic nano-adsorbents in environmental applications, Chemical Engineering Journal
(2014), doi: http://dx.doi.org/10.1016/j.cej.2014.06.119
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ABSTRACT
The application of magnetic nanoparticles (MNPs) as adsorbent materials in solving
environmental problems has recently received great attention due to their unique
physical and chemical properties, which make them superior to traditional adsorbents.
The ability of functionalization by anchoring specific functional groups on their surface
makes possible the synthesis of different types of engineered MNPs for the removal of a
large number of both organic and inorganic contaminants. However, the successful
implementation of the MNPs-based adsorption technology needs of the evaluation and
optimization of the magnetic recovery stages, the regeneration process and the
management of both the spent regeneration solution and the exhausted adsorbent. This
work presents a comprehensive review on the use of MNPs in the treatment of polluted
wastewaters with toxic metals and dyes. In addition, the magnetic recovery options and
the possible strategies that can be employed for the nanomaterials regeneration and
reuse are analyzed.
1. INTRODUCTION
In recent years, magnetic nanomaterials have attracted considerable attention because of
their unique properties that make them very useful in different fields. Magnetic
nanomaterials have at least one dimension smaller than 1 micron and are possible to be
manipulated under the influence of an external magnetic field [1]. In addition, below
certain critical dimensions, that vary with the material parameters, magnetic materials
become superparamagnetic [2,3] thus the nanomaterials exhibit no magnetic properties
upon removal of the external field and therefore have no attraction for each other,
offering the advantage of reducing risk of particle aggregation, and more importantly,
they provide a strong response to an external magnetic field [3-5].
Advances in the synthesis methods over the past decade have led to availability of
superparamagnetic nanoparticles with different shell and surface modifications [6-11].
Magnetic nanoparticles (MNPs) are generally composed of magnetic elements, such as
iron, cobalt, nickel, or their oxides like magnetite (Fe3O4), maghemite (-Fe2O3), nickel
ferrite (NiFe2O4), cobalt ferrite (CoFe2O4), etc. [4]. Usually MNPs are coated with
organic layers (e.g., surfactants or polymers such as dextran and polyethylene glycol) or
inorganic components, such as metallic elements (e.g., gold or platinum), metal oxides
(aluminum oxide, cobalt oxide), activated carbon, silica, etc. [2,7-9] in order to make
them stable against oxidation, corrosion and spontaneous aggregation, to increase their
physico-chemical stability and to provide a functionalizable surface [2].
Despite the significant advantages offered by MNPs, it was not until the last half of the
20th century when scientists began to study their characteristic behavior [3]. MNPs
exhibit great potential for their applications as catalytic materials, pigments, coatings,
gas sensors, magnetic recording devices, magnetic data storage devices, magnetic
resonance imaging, drug delivery, magnetic hyperthermia, bioseparation, etc. [1,4,5,7-
14]. On the other hand, the application of MNPs in solving environmental problems has
recently received great attention [12,15-18] due to several reasons first, the higher
economical and environmental efficacy of those processes based on the enhanced
physical and chemical properties of MNPs (i.e. high surface area, ease of
functionalization, chemical stability, etc.) [18] and second, the advantages that the
superparamagnetic behavior of MNPs provide to the design of separation and recovery
steps in complex multiphase systems [19].
The integrated design of an adsorption process based on the use of MNPs must take into
account different stages: i) adsorption separation, ii) magnetic recovery of the adsorbent
for further reuse, iii) adsorbent regeneration and, iv) management of both the spent
regeneration solution and the saturated adsorbent. Although the technical feasibility of
MNPs as adsorbent materials for water treatment processes has been widely reported in
the literature, the adsorbent regeneration stage and material reusability have received
much less attention in spite of their great importance for the process economy.
Moreover, the design of suitable magnetic separation devices, which allow the magnetic
recovery of the adsorbents should be considered as a crucial stage since it is required for
the further re-use of MNPs. Finally, the management of both the solid and liquid wastes
generated in the process by either material recovery or by final disposal is an issue of
concern which has not been previously reviewed in the literature.
Hence, this work aims at the analysis of the different individual stages taking part in the
design of MNPs-based adsorption process with the purpose of detecting their level of
development and bottlenecks thus, providing useful guidelines to conceive novel
integrated separation processes based on the use of nanoadsorbents and able to mitigate
environmental problems of concern. In particular the integration of MNPs in the design
of novel adsorption processes in either wastewater treatment or water remediation is
analyzed in this work through two different applications focused on the removal of two
groups of inorganic and organic model pollutants namely, heavy metals and dyes.
because of health concerns [32], in other regions they are still used, generating
hazardous effluents that are hardly remediated using conventional biological treatments
owing to their stability to light, heat and oxidizing agents thus being difficult to be
mineralized in conventional water treatment plants [32,33].
As consequence of the environmental hazards and health effects, drinking water and
wastewater regulations have been toughened thus promoting the development of
efficient processes able to accomplish with the concentration values imposed. Various
technologies have been developed for the removal of heavy metals and dyes from
industrial wastewater, such as coagulation/precipitation [34], ion exchange [35], solvent
extraction [36], electrodeposition [34], membrane filtration [34], electrodyalisis [37],
advanced oxidation processes [29], etc. However, the application at large scale must
face and solve many drawbacks shown by most of those methods such as their cost,
complexity, efficiency, or sludge generation [33,38]. Adsorption is considered as one of
the most promising technologies owing to its simplicity of design, ease of operation,
low cost, potential for regeneration, sludge free operation and high retention efficacy
when applied with the proper adsorbent [18,33].
MNPs have been studied as nanoadsorbent materials for heavy metals and dyes removal
and their superior characteristics in comparison with traditional adsorbents (i.e. large
surface area, high number of active surface sites, low intraparticle diffusion rate and
high adsorption capacities), make their use very promising for the treatment of polluted
waters, reducing costs and producing less contamination [39,40]. Moreover, the recent
advances in the synthesis methods allow the easy anchorage of different functional
groups on the surface of the nanoadsorbents which take part in the adsorption process as
specific binding sites, increasing the adsorption capacity and improving the selectivity
of the process for each specific pollution problem. Furthermore, their recovery can be
easily performed with magnetic separators, overcoming the pressure drop developed in
traditional fixed bed adsorption columns.
To provide a global overview of the state of the art, nearly two hundred scientific
publications dealing with the removal of heavy metals [18,19,21-24,38,40-152] and
dyes [20,26-28,30-33,39,153-188] by magnetic nanoadsorbents have been reviewed in
this work. Figure 1 shows the distribution of works classified by heavy metal (Figure
1a) and groups of MNPs (Figure 1b).
FIGURE 1 (a and b)
In the case of dyes, the number of studies related to their removal from wastewaters
using magnetic nanoadsorbents is limited. Dyes can be classified in two groups: acid or
anionic dyes, and basic or cationic dyes. Figure 2 illustrates the molecular structure of
methylene blue and methyl blue taken as model compounds of cationic and anionic dyes
mostly studied in the scientific literature focused on magnetic adsorbents.
