Chemosphere 285 (2021) 131432

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Recent advances in the application of water-stable metal-organic

frameworks: Adsorption and photocatalytic reduction of heavy metal
in water
Zhongwu Li a, Lei Wang a, Lei Qin b, *, Cui Lai b, **, Zhihong Wang b, Mi Zhou a, Linhui Xiao a,
Shiyu Liu b, Mingming Zhang b
a
College of Geographic Science, Hunan Normal University, Changsha, Hunan, 410081, PR China
b
College of Environmental Science and Engineering, Hunan University and Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry
of Education, Changsha, 410082, PR China

A R T I C L E I N F O A B S T R A C T

Handling Editor: X. Cao Heavy metals pollution in water is a global environmental issue, which has threatened the human health and
environment. Thus, it is important to remove them under practical water environment. In recent years, metal-
Keywords: organic frameworks (MOFs) with water-stable properties have attracted wide interest with regard to the cap­
Heavy metals ture of hazardous heavy metal ions in water. In this review, the synthesis strategy and postsynthesis modification
Water-stable MOFs
preparation methods are first summarized for water-stable MOFs (WMOFs), and then the recent advances on the
Adsorption
adsorption and photocatalytic reduction of heavy metal ions in water by WMOFs are reviewed. In contrast to the
Photocatalytic reduction
conventional adsorption materials, WMOFs not only have excellent adsorption properties, but also lead to
photocatalytic reduction of heavy metal ions. WMOFs have coupling and synergistic effects on the adsorption
and photocatalysis of heavy metal ions in water, which make it more effective in treating single pollutants or
different pollutants. In addition, by introducing appropriate functional groups into MOFs or synthesizing MOF-
based composites, the stability and ability to remove heavy metal ions of MOFs can be effectively enhanced.
Although WMOFs and WMOF-based composites have made great progress in removing heavy metal ions from
water, they still face many problems and challenges, and their application potential needs to be further improved
in future research. Finally, this review aims at promoting the development and practical application of heavy
metal ions removal in water by WMOFs.

1. Introduction
Heavy metals pollution in water is a global problem, which has
attracted widespread attention (Fu and Wang, 2011; Hader et al., 2020).
The most common heavy metal pollution in water includes cations (e.g.,
Hg2+, Pb2+, Cd2+, and Cu2+) and oxygen anions (e.g., CrO2− 2−
4 /Cr2O7 ,
SeO2−
3 /SeO 2−
4 and HAsO 2−
4 /AsO3−
4 ) (Dinda et al., 2013; Bora and Dutta,
2019; Humelnicu et al., 2020; Upadhyay et al., 2021). These heavy
metal ions present in water are difficult to be degraded into environ­
mentally friendly substances by biodegradation, compared to organic
pollutants (Joseph et al., 2019). Gradually, heavy metals in water are
easily absorbed by organisms, then enter the food chain and accumulate
in organisms, thus causing toxic hazards to organisms and eventually
endangering the human health (Fu and Xi, 2020; Zheng et al., 2020).
Due to the complex and changeable actual water body conditions, the
purification of toxic metal ions remains a tough challenge. Thus, it is
important to explore suitable methods for the removal of heavy metal
ions in actual water bodies.
In the past decades of study on the treatment of heavy metal ion
pollution in water, many treatment methods have been developed, such
as adsorption (Wen et al., 2013; Cheng et al., 2019; Chai et al., 2021),
photocatalysis (Hoch et al., 2008), biological treatments (Narayani and
Shetty, 2013), and membrane filtration (Gao et al., 2014), etc. It is worth
noting that adsorption technology has many advantages in capturing
heavy metal ions, such as high efficiency, simple design, and convenient
operation, which endow it one of the most widely used practical

* Corresponding author. College of Environmental Science and Engineering, Hunan University, Changsha, Hunan, 410082, China.
** Corresponding author.
E-mail addresses: leiqin@hnu.edu.cn (L. Qin), laicui@hnu.edu.cn (C. Lai).

