Journal of Cleaner Production 434 (2024) 140259

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Covalent integration of Fe-based metal–organic framework and

triazine-containing covalent organic framework for enhanced adsorptive
removal of antibiotics
Ning Yuan *, Chuan Zhang , Xinling Zhang , Ronghua Zhang
School of Chemical and Environmental Engineering, China University of Mining and Technology, Beijing, 100083, China

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

Handling Editor: Zhen Leng Currently, the issue of antibiotic pollution in water bodies has been increasingly capturing people’s attention.
The use of high-performance adsorbents for removing antibiotics from water is an effective solution. In this
Keywords: study, NH2-MIL-53(Fe) and triazine-containing Tp-TTA were successfully combined to produce a novel MOF/
Metal–organic frameworks COF composite named NMF/TT, capable of effectively adsorbing and removing antibiotics. Various character­
Covalent organic frameworks
ization techniques were employed to determine the properties and morphology of NMF/TT, and the adsorption
Antibiotics
performance for four representative antibiotics (tetracycline, ciprofloxacin, ofloxacin, and norfloxacin) was
Adsorption
Water treatment investigated. Results indicated that NMF/TT-90 exhibited the optimal adsorption quantity, significantly
enhancing the adsorption quantity compared to the pure components. The adsorption processes of the four
antibiotics followed the pseudo-second-order kinetic model and Langmuir isotherm model. Among them, NMF/
TT-90 demonstrated the highest adsorption quantity for tetracycline, with a maximum adsorption quantity of
118.48 mg g− 1, and also exhibited an adsorption quantity of 55.93 mg g− 1 for ciprofloxacin. Thermodynamic
results confirmed the spontaneous nature of the adsorption processes for tetracycline and ciprofloxacin. NMF/
TT-90 showed the strongest adsorption quantity for tetracycline at pH 7. Furthermore, the effects of adsor­
bent dosage, interfering ions, real water samples, and the regenerability of the adsorbent were investigated. The
high adsorption quantity of the adsorbent is attributed to the π–π interactions, hydrogen bonding, and coordi­
nation between NMF/TT-90 and antibiotic molecules, as well as the possible defect effects during the composite
formation process.

tetracycline (TC), gradually accumulate in the environment, enter water

1. Introduction
Water resources are of critical significance to human beings. With the
progress of human society and the accelerated process of industrializa­
tion, various organic pollutants continuously invade water bodies,
polluting the environment (Elgarahy et al., 2021). In modern times, the
discovery of antibiotics has become a significant breakthrough in the
field of human medicine, which saves many lives. However, the misuse
of antibiotics has also brought about environmental pollution and has
had impacts on human health (Ajala et al., 2023). Some antibiotics are
not fully metabolized after ingestion and are excreted through waste.
Hospitals, pharmaceutical companies, and agriculture extensively use
antibiotics, leading to the frequent escape of antibiotics into the envi­
ronment and the generation of difficult-to-treat wastewater and waste
containing antibiotics (Maged et al., 2023). Antibiotics, including
bodies, and contribute to the emergence of antibiotic-resistant bacteria
and resistance genes. It is reported that drug-resistant bacteria cause
tens of thousands of deaths each year (Mangla et al., 2022). And the
COVID-19 pandemic has further intensified the contamination and
hazards of antibiotics (Hawash et al., 2023). So far, methods for
removing organic pollutants in water include adsorption (Fan et al.,
2023), photocatalysis (Guo et al., 2021), membrane separation (Zhang
et al., 2019), etc. Compared to other methods, adsorption has advan­
tages such as easy operation, reasonable cost, and ease of recovery (Ajala
et al., 2023), making it suitable for removing antibiotics. Therefore, the
facile removal of antibiotics by high-efficiency adsorbents from water
has become an imperative task and a hot research topic.
Metal–organic frameworks (MOFs), a type of porous crystalline
materials, are formed by connecting organic linkers and metal ions/
clusters via coordination bonds (Yuan et al., 2018). The high porosity,

* Corresponding author.
E-mail address: ning.yuan@cumtb.edu.cn (N. Yuan).

