Removal of Contaminants of Emerging Concern by Metal-Organic Framework Nanoadsorbents - A Review

Chemical Engineering Journal 369 (2019) 928–946
Contents lists available at ScienceDirect
Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej
Review
Removal of contaminants of emerging concern by metal-organic framework T

nanoadsorbents: A review
Lesley Josepha, Byung-Moon Juna, Min Jangb, Chang Min Parkc, Juan C. Muñoz-Senmached,
Arturo J. Hernández-Maldonadod, Andreas Heydene, Miao Yuf, Yeomin Yoona,
⁎
a
Department of Civil and Environmental Engineering, University of South Carolina, Columbia, 300 Main Street, SC 29208, USA
b
Department of Environmental Engineering, Kwangwoon University, 447-1 Wolgye-Dong Nowon-Gu, Seoul, Republic of Korea
c
Department of Environmental Engineering, Kyungpook National University, 80 Daehak-ro, Buk-gu, Daegu 41566, Republic of Korea
d
Department of Chemical Engineering, University of Puerto Rico-Mayagüez Campus, Mayagüez, PR 00681, USA
e
Department of Chemical Engineering, University of South Carolina, Columbia, 300 Main Street, SC 29208, USA
f
Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, USA
HIGHLIGHTS
• Removal of contaminants of emerging concern by MOF nanoadsorbents was comprehensively reviewed.

• Comprehensively information was provided for applications of MOF nanoadsorbents in water industry.
• Areas of future research for the removal of various contaminants in MOF nanoadsorbents were suggested.
ARTICLE INFO ABSTRACT
Keywords: Over the last two decades, various contaminants of emerging concern (CECs), such as endocrine disrupting
Adsorption compounds, along with pharmaceuticals and personal care products (PPCPs), have been of interest to the water
Metal-organic frameworks industry because of their incomplete removal during the typical water and wastewater treatment processes.
Contaminants of emerging concern Recently, the potential environmental applications of metal-organic frameworks (MOFs) and MOF-based na-
Water treatment
noadsorbents (MOF-NAs) have been widely studied. In particular, the use of these nanoadsorbents for CECs in
water and wastewater treatment processes has been a rapidly growing area of interest in the recent literature due
to their unique physicochemical properties. Therefore, it is necessary to understand the adsorption phenomena
of various CECs by MOF-NAs, particularly because the physicochemical properties of various CECs create unique
challenges for the removal of these compounds from water. In addition, the adsorption of CECs on MOF-NAs is
significantly influenced by the physicochemical properties of the MOF-NAs and the water quality conditions.
Therefore, this review provides a comprehensive assessment of recent studies on the removal of various CECs
(e.g., analgesics, antibiotics, antiepileptics, antiseptics, and etc.) with different physicochemical properties by
various MOF-NAs under various water quality conditions (e.g., pH, background ions/ionic strength, natural
organic matter, and temperature). In addition, this review briefly discusses the recent literature on the synthesis
of MOF-NAs, regeneration of MOF-NAs, and removal of CECs during water and wastewater treatment processes.
1. Introduction plasticizers, stimulants, and sunscreens, have frequently been detected

in wastewater treatment plant effluents, indicating that these micro-
Over the last two decades, various contaminants of emerging con- pollutants are inadequately removed during the typical wastewater
cern (CECs), such as endocrine-disrupting compounds (EDCs) and treatment processes [3]. Although some difficulty exists in explicitly
pharmaceuticals and personal care products (PPCPs), have been a defining the term “EDCs,” exogenous agents that inhibit the behavior of
major issue in the water industry [1,2]. Numerous CECs, including natural hormones in the body are generally classified as EDCs by the
analgesics, antibiotics, antiepileptics, antiseptics, hormones, United States Environmental Protection Agency [4]. Stumm-Zollinger
⁎
Corresponding author.
E-mail address: [email protected] (Y. Yoon).
https://doi.org/10.1016/j.cej.2019.03.173
Received 31 January 2019; Received in revised form 17 March 2019; Accepted 19 March 2019
Available online 20 March 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
L. Joseph, et al. Chemical Engineering Journal 369 (2019) 928–946
Mechanochemistry, High-throughput
ex-situ extended methods,
X-ray absorption fine sonochemistry, & in-
Precursor & structure, & situ atomic force
Mineralizer structure-directing agents in-situ linker microscopy
2002 2003 2004 2005 2006 2007 2008 2009
Nanoparticles Thin films, electrochemistry, & In-situ static light Modulator, ionic
microwave synthesis scattering liquids, & aerogels
Several post-synthetic
covalent reactions on Sequential linker Interior and surface First example of post-synthetic
IRMOF-74-III installation in PCN-700 modification linker exchange
2017 2016 2015 2014 2013 2012 2011 2010
Post-synthetic Creation of ordered Covalent and dative post- In-situ energy-

ligand installation in vacancies by post- synthetic modification dispersive X-ray
MIL-88B synthetic elimination diffraction &
monoliths
Fig. 1. Historical developments in the synthesis of various MOFs modified from [51,54].
and Fair (1965) and Tabak and Bunch (1970) raised the first alarms by MOF-NAs because their physicochemical properties create unique
regarding the possible adverse effects of various pharmaceuticals in challenges for the removal of these compounds in water. In particular, it
municipal wastewater [1,5–9]. is essential to develop an understanding of the mechanisms of removal,
Numerous studies have examined the fate and transport of EDCs and such as by electrostatic interactions, metal effects, acid-base interac-
PPCPs in water and wastewater treatment processes because several of tions, π- π interactions, and H-bonding. Additionally, the adsorption of
these compounds have been detected in drinking water sources and EDCs and PPCPs on MOF-NAs is significantly influenced by the physi-
wastewater effluents [3,10–19]. The fate and transport of EDCs and cochemical properties of the compounds (e.g., size/shape, hydro-
PPCPs vary greatly depending on the treatment processes that are used, phobicity, functional group, and charge), as well as the physicochem-
including coagulation-flocculation-sedimentation-filtration [20,21], ical properties of the adsorbent itself (e.g., surface area, hydrophobicity,
activated carbon treatment [22], ozonation [23], chlorination [24], charge, and functional group) and water quality properties (e.g., pH,
sonodegradation [25,26], and biodegradation [27,28]. Among these temperature, solute concentration, natural organic matter (NOM), and
commonly used technologies, adsorption is typically considered the background anions/cations). It is very important to understand the
most promising method for drinking water and wastewater treatment problems that we have been faced for the potential use of MOF-NAs in
due to its adaptability, extensive applicability, and cost-effectiveness the adsorptive removal of various EDCs and PPCPs from aqueous sys-
[29]. While granular or powdered activated carbon is commonly used tems.
in water and wastewater treatment, relatively new adsorbents such as Therefore, the primary goal of this review is to provide a compre-
carbon nanotubes, graphenes or graphene-based adsorbents, and metal- hensive assessment of the removal of various EDCs and PPCPs that have
organic frameworks (MOFs) have been investigated recently for the different physicochemical properties by various MOF-NAs under dif-
removal of EDCs/PPCPs [30–32]. ferent water quality conditions. To accomplish this goal, this review
MOFs are an emerging class of porous materials fabricated from briefly surveys recent literature on the synthesis of MOFs, regeneration
metal-containing nodes and organic linkers [33]. Over the past two of MOF-NAs, and removal of EDCs and PPCPs during water and was-
decades, several hundred different MOFs have been studied for dif- tewater treatment processes.
ferent applications, including gas purification, gas separation, gas sto-
rage, energy storage, and environmental applications (e.g., adsorption, 2. Synthesis of MOFs
membrane preparation, and catalysis) [34–38]. Particularly in the en-
vironmental area, MOFs and MOF-based nanoadsorbents (MOF-NAs), Tomic (1965) first introduced materials that have metal–organic
such as Zr-benzenedicarboxylate (UiO-66), Zr-biphenyldicarboxylate polymers or supramolecular structures, which are currently called
(UiO-67), metal-benzenetricarboxylate (MIL-100; metal = Fe3+, Cr3+, MOFs [47]; however, the term “MOF” was widely disseminated by
or Al3+), metal-benzenetricarboxylate (MIL-96; metal = Al3+, Cr3+, Yaghi et al. in 1995 [48]. Detailed historical developments in the
Ga3+, or In3+), Zn-2-methylimidazolate (ZIF-8), MIL-101-graphene synthesis of MOFs are described in Fig. 1. Since both nonflexible and
oxide (GO), UiO-67/GO, Fe3O4@MIL-100(Fe), and urea-MIL-101(Cr), flexible porous MOFs (i.e., MIL-47 and MIL-53) were first reported in
have been widely studied for the removal of various EDCs and PPCPs in 2002 [49,50], studies have shown that the synthesis of MOFs coupled
water [37,39–44]. In addition, due to the unique physicochemical with functionalization (i.e., post-synthetic modification) may be an ef-
properties of MOF-NAs, the use of these nanoadsorbents for EDCs and fective and practical tool for the modification of their structure and
PPCPs in water and wastewater treatment processes has been an area of other properties [51]. Bi- and trivalent aromatic carboxylic acids have
rapidly growing interest in the recent literature. While a few recent already been employed for fabrication of frameworks with Al, Fe, Ni, U,
review studies have documented the removal of organics and heavy Th, and Zn, resulting in interesting features, such as high metal content
metals using various MOFs [45,46], it remains critical to develop an and thermal stability [52]. For various applications, the main purpose
understanding of the adsorption phenomena of various EDCs and PPCPs of MOF fabrication is to determine the optimal synthesis conditions to
929
(a)
Conventional Electrochemistry Microwave- Mechanochemistry

