Journal of Water Process Engineering 33 (2020) 101004

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Journal of Water Process Engineering

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MOF [NH2-MIL-101(Fe)] as a powerful and reusable Fenton-like catalyst T

a,b c d a,
Ahmed Aboueloyoun Taha , Libing Huang , Seeram Ramakrishna , Yong Liu *
a
College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, China
b
Soils, Water and Environment Research Institute, ARC, Giza, 12112, Egypt
c
College of Mechanical and Electrical Engineering, Beijing University of Chemical Technology, Beijing, 100029, China
d
Nanoscience and Nanotechnology Initiative, National University of Singapore, Singapore, 1157, Singapore

A R T I C LE I N FO A B S T R A C T

Keywords: Several metal-organic frameworks (MOFs) were evaluated as a Fenton-like catalyst for water treatment in a
Metal-organic frameworks (MOFs) screening process. Herein, we report hydrothermally prepared NH2-MIL-101(Fe) can offer a dual function of
Adsorption good adsorption and excellent Fenton-like catalytic performances for organic pollutant removal. To understand
Fenton-like catalyst the mode of action of both –NH2 and Fe, MIL-101(Fe) and NH2-MIL-101(Al) were comparatively investigated. It
Organic dyes
was found that the adsorption followed Langmuir isotherm and correlated well with pseudo-second-order kinetic
Real wastewater
Degradation
model. Pseudo-first-order model was used to describe the catalysis performance. A complete decoloration of a
relatively high concentration of RhB (0.25 mmol/L) by was achieved within only 4–10 min at a wide range of
pH, and attained a high degradation rate constant (K) of 0.66 min−1 and 1.09 min−1at pH 7.2 and pH 11,
respectively. These results were comparatively high, and tackling the problem of strict pH value (3.1) of Fenton
reaction, and even of most of the Fenton-like catalysts, which are active only in acidic or near natural pH.
Moreover, that outstanding performance was maintained after five successive reuse cycles. More importantly,
the material potential use in the real application was validated by RhB mineralization (97.7 % TOC removal in
20 min), and by treating real textile wastewater (83 % TOC removal in 30 min). That excellent performance is a
result of the synergetic effect between the high adsorption, fast electron transfer, and sustainable Fe ions release.
The possible degradation mechanism was proposed.

1. Introduction
Water pollution is paramount global environmental problems.
Fenton reaction (consists of Fe2+/H2O2) is widely used in wastewater
treatment plants as a powerful producer of hydroxyl radicals (OH,
E0 = 2.80 V/NHE), which can cause nonselective oxidation of organic
pollutants. However, it’s limited operating pH (pH 2.8–3.5), production
of iron-containing sludge and loss of catalyst are crucial drawbacks.
Heterogeneous Fenton reaction or Fenton-like technology (consist of
solid catalyst and H2O2) is an attractive alternative for wastewaters,
gases and soils remediation that can overcome the above-mentioned
shortcomings [1]. Although there are some metals have higher redox
couple (e. g. [(E0(Al3+/Al0) = −1.66 V)], [E0(Co3+/Co2+) =
+1.92 V]) than Fe2+ [E0(Fe3+/Fe2+) = +0.776 V], iron possesses key
advantages over them including being highly abundant, lower in cost,
reduced toxicity, and highly reactive, hence Fe-based Fenton-like cat-
alysts (impregnated or supported in natural or synthetic matrixes) have
gained great attention [2]. However, most of the iron-impregnated
catalysts, mainly holding Fe3+, need UV irradiation to increase the
frequency of the Fe2+ reductive generation. Another drawback for most
reported Fenton-like catalysts is that they are active only in acidic or
near-neutral pH [1,3]. Therefore, finding catalysts with high activity
and stability at a wide range of pH which can have potential practical
application in wastewater treatment still a challenge [1].
Iron can be coordinated with organic linkers forming Fe-based
metal-organic frameworks (MOFs). Generally, MOFs are known for
their high surface areas which highlighted them with superior adsorp-
tion capacity and thus have attracted considerable interest in many
application including Fenton-like reaction [1,4]. However, the weak
performances of pure MOF in activating H2O2 require UV or visible-
light assistance [5–7]. To improve MOF’s performance, Lv et al. in-
creased the Fe concentration in MIL-100(Fe) to increase the active sites
[4]. They compared the efficiency of MIL-100(Fe), Fe3O4 and FeII@MIL-
100(Fe) in MB removal by the combination of adsorption and Fenton
reaction at a wide pH range of 3.0–8.0. FeII@MIL-100(Fe) displayed the
best catalytic performance in the Fenton reaction due to the synergistic
effect between Fe(II) and Fe(III), and 91 % of the MB dye was com-
pletely mineralized after about 25 h, while the MIL-100(Fe) was

⁎
Corresponding author.
E-mail address: yongliu@mail.buct.edu.cn (Y. Liu).