https://doi.org/10.1016/j.jclepro.2023.140259
Received 27 March 2023; Received in revised form 26 June 2023; Accepted 15 December 2023
Available online 16 December 2023
0959-6526/© 2023 Elsevier Ltd. All rights reserved.
N. Yuan et al.
Abbreviations
COFs Covalent organic frameworks
CIP Ciprofloxacin
DMF Dimethylformamide
FT-IR Fourier-transform infrared
MOFs Metal–organic frameworks
NMA/TT NH2-MIL-53(Al)/Tp-TTA
NMF/TT NH2-MIL-53(Fe)/Tp-TTA
NH2-BDC 2-Aminoterephthalic acid
NOR Norfloxacin
OFL Ofloxacin
PXRD Powder X-ray diffraction
SEM Scanning electron microscope
TC Tetracycline
TG Thermogravimetric
THF Tetrahydrofuran
Tp 1,3,5-Triformylphloroglucinol
TTA 4,4′,4’’-(1,3,5-triazine-2,4,6-triyl)triphenylamine
XPS X-ray photoelectron spectroscopy
high specific surface area, and various and regular morphologies of
MOFs make them have broad application prospects in many fields, such
as gas separation (Wang et al., 2020), organic pollutant adsorption (Yu
et al., 2019), heavy metal adsorption (Yang, B. et al., 2022), super­
capacitor electrodes (Sun et al., 2023), lithium-ion batteries (Du et al.,
2019), catalytic reactions (Ye et al., 2022), etc. MOFs have become one
of the most interesting materials for researchers due to their structural
and functional tunability and expanding range of applications (Yuan
et al., 2018). As another emerging category of organic crystalline porous
materials, covalent organic frameworks (COFs) typically consist of light
elements (such as H, C, B, N, and O), which are firmly linked by covalent
bonds through organic building blocks to create two- or
three-dimensional networks. Similar to MOFs, COFs also have excellent
properties, such as low density, intrinsic high porosity, high surface
area, ordered channel structure, tunable structure, etc (Li et al., 2021).
In recent years, the application of COFs materials in different fields has
attracted the ever-increasing attention of researchers, such as gas sep­
aration (Fan et al., 2020), photocatalysis (Pachfule et al., 2018), sus­
tained drug release (Fang et al., 2015), supercapacitor electrodes (Xu
et al., 2019), fluorescence sensing (Afshari et al., 2022), membrane
separation (Guo et al., 2022), metal ion adsorption (Jiang et al., 2019)
and so on. Both MOFs and COFs are two of the most representative types
of porous crystal frameworks, sharing many common features while also
exhibiting significant differences and complementarities (Chen et al.,
2021). Compared to MOFs, COFs typically do not contain metals. On the
other hand, compared to COFs, MOFs have higher density, and the
design of pore structures is more challenging (Li et al., 2021; Liu et al.,
2021). These limitations often lead to unsatisfactory adsorption quantity
in single-component MOFs or COFs. To obtain materials with enhanced
performance, it is necessary to adopt strategies that combine their
respective advantages.
In recent years, researchers have begun to composite MOFs with
COFs to prepare new MOF/COF hybrid adsorbents with excellent
properties. Firoozi et al. prepared a zinc-based composite, MOF-5/COF
(M5C), which is able to remove the cationic dyes auramine O (AO)
and rhodamine B (RhB) from aqueous solutions (Firoozi et al., 2020).
Zhong et al. constructed the material NH2-MIL-125(Ti)@TpPa-1, which
could adsorb and remove the radioactive elements UO2+ 2 and Eu
3+
ions,
and the adsorption capacities were 536.73 mg g− 1 and 593.97 mg g− 1,
respectively (Zhong et al., 2021). Wang et al. prepared three ternary
magnetic core–shell materials Fe3O4@MOF (M = Fe, Ti, Zr)@COF,
which exhibited high adsorption for the azo dyes Congo red (CR) and
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Journal of Cleaner Production 434 (2024) 140259
chrysoidine (CYD), and the maximum uptake capacities were 1250.02
mg g− 1 and 294.12 mg g− 1, respectively (Wang et al., 2021). In a study
by Dinari et al., a triazine-based covalent organic framework was inte­
grated onto the surface of amino-modified MIL-101(Cr), which could
effectively adsorb acid blue 9 with a maximum adsorption quantity of
256 mg g− 1 (Dinari and Jamshidian, 2021). However, currently,
MOF/COF composite adsorbents are mainly used for the adsorption of
pollutants such as dyes, and there is limited research on the adsorption
removal of antibiotics. The development of MOF/COF adsorbents for
adsorbing antibiotics is still underway. It is foreseeable that both MOFs
and COFs possess unsaturated conjugated structures and functional
groups with heteroatoms, making them promising adsorbents for anti­
biotics based on synergistic effects.
Inspired by the aforementioned considerations, in the present work,
we combined Fe-based NH2-MIL-53(Fe) and triazine-containing Tp-TTA
to obtain a new composite adsorbent NH2-MIL-53(Fe)/Tp-TTA (abbre­
viated as NMF/TT). NH2-MIL-53(Fe) was introduced to the precursor
solution of Tp-TTA and the NMF/TT adsorbent was fabricated through a
solvothermal method. The hybrid material was characterized using a
