Sulfonic-functionalized MIL-100-Fe MOF for the removal of diclofenac from water

Microporous and Mesoporous Materials 348 (2023) 112398

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Microporous and Mesoporous Materials
journal homepage: www.elsevier.com/locate/micromeso

Sulfonic-functionalized MIL-100-Fe MOF for the removal of diclofenac
from water
´nchez , Gemma Turnes Palomino **, Carlos Palomino Cabello *
Neus Crespí Sa
Department of Chemistry, University of the Balearic Islands, Palma de Mallorca, E-07122, Spain

A R T I C L E I N F O

A B S T R A C T

Keywords:
Sulfonic-grafted metal-organic frameworks
3D printing
Functional devices
Removal of pollutants
Diclofenac

In this work, a novel adsorbent (MIL-100-Fe-AMSA), for the removal of the nonsteroidal anti-inflammatory drug
sodium diclofenac (DCF), was prepared by grafting aminomethanesulfonic acid to the open iron sites in a porous
MIL-100-Fe MOF obtained by a green microwave-assisted synthesis. The obtained materials were characterized
by XRD, N2 adsorption-desorption, FTIR spectroscopy of adsorbed CO, electron microscopy and EDS spectros­
copy. MIL-100-Fe-AMSA showed fast adsorption kinetics and an excellent maximum adsorption capacity of 476
mg/g. Synergistic effect of H-bonding, between the electronegative ionized –SO3H groups of MIL-100-Fe-AMSA
and –NH group of DCF, and π− π interactions between the aromatic rings that are present in both MOF and

pollutant, is probably the main mechanism of adsorption. In addition, the developed functionalized-MOF showed
excellent reusability for at least five consecutive adsorption-desorption cycles, demonstrating its stability and
potential for the removal of DCF. For practical applications, the prepared MIL-100-Fe-AMSA was incorporated
into a 3D printed column for flow-through solid-phase extraction of pharmaceuticals pollutants before HPLC
determination. The functional device showed excellent performance for the preconcentration and further
detection and quantification of ketoprofen and DCF pollutants.

1. Introduction
Water is one of the most important natural resources for life on our
planet [1]. Nowadays, the rapid progress of modern industry and pop­
ulation growth have led to the contamination of water with a variety of
different organic pollutants, this having become a major global problem
[2,3]. Particularly, pharmaceutical compounds, such as antibiotics,
anti-inflammatory drugs, analgesics, and hormones, and their metabo­
lites have attracted attention due to their potential harmful effects to
human health and ecosystems [4,5]. The inadvertently release of these
compounds into the environment and their ineffective removal by
wastewater treatment plants (WWWTPs) have led to their detection in
different water resources, including drinking water [6–8]. Therefore, a
lot of research is being carried out on the elimination of pharmaceuticals
from water.
Various strategies have been explored to remove pharmaceuticals
from water bodies, such as chlorination [9], biodegradation [10], pho­
tocatalysis [11], coagulation-flocculation [12] or advanced oxidation
processes (AOPs) [13]. However, these methodologies are limited due to

their high energy consumption, low effectiveness and the generation of
residual byproducts that can also be toxic. Adsorption by porous mate­
rials is considered one of the cheapest, simplest, most efficient and
competitive methods for pharmaceuticals removal [14–16]. Common

adsorbents include carbonaceous materials [17,18], zeolites [19,20],
and mesoporous silica [21,22]. However, most of these solids have
shortcomings such as low extraction capacity and poor adsorption
selectivity, and therefore, there is a need to develop novel porous ma­
terials with high adsorption efficiency.
Recently, metal-organic frameworks (MOFs), a relatively new family
of materials that are built up from the union of organic ligands and metal
centers, have shown high potential in the adsorption removal of phar­
maceuticals from water due to their unique characteristics, such as
simple synthesis, large surface area, tunable pore size and presence of
metal active sites [23–27]. Compared to conventional adsorbents, many
MOFs exhibit superior extraction performance thanks to their ability of
establishing different and multiple interactions with organic pollutants,
including electrostatic interactions, acid-base interactions, H-bonding
and π-π stacking [28–30]. In this context, it has been reported that the