https://doi.org/10.1016/j.chemosphere.2021.131432
Received 5 May 2021; Received in revised form 23 June 2021; Accepted 1 July 2021
Available online 6 July 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
Z. Li et al.
technologies for heavy metal pollution remediation. Traditional
adsorption materials include metal oxides (Tan et al., 2009), zeolite
molecular sieves (Santasnachok et al., 2015; He et al., 2020), activated
carbon (Ren et al., 2013), carbon nanotubes (Li et al., 2014a), nano
zero-valent iron (Zou et al., 2016), organic resin (Bhatti et al., 2014), etc.
Most of these traditional adsorbents are organic or inorganic porous
materials, which have certain disadvantages in the process of absorbing
heavy metals in water (Kumar et al., 2017). For example, metal oxides
have slow adsorption kinetics and limited selectivity, activated carbon
has small pore sizes, and organic resin shows poor reusability (Li et al.,
2018). Therefore, it is necessary to explore more efficient porous ma­
terials to overcome the limitations of traditional adsorption materials.
Besides, a single adsorbent material is insufficient to target heavy
metals in water and results in efficient adsorption of heavy metals,
because some heavy metals are highly toxic in the high-valence state and
low-toxic or non-toxic in the low-valence state (Feng et al., 2018;
Veerakumar and Lin, 2020). Hence, a matching and effective method is
needed to remove heavy metal ions whose toxicity varies greatly with
valence. Fortunately, photocatalytic technology can transform light
energy into chemical energy to degrade and reduce pollutants in water,
which is green, efficient, and sustainable (Qin et al., 2021; Wang et al.,
2021). Photocatalytic reduction of such heavy metal ions is an efficient
way to reduce high-valence state and highly toxic heavy metal ions into
low-valence state and low-toxic or non-toxic heavy metal ions. There­
fore, the combination of adsorption and photocatalysis technology is a
good idea to remove these heavy metal ions and reduce the toxicity of
them. In this respect, metal-organic frameworks (MOFs) are ideal ma­
terials for heavy metal adsorption and photocatalytic reduction, and
have the potential to become dual-functional materials.
MOFs is one kind of organic-inorganic hybrid material formed by
self-assembly of organic ligands and metal ions or clusters through co­
ordination bonds (Li et al., 1999; Liu et al., 2020b). It has the unique
characteristics of porosity, large specific surface area, and open metal
sites. MOFs enables structural and functional diversity through changing
metal center and organic ligand (Furukawa et al., 2010; Wang et al.,
2020d). These features, coupled with the ordered porous structure and
modifiable properties of MOFs, make it a great advantage in removing
heavy metal ions from water (Wang et al., 2016b; Lai et al., 2021). In
addition, MOFs is photoresponsive and can absorb light through organic
linkers or metal centers. As a photocatalyst, MOFs has the advantages of
good topology and high specific surface area, which can promote the
rapid translocation and good adjustment of target molecules (Zhang
et al., 2020e; Fu et al., 2020). It has shown great potential in the
application of photocatalytic reduction of heavy metal ions. However,
the water stability of MOFs is an important factor for their practical
application in the treatment of heavy metal pollution in water (Wang
et al., 2016a; Zhang et al., 2020c). The presence of water in the reaction
environment of water sensitive materials will have harmful effects on
the materials, and even lead to the structural degradation of the mate­
rials. Water-stable MOFs (WMOFs) is able to maintain structural and
functional stability in the aqueous environment to ensure that its reac­
tion of removing heavy metal ions from water can proceed smoothly
(Wang et al., 2016a). Due to the unique characteristics and advantages
of WMOFs, there have been many studies on WOMFs adsorption/pho­
tocatalytic reduction of toxic heavy metals in wastewater.
In previous studies, several reviews have focused on the synthesis
strategies and applications of WMOFs (Wang et al., 2016a; Feng et al.,
2018; Yuan et al., 2018; Liu et al., 2020a; Zhang et al., 2020c). Among
them, Liu et al. summarized the construction strategy of WMOF and
introduced the synthesis and application of representative WMOFs (Liu
et al., 2020a). Wang et al. discussed the application of WMOFs in the
fields of adsorption, catalysis, sensing, membrane separation, and pro­
ton conduction. A comprehensive discussion of the studies related to
moisture content in these fields was presented by Wang et al. (2016a).
So far, there is no article systematically discussing the WMOFs adsorp­
tion and photocatalytic reduction of heavy metals with different
2
Chemosphere 285 (2021) 131432
properties and the synergistic effect of adsorption and photocatalysis.
Therefore, this paper summarizes the post-synthesis modification
method to synthesize WMOFs, systematically reviews the applications of
WMOFs and their composites in the adsorption removal and photo­
catalytic reduction of heavy metals in aqueous solution. Finally, the
synergistic effect of WMOFs in the removal of heavy metal ions from
water is discussed.
2. Water stable metal¡organic frameworks (WMOFs)
2.1. Synthesis strategy of WMOFs
According to the definition, WMOFs are categorized as MOFs that do
not undergo structural damage and maintain functional stability when
exposed to water (Wang et al., 2016a). To determine the water stability
of MOFs, the degree of change in typical chemical characteristics of
MOFs after exposure to aqueous environment was used as a criterion.
The factors affecting the water stability of MOFs can be broadly classi­
fied into internal and external operational factors. Internal factors
include metal ions, organic ligands, metal-organic coordination bond
strength, metal-ligand coordination geometry, pore surface hydropho­
bicity, crystallinity and porosity; external factors include temperature,
pH, humidity, etc. (Canivet et al., 2014). Among them, the strength of
metal-organic coordination bonds (thermodynamic stability), hydro­
phobicity of the pore surface and spatial potential resistance (kinetic
stability) are important factors affecting the water stability of MOFs
(Burtch et al., 2014). Therefore, in order to prevent the structure of
MOFs from being destroyed by water molecules, it is necessary to fully
understand the interaction between water molecules and MOFs (Liu
et al., 2020a).
In an aqueous solution, the weaker metal-organic coordination
bonds are easily attacked by water molecules, and the organic ligands
are replaced by water molecules or hydroxide, destroying the structure
of MOFs (Wang et al., 2016a). Thus, enhancing the strength of
metal-organic coordination bonds can enhance the water stability of
MOFs (Yuan et al., 2018). Under the same coordination environment,
metal-organic coordination bonds formed by high-valent metal ions
with high charge density are stronger (Yuan et al., 2018). According to
Pearson’s hard/soft acid/base (HSAB) theory, the strong interaction
between hard acid and hard base or soft acid and soft base can form
strong coordination bonds, thereby building a stronger framework
(Miranda-Quintana, 2017). Usually, the high-valent metal units of MOFs
form a larger rigid structure, allowing the metal center to resist the
attack of water molecules to a certain extent (Qadir et al., 2015; Ding
et al., 2019). Hence, WMOFs can be constructed using carboxylate-based
ligands (hard Lewis bases) and high-valent metal ions (hard Lewis acids)
(Yuan et al., 2018). For example, Ferey and his colleagues have devel­
oped Material Institut Lavoisier (MIL) series: MIL-53(AI), MIL-100(Fe)
(Ferey et al., 2004), MIL-101(Cr) (Hupp, 2005), etc., which are chemi­
cally stable in various solvents for months (Liu et al., 2020a). In addi­
tion, there is the University of Oslo (UiO) series, based on the Zr4+
synthesis of UiO-66, which remains stable under acidic conditions
(Cavka et al., 2008). Soft azolate ligands are regarded as soft Lewis
bases, and soft divalent metal ions are regarded as soft Lewis acids.
WMOFs can also be constructed using carboxylate ligands and
high-valent metal ions (Park et al., 2006). The imidazoline zeolite
frameworks (ZIFs) in this type of structure are the most representative,
which use Zn2+ and imidazolate linkers to construct stable crystals
similar to the zeolite topology (Demessence et al., 2009).
According to the HSAB theory, the strengthening of metal-organic
coordination bonds determines the thermodynamic stability, making
the metal center and organic ligands be less susceptible to attacking by
water molecules. Besides, kinetic factors are also considered. The link
length of the metal-organic coordination bond is negatively related to
the stability of the framework (Yuan et al., 2018). The increase of the
bond length will lead to the decrease of stability, which is caused by an
Z. Li et al.
increase in the length of the coordination bond affecting its rigidity and
thus its dynamic stability (Cavka et al., 2008). In addition, it prevents
water molecules from approaching and attacking by functionalizing
enhanced steric hindrance and designs hydrophobic surfaces or adding
an additional layer of protection from metal ions (Fig. 1) (Yang and
Park, 2012)
2.2. Enhancement of water stability of MOFs by postsynthesis
modification (PSM)
Due to the characteristics of MOF materials and PSM methods, the
PSM methods are particularly suitable for use with MOFs, which can
improve the water stability and expand application range of MOFs, and
also can save time and cost (Mandal et al., 2020). The concept of PSM is
the introduction of target functional group into an already synthesized
material through coordination or functional group conversion reactions
Fig. 1. Mechanisms and experimental methods for improving the water stability in existing MOFs. Reproduced with permission (Burtch et al., 2014). Copyright
2014, American Chemical Society.
3
Chemosphere 285 (2021) 131432
(Nguyen and Cohen, 2012). It was first proposed by Hoskins and Robson
when they reported on metallo-cyanides that functionalized rod-like
substituents could be introduced into the framework (Hoskins and
Robson, 1990). Until 2007, when Cohen’s group synthesized the
amino-functionalized IRMOF-3 and realized the post-synthetic modifi­
cation of NH2, the post-synthetic modification approach was increas­
ingly used in MOFs (Batten et al., 2013). The synthesis of functional
MOFs by PSM has the following advantages: (1) When the target func­
tional group is incompatible with the synthesis conditions, the ligand
can be pre-functionalized to construct MOFs and then the target func­
tional group will be generated to synthesize the MOF material with
desired function; (2) MOFs are highly porous materials with uniform
pores, which can be modified not only by the outer surface of the ma­
terial, but also by the inner surface of the pores; (3) The topology of
MOFs is the same before and after modification, because PSM only reacts
on the skeleton of MOFs and does not change the original skeleton
Z. Li et al.
structure of them. Therefore, the water stability of MOFs can be
enhanced by hydrophobization, ligand functionalization, and metal
clustering modifications using PSM (Joyaramulu et al., 2019).
2.2.1. Hydrophobization
Enhancement of hydrophobicity is the most direct way to enhance
the water stability of MOFs, and the use of PSM to enhance the hydro­
phobicity of MOFs has received much attention. The internal and
external surfaces of MOFs can be hydrophobized using the PSM method.
The hydrophobicity of the internal pores of MOFs is internal surface
hydrophobicity, which can be judged through detecting the crystal
structure of MOFs. The hydrophobic surfaces of MOFs crystals are
external surface hydrophobic, which can be judged by measuring the
water contact angle.
(1) Internal surface hydrophobization
The internal surface of MOFs can be hydrophobized through the PSM
of the ligands. In 2008, Cohen et al. performed postsynthetic hydro­
phobization of IRMOF-3 ([Zn4O(1,4-bdc-NH2)3]) and MIL-53(Al)–NH2
([Al(OH)(1,4-bdc-NH2)]) (Cohen and Cohen, 2010). The PSM reaction
of amine groups and alkylic anhydride generated amide substituents,
which introduced a bulky or long hydrophobic alkyl group on its pore
surface. The integration of long or bulky alkyl groups within IRMOF-3
transformed it into a hydrophobic material, and water contact angle
increased from 0◦ to 105◦ –125◦ . Similarly, the water contact angles of
MIL-53(Al)–NH2 modified by alkyl anhydrides became very large. Its
crystallite size and the combination of hydrophobic functional groups
are the main reasons for the superhydrophobicity. In addition, Rubin
et al. modulated the hydrophobicity of [Cu3(NH2BTC)2] by the reaction
of alkyl anhydrides with amine groups to form amides (Rubin and
Reynolds, 2017). Hence, the water contact angle of Cu3(NH2BTC)2
samples with long alkyl chains was greatly improved.
The coordination of new ligands with metal centers via PSM is also a
way to improve the hydrophobicity of MOFs. Bae and his colleagues
modified Ni-MOF-74 with pyridine molecules by the dative PMS
method. The pyridine molecules occupy open metal sites, resulting in
hydrophobization of the hydrophilic Ni-MOF-74 internal surface (Bae
et al., 2014). Drache et al. exchanged fluorinated monocarboxylates to
monocarboxylate ligand of DUT-67([Zr6O6(OH)2(tdc)4(CH3COO)2]) by
the PSM method (Drache et al., 2016). The experimental results showed
that the exchange of ligands achieved internal hydrophobicity of
DUT-67. It was also discovered that water stability was improved by
PSM-exchange of DUT-67.
The hydrophobicity of MOFs is regulated by covalent bonding be­
tween the active substance and the inorganic SBUs. Decoste et al. re­
ported that the PSM of Cu-BTC (1,3,5 benzenetricarboxylic acid, BTC)
was obtained by a plasma-enhanced chemical vapor deposition of per­
fluorohexane (Decoste et al., 2012). Monte Carlo simulation revealed
that the aggregation of water clusters was hindered by fluorohexane,
thereby preventing the hydrolysis of Cu-BTC. Ding et al. polymerized 1,
2-divinylbenzene in the internal channel of MOF-5 by the PSM method,
which divided the channels of MOFs to form closed hydrophobic com­
partments. The surface of PN@MOF-5 exhibited hydrophobicity, and
the water contact angle increased from 0◦ to 135◦ (Ding et al., 2016).
(2) External surface hydrophobization
The hydrophobicity and stability of MOFs can also be improved by
modifying their external surface. Modification of the outer surface of
MOFs can be done using inorganic materials, hydrophobic small mole­
cules/ligands and organic polymers. Yang and Park prepared
amorphous-carbon coated MOF-5 in a N2 atmosphere at 480–530 ◦ C.
MOF-5 coated with amorphous carbon could still maintain a stable
structure after being soaked in aqueous solution for 2 h (Yang and Park,
2012). All the findings indicated that the coating of MOF-5 crystal
4
Chemosphere 285 (2021) 131432
surface with a hydrophobic amorphous-carbon could prevent the hy­
drolysis of MOFs to a certain extent. Liu et al. achieved hydro­
phobization on the external surface of ZIF-8 through a shell-ligand
exchange reaction. ZIF-8 hydrolysis was still observed in excessive
water, although it was considered as a stable MOF (Liu et al., 2013).
However, the 2-methylimidazole ligand in the outermost layer of ZIF-8
is replaced with hydrophobic 5,6-dimethylbenzimidazole (DMBIM)
through a ligand exchange reaction. The water contact angle of ZIF-8
increased from 60◦ to 121◦ , which indicates the enhancement of hy­
drophobicity and water stability of ZIF-8-DMBIM. This is because
DMBIM ligands are hydrophobic and produce steric hindrance. Some
studies have shown that MOFs can be hydrophobized by coating some
hydrophobic polymers. For instance, Zhang et al. reported a method for
preparing MOFs with polydimethylsiloxane (PDMS) -coating. It was
achieved by thermal degradation of PDMS to deposit volatile silicon
molecules and then cross-linking them to the surface of MOF (Fig. 2)
(Zhang et al., 2014). The water contact angle of MOF-5, HKUST-1, and
ZnBT are all close to 0◦ . After PDMS modification, their water tentacles
increase to 128◦ , 130◦ and 130◦ , respectively. The BET surface area of
HKUST-1 coated with PDMS remains essentially unchanged after being
soaked in water for 3 days. The PDMS coating can effectively prevent
water molecules from attacking the fragile coordination bonds, thereby
ensuring the stability of the MOF.
2.2.2. Ligand functionalization and metallic cluster modification
The hydrophobic and spatial properties of metallic ligands have been
greatly improved by the functionalization of organic ligands. The water
absorption isotherm can also be used to determine whether the
enhanced water stability is due to the strengthened framework stability
or increased hydrophobicity (Burtch et al., 2014). In addition, the water
stability of pillared MOFs can be enhanced by properly utilizing and
controlling the catenation (Jiang et al., 2013). For example, Lee et al.
reported a novel microporous metal organic framework JCM-1 ([Co
(PzIm)(NO3)]) that possessed the pyrazolate metal binding site and
imidazolium groups (Lee et al., 2018). The structure of JCM-1 is basi­
cally unchanged after being soaked in water for 2 months. The strong
water stability of JCM-1 was due to the methyl groups in the ligand and
the strong metal-pyrazolate bond.
Thermodynamically stable MOFs do not collapse after chronically
exposing in an aqueous environment. Inert metal cluster is the key
structural property of thermodynamically stable MOFs, which prevents
irreversible hydrolysis reactions under high water loads, and the metal
clusters of MOFs can be replaced by inert metals through cation ex­
change (Burtch et al., 2014). For example, Li et al. synthesized MOF-5s
doped with Ni ions to improve their water stability (Li et al., 2012). The
new NixZn4-xO6+ secondary units were more stable than the Zn4O6+
units, therefore, the water resistance of the framework was significantly
improved by the Ni-doped MOF-5s. In addition, ZIF-8 (Li et al., 2014b),
MIL-100(Cr) (Hall and Bollini, 2020), and Ni3(BTP)2 (Shearer et al.,
2013) all have strongly bound ligands, or in the absence of strongly
bound ligands, they all have highly inert metallic species (Cr3+), in order
to maintain good water stability.
The synergistic effect of ligand functionalization and metal cluster
modification also enables the synthesis of more stable MOFs. Zhang
et al. designed new Zr(IV)-MOFs using hexacarboxylate ligands as
functional group (Zhang et al., 2018b). The modification of metal
clusters using different functional groups such as HCOO− , PhCOO− ,
H2O/OH, and CH3COO− could adjust their water absorption properties.
All four MOFs exhibited good regeneration and water adsorption cycling
properties under mild conditions. Thus, the synergistic effect can
enhance the stability of MOFs while optimizing other properties.
Z. Li et al.
Fig. 2. Coating PDMS on the surface of MOFs and improving the moisture/water resistance of MOFs. Reproduced with permission (Zhang et al., 2014). Copyright
2014, American Chemical Society.
3. Heavy metals adsorption by WMOFs
3.1. Cation adsorption
3.1.1. Hg2+
Mercury is widespread in nature and human society and affects
human health due to its high toxicity. Organic mercury is more toxic
than inorganic mercury. Microorganisms in soil and water induce the
methylate inorganic mercury to form methylmercury and eventually
accumulate in animals and humans through the food chain (Rahman and
Singh, 2019; Wang et al., 2020c). High concentrations of mercury can
damage the cells, inhibit the enzyme activity and even threaten the
nervous and immune systems (Ali et al., 2019). In recent years, the
adsorption and removal of mercury ions (Hg2+) from water by various
WMOFs have been studied, and WMOFs have been found to have great
potential as effective adsorbents.
Sulfur functionalization or sulfide modification of MOFs can effec­
tively and selectively facilitate the adsorption and removal of Hg2+
because Hg2+ can bond with S and form strong affinity with it (Lai et al.,
2018; Qin et al., 2018). In 2014, Liu et al. synthesized alkenyl com­
pounds functionalized MOFs by PSM method. Cr-MIL-101-AS with
alkenyl side chains and thiol side chains had excellent adsorption per­
formance of Hg2+ from water and had good water stability (Liu et al.,
2014). In 2016, Mon et al. reported a newly synthesized Bio-MOF with a
honeycomb structure for mercury ions adsorption. The alkyl thiol chains
functionalized MOF not only have a special adsorption capacity for
mercury ions, but more importantly, it can be reused by using dimethyl
sulfide to reverse the adsorption process (Mon et al., 2016). In 2019, Li
et al. prepared NH2-MIL-68(In) to more clearly reflect the function of the
thioglycolic acid group. The exposed –NH2 group in the NH2-MIL-68(In)
channel provided accessible sites for surface functionalization by bind­
ing to the aldehyde/carboxylic acid. Generation of aramid groups from
thioglycolic acid was fixed on the channel wall of NH2-MIL-68(In) by
PSM method. Isothermal adsorption experiments revealed that the
introduction of mercaptoacetic acid groups made a key contribution to
the improved removal of Hg2+ from SH-MIL-68(In) (Li et al., 2019).
Hg2+ not only binds strongly to sulfur, but also to carboxyl, acyla­
mide, and hydroxyl groups. Therefore, the modification of MOFs with
these groups can greatly improve the adsorption capacity of MOFs to
Hg2+. In 2015, Luo et al. reported an acylamine and hydroxyl-
5
Chemosphere 285 (2021) 131432
functionalized MOF([Zn(hip)(L)]⋅(DMF)(H2O)) to remove Hg2+ from
aqueous solutions (Luo et al., 2015). [Zn(hip)(L)]⋅(DMF)(H2O) had 1-D
hexagonal channels with a pore size of 5.4 Å. The pore walls were
decorated with a large number of acylamines and hydroxyl groups
(Fig. S1). Data from EDS and FT-IR indicated that Hg2+ was inserted in
the form of HgCl2; Hg2+ species had strong interactions with imides and
hydroxyl functional groups. In 2019, Wu et al. synthesized
UiO-66-EDTA multifunctional adsorbent with octahedral structure and
amine and carboxyl groups, which remained stable under acidic con­
ditions at pH 1 (Wu et al., 2019). Notably, UiO-66-EDTA achieved a
removal rate of more than 99% for 11 metal ions in the coexisting sys­
tem. The results of XPS analysis showed that Hg2+ coordination with
carboxyl groups and tertiary amines was the reason for its high removal
efficiency.
Recently, Tian et al. prepared an adaptive MOF FJI-H30 using a
flexible TPMA[tris(pyridine- 4-ylmethyl)amine] ligand and Co(SCN)2
(Tian et al., 2020). FJI-H30 had anti-interference ability and could resist
various interference ions. Most interestingly, the Hg2+ ions adsorbed by
FJI-H30 would bind to the S atom of the SCN group, leading to the in-situ
deformation of FJIH-30 to form an extended framework (FJI-H30-Hg).
This adaptive deformation decreased the potential repulsion between
adsorbed Hg2+, which further promoted the adsorption of Hg2+ by
FJIH-30. Therefore, FJI-H30 with in situ adaptive deformation perfor­
mance was a promising and efficient heavy metal ion adsorption ma­
terial. Compared with previous studies, the development of MOFs is not
only about the enhancement of the adsorption capacity of Hg2+, but also
the potential of MOFs to be applied in the actual environment. Finally, a
summary of WMOFs that have been used in recent years for Hg2+
removal from water is presented in Table 1.
3.1.2. Pb2+
Lead is generally available in both inorganic and organic forms, and
divalent lead compounds include water-soluble and insoluble salts, such
as lead acetate and lead oxide. In humans and animals, lead exposure
and ingestion may have significant neurological, developmental, im­
mune, and renal health effects. Through biochemical processes, lead
inhibits or mimics the behavior of calcium and protein interactions to
exert lead toxicity, and Pb2+ emission is a serious problem and its
removal from water is critical to the human health (Shen et al., 2019;
Kumar et al., 2020).
Z. Li et al. Chemosphere 285 (2021) 131432

