Chemosphere 241 (2020) 125002

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Iron-copper bimetallic metal-organic frameworks for efficient Fenton-

like degradation of sulfamethoxazole under mild conditions
Juntao Tang a, Jianlong Wang a, b, *
a
Collaborative Innovation Center for Advanced Nuclear Energy Technology, INET, Tsinghua University, Beijing, 100084, PR China
b
Beijing Key Laboratory of Radioactive Waste Treatment, INET, Tsinghua University, Beijing, 100084, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

A novel bimetallic MOF catalyst

(FexCu1-x(BDC)) was prepared.

FexCu1-x(BDC)/H2O2 system can work
efficiently at slightly basic pH
conditions.

Complete SMX degradation was ach-
ieved over a Fe0.75Cu0.25(BDC)
catalyst.

Cu species promoted the
OH forma-
tion by facilitating the redox rate of
Fe(III)/Fe(II).

a r t i c l e i n f o a b s t r a c t

Article history: Iron and copper bimetallic MOF material (FexCu1-x(BDC)) as a novel Fenton-like catalyst was prepared by
Received 27 June 2019 a simple solvothermal method, and its performances were evaluated in the catalytic degradation of
Received in revised form sulfamethoxazole (SMX) in the presence of hydrogen peroxide. The results indicated that the FexCu1-
22 August 2019
x(BDC)/H2O2 system was highly effective for SMX degradation over a wide pH range (4.0e8.6). At
Accepted 27 September 2019
initial solution pH of 5.6, the bimetallic Fe0.75Cu0.25(BDC) catalyst exhibited a 100% SMX (20 mg L1)
Available online 27 September 2019
removal within 120 min, which was superior to the SMX removal efficiency over monometallic Fe(BDC)
Handling Editor: Jun Huang and Cu(BDC) catalysts. Combined with the physical-chemical characterization, the synergistic effect
between Fe and Cu species were responsible for the efficient catalytic activity. Moreover, the
Keywords: Fe0.75Cu0.25(BDC) catalyst showed good reusability for SMX degradation. The possible reaction mecha-
Fenton-like catalyst nism in FexCu1-x(BDC)/H2O2 system was also tentatively proposed. This work has not only suggested the
Bimetallic MOF potential of bimetallic FexCu1-x(BDC) catalysts in Fenton-like treatment of antibiotics, but also provided
Synergistic effect useful information to develop MOF-based catalysts for efficient environmental remediation.
Sulfamethoxazole
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction

Sulfamethoxazole (SMX) is one of the major pharmaceutical

pollutants detected in aquatic environment because of its abuse in
the therapy of human diseases and incomplete metabolism in hu-
* Corresponding author. Energy Science Building, INET, Tsinghua University,
man body (Wang et al., 2019). Long-term exposure to SMX might
Beijing, 100084, China.
E-mail address: wangjl@tsinghua.edu.cn (J. Wang).
alter microbial community structure, induce the evolution and