* Corresponding author.
** Corresponding author.
E-mail addresses: (G. Turnes Palomino), (C. Palomino Cabello).
/>Received 8 October 2022; Received in revised form 5 December 2022; Accepted 7 December 2022
Available online 9 December 2022
1387-1811/© 2022 The Authors. Published by Elsevier Inc. This is an open access article under the CC BY-NC-ND license ( />

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Microporous and Mesoporous Materials 348 (2023) 112398

incorporation of functional groups in MOFs, through functionalization
of the organic linker or the inorganic building blocks, is key to favoring

and strengthening these interactions, thus improving the adsorption of
pharmaceuticals [31,32]. For example, Hasan et al. [33] synthesized
MIL-101 functionalized with acidic (-SO3H) and basic (-NH2) groups, by
grafting them to the coordinatively unsaturated Cr3+ centers of the
MOF, and used the functionalized MOFs to extract naproxen and clofi­
bric acid. In the case of the adsorption of naproxen and clofibric acid
over the amino-functionalized MIL-101 was 1.17 and 1.10 times higher
than that of the bare MIL-101, respectively, due to the acid-base inter­
action between the basic adsorbent and the acidic adsorbates. A similar
approach was used by Song et al. [34] to prepare MIL-101 MOFs with
different number of –OH groups for the extraction of five pharmaceu­
ticals and personal care products. The MIL-101 material with the highest
concentration of –OH groups, MIL-101-(OH)3, showed a maximum
adsorption capacity of 80 and 156 mg/g for the ketoprofen and nap­
roxen, respectively, which was attributed to H-bonding between the
adsorbent (H-donor) and the pollutants (H-acceptors). On the other
hand, using 2-sulfoterephthalic acid monosodium salt as a linker,
MIL-101-SO3H material with high surface area (1760 m2/g) has been
obtained and tested in the extraction of three fluoroquinolone antibi­
otics [35]. Thanks to the electrostatic interaction between the ionized
sulfonic acid groups and positive charged segment of fluoroquinolone
molecules, very high adsorption capacities between 408 and 426 mg/g
were obtained. Very recently, it has also been reported the functionali­
zation of UiO-66-(COOH)2 with copper and iron and their use as sor­
bents for the removal of the nonsteroidal anti-inflammatory drug
diclofenac sodium [36]. Due to H-bonding and metal-π interactions,
UiO-66-(COOFe)2 showed the maximum adsorption capacity followed
by UiO-66-(COOCu)2 and UiO-66-(COOH)2.
One of the most important limitations for the removal of pollutants
from water by MOFs is their recovery after extraction, since it includes

tedious and incomplete filtration and centrifugation steps. In order to
facilitate the post-extraction procedure, and thus enhance the applica­
bility of MOFs as sorbents, different strategies have been developed,
including the preparation of MOFs with magnetic properties or their
immobilization on robust supports [37,38]. Through this last approach,
promising functional materials for the extraction of organic pollutants
have been obtained, such as MIL-125(Ti)-chitosan membranes [39],
ZIF-8/polyacrylonitrile fibers [40], polydopamine/Zr-MOF foams [41],
and MIL-101(Cr)/chitosan composite beads [42], among others. In this
context, recently, additive manufacturing (3D printing) has emerged as
a powerful tool for the preparation of novel functional 3D printed de­
vices for the removal of pollutants from water [43–45].
In this work, we report the preparation of a novel adsorbent by
grafting aminomethane sulfonic acid (AMSA) to coordinatively unsat­
urated iron sites of MIL-100-Fe, an iron-benzenetricarboxylate MOF
characterized by its low cost, great porosity and water stability, that was
prepared in 10 min by microwave-assisted method. The developed
sulfonic-functionalized MIL-100-Fe was used for the removal of diclo­
fenac, the non-steroidal anti-inflammatory drug that presents the most
important acute toxic effects on biota. The kinetics, maximum adsorp­
tion capacity, reusability and the influence of the pH of the extraction
medium were studied. After batch experiments, the functionalized MIL100 material was immobilized in a 3D column by a simple and fast
coating method and used for the extraction and preconcentration of two
pharmaceutical compounds.