Table 1 MOFs with sulfur functionalization can also improve the adsorption
Adsorption data of Hg2+ by typical WMOFs in aqueous systems. of Pb2+ from aqueous solutions. In 2016, Zhang et al. prepared thiol-
Type of MOF Adsorption Equilibrium Optimal Ref. functionalized HS-mSi@MOF-5 and thiol-modified MOF-5 using silica
capacity time (min) pH gel layer as the Pb2+ adsorption medium (Zhang et al., 2016a). The
(mg g− 1) or n-value in the adsorption kinetics of HS-mSi@MOF-5 was larger than 1,
adsorption
which was much larger than the n value of the unmodified material,
rate
indicating that the thiol modification could significantly improve the
Cr-MIL-101-AS 99%(20 mg, 300 – Liu et al. adsorption capacity. The water stability test exhibited that the stability
10 ppm） (2014)
MIL-101-Thymine 52 200 6 Luo et al.
of the modified material was greatly improved compared to the original
(2016) sample.
In2S3/MIL-101 518 260 7 Liang et al. In addition, there are some MOFs composites with high adsorption
(2018) properties to Pb2+ while maintaining water stability. Zhao et al. syn­
SH-MIL-68(In) 450 360 4 Li et al.
thesized a highly loaded UiO-66-NH2-PAM-PET (PAM, polyacrylamide;
(2019)
UiO-66-NHC(S) 769 240 – Saleem et al. PET, polyethylene terephthalate) composite by growing MOFs on a
NHMe (2016) modified PET carrier, which was able to efficiently remove Pb2+ from
UiO-66-EDTA 371.6 30 7 Wu et al. water (Zhao et al., 2020a). The composites contained many –COOH,
(2019) –NH2, and –CO–NH2 groups for rapid capture of Pb2+ by ion exchange
UiO-66-DMTD 670.5 600 3 Fu et al.
(2019)
and electrostatic surface complexation. In general, the composites had
AC-UiO-66 205 1440 7 Solis et al. the advantages of simple synthesis, strong adsorption capacity for Pb2+,
(2020) which had a wide application prospect in practical water treatment.
Zr-DMBD 171.5 10 6 Ding et al. Finally, a summary of WMOFs that have been used in recent years for
(2018)
Pb2+ removal from water is presented in Table 2.
Zr-MAS 734 50 0–7 Yang et al.
(2019)
DUT-67 (Zr) 90%(10 mg, 60 6 Chen et al. 3.1.3. Cd2+
20 μg L− 1) (2018) Cadmium is used in a variety of industrial activities, including the
MOF-MA 1080 10 4 Wang et al. production of alloys, plastics and batteries, resulting in steadily
(2020b)
increasing concentrations of cadmium in the environment (Zhao et al.,
AMOF-1′ 78 1440 – Chakraborty
et al. (2016) 2020b). As a heavy metal, cadmium is a huge hazard to human health.
3D Co(II) MOF 70%（200 100 6 Abbasi et al. Most of the cadmium that enters the human body will accumulate in the
mg, 10 (2015) kidneys, liver and bones, causing various diseases such as anemia, high
ppm）
blood pressure, and nephritis (Dukic-Cosic et al., 2020).
2D-NCS 1698 270 4/9 Wang et al.
(2020a) Sulfonic acid functionalized MOF has a good adsorption and removal
LMOF-263 380 30 – Rudd et al. effect on Cd2+ in water, especially the selective adsorption capacity of
(2016) Cd2+. In 2015, Wang et al. functionalized HKUST-1 (Cu3(BTC)2) with
MFC-S 282 30 3 Huang et al. sulfonic acid and immobilized –SO3H on the surface of HKUST-1 by two
(2016)
post-synthetic modifications for the adsorption of Cd2+ (Wang et al.,
Fe-BTC/PDA 1634 1 7 Sun et al.
(2018) 2015b). Firstly, dithioglycol units were introduced into HKUST-1 and
MTV-MOF 99%（20 3 7 Mon et al. then converted to sulfonic acid by oxidation and acid treatment. The
mg, 1 ppm） (2019) chelation between Cd2+ and –SO3H group made Cu3(BTC)2-SO3H had a
FJI-H30 705 60 7 Tian et al.
fast-kinetic adsorption capacity of Cd2+. In 2016, Moradi et al. first
(2020)
Fe3O4@SiO2HKUST- 264 10 3 Huang et al.
functionalized water-stable MOF-235(Fe) by sulfonic acid and com­
1 (2015) plexed it with iron oxide nanoparticles to form a magnetic nanosorbent
Zn(hip)(L)⋅(DMF) 278 30 5 Luo et al. (Fe3O4@MOF-235(Fe)–OSO3H), which not only had high stability, low
(H2O) (2015) toxicity, and good reusability, but also could extract Cd2+ from water by
0.5HgCl2@CuII4[(S, 99.95%（50 15 Mon et al.
magnetic solid phase extraction (Moradi et al., 2016).
–
S)-methox]2}⋅ mg, 10 (2017)
5H2O ppm） In a stable zinc-based MOF, Ahmadijokani et al. synthesized
{[Ni1.5(L)(NH2- 93.69 300 3 Shao et al. ethylenediamine-functionalized UiO-66-EDA and investigated its ability
bpy)-(H2O)]⋅ (2018) to adsorb Cd2+ in water (Ahmadijokani et al., 2020). The adsorption of
7.5H2O}n
Cd2+ on UiO-66-EDA was consistent with the pseudo-second-order ki­
netic model and the Langmuir isotherm model, indicating that the
The amino functionalization of MOFs can effectively improve the adsorption was chemisorption and monolayer adsorption. The strong
adsorption performance of Pb2+ adsorption. In 2015, Ricco et al. first adsorption of Cd2+ by UiO-66-EDA was mainly due to the interaction
reported an amino-functionalized MIL-53(Al) water-resistant magnetic between metal ions, and the abundant functional groups on its surface.
composite for Pb2+ adsorption in aqueous samples by adjusting the NH2 The removal of Cd2+ by UiO-66-EDA could be improved by increasing
group concentration (Ricco et al., 2015). The magnetic frame composite the reaction temperature.
(MFC) reacts rapidly to external magnetic force, so it is easier to recycle. In addition, Esrafili investigated the adsorption of heavy metal ions
In 2018, Yin et al. synthesized novel melamine-modified MOFs to adsorb by MOFs with diverse functional groups in the pillar structure (Esrafili
Pb2+ in low-salt solutions (Yin et al., 2018). The calculations showed et al., 2018). Among them, the adsorption efficiency of MOFs with
that there was charge transfer and orbital transition between melamine amide functional group was higher than that of MOFs with imine
and MOFs. Furthermore, MOFs containing N atoms in the ligand showed functional group for metal ions. This was due to the stronger alkalinity of
better adsorption capacity for Pb2+. In 2019, Zhang et al. reported a the amide-biased amine group, which leads to a stronger interaction of
WMOFs (CAU-7-TATB) with ligands containing N to provide binding the Cd2+ with the MOFs coordination sites. Moreover, the electronic
sites for metal ions (Zhang et al., 2019a). CAU-7-TATB remained highly structure of the ligands of MOF is the main reason for its different
selective adsorption towards Pb2+ in the presence of multiple interfering adsorption modes. TMU-23 had suitable functional groups, high
ions. porosity and water stability. DFT calculations showed that the main
reason for the adsorption of Cd2+ by MOFs was the electrostatic

6
Z. Li et al. Chemosphere 285 (2021) 131432

Table 2
Adsorption data of Pb2+ by typical WMOFs in aqueous systems.
Type of MOF Adsorption capacity (mg g− 1) Equilibrium time (min) Optimal pH Ref.

HKUST-1-MW@H3PW12O40 98.18 120 7 Zou et al. (2013)

TMU-5 251 5 10 Tahmasebi et al. (2015)
MIL-53(Al) MFC 492.4 360 – Ricco et al. (2015)
MIL-101(Fe)/GO 128.6 15 6 Lu et al. (2019)
ZIF-8-0 1321.21 120 5 Song et al. (2019)
UiO-66-NH2 1795.3 40–45 4.5 Yin et al. (2016)
UiO-66-NHC(S)NHMe 232 240 – Saleem et al. (2016)
Melamine-modified Zr-MOFs 122 120 5 Yin et al. (2018)
UiO-66-NH2@CA 89.4 3660 – Lei et al. (2019)
UiO-66-EDA 243.9 360 7 Song et al. (2019)
UiO-66-NH2-PAM-PET 711.99 240 5 Zhao et al. (2020a)
Zn(Bim)(OAc)-NS 253.8 60 5.5 Xu et al. (2020)
MOF-MA 510 960 4 Wang et al. (2020b)
Dy-MOF 3.05 10 6.5 Jamali et al. (2016)
HS-mSi@MOF-5 312 30 6 Zhang et al. (2016a)
AMOF-1′ 71 1440 – Chakraborty et al. (2016)
Fe-BTC/PDA 394 1 7 Sun et al. (2018)
CAU-7-TATB 63 45 5 Zhang et al. (2019a)

interaction between the amine group of TMU-23 and metal ions. Finally,
a summary of WMOFs that have been used in recent years for Cd2+
removal from water is presented in Table 3.
3.1.4. Cu2+
Copper ion is a heavy metal element required in humans and ani­
mals, mainly in the two oxidation states of Cu+ and Cu2+. However, the
cycling of copper between oxidized and reduced copper may generate
hydroxyl radicals and superoxide, resulting in its potential toxicity. In
addition, excessive exposure and ingestion of copper have damaging
effects on the stomach, liver and kidneys, with a narrow concentration
range of beneficial and harmful effects (Kumar et al., 2021). Thus,
developing efficient method to remove excessive copper is very impor­
tant and MOFs-based adsorption technology is efficient on this.
In 2015, Tahmasebi et al. reported three MOFs modified with azine
et al., 2016b). In the pH range of 3–6, ZIF-8 can effectively adsorb both
high and low concentrations of Cu2+. In aqueous solutions with low
concentrations of Cu2+, ZIF-8 adsorbs Cu2+ by ion exchange. At high
Cu2+ concentrations, the main reason for adsorption is the coordination
of Cu2+ with the nitrogen group on 2-methylimidazole. In 2019, Wei
et al. loaded ZIF-8 onto graphene oxide (GO) and then modified the
composite material using 3-amino amine. ZIF-8 complexed with GO
could improve the adsorption capacity of MOFs and eliminate the
agglomeration of MOFs to a certain extent (Wei et al., 2019). Finally, a
summary of WMOFs that have been used in recent years for Cu2+
removal from water is presented in Table 4.
3.2. Anion adsorption
3.2.1. CrO2−4 and Cr2O7
2-

and imine groups, which were used to remove Cu2+ in water (Tahmasebi
et al., 2015). The azine and imine groups had easily accessible Lewis
base sites, which facilitated the adsorption of heavy metal ions. In
TMU-6, two nitrogen atoms are in resonance with the benzene ring,
which reduce the charge density of TMU-6. In addition, because of the
presence of a space between the two nitrogen atoms, they are less
accessible for metal ions than the nitrogen atoms in the azine groups of
TMU-5, and so, they have less interaction with metal ions. Therefore, the
azine group was more alkaline than the imine group, and the adsorption
efficiency of TMU-5 and TMU-4 for metal ions was almost the same,
while that of TMU-6 was lower. Among them, TMU-5 has better
adsorption capacity.
In addition, zinc-based MOFs have a good effect on the adsorption
removal of Cu2+ from water. Without any pretreatment or surface
functionalization, the water-stabilized zeolite imidazolite framework
has a high adsorption capacity for Cu2+ in water (800 mg g− 1) (Zhang
Chromium is a naturally occurring element whose valence states
range from trivalent to hexavalent chromium. Among them, trivalent
chromium is more stable and is always found in natural ores. The
toxicity of chromium and its compounds depends mainly on the oxida­
tion state and solubility. The toxicity of hexavalent chromium is far
stronger than that of trivalent chromium, and it is a highly toxic
carcinogen. Hexavalent chromium and its compounds are released into
the environment mainly as oxygen anions (CrO2− 2−
4 , Cr2O7 ) from in­
dustrial activities such as welding, dyes, and leather tanning (Pavesi and
Moreira, 2020).
The exchange of anions into cation hosts is a common anion capture
method, and its capture capacity is limited by the process balance. A new
method for selective capture of anions was first proposed by Fei et al.
using the single-crystal-to-single-crystal (SC-SC) mode, which replacing
the trap with the metastable state of the cationic material and recrys­
tallizing it to a new structure (Fei et al., 2011). In 2014, Fu et al.

Table 3
Adsorption data of Cd2+ by typical WMOFs in aqueous systems.
Type of MOF Adsorption capacity(mg g− 1) or adsorption rate Equilibrium time (min) Optimal pH Ref.

AMOF-1′ 41 1440 – Chakraborty et al. (2016)

TUM-5 43 15 10 Tahmasebi et al. (2015)
TUM-23 55 10 8 Esrafili et al. (2018)
MOF-88/PAN 225.05 10 – Efome et al. (2018)
3D Co(II) MOF 70%（200 mg，10 ppm） 10 6 Abbasi et al. (2015)
HS-mSi@MOF-5 98 30 6 Zhang et al. (2016a)
HKUST-1-MW@H3PW12O40 33 80 7 Zou et al. (2013)
UiO-66-NHC(S)NHMe 49 240 – Saleem et al. (2016)
UiO-66-EDA 217.39 360 7 Ahmadijokani et al. (2020)
ED-MIL-101(Cd) 63.15 180 8 Elaiwi and Sirkecioglu (2020)
Cu3(BTC)2-SO3H 88.7 10 6 Wang et al. (2015b)
Fe3O4@MOF-235(Fe)–OSO3H 163.9 5 3 Moradi et al. (2016)

7
Z. Li et al. Chemosphere 285 (2021) 131432

Table 4
Adsorption data of Cu2+ by typical WMOFs in aqueous systems.
Type of MOF Adsorption capacity (mg g− 1) or adsorption rate Equilibrium time (min) Optimal pH Ref.

ZIF-8 800 30 4 Zhang et al. (2016b)

f-ZIF-8@GO 1872.24 300 6 Wei et al. (2019)
TUM-5 57 15 10 Tahmasebi et al. (2015)
UiO-66(Zr)–2COOH 11 60 6 Zhang et al. (2015)
UiO-66-EDA 208.33 360 7 Ahmadijokani et al. (2020)
ED-MIL-101(Cd) 69.9 180 6 Elaiwi and Sirkecioglu (2020)
Dy-MOF 5 10 6.5 Jamali et al. (2016)
MOF-1 379.13 – 6 (Yu et al., 2018)
MOF-2(Cd) 439.1 20 5–6 Ghaedi et al. (2018)
HKUST-1-MW@H3PW12O40 225 120 7 Zou et al. (2013)

synthesized large nanotube channels of FIR-53 ([Zn2(Tipa)2(OH)]⋅
3NO3⋅12H2O) and FIR-54([Zn(Tipa)]⋅2NO3⋅DMF⋅4H2O)) via Zn(II) ions
and Tipa(tris(4-(1H-imidazole-1-yl)phenyl)amine) ligands (Fu et al.,
2014). Single-crystal x-ray diffraction of the samples after ion exchange
showed that Cr2O2− 7 filling the nanotube channels was able to equili­
brate the skeletal charge, suggesting a SC-SC transition of ion exchange
(Fig. 3). Later, Fu et al. synthesized a water-stable MOF [Zn2(TI­
PA)2(OH)(NO3)3]⋅5H2O, consisting of four small channels. This MOFs
not only exhibited high selectivity to CrO2− 4 , but more importantly, it
had a space-limiting effect on CrO2− 2−
4 . It could capture CrO4 in water
through SC-SC transformation, which proved that MOFs with
space-limited properties were powerful single-crystal tools for CrO2− 4
trapping (Fu et al., 2018). In 2019, Othong et al. synthesized flexible
MOFs, which not only maintained good adsorption capacity and selec­
tivity for CrO2− 2−
4 and Cr2O7 , but more importantly, expanded the pH
range for effective adsorption of CrO2− 2−
4 and Cr2O7 (Fig. S2) (Othong
et al., 2019).
By functionalizing the ligands, it is possible to make some MOFs
materials exhibit excellent adsorption performance to CrO2− 4 and Cr2O7
2−
in water. In 2018, He et al. designed a functionalized T-shaped ligand
4,4′ ,4′′ -(1Hbenzo[d]imidazole-2,4,7-triyl)tribenzoic acid (H3BTBA) and
synthesized the luminescent Zr(IV)- MOF (BUT-39, BUT = Beijing Uni­
versity of Technology) (He et al., 2018). BUT-39 had a unique porous
framework structure with BTBA3− as a T-shaped 3-connected linker, and
Zr6 cluster as an unusual low-symmetric 9-connected node. It could
the contact of FJI-C11 with Cr2O2− 7 in aqueous solution, thus enhancing
the adsorption of Cr2O2−7 . In addition, the high positive charge density of
FJI-C11 framework had a stronger coulombic attraction with Cr2O2− 7 ,
thus it had a high selective adsorption to Cr2O2− 7 . In 2020, Jiang et al.
reported a kind of zirconium-based cation MOFs (Zr–C-MOFs) that
introduced methylated 2,5-pyridinedicarboxylic acid as a linker, which
had strong coordination bonds and high metal groups (Jiang et al.,
2020). The cluster structure could remain stable in acid, and the pyri­
dine salt could be used as an anion exchanger. Zr–C-MOF enhanced the
acid resistance, selectivity, and adsorption capacity of CrO2− 4 .
The construction of the cationic MOF by zwitterionic ligands is also
an effective way to enhance the adsorption capacity of CrO2− 4 and
Cr2O2−
7 in aqueous solutions. In 2018, Zhang et al. synthesized a cationic
MOF ([Cu2L(H2O)2]⋅(NO3)2⋅5.5H2O) based on Cu2+ and amphoteric
ligand 1,1′ -bis(3,5-dicarboxyphenyl)-4,4′ -bipyridinium chlorine ([H4L]
Cl2) (Zhang et al., 2018a). Such 3D cation framework had the expected
nbo-type network of a typical [Cu2(O2C)4] paddlewheel configuration.
The adsorption properties were due to ion exchange by the interaction of
the 3D cation framework with anions. Later, Zhang et al. synthesized
MOFs([In3(ipbp)2(μ2-OH)(μ2-O)3]) with cuboctahedra and triangular
antiprismatic structures based on the zwitterionic ligand 1-(3,5-dicar­
boxyphenyl)-4,4′ -bipyridinium bromide (H2(ipbp)Br) (Zhang et al.,
2020a). Because of the surface electrostatic interaction of the MOFs
crystal surface with the CrO2− 2−
4 and Cr2O7 oxygen anions. A summary of
WMOFs that have been used in recent years for CrO2− 4 and Cr2O7
2−

exhibit excellent selective sensing and high adsorption performance for removal from water is presented in Table S1.
Cr2O2−7 at low concentration. In 2019, Zou et al. synthesized
imidazoline-functionalized MOF FJI-C11, which was a positively 3.2.2. SeO2−
3 and SeO4
2-

charged cationic mesoporous MOF (Zou et al., 2019). The high-density Selenium is an essential element for the human body. An appropriate
positive charge of the imidazole functionalized framework facilitated amount of selenium can help to improve the body’s immunity and other