FIGURE 2
Figure 3 shows the magnetic nanoadsorbents reported in the literature for dyes removal
and the number of reviewed studies, classified by the type of dye removed (cationic or
anionic).
FIGURE 3
TABLE 1
TABLE 2
A vast number of studies has shown the applicability of nano zero-valent iron (nZVI) as
an effective heavy metal remediation technology. Although most studies are performed
at bench scale, several pilot tests and full scale applications have been reported as well
7
[17,189]. When nZVI is exposed to air or water, it is oxidized forming a layer of iron
oxides or hydroxides on the surface that is responsible for the adsorption process
[45,46,48]. The possible adsorption mechanisms for heavy metals removal by nZVI
include adsorption and/or surface precipitation, redox reduction and simultaneous coprecipitation as metal hydroxide or metal-iron hydroxides [42,51]. This material has
been widely reported in literature for the removal of chromium and arsenic from
polluted waters. Figure 4 shows the adsorption mechanisms of Cr(VI) that is first
reduced to Cr(III) and then is incorporated to the particle surface forming a Cr-Fe
(oxy)hydroxide layer [49,51]. For arsenate, Liu et al. [44] concluded that the main
removal mechanism was adsorption onto iron corrosion products. On the other hand,
Yan et al. [41] studied the chemical transformation of arsenite and observed that nZVI
was capable of inducing As(III) oxidation and reduction, due to the core-sell structure of
nZVI. As(III) oxidation occurred at the surface of the iron oxide shell, while the
reduction process was carried out at a subsurface layer near the iron core. nZVI has
reported adsorption capacities larger than 100 mg g-1 for the removal of chromium and
arsenic compounds from synthetic waters free of competing species as shown in Table 1
[43,49,51], although the presence of humic acid and competing anions (phosphate,
sulfate, carbonate, etc.) in the solution reduces the separation efficacy [44-47,50].
FIGURE 4
Iron oxide nanoparticles such as maghemite (-Fe2O3) and magnetite (Fe3O4) have
shown great applicability in the remediation of polluted waters with metallic oxyanions,
8
like arsenate and chromate, as well as cationic metal ions, like copper, nickel, zinc, lead
or cadmium due to their high adsorption capacities and their superparamagnetic
behavior which greatly simplifies their collection from the solution under magnetic
fields. According to Chowdhury et al. [64], the surfaces of iron oxides are covered with
hydroxyl groups due to the adsorption of water molecules or by structural reasons thus
being the surface functionality modified as follows:
FeOH + H+ FeOH2 +
(1)
(2)
The surface functionality of iron oxides varies in form depending on both the type of
iron oxide (maghemite or magnetite) and the solution pH. However, the dominant
functional groups of most iron oxides surfaces are FeOH+ or FeOH2+ under acid
conditions, while Fe(OH)20, FeO- and Fe(OH)3- are the predominant forms at basic pH
values [64,135]. Therefore, iron oxide nanoparticles can interact with anionic metallic
pollutants such as arsenate and chromate oxyanions at low pH, mainly through
electrostatic interaction with the positively charged groups on the surface [65,67].
However, ion exchange mechanisms have been reported in the literature for the removal
of metallic oxyanions at high pH values [65,66]. A study carried out by Hu et al. [65]
demonstrated that the removal of chromate anions by maghemite nanoparticles at pH
values above the zero point charge (pHzpc) of the material occurred through an ion
exchange reaction between the OH- functional groups and the chromate anions
according to the following reaction:
(FeOH)2 + CrO42- Fe2CrO4 + 2OH-
(3)
On the contrary, under alkaline conditions iron oxide materials are effective in the
uptake of metal cations such as Cu2+, Ni2+, Zn2+, Pb 2+, or Cd2+ [72,66,69]. Iron oxidesbased nanomaterials have reported similar or higher adsorption capacities than nZVI
[23,68], showing successful removal efficacies in the remediation of natural waters and
real wastewaters, Table 1 [70,73]. In addition, due to their large saturation
magnetization values, they can be separated from the solution with a permanent magnet
in a relatively short time [67,74].
Different nanoscale ferrites have been also tested for the removal of metals such as
arsenic [75,78,80,81], chromium [76,77] and cadmium [79]. Among them, manganese
and copper ferrites have shown the best performance, with adsorption capacities as high
as 100 mg g-1 [81]. As reported by Tu et al [80] (See Table 1) copper ferrites have
reported high removal efficacies for the arsenate present in natural waters and real
wastewaters.
The use of bare magnetic nanoparticles for dye remediation has been scarcely reported
in the literature. However, maghemite, magnetite and ferrite nanoparticles have been
reported as novel nanoadsorbents for dyes separation. Maghemite nanoparticles have
proved to be effective material adsorbents for the removal of anionic dyes such as Acid
Red 27 and Congo red [32,39] as shown in Table 2, reaching adsorption capacities
higher than 200 mg g-1. Figure 5 shows the main removal mechanism of anionic dyes by
iron oxide nanoparticles which is the electrostatic attraction between the positively
charged surface of the maghemite (below pHpzc) and the sulfonate group of the anionic
dyes. Thus, the adsorption efficacy increased as the pH value decreased, with high
removal efficacies in synthetic waters free of competing species. However, the presence
of coexisting anions in the solution, such as sulfate and bicarbonate, significantly
reduces the separation efficacy [39]. Iron oxides have also been applied to the removal
of cationic dyes such as Neutral Red, Acridine Orange or Methylene Blue showing
promising results [31,154,155], as shown in Table 2.
10
FIGURE 5
Figure 5. Removal mechanism of anionic dyes by maghemite nanoparticles [39].
Although pure metal nanoparticles and their metal alloys are effective adsorbents, they
suffer the disadvantage of having low stability in suspension medium, affecting the
long-term performance and applicability of the separation process. The most
straightforward strategy to make them stable against oxidation, corrosion and
spontaneous aggregation is their coating with organic or inorganic materials. This
protection method results in MNPs with a core-shell structure [7]. In general, the
external coating also extends the possibility of surface functionalization thus increasing
the adsorption capacity and selectivity towards the target pollutants. On the other hand,
the mass ratio between the magnetic core and the non-magnetic shell should be
controlled to preserve the magnetic properties (e.g. magnetic saturation) of the
composite material which are essential in the magnetic recovery stage.
Natural organic macromolecules, mostly biopolymers such as chitosan, cyclodextrin,
arabic gum, kondagogu gum, alginate, etc. are used as effective coatings due to the
presence of different functional groups in their structure which provides them high
capacity and selectivity towards heavy metals and dyes. Among these coatings, chitosan
is probably the best example being widely used in many studies.