ACROS Organics. Diclofenac sodium salt (DCF, ≥98.0%), poly­
vinylidene difluoride (PVDF, MW ~ 180,000), ketoprofen (≥98%) and
sodium hydroxide (NaOH, ≥97.0%) were obtained from Aldrich. Iron
(III) chloride hexahydrate (FeCl3⋅6H2O, >97%) was acquired from
Panreac. Ultrapure water (18.2 MΩ cm) was obtained from a Milli-Q

water generator.
2.2. Synthesis of MIL-100-Fe
Iron-based MIL-100 was synthesized using a rapid microwaveassisted method by adapting a procedure described in a previous
report [46]. Typically, 2.43 g of FeCl3⋅6H2O were dissolved in 30 mL of
water. After that, 0.84 g of 1,3,5-benzenetricarboxylic acid were added
under constant stirring. The resulting mixture was introduced to a
Teflon vessel and heated at 403 K for 10 min in a microwave oven. The
obtained light brown solid was separated by centrifugation and washed
three times with water and ethanol. Finally, the product was treated
with 150 mL of ethanol at 373 K for 24 h.
2.3. Synthesis of sulfonic-functionalized MIL-100 (MIL-100-Fe-AMSA)
MIL-100-Fe was functionalized following an adaptation of the
experimental procedure reported by Hasan et al. [33]. Before func­
tionalization, 0.5 g of MOF were activated at 453 K for 12 h in a round
bottom flask with continuous circulation of N2 to generate coor­
dinatively unsaturated sites (CUSs). After activation, MIL-100-Fe was
suspended in 50 mL of ethanol, and 1 mmol of AMSA was added. The
mixture was stirred under reflux overnight. The obtained solid was
filtered, washed with ethanol and then dried at room temperature.
2.4. Fabrication of 3D printed column
The design of the 3D printed column with integrated packing based
on interconnected cubes was carried out using the software Rhinoceros
5.0 SR11 32 (McNeel & Associates, USA). This device was 3D printed
vertically with stand with 1016 layers at a resolution of 0.500 mm using
the SLA technique. In order to remove unreacted monomers, the 3D
printed column was washed with 2-propanol and then dried at room
temperature. Finally, the UV post-curing was carried out for 4 h at 365
nm.
2.5. Immobilization of MIL-100-Fe-AMSA in 3D printed column
MIL-100-Fe-AMSA/3D column was prepared by an easy coating

method using a concentrated ink [47]. Basically, 150 mg of
MIL-100-Fe-AMSA were dispersed in 5 mL of acetone through sonication
for 30 min. Then, the dispersion was mixed with 1 g of PVDF solution
(7.5 wt% in DMF), and the resulting mixture was sonicated for another
30 min, and subsequently concentrated by acetone evaporation using
gentle nitrogen flow. The obtained dispersion was pumped through the
3D printed column and, after removing the excess of dispersion using a
nitrogen stream, the 3D device was introduced in an oven at 333 K to
eliminate DMF.
2.6. Characterization
Nitrogen adsorption-desorption isotherms were acquired at 77 K by
using a TriStar II (Micromeritics) gas adsorption instrument. The sam­
ples were previously activated at 423 K for 15 h. Data were analysed
using the Brunauer-Emmett-Teller model (BET) to obtain the specific
surface area and the two-dimensional non-local density functional the­
ory model (2D-NLDFT) to determine the pore size distribution. The Xray diffraction (XRD) patterns were obtained using CuKα radiation on a
Bruker D8 Advance diffractometer. The morphology and elemental
distribution of the prepared materials were studied by using a scanning
electron microscope (SEM) Hitachi S–3400 N, equipped with a Bruker