https://doi.org/10.1016/j.chemosphere.2019.125002
0045-6535/© 2019 Elsevier Ltd. All rights reserved.
2 J. Tang, J. Wang / Chemosphere 241 (2020) 125002
dissemination of drug-resistant bacteria and genes, and cause other
adverse effects to ecosystem and human health (Baran et al., 2011;
Underwood et al., 2011). Moreover, SMX shows poor activity (20%e
30% removal) toward conventional biological wastewater treat-
ment due to its polarity and antibacterial nature (Wang and Wang,
2018a, 2018b). Consequently, the awareness of environmental risks
pertaining to the presence of SMX in the aquatic environment has
spurred the development of efficient and environmental-friendly
technologies, especially the advanced oxidation processes (AOPs)
for the removal, of SMX from water and wastewater (Liu and Wang,
2013; Wang and Chu, 2016; Wang and Bai, 2017; Wang and Wang,
2018c, 2019; Zhuan and Wang, 2019).
The Fenton process based on the production highly reactive
hydroxyl radicals (
OH) from Fe2þ and H2O2, as one of the most
effective advanced oxidation processes, has indicated a certain
success in the treatment of pharmaceutical-contaminated waters
due to its high efficiency, simple operation and convenient control
(Wang and Xu, 2012; Wang and Wang, 2016). Despite the effec-
tiveness of the Fenton treatment, it presents several inherent
drawbacks, mostly related to the narrow working pH range and the
production of undesired iron sludge which requires further
disposal (Pignatello et al., 2006; Chen et al., 2018; Liu and Wang,
2019). As an alternative, heterogeneous Fenton process with
insoluble solid catalysts and H2O2 can overcome these problems,
and various heterogeneous Fenton-like catalysts have been suc-
cessfully employed in the degradation of SMX, including Fe3O4
(Munoz et al., 2018), ZneFe-CNTs (Liu et al., 2018), Fe@MesoC (Tang
and Wang, 2018a) and CX/CoFe (Ribeiro et al., 2016). However, the
favorable catalytic activity of these catalysts is usually achieved
under acidic conditions or with the assistance of external energy.
Accordingly, it is crucial to explore other alternative materials that
can initiate more efficient Fenton-like process under mild
conditions.
Metaleorganic frameworks (MOFs) are porous materials with
periodic network structures comprised of metal ions/clusters and
organic bridging ligands (Cheng et al., 2018; Huang et al., 2017;
Furukawa et al., 2013). The peculiar structure of MOFs endows
them with many fascinating properties, such as large surface area,
open pore channels, and tunable porosity, favoring the diffusion of
reactants and products during catalysis (Corma et al., 2010; Yang
et al., 2018). In addition, the wide distribution of metallic compo-
nents in MOFs can also serve as active sites for catalytic reactions,
making them promising candidates for heterogeneous Fenton re-
action (Cheng et al., 2018). Recently, several MOF-based materials
like MIL-53(Fe), CUS-MIL-100(Fe) and FeII@MIL-100(Fe) have been
studied in heterogeneous Fenton-like oxidation of refractory
organic contaminants, yet the catalytic performance of most of
these catalysts still needs to be improved (Cheng et al., 2018; Ai
et al., 2014; Tang and Wang, 2018b; Lv et al., 2015). Generally, the
efficiency of the MOF-catalyzed Fenton-like reaction is closely
related to their metallic components. Doping or introducing addi-
tional active metal center to pristine MOFs is deemed as an effective
way to improve their catalytic performance taking into account the
possible synergistic effect between the two active metal species in
Fenton process, and have attracted much attention in recent years
(Rahim Pouran et al., 2014). For instance, Sun et al. fabricated three
series of bimetallic Fe-based MOFs by partial isomorphic substitu-
tion of iron center with manganese, cobalt, or nickel, and studied
their application in Fenton-like degradation of phenol (Sun et al.,
2017). The results showed that the phenol removal efficiency of
these catalysts was decreased in the orders: Fe/Mn-MOFs > Fe/Co-
MOFs z Fe-MOFs > Fe/Ni-MOFs. It is suggested that the enhanced
catalytic activity of Fe/Mn-MOFs was ascribed to the synergetic
effect between Fe and Mn. It was also reported that the Fenton-like
activity of MIL-101(Cr) can be evidently improved by the
incorporation of Fe atoms (Vu et al., 2014).
Similar to iron, copper is also a redox-active metal species that
could exhibit somewhat Fenton-like behaviors to generate hy-
droxyl radicals (Bokare and Choi, 2014). Previous reports suggest
that the interaction between the two metal redox couples of iron
and copper could accelerate the interfacial electron transfer and
thus improve the performance of catalyst for activating H2O2
(Wang et al., 2006, 2018). Development of iron-copper bimetallic
catalyst has become one of the hotspot in Fenton chemistry.
Moreover, several researches have reported the use of Cu-based
MOFs in environmental remediation (Zhang et al., 2013; Phan
et al., 2013). Therefore, given the possibility to improve catalytic
performance of MOFs by introducing a second metal component as
well as the good compatibility of terephthalic acid (linker) with Fe
and Cu (node) (Xie et al., 2017; Rostamnia et al., 2016), a series of
new bimetallic FexCu1-x(BDC) were successfully synthesized and
for the first time employed as Fenton-like catalysts for SMX
degradation in this work. The catalytic performance of the new
bimetallic catalysts was evaluated under various reaction parame-
ters (e.g. solution pH, H2O2 concentration and catalyst dosage). The
physicochemical properties of these catalysts were characterized
and linked to their catalytic behaviors in SMX degradation. Addi-
tionally, the reusability of catalysts and possible reaction mecha-
nism were also investigated.
2. Materials and methods
2.1. Chemicals
The chemicals used in this study were iron(III) chloride hexa-
hydrate (FeCl3$6H2O, Aladdin Chemistry), copper nitrate trihydrate
(Cu(NO3)2$3H2O, Aladdin Chemistry), terephthalic acid (H2BDC,
Ourchem Chemical Reagent), N,N-dimethylformamide (DMF, Bei-
jing Chemical Reagent), anhydrous ethanol (C2H5OH, Beijing
Chemical Reagent), sulfamethoxazole (SMX, Alfa Aesar), hydrogen
peroxide (H2O2, Beijing Chemical Reagent), sulfuric acid (H2SO4,
Beijing Chemical Reagent), sodium hydroxide (NaOH, Beijing
Chemical Reagent), n-butanol (Beijing Chemical Reagent) and po-
tassium iodide (KI, Beijing Chemical Reagent). All chemicals were
analytical grade and used without further purification.
2.2. Preparation of catalysts
Iron and copper bimetallic MOF catalysts were prepared by a
simple solvothermal method. In a typical synthesis, 30 mL of DMF
containing required amounts of FeCl3$6H2O and Cu(NO3)2$3H2O
and another 30 mL of DMF containing 5 mmol H2BDC (0.830 g)
were poured into a 100 mL beaker under magnetic stirring at room
temperature for 30 min. After thoroughly mixing, the clear pre-
cursor solution was transferred into a 100 mL Teflon-lined stainless
steel autoclave and reacted at 110  C for 36 h. After cooling natu-
rally, the resulting precipitates were collected and washed with
DMF, ethanol and deionized water, and then dried in a vacuum
oven at 80  C for 12 h. The total molar amount of FeCl3$6H2O and
Cu(NO3)2$3H2O was fixed to be 10 mmol during the synthesis, and