https://doi.org/10.1016/j.jwpe.2019.101004
Received 30 August 2019; Received in revised form 8 October 2019; Accepted 12 October 2019
Available online 07 November 2019
2214-7144/ © 2019 Elsevier Ltd. All rights reserved.
A.A. Taha, et al.
superior in the adsorption and total degradation process due to the
higher surface area. The surface H2O2 activation and efficient electron
transfer from active metal to absorbed H2O2 are the key factors that
determine the performance of heterogeneous Fenton catalyst [8].
Amination of MIL-100(Fe) can be achieved by merely using ami-
nated linkers which were found to be able to absorb the light at broader
wavelength range and can enhance the electron transfer. Wang et al.
found that aminated Fe-containing MOFs (NH2-MIL-101(Fe), NH2-MIL-
53(Fe) and NH2-MIL-88B(Fe)) exhibited enhanced CO2 photo-reduction
performance comparing with the non-functionalized because of the
dual excitation pathways of NH2 functionality followed by an electron
transfer to the Fe centres as well as the direct excitation of Fe–O clusters
(Fe3+ to Fe2+) [9]. Most recently, He et al., reported the microwave
synthesized NH2-MIL-88B(Fe) as an active and recyclable Fenton-like
catalyst at a wide working pH range (pH 3.0–11.0) for MB removal
[10]. However, it took 45 min to completely remove the dye under the
optimal conditions. On the other hand, lots of attempts to improve the
catalytic performance of MOFs by depositing or doping with other
metals [1,11,12], which may require multiple preparation steps making
their reproduction difficult, and the possibility for the dopant detach-
ment that can lower their stability. Another important fact is that most
reported Fenton-like MOFs, except very few cases, have used synthetic
wastewater, which momentously differs from the real wastewater [1].
Therefore, finding an efficient MOF Fenton-like catalyst without mod-
ification that is simply prepared with high stability and reusability is
highly desirable.
Herein, we report the use of hydrothermally prepared NH2-MIL-
101(Fe) for the first time as a powerful Fenton-like catalyst. NH2-MIL-
101(Fe) adsorption and degradation performances were studied in
terms of the main variables, reaction kinetics, catalyst stability, de-
gradation mechanism, as well as the role of NH2 and Fe by comparing
the performance with MIL-101(Fe) and NH2-MIL-101(Al). Furthermore,
its application for treating real textile wastewater was examined. The
strong adsorption and H2O2 activation on the catalyst surface and the
fast electron transfer from the Fe3O cluster to the substrate as well as
the role of leached Fe ions in activating the rest of H2O2 in the solution
were the main reasons for the superior catalytic performance over other
tested MOFs.
2. Materials and methods
FeCl3·6H2O, 2-aminoterephthalic acid (H2ATA), 5,5-dimethyl-L-
pyrroline-N-oxide (DMPO), p-benzoquinone (BQ), isopropanol alcohol
(IPA) were purchased from TCI (Shanghai) Development Co. Ltd.
Methanol (MeOH), tert-butyl alcohol (TBA), N,N-dimethylformamide
(DMF), AlCl3·6H2O, terephthalic acid (99 %), Rhodamin B (RhB), and
H2O2 (30 %, w/w) and other reagents were obtained from Sinopharm
Chemical Reagent Co. Ltd. All chemicals were of analytical grade purity
and used directly without further depuration.
2.1. Preparation of MOFs
The main aim of the present work is to investigate the NH2-MIL-
101(Fe) as a Fenton-like catalyst. However, to understand the role of
NH2 and Fe, MIL-101(Fe) and NH2- MIL-101(Al) were synthesized and
used for comparative studies.
NH2-MIL-101(Fe) can be synthesized in grams by the simple hy-
drothermal method [13]. Firstly, 0.675 g (2.497 mmol) of FeCl3·6H2O
was dissolved in 7.5 mL of DMF to obtain solution A. Secondly, 0.225 g
(1.242 mmol) of 2-aminoterephthalic acid was dissolved in 7.5 mL of
DMF to obtain solution B. Then solutions A and B were mixed together
under vigorous stirring for 1 h in room temperature. After complete
dissolving of the solution mixture, it was sealed in a stainless Teflon-
lined autoclave for 24 h at 110 °C. The resultant product was collected
and filtered with DMF and methanol for several times and dried in an
oven at 60 °C for 12 h to obtain NH2-MIL-101(Fe).
2
Journal of Water Process Engineering 33 (2020) 101004
MIL-101(Fe) was synthesized using the same procedure used for
NH2-MIL-101(Fe) using terephthalic acid as a ligand instead of 2-ami-
noterephthalic acid.
NH2-MIL-101(Al) was prepared following a reported method [14].
First 0.51 g of AlCl3·6H2O and 0.56 g of 2-aminoterephthalic acid were
added in 30 mL of DMF and stirred for 30 min. After complete dis-
solution of the above reaction mixture, it was sealed in a Teflon-lined
autoclave at 130 °C for 72 h. Next, the autoclave was allowed to natu-
rally cool to room temperature. Finally, the resulting yellow powder
was filtered and washed with DMF several times, activated with me-
thanol and dried at 200 °C for 12 h.
2.2. Adsorption performance test
RhB was chosen as an organic pollutant model because it’s water-
soluble, chemically stable, carcinogenic, non-biodegradable, and it’s