2. Experimental section
2.1. Chemicals
Hydrochloric acid (HCl, 37.0%), methanol (≥99.8%), N,Ndimethylformamide (DMF, 99.5%) and acetone (≥99.8%) were ac­
quired from Scharlau. 1,3,5-benzenetricarboxylic acid (H3BTC, >98%)
and aminomethanesulfonic acid (AMSA, 97%) were obtained from
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AXS Xflash 4010 energy-dispersive X-ray spectroscopy (EDS) system,
and transmission electron microscope (TEM) ThermoScientific Talos
F200i operated at 200 kV. Fourier transform infrared (FTIR) spectra
were acquired using a Bruker 80v spectrometer equipped with an MCT
cryodetector. For IR experiments, thin self-supported wafers of the MOF
samples were prepared and outgassed in a dynamic vacuum at 453 K for
8 h. After this activation treatment, carbon monoxide was dosed into the
cell to study the open metal centers. Zeta potential was measured by
employing a Zetasizer Nano ZS90 (Malvern). A Formlabs Form 2 3D
Printer and clear photoactive resin composed of methacrylate mono­
mers/oligomers and initiator (Formlabs Clear V4 (FLGPCL04)) were
used for device fabrication. For post-curing the 3D printed devices, an
Upland CL-1000 ultraviolet crosslinker with a 365 nm UV lamp was
used.

3. Results and discussion

compared to the solvothermal method [50]. Then, using a simple pro­
cedure, sulfonic-functionalized MIL-100 MOF (MIL-100-Fe-AMSA) was
obtained by grafting aminomethanesulfonic acid onto the coor­
dinatively unsaturated iron sites of MIL-100. Fig. 1a shows the X-ray
diffraction patterns of MIL-100-Fe before and after functionalization.
Both diffractograms show good crystallinity and matched well with
those previously reported [51], indicating that the grafting process did
not alter the structure of MIL-100-Fe.
The textural properties of the materials were investigated by N2
adsorption-desorption measurements. As shown in Fig. 1b, the N2 iso­

therms of the prepared MIL-100-Fe and MIL-100-Fe-AMSA are a com­
bination of type I and IV isotherms with a significant N2 uptake at lower
P/P0 values, suggesting that the obtained materials were mainly
microporous. Both materials exhibit a multimodal distribution with
pores centered at around 10, 15 and 20 Å (inset of Fig. 1b). The BET
specific surface and total pore volume of the MIL-100-Fe material were
1245 m2/g and 0.77 cm3/g, respectively, which are comparable to those
reported in the literature [52]. In the case of MIL-100-Fe-AMSA, the
values of surface area and the total pore volume decreased to 845 m2/g
and 0.50 cm3/g, respectively, what could be attributed to the partial
occupation of the pores of MIL-100-Fe by the aminomethanesulfonic
acid molecules. Similar results have been described in the literature for
the functionalization of uncoordinated metal centers of MOFs with
organic molecules [33,34].
The prepared materials were characterized by FTIR spectroscopy
(Fig. S1). The FTIR spectrum of the MIL-100-Fe shows bands at 1629,
1452, 1380, 760 and 711 cm− 1, which match well with those of MIL100-Fe MOF previously reported by other authors [53,54]. The band
at 1629 cm− 1 is attributed to C–O stretching vibration of carboxylic
groups, while the bands at 1452 and 1380 cm− 1 can be assigned to the
symmetric and asymmetric vibration of the OCO group, respectively.
The last two peaks at 760 and 711 cm− 1 corresponds to the C–H vi­
brations of benzene ring. The MIL-100-Fe-AMSA sample exhibits addi­
tional absorption bands at 1223 and 1152 cm− 1, which are assigned to
– S–
– O asymmetric and symmetric stretching modes, respectively,
the O–
and at 1041 that comes from the stretching mode of S–O [55,56], con­
firming the incorporation of the sulfonic groups in the grafted sample.
The functionalization of MIL-100-Fe was also checked by infrared
spectroscopy of adsorbed carbon monoxide at 100 K. For that, after

activation of the obtained materials, a saturation dose of CO was
introduced into the IR cell and the corresponding spectra were regis­
tered (Fig. 1c). The IR spectrum of adsorbed CO on MIL-100-Fe shows an
intense IR absorption band at 2170 cm− 1 that corresponds to the
fundamental C–O stretching mode of carbon monoxide interacting
(through the carbon atom) with coordinatively unsaturated iron cations
of MIL-100-Fe [57,58]. The IR spectrum of the MIL-100-Fe-AMSA ex­
hibits the IR absorption band at 2170 cm− 1, although much less intense,
indicating a partial functionalization of the open metal sites with the
sulfonic acid groups. In both cases, the spectra show an additional
weaker band at 2135 cm− 1, which, in agreement with the literature, is
assigned to physisorbed CO [57]. The incorporation of AMSA molecules
into the MIL-100-Fe sample was corroborated by EDS analysis (Fig. 1d),
in which a band at 2.31 KeV, corresponding to S (Kα) signal, was
detected.
To study the morphology of the obtained MOFs, they were charac­
terized by scanning electron microscopy (Fig. 2a and b) and trans­
mission electron microscopy (Fig. 2c and d). As can be seen in the
micrographs, both materials are formed of agglomerates of particles
with an average crystal size of about 400 nm and octahedral shaped
morphology, indicating that both, the morphology and the particle size,
remain unchanged after the functionalization process.