heating assisted heating Sonochemistry
(b) Conventional Conventional

methods autoclave
High-throughput
High-throughput
methods
autoclave
Temperature
Room Elevated Solvothermal
temperature temperature conditions
(c)
Size
1 nm – 1 mm Morphology Membranes Composites
Thin films
Fig. 2. Overview of (a) synthesis methods, (b) possible reaction temperatures, and (c) final reaction products in MOF synthesis. Reproduced with permission from
Ref. [54], © American Chemistry Society 2011.
result in distinct inorganic building blocks without decay of the organic in situ studies [54]. The degree of MOF crystallization varies depending
linker, while the kinetics of crystallization must be suitable to permit on the ex situ and in situ methods. In the ex situ method, the reaction is
nucleation and growth of the desired phase [53]. Fig. 2 provides an allowed to proceed for limited time intervals, which can result in
overview of synthesis methods (e.g., conventional heating, electro- changes in the composition of the sample and non-reliable outcomes;
chemistry, microwave-assisted heating, mechanochemistry, and so- however, this method is advantageous because it can be conducted in a
nochemistry), possible reaction temperatures (e.g., room temperature, laboratory using relatively easy and uncomplicated methods [60]. In
elevated temperatures, and solvothermal conditions), and final reaction the in situ method, specific equipment and synchrotron radiation are
products (e.g., thin films, membranes, and composites) of MOF synth- often required to monitor the reactions continuously; however, this
esis based on the various synthesis methods that have been applied in results in relatively better time-resolution data [61]. Overall, it is im-
the last two decades [54]. While conventional synthesis includes reac- portant to examine the mode of synthesis when comparing results be-
tions associated with conventional electric heating, excluding any cause different methods of synthesis can affect the adsorption proper-
parallelization of reactions, the two temperature ranges that include the ties of MOFs.
solvothermal and non-solvothermal are generally distinguished from
these [55]. Solvothermal reactions occur above the boiling point of the
3. Removal of CECs in conventional and advanced wastewater and
solvent at autogenous pressure in closed vessels, whereas non-sol-
water treatment processes
vothermal reactions take place below the boiling point of the solvent at
room or elevated temperatures [56].
3.1. Removal in wastewater treatment processes
Systematic examination of the synthesis of MOFs is important be-
cause the properties of MOFs are greatly influenced by the synthetic
Numerous studies have described the occurrence of various EDCs
methods employed. Detailed descriptions of these synthetic methods
and PPCPs at different stages during wastewater treatment processes,
have been published previously [51,54]. Briefly, a high-throughput
which implies that the effectiveness of the removal of these micro-
method was first employed in the late 1990s for zeolites using sol-
contaminants is significantly influenced by the physicochemical prop-
vothermal synthesis [57]. This method is a powerful tool that enables
erties of the contaminants (e.g., pKa, functional groups, and hydro-
the use of solvothermal synthesis to accelerate the discovery of new
philicity) and the type of wastewater treatment method employed (e.g.,
MOFs and to enhance synthesis procedures [58]. Optimal conditions by
methods involving biological treatment, dilution of wastewater effluent
which new compounds are fabricated can be determined by time-re-
or combined sewer overflow, or variations in rainfall or temperature)
solved examination of MOF crystallization, which can be used to detect
[62–64]. However, it is difficult to determine the exact transport and
crystalline intermediates, determine reaction parameters (i.e., reaction
fate mechanisms of various EDCs and PPCPs during the processes of
rate constants and activation energies), and provide insight into the
biodegradation (anaerobic/anoxic/aerobic), sorption to sludge, or oxi-
mechanisms of crystallization [59]. Different measurement methods are
dative degradation by chlorine or ozone [3]. Ryu et al. found that the
used in ex situ and in situ studies of MOF crystallization: Extended X-ray
approximate degradation rates of four antibiotics during wastewater
absorption fine structure, electron spray ionization-mass spectrometry,
treatment processes were as follows: triclocarban (85%) > sulfa-
and X-ray powder diffraction are commonly used for ex situ studies,
methoxazole (70%) ≥ triclosan (65%) > trimethoprim (20%) [3].
whereas energy-dispersive X-ray diffraction, atomic force microscopy,
Different degradation mechanisms can be employed. For example, for
small-angle X-ray scattering, wide-angle X-ray scattering, static light
triclocarban and triclosan, sorption to sludge is a main method of de-
scattering, and surface plasmon resonance are commonly employed for
gradation due to the relatively high hydrophobicity of these compounds
930
(log KOW = 4.90 and 4.76, respectively) [65], whereas biodegradation high hydrophilicity (log KOW = −1.00 for sucralose and −1.33 for
of these chemicals is relatively difficult [66]. During the degradation acesulfame) [3]. Table 1 describes the degree of removal for selected
processes, some degree of removal may also result from oxidation of CECs in wastewater treatment plants under dry-weather conditions
these compounds by chlorine [23]. In particular, relatively high reusing a representative sample of the existing literature regarding bio-
moval efficiency was observed for hydrophilic sulfamethoxazole (log degradability, along with trends concerning adsorption to sludge and
KOW = 0.89), probably due to the oxidation of the compound during oxidation by chlorination.
chlorination [67]. However, hydrophilic trimethoprim (log
KOW = 0.91) demonstrated a very low degree of removal due to its low
biodegradability [68] and limited adsorption to sludge [69], whereas 3.2. Removal in water treatment processes
oxidation by chlorine may have an insignificant influence [23].
The removal efficiencies of analgesics and anti-inflammatories can The majority of the population of the United States (approximately
be elucidated by investigating the various mechanisms by which they 95%) has access to drinking water from community water systems that
are degraded, such as biodegradation, sorption to sludge, and oxidation employ conventional water treatment processes (coagulation-floccula-
[3]. Diclofenac was significantly removed during chlorination [70] but tion, sedimentation, filtration, and disinfection) [75]. However, nu-
exhibited minimal biodegradability and adsorption to sludge [71,72]. A merous studies focusing on various CECs, such as EDCs, PPCPs, herbi-
separate study revealed that compounds such as diclofenac, sulfa- cides, pesticides, and polyaromatic hydrocarbons, have shown that
methoxazole, and trimethoprim, which contain primary or secondary conventional processes can remove these compounds at only minimal
amines, can be significantly oxidized by chlorine, which mainly occurs levels [1,76]. The potential fate and transport of EDCs/PPCPs in con-
when the amines form heterocyclic ring structures [23]. In addition, ventional drinking water treatment processes are described in Fig. 3.
chlorine was found to enhance naproxen removal, whereas removal of Aluminum- or iron-based salts are commonly used to precipitate com-
ibuprofen was relatively insignificant, presumably due to the electron- pounds as metal hydroxides during the chemical coagulation processes
capturing functional group on its aromatic ring [23]. High concentra- used in drinking water treatment. Westerhoff et al. reported that 26 of
tions of artificial sweeteners (sucralose and acesulfame) were detected 28 EDCs and PPCPs exhibited < 20% removal during coagulation using
in raw wastewater at levels of approximately 5300 and 3900 ng/L, re- aluminum sulfate, whereas slightly more removal (> 20%) was
spectively, and relatively low removal of these compounds (< 25%) achieved for herbicides, pesticides, and polyaromatic hydrocarbons (10
was achieved during wastewater treatment processes [3]. Similarly, it of 25 compounds) [23]. This is presumably because the compounds
was found that degradation of these compounds through both aerobic with higher removal efficiencies are considered relatively hydrophobic
and anaerobic biological processes was insignificant [73,74]. Sucralose (based on their log octanol-water partition coefficients; log
and acesulfame also appeared to be poorly oxidized by chlorine under KOW = 2.16–6.13) and partitioned either onto particulate matter or
typical wastewater treatment plant operating conditions and demon- onto precipitated solids that contained adsorbed NOM during removal.
strated negligible partition coefficients in activated sludge due to their Adsorption with activated carbon has been widely used to remove
various organic and inorganic contaminants in aqueous solutions [77].
Table 1
Removal efficiencies of selected CECs at wastewater treatment plant under dry weather conditions with examples of previously published literature related to
biodegradability, tendency of adsorption to sludge, and tendency of oxidation by chlorination.
Compound Use MW (g/mol) pKab Log KOWc Inf. (ng/L) Eff. (ng/L) Rem. (%) Bio. Ads. Oxi. Ref.
Acesulfame Sugar substitute 201.2 2.0 −1.33 3863 3705 4 L L L [73]B,A; [161]O
Atrazine Herbicide 215.1 < 2 (1.6) 2.61 ND ND NA L M L [162]B,A; [163]O
Atenolol Oral beta blocker 266.3 9.6 −0.03 1040 529 49 M L L [164]B,A; [144]O
Benzophenone Ultraviolet blocker 182.2 <2 3.18 88 47 47 L M L [165]B; [166]A; [167]O
Benzotriazole Heterocyclic 119.2 8.2 1.44 88 47 47 M L L [168]B,A; [169]O
Caffeine Stimulant 194.2 6.1 −0.07 8810 236 97 H H M [162]B; [170]A; [23]O
Carbamazepine Analgesic 236.3 <2 2.45 188 156 17 L L H [171]B; [72]A; [23]O
DEET Insect repellent 191.3 <2 2.18 47 46 2 M L L [162]B,A; [23]O
Diltiazem Calcium channel blockers 414.5 12.9 2.79 ND ND NA M M L [172]B; [170]A; [144]O
Diclofenac Arthritis 318.1 (4.2) 0.7 6897 359 95 L L H [71]B; [72]A; [23]O
Diphenhy dramine Antihistamine 255.5 9.0 3.27 171 142 17 L M NF [173]B; [65]A
E1 Steroid 270.4 10.3 3.13 ND ND NA H M H [162]B,A; [23]O
Gemfibrozil Anticholesterol 250.2 4.7 4.72 45 33 27 H M H [162]B,A; [23]O
Ibuprofen Analgesic 206.1 4.5 (4.9) 3.97 2724 241 91 H M M [174]B; [72]A; [163]O
Iohexol Contrast agent 821. 1 11.7 −3.05 14,432 16,008 −11 L L L [175]B,A
Iopamidol Contrast agent 777.1 10.7 −2.42 8518 10,091 −18 L L NF [175]B,A
Iopromide Contrast agent 790.9 < 2 and > 13 −2.10 11,133 12,895 −16 L L L [162]B,A; [163]O
Meprobamate Anti-anxiety 218.3 <2 0.70 ND ND NA M L L [162]B,A; [163]O
Naproxen Analgesic 230.1 4.5 (4.2) 3.18 5113 482 91 M M H [162]B; [65]A; [163]O
Primidone Anticonvulsant 218.3 11.5 0.73 100 40 60 M L H [176]B; [177]A; [144]O
Propylparaben Preservative 180.2 8.5 3.04 520 7 99 H H H [165]B,A; [178]O
Simazine Herbicide 201.7 1.62 2.18 ND ND NA H M M [164]B,A; [179]O
Sucralose Sweetener 397.6 NA −1.00 5289 4043 24 L L L [74]B,A,O
Sulfamethoxazole Antibiotic 253.1 2.1 & < 2 (5.7) 0.89 400 117 71 L H H [162]B,A; [23]O
TCEP Fire retardant 285.5 NA 1.44 439 348 21 L M L [180]B,A; [162]A;
[163]O
Triclocarban Antibiotic 315.6 NA 4.90 198 33 83 L H NF [66]B; [65]A
Triclosan Antibiotic 289.6 8 (7.9) 4.76 190 63 67 L H H [162]B,A; [23]O
Trimethoprim Antibiotic 290.1 6.3, 4.0, < 2 (7.1) 0.91 150 118 21 L L H [68]B; [69]A; [23]O
Source: Modified from [3].