Fig. 3. The structures of FIR-53 before and after ion exchange. a) 3D structure of FIR-53 containing NO3− along the c-axis; (b) 3D structureof FIR-53 containing NO3−
along the b-axis; (c) 3D structure of FIR-53 containing Cr2O2− 2−
7 along the c-axis; (d) 3D structure of FIR-53 containing Cr2O7 along the b-axis. Reproduced with
permission (Fu et al., 2014). Copyright 2014, American Chemical Society.

8
Z. Li et al.
functions. An intake of less than 40 μg per day will lead to selenium
deficiency in the human body, and an intake of more than 400 μg per day
is toxic (Li et al., 2018; Rayman, 2020). Selenium enters the water body
through many ways, such as the erosion of natural sediments, mining
and oil refinery discharge, etc., making the selenium pollution of the
water body become increasingly serious. Selenium is mainly present in
water in the form of SeO2− 2−
3 and SeO4 . In recent years, the use of MOFs
as adsorbents to remove SeO2− 2−
3 and SeO4 from water has emerged and
has shown great potential (Kumar et al., 2017).
The large pore size and large number of node adsorption sites are
very important for the MOF to adsorb SeO2− 2−
3 and SeO4 from aqueous
solutions quickly and efficiently. In 2015, Howarth et al. explored the
removal of SeO2− 2−
3 and SeO4 from water by a series of Zr-based WMOFs
and found that NU-1000([Zr6(l3-OH)8(OH)8(TBAPy)2], TBAPy =
1,3,6,8-tetrakis(p-benzoic acid)pyrene]) had the highest adsorption.
The NU-1000 was a 3D structure consisting of eight Zr6 nodes bridged by
TBAPy4+. These nodes were rich in hydroxyl groups, resulting in strong
adsorption of SeO2− 2−
3 and SeO4 by NU-1000 (Fig. S3). The NU-1000 had
triangular pores with a diameter of 12 Å and hexagonal pores with a
diameter of 30 Å, which resulted in fast adsorption speed because of the
large pores. In 2017, Li et al. designed Zr6 MOFs with different defects
and investigated the effect of defects on the capture of SeO2− 4 from
aqueous solutions (Li et al., 2017). The displaceable ligands and
weak-binding capping ligands on Zr6 nodes could be replaced by SeO2− 4 experiment. In short, As ions are adsorbed by oxygen fraction and
via an anion-exchange mechanism. The efficiency and rate of adsorption
of SeO2−4 by Zr6 MOFs increased with increasing density of missing
cluster defects and missing linkage defects. According to the experi­
mental results and DFT calculations, smaller Cl-, H2O- or HO- compen­
sation ligands were easier to be substituted. This modulator synthesis
strategy can effectively expand the pore size and introduce defects as
binding sites, thus improving the adsorption performance of MOFs.
In addition, some MOF-based composite materials have excellent
adsorption properties for SeO2− 2−
3 and SeO4 in water. In previous studies,
it was found that due to the low Fe density of some Fe-MOF channel
adsorption sites, the oxygen anion could not be adsorbed using these
channels (Wang et al., 2018). Wang et al. reported the use of Al3+ in situ
modified Fe-MOF to encapsulate aluminum in the pores (Wang et al.,
2019b). Because of the increase in adsorption site density, Al@Fe-MOF
improved its adsorption performance on SeO2− 3 . Compared with
Fe-MOF, the adsorption capacity of Al@Fe-MOF for selenite is increased
by 77%. In 2020, Solis synthesized AC-UiO-66 complex with large sur­
face area (Solis et al., 2020). The scanning electron microscope-energy
spectrum analysis results showed that the Se zone and the Zr-rich zone
completely overlap, indicating that the exposed UIO-66 surface was the
main reason for the adsorption of SeO2− 3 . The preparation of composite
materials is an effective way to improve the adsorption performance of
SeO2− 2−
3 and SeO4 , because it can be easier to achieve large pores and
more adsorption sites. Finally, a summary of WMOFs that have been
used in recent years for SeO2− 2−
3 and SeO4 removal from water is pre­
sented in Table S2.
3.2.3. As(III) and As(V)
Arsenic is a very toxic heavy metal element that is widely distributed
in the natural environment. Arsenic exists in the environment in
different oxidation states, forming different species. The toxicity of
inorganic arsenic is far greater than that of organic arsenic. In the water
environment, arsenic mainly appears in the form of oxygen anions.
Arsenic pollution has been recognized as a catastrophic problem, and
arsenic in low concentrations in drinking water can cause serious health
effects (Sodhi et al., 2019). The mercapto reaction of arsenic with pro­
teins and enzymes inhibits the function of sensitive enzymes, and the
liver, kidney, gastrointestinal tract, nervous system and circulatory
system of the human body are seriously affected (Rahman and Singh,
2019).
The removal of arsenic from water by MOFs was first reported by Zhu
et al. (2012). Because of the low adsorption properties of iron-based
9
Chemosphere 285 (2021) 131432
MOFs monomers, Xie et al. synthesized the amino-functionalized
MIL-88(Fe), which can accurately monitor trace arsenic in aqueous so­
lution and has excellent arsenic removal performance (Xie et al., 2017).
Its excellent adsorption performance is due to the open pores, large
specific surface area and abundant active sites of NH2-MIL-88(Fe).
Bimetallic MOFs can further enhance the adsorption performance of
arsenic-oxygen anions. In 2019, Gu et al. prepared a bimetallic
Fe/Mg-MIL-88B by introducing Mg ions into MOFs (Gu et al., 2019). Due
to the replacement of Fe3+ by some Mg2+, the crystal lattice of
Fe/Mg-MIL-88B changes and its specific surface area increases.
Fe/Mg-MIL-88B(0.5) formed Fe–O–As and Mg–O–As bonds due to the
interaction of H2AsO4 with metal ions, which rapidly reached adsorp­
tion equilibrium within 30 min. In addition, there are composites with
iron-based MOFs, which also improve their adsorption properties. In
2020, Pandi et al. prepared Fe-MIL-88B@PGCx% composite material by
growing MOFs on alginate-derived porous graphitic carbon (PGC)
(Pandi et al., 2020). After As(III) adsorbed on Fe-MIL-88B@PGC20%
composite, the Fe 2p peak marginally shifted to a higher EB, indicating
that iron actively participated in the adsorption of As(III)/As(V) through
chemical contacts as a result of the formation of Fe–O–As bonds. As
(III)/As(V) exchanged with hydroxyl groups of iron octahedral to suc­
cessfully form an internal spherical bidentate/monodentate complex. As
(III) was adsorbed and cum oxidized into As(V) during the adsorption
combined with iron clusters and exchanged for ligands through hy­
droxyl groups on the adsorbent surface.
Zirconium-based MOFs were also studied for As(V) sorption. In 2015,
Wang et al. synthesized the zirconium-based WMOFs (UiO-66), which
was first used as an adsorbent material to remove arsenate from water
(Wang et al., 2015a). The excellent adsorption capacity of UiO-66 is due
to the porous crystal structure of zirconia clusters, which affords a
number of active sites per unit space. UiO-66 has a two arsenic binding
sites, namely hydroxyl and phthalate ligands. In equilibrium, a Zr6
cluster captures 7 equivalent arsenic by forming Zr–O–As coordination
bonds. In 2019, Muthu Prabhu et al. synthesized a benzoic acid-driven
zirconium fumarate (Zr-fum) MOF (Muthu Prabhu et al., 2019). In the
absence of benzoic acid, zirconium and fumarate quickly precipitate to
form amorphous MOF. Using different amounts of benzoic acid to adjust
the surface charge of the MOF is beneficial to obtain defect-free Zr-fum
MOF and enhance the adsorption of AsO3− 3−
4 and AsO3 . In 2019, Huo
et al. prepared a magnetic Fe3O4@UiO-66 composite, which has a
unique core-shell structure with more active sites and abundant pores
(Huo et al., 2019). In addition, its magnetic properties facilitate the
separation of composites from aqueous solutions. Finally, a summary of
WMOFs that have been used in recent years for As(III) and As(V)
removal from water is presented in Table S3.
4. Heavy metals catalytic reduction by WMOFs
4.1. Photocatalytic mechanism
The common semiconductor photocatalyst is an n-type semi­
conductor material, which has an energy band structure of valence
band, conduction band, and forbidden band. The photocatalyst absorbs
light, and when the photon energy is above the absorption threshold of
the catalyst, the photocatalyst’s valence band electrons undergo an
inter-band jump from the valence band to the conduction band, result­
ing in photogenerated electrons (e− ) and holes (h+). The e− or h+ are in
a bound state due to Coulomb gravity. In the presence of electric and
"chemical" fields (When the photocatalyst is immersed in a solution, a
"self-built electric field" is created due to the formation of a double
electric layer; the oxidant or reductant at the particle/solution interface
captures e− or h+, which can be regarded as a "chemical field"), e− or h+
are separated and migrated to the surface of the photocatalyst by electric
field forces or diffusion (Li et al., 2020). The cavities that migrate to the
catalyst surface are usually captured by OH- and H2O to produce
Z. Li et al.
hydroxyl radical (OH•), which is a free radical with strong oxidizing
ability and can oxidatively degrade many organic substances. The e−
that migrate to the surface of the catalyst are usually captured by the
electron acceptor O2 adsorbed on the surface, generating a series of free
radicals such as O2− and HOO-, which can participate in several redox
processes and can be used to reduce heavy metal ions. Meanwhile, e− or
h+ can also be compounded inside or on the surface of the catalyst and
release the excitation energy as heat, reducing the quantum efficiency of
the photocatalytic reaction, which is very detrimental to the photo­
catalytic reaction. Therefore, the photocatalytic activity of the catalyst
can be enhanced by increasing the light absorption and decreasing the
complexation rate of e− or h+ (Fig. 4) (Henderson, 2011; Banerjee et al.,
2014; Schultz and Yoon, 2014; Litter, 2015; Loeb et al., 2018; Buzzetti
et al., 2019).
4.2. Heavy metals photocatalytic reduction
According to theoretical calculations, MOFs are semiconductors or
insulators with a band gap of 1.0–5.5 eV (Pham et al., 2014). When
MOFs are used as photocatalysts, they can afford a number of dispersed
active sites, which can reach the substrate/product through open
channels. In addition, each active site in MOFs can be seen as a single
quantum dot, acting as a light absorber, charge generator, and catalytic
site, just like a small semiconductor. The organic connectors in MOFs act
like antennas to absorb light (UV light, visible light and infrared light)
and transfer energy to the active site through ligand-metal charge
transfer. Due to the open framework structure of MOFs, their photo­
catalytic activity can be enhanced by modifying and functionalizing
MOFs and by synthesizing MOF-based composites that increase light
absorption and weaken the complexation rate of e− and h+ (Liu et al.,
2019; Wang et al., 2019a; Wu et al., 2020). Therefore, MOFs as photo­
catalysts can effectively reduce heavy metal ions in aqueous solutions. In
recent years, MOFs and MOFs-based composites have been used as
photocatalysts to reduce heavy metals, and the photocatalysis of chro­
mium in aqueous solutions is the main focus. We take chromium ions as
the main object to discuss the research of WMOFs photocatalytic
reduction of heavy metal ions in water.
Ammonia functionalized UiO-66 was first used by Shen and his
colleagues for the photocatalytic reduction of Cr(VI) to Cr(III) in water
(Shen et al., 2013). The introduction of amino groups on the organic
ligand of UiO-66 extends its light absorption range to the visible region.
UiO-66 is almost in an inactive state, while the photocatalytic reduction
reaction of UiO-66 (NH2) proceeds very smoothly under visible light
irradiation. Because the zirconium oxide clusters in UiO-66 (NH2) can be
Fig. 4. Schematic of semiconductor photocatalysis. Reproduced with permission (Banerjee et al., 2014). Copyright 2014, American Chemical Society.
10
Chemosphere 285 (2021) 131432
regarded as quantum dots, electron-hole pairs are excited when the
energy of the incident photon exceeds the energy band. In 2019, Zhang
et al. prepared ammonia-functionalized UiO-66 and then loaded silver
nanoparticles to form Ag/UiO-66-NH2 composites (Zhang et al., 2019b).
The local surface plasmon resonance effect of Ag facilitates the photo­
catalytic reduction of Cr(VI) by the composite. However, excessive Ag
loading reduces the separation efficiency of UiO-66-NH2, but Ag oc­