3.1. Synthesis and characterization of MIL-100-Fe-AMSA

3.2. Extraction of diclofenac under batch conditions

MIL-100-Fe precursor was prepared by a green microwave-assisted
synthesis, which allowed a significant decrease in the reaction time

To evaluate the adsorption capacity of the sulfonic-functionalized
MIL-100-Fe material as an adsorbent, diclofenac, one of the most

2.7. Adsorption experiments in batch conditions
DCF solutions with different concentrations were obtained by
diluting a stock solution of DCF (1 g/L) with deionized water. All the
batch experiments were carried out at room temperature with 1 mg of
sample (MIL-100-Fe or MIL-100-Fe-AMSA) per ml of DCF aqueous so­
lution. Adsorption isotherms experiments were conducted in a concen­
tration range of 10–700 mg/L of DCF during 24 h to ensure the
equilibrium conditions. The pollutant concentration after the adsorption
process was determined by UV–Vis spectrophotometer (Cary 300 Bio) at
276 nm. The maximum adsorption capacity was obtained using the
linearized form of the Langmuir equation [48], which is commonly
represented as:
Ce Ce
1
=
+
qe qmax qmax ⋅k
where Ce is the remaining DCF concentration (mg/L) at equilibrium, qe
(mg/g) is the quantity of DCF adsorbed, qmax is the maximum adsorption
capacity (mg/g), and k is the Langmuir constant (L/mg).
Kinetic studies were carried out with the initial DCF concentration of
100 mg/L and measuring the concentration of remaining pollutant in
solution at appropriate time intervals. Adsorption data was analysed
with a pseudo-second-order adsorption model [49], whose
linearized-integral form is expressed by the following equation:
t
t

1
= +
qt qe k2 ⋅q2e
where qt and qe (mg/g) are the amount of DCF per unit mass of the
adsorbent at time t (min) and at equilibrium, respectively, and k2 is the
rate constant (g/mg min).
2.8. Flow-through extraction and preconcentration of diclofenac and
ketoprofen
The 3D printed device with integrated packing was connected to a
multi-syringe pump equipped with 5 and 10 mL glass syringes. Syringe 1
contained an aqueous solution of a mixture of DCF and ketoprofen (1
ppm, each), and Syringe 2 contained methanol. First, 50 mL of a solution
of the pharmaceutical products were automatically circulated through
the column to preconcentrate them. After that, the retained compounds
were eluted by running 2 mL of methanol through the column. The
output liquid was analysed by HPLC for the simultaneous determination
of enrichment factors of both pharmaceuticals, DCF and ketoprofen.

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Fig. 1. Characterization of MIL-100-Fe and MIL-100-Fe-AMSA samples: (a) XRD patterns, (b) N2 adsorption-desorption isotherms. Inset: Pore size distribution, (c)
FTIR spectra of CO adsorbed at 100 K, and (d) energy dispersive X-ray spectra.

Fig. 2. SEM images of (a) MIL-100-Fe and (b) MIL-100-Fe-AMSA samples. TEM images of (c) MIL-100-Fe and (d) MIL-100-Fe-AMSA samples.

common pharmaceutical pollutants found in wastewater [59], was
chosen as model adsorption analyte. Fig. 3a shows the adsorption iso­
therms of DCF on MIL-100-Fe and MIL-100-Fe-AMSA recorded at room
temperature after 24 h of adsorption. Langmuir model was used to fit the
experimental results (Fig. 3b), obtaining, in both cases, good correlation
coefficients (R2 = 0.996–0.998), which confirms that this model is
suitable for describing the DCF adsorption on both MOFs samples.

