Critical Review

pubs.acs.org/est

Environmental Remediation and Application of Nanoscale Zero-

Valent Iron and Its Composites for the Removal of Heavy Metal Ions:
A Review
Yidong Zou,†,‡ Xiangxue Wang,†,§ Ayub Khan,† Pengyi Wang,† Yunhai Liu,‡ Ahmed Alsaedi,∥
Tasawar Hayat,∥,⊥ and Xiangke Wang*,†,§,∥
†
School of Environment and Chemical Engineering, North China Electric Power University, Beijing 102206, P. R. China
‡
School of Chemistry, Biological and Materials Sciences, East China Institute of Technology, Nanchang, 330013, P. R. China
§
Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions Jiangsu, P.R. China
∥
NAAM Research Group, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
⊥
Department of Mathematics, Quaid-I-Azam University, Islamabad 44000, Pakistan
*
S Supporting Information

ABSTRACT: The presence of heavy metals in the industrial effluents

has recently been a challenging issue for human health. Efficient
removal of heavy metal ions from environment is one of the most
important issues from biological and environmental point of view, and
many studies have been devoted to investigate the environmental
behavior of nanoscale zerovalent iron (NZVI) for the removal of toxic
heavy metal ions, present both in the surface and underground
wastewater. The aim of this review is to show the excellent removal
capacity and environmental remediation of NZVI-based materials for
various heavy metal ions. A new look on NZVI-based materials (e.g.,
modified or matrix-supported NZVI materials) and possible interaction
mechanism (e.g., adsorption, reduction and oxidation) and the latest
environmental application. The effects of various environmental
conditions (e.g., pH, temperature, coexisting oxy-anions and cations)
and potential problems for the removal of heavy metal ions on NZVI-based materials with the DFT theoretical calculations and
EXAFS technology are discussed. Research shows that NZVI-based materials have satisfactory removal capacities for heavy metal
ions and play an important role in the environmental pollution cleanup. Possible improvement of NZVI-based materials and
potential areas for future applications in environment remediation are also proposed.

1. INTRODUCTION environment is still a very significant but challenging project for

Rapid growth of industrialization, results in the high demand of
metals for their applications in various products, such as storage
batteries pigments, automobile fuels, photographic films, various
explosives, coating materials, aeronautics and steel industries.1−5
Apart from their goodness, heavy metal ions are also responsible
for environmental pollution and attracted considerable attention
due to their potential hazards to human safety and the
environmental stability.6,7 Compared with traditional organic
pollutants, heavy metal ions, such as Cr(VI), Pb(II), Fe(III),
Cu(II), Zn(II), Hg(II), and Ni(II), are difficult to degrade into
cleaning products,5 which accumulated in living organisms and
most of those are known to be highly toxic or carcinogenic.3,8−10
For example, lead poisoning can cause severe injuries to basic
cellular processes, kidney, brain functions, and liver via its
progressive accumulation and multiple-toxicity.11−14 Thus, in
order to maintain ecological stability and public safety, effectively
separate and enrichment undesirable heavy metal ions from
environmental pollution control.
During the past few decades, a variety of conventional and
modern methods including chemical precipitation,15−17 electro-
chemical treatment,16 electro dialysis,16 evaporative recovery,18
solvent extraction,19 ultra filtration,20 ion-exchange,21,22 oxida-
tion/reduction,23−25 reverse osmosis,26 filtration,27 adsorp-
tion28−34 and membrane20,35 technologies have been proposed
to separate heavy metal ions from contaminated water. However,
most of these processes suffer from various drawbacks, for
example, chemical precipitation is comparably simple and
reliable but requires high installation cost for its large tanks to
obtain the effective precipitation. Of all the known methods,
adsorption technique has been regarded as a simple and effective
Received: April 22, 2016
Revised: June 1, 2016
Accepted: June 22, 2016
Published: June 22, 2016