discharged with large amounts in industrial wastewater. A stock solu-
tion of RhB dye (0.01 mol/L) was prepared and diluted to the required
initial concentrations (0.1-0.5 mmol/L). The batch experiments were
carried out in 100 mL beaker containing 50 mL of RhB dye solution. The
effects of the contact time, initial dye concentration, pH and sorbent
doses on the adsorption capacity of NH2-MIL-101(Fe) were investigated
at room temperature (25 °C ± 1). The pH was adjusted with NaOH
(0.1 M) or H2SO4 (0.1 M). At a predesigned timing, samples were
withdrawn and filtered through 0.45 μL membrane filters to remove
MOF’s particles. Then the absorbance spectra of RhB were collected at
400–650 nm using UV–vis spectrophotometer (Shimadzu, Japan), and
the RhB concentrations were calculated based on a standard curve
previously prepared at maximum adsorption of 553 nm. RhB adsorbed
at equilibrium was calculated using the following Eq. (1):
C0 − Ce
qe = ⎛ ⎞V
⎝ m ⎠ (1)
where C0 and Ce are initial and equilibrium concentrations of RhB,
respectively, m is the mass of adsorbent and V is the solution volume.
The adsorption data were described using the Langmuir model fol-
lowing this mathematical form of Eq. (2):
qm KL Ce
qe =
1 + KL Ce (2)
where qm and KL are Langmuir constants related to maximum adsorp-
tion capacity and energy of adsorption, respectively. By plotting Ce/qe
against Ce a straight line can be obtained, the values of qm and b could
be calculated from slopes and intercepts.
In terms of kinetic modelling, pseudo-first-order and pseudo-second-
order equations were used to fit the experimental data, and expressed as
Eq. (3) and Eq. (4), respectively.
Loge (qe − qt ) = Loge qe − k1 t (3)
where qt and qe are the amounts of RhB adsorbed at time t and at
equilibrium, respectively. k1, qe (correlation coefficient) values can be
obtained from plotting log (qe - qt) versus t.
t 1 t
= +
qt Kp qe2 qe (4)
By plotting t/qt against t a straight line can be obtained, and the values
of qe and k2 can be calculated from slopes and intercepts.
2.3. Fenton-like activity test
RhB (0.25 mmol/L) was selected as a target pollutant to evaluate the
catalytic activity of NH2-MIL-101(Fe). The degradation experiments
were carried out in a batch mode using three-necked flasks (100 mL) at
room temperature (25 °C ± 1). The pH was adjusted with NaOH (0.1 M)
or H2SO4 (0.1 M). Mimicking the practical application and combining
the advantage of the adsorption and catalytic effectiveness, NH2-MIL-
A.A. Taha, et al.
Fig. 1. The adsorption capacity of NH2-MIL-101(Fe) at (A) different pH, (B) with different concentration, (C) with different NH2-MIL-101(Fe) doses, and (C) the
adsorption capacity of different types of MOFs [50 mL RhB, 0.25 mmol/L, 0.05 g sorbent].
101(Fe) (0.05 g) was dispersed in RhB solution (0.25 mmol/L, 50 mL)
without pH adjustment (pH = 7.22), and the degradation reaction was
initiated by adding H2O2 (0.5 mL) under magnetic stirring. At pre-
defined time intervals, samples were withdrawn and filtered through
0.45 μL membrane filters to remove suspended MOFs. Meanwhile,
10 mmol tert-butyl was immediately added to quench the reaction, and
then the absorbance spectra were collected at 400–650 nm using
UV–vis spectrophotometer, and the RhB concentrations were calculated
according to the standard curve previously prepared at maximum ad-
sorption of 553 nm. To test the catalyst stability and recyclability, NH2-
MIL-101(Fe) were collected and reused directly for several circles fol-
lowing the previous process. For comparison studies, the catalytic
performances of non-aminated Fe-containing MOF (MIL-101(Fe)) and
aminated Al-containing MOF (NH2- MIL-101(Al)) were also evaluated
using the same procedure. The control experiments included using
H2O2 as an oxidation agent in the absence of NH2-MIL-101(Fe). The
data were fitted with the pseudo-first-order kinetic model, which is
described by Eq. (5).
ln(C0/Ct) = kt (5)
Where C0 and Ct (mole) stands for the concentration at initial and time
t, and k (min−1) is the rate constant of this reaction. By plotting time
against ln(C0/Ct) against time, slopes of the obtained straight line re-
present K values.
2.4. Regeneration experiment
To assess the reusability of the NH2-MIL-101(Fe), the degradation
experiment were carried out using 0.05 g catalyst with 0.25 mmol/L
RhB, 50 mL, 0.05 mL without pH adjustment (pH = 7.22). After 5 min
the solution was filtered and MOF particles were collected and used
directly with fresh RhB solution and H2O2. This process was repeated
for five times.
3
Journal of Water Process Engineering 33 (2020) 101004
2.5. Organic pollutants mentoring
RhB (50 mL, 0.25 mmol/L, 0.05 g catalyst, 0.5 mL H2O2) miner-
alization and real wastewater treatment (50 mL of wastewater, 0.1 g
catalyst, 0.5 mL H2O2) was monitored by measuring the total organic
carbon (TOC) in the samples at different times using Shimadzu TOC-
5000 analyzer. 0.1 M KH2PO4, 0.1 M KI, and 0.05 M NaOH were added
to remove the H2O2 residual after collecting and filtering the samples.