MIL-100-Fe-AMSA has a maximum adsorption capacity of DCF of 476
mg/g, which is higher than most of the values of adsorption capacity of
DCF reported in the literature (Table S1) and was significantly better
than that of the MIL-100-Fe (357 mg/g), demonstrating that the incor­
poration of the sulfonic acid groups improves the adsorbent properties of
the MOF.
The adsorption rate is an important parameter to consider when
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Fig. 3. DCF adsorption isotherms (a), and corresponding Langmuir plots (b) of MIL-100-Fe and MIL-100-Fe-AMSA. (c) Kinetic adsorption data (c) and corresponding
linear fit of pseudo-second order kinetics model (d) for the adsorption of DCF (100 mg/L) on MIL-100-Fe and MIL-100-Fe-AMSA.

designing adsorbents for the removal of pollutants, and can be assessed
by evaluating the effect of the contact time on the adsorption. Fig. 3c
shows the percentage of DCF adsorbed by MIL-100-Fe before and after

functionalization at different time intervals. As can be observed, DCF
was extracted faster using the MIL-100-Fe-AMSA MOF, reaching after
only 4 min, a percentage of extraction higher than 80%, showing the
remarkable fast uptake of DCF by this material. The adsorption kinetic
data were analysed using a pseudo-second-order kinetic model (Fig. 3d).
In both cases, correlation coefficients of 0.999 were obtained, indicating
that the experimental data are well described by this model.
To gain a better understanding of the DCF adsorption efficiency of
MIL-100-Fe-AMSA, the possible interactions involved during the
extraction process were studied. For that, since the protonation/
desprotonation of adsorbates and the surface charges of adsorbents de­
pends on the solution pH, DCF adsorption over MIL-100-Fe-AMSA was
carried out in a wide pH range (4.5–10.5). As shown in Fig. 4a, the
extraction capacity of MIL-100-Fe-AMSA was hardly affected by the pH
of the solution and only a slight decrease of 8% was observed in the
adsorption capacity when the pH changes from 4.5 to 10.5. Considering
the isoelectric point of MIL-100-Fe-AMSA (Fig. 4b) and the pKa of DCF
(4.2) [60], this decrease could be due to the electrostatic repulsion be­
tween the negatively charged surface of the MIL-100-Fe-AMSA, that

becomes more negative as the pH increases, and the DCF molecules,
which are negatively charged over the pH range studied. However, the
small variation of the DCF adsorption on MIL-100-Fe with the pH sug­
gests that the electrostatic interactions are not significant in the
extraction process. So the superior extraction capacity of
MIL-100-Fe-AMSA can be due by the synergistic effect of H-bonding and
π-π interactions. As DCF has hydrogen bond donor atoms (− NH group)
and the sulfonic acid group of the MIL-100-Fe-AMSA, which is ionized in
the pH range studied, can act as hydrogen bond acceptor, strong inter­
molecular hydrogen bonds can be established between them [61]. In

order to confirm this interaction, FTIR analysis was carried out (Fig. S2).
The FTIR spectrum of MIL-100-Fe-AMSA after DCF adsorption shows a
shift of the stretching vibration of sulfonic group, which, in agreement
with the literature, proves the interaction between the sulfonic groups
and DCF molecules [30,62]. Accordingly, after washing and removing
the adsorbed DCF, the original MIL-100-Fe-AMSA spectrum is recov­
ered. On the other hand, the adsorption of DCF over MIL-101-Fe-AMSA
can also be facilitated by the π− π interactions between the benzene rings
of both DCF and the skeleton of MIL-100-Fe-AMSA [28,63]. The sug­
gested mechanism for DCF adsorption on MIL-100-Fe-AMSA is shown in
Fig. 5.
To evaluate the reusability of MIL-100-Fe-AMSA in the adsorption

Fig. 4. (a) Effect of pH of solution on the extraction of DCF over MIL-100-Fe-AMSA. (b) Zeta potential of the MIL-100-Fe-AMSA at different pH values.
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Fig. 5. Proposed adsorption mechanism for DCF removal using MIL-100-Fe-AMSA.