series of typical characterization techniques. The adsorption quantity of
the prepared hybrid material was evaluated using tetracycline (TC),
ciprofloxacin (CIP), ofloxacin (OFL), and norfloxacin (NOR) as typical
antibiotics, respectively. The adsorption behavior of antibiotics was
theoretically studied through adsorption kinetics, adsorption isotherms,
and thermodynamic analysis. In addition, the effects of different factors
such as pH, dosage, and interfering ions on TC adsorption during the
adsorption removal process, as well as the reusability of the adsorbent,
were discussed in detail. Finally, possible adsorption mechanisms were
inferred based on the experimental results.
2. Experimental section
2.1. Synthesis of NH2-MIL-53(Fe)
The synthesis of NH2-MIL-53(Fe) was conducted with reference to
previous literature, albeit with some modifications (Zhang, K. et al.,
2022; Zheng et al., 2018). In the synthesis process, 2 mmol of
FeCl3⋅6H2O (540 mg) and 2 mmol of NH2-BDC (362 mg) were placed in
24 mL of DMF. After sonication for 15 min to ensure complete dissolu­
tion, the mixture was placed into a Teflon-lined autoclave, sealed, and
heated at 150 ◦ C for 15 h. Once the reaction kettle was cooled to room
temperature, the resulting red-brown powder was gathered through
centrifugation, washed several times with DMF and absolute ethanol,
and finally, vacuum dried overnight at 80 ◦ C.
2.2. Synthesis of Tp-TTA
The synthesis of Tp-TTA is based on previous literature (Zhu et al.,
2017). 0.15 mmol of Tp (32 mg) and the same molar amount of TTA (53
mg) were added to a Pyrex tube, followed by 3 mL of dioxane. The
obtained mixture was sonicated for 10 min to fully dissolve, and then
0.6 mL of 3 M acetic acid was added. Following degassing through 3
freeze-pump-thaw cycles in a liquid nitrogen bath, the samples were
subjected to heating at 120 ◦ C for 3 days. Upon reaching room tem­
perature after cooling, the resulting powders were washed through
suction filtration with DMF and THF, respectively. The powders were
then soaked in THF for 24 h and ultimately collected by suction filtration
as orange-yellow powder. They were subsequently vacuum-dried over­
night at 80 ◦ C.
2.3. Synthesis of NMF/TT composites
The synthesis process of the composites was displayed in Scheme 1.
34 mg of Tp, 43 mg of TTA, and x mg of NH2-MIL-53(Fe) (x = 50, 90,
130) were dispersed in 3 mL of dioxane. The mixture was sonicated for
10 min and then supplemented with 0.6 mL of 3 M acetic acid. Following
N. Yuan et al.
Scheme 1. Schematic diagram of the synthesis of NH2-MIL-53(Fe)/Tp-TTA (abbreviated to NMF/TT) composites.
degassing via three freeze-pump-thaw cycles in a liquid nitrogen bath,
the samples were heated at 120 ◦ C for 3 days. Upon reaching room
temperature after cooling, the powders were washed by suction filtra­
tion with DMF and THF, respectively. Subsequently, the powders were
soaked in THF for 24 h and ultimately collected as brown powder by
suction filtration. The products were then vacuum dried overnight at
80 ◦ C and denoted as NMF/TT-x (x = 50, 90, 130).
3. Results and discussion
3.1. Characterization
The scanning electron microscope (SEM) can be used to observe the
microscopic morphologies of the adsorbents that were obtained in this
work. Fig. 1 displays the SEM micrographs of NH2-MIL-53(Fe), Tp-TTA,
and NMF/TT-90. NH2-MIL-53(Fe) exhibits a very smooth surface and a
regular biconical multi-prismatic structure (Yu et al., 2019) with a
length of about 600 nm. Tp-TTA exhibits a porous fibrous structure, and
Fig. 1. SEM micrographs of NH2-MIL-53(Fe) (a), Tp-TTA (b), and NMF/TT-90 (c, d).
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Journal of Cleaner Production 434 (2024) 140259
the hollow interior space can be evidently observed. In the NMF/TT-90,
it can be apparently observed that the structure of MOF is dispersed in
the fiber network structure of COF. In contrast to the pure MOF, the
surface of the MOF structure in the composite system exhibited rough­
ness, and the COF fibers were firmly adhered, indicating the presence of
two constituents in the composite and their successful combination.
Powder X-ray diffraction (PXRD) analysis is typically utilized to
examine the crystallinity of powder samples. Fig. 2(a) shows the PXRD
patterns of NH2-MIL-53(Fe), Tp-TTA, and NMF/TT composites. The
diffraction peaks observed for NH2-MIL-53(Fe) at 2θ = 9.3, 10.1, 18.6,
and 25.7◦ are mostly in line with those reported in the literature (Zheng
et al., 2018). The diffraction peaks of Tp-TTA at 2θ = 5.6, 9.8, and 14.9◦
are assigned to the (100), (110), and (210) crystal planes(Yang, L. et al.,
2022). Due to the weak crystallinity of COF, the diffraction peaks of
Tp-TTA cannot be apparently observed in the NMF/TT composite. The
diffraction peak intensity of the composites gradually increases with the
elevation of MOF addition, but the intensity is far less than that of pure
MOF, which may be caused by the partial decomposition of NH2-MIL-53
N. Yuan et al. Journal of Cleaner Production 434 (2024) 140259