Chitosan (poly--(14)-2-amino-2-deoxy-D-glucose) is a natural polysaccharide
produced by the N-deacetylation of chitin [21]. This biopolymer possesses good
sorption capacity for several heavy metal ions and almost all kinds of dyes due to its
high amino content on the polymer matrix which provides selectivity to the adsorption
process [89,92,159]. To improve its chemical stability in acid media, chitosan is usually
cross-linked introducing another compound (e.g. glutaraldehyde, ethylenediamine, 11
cyclodextrin, epichlorohydrin, etc.) into the chain [21,159,163]. However, the coating of
magnetic materials by non-magnetic polymeric compounds decreases the saturation
magnetization value (since this property is defined on a per gram basis), and therefore
polymer coatings adversely affect the magnetic separation performance.
The amino and hydroxyl groups within the structure of chitosan can interact with heavy
metals by ion exchange or complexation reactions [21,91], although electrostatic
interactions can also contribute to the metallic removal [90]. Xiao et al. [91] studied the
removal mechanisms of dichromate and copper by MnFe2O4@Chitosan and their results
suggested that the chelation between chitosan and metal ions played a much important
role than the electrostatic interactions in the process. They also carried out competitive
adsorption experiments of Cu2+ and Cr2O72- by MnFe2O4@Chitosan leading to the
conclusion that the affinity of the adsorbent towards copper is much higher than the
observed towards chromium. According to the hard and soft acids and bases theory
introduced by Pearson in 1963, amino and hydroxyl groups (hard bases) form a stable
complex with hard Lewis acids such us Cr3+, Co 3+, As3+, Cr6+, Co2+, Ni2+, Cu 2+, Zn2+,
Pb2+ etc. [190]. Thus, the functional groups located on the surface of the adsorbent are
hard bases and tend to form strong bonds with hard acids such as the copper cation.
Nevertheless, chitosan coated MNPs have proved to be effective adsorbents for the
removal of metallic oxyanions too. For example, Gupta et al. [89] applied nZVI coated
with chitosan to the removal of arsenite and arsenate attaining maximum adsorption
capacities ranging from 94 to 119 mg As g-1 as shown in Table 1. Also, the adsorbent
was capable of operating in a wide range of pH values and interfering species like
sulfate, silicate or phosphate marginally affected the adsorption performance, reducing
the total arsenic concentration down to the World Health Organization drinking water
standards (10 g L-1) for arsenic contaminated natural groundwater.
12
Chitosan and chitosan derivatives coated MNPs have been successfully applied for acid
dyes such as Acid Orange 7 and 10, Alizarin Red, Methyl Blue, Crocein Orange G,
Acid Green 25, etc., showing adsorption capacities larger than 3000 mg g-1 as depicted
in Table 2, and, in comparison with traditional adsorbents, these nanocomposites have
reported higher adsorption capacity and faster adsorption rate of anionic dyes
[157,159,160,163]. The main removal mechanism is expected to be electrostatic
attraction at low pH [162]. The amino groups of chitosan are easily protonated under
acidic conditions, thus binding anionic dyes through ionic interaction with the sulfonate
groups of these dyes [160,163], according to the following reactions:
MNPs@Chitosan-NH2 + H+ MNPs@Chitosan-NH3 +
(4)
(5)
Besides chitosan, other organic coatings based on natural or synthetic polymers such as
cyclodextrins, arabic gum, kondagogu gum, alginate, poly-L-cysteine, polyacrylic acid,
polysiloxanes, polypyrrole, polyrhodanine, poly(-glutamic acid), etc. have reported
good results as heavy metal and dyes adsorbent materials due to the high content of
functional groups on their structure including hydroxyl, carboxyl, amine, ether, acetyl,
aliphatic, carbonyl, thiol, sulfur, oxygen and nitrogen groups [19,94-101,164-171]. The
performance of these polymers and other organic coatings, mainly surfactants and
organic acids, is summarized in Tables 1 and 2.
Inorganic coatings without further functionalization have been scarcely applied for
heavy metal and dye remediation. Only few studies reported the use of unmodified
inorganic compounds as coating materials and most of them are based on metal oxides
or activated carbon. In general, inorganic coatings need of further surface
functionalization to create specific binding sites improving the selectivity of the
adsorption processes. Mesoporous silica is one of the most promising coating materials
13
since it provides high adsorptive surface area with well-defined pore size and shape,
avoids the magnetic attractions between magnetic nanoparticles and protects the inner
magnetic core from leaching at low pH values [134,137,139,187]. In addition, the
existence of a uniform distribution of silanol groups on the silica surface facilitates the
grafting of selective functional groups [137,184]. Although silica by itself exhibits some
interesting applications, including the removal of harmful dyes from wastewater [186],
in order to achieve higher adsorption capacities and selectivities towards heavy metals
and dyes, various functional groups have been used to modify the surface of either
coated or uncoated MNPs.
Amine-functionalized silica coated magnetic nanoparticles (MNPs@SiO2-NH2) and
amine functionalized MNPs (MNPs-NH2) have demonstrated outstanding capability to
remove a wide variety of heavy metals [132,133,136]. The removal mechanisms of
heavy metals by amine-functionalized nanoadsorbents include electrostatic interactions,
ion exchange and coordination interactions due to the metal complexing capability of
amino groups [130,138]. In most cases, the removal efficiency is pH dependent. Heavy
metal cations are preferentially adsorbed at high pH values due to the deprotonation of
the amine groups, while anionic species are removed from the solution in acidic
conditions owing to the protonation of the functional groups at low pH values
[130,135,136].
As the amino groups serve as chelation sites, it is expected that the higher the content of
amino groups on the surface the higher the adsorption capacity. However, it has been
found that sorption capacities are not always proportional to the number of surface
functional groups. In fact, a study carried out by Chung et al. [139] (Table 1)
demonstrated that high amine density on silica coated magnetite nanoparticles had an
adverse effect on the sorption process of Pb2+ and Cu2+ cations. They observed that di-
14
and triamino groups caused pore blockage and limited the mass transfer into the silica
mesopores and found that the available adsorptive sites decreased due to changes in the
surface charge.
Although the presence of competing ions in the solution can negatively affect the
adsorption performance of the target metals [134], amine functionalized MNPs have
reported good performance in treating natural waters and industrial wastewaters. Tan et
al. [40] (Table 1), used Fe3O4-NH2 nanoparticles for the removal of Pb(II) from
industrial wastewater and tap water spiked with 1 mg L-1 of Pb(II), and the removal
efficacies obtained were about 98% and hardly influenced by the water matrix.
As amine functionalization, thiol-functionalized magnetic mesoporous silica
(MNPs@SiO2-SH) and thiol-functionalized MNPs (MNPs-SH) have been considered
promising materials in heavy metal remediation by many authors [143-145]. Thiolfunctionalized MNPs have been successfully employed in the removal of divalent heavy
metal cations, mainly Hg2+ and Pb2+ ions as shown in Table 1. According to Pearsons
theory, thiol groups show high affinity towards soft acids, such as Cd2+ and Hg2+ [190].