© 2016 American Chemical Society 7290 DOI: 10.1021/acs.est.6b01897

Environ. Sci. Technol. 2016, 50, 7290−7304
Environmental Science & Technology
tool for the enrichment of heavy metal ions from wastewater
owing to its wide adaptability, environment-friendly and low
cost.36−39 Especially in environmental remediation, adsorption
method has been extensively adopted to remove pollutants (e.g.,
organic and inorganic pollutants) from aqueous solutions.40,41
To the best of our knowledge, many researches have been
focused on carbon nanotubes,5,6 clay minerals,42,43 layered
double hydroxides (LDHs),43−45 nanosized metal oxides
(NMOs),9,45 activated carbon,46 carbon film,47,48 ordered
mesoporous carbon (OMC)28 and graphene oxides49,50 as
efficient adsorbents to separate heavy metal ions from environ-
ment. Nanoscale zerovalent iron (NZVI), an environmentally
benign material,40,41 has been used successfully to treat various
metal ions in aqueous solutions (e.g., Pb(II), Ba(II), Zn(II),
As(III), Cr(VI), As(V), Cu(II), Cd(II), and Co(II)),51−53 via its
controllable particle size, high reactivity and abundant reactive
surface sites.51,52,54,55 Besides, NZVI has also been applied for the
stabilization of biosolids,56,57 the removal of tetracycline,58
antibiotic metronidazole,59,60 nitrate pollution,61−65 and the
decolouration of dyes,55,66,67 as a membrane antifouling agent
and for the treatment of nuclear waste,54 atrazine68 and
herbicides.69 NZVI has showed great potentials to reductive
transformation of heavy metal ions,70,71 which is attributed to the
sufficient mobility, excellent reactive longevity and low toxicity of
NZVI.41 Unfortunately, tiny particle size and powder state
restricts the direct application of NZVI, and the intrinsic
characteristics of NZVI to react with surrounded media or
agglomerate during preparation process decreases the reactivity
of the nanoparticles and also results in poor mobility and
successful transport of NZVI to the contaminated area for the
continuous in situ remediation.72,73 Moreover, the agglomer-
ation of iron particles in fixed bed column or any other dynamic
flow system results in high-pressure drop, thus restricting the
direct use of NZVI for field scale application. To address this
issue, NZVI-based materials, including surface modified NZVI
(SM-NZVI), porous material supported NZVI (e.g., resin,67
silica,74,75 nanoscaled magnesium hydroxide (Mg(OH)2),76
activated carbon77,78 and multiwalled carbon nanotubes79) and
inorganic clay mineral supported NZVI (e.g., kaolinite,80
zeolite,81 clay,65 montmorillonite,82 rectorite,83 palygorskite,
and bentonite84,85) have been successfully synthesized as
efficient adsorbents to separate pollutants from environment.
Although NZVI-based materials as an efficient adsorbent for
separation and enrichment of heavy metal ions from aqueous
solutions has been investigated extensively, the review about the
mechanism and application of NZVI-based materials in environ-
mental pollution cleanup is still scarce.
This review presents a brief view on several typical pristine
NZVI, surface modified NZVI, porous material supported NZVI
and inorganic clay mineral supported NZVI, including their
synthesis, applications and adsorption behavior of heavy metals
(e.g., Pb(II), Cd(II), Ni(II), Cr(VI), and Cu(II) etc.) from water
system under varying experimental conditions, also the under-
lying mechanism responsible for the environmental behavior, as
well as their reusability and selectivity during environmental in
situ remediation. Furthermore, the various kinds of surface
modified NZVI and substrates supported NZVI were briefly
introduced according to their various physicochemical properties
and adsorption mechanism. In addition, similar adsorbents were
compared and summarized for their adsorptive performance on
heavy metal ions from natural environment.
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Critical Review
2. SYNTHESIS OF NZVI AND ITS COMPOSITES FOR
HEAVY METAL REMOVAL
2.1. Pristine NZVI. In the past two decades, NZVI has
attracted a great attention as a promising reactant for reductive
removal of various environmental contaminants86,87 (e.g.,
chlorinated solvents,78,88−92 trichloroethylene,71,93,94 organo-
chlorine pesticides,69,92,95,96 organic dyes,55,66,67,84,97,98 decabro-
modiphenyl99 and inorganic pollutants23,51) from agricultural
and industrial wastewaters, which can be readily produced by the
reduction of dissolved iron using sodium borohydride solutions
or by milling or grinding processes.100
The traditional method for pristine NZVI synthesized by the
liquid phase reducing method, and the detail process was showed
in Figure S1 (see Supporting Information).101 A novel
technology combining electrochemical and ultrasonic methods
was introduced to produce NZVI by electroplating iron particles
and to remove the nanoscale iron particles into the solution
instantaneously.102 The iron particle was plated on the cathode
by putting ferric chloride in solution to reduce the ferric ion to
iron particle. Compared with the common methods, the new
technology releases the strong reducing agent or effective
oxidants103 and reduces the use of sodium and boron in the
solvents. For the application in environmental pollution
management and environmental in situ remediation, the
synthesis of pristine NZVI should be inexpensive, convenience,
efficient in large-scale and simple. Therefore, not all these
methods are practical for environmental applications. To date,
only a few studies have investigated the synthesis of pristine
NZVI for environmental remediation applications. Boparai et
al.52 used the “bottom-up” method of dropwise addition of
NaBH4 aqueous solutions to FeCl3 solution with continuous
stirring to prepare pristine NZVI, and applied it to remove Cd2+
ions from aqueous solutions. In a similar manner, Ramos et al.23
reported that the pristine NZVI was prepared from sodium
borohydride reduction of ferric iron and it showed that NZVI
was an effective adsorbent for the removal of arsenic from
wastewaters. In general, pristine NZVI could apply to remove
and recycle many kinds of heavy metals and environmental in situ
remediation through reduction and oxidation processes.
2.2. Surface Modified NZVI. Pristine NZVI tends to
aggregate rapidly due to the weak van der Waals forces, high
surface energy and intrinsic magnetic interactions,53,95 making it
difficult for NZVI to interact with target contaminants and
difficult to disperse in water for the heavy metal ions
management, which limits their practical applications. To
improve its high dispersion and prevent aggregation of NZVI,
different kinds of surface modified NZVI have been synthesized
by adding functional groups on the surfaces with chemical
modification (covalent or noncovalent functionalization)78,104 or
attaching a stabilizer such as a soluble polymer or surfac-
tant.64,105,106 Through various surface chemical modification
technology or metal-doped methods (e.g., Pd, Pt, Ni, Ag, and
Cu),40,105−107 the physically more stable and chemically more
reactive NZVI could be obtained, and the removal ability of
pollutants was also enhanced.
Many researchers have focused on coating iron nanoparticles
with stabilizer via steric hindrance and electrostatic repulsion.
Various polyelectrolyte coatings have been studied with varying
success,108−110 including butyl methacrylate, caboxymethyl
cellulose, 4-styrenesulfonate, poly(acrylic acid),105,106 polystyr-
enesulfonate, cellulose,98 poly(methyl methacrylate), polyaspar-
tate, poly(vinyl alcohol)-co-vinyl acetate-co-itaconic,109 chito-
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san,111 triblock copolymers,75 and xanthan gum.104,112 These
surface stabilizers can be coated onto the surface of pristine
NZVI to provide electrostatic repulsion, and steric or
electrosteric stabilization, which could decrease the aggregation
and increase the mobility of NZVI for environmental heavy metal
ions in situ remediation.
All reported modifiers, including various polymer electrolytes
and surfactants, such as chitosan, xanthan gum, cetyltrimethy-
lammonium bromide (CTAB), and carboxy methylated cellulose
(CMC), has been applied to modify the pristine NZVI to
improve its dispersion and stability and to enhance its removal
ability of some various heavy metal ions from natural
environment.108−110,113,114 Liu et al.110 used 3-aminopropyl-
triethoxysilane (APS) as an effective microemulsion to
synthesize amino-functionalized NZVI, and this material could
rapidly separate Pb(II) from water system and easily recycled by
an external magnetic field, which might be suitable for heavy
metal remediation and had potential industrial applications. Su et
al.113 successfully demonstrated the Au doped NZVI, Cu doped
NZVI and Ag doped NZVI served as efficient adsorbents to
remove Cd(II) from aqueous solutions, and the synthetic process
and reaction process were shown in SI Figure S2. In general,
metal doped NZVI could reduce the aggregation and increase the
reactivity of pristine NZVI. Furthermore, Zhao et al.109 and
Dong et al.114 adopted different stabilizers (poly(vinyl alcohol)
(PVA), poly(acrylic acid) (PAA), Tween-20 and starch) to
modify the pristine NZVI due to their low cost and environ-
mental compatibility, and this kind of stabilizer can not only
control the particle size during the Fe0 formation process, but
also prevent the agglomeration of the NZVI nanoparticles in
liquid phase. Thus, the size and reactivity of NZVI are
significantly improved, which has been applied to remove
heavy metal ions (e.g., Cu(II), Sb(III) and Sb(V)) from
wastewater, and the results showed high efficiency and reaction
rate for the remediation of heavy metal ions.
Introducing modifiers or stabilizers to pristine NZVI has also
improved the surface oxygen-containing functional groups, such
as epoxide, hydroxyl and carboxyl, and these oxygen-containing
functional groups could form strong complexes with heavy metal
ions, and allow the various surface modified NZVI to act as
adsorbents for heavy metal ion preconcentration and elimi-
nation, which could create the beneficial conditions to
environmental in situ remediation and cleanup.
2.3. Porous Material Supported NZVI. Recently, there is
great interest in the synthesis of porous material supported NZVI
because of their high surface area, gap structure and unique
property. They can also provide stable sites for pristine NZVI
nanoparticles loading to prevent their oxidation and aggregation.
Researchers immobilized NZVI on porous solid support
material, such as PVDF membrane, resin,67 polystyrene resins,64
silica, nanoscale magnesium hydroxide,76 carbon,115 green-
tea,116 activated carbon,77,78 carboxymethyl cellulose,117 cellu-
lose acetate,93 multiwalled carbon nanotubes,79 mesoporous
carbon,48 mesoporous silica99 and reduced graphene oxide118 to
restrain the aggregation of NZVI and applied the porous material
supported NZVI particles to remove pollutants from aqueous
solutions. In these porous material supported NZVI, the