Inf. = influent; Eff. = effluent; Rem. = overall removal; Bio. = biodegradation (B); Ads. = adsorption to sludge (A); Oxi. = oxidation by chlorine (O);
Ref. = references; H = high; M = medium; L = low; ND = not determined because under detection limit (ND values = 15 ng/L for E1, 50 ng/L for diltiazem, 5 ng/L
for atrazine, 1.5 ng/L for simazine, and 0.5 ng/L for meprobamate) ; NA = not available or not applicable; NF = not found.
931
Wastewater Treatment Plant
Prim ary clarifier Anaerobic & anoxic basins Aeration
EDCs/PPCPs to WWTP
Disinfection by UV/O3 Filtration Secondary clarifier
EDCs/PPCPs in surface and

groundwater
Water Treatment Plant

Coagulants Disinfection
Coagulation Flocculation Sedim entation Filtration Treated water storage

Distribution
EDCs/PPCPs to WTP EDCs/PPCPs in

drinking water
Fig. 3. Possible fate and removal of EDCs and PPCPs in conventional wastewater treatment and drinking water treatment processes modified from [160].
Activated carbon treatment is a cost-effective process, and activated (90%) > > phenol (70%) > atrazine (55%) > carbamazepine
carbon is a popular adsorbent for water treatment due to its strong (32%) > > sulfamethoxazole (6.2%) [85]. In a separate study, re-
interactions, particularly with hydrophobic organic contaminants. moval of neutrally charged carbamazepine (pKa = 2.3) by two nano-
However, the physicochemical properties of activated carbon, including filtration membranes (NF-90 and NF-270) was fairly constant because
its pore size, shape, and charge, prevent the adsorption of large mole- removal is governed completely by steric exclusion in the absence of
cules [78]. Jung et al. showed that the degree of adsorption of three charged functional groups [88]. The removal of seven different phar-
EDCs and four active pharmaceutical compounds was in the maceuticals using an ultrafiltration membrane was relatively low
following order: ibuprofen > EE2 > atrazine > bisphenol A > (< 50%) in a pilot-scale municipal wastewater reclamation system,
carbamazepine > sulfamethoxazole > diclofenac; this order is pre- although the findings indicated that molecular weight, log D, and the
sumably due to varying degrees of competitive adsorption, particularly charge of the molecules were key factors influencing their retention
based on π–π bonding and hydro-bonding interactions in the mixture [89].
[79]. A separate study conducted a linear regression analysis to assess In drinking water treatment systems, the addition of free chlorine
the adsorption of 22 EDCs and PPCPs by a commercially available and ozone causes oxidation of reduced metals and organic compounds,
powdered activated carbon, arriving at the following equation: [per- as well as the inactivation of microorganisms [90,91]. In addition, the
centage removal] = 15 × [log KOW] + 27% (n = 22; R2 = 0.88) [23]. presence of nucleophilic sites (e.g., carbon-carbon double bonds), the
Overall, the findings implied that protonated bases are substantially electron density degree of functional groups, and the amount of pro-
removed by powdered activated carbon, whereas EDCs and PPCPs with tonation influence the reactivity of organic matter with these oxidants
relatively low log KOW values or deprotonated acid functional groups [92]. For instance, free chlorine reacts quickly with phenolic com-
were the most challenging to remove with powdered activated carbon. pounds, primarily through the reaction between hypochlorous acid and
Membrane processes such as forward osmosis, reverse osmosis, the deprotonated phenolate anion, which causes repeated addition of
nanofiltration, and ultrafiltration have been widely used in water and chlorine to the aromatic ring, followed by ring cleavage [93]. This re-
wastewater treatment processes [80–83]. However, the removal of activity of the phenolic functional group is likely the mechanism of the
EDCs and PPCPs using these membranes varies depending on their oxidation that occurs during chlorination of various estrogenic hor-
physicochemical properties (e.g., solute size/shape, pKa, and hydro- mones that contain phenolic moieties (e.g., ethynylestradiol, estriol,
philicity), water quality conditions (e.g., pH, temperature, background estradiol, and estrone) [94]. Of approximately 60 EDCs and PPCPs, the
anions/cations, and NOM), and membrane properties (e.g., membrane concentrations of some residual EDCs and PPCPs (e.g., sulfamethox-
pore size/density, porosity, charge, hydrophobicity) [84]. Heo et al. azole, diclofenac, estradiol, ethynylestradiol, estriol, naproxen, estrone,
reported the removal of several selected organic compounds by acetaminophen, oxybenzone, triclosan, and several polyaromatic hy-
forward osmosis: sulfamethoxazole (65–90%) ≈ carbamazepine drocarbons) were below the detection limit of 10 ng/L, demonstrating a
(65–85%) > > atrazine (35–50%) > 4-chloraphenol (30–40%) > high degree of oxidation with chlorine, whereas ozone had much
phenol (20%) [85]. The forward osmosis process uses an osmotic stronger oxidation reactivity with these compounds [23]. In particular,
pressure difference produced by a concentrated draw solution to steroids containing phenolic moieties (e.g., estradiol, ethynylestradiol,
transport water from a feed solution to the draw solution through a and estrone) were oxidized more effectively by ozone compared to
membrane [86]. Conversely, reverse osmosis, nanofiltration, and ul- those without benzene or phenolic moieties (e.g., androstenedione,
trafiltration processes use hydraulic pressure difference as the main progesterone, and testosterone). This is presumably because the OH
driving force to permeate water through a semipermeable membrane functional groups lose electrons to the benzene rings, which leads to
[87]. Removal by reverse osmosis exhibited different retention trends increased reactivity with ozone compared to non-aromatic ring struc-
compared to those observed with forward osmosis for selected tures or conjugated bonds with COOH functional groups [95]. Table 2
organic compounds, as follows: 4-chloraphenol (94%) > EE2 summarizes the expected performances of various technologies used in
932
Table 2
Unit processes and operations used for CEC removal.
Group Classification AC BAC MOFs/MOF- O3/AOPs UV Cl2/ClO2 Coagulation/ Softening/metal NF RO Degradation {B/P/
NAs flocculation oxides AS}*
EDCs Pesticides E E F - E L-E E P-E P G G E E {P}

Industrial chemicals E E F - E F-G E P P-L P-L E E G - E {B}
Steroids E E F - E E E E P P-L G E L - E {B}
Metals G G F - E P P P F-G F-G G E P {B}, E {AS}
Inorganics P-L F F - E P P P P G G E P-L
PhACs Antibiotics F-G E F - E L- E F- G P - G P -L P - L E E E {B}G - E {P}

Antidepressants G-E G -E F - E L- E F- G P - F P -L P - L G - E E G-E
Anti-inflammatories E G -E F - E E E P - F P P - L G - E E E {B}
Lipid regulators E E F - E E F- G P - F P P - L G - E E P {B}
X-Ray contrast media G-E G -E F - E L- E F- G P - F P -L P - L G - E E E {B and P}
Psychiatric control G-E G -E F - E L- E F- G P - F P -L P - L G - E E G-E
PCPs Synthetic scents G-E G-E F - E L - E E P-F P - L P - L G-E E E {B}

Sunscreens G-E G-E F - E L - E F-G P-F P - L P - L G-E E G-E
Antimicrobials G-E G-E F - E L - E F-G P-F P - L P - L G-E E F {P}
Surfactants/ E E F - E F - G F-G P P - L P - L E E L - E {B}
detergents
Source: Modified from [76].

