Science of the Total Environment 795 (2021) 148883

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Science of the Total Environment

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

Photothermal-boosted effect of binary Cu\\Fe bimetallic magnetic MOF

heterojunction for high-performance photo-Fenton degradation of
organic pollutants
Shuo Shi, Ximei Han, Jie Liu, Xi Lan, Jianxing Feng, Yuchen Li, Wentao Zhang, Jianlong Wang ⁎
College of Food Science and Engineering, Northwest A&F University, Yangling 712100, Shaanxi, 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

• Bimetallic Cu\\Fe MOF was fabricated

outside magnetic Cu\\Fe oxide via in-
situ derivation strategy.
• Photothermal effect of binary Cu\\Fe
magnetic MOF catalyst can enhance
the photo-Fenton activity towards
POPs degradation.
• FeIII/FeII and CuII/CuI binary redox cou-
ples enhance the activity of catalyst.
• MCuFe MOF works effcient with re-
duced H2O2 dosage and broaden the
pH range.

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

Article history: Overcoming the relatively low catalytic activity and strict acid pH condition of common photo-Fenton reaction is
Received 5 April 2021 the key to alleviate the serious global burden caused by common organic pollutants. Herein, a binary homologous
Received in revised form 2 July 2021 bimetallic heterojunction of magnetic CuFe2O4@MIL-100(Fe, Cu) metal-organic frameworks (MCuFe MOF) with
Accepted 3 July 2021
photothermal-boosted photo-Fenton activity is constructed as an ideal practical photo-Fenton catalyst for the
Available online 5 July 2021
degradation of organic pollutants. Through an in-situ derivation strategy, the formed homologous bimetallic
Editor: Baoliang Chen heterojunction with binary redox couples can simultaneously improve the visible light harvesting capacity and
expedite the separation and transfer of photogenerated electrons/holes pairs, leading to the continuous and
rapid circulation of both FeIII/FeII and CuII/CuI redox couples. Notably, the heterojunction shows intrinsic photo-
Keywords: thermal conversion effect, which is found to be beneficial to boost the photo-Fenton activity. Impressively,
Advanced oxidation processes MCuFe MOF shows remarkable catalytic performance towards the degradation of various organic pollutants by
Degradation comprehensively increasing H2O2 decomposition efficiency and decreasing the required dosage of MCuFe MOF
Homologous bimetallic heterojunction (0.05 g L−1) with a wide pH range (3.0–10.0). As such, a photo-Fenton catalyst consisting of binary homologous
Photothermal-enhanced
bimetallic heterojunction is first disclosed, as well as its photothermal-enhanced effect, which is expected to
Wide pH
drive great advance in the degradation of organic pollutants for practical applications.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction

Organic pollutant with high toxic, semi-volatile and bio-

accumulative is a serious and long-lasting problem during the past
⁎ Corresponding author. half century (Han and Currell, 2017; Varjani et al., 2017). It can be clas-
E-mail address: wanglong79@yahoo.com (J. Wang). sified into persistent toxic substances (PTS), pesticides and herbicides,

https://doi.org/10.1016/j.scitotenv.2021.148883
0048-9697/© 2021 Elsevier B.V. All rights reserved.
S. Shi, X. Han, J. Liu et al. Science of the Total Environment 795 (2021) 148883