supported materials on NZVI surface prevent the aggregation
of the nanoparticles to some extent, which thereby increases the
surface area and stable sites for the removal of pollutants from
environment.
Among these composites, graphene family nanomaterials
(GFNs) supported NZVI have attracted the most research
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interest due to the superior physicochemical properties of
GFNs.119,120 According to Jabeen’ reported,120 G-NZVI had a
higher adsorption capacity for Cr(VI) ions (up to 162 mg·g−1)
than the bare NZVI (148 mg·g−1). In 2016, Li et al.119 reported a
chemical reduction technology for the synthesis of graphene-
oxide nanosheets supported NZVI (NZVI/GNS), which had an
effective adsorption ability for in situ remediation of Cr(VI)-
polluted water, and the adsorption capacity was achieved to 21.72
mg·g−1. Interestingly, the reduced graphene oxide supported
NZVI (NZVI/rGOs) was also developed by a hydrogen/argon
plasma reduction method to increase the reactivity and stability
of NZVI, and the microstructure characteristics of NZVI/rGOs
have been reported by our groups in Figure 1.121 The NZVI/
Figure 1. SEM images of NZVI particles (A) and NZVI/rGOs (1:4)
(B); TEM images of the NZVI particles (C) and NZVI/rGOs (1:4)
(D); HRTEM of NZVI/rGOs (1:4) (E) and the corresponding EDS
pattern (F). Reproduced with permission from ref 121, Copyright 2016,
Elsevier.
rGOs showed excellent water treatment performance with
removal capacities for Cr(VI) (187.16 mg·g−1) and Pb(II)
(396.37 mg·g−1).118 At the same time, the as-prepared NZVI/
rGOs had been reported to remove U(VI) ions under anoxic
conditions, and the adsorption tendency of U(VI) on NZVI/
rGOs was similar to that on bare NZVI, achieving an equilibrium
capacity of 4174 mg·g−1.122 Wang et al.123 also used NZVI/rGOs
to remove As(III) and As(V) from wastewater, and the
adsorption capacities of As(III) and As(V) calculated from the
Langmuir model were 35.83 mg·g−1 and 29.04 mg·g−1,
respectively. The porous material supported NZVI can
effectively prevent the agglomeration of NZVI nanoparticles by
the electrostatic repulsion or steric hindrance, and it can also
increase the reactive active sites and improve the processing
efficiency of NZVI, thus improving the interaction activity with
various heavy metal ions.
2.4. Inorganic Clay Mineral Supported NZVI. To improve
the stability and increase the reaction active sites of NZVI,
inorganic clay mineral supported NZVI materials have been
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Environmental Science & Technology
developed rapidly and given great opportunity to environmental
in situ remediation. Common inorganic clay mineral and its
composites such as kaolinite,80 multifunctional kaolinite,124
zeolite,81 montmorillonite,82 clay,65 organobentonite,68,91,96
rectorite,83 calcium polysulfide,116 palygorskite and benton-
ite84,85,97 have been used to restrain the aggregation of NZVI and
applied to remove various pollutants from natural environment.
Clay is an abundant natural resource and is also a suitable
supporting material due to its potential applicability in pollutants’
adsorption and various composites. Compared with porous
material supported NZVI, inorganic mineral can not only
decrease the aggregation and improve the dispersion as well as
stabilization, but also interact with various natural pollutants and
prevent the migration and accumulation of pollutants.
In pollutant removal, matrix material supported NZVI,
especially the inorganic clay mineral supported materials, have
attracted the most research interest and been used as efficient
adsorbents to remove various heavy metal ions from wastewater.
According to the works of Shahwan’ group,13,80 kaolinite-
supported NZVI (NZVI-kaol) was prepared and applied to
remove Cu2+ and Co2+ ions from wastewater, and it showed that
the sizes could be adjusted between 10 and 80 nm. In order to
explore the various adsorption mechanism, the montmorillonite-
supported NZVI (Mt-NZVI) was synthesized by borohydride
reduction method,82 and Mt-NZVI showed high adsorption
capability toward inorganic arsenic in aqueous solutions. It
demonstrated that Mt-NZVI upon reaction with water and
oxygen formed a number of iron corrosion product and provided
new adsorption sites for As(III) and As(V), and then increased
the adsorption capacity for arsenic from aqueous solutions.
Various kinds of NZVI-based materials have shown great
adsorption capacity for heavy metal ions from environment, and
the main adsorption parameters was summarized in Table 1. The
specific surface area of NZVI is an important role to influence the
adsorption capacity for various heavy metal ions, and in general,
the adsorption capacity of NZVI-based materials can depend on
basic physicochemical properties of adsorbents and experimental
conditions, such as pH, ionic strength, temperature, concen-
tration of adsorbents and adsorbates. According to the results of
many researches (Table 1), the adsorption capacity and
physicochemical property improved obviously with various
complex methods and stabilizers, which might due to the
stability, surface active sites and oxygen-containing groups. It
indicated that various NZVI-based materials could be used
through complex with various stabilizers in practically environ-
mental heavy metal ions’ remediation.
According to literature survey, most inorganic clay mineral
supported NZVIs are used for the separation of heavy metal
ions.76,80−82,143,146,147 For instance, Uzum et al.80 reported a
borohydride reduction method to synthesize NZVI-kaol, which
decreased the aggregation of iron nanoparticles and enhanced
the activity of bare NZVI to remove Cu2+ and Co2+ ions from
aqueous solutions. This research indicated that NZVI-kaol
exhibited excellent removal abilities for Cu2+ and Co2+ ions from
wastewaters, and the various interaction mechanism could
attributed to adsorption and redox reactions, respectively. Cu2+
was mainly bonded with a redox reaction, and transfer into Cu2O
and Cu0, however, Co2+ was mainly bonded with an adsorption
process by various oxyhydrogen groups. Compared with the bare
NZVIs, the clay mineral supported NZVIs have lower
aggregation property, higher efficiency, higher sorption capacity
and more stability in the removal of heavy metal ions from
aqueous solutions.
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Critical Review
3. THE ROLE OF NZVI-BASED MATERIALS IN HIGHLY
EFFICIENT HEAVY METAL REMOVAL
3.1. Interaction Mechanism between NZVI-Based
Materials and Heavy Metals. NZVI-based materials have
been widely investigated for the treatment of heavy metal ions
and demonstrated tremendous potential and prosperous
application for the aggregation and in situ remediation of
heavy metal ions. However, the interaction mechanism of
contaminants with NZVI-based materials is still under debate.
Mechanistic study of heavy metal ions’ adsorption by NZVI-
based materials is paramount in the explanation of the reaction
process, which is beneficial for the optimization of the adsorption
conditions and desorption/regeneration conditions. The mech-
anistic studies have been carried out with either the assistance of
the DFT theoretical calculation models, EXAFS technology or
comprehensive experimental observations on adsorption char-
acteristics.60,148−150 The possible interaction mechanism of
heavy metal ions on NZVI-based materials is summarized in
Table 2. In the various adsorption systems, heavy metal ions
express various physiochemical properties, and interaction with
NZVI-based materials through physical and chemical reactions,
including adsorption, redox, aggregation, ion exchange, hydrox-
ylation as well as subsequent precipitation. Whereas the main
interaction mechanism could be regarded as adsorption,
reduction and oxidation process.
3.1.1. Adsorption Mechanism. Adsorption technology has
been considered as a typical reaction process for the removal of
heavy metal ions due to the abundant oxygen-containing
functional groups on the surface of various adsorbents, and
NZVI-based materials has been confirmed with large amount of
active sites or functional groups.121,123 Herein, the possible
mechanism of NZVI-based materials could attribute to
adsorption reaction. Moreover, iron hydroxides or oxides could
be formed on the surface of NZVI-based materials, which could
improve their adsorption capacities in a Fe0-H2O system in the
natural environment.60 Furthermore, adsorption process has
been considered to the main interaction mechanism and has
been used to explain various removal processes of heavy metal
ions with NZVI-based materials. Kanel et al.126 applied pristine
NZVI to remove As(III) from groundwater, and the Laser light
scattering analysis demonstrated the formation of NZVI-As(III)
inner-sphere surface complexes. Li et al.121 found that the NZVI/
rGO showed great adsorption capacity to Cd(II), and the
possible interaction mechanism is shown in Figure 2(A), which
indicates that the interaction is attributed to adsorption rather
than redox process. Han et al.149 reported that the mixture of
acid-washed ZVI and zerovalent aluminum (ZVAl) as reactive
medium in PRBs to treat heavy metal wastewater containing
Cr(VI), Cu(II), Cd(II), Ni(II) and Zn(II) ions, and the possible
interaction mechanism is shown in Figure 2(B). The removal
process was divided into four interaction processes, namely
reduction process, adsorption process, hydroxide precipitates
and electron transfer, however, the removal process was mainly
dominated by adsorption process. In compared to Lv et al.138 and
Wang et al.123 on the reported adsorption process of heavy metal
ions on NZVI-based materials (the XPS spectrum in SI Figure
S3), this interaction mechanism could be complex. However, in
real applications, the reaction system could include many kinds
of coexistent heavy metal ions, and the complex interaction
process should be considerable.
Recently, the adsorption mechanism studied by batch
experiments, advanced technologies in characterization and
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 Table 1. Adsorption Capacities and Mainly Parameters of Various Heavy Metal Ions Interaction with NZVI-Based Materials
BET optimum
adsorbents raw materials target metals (m2·g−1) pH initial C[tareget] (mg·L−1) adsorption capacity (mg·g−1) kinetic model isotherm model refs
bare NZVI FeCl3·6H2O + NaBH4 As(V) 33.5 7.0 11.1 38.2 na Langmuir isotherm 125
bare NZVI FeCl3·6H2O + NaBH4 As(III) 24.4 7.0 1.0 3.5 pseudo-first- Freundlich isotherm 126
order
bare NZVI FeCl3·6H2O + NaBH4 As(V) 25 7.0 1.0 1.0 pseudo-first- na 127
order
bare NZVI FeCl3·4H2O + NaBH4 Ba(II) na 7.0 13.7 1.1 pseudo-second- D-R isotherm 128
order
bare NZVI FeCl2·4H2O + NaBH4 Cu(II) na 6.5 50 250 na na 13
bare NZVI FeCl2·4H2O + NaBH4 Co(II) 14.2 8.0 800 172 na na 129
bare NZVI FeCl3 + NaBH4 Cd(II) na 7.0 112 769.2 pseudo-second- Langmuir isotherm 52
order
bare NZVI Nano iron Cr(VI) na 5.0 15.6 47.2 na na 130
Environmental Science & Technology