In fact, numerous studies reveal that thiol functionalized MNPs have exerted good
adsorption for Hg2+ [144,146], even in natural waters [142,145,147]. Therefore, it is not
surprising that thiol based magnetic nanoadsorbents have been presented as an
alternative treatment technology for mercury polluted waters since their adsorption
capabilities have proved to be superior to other commercial adsorbents [142].
Amino-functionalized silica coated magnetic nanoparticles (MNPs@SiO2-NH2) have
been tested as well for the separation of acid dyes such as Acid Orange 10 and Congo
Red, as is illustrated in Table 2 [184,185]. The removal mechanism of dyes by aminefunctionalized nanoadsorbents is electrostatic attraction, being the removal efficacy pH
dependent [184]. For removal of basic dyes, the use of carboxylic functionalized silica
15
coated MNPs has exhibited high adsorption capacity and rapid adsorption rate for
Methylene Blue and Acridine Orange [186].
From the analysis reported above it is concluded that the integration of MNPs in
environmental technologies offers many advantages owing to their high affinity towards
both organic and inorganic pollutants and their superior characteristics in comparison
with traditional adsorbents. In fact, the ability of functionalization by anchoring specific
functional groups on their surface makes possible the synthesis of different engineered
nanoadsorbents for the removal of a broad range of contaminants. In particular, coated
and functionalized MNPs have shown excellent structural and chemical characteristics
to carry out the removal of heavy metals and dyes from aqueous solutions, reporting
lower adsorbent doses and faster adsorption kinetics in comparison with bulk adsorbent
materials. However, the main benefit of employing MNPs, which is related to the
potential handling of these materials by the application of external magnetic fields, is
rarely discussed in the literature that is mainly focused on the synthesis and
performance of the magnetic nano-adsorbents. The following section analyzes the state
of the art on the design of magnetic separators.
16
solid suspension contact requires the separation of the adsorbent from the solution when
either the adsorption or the desorption stage are concluded. In comparison with nonmagnetic nanoparticles, where the separation is a difficult task owing to their small size,
the main advantage of MNPs materials is their magnetic nature, which greatly simplifies
their collection by applying an external magnetic field.
The manipulation of nanoparticles by the use of magnetic fields, which is called
magnetophoresis, has attracted great attention in recent years due to the high potential of
nanotechnologies and the several advantages offered by magnetic systems. On the one
hand, magnetic separation is more selective, efficient and generally much faster than
centrifugation or filtration processes which are conventionally applied for solid-liquid
separations [191]. On the other hand, the use of an external magnetic field provided by a
permanent magnet requires no power consumption. Furthermore, magnetic separations
are less sensitive to factors such as surface charge, pH and ionic concentration [192].
The motion of MNPs in a fluid under the influence of an applied magnetic field is
affected by several factors, including the magnitude and the gradient of the applied
magnetic field, the fluidic drag, gravity and buoyancy forces, particle-fluid and particleparticle interactions, etc. [193]. All these factors, which in turn will depend on the
operation conditions and the particle parameters, should be taken into account for the
selection and design of the magnetic separator.
As mentioned previously, the particles employed in these applications are usually
superparamagnetic, with diameters ranging from a few tens to hundreds of nanometers.
Since the magnetic force is proportional to the particle volume, MNPs with larger
diameters are preferred [194]. However, it is necessary to balance this increase on the
magnetic recovery efficacy with the reduction on the surface area, which implies a
reduction on the adsorption performance.
17
The recovery of MNPs by the use of magnetic gradients has been widely reported in the
literature [195]. Traditionally, the separation of magnetic materials is carried out by
batch magnetic filters (High Gradient Magnetic Separators, HGMS) where the particle
suspension is pumped through a column filled with ferromagnetic filaments. These
wires generate the high magnetic gradients inside the separator when an external
magnetic field is applied, producing large field gradients around the wires that attract
and trap the MNPs to their surfaces, as is depicted in Figure 6 [196-198]. MNPs will be
efficiently separated if the magnetic force, which attracts the particles to the filaments,
dominates the fluid drag, gravitational, inertial, and diffusional forces which act on the
MNPs as the solution flows through the column [197]. This technology has
demonstrated to be able to capture MNPs with sizes larger than 10 nm [198].
FIGURE 6
However, the most important disadvantage of the HGMS is the uncertainty over the
magnetic conditions under which the MNPs are separated, due to the inhomogeneous
magnetic gradients generated inside the column. This uncertainty results in a limited
comprehension of the magnetophoretic mechanisms and restricts the modelling and
optimization of the separation process [196,198]. In addition, there is a high risk of
particle aggregation on the surface of the wires, which could reduce the available
adsorptive surface area of the MNPs decreasing the adsorption performance in
following cycles, or even could permanently retain the materials in the column. In fact,
a study carried out by Mayo et al. [199] demonstrated that Fe3O4 nanoadsorbents that
18
were used for arsenic removal, could not be recovered from the HGMS filter, which was
employed after the sorption process. The commercial adsorbents used were irreversibly
adsorbed to the column packing, and could not be released when the magnetic field was
turned off, because their size (20 nm) and their agglomeration promoted a large
magnetic moment that provided a remanent magnetization at zero fields.
The next section analyses the potential regeneration and reusability of MNPs employed
in the removal of metallic pollutants and organic dyes from wastewaters. In addition,
the management of both the spent regeneration solutions and the loaded adsorbent
materials is also highlighted.
19
large number of sorption studies available in the literature dealing with the use of
nanoparticles for the removal of heavy metals and dyes, desorption and reuse of the
adsorbents has not been accurately analyzed.
The selection of a suitable eluent depends on the adsorbate and the adsorbent, but other
operation variables, such as pH, temperature, contact time between the solid and liquid
phases and the presence of competitive ions in the solution, may also affect the efficacy
of the desorption process [129]. However, the desorption efficacy might be enhanced by
gaining insight into the adsorption mechanisms [200]. Particularly, the desorption of
heavy metals and dyes from loaded adsorbents has been carried out with different
solutions, being most of them selected according to the influence of the pH value on the
adsorption process. Figures 7 and 8 depict a classification of the regeneration studies
that have been reported in the literature dealing with the desorption of heavy metals and
dyes from loaded MNPs, respectively. These figures show the number of regeneration
studies related to each pollutant and the eluent employed in the desorption stage. Also,
Table 3 summarizes the most relevant information obtained from those applications,
such as the adsorbent used, the target pollutant, the regeneration solution employed in
the desorption stage, the re-adsorption capacity and the number of cycles that the MNPs
could be reused in each specific case.
Table 3. Desorption and reusability of MNPs for heavy metals and dyes removal.
TABLE 3
Aqueous solutions of sodium hydroxide and strong acids are the most commonly used
regeneration solutions to elute heavy metals from loaded MNPs, as shown in Figure 7.