the molar ratio of Fe/Cu in the obtained bimetallic catalysts was
adjustable by varying the ratio of the two metallic precursors. As a
result, a series of bimetallic catalysts was prepared and named as
FexCu1-x(BDC), where x/1x refers to the initial molar ratio of Fe to
Cu. The resultant samples were donated as Fe0.80Cu0.20(BDC),
Fe0.75Cu0.25(BDC), and Fe0.67Cu0.33(BDC), respectively. For compar-
ison, two single-metal samples, Fe(BDC) and Cu(BDC), were also
prepared by adding only FeCl3$6H2O or Cu(NO3)2$3H2O, respec-
tively. The synthetic parameters of all samples were listed in
Table 1.
 J. Tang, J. Wang / Chemosphere 241 (2020) 125002
Table 1
Synthetic parameters of all prepared samples.
Sample n(FeCl3$6H2O) (mmol)
Fe(BDC) 10.0
Fe0.80Cu0.20(BDC) 8.00
Fe0.75Cu0.25(BDC) 7.50
Fe0.67Cu0.33(BDC) 6.67
Cu(BDC) 0.00
2.3. Characterization of catalysts
The crystal structures of the prepared catalysts were identified
by powder X-ray diffraction (XRD) measurements. The XRD pat-
terns were recorded in the 2q range of 3-60 with a scan rate of
0.4 $min1 on a D-8 Advance diffractometer (Bruker, Germany)
equipped with a Cu-Ka radiation (30 kV and 40 mA). The surface
morphologies of the prepared samples were obtained by a SU8000
field emission scanning electron microscope (FESEM; Hitachi,
Japan) operated at 15 kV and 10 mA. The specific surface area and
pore size distribution of all samples were determined by using
Brunauer-Emmett-Teller (BET) and Brunauer-Joyner-Hallenda
(BJH) method, respectively, based on the adsorption data of N2
adsorption-desorption isotherms collected at 77 K on a NOVA 4000
analyzer (Quantachrome, USA). Fourier transform infrared (FTIR)
spectra was recorded on a Nicolet 6700 spectrometer (Thermo
Fisher Scientific, USA) with a resolution of 2 cm1 in a wavenumber
range of 4000-400 cm1 at room temperature by means of the KBr
pressed disk technique. The chemical states of surface elements of
the prepared samples were examined by X-ray photoelectron
spectroscopy (XPS) which was conducted on an ESCALAB 250Xi
spectrometer (Thermo Scientific, USA) equipped with a mono-
chromatic Al-Ka X-ray (hn ¼ 1486.6 eV) source. The amount of
leached iron and copper ions was analyzed by using a ZA3000
atomic absorption spectroscopy (AAS, Hitachi, Japan).
2.4. Catalytic degradation experiments
The catalytic performance of the prepared samples was evalu-
ated by the oxidation of SMX in the presence of H2O2 as the typical
model reaction. Typically, the reaction was conducted in a 100 mL
sealed serum bottle placed in a constant temperature shaking table
(200 rpm, 25  C) and monitored by using an Agilent 1200 series
high-performance liquid chromatography (HPLC; Agilent, USA)
with an Agilent XDB-C18 (5 mm, 4.6 mm  150 mm) column. In each
run, 80 mL of 20 mg L1 SMX aqueous solution was added into the
serum bottle and adjusted to the desired pH value with 0.1 M H2SO4
or NaOH solution. Subsequently, required amounts of catalysts and
H2O2 were added into the solution in sequence to initiate the re-
action. At preset time intervals, 1 mL samples were withdrawn from
the reaction solution, quenched with excess pure n-butanol, and
filtered through a 0.22 mm polytetrafluoroethylene (PTFE) filter for
HPLC analysis. For the quenching experiments, a known concen-
tration of quencher (n-butanol or KI) was added into the reaction
solution before the addition of H2O2. For the recycling measure-
ment, the used catalysts were collected by centrifugation and then
reused without any treatment for the next run under the same
conditions.
3. Results and discussion
3.1. Physicochemical properties of catalysts
The XRD patterns in Fig. 1a displayed the crystal structures of as-
synthesized samples. The Fe(BDC) sample had the characteristic
3
n(Cu(NO3)2$3H2O) (mmol) n(FeCl3$6H2O)/n(Cu(NO3)2$3H2O)
0 e
2.00 4:1
2.50 3:1
3.33 2:1
10.0 0
peaks of MIL-101(Fe), while the main diffraction peaks of Cu(BDC)
were similar to those previously reported (Xie et al., 2017;
Rostamnia et al., 2016). After incorporating Cu species, the three
bimetallic FexCu1-x(BDC) samples displayed the similar XRD pat-
terns as Fe(BDC) except that the main diffraction peaks between 7
and 12 were broaden, which were attributed to the distortion of
MIL-101(Fe) structure caused by copper incorporation. Moreover, a
new peak (2q ¼ 10.2 ) assignable to the characteristic peak of
Cu(BDC) was also detected in the XRD patterns of FexCu1-x(BDC)
samples. The results indicate the successful incorporation of Cu
species into the Fe(BDC) framework.
Through FESEM analysis, the morphological structures of these
prepared samples were discerned. As observed from Fig. 1b and c,
the FESEM image of Fe(BDC) revealed the presence of octahedral
microcrystalline, while that of Cu(BDC) presented a cubic layered
structure. In comparison to the Fe(BDC) and Cu(BDC) samples, the
three FexCu1-x(BDC) samples showed significant changes in mor-
phologies (Fig. 1def). The introduction of Cu to the Fe(BDC)
framework caused the disintegration of the original octahedral
shape to small irregular particles. With the increase of copper ratio
in the FexCu1-x(BDC), the particle-like structure (Fig. 1d) grew in a
two-dimensional direction and formed an irregular flake-like
structure (Fig. 1f).
The nitrogen adsorption-desorption isotherms and pore size
distribution plots of as-prepared samples are plotted in Fig. 2. As
shown in Fig. 2a, the Fe(BDC) samples exhibited a sharp N2 uptake
at low relative pressure (below 0.05), implying higher micropo-
rosity. Besides, all catalyst samples had gradual N2 uptakes in the
middle relative pressure (from 0.2 to 0.9) indicating the presence of
mesopores in the structures. The pore size distribution curve of
Fe(BDC) in Fig. 2b presented a narrow pore size distribution from 1
to 3 nm with a sharp peak of around 1.942 nm, further confirming
the coexistence of micropores and mesopores. Moreover, a shift of
the pore size distribution from micropores to mesopores in FexCu1-
x(BDC) could be observed with increasing the copper ratio in the
bimetallic composites, probably due to the collapse of nanopores
induced by copper incorporation. The measured BET surface area of
Fe(BDC) is 715.8 m2 g1, which decreased to 264.9, 219.4 and
52.6 m2 g1 for Fe0.80Cu0.20(BDC), Fe0.75Cu0.25(BDC), and
Fe0.67Cu0.33(BDC), respectively (Table 2).
The chemical structure change of Fe(BDC), FexCu1-x(BDC) and
Cu(BDC) was studied by FTIR spectra. As shown in Fig. 3, these
samples all displayed similar absorption bands in general. The
broad band centered at 3440 cm1 originated from the OeH
stretching vibration of water molecules adsorbed on the catalyst
surface. The characteristic absorption bands appeared at 1680,
1590, 1391 and 1017 cm1 were identified as the vibration of the
carboxylate groups (Ai et al., 2014; Sun et al., 2017). The sharp band
at 744 was associated with the CeH bending vibration of benzene.
However, close observation at low wavenumber range showed the
difference among these curves. For Fe(BDC), the band at 543 cm1
referred to the stretching vibration of FeeOlinker mode, while for
Cu(BDC), the absorption band assignable to the CueOlinker
stretching vibration mode appeared at 568 cm1 (Bloch et al., 2011;
Li et al., 2018). When comparing the Fe(BDC) with FexCu1-x(BDC)
4 J. Tang, J. Wang / Chemosphere 241 (2020) 125002