amino-functionalized NZVI (APS-NZVI) FeCl3·6H2O + CTAB Pb(II) na 7.0 100 111 na Freundlich isotherm 110
NZVI-Fe3O4 FeCl3·6H2O + CTAB Cr(VI) na 8.0 20 29.43 pseudo-second- Langmuir isotherm 131
FeSO4·7H2O order
sineguelas waste-modified (S-NaOH- FeCl2·4H2O + S-NaOH Pb(II) 35.56 6.5 1000 266 pseudo-second- Freundlich isotherm 12
NZVI) order
coated NZVI FeSO4·7H2O + KBH4 Pb(II) na 5.0 100 100 na na 132
Au doped NZVI FeCl3·6H2O + NaBH4 Cd(II) na 8.5 40 188 na na 113
PVP modified NZVI FeSO4·7H2O + NaBH4 Sb(III)/Sb 11.3 7.0 5.0 6.99/1.65 pseudo-second- Langmuir isotherm 109
(V) order

7294
ultrasonic modified NZVI (US-NZVI) FeSO4·7H2O + NaBH4 Cr(VI) na 5.5 20 66.7 pseudo-first- na 133
order
activated carbon supported-NZVI (NZVI/ FeCl3·6H2O + NaBH4 As(III) 69.4 6.5 2.0 18.2 na Langmuir isotherm 134
AC)
carboxymethyl cellulose supported FeSO4·7H2O + NaBH4 Cr(VI) na 5.5 10 33 na na 117
G-NZVI FeCl3·6H2O + NaBH4 Cr(VI) 170 4.25 na 162 pseudo-second- Langmuir isotherm 120
order
MWCNT-NZVI FeSO4·7H2O + NaBH4 Cr(VI) na 7.0 20 200 pseudo-first- na 135
order
MWCNT-reinforced nanofibrous mats- FeCl3·6H2O + NaBH4 Cu(II) na 5.5 50 107.8 pseudo-second- Langmuir isotherm 136
supported NZVI order
G-NZVI FeCl3·6H2O + NaBH4 Pb(II) na 5.0 250 585.5 pseudo-second- Freundlich isotherm 137
order
magnetic Fe3O4/graphene -supported FeCl3·6H2O + Cr(VI) na 8.0 100 66.2 pseudo-first- Langmuir isotherm 138
NZVI FeSO4·7H2O order
NZVI/rGO FeSO4·7H2O + NaBH4 As(III)/ As na 7.0 7.0 35.83/29.04 pseudo-second- Langmuir isotherm 123
(V) order
NZVI/rGO FeCl3·6H2O + NaBH4 Cd(II) 117.97 5.0 150 425.72 pseudo-second- na 121
order
NZVI/rGO FeCl3·6H2O + NaBH4 Cr(VI)/ Pb 117.97 5.0 100 187.16/396.37 na Langmuir isotherm 118
(II)
Mg(OH)2-supported NZVI FeSO4·7H2O + NaBH4 Pb(II) 40.2 6.86 1000 1986.6 na na 76
cellulose-supported NZVI FeCl3 + NaBH4 Cr(VI) 9.55 3.0 10 562.8 pseudo-second- Langmuir/Freundlich 139
order isotherm
G-NZVI FeCl3·6H2O + NaBH4 Cr(VI) na 7.0 20 21.72 pseudo-first- Langmuir isotherm 119
Critical Review

order

DOI: 10.1021/acs.est.6b01897
Environ. Sci. Technol. 2016, 50, 7290−7304
Environmental Science & Technology Critical Review

theoretical calculation models, which has proposed more

140

141
142

143

144

145
refs
80
valuable reference basis for the application of NZVI-based
materials in environment remediation. The removal and
remediation of heavy metal ions was conducted in aqueous
isotherm model