2.6. Wastewater specifications
The wastewater sample was provided by textile manufacturing
Zhonghe Cashmere (Wuxi) Co., Ltd. is located at Meicun Hi-tech
Industrial Development Zone, Wuxi City, Jiangsu Province, China. The
wastewater was stored in a dark place at a temperature of 4 °C to pre-
vent degradation. As presented in Table 1S (supporting information),
the wastewater contains a high amount of organic matter with a low
BOD/COD ratio of 0.16, which illustrating being non-biodegradable.
TOC removal (%) was calculated according to the following equation:
[TOC0 − TOCe ]
TOC removal (%) = × 100
TOC0 (6)
2.7. Materials characterizations
The scanning electron microscopy (SEM XL30, Philips, Nether-
lands) was used to characterize the morphology. X-ray diffraction
(XRD) measurement was carried out using an X-ray diffractometer (D/
MAX-rB, Rigaku, Japan) at a continuous scanning with the step-size of
0.02° over a 2θ range 5-90°. X-ray photoelectron spectroscopy (XPS)
was performed on an RBD upgraded PHI-5000C ESCA system (Perkin
Elmer) with Mg Ka radiation (hn = 1253.6 eV). Surface areas were
calculated by the Brunauer–Emmett–Teller (BET) method based on the
data collected at 77 K on a Micrometrics ASAP 2020. The concentra-
tions of Fe ions were measured, after sample acidification with 0.1 M
A.A. Taha, et al.
HNO3 (2 %) to ensure that all Fe ions are dissolved, by an Inductively
Coupled Plasma Optical Emission Spectrometer (ICP-OES), (Optima
2100 DV, Perkin Elmer, USA). Elemental analysis was performed using
energy-dispersed X-ray spectroscopy (EDX). Fe2+ was analyzed using
the 1,10-phenanthroline method at 510 nm on a UV–vis spectro-
photometer, as described previously [15]. For electron spin resonance
(ESR) assay, 100 μL samples were collected from the RhB degradation
system with p-benzoquinone (BQ), and with isopropanol alcohol (IPA),
and immediately mixed with 20 μL of 0.2 mol/L DMPO to form
DMPO-•OH adduct, and the ESR spectra were obtained on an electron
paramagnetic resonance spectrometer (EMXnano, Bruker, Germany).
3. Results and discussion
The XRD patterns and FT-IR spectra of the synthesized MOFs display
that their pure phases have been obtained (Figs. S1 and S2) [16,17].
Fig. 1A shows the adsorption of RhB (50 mL, 0.25 mmol/L, 0.05 g
sorbent) from aqueous solutions using NH2-MIL-101(Fe) at different pH
as the function of the equilibrium adsorption capacity (qe) against the
equilibrium concentration (Ce). It indicates that the equilibrium was
reached only after 20 min with color removal of ∼96 % and ∼97.1 %
after 60 min. Moreover, there was no significant effect as a result of
changing the pH of the dye solution from 3.1–11, which indicated that
the adsorption is pH-independent. It’s reported that pH has no influence
on MOF’s adsorption of RhB, and the later has larger molecule size than
the size of MOF’s pores, illustrating the adsorption mainly depends on
the electrostatic nature π-π interactions and not on the porosity
[18,19]. The absorption spectra of RhB under different pH are pre-
sented in Fig. S3.
Fig. 1B shows the result of changing the initial concentration of the
RhB. It reveals that the saturation point increased significantly with
increasing the concentration, which can be attributed to the contact of
RhB molecules with available surface adsorption sites. A similar posi-
tive relation was recorded with increasing the dose of NH2-MIL-101(Fe)
(Fig. 1C), which implies that more the particles dispersed in the solu-
tion the more the surface exposed to interact with the dye in the so-
lution. These results also suggest that there was no significant nano-
particles aggregation took place in both cases. The absorption spectra of
RhB with different concentration are presented in Fig. S4.
Fig. 1D shows the comparison of RhB adsorption by using different
types of MOF, and their corresponding absorption spectra are shown in
Fig. 2(B–D). Interestingly, the removal efficiency of RhB using NH2-
MIL-101(Fe) was remarkably higher, and it was the order of NH2-MIL-
101(Fe) > MIL-101(Fe) > NH2-MIL-101(Al), with maximum removal
percentages of about 97.1 % after 60 min, 88 % after 60 min, and 60 %
after 10 min, respectively. That demonstrates the vital role of both the
amine groups (-NH2) and the Fe in the adsorption process. It’s also
necessary to mention that the BET surface areas of NH2-MIL-101(Fe),
MIL-101 (Fe), and NH2-MIL-101(Al), were found to be 2572.3 m2/g,
2122.6 m2/g, and 2073.8 m2/g, respectively, which are consistent with
previous reports [16,17]. Although the porosity has no direct effect on
adsorption because of the large molecule size of RhB, higher surface
area could provide more interacting sites to absorb the dye molecules.
Langmuir sorption isotherm model is commonly used for the sorp-
tion of a solute from a liquid solution as it assumes that the sorption
takes place at specific homogeneous sites within the sorbent, and once a
dye occupies a site, no further sorption can take place at that site. The
data were analyzed using the linear form of the Langmuir equation and