Fig. 1. (a) XRD patterns of Fe(BDC), Fe0.80Cu0.20(BDC), Fe0.75Cu0.25(BDC), Fe0.67Cu0.33(BDC) and Cu(BDC), and FESEM images of (b) Fe(BDC), (c) Cu(BDC). (d) Fe0.80Cu0.20(BDC), (e)
Fe0.75Cu0.25(BDC) and (f) Fe0.67Cu0.33(BDC).

Fig. 2. (a) N2 adsorption-desorption isotherms and (b) pore size distribution plots of Fe(BDC), Fe0.80Cu0.20(BDC), Fe0.75Cu0.25(BDC), Fe0.67Cu0.33(BDC) and Cu(BDC).

Table 2
Textural properties of Fe(BDC), Fe0.80Cu0.20(BDC), Fe0.75Cu0.25(BDC), Fe0.67Cu0.33(BDC) and Cu(BDC).

Sample SBET (m2 g1) Total pore volume (cm3 g1) Average pore diameter (nm) Surface atomic content

C (%) O (%) Fe (%) Cu (%)

Fe(BDC) 715.8 0.638 3.568 60.69 31.52 7.79 0.00

Fe0.80Cu0.20(BDC) 264.9 0396 7.089 60.88 31.29 6.21 1.62
Fe0.75Cu0.25(BDC) 219.4 0.429 9.253 59.99 32.12 6.02 1.88
Fe0.66Cu0.37(BDC) 52.6 0.522 4.660 60.27 31.04 6.01 2.68
Cu(BDC) 17.5 0.027 6.906 61.50 29.56 0.00 8.94