antibiotic drugs, phenols and so on, which are released into the environ- in situ surface pyrolysis of CuFe2O4 nanoparticles and complexation
ment frequently by industrial accidents and discharges, leakage from with trimesic acid (H3btc) to derive MIL-100(Fe, Cu) with mesoporous,
landfills, and incomplete incineration (Bacha et al., 2019; Jamieson which has homologous bimetal Fe and Cu with CuFe2O4 nanoparticle,
et al., 2017; Liu et al., 2019a). Due to their mutagenic and carcinogenic thus forming homologous bimetallic core–shell CuFe2O4@MIL-100(Fe,
properties, most organic pollutants are extremely harmful to organis- Cu) heterojunction (MCuFe MOF). Importantly, with strong visible
mal health, causing harms to the immune and nervous system, light absorption and high photo-thermal conversion efficiency,
impairing reproductive and endocrine systems, and accelerating cancer CuFe2O4 core can convert visible light into thermal energy; then, the
(Wang et al., 2017). In addition, the long-term residual of organic pol- generated “hot electrons” induced by photothermal effect can acceler-
lutants leads to the serious destruction of the ecological balances. ate the separation of photogenerated electron-hole pairs. As such,
Therefore, the removal of organic pollutants is under urgent demand photothermal effect was creatively introduced to synergistically
in both human health and environmental protection. Among the devel- enhance photo-Fenton nanocatalysis under visible light, which has
oped approaches, advanced oxidation processes (AOPs) have obtained never been reported before. Hence, the formed binary homologous bi-
wide spread acceptance in the field of organic pollutant degradation metallic heterojunction with mesoporous integrating various tactics is
for its high oxidation efficiency and environmental friendliness. As the expected to present ideal photo-Fenton degradation efficiency for or-
most prominent example in AOPs, the heterogeneous photo-Fenton re- ganic pollutants. One can be speculated that a catalyst integrating all
action with enhanced FeIII/FeII transformation (Eq. (1)) and interfacial above tactics should possess high-efficient photo-Fenton catalytic effi-
Fenton reaction activity (Eq. (2)) facilitated by the photogenerated elec- ciency for organic pollutant degradation, not resulting in the reduced
tron has been regarded as the most promising alternative to common H2O2 dosage, but enhancing the structural stability via the direct solid
Fenton reaction (Cheng et al., 2019; Zheng et al., 2021). However, they phase reduction of FeIII by electrons and broadening the optimal pH
still suffer from several drawbacks, such as low efficiency and pH con- range to avoid metal ions leaching from common catalysts at strictly
trol, which consequently decreasing the removal efficiency of organic controlled pH (2.8–3.5). Subsequently, the physical and chemical prop-
pollutants. Therefore, considering the catalytic activity has a strong rela- erties of MCuFe MOF are carefully measured. The photothermal-
tionship with the composition and structure of photo-Fenton catalyst, enhanced photo-Fenton catalytic activities towards different organic
great efforts should been devoted to the development of photo-Fenton pollutants are implemented with low-dosage H2O2 under visible light
catalysts for organic pollutant degradation. irradiation. The effect of wide range pH values is examined. The reus-
ability as well as stability are measured. And a possible photothermal-
≡FeIII þ hν þ H2 O ! ≡FeII þ OH þ Hþ ð1Þ enhanced synergistic catalytic mechanism of MCuFe MOF was first
disclosed. We believe that this work will advance the development of
≡FeII þ H2 O2 ! ≡FeIII þ OH þ OH− ð2Þ practical binary homologous bimetallic heterojunction photo-Fenton
nanocatalysts for organic pollutant degradation.
Bimetallic catalysts composed of iron and transition metals are ben-
eficial for the reduction of FeIII in Fenton-like reactions. Copper as a
2. Experimental
redox-active metal species also exhibits Fenton-like behaviors to gener-
ate hydroxyl radicals. Previous reports suggested that the cooperation
2.1. Chemicals and regents
between the redox couples of iron and copper, presenting as Cu\\Fe bi-
metallic oxide or Cu\\Fe bimetallic metal-organic frameworks (MOFs)
Ferric chloride (FeCl3·6H2O), copper chloride (CuCl2 2H2O), sodium
etc., (Cheng et al., 2019; Tang and Wang, 2020; Tian et al., 2020) can ac-
acetate (CH3COONa), polyethylene glycol (PEG), methylene blue (MB),
celerate the interfacial electron transfer to promote the rapid reduction
rhodamine b (Rh B), tetracycline (TC) and p-Nitrophenol (PNP) were
of FeIII (Eq. (3)), which has become a hotspot in Fenton chemistry (Sun
purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai,
et al., 2019b). Construction of the heterojunction structure is another
China). 1, 3, 5-Trimesic Acid (H3BTC), 2, 4-dichlorophenoxyacetic acid
way to enhance the photo-Fenton catalytic efficiency by improving
(2, 4-D) were purchased from Aladdin Co., Ltd. All analytically pure
the visible light harvesting capacity and separation and transport effi-
chemicals were used without any further purification. Deionized
ciency of photogenerated electrons and holes. On the other hand, mak-
water was used in all experiments.
ing mesoporous in photocatalyst, such as MOFs, oxide and C3N4, is also
beneficial via facilitating to mass transfer and light harvesting (Wang
et al., 2020; Xu et al., 2019; Yang et al., 2019). However, inherent chal- 2.2. Synthesis of CuFe2O4 particles
lenges still exist in the heterogeneous photo-Fenton process for practi-
cal application, such as how to further reduce H2O2 dosage, avoid the CuFe2O4 nanoparticles were first synthesized via a typical
usage of noble metals or UV light, and broaden optimal pH range to min- solvothermal method (Deng et al., 2005). Briefly, a mixture of
imize metal ions leaching with a conveniently recyclable catalyst. These FeCl3·6H2O (1.35 g, 5 mmol) and CuCl2 2H2O (0.426 g, 2.5 mmol)
also represent the requirements for an ideal practical photo-Fenton cat- were dissolved in 40 mL ethylene glycol to form a clear solution,
alyst. However, previous research of heterogeneous photo-Fenton followed by mixing of 3.6 g NaAc and 1.0 g polyethylene glycol. After
catalyst has been largely considered on either creating bimetallic vigorously stirring for 30 min, the mixture was transferred to a
component, constructing heterojunction, or making mesoporous sepa- teflonlined stainless-steel autoclave (50 mL capacity) and maintained
rately, while an integrated synergy of the two or more has rarely been for 8 h at 200 °C. The final product was harvested using a magnet and
considered. Therefore, it is of both fundamental and industrial impor- washed and dried at 60 °C in a vacuum oven.
tance to develop a more comprehensive strategy to initiate more effi-
cient photo-Fenton process under mild conditions. 2.3. Synthesis of MCuFe MOF particles
 
≡FeIII þ ≡CuI ! ≡FeII þ ≡CuII △E0 ¼ 0:60 V, k ¼ 1:3  107 M−1 s−1 ð3Þ MCuFe MOF particles were synthesized using a one-step hydrother-
mal reaction. 30 mg of CuFe2O4 and 45 mg of H3BTC were dissolved in
With above theoretical and practical guidance, in this work, we pur- 5 mL mixed of water and ethanol (Aslam et al., 2017). The mixture
posefully design and construct a binary homologous bimetallic was then transferred to a Teflon-lined autoclave and heated at 150 °C
heterojunction, magnetic Cu\\Fe oxide@MIL-100 (Fe, Cu), via in-situ for 12 h. After hydrothermal synthesis, the obtained brownish red prod-
derivation strategy as a superior catalyst for photo-Fenton degradation uct was collected by a magnet, washed with deionized water, and dried
of organic pollutants over a wide pH range. The fabrication only involves in vacuum at 60 °C.