PhACs = pharmaceuticals; PCPs = personal care products; BAC = biological activated carbon; AOPs = advanced oxidation processes; UV = ultraviolet
NF = nanofiltration; RO = reverse osmosis; *B = biodegradation, P = photodegradation (solar); E = excellent (> 90%), G = good (70–90%), F = fair (40–70%),
L = low (20–40%), P = poor (< 20%).
both water and wastewater treatment plants based on literature reports influencing the porosity, surface area, and pore volume of MOF-derived
characterizing particular classes of compounds or their similarities to carbons. For example, highly porous MOF-derived carbons at 1000 °C
other EDCs and PPCPs that have been investigated in detail (See (total pore volume = 1.32 cm3/g) showed approximately 2.5 times
Table 3). higher porosity than that of the pristine MOF (ZIF-8; total pore vo-
lume = 0.51 cm3/g) employed to fabricate it, and thus the adsorption
4. Removal mechanisms of various CECs by MOF-NAs capacity of MOF-derived carbons was almost twenty times greater than
that of the pristine ZIF-8 for the pharmaceutical compound sulfa-
4.1. Removal influenced by the adsorption properties of MOF-NAs methoxazole [104]. Three MOFs (ZIF-8, UiO-66, and UiO-67) that have
different properties showed different adsorptive removal trends for
4.1.1. MOF-NA properties atrazine [105]. The removal efficiencies of atrazine aqueous solution at
The physicochemical properties of MOF-NAs can significantly in- pH 6.9 using the MOFs were as follows (mg atrazine/g adsorbent): UiO-
fluence removal of EDCs and PPCPs [96–98]. The porosity structure of 67 (11.0) > ZIF-8 (6.78) > UiO-66 (2.57). These findings can be ex-
MOF-NAs is one of the main factors affecting the adsorption perfor- plained by their pore size, pore volume, and surface area: the higher
mance, particularly when no specific adsorption mechanism exists, adsorption capacity of UiO-67 is presumably due to its larger total pore
excluding van der Waals interactions [99]. For example, a Cu–benzene- volume (1.249 cm3/g) and surface area (2345 m2/g) than those of ZIF-8
1,3,5-tricarboxylic acid-cotton composite was reported to have a high (0.714 cm3/g and 1875 m2/g, respectively) and UiO-66 (0.656 cm3/g
sorption capacity for ethion insecticide due to the accessible binding and 1640 m2/g, respectively). The relatively small pore size of UiO-66
sites on the cellulose in the composite [96], which are particularly as- compared to that of UiO-67 may make it difficult for atrazine to access
sociated with chemical interactions and physical adsorption. Two fac- its pores, and while ZIF-8 also has relatively small pore size, almost all
tors may contribute to this effect. First, the physical adsorption can be atrazine is still removed by ZIF-8, presumably due to the relatively high
significant because the pores of Cu–benzene-1,3,5-tricarboxylic acid hydrophobic attraction between the hydrophobic ZIF-8 [106] and
may act as binding sites for the target molecules. Second, the antici- atrazine (log KOW = 2.67). However, the less hydrophobic UiO-66 does
pated chemical interactions between the solute and the composite may not enable effective adsorption of atrazine from aqueous solution even
occur by H-bonding between cellulose functional groups and the by surface interactions [107].
oxygen of ethion. In a separate study, nitrogen-doped porous carbons The adsorption performance for several CECs was compared be-
were prepared from MOF (ZIP-8) combined with ionic liquid via a ship- tween metal-azolate frameworks, porous carbon-derived metal-azolate
in-bottle method [100]. While ionic liquid@MOF-derived carbons are frameworks, and commercial activated carbon [98]. The findings for
less porous than MOF-derived carbons, the ionic liquid@MOF-derived the CECs revealed that adsorption values on these adsorbents were
carbons showed better adsorption performance than the MOF-derived partly reliant on the adsorbents' surface areas when few specific inter-
carbons. This finding indicates that ionic liquid loading in ZIF-8 com- action sites existed. Overall, the porous carbon-derived metal-azolate
bined with the increased nitrogen content of carbonaceous materials frameworks had greater adsorption capacities than did the metal-azo-
significantly influences adsorption. Fig. 4 illustrates a plausible ad- late frameworks. This was presumably because adsorption over metal-
sorption mechanism for six different compounds (atrazine, di- azolate frameworks occurs mainly due to simple filling resulting from
benzothiophene, sodium diclofenac, diuron, indole, and quinoline) over hydrophobic interactions, π-π interactions, and van der Waals interac-
ionic liquid@MOF-derived carbons. Of three different major forms of tions [108]. However, additional mechanisms, such as electrostatic
doped nitrogen on the surface of the material (N-6, N-5, or N-Q) [101], attraction, acid-base interactions, and H-bonding, which occur in
N-6 and N-5, which are primarily observed at the edge of the graphite porous carbon-derived metal-azolate frameworks, could enhance ad-
sheet, are the most chemically active nitrogen sites [102]. In addition, sorption [109]. Moreover, further study of the detailed mechanisms is
H-bonding and acid-base interactions readily occur at the N-6 and N-5 necessary due to the complex chemistry of adsorption and the nu-
nitrogen sites due to basic and H-bonding functionality [103]. merous functional groups of different CECs [45].
Pyrolysis temperature was found to be a significant factor
933
Table 3
Summary of the removal of selected CECs by MOFs and MOF-NAs.
CEC class Adsorbent Surface area (m2/ Co (mg/L) qm(mg/g) Main finding Ref.
L. Joseph, et al.
g)
Analgesics
Diclofenac CDM6-K1000 3123 50 503 The porosity and pore size of the carbons derived from metal azolate framework-6 increased [142]
remarkably on adding KOH before pyrolysis.
UiO-66 NA 20 189 The adsorptive removal of Alizarin Red S. from aqueous solutions has a record adsorption [40]
capacity of 400 mg/g in acidic conditions.
UiO-66 902 1–50 189 The functionalization of UiO-66 with SO3H groups resulted in an increase of approximately [145]
SO3H-UiO-66 910 263 40% in the diclofena adsorption capacity.
Ibuprofen CDM6-K1000 3123 50 408 The adsorption of ibuprofen could be explained by van der Waals and hydrophobic [142]
interactions.
Ketoprofen MIL-101-(OH)3 1838 50 80 H-bonding is a plausible interaction mechanism for adsorption. [151]
Ketorolac tromethamine UiO-66 1139 10–100 833 The adsorption process obeys the pseudo-second order kinetic model and could be fitted with [181]
the Langmuir isotherm.
Naproxen MIL-101 3014 10–50 132 Lower solution pH is proved to be more favorable for the adsorption of naproxen over MIL- [37]
MIL-100-Fe 1492 115 101.
MIL-101 3014 10–18 131 The adsorption of naproxen over ED-MIL-101 was shown to be less favorable at both low and [182]
AMSA-MIL-101 2322 93 high pH conditions, due to protonation and deprotonation of the adsorbents & adsorbates,
ED-MIL-101 2555 154 respectively.
MIL-101 3066 10–50 112 The adsorbent could be easily regenerated after adsorption of NAP by ethanol treatment [43]
MIL-101-GO 3259 155 without severe degradation.
MIL-101 3030 100 114 The MIL-101s with –OH and –NH2 groups were effective for naproxen adsorption, while MIL- [141]
MIL-101-OH 2170 185 101-NO2 was very poor at adsorption.
934
Antibiotics
Chloramphenicol PCN-222 2917 5–110 370 The finding indicates that H-bond and electrostatic interaction as well as the special pore [183]
structure of PCN-222 can play positive effect on the adsorption.
Ciprofloxacin MIL-101/Fe3O4 764 1–15 80.7 The increasing temperature caused a decrease in both adsorption and desorption efficiencies. [97]
ZIP-8 derived carbons 750 10 417 The adsorption rate of ciprofloxacin on the MOF can be satisfactorily fitted by pseudo-second- [124]
order kinetic model.
ZIF-67 derived hollow Co3S4 NA 10 472 The hollow Co3S4 could be efficiently regenerated and reused for Ciprofloxacin adsorption [41]
over five recycle steps.
MOF-235(Fe) 974 250 217 The sorption kinetics of CIP by Fe3O4@MIL-100(Fe) was found to fit the Elovich model and the [42]
MIL-100(Fe) 2800 303 pseudo-second-order model, indicating that sorption is both chemisorption and physical
Fe3O4@MOF-235(Fe) NA 256 adsorption.
Fe3O4@MIL-100(Fe) NA 322
Doxycycline MIL-35(Fe)/Fe3O4 75.5 20–300 477 Regeneration of the used adsorbent was performed for six regeneration cycles and the [184]
regenerated adsorbent retained most of its initial capacity.
Gatifloxacin PCN-224 1,900 300 1233 (298 K) This result suggested that electrostatic competition occurs and plays a certain role during [120]
1163 (308 K) adsorption.
892 (328 K)
Nitroimidazole Urea-MIL-101(Cr) 1970 10 185 (dimetridazole) The adsorption mechanism was suggested as H-bonding between the −NO2 of the [44]
188 (metronidazole) nitroimidazole antibiotics and −NH2 of the modified MOFs.
Oxytetracycline ZIF-8 1745 10–40 28.3 The highest removal rate of 60% for the 10 mg/L concentration was reached after 200 min. [185]
MIL-101 3588 10–80 149 The adsorption of oxytetracycline over ethylenediamine -MIL-101 is favorable at the pH values [186]
Ethylenediamine- 1834 455 located in a range of 4–10 due to the favorable electrostatic interaction.
MIL-101
Sulfachloropyridazine HKUST-1 1700 20–40 365 (298 K) Electrostatic interactions, π–π interactions, and hydrogen bonding, are the main factors in [113]
429 (308 K) sulfachloropyridazine removal.
501 (328 K)
(continued on next page)
Table 3 (continued)
g)
L. Joseph, et al.
Activated UiO-66 1155 5–45 403 (298 K) The pH effect on adsorption showed that the contribution from electrostatic interactions is [159]
339 (308 K) accounting for only 20%.
312 (328 K)
Sulfamethoxazole ZIF-8 968 100 22 Pyrolysis temperature was found to exert a significant effect on the characteristics of the [104]
ZIF-8 derived carbons 1855 435 prepared MOF-derived carbons, particularly the porosity.
MOF-5 derived carbons 1731 10–100 625 The surface area and pore structure of carbonaceous adsorbents should be of particular [187]
importance in removal of contaminants from aqueous solution.
Tetracycline UiO-66 592 10–100 23.1 (298 K) The adsorption behaviors of tetracycline on UiO-66 were studied with adsorption isotherms/ [130]
31.0 (308 K) dynamics, the effect of temperature, solution pH, humic acid and cations, as well as the
46.4 (318 K) competitive adsorption.
MIL-53 137 1–200 298 The adsorption mechanisms were also ascribed to pore/size-selective adsorption and influence [188]
MWCNT/MIL-53(Fe) 60.2 364 of framework metal ions in adsorption.
Antiepileptics
Carbamazepine UiO-67 1640 0.2–5 18.9c Carbamazepine adsorption was found to be independent of pH, indicating that the electrostatic [39]
2344 interaction is a dominant removal mechanism.
UiO-66 592 10–100 37.2 (298 K) The characterization of UiO-66 before/after adsorption of carbamazepine indicate that the [130]
42.2 (308 K) adsorption on UiO-66 is mainly a physisorption.
60.1 (318 K)
Antiseptics
Triclosan MIL-53(Al) 1030 50 447 The adsorption of the both adsorbents showed favorable stability under different water [158]
MIL-53(Al)-1 1270 488 chemistry; pH (4–9) and ionic strength (up to 40 mM).
IL@AIPCP 2084 10–50 326 The efficiency of the recycled adsorbent for triclosan adsorption did not diminish severely with [189]
935
an increasing number of recycles.
UiO-66-NH-CO-COOH 762 10–50 402 The remarkable adsorption over UiO-66-NH-CO-COOH can be explained in terms of H- [116]
bonding.
Perchlorate Amino sulfonic acid-Cu-4,4′- NA 100 134 The thermodynamic parameters, negative values of Gibbs free energy and enthalpy, indicated [131]
bipyridyl the spontaneous and exothermic nature of the process
Cu2(4,4′-bipy)2(O3SCH2CH2SO3) 100 120 The perchlorate ions preliminarily gathered on the surface of MOFs, and then exchanged with [121]
sulfonic acid group within interlayer.
Pesticides/herbicides/insecticides
Atrazine Ionic liqid@ZIF-8 derived carbons 1421 20 208 The pyridinic (N-6) or pyrrolic (N-5) nitrogen content of ionic liqid@ZIF-8 derived carbon [100]
ZIF-8 derived carbons 1889 168 increased with increasing the introduced ionic liqid content in MOF (before pyrolysis) or
decreasing the pyrolysis temperature.
UiO-66 1640 2–25 1.71–2.69 Regenerated UiO-67 maintained most of its atrazine adsorption capacity after the third use. [105]
UiO-67 2345 10.04–11.87
ZIF-8 1875 6.19–6.78
2,4-dichlorophenoxy-acetic acid MIL-53 1434 25–150 556 The reusability of MIL-53, after simple washing of the used MOF with water/ethanol, for the [190]
adsorption of 2,4-dichlorophenoxy acetic acid was also noticeable.
Diuron Ionic liqid@ZIF-8 1889 10–20 224 The remarkable adsorption capacity with faster adsorption kinetics may be explained by H- [136]
Ionic liqid@ZIF-8 derived carbons 1468 284 bonding with minor contributions from hydrophobic and π - π interactions.
Ethion Cu-BTC@cotton NA 25–125 3.21 (cotton) Feasibility studies of ethion adsorption onto composite suggest that binding sites of composite [96]
10.4 (5% Cu-BTC@ represented in reactive groups and Cu of cellulose and MOF, respectively, bound ethion via
cotton) sulfur.
12.8 (10% Cu-BTC@
cotton)
Glufosinate UiO-67 2172 5–68 537 The abundant active adsorbent anchorages, high specific surface area as well as the adequate [107]
pore size, lead to the remarkably enhanced adsorption capacities.
(continued on next page)