curves, the vibration mode at 543 cm1 was slightly shifted to
higher wavenumber, which was attributed to the incorporation of
Cu into the frameworks. The result also confirmed the formation of
bimetallic FexCu1-x(BDC) catalysts.
The chemical states of Fe and Cu on the surface of the as-
synthesized catalysts were investigated by XPS survey. As shown
in Fig. 4a, the high-resolution XPS spectra of Fe 2p of the Fe(BDC)
sample can be mainly deconvoluted into six peaks, in which the
fitted peaks centered at 711.3 and 713.9 eV were assigned to Fe 2p3/
2 of Fe(III) caption, the peaks located at 724.8 and 727.3 eV were
ascribed to Fe 2p1/2 of Fe(III) caption, and the two shake-up satellite
peaks at 717.8 and 731.7 eV were the fingerprint of Fe(III) species,
respectively (Tang and Wang, 2018b; Lv et al., 2015). This result
demonstrated that the iron species in the surface of Fe(BDC) is
predominantly in the Fe(III) oxidation state. After the Cu incorpo-
ration, new peaks at 709.6 and 723.1 eV, assigned to the Fe 2p3/2
and Fe 2p1/2 of Fe(II), respectively, were observed for the three
FexCu1-x(BDC) samples, indicating a chemical interaction between
Fe and Cu existed in the frameworks (Grosvenor et al., 2004).
In the Cu 2p region (Fig. 4b), the Cu 2p3/2 (Cu 2p1/2) can be fitted
with two peaks at 933.2 and 934.8 eV (953.0 and 954.6 eV), which
correspond to the characteristic peaks of Cu(II) species (Hu et al.,
2019; Huang et al., 2019). Besides, two shake-up satellite peaks of
Cu 2p3/2 were observed in the range of 937e947 eV, which further
suggested that the copper species mainly existed in the form of
Cu(II) on the surface of Cu(BDC) and FexCu1-x(BDC) samples (Hu
 J. Tang, J. Wang / Chemosphere 241 (2020) 125002 5

543 cm
-1 no SMX removal was observed when H2O2 alone was present,
revealing that the contribution from the self-oxidation of H2O2 it-
Fe(BDC) self was negligible. Meanwhile, without H2O2, all of the prepared
catalysts also could not induce significant SMX removal (less than

Transmittance (%)
Transmittance (%)

4.5%) after 150 min (inset in Fig. 5a), suggesting their limited
Fe0.80Cu0.20(BDC)
adsorption capacities. As expected, rapid degradation of SMX was
Fe0.75Cu0.25(BDC)
observed in the presence of bimetallic FexCu1-x(BDC) composites
and H2O2, and almost 100% of SMX was removed within 150 min,
Fe0.67Cu0.33(BDC) -1
which indicated that the combination of FexCu1-x(BDC) with H2O2
568 cm
possessed a high degradability for SMX. For comparison, two
Cu(BDC)
monometallic catalysts, Fe(BDC) and Cu(BDC) were employed to
catalyze the degradation of SMX under the same conditions and
4000 3500 3000 2500 2000 1500 1000 500 600 450 showed SMX removal of 95.5% and 8.4% after 150 min, respectively.
Wavenumber (cm )
-1
Wavenumber (cm )
-1 We hypothesized that the enhanced catalytic performance of
bimetallic FexCu1-x(BDC) was mainly ascribed to the synergistic
Fig. 3. FTIR spectra of Fe(BDC), Fe0.80Cu0.20(BDC), Fe0.75Cu0.25(BDC), Fe0.67Cu0.33(BDC) effect between iron and copper species in the catalyst structure
and Cu(BDC).
which facilitated the formation of more
OH radicals for SMX
degradation (Sun et al., 2017, 2019; Lyu et al., 2015). Besides,
compared with the Fe(BDC), the FexCu1-x(BDC) possessed larger
(a) Fe 2p Fe
3+
3+
Fe (b) Cu 2p
pore sizes (Table 2). The enlarged pore structure of FexCu1-x(BDC)
would favor the transport and contact of reactants into interior
Fe(BDC) reactive sites. Furthermore, from the XPS analysis (Fig. 4), the
Fe(BDC)
2+
incorporation of copper could induce the formation of Fe(II) in the
Cu
2+
Fe
Cu
2+
FexCu1-x(BDC) structure, which may also be responsible for their
increased catalytic activity.
Fe0.80Cu0.20(BDC) Fe0.80Cu0.20(BDC) In Fig. 5a, it could also be found that when the molar proportion
of Cu in the FexCu1-x(BDC) increased from 0.2 to 0.25, the SMX
removal efficiency obtained at 120 min was increased from 88.4%
Intensity (a.u.)
Intensity (a.u.)