Fig. 2. PXRD patterns (a), FT-IR spectra (b), N2 physical adsorption isotherms (c), and pore size distribution curves (d) of NH2-MIL-53(Fe), Tp-TTA and NMF/TT
hybrid materials.

(Fe) during the composite process.
Fig. 2(b) shows the Fourier-transform infrared (FT-IR) absorption
spectra of NH2-MIL-53(Fe), Tp-TTA, and NMF/TT. The bands located at
3463 and 3353 cm− 1 in NH2-MIL-53(Fe) belong to the N–H stretching
vibration, whereas the peak at 1258 cm− 1 is associated with the C–N
vibration of the amino group on the benzene ring. The presence of a
sharp peak at 770 cm− 1 corresponds to the C–H bending vibration on the
benzene ring (Xiong et al., 2018), while the peak near 566 cm− 1 cor­
responds to the Fe–O coordination bond (Zhang, K. et al., 2022; Zheng
et al., 2018). For Tp-TTA, the peaks observed at 1578 and 1286 cm− 1 are
connected to the asymmetric vibrations of the C– –C and C–N– –C bonds,
respectively ()(Yang, L. et al., 2022). The C––C bond vibration at 1578
cm− 1 is attributed to the tautomerism between the keto and enol forms
and is significantly different from the C– –C bond vibration at 1508,
1455 cm− 1, etc (Wang et al., 2022). The FT-IR spectrum of NMF/TT is
very similar to Tp-TTA, and the characteristic absorption bands of MOF
can be observed at 770 cm− 1 and 566 cm− 1, while the N–H stretching
vibration peak on the MOF disappears, which proves that the two
components were successfully compounded.
The pore structure characteristics of the material can be investigated
through N2 physical adsorption. Fig. 2(c) shows the N2 adsorp­
tion–desorption curves of NH2-MIL-53(Fe), Tp-TTA, and NMF/TT-90,
and Fig. 2(d) exhibits the corresponding pore size distribution curves
using the NLDFT model. The calculated parameters are summarized in
Table 1. All three materials have H4-type hysteresis loops, and all curves
correspond to type-I isotherms, indicating that they are all typical
microporous materials (Li et al., 2022). The prepared Tp-TTA has the
Table 1
Textural parameters of the prepared samples by N2 adsorption experiments.
Samples BET specific surface area Total pore volume Pore size
(m2 g− 1) (cm3 g− 1) (nm)
NH2-MIL-53 16.9 0.052 0.66
(Fe)
Tp-TTA 760 0.813 0.56
NMF/TT-90 359 0.588 0.56
highest specific surface area (760 m2 g− 1), while the specific surface area
of NH2-MIL-53(Fe) is very low (16.9 m2 g− 1). The addition of MOF re­
sults in a significant reduction in the specific surface area of NMF/TT-90
(359 m2 g− 1). The pore structure of NMF/TT-90 is similar to that of
Tp-TTA, the pore size is about 0.55 nm, and the pore volume is greatly
reduced.
Thermogravimetric (TG) analysis can evaluate the thermal stability
of materials. Fig. 3(a) illustrates the TG curves of NH2-MIL-53(Fe), Tp-
TTA, and NMF/TT-90 under the N2 atmosphere. From room tempera­
ture to 150 ◦ C, all materials show some mass loss as the temperature
increases, suggesting that the residual solvent molecules in the materials
are removed (Deng et al., 2020). With further increase in temperature,
the coordination and covalent bonds are gradually broken, the structure
collapses, and the materials gradually decompose. The figure indicates
that the thermal stability of NMF/TT-90 is enhanced compared to pure
NH2-MIL-53(Fe) and Tp-TTA.
X-ray photoelectron spectroscopy (XPS) is a technique used to
analyze the elemental composition of materials. Fig. 3(b) demonstrates
the survey spectra of NH2-MIL-53(Fe), Tp-TTA, and NMF/TT-90. All
three materials contain C, N, and O elements, and NH2-MIL-53(Fe) and
NMF/TT-90 also contain Fe elements. Fig. 3(c and d) shows the Fe 2p
and N 1s spectra of the material, respectively. The Fe 2p spectrum of
NH2-MIL-53(Fe) exhibits three main peaks that can be deconvoluted,
consistent with the literature (Zhang, K. et al., 2022). The peaks at
725.33 eV and 711.58 eV are associated with Fe 2p1/2 and Fe 2p3/2,
while the satellite peak of Fe 2p is located at 715.33 eV, indicating the
presence of Fe(III) in the material (Zhang et al., 2022a). Due to the low
amount of MOF addition and the possible partial disintegration of the
MOF structure in the synthesis process, the peak intensity of Fe 2p of
NMF/TT-90 is reduced. The interaction between Fe nodes and the
Tp-TTA framework causes a shift in the Fe peak in NMF/TT-90. The N on
the triazine ring and C–N bond correspond to the peaks at 398.24 eV and
399.66 eV in the N 1s spectrum of Tp-TTA, respectively (Wang et al.,
2022; Yang, L. et al., 2022). The absence of peaks at 399.82 eV (− N+− )
and 398.70 eV (− NH2) in the N 1s spectrum of NMF/TT-90 indicates
that the two components are connected by a covalent bond.

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N. Yuan et al. Journal of Cleaner Production 434 (2024) 140259

Fig. 3. TG curves (a) and XPS spectra of NH2-MIL-53(Fe), Tp-TTA, and NMF/TT-90. Survey (b), Fe 2p (c), and N 1s (d).

3.2. Adsorption kinetics

To understand the adsorption behavior of the materials, the impact
of contact time on the adsorption efficiency was initially examined. The
adsorption curve in 50 mg L− 1 TC is shown in Fig. 4(a). Except for NH2-
MIL-53(Fe), the adsorption quantity of other samples showed an
increasing trend as the contact time increased. At the beginning stage,
the adsorption occurred rapidly, the adsorption active sites gradually
tended to be saturated with time, and the adsorption also gradually
tended to equilibrium (Kim et al., 2022). Comparing the adsorption
performance of different samples, it was found through experimental
results that NMF/TT-90 exhibited the highest adsorption performance.
The adsorption process reached equilibrium after approximately 2 h.
The equilibrium adsorption quantity was observed to be significantly
higher than that of pure NH2-MIL-53(Fe) and Tp-TTA. NH2-MIL-53(Fe)
showed a gradual increase followed by a decrease in adsorption quan­
tity, which could be attributed to its low specific surface area and pore
volume. This makes it challenging to accumulate a significant amount of
TC and easier to desorb from the MOF surface.
The adsorption mechanism of TC was investigated using the pseudo-
first-order kinetic and pseudo-second-order kinetic models, as expressed
by the following equations (Li, Y. et al., 2019; Wang et al., 2021):
ln(Qe − Qt ) = ln Qt − k1 t (1)
t 1 t
= + (2)
Qt k2 Q2t Qe
where the adsorption quantity at equilibrium and at time t (min) are
denoted by Qe and Qt (mg g− 1) respectively. The rate constants for the
pseudo-first-order and pseudo-second-order kinetic models are repre­
sented by k1 (min− 1) and k2 (g mg− 1 min− 1), respectively.
Fig. 4(b and c) presents the results of linear fitting for the two
models, while Table 2 lists the relevant calculation outcomes. Upon
comparing the correlation coefficients (R2) in Table 2 and it can be
observed that the R2 value for the pseudo-second-order model is closer
to 1, which implies that the adsorption of TC by NH2-MIL-53(Fe), Tp-
TTA, and NMF/TT-90 was better fitted by the pseudo-second-order ki­
netic model. It can be inferred that the chemical adsorption mechanism
played a dominant role during the adsorption process (Kim et al., 2022).
The adsorption phenomenon of the samples in 30 mg L− 1 CIP solu­
tion was similar to that in the TC solution. Based on the data presented in
Fig. S2(a), it can be observed that the adsorption quantity of the five
adsorbents increased gradually with time and reached adsorption