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S. Shi, X. Han, J. Liu et al. Science of the Total Environment 795 (2021) 148883

2.4. Characterizations The transmission electron microscopy (TEM) shown in Fig. 1c exhib-
ited that copper proxied nanodots possessing particle size of about
Field emission scanning electron microscope (SEM) images were 10 nm were wrapped in dextran, which formed nanoaggregates with
performed by an S-4800 (Hitachi, Japan) (Yue, 2019). Transmission the size of about 100 nm. X-ray diffraction was carried out to analyze
electron microscopy (TEM) measurements were performed with a the crystal structure and crystal phase of DCPNAs. As depicted in
JEM-1230 (JEOL, Japan). Powder X-ray diffraction (XRD) patterns Fig. 1d, a broad peak (100) positioned at about 2θ = 13.1° can be attrib-
were recorded with a D8 Advanced Diffractometer System (Bruker uted to in-planar structural MCuFe MOF was then analyzed by XRD to
Corp., Billerica, MA, USA) using Cu-Kα radiation (40 kV, 40 mA). X-ray confirm the crystal structure of MIL-100(Fe, Cu) in the as-prepared
photoelectron spectroscopy (XPS) was conducted with an Axis Ultra composite. As shown in Fig. 1i, CuFe2O4 has well-defined peaks occur-
DLD X-ray photoelectron spectrometer (Kratos Analytical, Ltd., ring at 30.2, 35.5, 43.3, 53.6, 57.1, and 62.7°, corresponding to lattice
Manchester, UK) equipped with an Al-Kα X-ray source (1486.6 eV). planes (220), (311), (400), (422), (511), and (440), respectively
The specific area was determined using the Brunauer–Emmett–Teller (JCPDS card 77–0010) (Zheng et al., 2014). After reaction with H3BTC,
(BET) method. Magnetic properties were evaluated using a ferroelectric peaks assigned to CuFe2O4 still exist. Except for these peaks, the addi-
testing system (MPMS-SQUID VSM-094, Quantum Design, America) at tional peaks at 11.0°, 14.2°, 18.2°, 20.1°, 24.0°, and 27.7° appear, typically
room temperature. Fourier transform infrared (FTIR) spectroscopy indexed to the Fe-BTC (JCPDS card 640,536) with changed intensity
was recorded by a Vetex70 (BRUKER Corp., Germany), ultraviolet– caused by Cu incorporation. The incorporation of Cu ions would bring
visible diffuse reflectance spectra (UV–vis DRS) on UV2600 spectropho- a competitive coordination with Fe ions in bimetallic MOFs, which
tometer, Photoluminescence (PL) emission measurements were carried may result in the growth of some crystal faces and the formation of
out with a fluorescence spectrophotometer (FLS1000, Edinburgh pore structure (Zhong et al., 2020; Tang and Wang, 2020). The presence
Instruments) with an excitation wavelength of 325 nm. of MIL-100(Fe, Cu) crystals in the composites was also confirmed by FT-
IR spectroscopy (Fig. S1).
The mesoporous and BET surface area of CuFe2O4 and MCuFe MOF
2.5. Measurement of photo-Fenton reaction
were then analyzed. The N2 adsorption-desorption curves are shown
in Fig. S2. Both the curves exhibit small hysteresis loops and type IV iso-
The mixture of MCuFe MOF catalysts (5 mg), H2O2 (5 mM), and
therms with H3 hysteresis loop, indicating the formation of the mesopo-
aqueous solution of MB (50 ppm, 100 mL) were stirred for 30 min in
rous. The BET surface area of MCuFe MOF and CuFe2O4 are determined
the dark to reach adsorption equilibrium. Commercial 300 W xenon
to be 394.63 m2 g−1 and 117.22 m2 g−1. The increased surface area sug-
lamp (Perfectlight Technology, Beijing) equipped with a UV cut off filter
gests MIL-100(Fe, Cu) has been well dispersed on the surface of
(λ > 400 nm) served as the visible light source. The average power
CuFe2O4. In general, the enhanced specific area of MCuFe MOF with
energy density of the irradiation was about 0.1 W cm−2 (1 sun
mesoporous structure is easier to expose the active sites and beneficial
illumination) conducted by PL–MW2000 spectroradiometer (Beijing
for mass transfer and light harvesting, resulting in better catalytic
Perfectlight Technology Ltd., China). At a certain interval, 3 mL of the so-
performance. Magnetism plays an important role in the magnetic
lution was taken out and separated by a magnet. Then the supernatant
separation of practical catalysts after photo-Fenton process. As depicted