(Fe0.8Cu0.2(BDC)) to 100% (Fe0.75Cu0.25(BDC)), which could be

Fe0.75Cu0.25(BDC)
Fe0.67Cu0.33(BDC)
Cu(BDC)
Used Fe0.75Cu0.25(BDC)
740 735 730 725 720 715 710 705
Binding energy (eV)
Fig. 4. (a) Fe 2p XPS spectra and (b) Cu 2p XPS spectra of Fe(BDC), Fe0.80Cu0.20(BDC),
Fe0.75Cu0.25(BDC), Fe0.67Cu0.33(BDC), Cu(BDC) and used Fe0.75Cu0.25(BDC).
et al., 2019). Compared with Cu(BDC), the relative intensity of the
peak at 934.8 eV significantly decreased for the three FexCu1-x(BDC)
samples, which might be attributed to the change of the sur-
rounding electron density of the Cu(II) caused by the adjacent Fe
species. Moreover, according to the semi-quantitative analysis
(Table 2), the atomic ratios of Fe to Cu of all the FexCu1-x(BDC)
samples were approximate to the different Fe/Cu ratios in the feed
solution, further confirming the successful preparation of iron-
copper bimetallic composites.
Fe0.75Cu0.25(BDC) attributed to the positive effect caused by the incorporated Cu
species. Based on the XPS results of FexCu1-x(BDC) (Fig. 4a), it could
be found that the relative intensity of Fe(II) characteristic peak
gradually increased with the increased Cu proportion from 0.2 to
Fe0.67Cu0.33(BDC) 0.25, which means that the Fe0.75Cu0.25(BDC) had more surface
Fe(II) amounts than Fe0.8Cu0.2(BDC). The increased Fe(II) amounts
in the Fe0.75Cu0.25(BDC) could facilitate the decomposition of H2O2
to
OH radicals, thus promoting the degradation of SMX. Moreover,
Cu(BDC) in fact, copper has similar redox properties to iron, which can react
easily with H2O2 to generate reactive radicals in a process (Eqs. (1)
and (2)) analogous to the iron catalyzed Fenton reaction (Eqs. (3)
and (4)), but have higher reaction rate constants (Bokare and
Used Fe0.75Cu0.25(BDC) Choi, 2014; Wang et al., 2018; Pham et al., 2013). The more Cu
955 950 945 940 935 930 species existed in the Fe0.75Cu0.25(BDC) would also accelerate the
Binding energy (eV) generation of
OH for the fast degradation of SMX. Contrarily, the
efficiency of SMX removal obtained at 120 min was then decreased
to 85.1% (Fe0.67Cu0.33(BDC)) with the Cu proportion increasing from
0.25 to 0.33, which might be explained by the much low specific
surface area of Fe0.67Cu0.33(BDC) that leaded to limited active sites
for H2O2 activation as well as the inhibiting effect of excess Cuþ by
molecular oxygen in acidic and near-neutral conditions (Eq. (5))
(Bokare and Choi, 2014).
Therefore, Fe0.75Cu0.25(BDC) was selected to investigate the ef-
fect of reaction parameters on SMX degradation. Furthermore,
compared with other reported catalyst systems (Table 3), the
bimetallic Fe0.75Cu0.25(BDC) catalysts also exhibited the highest
catalytic activity in the near-neutral conditions, which indicated
that Fe0.75Cu0.25(BDC) could be a favorable Fenton-like catalyst for
the efficient degradation of SMX.

3.2. Catalytic performance of catalysts Cu2þ þ H2O2 / Cuþ þ HO2
þ Hþ k ¼ 4.6  102 M1 s1 (1)

In a proof of concept that the bimetallic FexCu1-x(BDC) com- Cuþ þ H2O2 / Cu2þ þ
OH þ OH k ¼ 1.0  104 M1 s1 (2)
posites can be applied as an effective Fenton-like catalysts, various
control experiments were conducted by using the model reaction Fe3þ þ H2O2 / Fe2þ þ HO2
þ Hþ k ¼ 0.001e0.01 M1 s1 (3)
of SMX degradation under the assistance of H2O2 (Fig. 5a). Nearly
6 J. Tang, J. Wang / Chemosphere 241 (2020) 125002

Fig. 5. (a) Comparison of the catalytic performances and adsorption capabilities (inset) of samples under different conditions; the effect of (b) initial solution pH, (c) initial H2O2
concentration, and (d) catalyst dosage on the SMX degradation in Fe0.75Cu0.25(BDC) catalyzed Fenton-like system. Unless otherwise stated, the reaction conditions are: natural pH
(ca. 5.6 ± 0.1), initial SMX 20 mg L1, H2O2 concentration 6 mM, catalyst dosage 0.5 g L1, and temperature 25  C.

Table 3
Comparison of the catalytic performance of the Fe0.75Cu0.25(BDC) catalysts with other Fenton-like catalysts reported in literature.

Target pollutants Catalysts Reaction conditions Catalytic performance References

1 1 
Sulfamethoxazole Fe0.75Cu0.25(BDC) pH: 5.6; Catalyst: 0.5 g L ; [H2O2]: 6.0 mM; [SMX]0: 20 mg L ;T: 25 C 100% removal in This work
(SMX) 120 min
1 1 
Sulfamethoxazole Fe0.75Cu0.25(BDC) pH: 7.2; Catalyst: 0.5 g L ; [H2O2]: 6.0 mM; [SMX]0: 20 mg L ;T: 25 C 100% removal in This work
(SMX) 150 min
Sulfamethoxazole Fe3O4 pH: 5.0; Catalyst: 1.0 g L1; [H2O2]: 25 mg L1; [SMX]0: 5 mg L1;T: 25  C 100% removal in Munoz et al. (2018)
(SMX) 210 min
Sulfamethoxazole CX/CoFe pH: 3.0; Catalyst: 80 mg L1; [H2O2]: 500 mg L1; [SMX]0: 500 mg L1;T: 25  C 96.8% removal in Ribeiro et al. (2016)
(SMX) 360 min
Sulfamethazine (SMT) CUS-MIL-100(Fe) pH: 4.0; Catalyst: 0.5 g L1; [H2O2]: 6.0 mM; [SMT]0: 20 mg L1;T: 30  C 98.4% removal in Ai et al. (2014)
180 min
1 1
Sulfamethazine (SMT) Fe3O4/Mn3O4 pH: 3.0; Catalyst: 0.5 g L ; [H2O2]: 6.0 mM; [SMT]0: 20 mg L ;T: 35  C 95% removal in 240 minBokare and Choi
(2014)
Sulfanilamide (SA) Fe/Cu/Al-pillared pH: 3.5; Catalyst: 2.0 g L1; [H2O2]: 5.23 mmol L1; [SMX]0: 0.29 mmol L1;T: 98% removal in 240 min Wan and Wang
clays 50  C (2017)