Fig. 4. Adsorption kinetics of TC on adsorbents (a). The fitting curves of pseudo-first-order kinetic (b) and pseudo-second-order kinetic (c). Experimental conditions:
Adsorbent dosage of 0.5 g L− 1, temperature of 25 ◦ C, initial concentration of 50 mg L− 1, and initial pH of 7.

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N. Yuan et al. Journal of Cleaner Production 434 (2024) 140259

Table 2 driving force for the diffusion of TC molecules into the adsorbent ().
Kinetic parameters of the prepared adsorbents for TC adsorption. The adsorption process of TC on NMF/TT-90 can be analyzed using
Adsorbent Pseudo-first order model Pseudo-second order model two different adsorption isotherms, namely the Langmuir model and the
2 Freundlich model. These models can be expressed by the following
Qe,cal k1 R Qe,cal k2 (g R2
(mg (min− 1) (mg mg− 1 equations (Afridi and Kim, 2022; Wang et al., 2021):
g− 1) g− 1) min− 1)
Ce Ce 1
NH2-MIL- / / / 20.31 − 2.45 × 0.996
= + (3)
Qe Qm KL Qm
53(Fe) 10− 3
Tp-TTA 13.00 6.71 × 0.850 25.35 1.25 × 0.991 1
10− 3 10− 3 ln Qe = ln KF + ln Ce (4)
NMF/TT-90 27.27 7.69 × 0.913 69.49 7.65 × 0.998
n
10− 3 10− 4 In the formula, Qe and Qm (mg g− 1) denote the equilibrium adsorp­
tion quantity and the maximum adsorption quantity, respectively, Ce
(mg L− 1) represents the solute concentration in the solution at the
equilibrium after approximately 1.5 h. Notably, NMF/TT-90 exhibited
adsorption equilibrium, while KL and KF are the equilibrium constants of
the highest adsorption quantity upon reaching adsorption equilibrium,
the Langmuir and the Freundlich models, respectively. Additionally, n is
which was significantly greater than that of pure NH2-MIL-53(Fe) and
the adsorption strength parameter of the Freundlich model.
Tp-TTA. Figs. S2(b and c) displays the results of fitting NH2-MIL-53(Fe),
The Langmuir model and Freundlich model adsorption isotherms, as
Tp-TTA, and NMF/TT-90 using both the pseudo-first-order and pseudo-
well as the corresponding fitting results, are depicted in Fig. 5(b and c).
second-order kinetic models, with corresponding calculation results
The insets in the figure represent the linear fitting results obtained using
listed in Table S1. By comparing the R2 values of the two models, it can
the formula, and the acquired parameters are listed in Table 3. Upon
be inferred that the pseudo-second-order kinetic model fits the adsorp­
comparing the R2 of the two models, it was determined that the Lang­
tion of CIP by the three adsorbents very well, as the R2 obtained is almost
muir model was better suited to describe the adsorption of TC on NMF/
equal to 1. Based on the experimental results of TC and CIP adsorption
TT-90, thereby signifying that the adsorption behavior was primarily
by the synthesized adsorbents, NMF/TT-90 exhibited the highest
monolayer adsorption (Afridi and Kim, 2022). According to the
adsorption quantity for both antibiotics, and thus the subsequent
maximum adsorption quantity obtained by fitting at different temper­
experimental studies mainly focused on NMF/TT-90.
atures, the adsorption quantity of NMF/TT-90 for TC increases as the
Fig. S3(a) illustrates the adsorption characteristics of NH2-MIL-53
temperature increases, and the highest adsorption quantity under the
(Fe), Tp-TTA, and NMF/TT-90 adsorbents in a 10 mg L− 1 OFL solution.
experimental conditions was found to be 118.48 mg g− 1.
NMF/TT-90 was found to reach the adsorption equilibrium after
Similar to TC, the adsorption quantity of CIP on NMF/TT-90
approximately 1.5 h and exhibited better adsorption performance than
increased with the increase in initial concentration, as shown in
pure NH2-MIL-53(Fe) and Tp-TTA. The fitting results of the two
Fig. S5(a). The obtained data were analyzed using two adsorption
adsorption models are illustrated in Figs. S3(b and c), and the relevant
isotherm models, and the fitting results are shown in Figs. S5(b and c).
calculation results are listed in Table S2. The adsorption process of
Table S4 presents the calculated parameters, with the R2 value for the
NMF/TT-90 demonstrated a good fit with the pseudo-second-order ki­
Langmuir model being closer to 1, indicating that the adsorption process
netic model. Furthermore, the adsorption of 10 mg L− 1 NOR by NMF/
follows this model. The adsorption quantity of NMF/TT-90 for CIP
TT-90 reached equilibrium after approximately 1.5 h and exhibited
slightly increases with the rise in temperature, with the highest observed
better adsorption quantity than pure NH2-MIL-53(Fe) and Tp-TTA, as
adsorption quantity under the experimental conditions being 55.93 mg
illustrated in Fig. S4(a). From the fitting results in Figs. S4(b and c) and
g− 1.
the fitting data listed in Table S3, it can be concluded that the adsorption
The Langmuir model and Freundlich model were adopted to fit the
process of NMF/TT-90 for 10 mg L− 1 NOR is best described by the
pseudo-second-order kinetic model.
Table 3
Adsorption isotherm parameters of adsorbent NMF/TT-90 for TC adsorption.
3.3. Adsorption isotherm
Model Parameters 298.15 K 308.15 K 318.15 K
− 1
To gain an in-depth understanding of the adsorption mechanism of Langmuir Qm,cal (mg g ) 108.58 117.10 118.48
KL (L mg− 1) 0.115 0.117 0.184
NMF/TT-90 on antibiotic molecules, the relationship between the
R2 0.993 0.981 0.994
adsorption amount and initial concentration was evaluated at different Freundlich KF ((mg g− 1)⋅(L mg− 1)1/n) 19.76 19.93 27.44
temperatures, as shown in Fig. 5(a). When increasing the solution con­ 1/n 0.420 0.448 0.388
centration, the adsorption quantity of the adsorbent for TC climbs, R2 0.878 0.829 0.835
which is attributed to the high initial concentration provides a high