presented in Fig. 3(A–D). And the correlation coefficients (R2) were
calculated from the slopes and intercepts and listed in Table 1. Gen-
erally, the data were fairly fitting Langmuir isotherm with R2 va-
lues > 0.99 except with MIL-101(Fe) it was 0.982. In the case of dif-
ferent pH, the adsorption capacity (qm) values were slightly higher at
near-neutral pH and in alkaline condition.
With increasing the concentration of RhB from 0.1 mmol/L to
0.5 mmol/L, the adsorption capacity was increased to reach 0.41 mmol/
4
Journal of Water Process Engineering 33 (2020) 101004
g at a concentration of 0.5 mmol/L. On the other hand, increasing the
dose of NH2-MIL-101(Fe) from 0.025 g to 0.75 g has decreased the qm
values 0.39 to 0.15 mmol/g. Finally, when different MOF types were
compared with NH2-MIL-101(Fe), the later has shown the highest qm of
0.21 mmoL/g and remarkably higher KL value followed by MIL-101(Fe)
and then by NH2-MIL-101(Al). Moreover, the pseudo-first-order and
pseudo-second-order kinetic models were applied to fit the experi-
mental data. The kinetic model fitted the pseudo-second-order kinetic
model the best with correlation coefficient R2 > 0.99. Data plotting are
shown in Fig. 3(E–H), and the values of qe, K2 and R2 are listed in
Table 1. The values of the theoretical qe were almost similar to those
obtained experimentally, which suggest that the adsorption process is
chemically controlled.
The catalytic efficiency of NH2-MIL-101(Fe) was investigated in
Fenton-like reaction. Fig. 4A shows the efficiency of NH2-MIL-101(Fe)
at different pH (0.05 g catalyst, 0.5 mL H2O2, 0.25 mmol/L RhB). In-
terestingly, > 70 % of the dye was decolored in the first 30 s at a wide
pH range from 3.1–11, and complete color removal in less than 10 min.
Interestingly, the degradation performance was better at a higher pH,
where more than 99 % of the color removal was achieved after 10 min
at pH 3.1 whereas, at pH 11, it took only 4 min. That indicates NH2-
MIL-101(Fe) favors neutral and alkaline condition, which is not in
agreement with most of the Fenton-like catalysts (the possible reasons
for this phenomenon are discussed later with the discussion of the
isotherm results). These outstanding results increase the potentiality of
using NH2-MIL-101(Fe) in practical application because of the short
reaction time and the excellent overall catalytic performance at a broad
range of pH.
Fig. 4B displays the effect of using different doses of H2O2 (0.125-
0.5 mL), and their corresponding absorption spectra are shown in Fig.
S7. Interestingly, the overall performance with different doses was
moderately high, and it was the highest with 0.5 mL H2O2 reaching 78
% after 30 s and more than 99 % after 5 min. The comparison of NH2-
MIL-101(Fe) with MIL-101(Fe) and NH2-MIL-101(Al) are presented in
Fig. 4C, and their corresponding absorption spectra are shown in
Fig. 5(B–C). It was found that NH2-MIL-101(Fe) has a superior perfor-
mance with > 99 % color removal after 5 min, while MIL-101(Fe) and
NH2-MIL-101(Al) showed only 61.2 % and 76.51 % after the same time,
respectively. The maximum removal of both MIL-101(Fe) and NH2-MIL-
101(Al) was 76.7 % and 72.3 % after 10 and 8 min, respectively. That
further confirms the synergetic effect between the amine groups and Fe
in enhancing the catalytic performance of NH2-MIL-101(Fe).
Fig. 6 represents the pseudo-first-order kinetic model used to ana-
lyse the catalytic data, and Table 2 lists the calculated R2 and K con-
stants. The fittings of the data obtained from using NH2-MIL-101(Fe)
with different H2O2 doses (0.125-0.75 mL) have acceptable R2 values
≥ 0.96, and the rate constant (K) values have increased with increasing
the dose of H2O2 from 0.34 to 0.66 min−1. These values revealed the
ability of NH2-MIL-101(Fe) to activate higher doses of H2O2 and pro-
ducing more hydroxyl/hydroperoxyl/superoxide (OH•/HO2•/O2-•).
On the other hand, when the pH was changed from 3.1–11, the R2
values were still ≥ 0.96 and K values have remarkably increased from
0.46 to 1.09 min−1 by increasing the pH, demonstrating the preference
of the alkaline condition over the acidic. It is noteworthy that Fenton-
like catalysts are more active in acidic and near-neutral pH [1,3],
especially Fe/H2O2 in Fenton/Fenton-like reaction [20]. For instance,
MIL-53(Fe)/H2O2/visible-light system was highly dependent on the
initial solution pH, where the rate constant of carbamazepine de-
gradation at pH 3 was > 6 times faster than that at pH 7 [4]. The NH2-
MIL-101(Fe) adsorption performances were found to be pH-in-
dependent, meaning that there should be another reason explaining this
phenomenon. Thus, the release of Fe ions from NH2-MIL-101(Fe) was
investigated at different pH after 5 min of the reaction time (see Fig.
S8), and it was found that the lowest released Fe concentration was at
pH 11 (0.27 ppm) comparing with 1.45 ppm at pH 7.2. Therefore, the
possible explanation for this phenomenon is that at high pH the
A.A. Taha, et al. Journal of Water Process Engineering 33 (2020) 101004