Table 3 (continued)
g)
L. Joseph, et al.
Glyphosate NH2-MIL-101(Cr) NA 5–300 64.3 The structural and electrical properties change of functional MOFs could meet specific [191]
requirements, which plays an important role in practice.
UiO-67/GO NA 40 483 The dominant mechanisms of glyphosate adsorption mechanism are verified to form surface/ [137]
inner-complexation with functional groups ofUiO-67/GO.
Mecoprop UiO-66 982 20–170 370 The reusability of UiO-66, after simple washing of the used MOF with water/ethanol, for the [147]
adsorption of MCPP was also confirmed.
Plasticizer
Bisphenol A Bio-MOF-1-derived porous carbons 1078–1365 100 390–710 Hydrophobic and π-π interactions also play an important role in bisphenol A adsorption, [132]
especially at pH > pKa.
MOF-5 derived carbons 1731 10–100 757 The important contribution of electrostatic interaction in the adsorption of bisphenol A on the [187]
adsorbent.
Stimulant
Caffeine UiO-66 1391 500–3000 24.3 The adsorption of caffeine was significantly influenced by the properties of adsorbents [192]
UiO-66-NH2 973 14.4 including pore volume, pore diameter, and surface area.
MIL-125-NH2 1484 11.1
Sunscreen
Oxybenzone MAFs-4 to 6 938–1642 10–50 65–440 H-bonding (H-donors mainly from adsorbates) was proposed as the principal mechanism for [98]
CDMs-4 to 6 the adsorption over me azolate framework-6 derived carbons.
Sweetener
Saccharin MDC-4h 1502 10–50 93.3 MDC-6h is the most remarkable adsorbent for saccharin due to its high concentration of [193]
MDC-6h 1525 99.2 functional groups, especially phenolic groups.
936
MDC-12h 1610 94.5
MIL-101 3030 10 53.4 Third, the very favorable adsorption over urea-MIL-101 and melamine-MIL-101 could be [38]
Urea-MIL-101 1970 86.4 explained by H-bonding, and the direction of the H-bonding.
Meamine-MIL-101 1350 70.1
O2N-MIL-101 1620 18.7
Co = EDC/PPCP initial concentration; NA = not available; qm = maximum sorption capacity; cKF = capacity factor (μg/g)/(m3/mg) for the Freundlich model; CDM6-K1000, MAFs-4 to 6, and CDMs-4 to 6 = metal
azolate framework-6-derived porous carbon; ZIF-8 = Zn-[2-methylimidazolate] frameworks; IL@AIPCP = ionic liquid-loaded Al-based porous coordination polymers; MDC = metal azolate framework-6 derived porous
carbons; MWCNT = multi-walled carbon nanotube; GO = graphene oxide.
Diuron interactions were irrelevant as a possible main mechanism at pH <