Since in most of the studies previously reported the adsorption of heavy metals is pH
20
dependent, the desorption stage is usually carried out by controlling the pH of the
eluent. Reverse to the adsorption process, metallic oxyanions are usually desorbed with
basic solutions, being NaOH the most preferred desorption agent in most of these
studies, as depicted in Figure 7a for arsenic and chromium. NaOH solutions with
concentrations ranging from 0.01 to 0.1 mol L-1 have been successfully applied in the
regeneration of MNPs loaded with heavy metal anions with no appreciable loss in the
sorbent capacities as reported in Table 3 [65,74,76,81]. The reusability of the materials
regenerated with NaOH solutions has been demonstrated in some of the related studies
during successive adsorption-desorption cycles [67,89,108,128,129]. Hu et al [66]
analyzed the desorption of chromate anions from loaded maghemite nanoparticles using
different basic eluents (NaOH, NaHCO3, Na3PO4, etc.) concluding that the most
effective agent was 0.01 mol L-1 NaOH. Besides, the CrO42- adsorption capacity of the
regenerated MNPs remained almost constant after six cycles, and the chromate ions
were concentrated 10 times during the regeneration process into a smaller volume.
On the other hand, the regeneration of the MNPs loaded with heavy metal cations is
normally conducted with acid solutions. As presented in Figure 7b, desorption eluents
based on HNO3 and HCl are widely reported in the literature due to their high
desorption efficacies [116,125,134,137]. Hao et al [22] (Table 3) employed Fe3O4-NH2
nanoparticles for the removal of Cu(II) ions being the reusability of the adsorbent
studied during successive sorption-desorption cycles. The results indicated that Cu(II)
ions could be desorbed completely in 1 minute in the presence of 0.1 mol L-1 HCl and
no differences in the adsorption capacity of the adsorbent were observed after 15 cycles
of operation. However, the use of strong acids is limited by the possible damage caused
to the adsorbent material since it promotes the magnetic core dissolution, especially for
bare magnetic nanoparticles. To avoid this problem, ethylendiamine tetraacetic acid
21
(EDTA), which is a very strong chelating agent for many heavy metal ions, could be
used as the eluent for metal cations desorption [92]. The use of EDTA solutions has
exhibited similar or superior desorption performance in comparison with strong acids
such as HCl or HNO3 for MNPs regeneration, as reported in Table 3 [38,92,136].
FIGURE 7
Figure 7. Regeneration solutions reported in the literature for anionic (a) and cationic
metallic pollutants (b).
Regarding dyes, acid or basic organic solutions using methanol (MetOH) or ethanol
(EtOH) as solvents are usually reported in the literature for the MNPs regeneration step
as reported in Figure 8, since these pollutants are easily dissolved in organic solvents.
Considering that most of dyes are adsorbed onto MNPs through electrostatic interaction,
the dyes desorption is successfully achieved by changing the pH of the solution. For
desorption of cationic/basic dyes, acid solutions with concentrations of 4-6% (v/v)
acetic acid in methanol (HAcMetOH) have reported high regeneration capacities of the
nanoadsorbents, with desorption percentages ranging from 80 to 100%
[27,155,164,171]. In addition, the reusability studies carried out suggest that the
adsorption capacity of the nanoadsorbents had no significant loss after being recycled
several times using these eluents (see Table 3) [27,165,174]. The regeneration study
carried out by Afkhami et al. [20] showed that, for Brilliant cresyl blue desorption from
sodium dodecyl sulfate coated maghemite nanoparticles, a mixture of acetic acid in
methanol could completely desorb the cationic dye from the loaded MNPs. Also, the
reusability of the adsorbent was longer than 15 cycles without any loss in its sorption
22
capacity. Besides HAcMetOH, HCl aqueous solutions (HClaq) and HCl ethanolic solutions
(HClEtOH) have reported good desorption performance for cationic dyes as shown in
Table 3 [168,175,177,186].
To elute anionic/acid dyes from exhausted MNPs, different eluents have been tested
showing the NaOH aqueous solutions (NaOHaq) and NaOH ethanolic solutions
(NaOHEtOH) higher desorption efficacy compared to other eluents [20,39,159,177].
Regeneration solutions based on NaOH, at concentrations ranging from 0.001 to 2 mol
L-1, have reported desorption efficacies ranging from 80-100% with negligible loss of
the materials properties through successive adsorption-desorption cycles
[159,162,184,185]. As representative example Fan et al [160] reported that the
desorption efficacy of Alizarin Red from loaded Fe3O4@Chitosan was higher than 90%
using 0.1 mol L-1 NaOHaq as eluent. Also, the adsorption percentages obtained with the
regenerated MNPs remained constant at 90% after 5 cycles of operation. Anionic dyes
have also been desorbed using basic solutions of NH4OH/NH4Cl in methanol as
illustrated in Figure 8, maintaining the adsorbent its initial adsorption capacity in
successive cycles [163,176].
FIGURE 8
Figure 8. Regeneration solutions reported in the literature for the anionic and cationic
dyes desorption stage.
As seen in Figure 8, in some of the reviewed works the desorption process of cationic
and anionic dyes was successfully carried out with pure methanol (MetOH)
[30,156,172,173,187]. As reported in Table 3, methanol solutions have been employed
23
to desorb Thionine and Janus Green (as models of cationic dyes) from chitosan coated
magnetite nanoparticles with regeneration percentages ranging from 93 to 97%, with a
negligible reduction of the adsorption capacity after 15 adsorption-desorption cycles
[20]. Besides the pH conditions, it has been demonstrated that high ionic strength of the
regeneration solution positively affects the desorption process [157].
The analysis reported above leads to the conclusion that the regeneration of magnetic
nanoadsorbents loaded with cationic or anionic metallic pollutants has been performed
with aqueous solutions of acids or bases, respectively. In the case of dye removal, acid
or basic solutions in alcohols such as ethanol or methanol have been reported as
effective regeneration solutions. Although most of the regenerated materials keep their
adsorption capacity, the concentration of the regeneration agent and the contact time
during the desorption process should be controlled to avoid modifications of the
morphological and chemical structure of the MNPs.
In spite of the adsorbent regeneration benefits the long-term performance of adsorption
processes, the desorption process generates waste solutions containing the pollutant in a
concentrated form, which have to be managed. On the other hand, the reusability of the
material may be limited because the nanoadsorbents generally loss their adsorptive
abilities after multiple cycles, generating a solid waste which needs also to be handled.
Different end-of-life scenarios for the aforementioned wastes are presented in the
following sections.
24
very few works have addressed the management of the spent desorption solutions.
There are three main alternatives for handling these effluents: i) the recovery of the
desorbed species from the eluent solutions for reuse, ii) the degradation of the pollutant
by destructive technologies such as incineration and, iii) the disposal of the solution
after its treatment by solidification/stabilization process.
In the case of heavy metals, the recovery and purification processes could be a
promising alternative for those materials with relatively high market prices such as
nickel, copper, palladium, platinum, etc. Different technologies have been reported in
the literature for the recovery of heavy metals from various liquid wastes including ion
flotation, electrodeposition, electrodialysis, membrane-based solvent extraction, etc.