Fig. 2. Absorption spectrum of (A) original 0.25 mmol/L RhB, (B) absorption spectra of RhB on NH2-MIL-101(Fe), (C) absorption spectra of RhB on MIL-101(Fe), and
(C) absorption of RhB on NH2-MIL-101(Al), [50 mL RhB, 0.25 mmol/L, 0.05 g sorbent].

material maintained its physicochemical properties to the greatest ex-
tent, such as the porous structure and metal-organic coordination,
where more rooms being available for the reaction to take place.
Moreover, more Fe3O clusters being maintained in the frameworks,
which could facilitate the transfer of formed electrons effectively from
the metal center to the substrate. Meanwhile, the lowest release of Fe
ions at pH 11 could be the optimum concentration to activate the H2O2
in the surrounding environment effectively. Furthermore, it was found
that •O−2 is predominant active species generated during NH2-MIL-
101(Fe)/H2O2 reaction. These findings agree with a recent report by Su
et al. reported that the catalytic activity of the Cu@CuO NWs mesh
significantly increased with the rising of pH value, and the rate constant
at pH 11.3 was more than twice that at the pH 2.1 [21]. They found the
enhanced activity at higher pH was associated with the lower release of
cobber ions and the higher formation of •O−2 .
Finally, the results of using different types of MOF (Fig. 6C and
Table 2) show that the highest R2 = 0.96 and the highest
K = 0.66 min−1 was achieved by NH2-MIL-101(Fe), while it shows the
lowest R2 values of 0.92 for MIL-101(Fe) and only 0.88 for NH2-MIL-
101(Al) with as low K values as 0.08 and 0.05 min-1, respectively. That
means the reaction rate constant of NH2-MIL-101(Fe) was 8.3 and 13.2
times faster than MIL-101(Fe) and NH2-MIL-101(Al), respectively. De-
spite the fact that MIL-101(Fe) has also shown higher adsorption ca-
pacity than NH2-MIL-101(Al), that also emphasizes the role of Fe in the
Fenton reaction which is highly active in producing OH•/O2-• than Al,
and that is more obvious when comparing the NH2-MIL-101(Fe) and
NH2-MIL-101(Al) as both contain the amine groups but the perfor-
mance of the first is remarkably higher than the later. The dissolved Fe
and Fe2+ were monitored during the reaction time [50 mL, 0.5 mmol/L
RhB, 0.05 g NH2-MIL-101(Fe), and 0.5 mL H2O2] and the results are
shown in Fig. 7. It can be seen that it started at 0.85 ppm at the first
half-minute, reaching 1.44 ppm after 3 min, and maintained to the end
of the reaction. Additionally, the measured Fe2+ in the same reaction
began with 0.2 ppm and maintained an average of 0.35 ppm throughout