was measured with the UV spectrophotometer. The pH value was
in Fig. S3, pure CuFe2O4 has saturation magnetization values of
adjusted by 0.1 M HCl and NaOH and the whole degradation reaction
47.43 emu g−1. After decomposition of MIL-100(Fe, Cu), the saturation
were carried out without buffer solution. Different organic pollutants,
magnetization of as-prepared MCuFe MOF is measured to be 39.43 emu
including RhB, TC, PNP and 2,4-D, with same concentration of
g−1. The decrease saturation magnetization of MCuFe MOF also implies
100 ppm were also measured by a UV spectrophotometer, The degrada-
the MIL-100(Fe, Cu) have been dispersed on the surface of CuFe2O4.
tion of pollutants follows the pseudo-first-order kinetics: ln(C0/Ct) = kt,
Furthermore, the excellent magnetism makes MCuFe MOF catalyst
where k, t, C0 and Ct are the rate constant, reaction time, initial dye con-
easy to be perceived and isolated from the system just by applying an
centration, and the dye concentration at t min, respectively.
external magnetic field, which confirms the technical and economic fea-
sibility in the practical application (Cheng et al., 2019).
3. Results and discussion The 57Fe Mössbauer analysis at room temperature was carried out
to support the formation of MCuFe MOF (Fig. 1j). Due to the
3.1. Characterization of MCuFe MOF superparamagnetic effect of CuFe2O4 and MCuFe MOF, both of the spec-
tra are fitted with two distinct sextet patterns, which correspond to the
As demonstrated in Fig. 1a, the bimetallic CuFe2O4 is prepared di- two different types of Fe in tetrahedral (A) and octahedral (B) site in the
rectly via a hydrothermal reaction. Then, with CuFe2O4 as both of mag- crystal structure. According to the quadruple splitting (QS) and isomer
netic substrate and metal precursor, H3BTC reacts with trivalent Fe and shift (IS) as summarized in Table S1, the values are well matched with
divalent Cu ions interfacially, resulting in the in-situ generation of MIL- to the FeIII ions in tetrahedral coordination site and FeII in octahedral co-
100(Fe, Cu) on surface of magnetic CuFe2O4, which have homologous ordination site (Jia et al., 2018; Kramm et al., 2019; Li et al., 2016). The
bimetallic Cu and Fe elements. SEM and TEM were conducted to track values of obtained IS and QS in CuFe2O4 and MCuFe MOF are slightly
the formation process of MCuFe MOF. Fig. 1b exhibits a SEM image of different. Such a small variation signifies that the neighbor nature or
pristine CuFe2O4 which has regular near-spherical morphology with bonding interactions of the iron atoms have changed (Torres et al.,
an average particle size of 262 nm (Fig. 1d). By epitaxial derivation of 2018). Thus, the electronic charge around the iron atoms is redistributed,
MIL-100(Fe, Cu), the MCuFe MOF spheres show more rugged surface which might result from the fixation of MIL-100(Fe, Cu) on CuFe2O4 in-
(Fig. 1e) with an average particle size of 218 nm (Fig. 1g), preliminary terfering with the supertransferred hyperfine field (Zhang et al., 2017).
proving the change of CuFe2O4. The TEM images of CuFe2O4 and The aforementioned results confirm the successful preparation of binary
MCuFe MOF are shown in Fig. 1c and f. Compared with CuFe2O4, the homologous bimetallic magnetic oxide@MOFs heterojunction through
surface of MCuFe MOF becomes rough and the decorated of MIL-100 in suit growth MIL-100(Fe, Cu) on the CuFe2O4 interface.
(Fe, Cu) can be distinguished from CuFe2O4 as the latter looks more The composition and valence state of MCuFe MOF were further eval-
transparent than the former in the TEM images. The corresponding ele- uated via X-ray photoelectron spectroscopy (XPS) analysis. The wide
mental mapping images of MCuFe MOF are shown in Fig. 1h. These im- scan XPS spectra in the Fig. S4 disclose the coexistence elements of C,
ages reveal the coexistence of Fe, Cu, O and C elements with a uniform O, Cu and Fe in different prepared samples. Fig. 2a shows the high reso-
distribution, confirming MIL-100(Fe, Cu) in MCuFe MOF has homolo- lution XPS of Cu 2p in MCuFe MOF. As can be seen, Cu 2p is composed of
gous bimetallic Cu and Fe elements with CuFe2O4. two characteristic peaks corresponding to Cu 2p1/2 and Cu 2p3/2 at the