cupies the NH2 site, resulting in a relatively stable reduction rate. In
2020, Hussain et al. synthesized UiO-66-NH2@ZnIn2S4 composite with
high visible light-driven activity (Hussain et al., 2020). UiO-66-NH2
octahedron is bound by ZnIn2S4 nanoflakes. From the analysis of pho­
toluminescence spectra and ultraviolet and visible spectra, it can be seen
that the formed UiO-66-NH2@ZnIn2S4 heterostructure has a synergistic
effect.
Among the many MOFs series, iron-based MOFs exhibit better
property in photocatalytic reduction of Cr(VI) in water, and many iron-
based MOFs and various composite materials have emerged for this
application. In 2015, Liang et al. immobilized precious metal nano­
particles on MIL-100(Fe) by photo-deposition technique (Liang et al.,
2015). Under visible light irradiation, the reduction activity of the
synthesized M@MIL-100(Fe) for Cr(VI) was enhanced compared to
blank-MIL-100(Fe). The photoelectrochemical analysis showed that the
charge separation efficiency was effectively improved by the
noble-metal deposition. In 2018, Lin et al. synthesized MIL-53(Fe)/CQD
composite photocatalytic reduction of Cr(VI) by generating carbon
quantum dots (CQDs) in situ in MIL-53(Fe) (Lin et al., 2018). The CQDs
generated in the MOF pores have more opportunities to contact the
photocatalytic unit than those on the surface and are able to form many
small heterojunction structures. The internally generated CQDs can act
as a local electron acceptor and have a better ability to inhibit the
complexation of photogenerated electrons with metal-oxygen clusters
(Fig. S4). In addition, CQDs can also act as photosensitizers to sensitize
part of the visible light, improve the light absorption of the composites
in the long-wave visible region, and improve its catalytic activity (Zhang
et al., 2020b). In 2019, Yuan et al. synthesized TiO2@NH2-MIL-88B(Fe)
composites for the photocatalytic reduction of Cr(VI) in neutral aqueous
solutions (Yuan et al., 2019). Because H+ is required to reduce Cr(VI),
the pH of the reaction solution has a strong influence on the photo­
catalytic activity. The composites reduce Cr(VI) by trapping hydrogen in
water or pore scavengers. In addition, it was found that the
small-molecule organic substances could help to inhibit the recombi­
nation of photogenic carriers. The hole scavenger added during the
reduction process, especially ammonium oxalate, significantly improves
the reduction efficiency of Cr(VI) (Fig. S5).
Z. Li et al.
Except for Cr(VI), there is no example of using MOFs as photo­
catalysts to catalyze the reduction of other heavy metal ions. In previous
reports, some studies on the reduction of heavy metals by TiO2 and its
composites as photocatalysts have been found, such as photocatalytic
reduction of Ni(II) in water by TiO2 (Saien et al., 2019), TiO2 hollow
sphere photocatalytic reduction of As(III) and Cr(VI) in water (Cai and
Li, 2020), Pb(II) in Cu–TiO2 photocatalytic reduction of water (Sree­
kantan et al., 2014), and other materials photocatalytic reduction of Zn
(II) in water, Cu (II), Hg(II), etc. (Mohamed and Aazam, 2012; He et al.,
2019; Shahzad et al., 2019). Therefore, photocatalytic materials have
potential for photocatalytic reduction of heavy metals in water. MOFs
materials have unique advantages, and its photocatalytic reduction of
heavy metals in water needs further development. Finally, a summary of
WMOFs as photocatalysts for the reduction of Cr(VI) is presented in
Table S4.
4.3. Synergistic effect of adsorption and photocatalysis
Adsorption and photocatalytic reduction of heavy metal ions in
water are not independent, there is always a coupling and synergistic
effect between them. WMOFs with unique properties have a better effect
by using both of adsorption and photocatalytic reduction properties
when treating a single pollutant or different pollutants.
In 2015, Liang et al. synthesized dual-functional MIL-53(Fe) photo­
catalytic degradation of organic dyes and reduction of Cr(VI) in water
(Liang et al., 2015c). In a mixed solution system, MIL-53(Fe) can oxidize
organic dyes and reduce Cr(VI) to Cr(III) at the same time. The presence
of Cr(VI) promotes the photocatalytic oxidation of malachite green and
Fig. 5. (a) The reusability of BT-1 for the removal of Cr ions. (b) PXRD patterns of BT-1 before and after three recycles for Cr removal. (c) XPS scanning spectra before
and after the photocatalysis-adsorption process of BT-1. (d) Possible photocatalytic and adsorption reaction mechanism of BT-1. Reproduced with permission (Wang
et al., 2019d). Copyright 2019, Elsevier Ltd.
11
Chemosphere 285 (2021) 131432
rhodamine B. The synergistic effect of the photocatalytic reduction and
oxidation processes significantly enhanced the photocatalytic activity of
MIL-53(Fe) in the mixed solution system. The organic dyes are oxidized
to hole scavengers and the Cr(VI) ions are reduced to photogenerated
electron acceptors. In 2019, Wang et al. synthesized BUC-21 composites
with Titanate nanotube composites (TNTs) by a ball milling process,
which can achieve photocatalytic reduction of Cr(VI) to Cr(III) and
adsorption of the reduced Cr(III) products in one system (Wang et al.,
2019d). First, the composite photocatalytically reduces Cr(VI) ions to Cr
(III) ions, and then the formed Cr(III) ions accumulates around BUC-21
through electrostatic interactions. Due to the high concentration on the
BUC-21 surface, even Cr(OH)3 precipitates were formed, which further
inhibited the photocatalytic reduction of Cr(VI). However, TNTs can
trap the Cr(III) formed on the BUC-21 surface, eliminating the possible
Cr(OH)3 precipitate. The transfer of Cr(III) from BUC-21 to TNTs
resulted in release of the photocatalytic site of BUC-21, which promotes
the photocatalytic reduction of Cr(VI) (Fig. 5). The synergistic effect of
adsorption and photocatalysis allows the removal of Cr(III) adsorption
generated during photocatalysis, while enhancing the performance of Cr
(VI) photocatalytic reduction. Recently, Valizadeh et al. developed an
integrated adsorption photoreduction system for capturing Cr(VI) in
actual water and reducing it to Cr(III) (Valizadeh et al., 2020). For this
purpose, the researchers functionalized the UiO-66 with a double amino
group, makes the newly synthesized Zr-BDC-(NH2)2 have the dual
functions of adsorption and photocatalysis. It is assumed that the ideal
application is based on separation from water. The polymer needs to be
carefully selected to ensure that the polymer is sufficiently hydrophilic.
Since polyethersulfone (PES) is highly hydrophilic, PES is selected and
Z. Li et al.
modified with carboxyl groups to enhance its hydrophilicity. A com­
parison between un-modified and modified PES indicates a significant
decrease in the water contact angle from 89◦ to 25◦ , respectively. Next,
Zr-BDC-(NH2)2 was combined with polyethersulfone into MOF@pol­
ymer beads (M@PB). The researchers designed a simple separation
process, including two glass columns for placing the material and an
excitation light source. Zr-BDC-(NH2)2@PB provides the highest Cr(VI)
absorption capacity reported so far, fast extraction rate, high Cr(VI)
selectivity in actual water, and complete recovery capability. The ca­
pacity of Zr-BDC-(NH2)2@PB is attributed to the Zr-BDC-(NH2)2 crystals
and the synergistic effect between the MOF and polymer. Due to the
synergistic effect between MOF and polymer, which might promote the
formation of molecular pockets in the polymer matrix at the MOF
polymer interface; the latter could introduce new adsorption sites within
the polymer matrix.
5. Conclusions and prospects
By reviewing the WMOFs and its application in the removal of heavy
metal ions in water in the past few years, we have a clearer under­
standing of its development. First, water stability is an important
consideration factor for any material used in an aquatic environment. In
this paper, we focus on PSM method to improve the water stability of
MOFs, and discuss the strategies to improve the water stability of MOFs
in terms of hydrophobization, ligand functionalization, and modifica­
tion of metal clusters. A great number of WMOFs have been successfully
constructed, and their applications in the water environment have been
further developed. Then, WMOFs and MOF-based composites are green
materials with excellent performance in removing cationic and anionic
heavy metal ions from an aqueous environment. It not only is an
excellent adsorption material, but also can exert the performance of
photocatalytic reduction of heavy metal ions. By introducing appro­
priate functional groups into MOFs or synthesizing MOF-based com­
posites, the ability to remove heavy metal ions can be effectively
enhanced, and the stability of MOFs can be improved. MOFs as adsor­
bents can quickly and effectively adsorb heavy metal ions in an aqueous
solution through a large number of nodes and pores. MOFs as photo­
catalysts can produce electron and hole pairs under visible light
photoexcitation, and electrons and superoxide radicals as strong oxi­
dants can effectively reduce heavy metal ions. It is worth paying
attention to the application of the photocatalytic reduction performance
of WMOFs and WMOF-based composite materials. They synergize the
adsorption performance and the photocatalytic reduction performance
to better remove heavy metal ions in the water.
Although the construction of WMOFs and their application in the
water environment have been well developed, we still found problems in
their development. Firstly, it is limited by the synthesis cost of MOFs. At
present, most MOFs are still in the experimental stage, and the high price
of organic linkers such as H3BTC and H2BDC used in the synthesis
process leads to the high cost of their synthesis. Secondly, many MOFs
require organic solvents such as methanol and N, N-dimethylformamide
in the synthesis process, and the toxicity of using organic solvents to the
environment should also be fully considered. Last but not least, MOFs
are influenced by pH, ionic strength, and other ions in a complex real
water environment. In addition to practical application issues, many of
the reported porous MOFs are microporous, which is not conducive to
the migration of large metal ions within the framework. The slow
adsorption kinetics of many MOFs is also an important issue.
Faced with these problems and challenges, the application potential
of WMOFs needs to be further improved in the future research. The
development of green synthesis and inexpensive organic linkers for
aqueous phase is the direction in which WMOFs can be practically
applied in the future. The adsorption and catalytic properties of WMOFs
are improved and structural stability is enhanced by modifying various
functional groups and combining them with other materials. It is worth
paying attention to the application of the photocatalytic reduction
12
Chemosphere 285 (2021) 131432
performance of WMOFs and WMOF-based composites, which synergizes
the adsorption performance and photocatalytic reduction performance.
The photocatalytic reduction can be obtained during the adsorption of
heavy metal ions, forming a green and sustainable removal process.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This study was financially supported by the Program for the National
Natural Science Foundation of China (51879103, 51779090), Hunan
Natural Science Foundation (2020JJ3009), Hunan Researcher Award
Program (2020RC3025), and the Fundamental Research Funds for the
Central Universities (531118040083, 531118010473).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.chemosphere.2021.131432.
References
Abbasi, A., Moradpour, T., Van Hecke, K., 2015. A new 3D cobalt (II) metal–organic
framework nanostructure for heavy metal adsorption. Inorg. Chim. Acta. 430,
261–267.
Ahmadijokani, F., Tajahmadi, S., Bahi, A., Molavi, H., Rezakazemi, M., Ko, F.,
Aminabhavi, T.M., Arjmand, M., 2020. Ethylenediamine-functionalized Zr-based
MOF for efficient removal of heavy metal ions from water. Chemosphere 264,
128466.
Ali, H., Khan, E., Ilahi, I., 2019. Environmental chemistry and ecotoxicology of
hazardous heavy metals: environmental persistence, toxicity, and bioaccumulation.
J. Chem. 1–14.
Bae, Y.S., Liu, J., Wilmer, C.E., Sun, H., Dickey, A.N., Kim, M.B., Benin, A.I., Willis, R.R.,
Barpaga, D., LeVan, M.D., Snurr, R.Q., 2014. The effect of pyridine modification of
Ni-DOBDC on CO2 capture under humid conditions. Chem. Commun. 50,
3296–3298.