[201-203]. The technology chosen depends on several factors, such as the composition
of the solution, the initial concentration of the material to be recovered, the capital
investment, the operational cost, etc. Ion flotation may be a promising technology for
the recovery of heavy metal ions from dilute solutions such as regeneration solutions,
where the metal concentration is in the order of mg L-1. This process involves the
addition of a surfactant into the solution, which is attached to the metal ions by
electrostatic or chelating interactions, and then both are separated due to the creation of
a foam phase when a gas is sparged into the mixture [201]. The surfactant can be later
recovered and recycled [202]. This technology has been successfully applied for the
recovery of nickel, cadmium, zinc, copper, etc. On the other hand, electrodeposition
could be also applied for the recovery of valuable metals from desorption solutions.
This technology has been able to recover zinc and manganese from chloride media with
conversion values close to 100% and current efficiencies as high as 90% [204,205].
Although these technologies have not been widely studied for the recovery of valuable
compounds from desorption solutions, these methods are considered as an attractive
25
option for the management of these wastes because they not only provide an interesting
alternative from the economic point of view generating a marketable product, but also
avoid environmental problems associated to the solution disposal, contributing to
resource and environmental sustainability at the same time.
In the case of more problematic metal wastes like arsenic, where recovery is not
profitable owing to its limited markets and other conventional treatment methods such
as incineration are not feasible because of the possible escape into the atmosphere of
hazardous products, an alternative method is the material encapsulation through
solidification/stabilization (S/S) processes followed by the disposal in secure landfills
[200,206,207]. The S/S methods aim to make hazardous liquid/solid wastes safe prior to
disposal. Several studies reported the incorporation of hazardous wastes such as arsenic
into storable solids through different S/S processes, being the cement-based S/S process
the technology mostly investigated, because it seems to be the most successful
technique [206]. In addition, the treated wastes can be incorporated into bricks or
concrete for construction purposes [208].
Regarding dyes desorption solutions, various authors have proposed thermal methods
such as distillation or evaporation to the recovery of the different components of the
regeneration solutions [154,174]. For eluents based on organic solvents such as acetone
or methanol, which have a low boiling point (56 and 65C respectively), these
technologies can be straightforward methods for the recovery of dyes, and also the
regeneration media for recycling purposes. However, these technologies are
energetically expensive, and the recovery and purification processes are not always
economically feasible. In those cases, degradation processes are mostly preferred.
However, most dyes are persistent organic molecules and conventional methods such as
biological degradation are not effective, and destruction methods such as incineration
26
are not appropriate solutions for treating chloride-containing dyestuffs owing to the
possible production of dioxins and furans, which remain during the process as thermally
persistent species [209]. An attractive approach to decolorize those solutions may be the
application of electrochemical technologies including electrocoagulation and
electrochemical oxidation, which have been considered as cost-effective dye treatment
methods in different works [210,211]. Electrochemical oxidation, which is considered
the most popular electrochemical method for degrading organic compounds, has been
able to completely remove a wide variety of dyes from dilute solutions in short times
with current densities ranging from 0.5 to 50 mAcm-2 [211]. Also, in the case of
chloride-containing solutions, such as the HCl based eluents, the presence of chloride
anions in the solution promotes the electrogeneration of active chlorine species such as
hypochlorite ions, which reduce the electrolysis time and enhance the dye oxidation
capability of these systems [211,212]. Although these techniques have not been directly
employed to remove organic dyes from desorption solutions, their integration with the
adsorption technology could lead to a more sustainable process.
27
The management of the exhausted MNPs is an issue, which has been scarcely studied.
However, MNPs may have some potential risks to humans, environment and biological
systems, owing to their mobility and their increased reactivity, and therefore, the
management of these materials should be taken into consideration. Since nanoparticles
can interact with the environment through multiple ways and can alter the behavior or
react with a variety of chemicals, their handling and management must be controlled to
ensure the environmental welfare.
Little information is available in the literature on how to handle discarded nanoparticles.
The best end-of-life scenario is the recycling of the nanomaterials [15]. This approach
has been considered for noble-metal nanoparticles due to their high prices [213]. Other
methods which have been suggested to handle nanomaterial wastes include their storage
or destruction. Storage of MNPs should be carried out in a safe manner to avoid the
release of MNPs into the environment, and it should be noted that standard tests, which
are suitable for normal wastes to predict the fate of the materials disposed in landfills, in
this case are not applicable owing to their different behavior [214]. On the other hand,
destruction of MNPs by irreversible aggregation or dissolution could be an efficient
way to recover or process the materials in a conventional way [213].
However, any approach proposed for the management of these wastes requires
understanding of their chemical, physical and biological properties [213,214]. Much
work is still needed to understand the potential risks and toxicity of these materials and
although they have not been classified as hazardous wastes by the actual regulation, it is
essential to set specific legislation for their proper disposal [1,215].
The previous sections discussed the benefits and limitations of employing nanoadsorbents to tackle environmental problems taking into account the management of
both the spent regeneration solutions and the spent adsorbents.
28
29
such as maghemite and magnetite) to 2255 $/kg (for nZVI) [54], which are higher than
the cost of novel adsorbents based on agricultural or industrial wastes. However, it
should be noted that the cost per volume of treated water could be lower due to several
reasons. On the one hand, since both the required dose of the MNPs and the time
needed to carry out the separation are very low, the volume of treated water will be
much greater for MNPs than for other methods when using the same amount of
materials. On the other hand, the reusability of the MNPs could be satisfactorily carried
out with a simple regeneration step, unlike other adsorbents, and thus the cost of the
treatment would be reduced. Also, due to the small amounts of the material used, the
wastes generated during the desorption stage and those due to the exhausted MNPs will
be minimal in comparison with the use of other materials. This work also promotes the
so called zero-discharge processes, through the use of MNPs coupled with other
technologies, aiming to recover marketable products from the regeneration solutions,
thus being the global process more sustainable. Finally, although direct comparison is
not possible due to the different working conditions, it should be noted that low cost
adsorbents are generally effective in the removal of pollutants whose permissible limits
are at milligram per liter level. On the contrary, MNPs have reported outstanding
capability for removing hazardous contaminants with permissible levels in the order of
microgram per liter [15]. For these reasons, the use of MNPs in adsorption processes
seems to be environmentally and economically beneficial.
6. CONCLUSIONS
Water pollution by inorganic and organic compounds such as heavy metals and dyes has
become a serious problem because of their extremely hazardous effects on humans and
the ecological systems. The use of MNPs as adsorbent materials for environmental
30
remediation has a great potential due to their superior physical and chemical properties
in comparison to bulk materials. The easy functionalization of MNPs allows the
synthesis of specific nanoadsorbents to perform the selective removal of a large variety
of pollutants. However, the regeneration process of loaded MNPs that needs of a first
step for the recovery of the MNPs and the final management of both the spent
regeneration solution and the exhausted adsorbent are crucial stages that should be
evaluated in order to bring the MNPs-based adsorption technology a step forward. For
the first time, in this work the viability of these individual stages is reviewed and
analyzed in order to contribute to the development of novel integrated separation
processes based on the use of nanoadsorbents.