removal of the DCF, its recyclability was tested by doing five consecu­
tives adsorption-desorption cycles. As can be seen in Fig. 6a, after the
five cycles, the extraction capacity of the material exceeded 93% in both
cases, without its structure and iron content being affected (Fig. 6b and
Fig. S3), which demonstrates the excellent recyclability of the prepared
MIL-100-Fe-AMSA. In addition, the leaching of iron ions into the water,

after the extraction of DCF, was negligible, corroborating the stability of
MIL-100-Fe-AMSA.
3.3. MIL-100-Fe-AMSA/3D device for the enrichment of pharmaceuticals
In order to facilitate and improve the applicability of the MIL-100-FeAMSA for pollutant extraction from water, the material was immobilized
into a 3D printed device by a simple and fast coating method. Basically, a
MIL-100-Fe-AMSA/PVDF ink was prepared and incorporated to the 3d
printed column obtaining a functional device (Fig. 7).
To exemplify the application of the developed MIL-100-Fe-AMSA/3D
column, it was tested for the simultaneous adsorption and enrichment of
DCF and ketoprofen from water. Fig. 8 shows the chromatograms of
standard solution of the two pharmaceutical products (1 mg/L, each)
before and after solid-phase extraction with the MIL-100-Fe-AMSA/3D
column. It can be observed that the signals corresponding to both pol­
lutants in the direct analysis are very weak, however, after preconcen­
tration with the MIL-100-Fe-AMSA/3D column and using 2 mL of
methanol as eluent, these signals significantly increase, reaching

Fig. 7. Schematic representation of the preparation of the MIL-100-Fe-AMSA/
3D column with integrated packing based on interconnected cubes.

Fig. 6. (a) Recyclability of MIL-100-Fe-AMSA for the adsorption of DCF from water. (b) X-ray diffraction patterns of MIL-100-Fe-AMSA before and after
DCF extraction.
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Data availability
Data will be made available on request.
Acknowledgements
N. Crespí acknowledges the support from the Spanish Ministerio de
´n y Ciencia (FPU pre-doctoral fellowship). Financial support
Educacio
´n and Agencia Estatal
from the Spanish Ministerio de Ciencia e Innovacio
´n
de
Investigacio
(project
PID2019-107604RB-I00/MCIN/AEI/
10.13039/501100011033) is gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2022.112398.
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Fig. 8. Chromatograms of pharmaceutical standard solutions before and after
solid-phase extraction by using MIL-100-Fe-AMSA/3D column.

enrichment factors of 17 and 9 for DCF and ketoprofen, respectively. The
obtained results demonstrate the suitability of the MIL-100-Fe-AMSA/

3D device for the adsorption and preconcentration of pharmaceuticals
pollutants from water.
4. Conclusions
In this study, the use of sulfonic-functionalized MIL-100-Fe metalorganic framework (MIL-100-Fe-AMSA) as sorbent for the removal of
diclofenac has been explored for the first time. The MIL-100-Fe-AMSA
was prepared by grafting the coordinatively unsaturated iron sites of
MIL-100-Fe with aminomethanesulfonic acid, obtaining a functional
adsorbent with high surface area. The developed material showed fast
uptake (>80% of extraction after only 4 min), high reusability and
excellent adsorption capacity of 476 mg/g, which is higher than that of
the MIL-100-Fe, confirming the role of the sulfonic groups on the
extraction process. Adsorption mechanism analysis indicated that elec­
trostatic interactions between DCF and MIL-100-Fe-AMSA were not
significant in the removal of DCF, and synergistic effect of H-bonding
and π− π interactions was suggested to be the main mechanism for
explaining the improved efficiency of the MIL-100-Fe-AMSA. The ob­
tained MIL-100-Fe-AMSA was used for the preparation of a functional
device (MIL-100-Fe-AMSA/3D column), which showed high efficiency
for the simultaneous extraction and preconcentration of DCF and keto­
profen, making it a promising device for the analysis of low levels of
emerging pollutants from water.
CRediT authorship contribution statement
´nchez: Writing – original draft, Visualization,
Neus Crespí Sa
Methodology, Investigation. Gemma Turnes Palomino: Writing – re­
view & editing, Writing – original draft, Supervision, Funding acquisi­
tion. Carlos Palomino Cabello: Writing – review & editing, Writing –
original draft, Visualization, Supervision.
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.

7


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