Fig. 3. Langmuir isotherms for the sorption of RhB (A–D), and pseudo-second-order kinetics of RhB adsorption (E–H).

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A.A. Taha, et al. Journal of Water Process Engineering 33 (2020) 101004

Table 1 the self-regeneration ability without any intermediate treatments.

Langmuir isotherm and pseudo-second-order kinetics parameters. Moreover, the sustainable release of Fe ions was examined after each
Langmuir Pseudo-second-order cycle, and as can be seen from Fig. 8B, the release behavior was gen-
erally stable and the released amount fluctuated between 0.75 ppm and
2
pH qm KL (L/mmol) R qe (mmol/g) K2 R2 1.4 ppm. The stability and sustainability of NH2-MIL-101(Fe) were
(mmol/ (mmol/g further confirmed using SEM and EDX elemental analysis, which are
g) min)
shown in Fig. 9. The SEM images of NH2-MIL-101(Fe) nanoparticles
3.1 0.18 535.85 0.993 0.24 2.23 0.999 after the fifth cycle of catalytic reaction has maintained its structure
5.0 0.17 395.44 0.991 0.23 1.56 0.999 with slightly smaller sizes compared with the original sample. From the
7.2 0.21 813.72 0.999 0.24 2.27 1 spectra of the elemental analysis shown in Fig. 9C, we can notice the
9.0 0.20 853.71 0.996 0.25 2.47 1
change in the Fe content before and after the reaction. A detailed ele-
11 0.21 1203.97 0.997 0.25 3.12 1
mental content is given in Table S1 (in supporting information).
RhB (mmol/L) Moreover, the FT-IR spectra were collected for original NH2-MIL-
0.1 0.06 685.06 0.991 0.10 1.54 1 101(Fe), and after adsorption and catalytic reactions (Fig. S9), showing
0.2 0.15 723.76 0.996 0.17 2.14 1
that original function groups are shown on the spectra e. g. –NH2, Fe-O,
0.25 0.21 813.72 0.999 0.24 2.27 1
0.3 0.21 646.39 0.998 0.24 2.10 1
except the band at 1664.53 cm−1 has disappeared after the adsorption
0.4 0.28 223.64 0.992 0.39 1.89 1 and the catalytic reaction, which could be because of the interactions
0.5 0.41 403.75 0.999 0.49 3.80 1 with the dye.
In practical application, COD or/and TOC measurements are used in
Wight (g)
wastewater treatment industry. Therefore, we have monitored the TOC
0.025 0.39 347.49 0.999 0.47 3.30 1
0.05 0.21 813.72 0.999 0.24 2.27 1 removal of RhB (0.25 mmol/L) as well as for real textile wastewater.
0.075 0.15 4686.8 0.999 0.17 10.57 1 From Fig. 10 it can be seen that about 83 % of RhB TOC was removed in
the first 5 min and more than 97 % after 20 min. From the above results,
Type of MOF
we can notice that the major mineralization took place at the first few
NH2-MIL- 0.21 813.7 0.999 0.24 2.27 1
101(Fe)
minutes and after 10 min the mineralization rate was very low with
MIL-101(Fe) 0.123 58.08 0.983 0.22 1.36 0.998 time increasing, which implies that it was mainly attributed to catalytic
NH2-MIL- 0.07 17.82 0.998 0.18 1.48 0.999 oxidation rather than adsorption. [26] In the case of real wastewater,
101(Al) which is much more complicated than the synthetic wastewater (RhB
solution), and contains a relatively high concentration of Cl− that
normally suppress the oxidation of H2O2, it took 30 min to degrade
the reaction. Xu et. al., reported the release behavior of Fe ions from
about 83 % of its TOC, demonstrating that a residual amount of organic
Fe3O4/CeO2 composite, which was much higher leaching and increased
compounds remained in solution even after the complete colour re-
as time increases reaching 12 ppm. [22] This implies NH2-MIL-101(Fe)
moval. However, this result is considered to be feasible for practical
is more sustainable and would stand in the catalytic reaction for a
application. It’s worth noting that using H2O2 without catalyst had no
longer time. On the other hand, The leaching of Fe ions from MIL-
significant effect on the color or TOC within the 30 min, which confirms
101(Fe) was checked after 15 min of the reaction and was found to be
the high stability of the organic contaminants.
much higher than that of NH2-MIL-101(Fe) (23.4 ppm), this may ex-
plain the superior degradation performance of NH2-MIL-101(Fe),
which leaches the iron ions much slower and the released dose ap- 4. Reaction mechanism
peared to be optimum for Fenton reaction especially at higher pH with
the lowest leaching record and the best degradation performances. It’s Firstly, it’s important to note the role of the superior adsorption
also worth stating that the rate constant of RhB degradation at pH 7.2 is capacity of NH2-MIL-101(Fe) comparing with the other tested MOFs
remarkably higher than all reports to date, and some of these results are (MIL-101(Fe) and NH2-MIL-101(Al)), which prominently increased the
summarized in Table 3. contact between the dye molecules and H2O2 on the active sites of the
Catalyst reuse is a crucial characteristic for practical application in catalyst. As the formed electron in the Fe3-O clusters would be effec-
wastewater treatment. Therefore, the NH2-MIL-101(Fe) reuse in tively transferred from the metal centers to the substrate. Toma et al.,
Fenton-like reaction was conducted using non-adjusted pH of RhB so- and other found that formation of electronic delocalization state in the
lution (50 mL, 0.25 mmol/L RhB, 0.05 g catalyst, 0.5 mL H2O2). Fig. 8A μ3-O cluster by the μ3-O atoms could facilitate electron transfer from
shows that the catalyst has maintained its excellent performance the metal ions to the oxidant and subsequently the formation of the
with > 98 % color removal after 4 cycles and decreased slightly to 93 % reactive oxygen species [27,28]. Meanwhile, the leached Fe ions could
after the fifth cycle. That reveals the high stability of the catalyst and activate the rest of H2O2 and decompose the rest of the dye in the so-
lution. As a result, more than 78 % (at pH 7.2) of the color was removed

Fig. 4. Fenton-like catalysis efficiency of NH2-MIL-101(Fe) for RhB degradation (0.05 g catalyst, 0.25 mmol/L RhB, 50 mL) at (A) different pH, (B) different H2O2
concentration, (C) using a different type of MOF.

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A.A. Taha, et al. Journal of Water Process Engineering 33 (2020) 101004

Fig. 5. Absorption spectra of (A) original 0.25 mmol/L RhB, (B) Fenton-like degradation of RhB by NH2-MIL-101(Fe), (C) by MIL-101(Fe), and (C) by NH2-MIL-
101(Al).

Fig. 6. The corresponding pseudo-first-order fittings for different pH (A), different H2O2 doses (B), and (C) different types of MOF; [50 mL, 0.25 mmol/L RhB, and
0.05 g catalyst].

Table 2
Pseudo-first-order isotherm constants.
H2O2 (mL) K (min−1) R2

0.25 0.34 0.98

0.5 0.45 0.99
0.75 0.58 0.98
1.0 0.66 0.96

pH
3.1 0.46 0.99
5.0 0.62 0.96
7.2 0.66 0.96
9.1 0.74 0.97
11 1.09 0.98

Type of MOF
NH2-MIL-101(Fe) 0.66 0.96
MIL-101(Fe) 0.08 0.92
NH2-MIL-101(Al) 0.05 0.88
Fig. 7. Dissolved Fe and the Fe2+ during the reaction time [50 mL, 0.5 mmol/L
RhB, 0.05 g NH2-MIL-101(Fe), and 0.5 mL H2O2].

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A.A. Taha, et al. Journal of Water Process Engineering 33 (2020) 101004

Table 3
The reaction rate constant (K) of RhB over different catalysts.
Catalyst Reaction Condition K (min−1) Reaction time (min) Refs.