8.1. The adsorption of triclosan is expected to be very low because
Atrazine
triclosan is neutral under this pH condition, and thus no electrostatic
interactions could occur with any species. However, a relatively high
Diclofenac adsorption capacity (approximately 120–140 mg/g) was achieved at pH
sodium 2–8, mainly due to H-bonding interactions between triclosan and the
functionalized MOF, which had positive (–NH2+) and negative
(–COO−) ions in its structure [116]. The adsorption capacity for tri-
closan increased with increasing pH from 2 to 8 and decreased rapidly
with further increases in solution pH (from 8 to 12). Thus, the H-bond
interactions might occur between triclosan (H-bond donor = H of the
phenolic group) and the MOF (H-bond acceptor = O and N species).
The increase in adsorption capacity with increasing pH (from 2 to 8)
could be because the ability of the –NH2+–CO-COO− group to act as an
H-bond acceptor is greater than that of –NH2+–CO–COOH. While the
N-doped H-bond accepting ability of –NH–CO–COO− (i.e., the group produced
carbon on the MOF at a high pH) is high, no hydrogen (H-bond donor) is
present on the phenolic group of triclosan at pH > 8.1 due to depro-
tonation [116].
It should be noted that the choice of pH during adsorption from
water might result in severe degradation of certain MOF structures,
Quinoline Indole Dibenzothiophene
sometimes to the point of complete destruction or transformation of the
Fig. 4. Plausible adsorption mechanism of the six adsorbates over ionic liquid@ original phase and resulting in loss of most if not all adsorption capa-
MOF-derived carbons through H-bonding (dotted lines). Reproduced with city. For instance, Bezverkhyy et al. found that the structural stability of
permission from Ref. [100] © American Chemistry Society 2017. iron-containing MOFs, MIL-100(Fe) and MIL-53(Fe) that were synthe-
sized under fluoride-free conditions is severely degraded when these
materials are exposed to water and the pH was brought to neutral using
4.1.2. Environmental parameters that influence MOF-NA adsorption buffer solutions [117]. This process yields hydrated iron oxide species
properties and, therefore, a structural collapse in both MOFs. In general, the check
4.1.2.1. Influence of pH. One of the most important parameters that for stability of a specific MOF to acidic or alkaline conditions should be
affects adsorption capacity is solution pH, because both inorganic/ considered paramount prior to considering it effective for water pur-
organic speciation and adsorbent surface functional groups vary ification. In acidic conditions, the degradation may be driven by com-
depending on solution pH [110]. Adsorption of sulfamethoxazole on petition of a proton and a metal ion for the coordination with the li-
porous MOF-derived carbons varies within a wide range of pH values, gand, while in alkaline conditions decomposition may take place due to
from 2 to 12 [104], which can be explained by the electrostatic replacement of linkers by hydroxide [118]. This should be considered
interactions between the solute and adsorbent (pH point of zero guidance and not certainty since there are other factors that may inhibit
charge, pHpzc = 4.9) [46]. At pH < 1.6, the sulfamethoxazole is these processes to take place. In fact, there are several ways to improve
positively charged, whereas at pH > 5.7 it is negatively charged due stability of MOFs under certain pH conditions, some even capable of
to its two pKa values associated with the protonated –NH3+ and acidic eliminating any detrimental effects on the structure [119].
NH groups [111]. Therefore, at pH > 5.7, where the acidic –NH group
of the sulfamethoxazole molecule becomes deprotonated, electrostatic 4.1.2.2. Influence of background ions and ionic strength. Porous carbon
repulsion is expected because, at pH > 4.9, the surface charge of the derived from metal azolate framework-6 demonstrated various degrees
adsorbent also becomes negative [104]. In a separate study, the of adsorption for different CECs, such as bisphenol-A, clofibric acid,
adsorption of atrazine on different MOFs was found to be sodium diclofenac, oxybenzone, and salicylic acid [98]. The presence of
insignificantly influenced by solution pH, because the electrostatic background ions (NaCl, 0–40 mM) had almost no effect on the
interactions that occur between the MOFs and the neutral form of adsorption of these CECs by the MOF, indicating that the MOF would
atrazine are negligible (i.e., the neutral form is dominant over the be usable in the presence of various salts. Chen et al. reported the effects
protonate form in water) [112]. A copper-based MOF demonstrated of ionic strength based on NaCl on the adsorption of the antibiotic
varying adsorption trends for sulfonamide antibiotics under different gatifloxacin on Zr(IV)-based porphyrinic MOFs [120]. The adsorption
pH conditions [113]. Sulfonamide exists in cationic and neutral forms was found to be enhanced with increasing NaCl concentration (from 0
at pH < 5.5 and in an anionic form at pH > 5.5 due to its pKa value of to 0.75 mol/L). This increase is presumably due to the decrease in
5.5 [114], whereas the copper-based MOF is positively charged at gatifloxacin solubility by the salting out effect, which may impel the
pH < 4 and negatively charged at pH > 4 [115]. In general, the diffusion of gatifloxacin onto the hydrophobic surface of the MOF and
adsorption capacity of the copper-based MOF decreased with increasing increase the adsorption capacity. However, different results were
solution pH (ranging from 3.5 to 11.5). The highest adsorption was observed for the removal of ciprofloxacin by ZIF-67-derived hollow
achieved at pH 3.5, at which a cationic form of sulfonamide is more CO3S4, particularly in the presence of CaCl2 [41]. The adsorption
likely to be dominant based on the protonation of heterocyclic nitrogen capacity of ciprofloxacin decreased from 118 to 83.2 mg/g and 118 to
(in the strongest basic form of the sulfonamide molecule, 18.6 mg/g with increasing NaCl and CaCl2 concentrations (0–1 mol/L),
sulfonamide+). Therefore, the greater adsorption capacity of respectively. This finding is presumed to be attributed to the
sulfonamide at this pH is due mainly to electrostatic attraction competition of Na+ or Ca2+ with ciprofloxacin for the active
associated with H-bonding and π-π interactions [113]. adsorptive sites, while the presence of salt also negatively influenced
Sarker et al. reported that triclosan adsorption was significantly electrostatic interactions for adsorption between ciprofloxacin and the
influenced by carboxylic-acid-functionalized UiO-66-NH2 at different MOF [41].
pH conditions in aqueous solutions [116]. Of various adsorption me- Zhang et al. employed two-tailed cationic MOFs (i.e., α,β-etha-
chanisms, such as electrostatic interactions, acid-base interactions, co- nebbbdisulfonic-Cu-(4,4′-bipy)2 and sulfamic-Cu-(4,4′-bipy)2) to re-
ordination, π-π interactions, and hydrophobic interactions, electrostatic move ClO4− in the presence of co-existing anions in aqueous solution
937
[121]. For the removal of ClO4−, two potential mechanisms were in- hydrochloride increase with increasing temperature, indicating that
vestigated: electrostatic attraction and ion exchange. SO3H groups on endothermic reactions are dominant for the process of adsorption
these MOFs were found to act as selective anion displacers in solutions [130]. During the adsorption process of ClO4− onto the cationic
containing ClO4− and/or PO43−, and the receptors exhibited favorable MOF, the negative value of ΔH0 (−38.2 kJ/mol) indicated that the
selection of tetrahedron oxoanions. Therefore, the MOFs were capable adsorption on MOF is exothermic, while the negative entropy change
of trapping both ClO4− and PO43− due to interactions with the cationic ΔS0 (−0.113 J/mol·K) indicated that the free energy was reduced at the
MOFs and exchange with SO42− groups. Anions with properties com- solid-solution interface throughout the adsorption process [131]. In
parable to SO3H groups can be removed using cationic MOFs. These addition, the decreasingly negative ΔG0 values (from −6.29 to
findings are consistent with previous research for the removal of arsenic −1.67 kJ/mol) with increasing temperature (from 283 to 323 K)
by MOFs, in which the mechanism of removal was found to operate indicate that the adsorption is unfavorable at high temperatures and
primarily due to electrostatic interactions and ion-exchange [122]. occurs spontaneously.
Additionally, the free-energy change (ΔG0) of ClO4− was lower than the
ΔG0 values of PO43− and the mixture of ClO4− and PO43−, which also 4.2. Removal of selected CECs by MOF-NAs
indicates that ClO4− may be more favorably adsorbed onto MOFs than
PO43− and the mixture of ClO4− and PO43−. Although as an anionic 4.2.1. Edcs
species, SO42− has similar physicochemical properties to those of 4.2.1.1. Bisphenols. Bisphenol A is an EDC. Bhadra et al. synthesized
ClO4− and PO43−, the R-SO4, which is the main functional group of the Bio-MOF-1-derived carbons that were employed as an adsorbent to
MOFs, may create difficulties for the direct swap of ClO4− and PO43− remove bisphenol A [132]. The adsorption results implied that an
with SO42− [121]. important parameter in the adsorption of bisphenol A is the porosity or
surface area of the adsorbent. Electrostatic interactions may be minimal
4.1.2.3. Influence of NOM. Various types of NOM are found widely in between neutral bisphenol A at pH < its pKa and Bio-MOF-1-derived
natural water and wastewater at different levels. It is therefore carbons (pHpzc = 4.3) [104]. H-bonding interactions may be the
necessary to evaluate the effects of NOM on the removal of CECs by applicable adsorption mechanism, because the Bio-MOF-1-derived
MOF-NAs. Liang et al. examined the effects of humic acid (0–30 mg/L) carbons have some acidic functional groups, as well as N-containing
on ciprofloxacin removal by ZIF-67-derived hollow CO3S4 at an initial basic groups, and bisphenol A has two –OH groups, providing H-bond
concentration of 10 mg/L at pH 7 [41]. The results revealed that the donors and acceptors [133]. Two findings support the conclusion that
adsorption capacity of the MOF-NA for ciprofloxacin was barely the H atom of the phenol group of Bio-MOF-1-derived carbons also acts
influenced by the presence of humic acid, whereas the presence of as an H donor for the oxygen atom of bisphenol A at pH < 9.6: the
humic acid decreased adsorption for the removal of ciprofloxacin by a variation in the total concentrations of nitrogen and oxygen between
magnetic carbon composite [123]. Nanoporous carbons derived from different Bio-MOF-1-derived carbons was minimal, even when the
carbonization of zeolitic imidazolate framework-8 were employed to adsorption rates were very different; and the phenol groups of both
remove ciprofloxacin in the presence of humic acid in water [124]. The bisphenol A and the MOF should be similar in terms of chemical
results did not support the original assumption that adsorption of properties [132].
ciprofloxacin would decrease in the presence of humic acid due to
competition between ciprofloxacin and humic acid for the adsorption 4.2.1.2. Pesticides and herbicides. Organophosphate pesticides are
sites of the MOF-NA. The findings instead revealed that adsorption of commonly used to control various pests in different crops by
ciprofloxacin on the MOF-NA was enhanced as humic acid preventing acetyl cholinesterase enzyme activity [134]. Several
concentration increased (from 0 to 5 mg/L), and then remained billion United States dollars are spent every year on these types of
nearly constant at high humic acid levels (5–40 mg/L), presumably pesticides, indicating that an enormous quantity of pesticide is used
due to various interactions between humic acid, ciprofloxacin, and [135]. Over 97% of ethion (an insecticide, maximum adsorption
MOF. The initial enhancement in the degree of adsorption may be due capacity = 182 mg/g) was removed by adsorption to the stable and
to adsorption of humic acid on MOF-NA carbon materials [125], which readily recyclable Cu–benzene-1,3,5-tricarboxylic acid that was
may provide additional adsorption sites by creating hydrogen bonds effectively composited with cotton materials [96]. Sarker et al.
between multiple hydroxyl groups and the amine of ciprofloxacin. employed ion liquid@ZIF-8 adsorbent to remove two herbicides
However, due to the limitation of the adsorption capacity of carbon (diuron and 2,4-dichlorophenoxyacetic acid (2,4-D)) [136]. Their
materials for humic acid [126], the additional increase in humic acid removal phenomena were described as having occurred mainly
concentration would be unfavorable to the adsorption behavior of the through the mechanism of H-bonding. While electrostatic attraction
MOF-NA, particularly under the more neutral pH condition (pH 6) was considered a factor in the removal, the influence of these
[124]. interactions appeared to be minimal based on their properties (ion
liquid@ZIF-8, pHpzc = approximately 3.0; 2,4-D, pKa = 2.7–2.8). For
4.1.2.4. Influence of temperature. Thermodynamic assessments in terms the removal of diuron and 2,4-D by liquid@ZIF-8, H-bonding was found
of ΔG0, the standard enthalpy change (ΔH0), and the standard entropy to be very strong between target compounds having a polar nature and
change (ΔS0) provide detailed information on the internal energy the adsorbent, which possesses several surface functional groups
variations associated with adsorption [127]. A copper-based MOF was (lactonic, carboxylic, and phenolic groups) along with its surface
reported to demonstrate different adsorption capacities for sulfonamide pyridinic and pyrrolic species [100]. While the adsorbents and
at varying solution temperatures [113]. In that study, a linear adsorbates may contribute as H-bond donors or acceptors, the degree
relationship was observed between ln ΔG0 and 1/temperature for the of H-bonding varies depending on the pH conditions. For example, the
ΔH0 and ΔS0 calculations at various temperatures (from 298 to 318 K), adsorption of diuron was relatively constant between pH 4 and 7, while
indicating that the positive ΔH0 (4.0 kJ/mol) and ΔS0 (110.3 J/mol·K) it decreased at pH < 4 and pH > 7, which can be explained by the
values imply an endothermic process and increased randomness for the influence of electrostatic interactions (i.e., repulsion) between
adsorption of sulfonamide, respectively. Additionally, the ΔH0 and ΔS0 protonated diuron and the positively charged liquid@ZIF-8 surface
values imply negligible desorption of pre-adsorbed H2O molecules (pH < 3) and a reducing contribution of H-bonding caused by
[128]. This finding also provides support for the presence of protonated diuron when the compound acts as an H-acceptor [136].
unsaturated metal sites in the copper-based MOF that occur as a Yang et al. fabricated a UiO-67/graphene oxide hybrid nano-
result of the removal of H2O molecules [129]. Chen et al. observed composite, which was employed to remove glyphosate in water [137].
that the adsorption capacities of both carbamazepine and tetracycline The dominant mechanisms of glyphosate adsorption on UiO-67/
938
graphene oxide were revealed through Fourier-transform infrared [145]. The removal mechanisms can be explained based on the prop-
(FTIR) spectroscopy analysis to be the formation of surface/inner- erties of diclofenac and UiO-66/SO3H-NH2. For example, at a pH of
complexes between the various functional groups and the UiO-67/ approximately 4–5.5, electrostatic attraction is expected to be favorable
graphene oxide surface. The FTIR analysis data revealed that the between negatively charged diclofenac (pHpzc = 4 [146]) and posi-
spectra of UiO-67/graphene oxide had clear differences in bonds before tively charged UiO-66/SO3H-NH2 (pHpzc = 5.5 [147]). However, both
and after glyphosate adsorption due to interactions between the target diclofenac and UiO-66/SO3H-NH2 exist in negatively charged states at a
compound and the adsorption sites of UiO-67/graphene oxide [137]. In pH > 5.5, resulting in a rapid decrease in diclofenac adsorption with
particular, the glyphosate adsorption exhibited a new transmittance pristine UiO-66. Thus, the influence of electrostatic interactions would
band at 941 cm−1 based on the spectrum of UiO-67/graphene oxide, be minimal under high-pH conditions. A similar influence of pH was
which indicates a Zr-O-P stretching vibration [138]. Additionally, new observed in adsorption of p-arsanilic acid and phthalic acid [148,149].
bands were observed at 1157 and 1075 cm−1, which appeared to be The adsorption of diclofenac at varying pH conditions (4.5, 7.5, and
P]O and Pe O bonds, respectively, indicating that the Zr-OH of UiO- 10.5) may be due to π–π stacking between the diclofenac benzene rings
67/graphene oxide may be an active node for the binding of the target and the pristine UiO-66 [150].
compound molecules, thus enhancing the removal efficiency of gly-
phosate. Moreover, after the adsorption of glyphosate, the vibration 4.2.2.2. Antibiotics. For various hazardous compounds, one of the main
intensity of C-O-Zr (1500–1650 cm−1) reduces significantly due to the adsorption mechanisms is H-bonding [151]. Ahmed et al. observed that
influences of the generation of C-O-Zr-O-P, which implies that chemical the extraordinary adsorption of sulfamethoxazole on highly porous
integration is the key parameter affecting glyphosate removal by UiO- MOF-derived carbons was due mainly to H-bonding because the MOF-
67/graphene oxide [137]. NA has several acidic groups, such as carboxylic and phenolic groups,
that engage in H-bonding [104]. The findings also indicated that both
4.2.1.3. Perchlorate. Perchlorate (ClO4−) is an EDC [139]. Colinas sulfamethoxazole and MOF-NA act as H-bonding donors and acceptors.
et al. reported removal of a high concentration of ClO4− (initial Increased attention has been given to ciprofloxacin (a second-
concentration = 35 mg/L) through complete anion exchange using generation fluoroquinolone antibiotic) due to its extensive use in both
cationic MOF (silver 4,4′-bipyridine nitrate, adsorption humans and animals [152]. Liang et al. demonstrated the effective
capacity = 354 mg/g, with a contact time of 90 min). In a separate adsorption performance of ZIF-67-derived hollow CO3S4 for the removal
study, a cationic MOF based on amino sulfonic acid ligand linked with of ciprofloxacin [41]. Of four different kinetic models (intra-particle
Cu-4,4′-bipyridyl chains was fabricated using the solvothermal method diffusion, liquid-film diffusion, pseudo-first-order kinetic, and pseudo-
and was used as an adsorbent for efficient removal of ClO4− in water second-order kinetic), the fitted results exhibited the highest correlation
[131]. The findings demonstrated that the maximum sorption amount coefficient (0.999) when using a pseudo-second-order kinetic model. In
of ClO4− was approximately 135 mg/g at pH 7 and that the ClO4- could addition, the findings indicated chemisorption behavior of
be removed effectively at a wide range of pH values (2–11). For ClO4- ciprofloxacin on the hollow CO3S4 on the ZIF-67 surface, which was
removal, one of the primary mechanisms is ion exchange, presumably verified by FTIR measurements. After adsorption by the MOF, two
because SO3- groups in the MOF are exchanged with ClO4- after bands shift to 1269 and 1710 cm−1 (assigned to stretching of CeO and
adsorption [140]. In addition, electrostatic adsorption cannot be OeH deformation of the carboxyl group, and CeO stretching in the
ignored because the stretching vibration of N–H in the –NH2 groups carboxyl group, respectively [153]) and their peaks are reduced. This
was not present after the adsorption process, indicating that the –NH2 phenomenon is presumably due to surface complexation between the
groups may be surrounded by ClO4- due to its positive charge [131]. –COOH of ciprofloxacin and the hollow CO3S4 on the ZIF-67 surface
[154].
4.2.2. Ppcps Seo et al. reported removal of nitroimidazole by MIL-101(Cr)
4.2.2.1. Analgesics. H-bonding and electrostatic interactions were modified with urea, melamine, and O2N [44]. While electrostatic in-
previously discussed to describe the adsorption of organic compounds teractions were considered as a potential mechanism for the removal of
on MOF-NAs [99,141]. However, recent findings have revealed that the nitroimidazole, they do not appear to be the main mechanism for the
adsorption of carbamazepine on UiO-67 is not significantly influenced effective adsorption of nitroimidazole by these modified MOF-NAs. The
by electrostatic interactions at varying pH conditions, and the influence adsorption capacity values for nitroimidazole by the MOF-NAs are in
of H-bonding is anticipated to be minimal [39]. Unlike H-bonding and the following order: MIL-101-urea > MIL-101-melamine > MIL-
electrostatic interactions, the study observed that the hydrophobic and 101 > MIL-101-O2N; however, the surface area values of each ad-
π-π interactions between the benzene rings of carbamazepine molecule sorbent are as follows: MIL-101 (3030 m2/g) > MIL-101-urea
and the MOF linkers were dominant mechanisms of the adsorption. The (1970 m2/g) > MIL-101-O2N (1620 m2/g) > MIL-101-melamine
benzene rings of carbamazepine, which have a strong electron-donating (1350 m2/g). The results suggest that the influence of the –NH2 group
group (i.e., –NH2; π donor), can form a strong bond with the oxygen- (in melamine and urea) on the adsorption of nitroimidazole needs to be
containing functional group on the surface of the UiO-67 (electron evaluated to verify the adsorption mechanisms. H-bonding interactions
acceptor; π acceptor) [39]. An et al. observed that porous metal azolate between MIL-101 and nitroimidazole can be considered as a possible
framework-6 carbon (a subclass of MOFs; qmax = 408 mg/L) was mechanism due to their –NH2 and –NO2 groups, respectively [133]. In
significantly more effective for removal of ibuprofen than particular, effective H-bonding through the solid six-membered ring
commercially available activated carbon (qmax = 168 mg/L) [142]. takes place between the –NO2 and –NH2 groups, which is comparable to
This is presumably because hydrophobic interactions play an the interactions between sweeteners and the –NH2 group on MIL-101
important role in the adsorption between the hydrophobic adsorbate [38]. MIL-101-O2N demonstrated unfavorable adsorption of ni-
(ibuprofen, log KOW = 3.97) and the hydrophobic adsorbent, i.e., the troimidazole, presumably due to the lack of possible H-bonding be-
hydrophobicity of metal azolate framework-6 carbon is much higher tween the two –NO2 groups in MIL-101 and nitroimidazole. Thus, the
than that of activated carbon [143]). Additionally, π-π interactions –NO2 on nitroimidazole and the –NH2 groups on MIL-101-urea or MIL-
should also be considered for adsorption, because the ibuprofen and 101-melamine would be the H-acceptor and H-donor, respectively [44].
metal azolate framework-6 carbon have an aromatic benzene ring and a
graphitic layer, respectively [142]. 4.2.2.3. Antiepileptics. Several possible mechanisms were evaluated for
Diclofenac is one of the most commonly detected pharmaceuticals the adsorption of carbamazepine by UiO-66 [130]. Adsorption due to
in drinking water sources [144]. Zr-based functionalized MOFs (UiO- hydrophobic interactions can be explained mainly by the
66/SO3H-NH2) were tested to remove diclofenac in aqueous solutions hydrophobicity of carbamazepine (log KOW = 2.77); however, the
939
Oxygen atom
Nitrogen atom
[Zr6O4(OH)4] clusters
Carbon atom
Coordinate bonds
Hydrogen atom
Ziconium atom
Tetracycline
hydrochloride
Carbamazepine
Hydrophobic
interaction UiO-66 Zr6O4(OH)4(BDC)12
π -π electron
Electrostatic
donor-acceptor
attraction
interaction
π -π interactions/stacking
π -π interactions/stacking
Fig. 5. Schematic illustration adsorption mechanism between zirconium MOF UiO-66 and carbamazepine/tetracycline hydrochloride. Reproduced with permission
from Ref. [130], © American Chemical Society 2017.
influences of electrostatic attraction and π-π interactions/stacking removal of triclosan at various initial concentrations (0–60 mg/L)
should also be considered. The intermolecular electrostatic attraction [158]. The modified MOF with relatively high meso-porosity and
between carbamazepine and UiO-66 is relatively weak because both are total pore volume demonstrated greater adsorption capacity (488 mg/
negatively charged at pH > 5 based on their pHpzc values (4.81 for g) than that of microporous MIL-53(Al) (447 mg/g), and the triclosan
UiO-66 and 2.45 for carbamazepine). π-π interactions/stacking are adsorption was approximately 4.5 times faster with the modified MOF.
commonly found in the absence of electrons or in electron-rich In addition, the adsorption capacity values for different compounds by
chemicals [45]. π-π electron donor-acceptor interactions readily occur the modified mesoporous MIL-53(Al) were in the following order:
between carbamazepine, which possesses NH2 groups (i.e., electron triclosan > bisphenol A > 1-naphthol > phenol, which was
donor), and UiO-66, which possesses a benzene ring (i.e., electron proportional to their hydrophobicity (log KOW = 4.84, 2.84, 2.76, and
acceptor) [155]. Moreover, π-π stacking (aromatic-aromatic 1.46, respectively). This implies that higher selectivity for triclosan
interactions) was found to occur between the benzene rings in adsorption on the modified MOF occurs in the presence of coexisting
carbamazepine and in the organic ligands of UiO-66 [130]. Fig. 5 compounds with relatively low hydrophobicity. FTIR measurements
describes the potential adsorption mechanisms that occur with provide more insights into the interactions between triclosan and the
carbamazepine and tetracycline hydrochloride. Akpinar and Yazaydin MOF. Bands were observed at 3660 and 995 cm−1, which were
compared the removal efficiencies of carbamazepine with UiO-67 and assigned to the asymmetric/symmetric stretching of the hydroxyl
commercial activated carbon (F400) [39]. Significant removal of groups of AlO4(OH)2. The band at 3660 cm−1 moved to a lower
carbamazepine was demonstrated by UiO-67 (95%), whereas F400 frequency and an extra vibrational band at 3540 cm−1 was detected
removed only 35% of the compound within a contact time of 2 min, after triclosan adsorption, implying H-bond interactions between
which may have been due to UiO-67’s relatively small particle size/pore triclosan and AlO4(OH)2 groups, which indicates that H-bond
volume and the very active adsorption sites generated by the missing- interactions are an additional parameter affecting triclosan
linker defects. Twelve linkers are found in defect-free samples of UiO- adsorption. Additionally, adsorption of triclosan on the modified MOF
67 nodes, while binding around the node can be changed to have less was confirmed by the presence of both a vibrational band at 660 cm−1
than twelve carboxylates. The sites that are missing carboxylate are (–C–Cl) and small stretching bands at 1025–1245 cm−1 (aromatic
covered with –OH and H2O groups. Thus, carbamazepine may create C–O–C) [158]. Sarker et al. reported effective adsorption performance
particular interactions with these functional groups on nodes [39]. In for the removal of triclosan by carboxylic-acid-functionalized UiO-66-
addition, some missing-linker defects result in improved porosity, NH2 [116]. While UiO-66-NH-CO-COOH has the smallest porosity
which may expedite quicker adsorption and higher adsorption (0.37 cm3/g) of the tested adsorbents, including activated carbon,
capacity [156]. UiO-66, UiO-66-NH2 (0.56, 0.53, and 0.48 cm3/g, respectively), it
demonstrated better adsorption performance for triclosan compared
4.2.2.4. Antiseptics. Triclosan is a broad-spectrum bacteriostatic to the other adsorbents, implying that the functional groups on the MOF
germicide that is used widely in a number of PPCPs [157]. Structure- may play an important role in the adsorption of triclosan. The potential
directing agent-modified mesoporous MIL-53(Al) was examined for mechanisms that may be important for the adsorption of CECs on MOF-
940
Electrostatic interaction Influence framework metal