Fe2þ þ H2O2 / Fe3þ þ
OH þ OH k ¼ 63-76 M1 s1
4Cuþ þ 4Hþ þ O2 / 4Cu2þ þ 2H2O
Fig. 5b displayed the effect of solution pH on the SMX degra-
dation in Fe0.75Cu0.25(BDC)/H2O2 system. It was apparent that the
removal efficiency of SMX in 150 min decreased slightly from 100
to 82.6% with increasing the initial pH from 4.0 to 8.6, which could
be ascribed to the lower oxidation potential of
OH (þ2.8 V at pH
0; þ2.0 V at pH 14) and the auto-decomposition of H2O2 at higher
pH values (Eq. (6)) (Xu and Wang, 2012a; Gao et al., 2017). In
addition, the Fe0.75Cu0.25(BDC)/H2O2 system still exhibited good
catalytic activity at slightly basic pH, which demonstrated that the
Fe0.75Cu0.25(BDC) catalyst had good pH adaptability and could be
(4) able to work in a wide pH range.
Fig. 5c showed the effect of initial H2O2 concentration on SMX
(5) degradation. When initial H2O2 concentration was 1.5 mM, the
removal efficiency of SMX was 81.1% within 120 min. As the con-
centration increased to 6.0 mM, complete removal of SMX was
achieved at the same time. The enhanced removal of SMX was
probably due to that more H2O2 molecular could be activated by the
Fe0.75Cu0.25(BDC) catalyst to generate more
OH radicals to degrade
SMX. However, further increase of H2O2 concentration to 9.0 mM
resulted in a slight decrease of SMX removal (89.8% at 120 min),
attributing to the scavenging effect of excessive H2O2 to
OH radi-
cals (Eqs. (7) and (8)) (Wang and Xu, 2012). The effect of variable
catalyst dosage on SMX removal was also investigated in Fig. 5d.
The removal efficiency of SMX in 120 min was dramatically
 J. Tang, J. Wang / Chemosphere 241 (2020) 125002
increased from 43.8% to 100% with the dosage of Fe0.75Cu0.25(BDC)
increased from 0.1 g L1 to 0.7 g L1. This is reasonable since higher
catalyst dosage could supply more catalytically active sites for H2O2
activation, generating more
OH radicals to promote SMX
degradation.
2H2O2 / 2H2O þ O2
H2O2 þ
OH / HO2
þ H2O
HO2 þ OH / H2O þ O2