Langmuir isotherm

Langmuir isotherm

Langmuir isotherm
solutions, and the main solvent molecule, that is, water, played an

D−R isotherm
important role in the adsorption process. Hence a further
research could be discussed between water and NZVI-based
materials, and then the interaction process of heavy metal ions
could be understood. The interaction mechanism of heavy metal
na

na

na

ions on NZVI-based materials can also be theoretically modeled,

and the main mechanism of water with iron surface by (NZVI)/
pseudo-second-

pseudo-second-

pseudo-second-
kinetic model

H2O system in an oxygen environment was investigated with

pseudo-first-

pseudo-first-
density functional theory (DFT) calculations.151,152 Lazar et
order

order

order

order

order al.151 demonstrated DFT study of the adsorption process in

na

na

water system at the (100) and (111) surfaces of iron, which could
interact with heavy metal ions, and the results of DFT calculation
adsorption capacity (mg·g−1)

was shown in Figure 3. It indicated that the adsorbed water

molecule could transfer into H + OH (H−Fe−OH) species with
33.74/32.25

43.86/44.05

an activation barrier of 15.7 kcal/mol for the (100) surface, and

30.2/29.0

the positive activation barrier was beneficial to the adsorption

49/65

105.5

process of heavy metal ions on NZVI-based materials.

7.3

48

3.1.2. Reduction Mechanism. Generally, for multivalent

heavy metal ions, the interaction is mainly attributed to the
reduction process, and the reducing action of Fe0 in natural
environment is multistep processes, where Fe0 acts as an electron
initial C[tareget] (mg·L−1)

donor to many heavy metal ions.66,88 Reduction reaction as an

important interaction between heavy metal ions and NZVI-based
39/18

500
200

materials, influenced the valence and physicochemical properties

73

50

50

50

of heavy metal ions in aqueous solutions. The reduction of

NZVI-based materials for the heavy metals includes two distinct
mechanism: (1) the reduction of heavy metals by Fe0 directly;76
(2) the primarily adsorption of heavy metals on the core−shell
optimum
pH

structure of NZVI and then gradually reduction of adsorbed

6.0

6.0

5.1
5.5

7.0

5.0

6.0

heavy metals by Fe2+ derived from NZVI.85 For most heavy

metals, which has no intermediate valence could be reduced to
(m2·g−1)

141.42

the lowest valence. However, for few intermediate valent heavy

BET

39.94

26.11

40.76
29.1

metals, adsorption process and reduction by Fe2+ is also possible.

6.7

na

At the same time, for some multivalent elements, reduction

process could consist in most heavy metal ions’ interaction with
target metals
Cu(II)/ Co

Zn(II)/ Pd
Cu(II)/ Ni

Cr(VI)/Pd

matrix in the natural environment, and the biotoxicity of the

Cr(VI)

Pb(II)
Pb(II)

initial valence heavy metal ions reduced and formed more stable
(II)

(II)

(II)

(II)

valence with the reduction process. Liu et al.76 reported that a

novel composite (Mg(OH)2) supported NZVI (NZVI@Mg-
Fe(NO3)3·9H2O + NaBH4

(OH)2) showed exceptional removal capacity because of

FeCl2·4H2O + NaBH4

FeCl3·6H2O + NaBH4

FeCl3·6H2O + NaBH4

FeCl3·6H2O + NaBH4

FeCl3·6H2O + NaBH4

synergistic effect, which included at least three paths as shown

raw materials

in SI Figure S4, and NZVI showed possible reduction process of

Fe2O3 + NaBH4

Pb(II) to Pb0, and about 47% Pb0 was formed by reduction

reaction. And the main reactions, including reduction, adsorption
and precipitation, are listed as eqs 1−5. Moreover, the reduction
mechanism has been confirmed through many experiments and
characterization. Zhou et al.150 investigated that more than 80%
Sb(III) could be restored into Sb(0) by beta zeolite supported
NZVI, which could be affirmed with XPS analysis, and the
reduction process controlled the reaction process and showed
great challenges to other stable metal elements. While for
bentonite-supported NZVI

unstable metal elements, reduction process could be useful and

adsorbents

sepiolite-supported NZVI
Table 1. continued

zeolite-supported NZVI

benefit to the in situ remediation of heavy metal ions from the

na: not applicable.

natural environment. With the further research of the reduction

process about heavy metal ions on NZVI-based materials,
EXAFS technology has also been applied to characterize the
NZVI-kaol

NZVI-kaol

NZVI-kaol

Mt-NZVI

products. Li et al.85 reported that the positively charged pillared

bentonite supported NZVI (NZVI/Al-bent) could improve the
reductive transformation and the removal of Se(VI) into less
a

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Environmental Science & Technology Critical Review

Table 2. Pathways and Mechanism of Various Heavy Metal Ion Interaction with NZVI-Based Materials
target
adsorbents metals interaction mechanism or reaction ref
NZVI@Mg(OH)2 Pb(II) (synergistic process) adsorption, reduction, ion exchange reaction, hydroxylation and subsequent precipitation. 76
NZVI/rGO Cr(III) precipitation and reduction sorption. 118
(1) 2HCrO4− + 3Fe0 + 14H+ → 3Fe2+ + 2Cr3+ + 8H2O
(2) HCrO4− + 3Fe0 + 3H+ → 3Fe2+ + Cr3+ + 2H2O
(3) (1-x)Fe3+ + xCr3+ + 3H2O → (CrxFe1‑x) (OH)3↓+ 3H+
(4) (1-x)Fe3+ + xCr3+ + 2H2O → CrxFe1‑xOOH↓+ 3H+
NZVI/rGO Cd(II) adsorption (electrostatic interactions and specific surface bonding). 121
Bare NZVI As(III) surface adsorption or formation of arsenic−iron coprecipitates. 153
chitosan beads- Cu(II) reduction and the formation of Fe(III)-heavy metals coprecipitate. 102
supported NZVI
Mt-NZVI Zn(II) van der Waals forces, magnetic interactions forces, and/or surface complexation. 144
NZVI-kaol Ni(II) redox, adsorption, precipitation, and coprecipitation. 143
(1) Fe0 + 2H2O + 1/2O2 → Fe2+ + 4OH− (basic solution)
(2) Fe0 + 2H2O → Fe2+ + H2 + 2OH− (acid solution)
(3) Ni2+ + Kaolinite → Ni2+ − Kaolinite (adsorption)
(4) Ni2+ + FexOyHz → Ni2+ − FexOyHz (adsorption)
bentonite- Se(VI) reduction and electron transport (Fe0 oxidized to ferrous ions through anoxic corrosion or reductive dissolution of iron by 85
supported NZVI Se(VI) under anaerobic conditions)
beta zeolite- Sb(III) Sb(III) adsorbed on the surface of NZVI-zeolite, and reduced into Sb(0) immediately accompanied by the oxidation of NZVI. 150
supported NZVI Fe(0) and iron oxides kept evolution, and the degree of oxidation was promoted.