Banerjee, S., Pillai, S.C., Falaras, P., O’Shea, K.E., Byrne, J.A., Dionysiou, D.D., 2014.
New insights into the mechanism of visible light photocatalysis. J. Phys. Chem. Lett.
5, 2543–2554.
Batten, S.R., Champness, N.R., Chen, X.-M., Garcia-Martinez, J., Kitagawa, S.,
Öhrström, L., O’Keeffe, M., Paik Suh, M., Reedijk, J., 2013. Terminology of
metal–organic frameworks and coordination polymers (IUPAC Recommendations
2013). Pure Appl. Chem. 85, 1715–1724.
Bhatti, A.A., Memon, S., Memon, N., 2014. Dichromate extraction by calix [4] arene
appended amberlite XAD-4 resin. Separ. Sci. Technol. 49, 664–672.
Bora, A.J., Dutta, R.K., 2019. Removal of metals (Pb, Cd, Cu, Cr, Ni, and Co) from
drinking water by oxidation-coagulation-absorption at optimized pH. J. Water
Process Eng. 31, 100839.
Burtch, N.C., Jasuja, H., Walton, K.S., 2014. Water stability and adsorption in metal-
organic frameworks. Chem. Rev. 114, 10575–10612.
Buzzetti, L., Crisenza, G.E.M., Melchiorre, P., 2019. Mechanistic studies in
photocatalysis. Angew. Chem. Int. Ed. 58, 3730–3747.
Cai, J., Li, H., 2020. Electrospun polymer nanofibers coated with TiO2 hollow spheres
catalyze for high synergistic photo-conversion of Cr(VI) and As(III) using visible
light. Chem. Eng. J. 398, 125644.
Canivet, J., Fateeva, A., Guo, Y., Coasne, B., Farrusseng, D., 2014. Water adsorption in
MOFs: fundamentals and applications. Chem. Soc. Rev. 43, 5594–5617.
Cavka, J.H., Jakobsen, S., Olsbye, U., Guillou, N., Lamberti, C., Bordiga, S., Lillerud, K.P.,
2008. A new zirconium inorganic building brick forming metal organic frameworks
with exceptional stability. J. Am. Chem. Soc. 130, 13850–13851.
Chai, W.S., Cheun, J.Y., Kumar, P.S., Mubashir, M., Majeed, Z., Banat, F., Ho, S.-H.,
Show, P.L., 2021. A review on conventional and novel materials towards heavy
metal adsorption in wastewater treatment application. J. Clean. Prod. 296, 126589.
Chakraborty, A., Bhattacharyya, S., Hazra, A., Ghosh, A.C., Maji, T.K., 2016. Post-
synthetic metalation in an anionic MOF for efficient catalytic activity and removal of
heavy metal ions from aqueous solution. Chem. Commun. 52, 2831–2834.
Chen, S., Feng, F., Li, S., Li, X.-X., Shu, L., 2018. Metal-organic framework DUT-67 (Zr)
for adsorptive removal of trace Hg2+ and CH3Hg+ in water. Chem. Speciat.
Bioavailab. 30, 99–106.
Cheng, S.Y., Show, P.L., Lau, B.F., Chang, J.S., Ling, T.C., 2019. New prospects for
modified algae in heavy metal adsorption. Trends Biotechnol. 37, 1255–1268.
Cohen, J.G., Cohen, S.M, 2010. Moisture-resistant and superhydrophobic metal-organic
frameworks obtained via postsynthetic modification. J. Am. Chem. Soc. 132,
4560–4561.
Z. Li et al.
Decoste, J.B., Peterson, G.W., Smith, M.W., Stone, C.A., Willis, C.R., 2012. Enhanced
stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor
deposition. J. Am. Chem. Soc. 134, 1486–1489.
Demessence, A., D’Alessandro, D.M., Foo, M.L., Long, J.R., 2009. Strong CO2 binding in a
water-stable, triazolate-bridged metal-organic framework functionalized with
ethylenediamine. J. Am. Chem. Soc. 131, 8784–8786.
Dinda, D., Gupta, A., Saha, S.K., 2013. Removal of toxic Cr(VI) by UV-active
functionalized graphene oxide for water purification. J. Mater. Chem. 1,
11221–11228.
Ding, N., Li, H., Feng, X., Wang, Q., Wang, S., Ma, L., Zhou, J., Wang, B., 2016.
Partitioning MOF-5 into confined and hydrophobic compartments for carbon capture
under humid conditions. J. Am. Chem. Soc. 138, 10100–10103.
Ding, L., Luo, X., Shao, P., Yang, J., Sun, D., 2018. Thiol-functionalized Zr-based
metal–organic framework for capture of Hg(II) through a proton exchange reaction.
ACS Sustain. Chem. Eng. 6, 8494–8502.
Ding, M.L., Cai, X.C., Jiang, H.L., 2019. Improving MOF stability: approaches and
applications. Chem. Sci. 10, 10209–10230.
Drache, F., Bon, V., Senkovska, I., Marschelke, C., Synytska, A., Kaskel, S., 2016.
Postsynthetic inner-surface functionalization of the highly stable zirconium-based
metal-organic framework DUT-67. Inorg. Chem. 55, 7206–7213.
Dukic-Cosic, D., Baralic, K., Javorac, D., Djordjevic, A.B., Bulat, Z., 2020. An overview of
molecular mechanisms in cadmium toxicity. Curr. Opin Toxicol. 19, 56–62.
Efome, J.E., Rana, D., Matsuura, T., Lan, C.Q., 2018. Insight studies on metal-organic
framework nanofibrous membrane adsorption and activation for heavy metal ions
removal from aqueous solution. ACS Appl. Mater. Interfaces 10, 18619–18629.
Elaiwi, F.A., Sirkecioglu, A., 2020. Amine-functionalized metal organic frameworks MIL-
101(Cr) adsorbent for copper and cadmium ions in single and binary solution. Separ.
Sci. Technol. 55, 3362–3374.
Esrafili, L., Safarifard, V., Tahmasebi, E., Esrafili, M.D., Morsali, A., 2018. Functional
group effect of isoreticular metal–organic frameworks on heavy metal ion
adsorption. New J. Chem. 42, 8864–8873.
Fei, H., Bresler, M.R., Oliver, S.R., 2011. A new paradigm for anion trapping in high
capacity and selectivity: crystal-to-crystal transformation of cationic materials.
J. Am. Chem. Soc. 133, 11110–11113.
Feng, M., Zhang, P., Zhou, H.C., Sharma, V.K., 2018. Water-stable metal-organic
frameworks for aqueous removal of heavy metals and radionuclides: a review.
Chemosphere 209, 783–800.
Ferey, G., Serre, C., Mellot-Draznieks, C., Millange, F., Surble, S., Dutour, J.,
Margiolaki, I., 2004. A hybrid solid with giant pores prepared by a combination of
targeted chemistry, simulation, and powder diffraction. Angew. Chem. 43,
6296–6301.
Fu, F.L., Wang, Q., 2011. Removal of heavy metal ions from wastewaters: a review.
J. Environ. Manag. 92, 407–418.
Fu, Z.S., Xi, S.H., 2020. The effects of heavy metals on human metabolism. Toxicol.
Mech. Methods 30, 167–176.
Fu, H.-R., Xu, Z.-X., Zhang, J., 2014. Water-stable metal–organic frameworks for fast and
high dichromate trapping via single-crystal-to-single-crystal ion exchange. Chem.
Mater. 27, 205–210.
Fu, H.R., Wang, N., Qin, J.H., Han, M.L., Ma, L.F., Wang, F., 2018. Spatial confinement of
a cationic MOF: a SC-SC approach for high capacity Cr(VI)-oxyanion capture in
aqueous solution. Chem. Commun. 54, 11645–11648.
Fu, L.K., Wang, S.X., Lin, G., Zhang, L.B., Liu, Q.M., Fang, J., Wei, C.H.N., Liu, G., 2019.
Post-functionalization of UiO-66-NH2 by 2,5-Dimercapto-1,3,4-thiadiazole for the
high efficient removal of Hg(II) in water. J. Hazard Mater. 368, 42–51.
Fu, Y.K., Zeng, G.M., Lai, C., Huang, D.L., Qin, L., Yi, H., Liu, X.G., Zhang, M.M., Li, B.S.,
Liu, S.Y., Li, L., Li, M.F., Wang, W.J., Zhang, Y.J., Pi, Z.J., 2020. Hybrid architectures
based on noble metals and carbon-based dots nanomaterials: a review of recent
progress in synthesis and applications. Chem. Eng. J. 399, 125743.
Furukawa, H.F., Ko, N., Go, Y.B., Aratani, N., Choi, S.B., 2010. Ultrahigh porosity in
metal-organic frameworks. Science 329, 424–428.
Gao, J., Sun, S.P., Zhu, W.P., Chung, T.S., 2014. Chelating polymer modified P84
nanofiltration (NF) hollow fiber membranes for high efficient heavy metal removal.
Water Res. 63, 252–261.
Ghaedi, A.M., Panahimehr, M., Nejad, A.R.S., Hosseini, S.J., Vafaei, A., Baneshi, M.M.,
2018. Factorial experimental design for the optimization of highly selective
adsorption removal of lead and copper ions using metal organic framework MOF-2
(Cd). J. Mol. Liq. 272, 15–26.
Gu, Y., Xie, D., Wang, Y., Qin, W., Zhang, H., Wang, G., Zhang, Y., Zhao, H., 2019. Facile
fabrication of composition-tunable Fe/Mg bimetal-organic frameworks for
exceptional arsenate removal. Chem. Eng. J. 357, 579–588.
Hader, D.P., Banaszak, A.T., Villafane, V.E., Narvarte, M.A., Gonzalez, R.A., Helbling, E.
W., 2020. Anthropogenic pollution of aquatic ecosystems: emerging problems with
global implications. Sci. Total Environ. 713, 9742–9746.
Hall, J.N., Bollini, P., 2020. Enabling access to reduced open-metal sites in metal-organic
framework materials through choice of anion identity: the case of MIL-100(Cr). ACS
Mater. Lett. 2, 838–844.
He, T., Zhang, Y.Z., Kong, X.J., Yu, J., Lv, X.L., Wu, Y., Guo, Z.J., Li, J.R., 2018. Zr(IV)-
based metal-organic framework with T-shaped ligand: unique structure, high
stability, selective detection, and rapid adsorption of Cr2O2- 7 in Water. ACS Appl.
Mater. Interfaces 10, 16650–16659.
He, F., Lu, Z., Song, M., Liu, X., Tang, H., Huo, P., Fan, W., Dong, H., Wu, X., Han, S.,
2019. Selective reduction of Cu2+ with simultaneous degradation of tetracycline by
the dual channels ion imprinted POPD-CoFe2O4 heterojunction photocatalyst. Chem.
Eng. J. 360, 750–761.
He, J.F., Lai, C., Qin, L., Li, B.S., Liu, S.Y., Jiao, L.J., Fu, Y.K., Huang, D.L., Li, L.,
Zhang, M.M., Liu, X.G., Yi, H., Chen, L., Li, Z.W., 2020. Strategy to improve gold
13
Chemosphere 285 (2021) 131432
nanoparticles loading efficiency on defect-free high silica ZSM-5 zeolite for the
reduction of nitrophenols. Chemosphere 256, 127083.
Henderson, M.A., 2011. A surface science perspective on TiO2 photocatalysis. Surf. Sci.
Rep. 66, 185–297.
Hoch, L.B., Mack, E.J., Hydutsky, B.W., Hershman, J.M., Skluzacek, J.M., Mallouk, T.E.,
2008. Carbothermal synthesis of carbon-supported nanoscale zero-valent iron
particles for the remediation of hexavalent chromium. Environ. Sci. Technol. 42,
2600–2605.
Hoskins, B.F., Robson, R., 1990. Design and construction of a new class of scaffolding-
like materials comprising infinite polymeric frameworks of 3D-linked molecular
rods. J. Am. Chem. Soc. 112, 1546–1554.
Huang, L., He, M., Chen, B., Hu, B., 2015. A designable magnetic MOF composite and
facile coordination-based post-synthetic strategy for the enhanced removal of Hg2+
from water. J. Mater. Chem. 3, 11587–11595.
Huang, L., He, M., Chen, B., Hu, B., 2016. A mercapto functionalized magnetic Zr-MOF
by solvent-assisted ligand exchange for Hg2+ removal from water. J. Mater. Chem. 4,
5159–5166.
Humelnicu, D., Lazar, M.M., Ignat, M., Dinu, I.A., Dragan, E.S., Dinu, M.V., 2020.
Removal of heavy metal ions from multi-component aqueous solutions by eco-
friendly and low-cost composite sorbents with anisotropic pores. J. Hazard Mater.
381, 120980.
Huo, J.-B., Xu, L., Chen, X., Zhang, Y., Yang, J.-C.E., Yuan, B., Fu, M.-L., 2019. Direct
epitaxial synthesis of magnetic Fe3O4@UiO-66 composite for efficient removal of
arsenate from water. Microporous Mesoporous Mater. 276, 68–75.
Hupp, J.T., 2005. Chemistry: enhanced: Better living through nanopore chemistry.
Science 309, 2008–2009.
Hussain, M.B., Azhar, U., Loussala, H.M., Razaq, R., 2020. Synergetic effect of ZnIn2S4
nanosheets with metal-organic framework molding heterostructure for efficient
visible- light driven photocatalytic reduction of Cr(VI). Arabian J. Chem. 13,
5939–5948.
Jamali, A., Tehrani, A.A., Shemirani, F., Morsali, A., 2016. Lanthanide metal-organic
frameworks as selective microporous materials for adsorption of heavy metal ions.
Dalton Trans. 45, 9193–9200.
Jiang, H.-L., Makal, T.A., Zhou, H.-C., 2013. Interpenetration control in metal–organic
frameworks for functional applications. Coord. Chem. Rev. 257, 2232–2249.
Jiang, C., Sun, R., Du, Z., Singh, V., Chen, S., 2020. A cationic Zr-based metal organic
framework with enhanced acidic resistance for selective and efficient removal of
CrO2−4 . New J. Chem. 44, 12646–12653.
Joseph, L., Jun, B.M., Flora, J.R.V., Park, C.M., Yoon, Y., 2019. Removal of heavy metals
from water sources in the developing world using low-cost materials: a review.
Chemosphere 229, 142–159.
Joyaramulu, K., Geyer, F., Schneemann, A., Kment, S., Otyepka, M., Zboril, R.,
Vollmer, D., Fischer, R.A., 2019. Hydrophobic metal-organic frameworks. Adv.
Mater. 31, 1900820.
Kumar, P., Pournara, A., Kim, K.-H., Bansal, V., Rapti, S., Manos, M.J., 2017. Metal-
organic frameworks: challenges and opportunities for ion-exchange/sorption
applications. Prog. Mater. Sci. 86, 25–74.
Kumar, A., Kumar, A., Cabral-Pinto, M.M.S., Chaturvedi, A.K., Shabnam, A.A.,
Subrahmanyam, G., Mondal, R., Gupta, D.K., Malyan, S.K., Kumar, S.S., Khan, S.A.,
Yadav, K.K., 2020. Lead toxicity: health hazards, influence on food chain, and
sustainable remediation approaches. Int. J. Environ. Res. Publ. Health 17, 2179.
Kumar, V., Pandita, S., Sidhu, G.P.S., Sharma, A., Khanna, K., Kaur, P., Bali, A.S.,
Setia, R., 2021. Copper bioavailability, uptake, toxicity and tolerance in plants: a
comprehensive review. Chemosphere 262, 127810.
Lai, C., Liu, S., Zhang, C., Zeng, G., Huang, D., Qin, L., Liu, X., Yi, H., Wang, R., Huang, F.,
Li, B., Hu, T., 2018. Electrochemical aptasensor based on sulfur-nitrogen Co-doped
ordered mesoporous carbon and thymine Hg2+-thymine mismatch structure for Hg2+