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S. Shi, X. Han, J. Liu et al. Science of the Total Environment 795 (2021) 148883

Fig. 1. (a) Schematic Diagram of the syntheses process of MCuFe MOF. SEM images of (b) CuFe2O4 and (e) MCuFe MOF. TEM images of (c) CuFe2O4 and (f) MCuFe MOF. Size distribution of
the (d) CuFe2O4 and (g) MCuFe MOF nanoparticles, over 100 particles were counted. (g) Scanning TEM image of MCuFe MOF and (h) element mappings of O Fe and Cu. (i) XRD patterns of
CuFe2O4, MCuFe MOF and simulated Fe-BTC (JCPDS card 640,536). (j) 57Fe Mössbauer spectra of CuFe2O4 and MCuFe MOF measured at room temperature.

position of 954.37 eV and 934.77 eV with the associated high-intensity located at 724.81 and 711.37 eV can be assigned to the Fe 2p1/2 and Fe
shake-up satellites. The broad Cu 2p3/2 peak can be further divided 2p3/2, respectively. The splitting peaks of Fe 2p3/2 at 713.02 and
into two peaks at 933.61 and 935.17 eV, which are respectively attrib- 711.00 eV are related to FeIII and FeII, respectively. The characteristic
uted to the co-existence of CuI and CuII phase. The peaks located at Fe 2p1/2 peak located at 724.81 eV also confirms the presence of FeIII
944.22 and 940.12 eV are the satellite peaks of Cu 2p3/2 in the MCuFe and FeII (Liu et al., 2020). The presence of CuI and FeII in MCuFe MOF
MOF, respectively, confirming the coexistence of the CuI and CuII could be attributed to the partial reduction of CuII and FeIII during the
(Feng et al., 2018; Shi et al., 2019). For the high resolution XPS of Fe two-step solvothermal reaction under high temperature. It is worth
2p spectrum in MCuFe MOF exhibited in Fig. 2b, two separated peaks noting that binding energies of Fe 2p and Cu 2p for MCuFe MOF shift

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S. Shi, X. Han, J. Liu et al. Science of the Total Environment 795 (2021) 148883

Fig. 2. High resolution XPS spectra of (a) Cu 2p for MCuFe MOF and (c) CuFe2O4 and (b) Fe 2p for MCuFe MOF and (d) CuFe2O4. (e) Steady-state PL spectra of CuFe2O4, MIL-100(Fe, Cu) and
MCuFe MOF, (f) time-resolved transient PL decay of MCuFe MOF, (g) UV–vis absorption spectra and bandgap energies, (h) XPS valence spectrum of CuFe2O4, MIL-100(Fe, Cu) and MCuFe
MOF, (i, j) schematic diagram of the band position and electron transport of CuFe2O4 and MIL-100(Fe, Cu).

to the higher values when compared to the pristine CuFe2O4 (Fig. 2c, d). average lifetimes of the carriers (τavg) for the samples of CuFe2O4, MIL-
Therefore, the XPS illustrates that the electron transfer from CuFe2O4 to 100(Fe, Cu) and MCuFe MOF are measured to be 1.23, 0.94 and 1.64 ns, re-
the MIL-100(Fe, Cu) on the interface of MCuFe MOF, manifesting the spectively. The improvement of τavg confirms that forming heterojunction
formation of heterojunction (Qin et al., 2019). Also, the coexistence of is beneficial for the efficient charge separation between CuFe2O4 and MIL-
FeIII/FeII and CuII/CuI binary redox couples can enhance the ability of 100(Fe, Cu) heterojunction. Therefore, the efficient separation and migra-
MCuFe MOF to catalyze H2O2 into active •OH. tion of charge carriers are achieved in the binary homologous bimetallic
MCuFe MOF heterojunction.
3.2. Optical properties Elucidation of the energy-band configuration of the MCuFe MOF
heterojunction structure is important to deeply comprehend the elec-
As a crucial factor in controlling photocatalytic activity, the optical tron transfer induced by the visible light irradiation. Thus, the band
properties of as-prepared MCuFe MOF were evaluated. Considering gap energy (Eg) of the prepared samples were experimentally resolved
that steady-state photoluminescence (PL) properties are related with via the UV–vis DRS analysis. As shown in Fig. 2g, the CuFe2O4 exhibits a
the separation of photogenerated electron–hole pairs (Miao et al., wide light absorption in the whole adsorption spectra, illustrating its
2020), PL spectra of CuFe2O4, MIL-100(Fe, Cu) and MCuFe MOF were excellent light-harvesting capability. After decomposition of MIL-100
first collected at room temperature with the excited wavelength of (Fe, Cu), the MCuFe MOF displays a combined absorption ability of the
325 nm. As shown in Fig. 2e, the emission of MIL-100(Fe, Cu) is stron- CuFe2O4 and MIL-100(Fe, Cu). Further, Eg were estimated using the
gest, followed by CuFe2O4, which is resulted from the quick recombina- plots of (αhν)2 vs. photon energy based on the Kubelka–Munk formula
tion of photogeneration electron–hole pairs. On the contrary, the (Lu et al., 2019):
emission of MCuFe MOF is least compared with that of the CuFe2O4 and

2
MIL-100(Fe, Cu), illustrating that the recombination of photogenerated ðαhνÞ ¼ A hν − Eg ð4Þ
electron/hole pairs in MCuFe MOF is forcefully suppressed. Therefore,
the photogeneration electron/hole pairs of MCuFe MOF are successfully where A, h, ν and Eg are absorption coefficient, Planck's constant, light
separated and migrated by forming the CuFe2O4@MIL-100(Fe, Cu) frequency and band gap, respectively. The values of Eg for CuFe2O4
heterojunction (Luan et al., 2018) (Qin et al., 2019). Meanwhile, the and MIL-100(Fe, Cu) are easily extrapolated to be 1.42 and 1.55 eV by
time-resolved fluorescence spectra were also conducted to confirm the fitting the formula and the result is inserted in Fig. 2g, whereas the band
efficient charge separation. As displayed in Figs. 2f, S5 and S6, the carrier gap of heterojunction MCuFe MOF is about 1.52 eV. The relatively small