As illustrated in this review, the use of engineered MNPs for heavy metals and dyes
removal has numerous benefits including higher adsorption capacities and faster
removal rates in comparison to traditional sorbent materials. In addition, the magnetic
separation alternatives are presented, showing the advantages and limitations of
conventional separators. Also, the regeneration of MNPs for further reuse can be
successfully achieved by adequately contacting the MNPs with the proper eluent.
Moreover, the management alternatives of both the solid and liquid wastes generated in
the process by either material recovery or final disposal are reviewed, promoting the
zero-discharge processes for ensuring the environmental welfare.
Concluding, there is a growing interest in the use of MNPs for environmental
remediation. However, the application of MNPs in environmental technologies is still in
the early stage and much work is still needed for the establishment of the
nanotechnologies. Nevertheless, the future problems related to poor water quality and
water scarcity in many countries of the world make their future quite promising. In this
regard, this work aims to provide valuable guidelines to accomplish the successful
31
ACKNOWLEDGEMENTS
Financial support from the Spanish Ministry of Economy and Competitiveness under
the project CTQ2012-31639 (FEDER 2007-2013) is gratefully acknowledged.
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57
Figure captions:
Figure 1. Literature references focused on the removal of heavy metals by adsorption
with MNPs: a) number of references per heavy metal; b) percentage of references per
type of material.
Figure 2. Molecular structure of methylene blue and methyl blue.
Figure 3. Studies about the removal of dyes with MNPs.
Figure 4. Removal mechanisms of hexavalent chromium by nZVI [51].
Figure 5. Removal mechanism of anionic dyes by maghemite nanoparticles [39].
Figure 6. MNPs capture by HGMS filter [197].
Figure 7. Regeneration solutions reported in the literature for anionic (a) and cationic
metallic pollutants (b).
Figure 8. Regeneration solutions reported in the literature for the anionic and cationic
dyes desorption stage.
Figure descriptions:
Figure 1
Figure 1 shows a statistical distribution of nearly 100 scientific publications dealing
with the removal of heavy metals by magnetic nanoparticles. These works have been
classified by heavy metal (Figure 1a) and groups of MNPs (Figure 1b).
Figure 2
58
Figure 2 schematizes the molecular structure of methylene blue and methyl blue taken
as representative model cationic and anionic dyes mostly studied in the scientific
literature focused on magnetic adsorbents.
Figure 3
Figure 3 shows the magnetic nanoadsorbents reported in the literature for dyes removal
and the number of reviewed studies, classified by the type of dye removed (cationic or
anionic).
Figure 4
Figure 4 shows the possible removal mechanisms for heavy metals (in this case
hexavalent chromium) by nano zero-valent iron (nZVI). These mechanisms include
adsorption and/or precipitation followed by reduction and simultaneous co-precipitation
as metal hydroxide or metal-iron hydroxides. The figure also intends to provide a
description of the nZVI particle structure.
Figure 5
Figure 5 represents the removal of anionic dyes by maghemite nanoparticles. This
removal mechanism is based on the electrostatic attractions between the positively
charged surface of the maghemite (below pHpzc) and the sulfonic group present in
anionic dyes.
Figure 6
Figure 6 represents the recovery of MNPs by the HGMS (High Gradient Magnetic
Separator) filter. In this case, the MNPs suspension is pumped through a column filled
with ferromagnetic filaments, which generate the high magnetic gradients inside the
59
separator when an external magnetic field is applied, producing large field gradients
around the wires that attract and trap the MNPs to their surfaces.
Figure 7
Figures 7 depicts a classification of the regeneration studies that have been reported in
the literature dealing with the desorption of heavy metals from loaded MNPs. This
figure shows the number of regeneration studies related to each pollutant and the eluent
employed in the desorption stage.
Figure 8
Figures 8 depicts a classification of the regeneration studies that have been reported in
the literature dealing with the desorption of dyes from loaded MNPs. This figure shows
the number of regeneration studies related to each pollutant and the eluent employed in
the desorption stage.
60
Figure 1A
Figure 1B
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Adsorbent
Material characteristics
Surface
Saturation
Size
area
magnetization
(nm)
(m2 g-1)
(emu g-1)
pHz
pc
Target heavy
metals
nZVI
60
Cr(VI)
nZVI
56
7.8
As(III),
As(V)
-Fe2O3
7-12
168.73
54.197
Superparamagnetic
As(III),
As(V)
-Fe2O3
nanotubes
250
321.63
8
68.7
Superparamagnetic
6.8
Cu(II),
Zn(II), Pb(II)
Fe3O4
8-35
46-190
6.46.8
Cd(II),
Cr(VI),
Cu(II), Ni(II)
Fe3O4
19.3
60
6.47.2
As(III),
As(V)
Fe3O4-Fe2O3
mixture
4-52
9.8351.9
8-67
Ferromagnetic
5-7
Pb(II),
Cr(III),
Cd(II)
Ref.