Fig. 5. The adsorption quantity of NMF/TT-90 for TC varies with the initial concentration of TC (a). The fitting results of the Langmuir model (b) and the Freundlich
model (c) for the adsorption isotherms. Experimental conditions: Adsorbent dosage of 0.5 g L− 1, time of 4 h, and initial pH of 7.

6
N. Yuan et al.
adsorption isotherm of OFL on NMF/TT-90, and the fitting results are
shown in Fig. S6. Table S5 lists the relevant parameters. The Langmuir
model was found to be suitable for describing the adsorption process,
and the adsorption quantity of NMF/TT-90 for OFL slightly decreased
with increasing temperature under the experimental conditions, with
the highest adsorption quantity being 18.86 mg g− 1. The adsorption
isotherm of NOR on NMF/TT-90 was fitted, and the relevant parameters
are presented in Table S6. The fitting results are shown in Fig. S7,
indicating that the Langmuir model is suitable for describing the
adsorption process. The adsorption quantity of NMF/TT-90 for NOR
slightly decreased with increasing temperature, and the highest
adsorption quantity under the experimental conditions was found to be
14.23 mg g− 1.
3.4. Adsorption thermodynamics
To analyze the influence of temperature on the adsorption of TC and
CIP by NMF/TT-90, the thermodynamic analysis of adsorption was
conducted to determine the endothermic and exothermic conditions of
the adsorption process and whether it is spontaneous. The relevant
thermodynamic parameters are calculated according to the following
equations (Tran et al., 2021):
K = 1000KL MW C◦ (5)
ΔH ΔS
ln K = − + (6)
RT R
ΔG = ΔH − TΔS (7)
where K is the thermodynamic equilibrium constant, KL is the Langmuir
model equilibrium constant, MW is the relative molecular mass of TC or
CIP, T (K) is the thermodynamic temperature, and R is the ideal gas
constant with a value of 8.314 J mol− 1 K− 1. C◦ is the standard molar
concentration, taking 1 mol L− 1 ΔG, ΔH, and ΔS are Gibbs free energy,
enthalpy change, and entropy change, respectively.
Fig. 6 shows the lnK and 1/T relationship, and Table 4 lists the
corresponding thermodynamic parameters obtained from the slope and
intercept of the fitting curve. The positive value of ΔH indicates that the
adsorption of TC and CIP by NMF/TT-90 is an endothermic process,
where an increase in temperature favors adsorption. This is consistent
with the experimental results. The negative ΔG at different temperatures
suggests that the adsorption phenomenon is spontaneous, and the
adsorption process can occur at room temperature. The positive ΔS
value indicates a certain affinity between antibiotic molecules (TC and
Fig. 6. Van’t Hoff equation fitting curves.
7
Journal of Cleaner Production 434 (2024) 140259
Table 4
Thermodynamic parameters of adsorption of TC and CIP on NMF/TT-90.
Adsorbate ΔH (kJ ΔS (J ΔG (kJ mol− 1) R2
mol− 1) mol− 1
298.15 308.15 318.15
K− 1)
K K K
TC 18.34 151.71 − 26.89 − 28.41 − 29.93 0.760
CIP 15.22 147.13 − 28.64 − 30.12 − 31.59 0.970
CIP) and the prepared adsorbent, leading to an increase in system
randomness during the adsorption process (Abdi et al., 2017).
3.5. Effects of adsorbent dosage, interfering ions, and pH on adsorption
and recoverability of adsorbents
The impact of adsorbent dosage on adsorption was investigated by
altering the dosage of the NMF/TT-90 adsorbent, as depicted in Fig. 7(a
and b). As the adsorbent dosage increased, the adsorption quantity
gradually decreased. The reduced adsorption quantity could be ascribed
to the overlapping and competition of active sites on the adsorbent.
Additionally, the decrease in concentration gradient and increase in
steric hindrance would result in difficult diffusion of adsorbate mole­
cules, leading to a decline in adsorption quantity (Abdi et al., 2017). In
real wastewater, besides the adsorbate, there are numerous interfering
ions. The adsorption results in TC solutions containing 1 mmol L− 1 of
anions are shown in Fig. 7(c). The presence of different anions can either
promote or inhibit adsorption. However, overall, these anions have a
limited impact on the adsorption quantity.
The adsorption performance is significantly affected by the pH of the
solution, because pH can affect the ionization of adsorbents and active
functional groups of adsorbates ()(Li, Y. et al., 2019). The adsorption
quantity of the adsorbent at various pH levels is displayed in Fig. 7(d).
The results indicate that the highest adsorption quantity for TC occurs in
a neutral environment, while the adsorption quantity is significantly
diminished in an acidic environment. The material exhibits poor
adsorption quantity under alkaline conditions. The acid dissociation
constants (pKa) of TC are 3.32, 7.78, and 9.58, respectively, suggesting
that TC is predominantly positively charged at pH < 3.32, predomi­