Selectivity
Metal ions for A
(X/Y)
Ligands
Adsorption Selectivity
for B
Hydrogen bonding π-π interaction/stacking
(from MOF-NAs)
(from adsorbates)
Hydrophobic interaction
Acid-base interaction Hydrophobic
MOF-NAs
Water
molecule
Hydrophobic
adsorbate
Fig. 6. Schematic diagram of possible mechanisms for adsorptive removal of CECs on MOFs or MOF-NAs. Reproduced with permission from Ref. [45], © Elsevier B.V.
2015.
NAs are summarized in Fig. 6. regenerated by soaking in chloroform for 24 h to desorb the target
compounds [130], washing with methanol, and drying at 80 °C for 24 h.
5. Regeneration of MOF-NAs While the regeneration was relatively unsuccessful, the findings are
useful because they indicate that the adsorption of carbamazepine on
The regeneration capacity of MOF-NAs is a factor of concern be- UiO-66 is primarily physical adsorption, and that the absorbed carba-
cause extraordinary reusability may result in improved environmental mazepine in the micropores of the MOF was desorbed only during the
sustainability and cost efficiency in the treatment of various CECs. The degassing process. However, after the adsorption of tetracycline hy-
desorption degree of the CECs during regeneration of MOF-NAs is an drochloride, the BET surface area and total pore volume of the MOF
essential parameter for evaluation of the reusability of the MOF-NAs. reduced significantly from 592 to 285 m2/g and from 0.323 to
Successful regeneration was achieved for a Cu–benzene-1,3,5-tri- 0.183 cm3/g, respectively, which indicates that tetracycline hydro-
carboxylic acid/cotton composite, because ethion is well-dissolved in a chloride may be adapted to the micropore inner surface by strong in-
solvent (i.e., acetonitrile) [96]. An effective removal efficiency (> 85%) teractions, including H or chemical bonding [130].
of ethion was observed during a consecutive regeneration/reuse (des- In a separate study, ethanol washing was employed for regeneration
orption/adsorption) process after five cycles. Ahmed et al. observed that of used liquid@ZIF-8 after diuron adsorption [136]. The FTIR spectra
the adsorption capacity of atrazine by ionic liquid@MOF-derived car- revealed peaks at 1740 and 1291 cm−1 for fresh liquid@ZIF-8, pure
bons was not significantly reduced even after four cycles of washing diuron, diuron-adsorbed liquid@ZIF-8, and recycled liquid@ZIF-8; the
with ethanol [100]. Acetone was employed to regenerate MOF (UiO-67) stretching bands were detected for both diuron and diuron-adsorbed
after the adsorption of carbamazepine [39]. During the regeneration liquid@ZIF-8, implying the presence of adsorbed diuron on liquid@ZIF-
process, the used MOF was shaken at room temperature and reactivated 8. The disappearance of these bands in the recycled liquid@ZIF-8
under vacuum at 90 °C; it demonstrated a minor reduction in adsorption confirmed that it was effectively regenerated by ethanol washing [136].
capacity after five recycles. After sulfonamide adsorption, the re- After the adsorption of ciprofloxacin on ZIF-67-derived hollow CO3S4,
generation capacity of an MOF (UiO-66) was evaluated with NaOH ethanol was employed as a washing agent to desorb ciprofloxacin and
(0.01 M) [159]. While the MOF retained greater than approximately regenerate the hollow CO3S4 MOF [41]. However, ethanol removed
80% removal efficiency after three cycles, the N2 adsorption-desorption only a limited amount of ciprofloxacin (approximately 5%) from the
isotherm was not significantly affected by the adsorption of sulfona- MOF. An additional cleaning agent (HCl, 0.1 mol/L) was therefore used
mide, which indicates that the structure of the MOF was stable after for desorption of ciprofloxacin from the used MOF. Consequently, a
adsorption. Bhadra et al. used simple solvent washing (water (v):me- mixture of ethanol and HCl was adopted as the cleaning agent. While
thanol (v)) under ultrasonic irradiation to regenerate used Bio-MOF-1- the adsorption capacity was slightly reduced after the first use of the
derived carbons after bisphenol A adsorption [132]. After four cycles, MOF, the removal efficiency for ciprofloxacin was retained at > 80%
almost no reduction in the porosity of the recycled adsorbent occurred after five regeneration cycles, implying that the ZIF-67-derived hollow
compared to the pristine one. In a separate study, used MOF (UiO-66) CO3S4 MOF has high adsorption capacity for ciprofloxacin and is readily
after adsorption of carbamazepine and tetracycline hydrochloride was regenerated for acceptable reusability [41]. The maximum regeneration
941
performance for used structure-directing agent-modified mesoporous experiments to identify the adsorption properties all CECs. Therefore,
MIL-53(Al) was using 90% methanol at pH 11 [158]. This was pre- quantitative structure-activity relationship studies may be needed to
sumably because triclosan entirely dissociates into ionized forms at elucidate the adsorption mechanisms for CECs on different MOF-NAs,
high pH conditions, disturbing each part of the adsorption process by which may be useful in understanding interactions between the func-
splitting the H-bonds between (AlO4)OH2 and triclosan species ad- tional groups in the CEC molecules with the highest activity. Overall, to
sorbed on the modified MOF, which reduces the triclosan hydro- be competitive with other types of adsorbents that are currently used in
phobicity and enhances the solvation of triclosan molecules in water, water and wastewater treatment processes, MOF-NAs must be practical
therefore resulting in more favorable desorption of triclosan from the in terms of cost. While these emerging MOF-NAs are promising due to
modified MOFs [158]. It is strongly recommended that in addition to their high-performance adsorption, many challenges must still be
adsorption and desorption performance, the stability of MOF-NAs overcome to develop homogeneous pores, structures, and functional
should also be monitored throughout reusability/regeneration studies groups with long-term stability. In addition, more research is needed to
over prolonged periods provide comprehensive life-cycle analyses and ecotoxicological assess-
ments of MOF-NAs, particularly when considering its disposal.
6. Conclusions and areas of future study However, the use of MOFs and MOF-NAs for the adsorption of CECs
remains a very promising avenue of research.
Over the last two decades, several hundred different MOFs and
MOF-NAs have been studied for different applications, including gas Acknowledgements
purification, gas separation, gas storage, energy storage, and environ-
mental applications. Of the various environmental applications, nu- This research was supported by the National Science Foundation
merous recent studies have reported that MOF-NAs are effective for (OIA-1632824, USA). This research was also supported by the Korea
removal of organics and heavy metals, including different CECs. These Ministry of Environment (The SEM projects; 2018002470005, South
findings have shown that the removal/adsorption efficiency of CECs by Korea) and the Korea Environment Industry & Technology Institute
MOF-NAs is significantly influenced by the properties of the CECs and (KEITI) through Plant Research Program, funded by Korea Ministry of
MOF-NAs, as well as the water quality conditions. The porosity volume Environment (MOE) (1615009988, South Korea).
and structure of MOF-NAs appears to be a major factor in adsorption
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946