detection. ACS Sens. 12, 2–35.
Lai, C., Wang, Z., Qin, L., Fu, Y., Li, B., Zhang, M., Liu, S., Li, L., Yi, H., Liu, X., Zhou, X.,
An, N., An, Z., Shi, X., Feng, C., 2021. Metal-organic frameworks as burgeoning
materials for the capture and sensing of indoor VOCs and radon gases. Coord. Chem.
Rev. 427, 213565.
Lee, J., Chuah, C.Y., Kim, J., Kim, Y., Ko, N., Seo, Y., Kim, K., Bae, T.H., Lee, E., 2018.
Separation of acetylene from carbon dioxide and ethylene by a water-stable
microporous metal-organic framework with aligned imidazolium groups inside the
channels. Angew. Chem. 130, 7995–7999.
Lei, C., Gao, J., Ren, W., Xie, Y., Abdalkarim, S.Y.H., Wang, S., Ni, Q., Yao, J., 2019.
Fabrication of metal-organic frameworks@cellulose aerogels composite materials for
removal of heavy metal ions in water. Carbohydr. Polym. 205, 35–41.
Li, H., Eddaoudi, M., O’Keeffe, M., Yaghi, O.M., 1999. Design and synthesis of an
exceptionally stable and highly porous metal-organic framework. Nature 402,
276–279.
Li, H., Shi, W., Zhao, K., Li, H., Bing, Y., Cheng, P., 2012. Enhanced hydrostability in Ni-
doped MOF-5. Inorg. Chem. 51, 9200–9207.
Li, J., Chen, C., Zhang, S., Wang, X., 2014a. Surface functional groups and defects on
carbon nanotubes affect adsorption–desorption hysteresis of metal cations and
oxoanions in water. Environ. Sci. Nano 1, 488–495.
Li, R., Ren, X.Q., Ma, H.W., Feng, X., Lin, Z.G., Li, X.G., Hu, C.W., Wang, B., 2014b.
Nickel-substituted zeolitic imidazolate frameworks for time-resolved alcohol sensing
and photocatalysis under visible light. J. Mater. Chem. 2, 5724–5729.
Li, J., Liu, Y., Wang, X., Zhao, G., Ai, Y., Han, B., Wen, T., Hayat, T., Alsaedi, A.,
Wang, X., 2017. Experimental and theoretical study on selenate uptake to zirconium
metal–organic frameworks: effect of defects and ligands. Chem. Eng. J. 330,
1012–1021.
Z. Li et al.
Li, J., Wang, X., Zhao, G., Chen, C., Chai, Z., Alsaedi, A., Hayat, T., Wang, X., 2018.
Metal-organic framework-based materials: superior adsorbents for the capture of
toxic and radioactive metal ions. Chem. Soc. Rev. 47, 2322–2356.
Li, G.P., Zhang, K., Zhang, P.F., Liu, W.N., Tong, W.Q., Hou, L., Wang, Y.Y., 2019. Thiol-
functionalized pores via post-synthesis modification in a metal-organic framework
with selective removal of Hg(II) in water. Inorg. Chem. 58, 3409–3415.
Li, B.S., Liu, S.Y., Lai, C., Zeng, G.M., Zhang, M.M., Zhou, M.Z., Huang, D.L., Qin, L.,
Liu, X.G., Li, Z.W., An, N., Xu, F.H., Yi, H., Zhang, Y.J., Chen, L., 2020. Unravelling
the interfacial charge migration pathway at atomic level in 2D/2D interfacial
Schottky heterojunction for visible-light-driven molecular oxygen activation. Appl.
Catal., B 266, 118650.
Liang, R., Jing, F., Shen, L., Qin, N., Wu, L., 2015. M@MIL-100(Fe) (M = Au, Pd, Pt)
nanocomposites fabricated by a facile photodeposition process: efficient visible-light
photocatalysts for redox reactions in water. Nano Res 8, 3237–3249.
Liang, R., Jing, F., Shen, L., Qin, N., Wu, L., 2015c. MIL-53(Fe) as a highly efficient
bifunctional photocatalyst for the simultaneous reduction of Cr(VI) and oxidation of
dyes. J. Hazard Mater. 287, 364–372.
Liang, L., Liu, L., Jiang, F., Liu, C., Yuan, D., Chen, Q., Wu, D., Jiang, H.L., Hong, M.,
2018. Incorporation of In2S3 nanoparticles into a metal-organic framework for
ultrafast removal of Hg from water. Inorg. Chem. 57, 4891–4897.
Lin, R., Li, S., Wang, J., Xu, J., Xu, C., Wang, J., Li, C., Li, Z., 2018. Facile generation of
carbon quantum dots in MIL-53(Fe) particles as localized electron acceptors for
enhancing their photocatalytic Cr(vi) reduction. Inorg. Chem. Front. 5, 3170–3177.
Litter, M.I., 2015. Mechanisms of removal of heavy metals and arsenic from water by
TiO2-heterogeneous photocatalysis. Pure Appl. Chem. 87, 557–567.
Liu, X., Li, Y., Ban, Y., Peng, Y., Jin, H., Bux, H., Xu, L., Caro, J., Yang, W., 2013.
Improvement of hydrothermal stability of zeolitic imidazolate frameworks. Chem.
Commun. 49, 9140–9142.
Liu, T., Che, J.X., Hu, Y.Z., Dong, X.W., Liu, X.Y., Che, C.M., 2014. Alkenyl/thiol-derived
metal-organic frameworks (MOFs) by means of postsynthetic modification for
effective mercury adsorption. Chemistry 20, 14090–14095.
Liu, Y., Liu, Z.F., Huang, D.L., Cheng, M., Zeng, G.M., Lai, C., Zhang, C., Zhou, C.Y.,
Wang, W.J., Jiang, D.N., Wang, H., Shao, B.B., 2019. Metal or metal-containing
nanoparticle@MOF nanocomposites as a promising type of photocatalyst. Coord.
Chem. Rev. 388, 63–78.
Liu, B., Vikrant, K., Kim, K.-H., Kumar, V., Kailasa, S.K., 2020a. Critical role of water
stability in metal–organic frameworks and advanced modification strategies for the
extension of their applicability. Environ. Sci. Nano 7, 1319–1347.
Liu, S., Lai, C., Liu, X., Li, B., Zhang, C., Qin, L., Huang, D., Yi, H., Zhang, M., Li, L.,
Wang, W., Zhou, X., Chen, L., 2020b. Metal-organic frameworks and their
derivatives as signal amplification elements for electrochemical sensing. Coord.
Chem. Rev. 424, 213520.
Loeb, S.K., Alvarez, P.J.J., Brame, J.A., Cates, E.L., Choi, W., Crittenden, J., Dionysiou, D.
D., Li, Q., Li-Puma, G., Quan, X., Sedlak, D.L., David Waite, T., Westerhoff, P.,
Kim, J.-H., 2018. The technology horizon for photocatalytic water treatment: sunrise
or sunset? Environ. Sci. Technol. 53, 2937–2947.
Lu, M., Li, L., Shen, S., Chen, D., Han, W., 2019. Highly efficient removal of Pb2+ by a
sandwich structure of metal–organic framework/GO composite with enhanced
stability. New J. Chem. 43, 1032–1037.
Luo, F., Chen, J.L., Dang, L.L., Zhou, W.N., Lin, H.L., Li, J.Q., Liu, S.J., Luo, M.B., 2015.
High-performance Hg2+ removal from ultra-low-concentration aqueous solution
using both acylamide- and hydroxyl-functionalized metal–organic framework.
J. Mater. Chem. 3, 9616–9620.
Luo, X., Shen, T., Ding, L., Zhong, W., Luo, J., Luo, S., 2016. Novel thymine-
functionalized MIL-101 prepared by post-synthesis and enhanced removal of Hg2+
from water. J. Hazard Mater. 306, 313–322.
Mandal, S., Natarajan, S., Mani, P., Pankajakshan, A., 2020. Post-synthetic modification
of metal-organic frameworks toward applications. Adv. Funct. Mater. 4, 2006291.
Miranda-Quintana, R.A., 2017. Note: the minimum electrophilicity and the hard/soft
acid/base principles. J. Chem. Phys. 146, 064101.
Mohamed, R.M., Aazam, E.S., 2012. Enhancement of photocatalytic activity of ZnO–SiO2
by nano-sized Ag for visible photocatalytic reduction of Hg(II). Desalin. Water Treat.
50, 140–146.
Mon, M., Lloret, F., Ferrando-Soria, J., Martí-Gastaldo, C., Armentano, D., Pardo, E.,
2016. Selective and efficient removal of mercury from aqueous media with the
highly flexible arms of a BioMOF. Angew. Chem. 128, 11333–11338.
Mon, M., Qu, X., Ferrando-Soria, J., Pellicer-Carreño, I., Sepúlveda-Escribano, A., Ramos-
Fernandez, E.V., Jansen, J.C., Armentano, D., Pardo, E., 2017. Fine-tuning of the
confined space in microporous metal–organic frameworks for efficient mercury
removal. J. Mater. Chem. 5, 20120–20125.
Mon, M., Bruno, R., Tiburcio, E., Viciano-Chumillas, M., Kalinke, L.H.G., Ferrando-
Soria, J., Armentano, D., Pardo, E., 2019. Multivariate metal-organic frameworks for
the simultaneous capture of organic and inorganic contaminants from water. J. Am.
Chem. Soc. 141, 13601–13609.
Moradi, S.E., Haji Shabani, A.M., Dadfarnia, S., Emami, S., 2016. Sulfonated metal
organic framework loaded on iron oxide nanoparticles as a new sorbent for the
magnetic solid phase extraction of cadmium from environmental water samples.
Anal. Methods 8, 6337–6346.
Muthu Prabhu, S., Kancharla, S., Park, C.M., Sasaki, K., 2019. Synthesis of modulator-
driven highly stable zirconium-fumarate frameworks and mechanistic investigations
of their arsenite and arsenate adsorption from aqueous solutions. CrystEngComm 21,
2320–2332.
Narayani, M., Shetty, K.V., 2013. Chromium-resistant bacteria and their environmental
condition for hexavalent chromium removal: a review. Crit. Rev. Environ. Sci.
Technol. 43, 955–1009.
14
Chemosphere 285 (2021) 131432
Nguyen, J.G., Cohen, S.M., 2012. Postsynthetic methods for the functionalization of
metal-organic frameworks. Chem. Rev. 112, 970–1000.
Othong, J., Boonmak, J., Youngme, S., 2019. Highly selective Cr2O2- 7 removal in aqueous
medium by using a flexible 2D metal-organic framework through single-crystal-to-
single-crystal transformation. J. Environ. Chem. Eng. 7, 102998.
Pandi, K., Prabhu, S.M., Ahn, Y., Park, C.M., Choi, J., 2020. Design and synthesis of
biopolymer-derived porous graphitic carbon covered iron-organic frameworks for
depollution of arsenic from waters. Chemosphere 254, 126769.
Park, K.S., Ni, Z., Cote, A.P., Choi, J.Y., Huang, R., Uribe-Romo, F.J., Yaghi, O.M., 2006.
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc.
Natl. Acad. Sci. U.S.A. 103, 10186–10191.
Pavesi, T., Moreira, J.C., 2020. Mechanisms and individuality in chromium toxicity in
humans. J. Appl. Toxicol. 40, 1183–1197.
Pham, H.Q., Mai, T., Pham-Tran, N.N., Kawazoe, Y., Mizuseki, H., Nguyen-Manh, D.,
2014. Engineering of band gap in metal organic frameworks by functionalizing
organic linker: a systematic density functional theory investigation. J. Phys. Chem. C
118, 4567–4577.
Qadir, N.u., Said, S.A.M., Bahaidarah, H.M., 2015. Structural stability of metal organic
frameworks in aqueous media – controlling factors and methods to improve
hydrostability and hydrothermal cyclic stability. Microporous Mesoporous Mater.
201, 61–90.
Qin, L., Zeng, G., Lai, C., Huang, D., Xu, P., Zhang, C., Cheng, M., Liu, X., Liu, S., Li, B.,
2018. “Gold rush” in modern science: fabrication strategies and typical advanced
applications of gold nanoparticles in sensing. Coord. Chem. Rev. 359, 1–31.
Qin, L., Wang, Z., Fu, Y., Lai, C., Liu, X., Li, B., Liu, S., Yi, H., Li, L., Zhang, M., Li, Z.,
Cao, W., Niu, Q., 2021. Gold nanoparticles-modified MnFe2O4 with synergistic
catalysis for photo-Fenton degradation of tetracycline under neutral pH. J. Hazard
Mater. 414, 125448.
Rahman, Z., Singh, V.P., 2019. The relative impact of toxic heavy metals (THMs) (arsenic
(As), cadmium (Cd), chromium (Cr)(VI), mercury (Hg), and lead (Pb)) on the total
environment: an overview. Environ. Monit. Assess. 191, 419.
Rayman, M.P., 2020. Selenium intake, status, and health: a complex relationship. Horm.
Int. J. Endocrinol. Metab. 19, 9–14.
Ren, X., Li, J., Tan, X., Wang, X., 2013. Comparative study of graphene oxide, activated
carbon and carbon nanotubes as adsorbents for copper decontamination. Dalton
Trans. 42, 5266–5274.
Ricco, R., Konstas, K., Styles, M.J., Richardson, J.J., Babarao, R., Suzuki, K., Scopece, P.,
Falcaro, P., 2015. Lead(II) uptake by aluminium based magnetic framework
composites (MFCs) in water. J. Mater. Chem. 3, 19822–19831.
Rubin, H.N., Reynolds, M.M., 2017. Functionalization of metal-organic frameworks to
achieve controllable wettability. Inorg. Chem. 56, 5266–5274.
Rudd, N.D., Wang, H., Fuentes-Fernandez, E.M., Teat, S.J., Chen, F., Hall, G., Chabal, Y.
J., Li, J., 2016. Highly efficient luminescent metal-organic framework for the
simultaneous detection and removal of heavy metals from water. ACS Appl. Mater.
Interfaces 8, 30294–30303.
Saien, J., Azizi, A., Ghamari, F., 2019. Simultaneous photocatalytic reduction/
degradation of divalent nickel/naphthalene pollutants in aqueous solutions. Water
Sci. Technol. 79, 240–250.
Saleem, H., Rafique, U., Davies, R.P., 2016. Investigations on post-synthetically modified
UiO-66-NH2 for the adsorptive removal of heavy metal ions from aqueous solution.
Microporous Mesoporous Mater. 221, 238–244.
Santasnachok, C., Kurniawan, W., Hinode, H., 2015. The use of synthesized zeolites from
power plant rice husk ash obtained from Thailand as adsorbent for cadmium
contamination removal from zinc mining. J. Environ. Chem. Eng. 3, 2115–2126.
Schultz, D.M., Yoon, T.P., 2014. Solar synthesis: prospects in visible light photocatalysis.
Science 343, 1239176.
Shahzad, K., Tahir, M.B., Sagir, M., Kabli, M.R., 2019. Role of CuCo2S4 in Z-scheme
MoSe2/BiVO4 composite for efficient photocatalytic reduction of heavy metals.
Ceram. Int. 45, 23225–23232.
Shao, Z., Huang, C., Dang, J., Wu, Q., Liu, Y., Ding, J., Hou, H., 2018. Modulation of
magnetic behavior and Hg2+ removal by solvent-assisted linker exchange based on a
water-stable 3D MOF. Chem. Mater. 30, 7979–7987.
Shearer, G.C., Colombo, V., Chavan, S., Albanese, E., Civalleri, B., Maspero, A.,
Bordiga, S., 2013. Stability vs. reactivity: understanding the adsorption properties of