nantly zwitterionic at 3.32 < pH < 7.78, and predominantly negatively
charged at pH > 7.78 (Xiong et al., 2018; Yu et al., 2019). Fig. S8 pro­
vides the zeta potential of NMF/TT-90. In an alkaline environment, both
TC molecules and the adsorbent carry negative charges, and electro­
static repulsion severely interferes with adsorption. In an acidic envi­
ronment, the adsorbent still carries a negative charge. As the acidity
increases, the positively charged TC gradually increases, but the
adsorption quantity does not increase accordingly. The adsorbent ex­
hibits the highest adsorption quantity at pH = 7. At this pH, TC exists in
the form of zwitterionic ions and a small amount of negatively charged
ions, while the adsorbent has a zeta potential of − 18.9 mV, indicating a
certain repulsive effect (Zhu et al., 2020). Based on this, it can be
inferred that electrostatic interactions are not the main mechanism for
TC adsorption.
Recycling adsorbents is crucial for cost savings. After cleaning and
drying the used adsorbent, adsorption experiments were performed
again. As shown in Fig. 7(e), the adsorption of TC and CIP by the
adsorbent decreased after four cycles, but still maintained a certain
adsorption quantity. The reduction in adsorption quantity may be
attributed to the clogging and irreversible occupation of some adsorp­
tion sites (Fan et al., 2023).
Finally, the laboratory tap water and river water (Xiaoyue River,
Beijing) were used to configure TC and CIP solutions to simulate actual
water samples, as shown in Fig. 7(f). According to the experimental
results, the adsorption quantity of the adsorbent for TC and CIP in tap
water diminishes due to the presence of competing ions. However, it can
still be maintained at more than 70% of the original adsorption quantity,
reflecting good adsorption performance. On the other hand, the
N. Yuan et al.
Fig. 7. The effect of adsorbent dosage (a, b), interfering ions (c), and pH (d) on the adsorption performance of NMF/TT-90. The cycling performance of NMF/TT-90
(e) and its adsorption quantity in different water samples (f). Experimental conditions: Temperature of 25 ◦ C, time of 4 h, initial concentrations of TC at 50 mg L− 1,
CIP at 30 mg L− 1, OFL at 10 mg L− 1, and NOR at 10 mg L− 1.
components in the river water are more complex, and the interaction
with the adsorbent is also more complicated, which shows that the
adsorption inhibition effect on TC and CIP is more obvious. Compared to
other MOF- or COF-based TC adsorbents mentioned in the literature, the
NMF/TT-90 hybrid material demonstrates a decent adsorption quantity
for TC. The relevant data are summarized in Table S7.
3.6. Plausible adsorption mechanisms
The PXRD, FT-IR, and N2 adsorption–desorption curves of NMF/TT-
90 were analyzed before and after the adsorption of TC to determine the
potential adsorption mechanism of TC from an aqueous solution. Fig. 8
(a) illustrates that the intensity of the PXRD pattern of the adsorbent is
weakened after adsorption, but the overall change is not remarkable,
suggesting that the adsorption process does not significantly damage the
structure of the adsorbent. Fig. 8(b) illustrates that the shape of the FT-
IR spectra of the adsorbent remains consistent before and after TC
adsorption, indicating that the chemical composition of the adsorbent
did not change during the adsorption process. The C– –C bond vibration
peaks at 1578 and 1508 cm− 1 and the triazine ring vibration peak at
1286 cm− 1 are enhanced compared with those before adsorption,
potentially indicating the presence of π–π interaction between the
adsorbent and TC molecules (Zhang et al., 2022a,b). As shown in Fig. 8
(c), like other adsorbents (Huo et al., 2019; Zhang et al., 2022), there is a
Fig. 8. PXRD (a), FT-IR (b), and N2 adsorption–desorption curves (c) of NMF/TT-90 before and after adsorption.
8
Journal of Cleaner Production 434 (2024) 140259
noticeable decrease in the specific surface area of the adsorbent after
adsorption. The size of TC molecules is about 0.9 × 1.4 nm (Zhang et al.,
2022), which is larger than the pore size of the adsorbent, so it can be
inferred that the TC molecules primarily adsorb onto the surface of the
adsorbent, thereby decreasing the specific surface area. In addition, the
adsorbed TC can hinder the diffusion of N2, resulting in a decrease in the
measured specific surface area (Zhang et al., 2022a).
In addition, the adsorbent surface also has a large number of active
groups such as C– –O and Fe(III) Lewis acid binding sites, which can
adsorb antibiotic molecules through hydrogen bonding and coordina­
tion (Li et al., 2022; Yu et al., 2019), as illustrated in Scheme 2. As
mentioned before, NMF/TT-90 exhibits the highest adsorption quantity
for TC among the four antibiotics, with the adsorption quantity order