Removal of Contaminants of Emerging Concern by Metal-Organic Framework Nanoadsorbents - A Review

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Chemical Engineering Journal 369 (2019) 928–946

Contents lists available at ScienceDirect

Chemical Engineering Journal

Removal of contaminants of emerging concern by metal-organic framework T

• Removal of contaminants of emerging concern by MOF nanoadsorbents was comprehensively reviewed.

ARTICLE INFO ABSTRACT

1. Introduction plasticizers, stimulants, and sunscreens, have frequently been detected

2002 2003 2004 2005 2006 2007 2008 2009

2017 2016 2015 2014 2013 2012 2011 2010

Post-synthetic Creation of ordered Covalent and dative post- In-situ energy-

Conventional Electrochemistry Microwave- Mechanochemistry

(b) Conventional Conventional

Source: Modified from [3].

Wastewater Treatment Plant

Prim ary clarifier Anaerobic & anoxic basins Aeration

EDCs/PPCPs in surface and

Water Treatment Plant

Coagulation Flocculation Sedim entation Filtration Treated water storage

EDCs/PPCPs to WTP EDCs/PPCPs in

EDCs Pesticides E E F - E L-E E P-E P G G E E {P}

PhACs Antibiotics F-G E F - E L- E F- G P - G P -L P - L E E E {B}G - E {P}

PCPs Synthetic scents G-E G-E F - E L - E E P-F P - L P - L G-E E E {B}

Source: Modified from [76].

(continued on next page)

Diuron interactions were irrelevant as a possible main mechanism at pH <

Electrostatic interaction Influence framework metal

Hydrogen bonding π-π interaction/stacking

water, Environ. Sci. Technol. 43 (2009) 597–603. 1617–1627.

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