Figure 2. (A) Possible schematic mechanisms and reaction process of Cd(II) removal by NZVI/rGOs Reproduced with permission from ref 121,
Copyright 2015, Elsevier, (B) Possible mechanisms of the heavy metal ion removal by ZVI/ZVAl in PRBs (reduction process, adsorption process,
hydroxide precipitates and electron transfer). Reproduced with permission from ref 149, Copyright 2016, Elsevier.

Pb2 + + Fe 0(s) → Fe 2 + + Pb0(s) (3)

Fe2 + + 2H 2O → Fe(OH)2 (s) + 2H+ (4)

Fe0(s) + 2H 2O → Fe 2 + + H 2(g) + 2OH− (5)

3.1.3. Oxidation Mechanism. In some special environmental

Figure 3. Dissociation of water molecule on the Fe(100) surface
calculated PW91 density functional (black curve, dots) and HSE06
hybrid functional (red curve, dashed lines). The arrows show the heights
of energy barriers along the reaction path. Reproduced with permission
from ref 151, Copyright 2012, American Chemical Society.
soluble Se(II) from wastewater by Fe2+ and NZVI. And the
EXAFS results (SI Figure S5) show that the shell of Se−O bond
is not obtained for the samples of Se(VI) reacted with NZVI/Al-
bent, indicating that the absence of adsorbed Se(VI) on the solid,
and Se(VI) is completely reduced with the reduction process.
Mg(OH)2 (s) → Mg 2 + + 2OH− (1)
remediation systems, in contrast to the reduction process,
oxidation process is also considered as a possible react
mechanism,69,103 such as the Fe0−H2O mixture system, and it
has been controlled with the Fenton reaction in the presence of
oxygen, and then some strong oxidants are produced (as
followed eqs 6−8),90 which can improved the oxidization of
heavy metal ions in aqueous solutions, but in usual reaction
system of natural environment, the oxidation process could be
rare in the removal of heavy metal ions on NZVI-based materials.
Fe 0 + O2 + 2H+ → H 2O2 + Fe 2 + (6)
Fe 2 + + H 2O2 → Fe3 + + ·OH + OH− (7)

Pb2 + + 2OH− → Pb(OH)2 (s) (2) 2Fe3 + + Fe0 → 3Fe 2 + (8)