−5
Cu@CuO nanowires (NWs) 10 m L, 2.5 × 10 mol/L; pH 7.3; 1 mL H2O2 0.23 16 [21]
α-Ferrous oxalate dehydrate (MOF) 50 ml, 100 mg/L, pH 6, 0.05 mL H2O2 0.21 30 [23]
g-C3N4/LaFeO3 100 mL, 10 mg/L, pH 7.3, 0.5 mL H2O2 + visible-light 0.031 120 [24]
MIL-88A 500 ml, 10 mg/L, pH 3, 200 mg/L Persulfate + UV +50 °C 0.461 120 [25]
NH2-MIL-101(Fe) 50 mL 0.25 mmol/L, pH 7.2, 0.5 mL H2O2 0.66 5 This work
NH2-MIL-101(Fe) 50 mL 0.25 mmol/L, pH 11, 0.5 mL H2O2 1.09 4 This work

Fig. 8. RhB dye removal percentage after 5 cycles (A), and (B) the leached Fe ions after each cycle.

Fig. 9. SEM images of NH2-MIL-101(Fe) before (A) and after 5 cycles (B) of catalytic reaction, and their corresponding EDX elemental analysis (C).

Fig. 10. TOC degradation during Fenton-like reaction of RhB and textile was-
tewater.
in the first 30 s and more than 99 % in only 5 min. To have a profound
understanding of the mechanism, the Fenton-like reaction was run with
the addition of isopropyl alcohol and p-benzoquinone separately as •OH
and •O−2 scavengers, respectively. As demonstrated in Fig. 11A, with the
addition of isopropyl the reaction was slower, and only 45 % of the
color was removed after 30 s and 80 % after the 5 min, while in the case
of p-benzoquinone 69.7 % was removed after 30 s and > 99 % after the
5 min (Fig. 11C and 11D show the corresponding absorption spectra).
That means both •O−2 and •OH were generated during the reaction but
•O−2 was more dominating. Fig. 10B shows the pseudo-first-order iso-
therm; in both cases, the data was highly fitting the isotherm with R2
values > 0.99, and the K values were 0.2 and 0.88 min−1 with iso-
propyl and p-benzoquinone, respectively. These results were further
confirmed by the ESR analysis (Fig. 12), identical spectra were obtained
with the addition of both scavengers, but the beaks with the p-benzo-
quinone have shown higher intensity. These findings reveal that the
degradation reaction started with the replacement of coordinated water
molecules in iron sites with H2O2 and organic dye molecules, im-
mediately Fe (III) in the catalyst is reduced by H2O2 producing HO2•
and the generation of •O−2 (Eq 7). Meanwhile, dissolved iron (Fe2+ and
Fe3+) formed by dissolution of iron oxides in MOF nanoparticles would
diffuse into the bulk solution and started the activation of H2O2 through
the reactions (Eqs 8 and 9) to generate •OH in a slower rate. It was also
noticed that the competitive reaction took place and negatively affected
the oxidation process as the reaction rate constant was 4.4 times higher
when p-benzoquinone was added comparing with isopropyl alcohol
(Eq. 10) [22]. Finally, the organic dye was broken down to CO2 and
H2O. The proposed mechanism is presented in Fig. 13.
Fe3 + (in catalyst) + H2 O2 → HO2• → H+ + •O−2 (7)

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A.A. Taha, et al. Journal of Water Process Engineering 33 (2020) 101004

Fig. 11. Fenton reactions performances over NH2-MIL-101(Fe) with the addition of isopropyl and p-benzoquinone scavengers (A), their pseudo-first-order isotherm
fittings (B), and their corresponding absorption spectra (C&D).

Fig. 12. ESR spectra with the addition of isopropyl and p-benzoquinone as •OH
and •O−2 scavengers, respectively.
Fe3 + (dissolved) + H2 O2 ↔ Fe2 + + OH•+ O2 +H+ (8)
Fe3 + + H2 O2 ↔ Fe2 + + HO2•+ O2 +H+ (9)
OH•+•O−2 (•HO2) → O2 + H2 O(OH−) (10)
5. Conclusion
NH2-MIL-101(Fe) which was simply synthesized by the scalable
hydrothermal method has been systematically studied for adsorption
and Fenton-like reactions. Both -NH2 and Fe3-O clusters have played a
significant role in the adsorption and catalysis reactions which resulted
in remarkably higher performances in RhB removal from the aqueous
solution comparing with MIL-101(Fe) and NH2-MIL-101(Al). The high
degradation rate was maintained in a wide range of pH (3.1–11), and it
Fig. 13. Proposed catalytic mechanism of NH2-MIL-101(Fe).
was even higher at higher pH values. Moreover, NH2-MIL-101(Fe) has
exhibited high stability and excellent reusability with the sustainable
release of Fe ions, which further contributed to the degradation of or-
ganic molecules. More importantly, NH2-MIL-101(Fe) was validated for
TOC removal from the synthetic RhB dye solution as well as for the
treatment of real textile wastewater without any pH adjustment and has
shown extraordinary performances, which suggest its high potentiality
to be used in practical application. It’s also worth noting that by con-
trolling the release of Fe ions at a broad range of pH would further
enhance the performance and stability, which requires more in-
vestigations in future work.

9
A.A. Taha, et al.
Declaration of Competing Interest
The authors declare no competing interests.
Acknowledgments
Financial support from the National Natural Science Foundation of
China (21374008) and Project of Preparation and Application of
Polymer Nano Composite Fiber from Beijing Municipal Science &
Technology Commission are gratefully acknowledged. The authors
thank Prof.Yuhong Ma and Prof. Li from Collage of Material Science
and Engineering for facilitating analyzing the wastewater at their la-
boratories.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jwpe.2019.101004.
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