[49]
[43]
[67]
[71]
[72]
[73]
[23]
CuFe2O4
20120
48.3
62.52
Superparamagnetic
7.3
As(V)
[As(V)]=100 mg/L;
[MNPs]=2 g/L;
pH=3.7; T=27C;
[As]=1 mg/L;
[MNPs]=5 g/L;
pH=7; T=25C;
nZVI@Chit
osan
69
As(III),
As(V)
Fe3O4@
Chitosan
25
74
Ferromagnetic
Pb(II),
Cd(II), Cu(II)
31.6 Pb(II);
30.7 Cd(II);
29.7 Cu(II);
[85]
64.5 Pb(II);
27.7 Cd(II);
13.2 Ni(II);
[19]
[Cu(II)]=200 mg/L;
[MNPs]=5 g/L;
pH=5.1; T=27C;
38.5
[95]
[99]
[100]
Fe3O4@
Carboxymet
hyl-cyclodextrin
8-15
Superparamagnetic
4.4
Pb(II),
Cd(II),
Ni(II)
Fe3O4@Gu
m arabic
13-67
3.6
Cu(II)
Cd(II),
Cu(II),
Pb(II), Zn(II),
Ni(II), Hg(II)
3.5
Hg(II),
Cd(II),
Cr(III),
Mn(II)
[Hg(II)]=80 mg/L;
[MNPs]=0.5 g/L;
pH=4; T=25C;
Fe3O4@Gu
m
kondagogu
-Fe2O3@
Polyrhodani
ne
8-15
10
60
Ferromagnetic
94.65
28
Ferromagnetic
45.66
94 As(III);
119 As(V)
106.8 Cd(II);
85.9 Cu(II);
56.6 Pb(II);
37 Zn(II);
49 Ni(II);
35 Hg(II);
133 Hg(II);
19.4 Cd(II);
9.9 Cr(III);
8.8 Mn(II);
[80]
[89]
46.3 Cu(II);
50.4 Cd(II);
92.4 Pb(II);
97.7 Hg(II);
[106]
Fe3O4@
Humic acid
140
64
68.1
Hg(II),
Pb(II),
Cd(II), Cu(II)
Fe3O4@SiO
2-NH2
270
159.3
31.9
Superparamagnetic
9.9
Pb(II), Cd(II)
[Metal ions]=26.8-49.7
mg/L; [MNPs]=0.1 g/L;
pH=5.5; T=25C;
128.21 Pb(II);
51.81 Cd(II);
[136]
Fe3O4@SiO
2-Mono-,
Di-, Triamine
17.7
89.6165.1
14.5
Superparamagnetic
4.810
Pb(II),
Cu(II)
190.5-222.4
Pb(II);
50.6-57.9
Cu(II);
[139]
Fe3O4-NH2
50100
5.8
Pb(II)
40.1
[40]
Fe3O4-NH2
100
25.94
Cu(II),
Cd(II),
Pb(II)
523.6 Cu(II);
446.4 Cd(II);
369.0 Pb(II)
[133]
Fe3O4@SiO
2-SH
500
321
Hg(II), Pb(II)
260 Hg(II);
91.5 Pb(II);
[145]
Fe3O4@SiO
2-SH
111
<2
Hg(II)
207.7
[147]
861
6.87
Superparamagnetic
Hg(II),
Pb(II),
Cr(III),
Cu(II),
Zn(II), Ni(II)
256.76 Hg(II);
[146]
Fe3O4@SiO
2@SiO2-SH
100
77.32
Superparamagnetic
75
Superparamagnetic
38.4
Superparamagnetic
[Pb(II)]=10 mg/L;
[MNPs]=0.1 g/L;
pH=5; T=25C;
[Metal ions]=5 mg/L;
[MNPs]=0.2 g/L;
pH=7; T=room;
[Metal ions]=1 mg/L;
[MNPs]=0.01 g/L;
pH=6.5; T=25C;
[Hg(II)]=0.08 mg/L;
[MNPs]=0.008 g/L;
pH=6; T=22.5C;
[Metal ions]=94-110
mg/L; [MNPs]=5 g/L;
T=room;
Fe3O4-SH
5.8
114
Superparamagnetic
Hg(II), Pb(II)
Fe3O4@CN
50
12.1
Superparamagnetic
Cr(III)
227 Hg(II);
[142]
638.51
[150]
Adsorbent
Material characteristics
Surface
Saturation
Size
area
magnetization
(nm)
(m2 g-1)
(emu g-1)
pHzpc
Target dyes
6.3
Congo red
-Fe2O3
45
81.61
Fe3O4
8.323
1540
100
Methyl blue
62
Superparamagnetic
Crystal violet
Fe3O4@Chitosan
crosslinked with
ethylenediamine
Fe3O4@Chitosan
crosslinked with
-cyclodextrin
Fe3O4@Polyacry
lic acid
12
Fe3O4@3glycidoxipropyltr
imethoxysilane
@glycine
10
Fe3O4@Sodium
40
35.7
Superparamagnetic
25.6
Superparamagnetic
7.1
4.8
37
Superparamagnetic
6.5
Methylene
blue and
Congo Red
Acid orange
7 and acid
orange 10
Methylene
blue, orange
1, azure 1,
methyl blue
and acid red
18
Safranin O
Working conditions
Adsorption capacity
(mg g-1)
Removal efficiency
Ref.
[32]
50-53% in synthetic
water;
[155]
[163]
[159]
[165]
[Dyes]=200 mg/L;
[MNPs]=1 g/L;
pH=2.5-12; T=25C;
[177]
769.23
[173]
dodecyl sulfate
Fe3O4@CTAB
2080
2.3
Fe3O4@Humic
acid
140
64
61.2
Superparamagnetic
Fe3O4@SiO2NH2
52.09
Fe3O4@SilicaDimethyl
octadecyl
chlorosilane
1020
41.31
Superparamagnetic
Fe3O4@3chloropropyltriet
hoxysilane@Am
inoguanidine
8-10
38.9
Fe3O4-NH2
10
28.5
Superparamagnetic
Fe3O4-Carbon
composite
10.6
19.8
335
8.2
1050
161.8
[175]
61.33
[184]
[Dyes]=0.5-10 ng/L;
[MNPs]=0.5 g/L; pH=7;
60-90% in synthetic
water; 70-100% in
natural waters;
[187]
[Dyes]=200 mg/L;
[MNPs]=1 g/L; pH=1.32.5; T=25C;
40-85% in synthetic
water;
[176]
[185]
111.8
[182]
[Dyes]=1600-3484 mg/L;
[MNPs]=5 g/L; pH=7;
T=20C;
[Crystal violet]=240
mg/L; [MNPs]=1 g/L;
pH=8.5; T=50C;
[172]
Table 3. Desorption and reusability of MNPs for heavy metals and dyes removal.
Adsorbent
-Fe2O3
nZVI@Chitosan
Fe3O4-NH2
-Fe2O3@
Polyrhodanine
Fe3O4@SiO2-NH2
Fe2O3@Orange peel
Fe3O4@Chitosan
Adsorbate
Cr(VI)
As(III), As(V)
Cu(II)
Hg(II)
Desoprtion agent
NaOH aqueous solution
NaOH aqueous solution
HCl aqueous solution
HCl aqueous solution
Concentration
0.01 mol L-1
0.1 mol L-1
0.1 mol L-1
0.1 mol L-1
Desorption (%)
90
50-60
100
100
Re-adsorption (%)
90
90
100
96
N cycles
5
5
15
5
Ref
[74]
[89]
[22]
[100]
Pb(II)
Cd(II)
Cu(II)
90
98
96
98
90
5
4
[137]
[112]
[92]
Fe3O4@Polyacrylic
acid
-Fe2O3@Sodium
dodecyl sulfate
Fe3O4@3glycidoxipropyltrimet
hoxysilane@glycine
Crystal violet
6% (v/v)
100
100
[165]
93-97
100
15
[20]
90
[177]
90 Methylene blue;
58 Azure 1;
[177]
93.5
75
[160]
NaOH in ethanol
88.2
70
[159]
Fe3O4@3glycidoxipropyltrimet
hoxysilane@glycine
Fe3O4@Chitosan
Fe3O4@Chitosan
crosslinked with cyclodextrin
Thionine and
Janus Green
Orange 1,
methyl blue
and acid red
18
Methylene
blue, and
azure 1
Alizarin red
Methyl blue
MNPs adsorption for the removal of heavy metals and dyes is reviewed.
Magnetic separation of the loaded MNPs, desorption and reusability are analysed.
End-of-life scenarios for the exhausted adsorbent are proposed.
61