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S. Shi, X. Han, J. Liu et al. Science of the Total Environment 795 (2021) 148883

band gap of MCuFe MOF is resulted from the synergistic effect of MCuFe Therefore, for the first time, we explore the possibility of introducing
MOF composition and the metallic behavior with a substantial electron solar-photothermal effect to synergistically enhance photo-Fenton
density near the Fermi level (Zhong et al., 2020) (Qin et al., 2019). The nanocatalysis under visible light. The photothermal property of the
low band gap energy is beneficial to broaden the light response range MCuFe MOF under xenon lamp irradiation at a power density of 0.1 W
and ultimately enhance the photo-Fenton catalytic activity of MCuFe MOF. cm−2 (1-sun intensity) for 40 min was investigated and the tempera-
The valence band (VB) positions of CuFe2O4, MIL-100(Fe, Cu) and ture vibration was recorded by a non-contacting thermal infrared cam-
MCuFe MOF were further studied by the XPS valence band spectros- era (Zhang et al., 2018a). As shown in Fig. 3a, the MCuFe MOF exhibits a
copy. As illustrated in Fig. 2h, the VB values of CuFe2O4, MIL-100(Fe, concentration-dependent temperature increase after exposure to visi-
Cu) are determined to be 0.47 and 1.57 eV, respectively. Thus, according ble light irradiation. 0.15 g L−1 of MCuFe MOF can raise the temperature
to optical bandgaps and VB positions, the conduction band (CB) posi- by 21.4 °C, whereas no significant temperature changes of the pure
tions of CuFe2O4 and MIL-100(Fe, Cu) can be calculated (Chao et al., water is observed, implying the reasonable photothermal conversion ef-
2019). On the basis of the aforementioned analyses, the energy-band ficiency of the MCuFe MOF. The photothermal conversion abilty of
configuration of the MCuFe MOF is depicted in Fig. 2i and j. Upon the MCuFe MOF in the photo-Fenton reaction system was then further ana-
visible light irradiation to excite the electron/holes pairs of the MCuFe lyzed throughout the photo-Fenton process. As shown in Fig. 3d, the
MOF, the photogenerated electrons have a tendency to transfer from temperature can increase from 29.2 °C to 46.1 °C during 40 min visible
CuFe2O4 to MIL-100(Fe, Cu) and holes have a converse transfer due to light irradiation in aqueous solution containing 0.05 g L−1 MCuFe
the great potential difference between the conduction band of CuFe2O4 MOF, 50 ppm MB and 5 mM H2O2. The evaluated temperature of the
and MIL-100(Fe, Cu), forming a heterojunction electric field at the inter- light-irradiated reaction system is attributed to the photothermal prop-
face of CuFe2O4 and MIL-100(Fe, Cu). The existence of such an electric erty of CuFe2O4 core in MCuFe MOF (Liu et al., 2019b). Then to further
field inhibits the recombination probability of photogenerated electron- investigate the contribution of photothermal effect of MCuFe MOF cata-
hole pairs and accelerate the interfacial electron transfer to promote lyst on MB degradation in photo-Fenton reaction, experiments were
the rapid regeneration of FeII, thereby improving the photocatalytic activ- carried by keeping the reaction solution at a constant given temperature
ity (Zhang et al., 2018b). under same light irradiation condition (10 °C, 30 °C, 40 °C, and 50 °C). As
shown in Fig. 3b, higher temperatures of photo-Fenton system could ef-
3.3. Photo-Fenton catalytic activity fectively result in a higher degradation performance of MB degradation.
Also, the corresponding degradation rate constants increase with the
Taking above advantages, the photo-Fenton catalysis ability of raise of temperature (Fig. S9a and Table S3). Therefore, the evaluated
MCuFe MOF was tested by degrading organic pollutants with temperature induced by the photothermal MCuFe MOF has actively ac-
Methylene blue (MB) as the representative. The degradation perfor- celerating effect on the photo-Fenton catalytic degradation (Zapata
mance of MB in different reaction systems was firstly conducted. et al., 2010). The photothermal-enhanced catalytic effect could be
According to the results in the Fig. S7, the degradation of MB is not ob- summarized in the following possible reasons. On the one hand, studies
served without the catalyst and H2O2 in the dark. After introducing have reported that “hot electrons” can be generated in the photothermal
H2O2, negligible degradation of MB is observed in the absence of catalyst materials, which could accelerate the separation of photogenerated