7296 DOI: 10.1021/acs.est.6b01897

Environ. Sci. Technol. 2016, 50, 7290−7304
Environmental Science & Technology
Figure 4. (A) Comparison of various Fe materials with the same amount of Fe0 = 0.016 g in Cr removal. Reproduced with permission from ref 146,
Copyright 2013, Elsevier; (B) Removal of Cr(VI) in aqueous solutions over the NZVI/GNS with different GNS amounts; dash lines is the
corresponding pseudo-first-order kinetics fitting curves. Reproduced with permission from ref 119, Copyright 2016, Elsevier.
Bhowmick et al.82 prepared novel Mt-NZVI by the liquid
phase reducing method, and applied the Mt-NZVI for the
elimination of both As(III) and As(V) from aqueous solutions.
During the reaction process, Fe(II) and Fe(III) could be formed
by Fe0 and solution (eqs 9-(10)), and it can further produce
various derivatives of iron. As(III) could be oxidized partially to
As(V), moreover, the oxidation process of Fe0 can also form
various oxidizing medium in water system such as H2O2, HO0,
O20‑ (eqs 11−13).27,82 It indicated that the Fe0 could provide
great oxidizing capacity for various targets through forming
various derivatives of iron, and it was beneficial for the separation
of heavy metal ions.
2Fe 0 + O2 + 2H 2O → 2Fe 2 + + 4OH− (9)
4Fe2 + + 2H 2O + O2 → 4Fe3 + + 4HO− (10)
Fe 2 + + O2 → Fe3 + + O2 0 − (11)
Fe 2 + + O2 0 − + 2H+ → Fe3 + + OH 0 + HO− (12)
Fe 2 + + O2 0 − + 2H+ → Fe3 + + H 2O2 (13)
3.1.4. Other Special Interaction Mechanism. Generally, in
mixing reaction systems, various interactions could dominate the
removal process due to various environmental conditions.
Occasionally, the main interaction mechanism is controlled by
magnetic interaction forces, van der Waals forces, electrostatic
interactions and specific surface bonding. Wang et al.123 used
NZVI/rGOs to remove As(III) from aqueous solutions, and they
found that the removal of As(III) was attributed to surface
complexation at pH < 9.1 and electrostatic interactions at pH >
9.1. NZVI-based materials could also form amorphous
precipitate with heavy metal in aqueous solutions, Li et al.118
reported that NZVI/rGO exhibited excellent removal capacity
for Cr(III) with the forming precipitation of (CrxFe1−x) (OH)3
and CrxFe1−xOOH. In most reaction process, synergistic process
dominated the remediation process, for example, Liu et al.76 used
NZVI@Mg(OH)2 to remove Pb(II) from mixture solutions, and
the possible mechanism was shown in Table 2. It indicated that
the interaction mechanisms between adsorbents and target
metals were attributed to adsorption, reduction, ion exchange
reaction, hydroxylation and even subsequent precipitation, which
is benefical for the aggregation of pollutants.
In fact, during the practical environmental application,
adsorption process, reduction process, oxidation process even
other special interaction could be existed among various
materials. However, the main interaction could be attributed to
7297
Critical Review
one or two kinds of interactions due to the environmental
medium. Thus, the true interaction mechanism between heavy
metal ions and NZVI-based materials could be understood via to
real reaction conditions.
3.2. Effect of Environmental Conditions. In general, the
adsorption behavior of heavy metal ions on NZVI-based
materials can be described by batch experiments in various
conditions, including solution pH, contact time, dosage of
adsorbent, temperature, coexisting oxy-anions, and cations. Due
to the importance of heavy metal in environment, evaluation of
the migration, transfer, accumulation and environmental effect of
heavy metal ions in wastewater is important in environmental
pollution in situ remediation.
Among these parameters, pH values could affect the surface
properties of materials and species of the molecules or irons. The
pH values of the aquatic environment generally ranges from 5.0
to 9.0, and the adsorption of heavy metal ions, such as Pb(II),
Cu(II), Cr(VI) and Ni(II) by NZVI-based materials may
conduct in the pH range of 5.0−9.0,141,146 which can ensure
the consistency of natural conditions. In the lower pH or higher
pH values, the adsorption capacity of heavy metal ions on NZVI-
based materials tends to be decreased sharply as confirmed in refs
82,120, and 147, and the pH-dependent behavior can be
explained by ionization process between adsorbates and
adsorbents, which lead the repulsion effect and decrease the
net target adsorption. At lower pH values, the iron corrosion
increased and produced abundant hydrogen, which is beneficial
for hydrogenation reaction. At higher pH values, passive film of
iron hydroxide could be formed with the iron corrosion in
solution, which exhibited further adsorption process.154,155 A
plausible explanation is that more oxygen-containing groups
(e.g., oxide or oxyhydroxide) become deprotonated and the
surface becomes negatively charged as pH increases, which is
favorable for adsorbing more heavy metal ions via electrostatic
interactions. It assumes that the adsorption properties of NZVI
are influenced strongly by solution pH.
The interactive effects of redox and adsorption process for
heavy metal ions on NZVI-based materials could be described by
kinetic models, and the common models including pseudo-first-
order kinetics and pseudo-second-order kinetics. For example,
bare NZVI could remove about 40% of Cr(VI) in 60 min from
aqueous solutions, and the NZVI/GNS showed a higher
adsorption capacity for Cr(VI) (70% within 60 min), and the
maximum adsorption capacity was calculated to be 20 mg·g−1
(C(initial) = 25 mg·L−1).119 Interestingly, the Cr(VI) removal
processes using bare NZVI and NZVI/GNS could also be fitted
by the pseudo-first-order kinetics model, and the activity toward
DOI: 10.1021/acs.est.6b01897
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Environmental Science & Technology
Figure 5. (A) adsorption isotherms of Cd(II) removal by the rGOs, NZVI and NZVI/rGOs (1:4). Reproduced with permission from ref 121, Copyright
2015, Elsevier; (B) adsorption isotherms of Sb(III) on zeolite-supported NZVI. Reproduced with permission from ref 150, Copyright 2015, Springer
Science.
Cr(VI) removal by the NZVI/GNS was about 2.8 times as high
as that of the bare NZVI, which indicated that the adsorption
process was mainly attributed to physical interaction process
because of the high sorption capacity of GNS. On the contrary,
the adsorption process of Cr(VI) ions on Mt-NZVI was well
fitted by the pseudo-second-order kinetics, and 95% Cr(VI)
could be removed by the composites within 30 min, and the
maximum adsorption capacity was calculated to be 145 mg·g−1
(C(initial) = 20 mg·L−1), which showed that the process was
attributed to chemical interaction involving valence forces.131
The kinetics removal behavior of Cr(VI) in aqueous solutions
over the NZVI/GNS and Mt-NZVI is shown in Figure 4,119,156
and the removal of Cd2+ by NZVI/rGOs was also fitted better
with pseudo-second-order kinetics, which were shown in SI
Figure S6.121 At the same time, the fast adsorption velocity
showed that strong chemisorption, redox interaction or strong
surface complexation contributed to the coagulation of heavy
metal ions onto the surface of NZVI-based materials which was
important for the application of the NZVI-based materials to
remove pollutants from natural environment.
Generally, temperature can change the removal rate of
molecules and the energy of the reaction system. The common
adsorption isotherms employed to represent the sorption
equilibrium of heavy metal ions on NZVI-based materials
include Freundlich, Langmuir, Temkin, and Dubinin−Radush-
kevich (D-R). At the same time, solution temperature studies can
express the important thermodynamic parameters values, such as
Gibb’s free energy (ΔG0), entropy (ΔS0) and enthalpy (ΔH0).
Attempt to understand the thermodynamic behavior of heavy
metal ions on NZVI-based materials have generally been
inconclusive. Adsorption isotherm describes the interaction
process between adsorbates and adsorbents, which is essential in
optimizing the application of adsorbents. The As(V) adsorption
on bare NZVI follows Freundlich as well as Langmuir
isotherms,126 and the adsorption behavior was tended to a
spontaneous exothermic adsorption reaction. The adsorption
isotherms of Cr(VI) on NZVI-Fe3O4 nanocomposites proved
the fitness of the Langmuir and Freundlich models,131 and the
better imitative effect of Freundlich model showed higher
tendency of the heterogeneous surface of NZVI-Fe3O4 nano-
composites, and the adsorption process was confirmed by the
spontaneous character of the negative △G0 value. Figure 5A
shows the adsorption isotherms of Cd(II) on NZVI and its
composites,121 and it found that the adsorption process was
endothermic and spontaneous, which is beneficial for the
practical application of environmental remediation. With the
same mechanism, the adsorption isotherms of Sb(III) by zeolite-
supported NZVI were investigated at various temperatures
7298
Critical Review
(Figure 5B).150 In general, the temperature has a positive effect
on the adsorption capacity of heavy metal ions on NZVI-based
materials, which is beneficial for environmental in situ
remediation.
Dosage of adsorbent (NZVI-based materials) is an also
significant factor to affect the removal efficiency of pollutants,
because using an optimum dosage of adsorbent for removal
process in the natural environment is useful for its cost-effective
application. According to Arshadi et al.,12 a dose of 0.15 g
containing NZVI decorated sineguelas waste (S-NaOH-NZVI)
can be used to remove Pb(II) from aqueous solutions and
reached the maximum percentage removal (89%) for Pb(II) at
initial concentration of 10 mg·g−1. However, in order to obtain
higher percentage removal (93%) for Pb(II) at the same initial
concentration, a dose of 1.50 g was required. In another study,
sepiolite-supported NZVI (S-NZVI) was used to remove Cr(VI)
and Pb(II) ions from groundwater,145 and the removal
percentages of Cr(VI) and Pb(II) were 98.8% and 97.31%,
respectively, which were obtained within 10 min when the dose
of adsorbent was 3.2 g·L−1. Compared with the solid content of
0.05 g·L−1, the removal efficiency of target improved 1.5−2
times, which indicated that the optimum dosage could reduce the
cost of water environment manage.
There are many publications on the effect of coexisting oxy-
anions and cations on heavy metal ions’ adsorption/reduction by
NZVI-based materials.82,134,135 During the adsorption process,
the coexisting oxy-anions could lead chemical competition
reaction.82,119,157 For example, the effect of coexisting oxy-anions
on As(V) and As(III) adsorption by Mt-NZVI was found to
reduce in the order of PO43− > HCO3− > SO42− > NO3−, which
might be attributed to that the anions enhanced the ionic
strength and competed with targets, simultaneously.135 When
the promotional effect of ionic strength exceeds the driving force
of competitive adsorption, the overall effect is positive, otherwise
negative effect. The results showed that HCO3−, SO42− and
NO3− had insignificant effect on the adsorption for both the
species of As(V) and As(III) on Mt-NZVI.82 Interestingly, with
increase in C(PO43−) from 2 to 5 mg·L−1, the adsorption
percentage increased from 11.0% to 28.4% for As(V) and 13.0%
to 35.5% for As(III), which were via the inner-sphere complexes
formed by PO43− and competed for the adsorption sites on the
adsorbent surface. It could be explained that the higher valent
anions have greater interfering effect than other monovalent
anions in As(V)/As(III) adsorption by Mt-NZVI. Similarly,
various cations, such as Ca2+, Mg2+, Zn2+, Fe2+, Cu2+ and Cd2+,
have an important influence to the adsorption process. Zhu et
al.134 reported that NZVI/AC showed great adsorption capacity
to As(V)/As(III), and Fe2+ suppressed the adsorption process
DOI: 10.1021/acs.est.6b01897
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Environmental Science & Technology Critical Review