Ni3(BTP)2 by experimental and computational methods. Dalton Trans. 42,
6450–6458.
Shen, L., Liang, S., Wu, W., Liang, R., Wu, L., 2013. Multifunctional NH2-mediated
zirconium metal-organic framework as an efficient visible-light-driven photocatalyst
for selective oxidation of alcohols and reduction of aqueous Cr(VI). Dalton Trans. 42,
13649–13657.
Shen, X.Y., Chi, Y.K., Xiong, K.N., 2019. The effect of heavy metal contamination on
humans and animals in the vicinity of a zinc smelting facility. PloS One 14, 1–15.
Sodhi, K.K., Kumar, M., Agrawal, P.K., Singh, D.K., 2019. Perspectives on arsenic
toxicity, carcinogenicity and its systemic remediation strategies. Environ. Technol.
Innovation 16, 100462.
Solis, K.L.B., Kwon, Y.H., Kim, M.H., An, H.R., Jeon, C., Hong, Y., 2020. Metal organic
framework UiO-66 and activated carbon composite sorbent for the concurrent
adsorption of cationic and anionic metals. Chemosphere 238, 124656.
Song, Y.C., Wang, N., Yang, L.Y., Wang, Y.G., Yu, D., Ouyang, X.K., 2019. Facile
fabrication of ZIF-8/calcium alginate microparticles for highly efficient adsorption of
Pb(II) from aqueous solutions. Ind. Eng. Chem. Res. 58, 6394–6401.
Sreekantan, S., Lai, C.W., Mohd Zaki, S., 2014. The influence of lead concentration on
photocatalytic reduction of Pb(II) ions assisted by Cu-TiO2 nanotubes. Int. J.
Photoenergy 1–7.
Z. Li et al.
Sun, D.T., Peng, L., Reeder, W.S., Moosavi, S.M., Tiana, D., Britt, D.K., Oveisi, E.,
Queen, W.L., 2018. Rapid, selective heavy metal removal from water by a metal-
organic framework/polydopamine composite. ACS Cent. Sci. 4, 349–356.
Tahmasebi, E., Masoomi, M.Y., Yamini, Y., Morsali, A., 2015. Application of
mechanosynthesized azine-decorated zinc(II) metal-organic frameworks for highly
efficient removal and extraction of some heavy-metal ions from aqueous samples: a
comparative study. Inorg. Chem. 54, 425–433.
Tan, X., Fan, Q., Wang, X., Grambow, B., 2009. Eu(III) sorption to TiO2 (anatase and
rutile): batch, XPS, and EXAFS studies. Environ. Sci. Technol. 43, 3115–3121.
Tian, J., Shi, C., Xiao, C., Jiang, F., Yuan, D., Chen, Q., Hong, M., 2020. Introduction of
flexibility into a metal-organic framework to promote Hg(II) capture through
adaptive deformation. Inorg. Chem. 59, 18264–18275.
Upadhyay, U., Sreedhar, I., Singh, S.A., Patel, C.M., Anitha, K.L., 2021. Recent advances
in heavy metal removal by chitosan based adsorbents. Carbohydr. Polym. 251,
117000.
Valizadeh, B., Nguyen, T.N., Kampouri, S., Sun, D.T., Mensi, M.D., Stylianou, K., Smit, B.,
Queen, W.L., 2020. A novel integrated Cr(VI) adsorption-photoreduction system
using MOF@polymer composite beads. J. Mater. Chem. 8, 9629–9637.
Veerakumar, P., Lin, K.C., 2020. An overview of palladium supported on carbon-based
materials: synthesis, characterization, and its catalytic activity for reduction of
hexavalent chromium. Chemosphere 253, 126750.
Wang, C., Liu, X., Chen, J.P., Li, K., 2015a. Superior removal of arsenic from water with
zirconium metal-organic framework UiO-66. Sci. Rep. 5, 16613.
Wang, Y., Ye, G., Chen, H., Hu, X., Niu, Z., Ma, S., 2015b. Functionalized metal–organic
framework as a new platform for efficient and selective removal of cadmium(II) from
aqueous solution. J. Mater. Chem. 3, 15292–15298.
Wang, C., Liu, X., Keser Demir, N., Chen, J.P., Li, K., 2016a. Applications of water stable
metal-organic frameworks. Chem. Soc. Rev. 45, 5107–5134.
Wang, C.C., Du, X.D., Li, J., Guo, X.X., Wang, P., Zhang, J., 2016b. Photocatalytic Cr(VI)
reduction in metal-organic frameworks: a mini-review. Appl. Catal., B 193, 198–216.
Wang, R., Gong, Y., Xu, H.J., Wei, S.Y., Wu, D.Y., 2018. Characteristics and adsorption
properties of Se(IV) for MOF-Fe prepared with different conditioning agents. Chin. J.
Inorg. Chem. 34, 906–916.
Wang, C.C., Yi, X.H., Wang, P., 2019a. Powerful combination of MOFs and C3N4 for
enhanced photocatalytic performance. Appl. Catal., B 247, 24–48.
Wang, R., Xu, H., Zhang, K., Wei, S., Deyong, W., 2019b. High-quality Al@Fe-MOF
prepared using Fe-MOF as a micro-reactor to improve adsorption performance for
selenite. J. Hazard Mater. 364, 272–280.
Wang, X., Liu, W., Fu, H., Yi, X.-H., Wang, P., Zhao, C., Wang, C.-C., Zheng, W., 2019d.
Simultaneous Cr(VI) reduction and Cr(III) removal of bifunctional MOF/Titanate
nanotube composites. Environ. Pollut. 249, 502–511.
Wang, C., He, C., Luo, Y.H., Su, S., Wang, J.Y., Hong, D.L., He, X.T., Chen, C., Sun, B.W.,
2020a. Efficient mercury chloride capture by ultrathin 2D metal-organic framework
nanosheets. Chem. Eng. J. 379, 122337.
Wang, C., Lin, G., Xi, Y., Li, X., Huang, Z., Wang, S., Zhao, J., Zhang, L., 2020b.
Development of mercaptosuccinic anchored MOF through one-step preparation to
enhance adsorption capacity and selectivity for Hg(II) and Pb(II). J. Mol. Liq. 317,
113896.
Wang, L.W., Hou, D.Y., Cao, Y.N., Ok, Y.S., Tack, F.M.G., Rinklebe, J., O’Connor, D.,
2020c. Remediation of mercury contaminated soil, water, and air: a review of
emerging materials and innovative technologies. Environ. Int. 134, 105281.
Wang, Z., Lai, C., Qin, L., Fu, Y., He, J., Huang, D., Li, B., Zhang, M., Liu, S., Li, L.,
Zhang, W., Yi, H., Liu, X., Zhou, X., 2020d. ZIF-8-modified MnFe2O4 with high
crystallinity and superior photo-Fenton catalytic activity by Zn-O-Fe structure for TC
degradation. Chem. Eng. J. 392, 124851.
Wang, L.L., Xie, L.B., Zhao, W.W., Liu, S.J., Zhao, Q., 2021. Oxygen-facilitated dynamic
active-site generation on strained MoS2 during photo-catalytic hydrogen evolution.
Chem. Eng. J. 405, 127028.
Wei, N., Zheng, X., Ou, H., Yu, P., Li, Q., Feng, S., 2019. Fabrication of an amine-
modified ZIF-8@GO membrane for high-efficiency adsorption of copper ions. New J.
Chem. 43, 5603–5610.
Wen, T., Wu, X., Tan, X., Wang, X., Xu, A., 2013. One-pot synthesis of water-swellable
Mg-Al layered double hydroxides and graphene oxide nanocomposites for efficient
removal of As(V) from aqueous solutions. ACS Appl. Mater. Interfaces 5, 3304–3311.
Wu, J., Zhou, J., Zhang, S., Alsaedi, A., Hayat, T., Li, J., Song, Y., 2019. Efficient removal
of metal contaminants by EDTA modified MOF from aqueous solutions. J. Colloid
Interface Sci. 555, 403–412.
Wu, T., Liu, X.J., Liu, Y., Cheng, M., Liu, Z.F., Zeng, G.M., Shao, B.B., Liang, Q.H.,
Zhang, W., He, Q.Y., Zhang, W., 2020. Application of QD-MOF composites for
photocatalysis: energy production and environmental remediation. Coord. Chem.
Rev. 403, 213097.
Xie, D., Ma, Y., Gu, Y., Zhou, H., Zhang, H., Wang, G., Zhang, Y., Zhao, H., 2017.
Bifunctional NH2-MIL-88(Fe) metal–organic framework nanooctahedra for highly
sensitive detection and efficient removal of arsenate in aqueous media. J. Mater.
Chem. 5, 23794–23804.
Xu, R., Jian, M., Ji, Q., Hu, C., Tang, C., Liu, R., Zhang, X., Qu, J., 2020. 2D water-stable
zinc-benzimidazole framework nanosheets for ultrafast and selective removal of
heavy metals. Chem. Eng. J. 382, 122658.
15
Chemosphere 285 (2021) 131432
Yang, S.J., Park, C.R., 2012. Preparation of highly moisture-resistant black-colored metal
organic frameworks. Adv. Mater. 24, 4010–4013.
Yang, P., Shu, Y., Zhuang, Q., Li, Y., Gu, J., 2019. A robust MOF-based trap with high-
density active alkyl thiol for the super-efficient capture of mercury. Chem. Commun.
55, 12972–12975.
Yin, N., Wang, K., Wang, L., Li, Z., 2016. Amino-functionalized MOFs combining ceramic
membrane ultrafiltration for Pb (II) removal. Chem. Eng. J. 306, 619–628.
Yin, N., Wang, K., Xia, Y.a., Li, Z., 2018. Novel melamine modified metal-organic
frameworks for remarkably high removal of heavy metal Pb (II). Desalination 430,
120–127.
Yu, C., Shao, Z., Liu, L., Hou, H., 2018. Efficient and selective removal of copper(II) from
aqueous solution by a highly stable hydrogen-bonded metal–organic framework.
Cryst. Growth Des. 18, 3082–3088.
Yuan, S., Feng, L., Wang, K., Pang, J., Bosch, M., Lollar, C., Sun, Y., Qin, J., Yang, X.,
Zhang, P., Wang, Q., Zou, L., Zhang, Y., Zhang, L., Fang, Y., Li, J., Zhou, H.C., 2018.
Stable metal-organic frameworks: design, synthesis, and applications. Adv. Mater.
30, 1704303.
Yuan, R., Yue, C., Qiu, J., Liu, F., Li, A., 2019. Highly efficient sunlight-driven reduction
of Cr(VI) by TiO2@NH2-MIL-88B(Fe) heterostructures under neutral conditions.
Appl. Catal., B 251, 229–239.
Zhang, W., Hu, Y., Ge, J., Jiang, H.-L., Yu, S.-H., 2014. A facile and general coating
approach to moisture/water-resistant metal–organic frameworks with intact
porosity. J. Am. Chem. Soc. 136, 16978–16981.
Zhang, Y., Zhao, X., Huang, H., Li, Z., Liu, D., Zhong, C., 2015. Selective removal of
transition metal ions from aqueous solution by metal–organic frameworks. RSC Adv.
5, 72107–72112.
Zhang, J., Xiong, Z., Li, C., Wu, C., 2016a. Exploring a thiol-functionalized MOF for
elimination of lead and cadmium from aqueous solution. J. Mol. Liq. 221, 43–50.
Zhang, Y., Xie, Z., Wang, Z., Feng, X., Wang, Y., Wu, A., 2016b. Unveiling the adsorption
mechanism of zeolitic imidazolate framework-8 with high efficiency for removal of
copper ions from aqueous solutions. Dalton Trans. 45, 12653–12660.
Zhang, C., Liu, Y., Sun, L., Shi, H., Shi, C., Liang, Z., Li, J., 2018a. A zwitterionic ligand-
based cationic metal-organic framework for rapidly selective dye capture and highly
efficient Cr2O2-7 removal. Chem. Eur J. 24, 2718–2724.
Zhang, Y.Z., He, T., Kong, X.J., Lv, X.L., Wu, X.Q., Li, J.R., 2018b. Tuning water sorption
in highly stable Zr(IV)-metal-organic frameworks through local functionalization of
metal clusters. ACS Appl. Mater. Interfaces 10, 27868–27874.
Zhang, R., Liu, Y., An, Y., Wang, Z., Wang, P., Zheng, Z., Qin, X., Zhang, X., Dai, Y.,
Huang, B., 2019a. A water-stable triazine-based metal-organic framework as an
efficient adsorbent of Pb(II) ions. Colloids Surf., A 560, 315–322.
Zhang, W., Wang, L., Zhang, J., 2019b. Preparation of Ag/UiO-66-NH2 and its
application in photocatalytic reduction of Cr(VI) under visible light. Res. Chem.
Intermed. 45, 4801–4811.
Zhang, C., Shi, H., Yan, Y., Sun, L., Ye, Y., Lu, Y., Liang, Z., Li, J., 2020a. A zwitterionic
ligand-based water-stable metal-organic framework showing photochromic and Cr
(VI) removal properties. Dalton Trans. 49, 10613–10620.
Zhang, M.M., Lai, C., Li, B.S., Xu, F.H., Huang, D.L., Liu, S.Y., Qin, L., Fu, Y.K., Liu, X.G.,
Yi, H., Zhang, Y.J., He, J.F., Chen, L., 2020b. Unravelling the role of dual quantum
dots cocatalyst in 0D/2D heterojunction photocatalyst for promoting photocatalytic
organic pollutant degradation. Chem. Eng. J. 396, 13.
Zhang, X., Wang, B., Alsalme, A., Xiang, S., Zhang, Z., Chen, B., 2020c. Design and
applications of water-stable metal-organic frameworks: status and challenges. Chem.
Soc. Rev. 423, 213507.
Zhang, Y.J., Mao, F.X., Wang, L.J., Yuan, H.Y., Liu, P.F., Yang, H.G., 2020e. Recent
advances in photocatalysis over metal-organic frameworks-based materials. Sol. RRL
4, 29.
Zhao, F., Su, C., Yang, W., Han, Y., Luo, X., Li, C., Tang, W., Yue, T., Li, Z., 2020a. In-situ
growth of UiO-66-NH2 onto polyacrylamide-grafted nonwoven fabric for highly
efficient Pb(II) removal. Appl. Surf. Sci. 527, 146862.
Zhao, Y.J., Deng, Q.Y., Lin, Q., Zeng, C.Y., Zhong, C., 2020b. Cadmium source
identification in soils and high-risk regions predicted by geographical detector
method. Environ. Pollut. 263, 114338.
Zheng, S.N., Wang, Q., Yuan, Y.Z., Sun, W.M., 2020. Human health risk assessment of
heavy metals in soil and food crops in the Pearl River Delta urban agglomeration of
China. Food Chem. 316, 126213.
Zhu, B.-J., Yu, X.-Y., Jia, Y., Peng, F.-M., Sun, B., Zhang, M.-Y., Luo, T., Liu, J.-H.,
Huang, X.-J., 2012. Iron and 1,3,5-benzenetricarboxylic metal–organic coordination
polymers prepared by solvothermal method and their application in efficient As(V)
removal from aqueous solutions. J. Phys. Chem. C 116, 8601–8607.
Zou, F., Yu, R., Li, R., Li, W., 2013. Microwave-assisted synthesis of HKUST-1 and
functionalized HKUST-1-@H3PW12O40: selective adsorption of heavy metal ions in
water analyzed with synchrotron radiation. ChemPhysChem 14, 2825–2832.
Zou, Y., Wang, X., Khan, A., Wang, P., Liu, Y., Alsaedi, A., Wang, X., 2016.
Environmental remediation and application of nanoscale zero-valent iron and its
composites for the removal of heavy metal ions: a review. Environ. Sci. Technol. 50,
7290–7304.
Zou, Y.H., Liang, J., He, C., Huang, Y.B., Cao, R., 2019. A mesoporous cationic metal-
organic framework with a high density of positive charge for enhanced removal of
dichromate from water. Dalton Trans. 48, 6680–6684.