and visible light irradiation. While the presence of the MCuFe MOF and electron-hole pairs, thus improving the catalytic activity (Guo et al.,
H2O2, minor degradation occurs in the dark. Also, MB itself is hardly de- 2020; Zhang et al., 2020). And before the “hot electrons” release their en-
graded by visible light irradiation only. Even H2O2 is added, the degrada- ergy to form heat energy, they can participate in actuating the photoredox
tion efficiency of MB is not achieved under visible light irradiation. In reactions. Therefore, the two redox couples in MCuFe (FeII/FeIII and CuI/
contrast, the combination of MCuFe MOF, H2O2 and visible light irradia- CuII) might be accelerated by the “hot electrons” (Chen et al., 2019; Sun
tion result in an efficient degradation of MB, verifying the excellent et al., 2019a). On the other hand, by converting light energy specifically
photo-Fenton performance of MCuFe MOF. Meanwhile, CuFe2O4, MIL- to the heat energy, the generated thermal effect could supply a tempera-
100(Fe, Cu) and MCuFe MOF were tested under the same photo- ture gradient to facilitate the product diffusion in the crevices of the MOF
Fenton reaction condition for comparison. As showed in Fig. S8 and shell and be able to stimulate the reaction rates by bringing more success-
Table S2, the MCuFe MOF exhibits the highest catalytic degradation per- ful collisions to promote the free radicals generation and organic pollutant
formance. As mentioned above, the increased specific area of mesopo- degradation (Demir-Duz et al., 2019; Sanchez Perez et al., 2017; Wang
rous MCuFe MOF with the more active sites is contributed to the MB et al., 2016). These results elaborate that the photothermal-enhanced cat-
degradation. In addition, the efficient charge separation and excellent alytic activity induced by binary homologous bimetallic MCuFe MOF
light-harvesting capability are guaranteed after the formation of binary heterojunction can serve as a vital tool to promote the photo-Fenton
homologous bimetallic heterojunction, which is also conducive to the process.
effective MB degradation. The effects of MCuFe MOF concentrations and H2O2 concentrations
Indeed, catalysts with photothermal conversion could achieve en- on the photothermal-boosted photo-Fenton process were then calcu-
hanced photo-Fenton degradation efficiency via boosting the intrinsic lated. Fig. 4f shows effect of the different concentration of MCuFe MOF
activity. It has been shown that properly increasing the temperature on the MB degradation. As can be seen, 0.01 g L−1 of MCuFe MOF can
of Fenton process can improve the reaction efficiency and several at- achieve excellent photo-Fenton performance with 84% of MB degraded
tempts have taken the effect of temperature into account for reactor de- after 40 min irradiation. As the concentration of MCuFe MOF increases
sign and process performance (Farias et al., 2009). Ranging from 10 to to 0.05 g L−1, MB can be efficiently degraded under 40 min (Fig. 3e).
50 °C, approximately, the temperature elevation may substantially Further increasing the MCuFe MOF concentration cannot lead to a sig-
boost the potency of Fenton reaction; and there was a decrease in effi- nificant improvement of degradation efficiency, indicating that H2O2
ciency when above 50 °C (Hu et al., 2019; Zapata et al., 2009). As such, has been sufficiently catalyzed at a given concentration. Thus, the opti-
to boost the catalytic activity of catalyst, the appropriate introduction mal concentration of MCuFe MOF is 0.05 g L−1. Fig. 3f shows the effect of
of thermal could be a satisfied strategy. For practical application, water H2O2 concentration ranging from 1 mM to 50 mM on the degradation
remediation using solar-promoted processes should be conducted at efficiency of MB. The degradation efficiency of MB is 77% by 1 mM
environmental temperatures, and heating the reaction system may H2O2 after 40 min of visible light irradiation. By adding the concentra-
cause the increasing cost of water treatment. For this reason, a photo- tion of H2O2 to 5 mM, the degradation efficiency reaches to be 95%.
Fenton catalyst with heat-generating ability under environmental con- However, as the concentration of H2O2 continues to increase, the degra-
dition, scilicet solar-photothermal nanocatalyst, could be a promising dation efficiency has no obvious changes. Therefore, 5 mM of H2O2 is
candidate to meet the urgent demand of practical industrial application. sufficient to accomplish the degradation of 50 ppm MB.