while Ca2+ and Mg2+ had a positive effect to the reaction process.
However, compared with the effect of solution pH, coexisting
oxy-anions and cations were found to be insignificant to the
removal process.
3.3. Comparative Adsorption Capacity. To the best of
our knowledge, NZVI-based materials have shown various
adsorption capacities for heavy metal ions, which was attributed
to the surface characteristics and oxygen-containing functional
groups. For example, the removal of Pb(II) ions from wastewater
by various NZVI-based materials has been studied by Liu et al.,76
and the sorption capacities were calculated to be 775.4, 1718.4,
and 1986.6 mg·g−1 for Mg(OH)2, bare NZVI nanoparticles and
NZVI@Mg(OH)2, respectively. Interestingly, although the high
adsorption capacity was obtained by Mg(OH)2 or bare NZVI,
the removal performance has obviously improved with NZVI@
Mg(OH)2 composite. Compared with the NZVI-based materi-
als, such as NZVI-zeolite composite for Pb(II) (806.0 mg·g−1),81
NZVI-graphene composite for Pb(II) (585.5 mg·g−1),137
sineguelas waste supported NZVI for Pb(II) (225.0 mg·g−1)12
and NZVI-kaol for Pb(II) (440.5 mg·g−1),147 the NZVI@
Mg(OH)2 composite possesses the highest removal capacity for
Pb(II), which is regardless of the varied experimental conditions.
In order to better understand the adsorption behavior and
removal performance of heavy metal ions, various adsorption
thermodynamic parameters and sorption capacity with Pb(II)
ions as an example adsorbed on various materials are tabulated in
SI Table S1, including carbon-based materials,7,134,158 graphene-
based materials159−161 and other new materials,8,11,162−171 which
indicate that various materials have high adsorption capacity, and
various physicochemical property can control the adsorption
process.172,173 The NZVI-based materials show great application
potentials in environmental in situ remediation.
4. ENVIRONMENTAL SIGNIFICANCE AND FUTURE
APPLICATION
With the rapid development and extensive applications of heavy
metals and its composites, its release into the environment is
ions on NZVI-based materials in the natural environment and
would partly allow us to assess its environmental impact. At the
same time, NZVI-based materials are expected to be an efficient
adsorbent and reductant for heavy metal ions and used for in situ
environmental remediation, which could provide us a simple
method for the efficient elimination of environmental pollutants
from aqueous solutions.
In summary, NZVI-based materials can be a promising
material to remove heavy metal ions efficiently from aqueous
solutions by using a simple and rapid chemical reaction and
adsorption process. Although universal acceptance of NZVI-
based material as a remediation material may well occur, a further
understanding of environment behavior, remediation mecha-
nism and influence factor of heavy metal ions adsorbed on NZVI-
based materials has also not been demonstrated. Future research
should seek to establish a sound body of evidence upon the
interaction mechanism of NZVI-based materials in natural
environment, which could confirm that NZVI-based materials
applied in environment in situ remediation and reduce the effect
of heavy metal ions pollutants or other common pollutants.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge via the
Internet at The Supporting Information is available free of charge
on the ACS Publications website at DOI: 10.1021/
acs.est.6b01897.
Preparation of pristine nanoscale zerovalent iron (NZVI),
Figures S1 to S6 and Table S1 (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*Phone: 86-10-61772890; fax: 86-10-61772890; e-mail:
xkwang@ipp.ac.cn or xkwang@ncepu.edu.cn.
Notes
The authors declare no competing financial interest.

inevitable and poisonous. Therefore, the rapid adsorption of
heavy metal ions appears to be particularly important and urgent
due to its high activity and toxicity in the environment. Generally,
since the adsorption behavior strongly influences the toxicity,
accumulation, adhesion and migration of various heavy metal
ions in the environment, especially in clay minerals, NZVI as an
important environmentally benign reducing agent, has shown
great potentials to pollutant removal and environmental in situ
remediation. It is necessary and significant to investigate the
adsorption behavior and reduction mechanism of heavy metal
■
ACKNOWLEDGMENTS
Financial supports from NSFC (21225730, 91326202,
21577032, 21377132, 21307135, 41273134), the Fundamental
Research Funds for the Central Universities (JB2015001), the
Project of East China Institute of Technology Graduate Student
Innovation Fund (YC2015-S273), the Jiangsu Provincial Key
Laboratory of Radiation Medicine and Protection and the
Priority Academic Program Development of Jiangsu Higher
Education Institutions are acknowledged.

■
ions on NZVI-based materials from aqueous solutions, and it is
beneficial for us to understand the migration rules and LIST OF PROPER NOUN (FULL NAME AND
interaction mechanism of heavy metal ions in environmental ABBREVIATED NAME) IN THIS REVIEW PAPER
medium, especially in clay minerals, groundwater, and waste-
water. Full Name Abbreviated Name
To date, many researchers have confirmed that the adsorption nanoscale zerovalent iron NZVI
processes of heavy metal ions on NZVI-based materials from layered double hydroxides LDHs
natural environment are attributed to chemical reaction and nanosized metal oxides NMOs
monolayer molecule sorption by batch adsorption experiments ordered mesoporous carbon OMC
or theoretical study. Batch experimental results have also proved surface modified NZVI SM-NZVI
that the optimum pH values of adsorption process on most cetyltrimethylammonium bromide CTAB
NZVI-based materials is 4.0 to 7.0, which is conformed to the carboxy methylated cellulose CMC
aquatic environmental range (pH 5.0−9.0), and most of NZVI 3-aminopropyltriethoxysilane APS
composites with excellent properties show great adsorption poly(vinyl alcohol) APA
capacity and removal performance. These findings provide polyacrylic acid PAA
crucial insight regarding the fate and adsorption of heavy metal graphene family nanomaterials GFNs
7299 DOI: 10.1021/acs.est.6b01897
Environ. Sci. Technol. 2016, 50, 7290−7304
Environmental Science & Technology
graphene supported NZVI G-NZVI
graphene-oxide nanosheets supported NZVI NZVI/GNS
reduced graphene oxide supported NZVI NZVI/rGOs
kaolinite-supported zerovalent iron nanoparticles NZVI-kaol
montmorillonite-supported NZVI Mt-NZVI
amino-functionalized NZVI APS-NZVI
sineguelas waste-modified NZVI S-NaOH-
NZVI
ultrasonic modified NZVI US-NZVI
carboxymethyl cellulose supported NZVI CMC-NZVI
activated carbon supported-NZVI NZVI/AC
(Mg(OH)2) supported NZVI NZVI@Mg-
(OH)2
pillared bentonite supported NZVI NZVI/Al-
bent
zero-valent aluminum ZVAl
■
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7304 DOI: 10.1021/acs.est.6b01897

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