being TC > CIP > OFL > NOR. Compared with CIP, OFL, and NOR, TC
has more unsaturated bonds and active functional groups (Zhu et al.,
2020), which may be more advantageous for interacting with the surface
of adsorbents. The composite of MOF and COF changes the structure of
the two components to a certain extent, which exposes more active
adsorption sites and promotes the occurrence of adsorption. Previous
research has demonstrated that the introduction of defects in materials
can effectively enhance their adsorption performance (Xiang et al.,
2020). The introduction of monocarboxylic acids (such as formic acid,
acetic acid, etc.) is an important way to enable the formation of defects
in MOFs. In this study, acetic acid not only can play a role in the
N. Yuan et al.
Scheme 2. Possible adsorption mechanism of NMF/TT composites.
formation of COF as a catalyst but also may introduce defects in the MOF
structure and thus enhance the adsorption quantity.
In order to examine the influence of metal sites in MOF/COF hybrids
on their adsorption performance, NH2-MIL-53(Al)/Tp-TTA (abbreviated
to NMA/TT) adsorbents are prepared by the same method. As seen in the
SEM image of Fig. S9, the rod-like structure of NH2-MIL-53(Al) in the
NMA/TT-90 is dispersed in Tp-TTA. Figs. S10(a and b) shows the
adsorption curves of TC and CIP under the same adsorption conditions,
while the corresponding fitting results of the adsorption model are
presented in Figs. S10(c and d), and the relevant data can be found in
Table S8. Compared to pure NH2-MIL-53(Al) and Tp-TTA, NMA/TT-90
exhibited enhanced adsorption quantity for TC and CIP, and the
adsorption procedure followed pseudo-second-order kinetics. Under the
experimental conditions, the equilibrium adsorption capacities for TC
and CIP are 42.97 and 36.08 mg g− 1, respectively, which are inferior to
those of NMF/TT-90 (69.49 and 41.14 mg g− 1). It shows that the
different metals contained in the adsorbent will affect the adsorption
quantity.
4. Conclusions
In conclusion, we fabricated a novel composite material NMF/TT by
covalently combining NH2-MIL-53(Fe) and Tp-TTA, which exhibited
synergistic effects for adsorbing and removing antibiotics from water.
The successful preparation of NMF/TT was confirmed through various
characterizations. Among them, NMF/TT-90 showed the optimal
adsorption quantity and demonstrated higher adsorption quantities for
TC, CIP, OFL, and NOR compared to the pure components. The
adsorption processes of the four antibiotics followed pseudo-second-
order kinetics, and the adsorption isotherms aligned with the Lang­
muir model, indicative of monolayer adsorption. Particularly, NMF/TT-
90 exhibited the highest adsorption quantity for TC, with a maximum
adsorption quantity of 118.48 mg g− 1. NMF/TT-90 exhibited an
adsorption quantity of 55.93 mg g− 1 for ciprofloxacin as well. Ther­
modynamic analyses indicated that the adsorption process was sponta­
neous. NMF/TT-90 exhibited good anti-anion interference capability in
the adsorption experiment and had good cycle adsorption performance.
At pH 7, NMF/TT-90 exhibited the highest adsorption quantity for TC.
The experimental results suggest that π–π interaction, hydrogen bond
9
Journal of Cleaner Production 434 (2024) 140259
interaction, and coordination are the primary mechanisms involved in
the adsorption of TC molecules by the composite adsorbent, and the
defective structure generated in situ may also contribute to the
adsorption process. This study demonstrates that MOF/COF composite
materials can effectively adsorb and remove antibiotic pollutants from
aqueous solutions, providing valuable insights for the research and
application of MOF/COF adsorbent materials. It is expected that with
further research on MOF and COF materials, as well as continuous im­
provements in the structure and composition of MOF/COF, there will be
the emergence of MOF/COF composite materials with better adsorption
performance.
CRediT authorship contribution statement
Ning Yuan: Conceptualization, Methodology, Resources, Visualiza­
tion, Formal analysis, Supervision, Writing – review & editing. Chuan
Zhang: Investigation, Visualization, Formal analysis, Writing – original
draft. Xinling Zhang: Visualization, Formal analysis. Ronghua Zhang:
Visualization, Formal analysis.
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.
Data availability
Data will be made available on request.
Acknowledgments
This work was supported by the National Key Research and Devel­
opment Program of China (2019YFC1904304) and the Fundamental
Research Funds for the Central Universities (2023ZKPYHH05).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
N. Yuan et al.
org/10.1016/j.jclepro.2023.140259.
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