The reusability of Fe0.75Cu0.25(BDC), which is an important issue
regarding its potential application, was evaluated by consecutive
cycling tests of SMX removal under the same reaction conditions.
As shown in Fig. 6, the removal efficiency of SMX within 120 min
remained almost constant after three successive cycles, elucidating
the good reusability of Fe0.75Cu0.25(BDC) for pollutants removing. In
addition, the concentration of leached Fe and Cu ions after 120 min
reaction were 7.23 mg L1 and 0.11 mg L1, respectively, equivalent
to about 7.1% of total iron and 0.3% of total copper of 0.5 g L1
catalyst used.
3.3. Possible catalytic mechanism
It is generally accepted that highly reactive
OH radical origi-
nated from the activation of H2O2 is the predominant oxidative
species for pollutant degradation in the Fenton/Fenton-like reac-
tion system. Considering the leached metal ions may contribute to
the SMX degradation through the homogeneous Fenton reaction,
free radical quenching studies were performed by adding n-butanol
and KI to distinguish the dominant Fenton reaction (homogeneous
or heterogeneous) that contributed to SMX degradation. Previous
researches have reported that n-butanol readily reacts with both
the surface-bound
OH radicals (on catalyst surface) and free
OH
radicals (in the bulk solution) at high rates, whereas KI is mainly
reactive toward surface-bound
OH radicals (Xu and Wang, 2012b;
Martin et al., 1995). As displayed in Fig. 7, the removal efficiencies of
SMX were strongly inhibited with addition of both n-butanol (8.2%)
and KI (13.4%) compared to that without quenchers (100%), which
manifested that the rapid degradation of SMX was more relevant to
1.0
First cycle Second cycle Third cycle
0.8
0.6
C/C0
0.4
0.2
0.0
0 40 80 120 0 40 80 120 0 40 80
Time (min)
Fig. 6. Recyclability of Fe0.75Cu0.25(BDC) in Fenton-like degradation of SMX. Experi-
ment conditions: natural pH (ca. 5.6 ± 0.1), initial SMX 20 mg L1, H2O2 concentration
6 mM, catalyst dosage 0.5 g L1, and temperature 25  C.
7
1.0
0.8
(6) 0.6
C/C0
(7)
0.4
(8)
0.2 None
n-Butonal
KI
0.0
0 30 60 90 120 150
Time (min)
Fig. 7. Effects of radical scavengers for SMX degradation in the Fe0.75Cu0.25(BDC)/H2O2
system. Experiment conditions: natural pH (ca. 5.6 ± 0.1), initial SMX 20 mg L1, H2O2
concentration 6 mM, catalyst dosage 0.5 g L1, n-butanol 300 mM, KI 10 mM, and
temperature 25  C.
the surface-bound
OH radicals rather than free
OH radicals and
heterogeneous Fenton reaction played the dominant role.
On the basis of the observation above, the catalytic reaction
mainly occurred on the surface of FexCu1-x(BDC). In addition, in
order to elucidate the possible electron transfer during the catalytic
process, the valence-state change of Fe and Cu on the surface of
Fe0.75Cu0.25(BDC) before and after reaction was also examined by
XPS analysis (Fig. 4). The XPS spectra of Fe 2p of used
Fe0.75Cu0.25(BDC) shows that the main peaks assignable to the
characteristics of Fe(III) were keep the same, whereas the relative
intensity of the characteristic signal of Fe(II) was significantly
decreased as compared with those of fresh Fe0.75Cu0.25(BDC). This
variation further demonstrated that the catalytic reaction occurred
on the surface of Fe0.75Cu0.25(BDC) and the Fe(II) sites possibly
provided the electrons for H2O2 activation. To maintain the balance
of charge/electron on the catalyst surface, the formed Fe(III) site
would accept the electrons and turn back to Fe(II), which implied
the involvement of Fe (II-III-II) redox process during the catalytic
reaction. By comparing the high-resolution Cu 2p spectra of
Fe0.75Cu0.25(BDC) before and after reaction, the relative intensity of
the peak at 934.8 eV was increased after reaction, suggesting the
change of the surrounding electron density of the Cu(II) during the
catalytic reaction. This phenomenon implied that the Cu(II) species
might also participate in the catalytic process. Accordingly, a
possible mechanism for SMX degradation by the FexCu1-x(BDC)/
H2O2 system was proposed in Fig. 8.
It may involve four parts: (1) the Fe(II) active sites on the surface
of FexCu1-x(BDC) lost electron to activate H2O2 to produce
OH and
Fe(III). Meanwhile, the surface Fe(III) active sites captured electron
from H2O2 to form HO2
and regenerate Fe(II). (2) the surface Cu(II)
active sites could also catalyze H2O2 decomposition to generate
HO2
and Cu(I), which subsequently produced
OH and revert to the
initial forms. (3) considering the standard reduction potentials of
Cu (E0(Cu2þ/Cuþ) ¼ 0.17 V) and Fe (E0(Fe3þ/Fe2þ) ¼ 0.77 V), part
Cu(I) generated on the catalyst surface could promote the regen-
eration of Fe(II) through a thermodynamically favorable electron
120
transfer process (Eq. (9)), facilitating the formation of
OH from the
reaction of H2O2 with surfaced Fe(II). (4) the adjacent SMX mole-
cules were attacked by surface-bound
OH radicals and degraded to
small molecular substances.
8 J. Tang, J. Wang / Chemosphere 241 (2020) 125002
HO2• H2O2
Cu(I) (i) Cu(II)
H2O2 HO2•
•OH
H2O2
HO2•
Cu(I)
Fe(III) (ii) Fe(II)
Cu(II)
•OH H 2O 2 (iii)
Fe(II)
(iv)
Fe(III)
(iv)
Sulfamethoxazole •OH H 2O 2
Fig. 8. Possible reaction mechanism of SMX degradation in the Fe0.75Cu0.25(BDC)/H2O2
system.
Cuþ þ Fe3þ / Cu2þ þ Fe2þ △E0 ¼ 0.60 V (9)
4. Conclusion
In summary, a series of novel bimetallic FexCu1-x(BDC) were
prepared via a facile solvothermal method and applied as efficient
heterogeneous catalysts for H2O2 activation to degrade SMX. The
FexCu1-x(BDC)/H2O2 system can work efficiently in neutral or
slightly basic pH conditions. The Fe0.75Cu0.25(BDC) exhibited the
highest catalytic performance with complete removal of SMX in
120 min at pH of 5.6. Experimental observations revealed that the
Fe and Cu species on the surface of FexCu1-x(BDC) not only served as
the active sites for H2O2 activation but also presented synergistic
effects on the generation of
OH radicals that is responsible for SMX
degradation. Furthermore, the negligible loss of SMX removal after
three successive cycles indicated the Fe0.75Cu0.25(BDC) catalyst also
had satisfactory reusability. The findings of this study could provide
useful information to develop advanced MOF-based catalysts for
efficient environmental remediation.
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (51978368) and the Program for Changjiang
Scholars and Innovative Research Team in University (IRT-13026).
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