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S. Shi, X. Han, J. Liu et al. Science of the Total Environment 795 (2021) 148883

Fig. 3. (a) Photothermal heating curves of various concentrations of MCuFe MOF. (b) Relative concentration changes (Ct/C0) of MB with different temperature. (c) Schematic diagram of
photothermal performance of MCuFe MOF. (d) IR images of the MB solution temperature changes in the photo-Fenton reaction during different visible light irradiation times. Relative
concentration changes (Ct/C0) of MB with different (e) MCuFe MOF concentrations (10 mM H2O2), (f) H2O2 concentrations (0.05 g L−1 MCuFe MOF) and (g) pH values (0.05 g L−1
MCuFe MOF, 5 mM H2O2).

pH value is another factor affecting the photo-Fenton reaction after photo-Fenton reaction, but the percentage of FeIII/FeII decreases
(Ahmed et al., 2020). In this work, the effect of pH values (3, 5, 6, 7, 8, compared with the original MCuFe MOF. Similar, the percentage of
and 10) on MB degradation using MCuFe MOF as photo-Fenton catalyst CuII to CuI in the deconvoluted Cu 2p3/2 also decrease after photo-
was investigated. As shown in Fig. 3g, the degradation of MB is almost Fenton reaction, suggesting that the solid phases of FeIII and CuII on
unchanged at different pH values by using MCuFe MOF as catalyst in the MCuFe MOF take part in the photo-Fenton reaction and can be
the photo-Fenton system. Even at pH value of 10, 94% MB can be de- reduced to FeII and CuI by the photo generated electrons, respectively.
graded in 40 min with the rate constant of 0.068 min−1 (Table S6). This direct phase reduction of FeIII by electrons can maintain the
This outstanding catalytic performance over a wild pH range, on one structure stability and then broader the optimal pH range (Zhu et al.,
hand, may be contributed to the solid-acid property of MCuFe MOF, of 2018). Overall, the pH values have negligible influence on the degrada-
which the coordinatively unsaturated iron sites are able to coordinate tion of MB by using MCuFe MOF as catalyst in photo-Fenton reaction, in-
with H2O and release H+, thus forming the acidic microenvironment dicating MCuFe MOF can work efficiently under a wide range of pH
(Wu et al., 2020). Also, the generation of carboxylic acids during MB conditions, which shatters the strict control of pH (2.8–3.5) for traditional
degradation could also decrease the solution pH (Houas et al., 2001). Fenton catalysts. In this regard, the binary homologous bimetallic MCuFe
To verify this hypothesis, the pH values of solution after reaction are MOF heterojunction/H2O2/Vis system is conducive to the practical appli-
tracked and the corresponding results are shown in Fig. S10. Apparently, cations. More importantly, the consumption of MB caused by 1 g MCuFe
the pH values of all the solution are reduced, which change from the MOF and 1 g H2O2 per minute (g−1 min−1) was calculated. As shown in
original pH values of 3.0, 5.0, 6.0, 7.0, 8.0, and 10.0 to 2.23, 3.72, 4.27, Table 1, the MCuFe MOF exhibted the best photocatalytic performance
5.68, 6.03, and 8.41 after 40 min irradiation, indicating that the self- over the most reported catalysts, further demonstrating the excellent cat-
reduced pH microenvironment ability of MCuFe MOF is beneficial to alytic degradation performance and the good potential for industrial
the outstanding photo-Fenton catalytic performance over a wide pH application.
range. On the other hand, the direct solid phase reduction of the FeIII
and CuII by photo-generated electrons could also be a crucial aspect to 3.4. Photo-Fenton catalytic mechanism
broaden the pH range at the same time. The valence changes of Fe and
Cu elements in the MCuFe MOF before and after reaction are compared To obtain the deep insight into mechanism of the catalytic process,
by analyzing the XPS spectra. As shown in Fig. S11, two peaks belong to the valid generated free radicals are checked by using different scaven-
FeIII and FeII can be observed in the deconvoluted Fe 2p3/2 of MCuFe MOF gers to capture the radicals. TBA, EDTA-2Na and TBQ with different

7
S. Shi, X. Han, J. Liu et al. Science of the Total Environment 795 (2021) 148883

Fig. 4. Relative concentration changes (Ct/C0) of MB in the systems of MCuFe MOF / H2O2 with different dosages of (a) TBA, (b) EDTA-2Na and (c) TBQ. (d) DMPO spin-trapping EPR spectra
on H2O2 activation via the different systems. (e) Possible photo-Fenton reaction mechanism of the charge transfer for hydroxide radical generation over the MCuFe MOF under visible light
irradiation. Relative concentration changes (Ct/C0) of (f) RhB, (g) TC, (h) PNP and (i) 2, 4–D with 0.05 g L−1 of MCuFe MOF and 5 mM H2O2.

dosages are selected as ·OH, h+ and ·O2− scavengers, respectively (Yao agent. As shown in Fig. 4d, the relative EPR signal intensity is weak
et al., 2019). As shown in Fig. 4a-c, the adding of TBA causes obviously under dark condition, and no such signal is observed in the absence of
deactivation of photo-Fenton process. With increasing the ratios of H2O2. Obviously, the strong quartet signals with intensity of 1:2:2:1 in
TBA to H2O2, the remove efficiency of MB decreases to 74.5% (500:1), the system of MCuFe MOF/H2O2/Vis are detected, suggesting the gener-
54.1% (1000:1) and 7.2% (2000:1) within 40 min. By adding EDTA- ation of ·OH radicals. The EPR results are consistent with the trend of re-
2Na for comparison, the remove efficiencies of MB show slight moval efficiency in different systems, illustrating that the role of the
reductions of 4.6% (500:1), 10.9% (1000:1) and 21.8% (2000:1), respec- photo-Fenton system is responsible for the generation of ·OH by the bi-
tively. In the presence of TBQ, the remove efficiencies of MB are not sig- nary homologous bimetallic heterojunction for organic pollutant degra-
nificantly restrained. As a result, the ·OH radicals play a dominate role dation (Li et al., 2019; Yang et al., 2020).
for MB degradation in the MCuFe MOF/H2O2/Visible light system with Based on aforementioned experiment results, a possible photo-
some contributions of h+ and ·O2−. To intuitively observe the genera- Fenton reaction mechanism has been proposed and the schematic
tions and changes of ·OH, the electron paramagnetic resonance (EPR) diagram of photoexcited electron transfer and hydroxide radical gener-
spectroscopy was performed with DMPO as the radical spin trapping ation is elucidated in Fig. 4e. Under visible light irradiation, both

Table 1
Comparison of MB degradation performance catalyzed by various photo-Fenton catalysts.

Catalysts mca. CMB mH 2O 2 V t Q Qt Ref.

(mg) (ppm) (mg) (mL) (min) (g−1) (g−1 min−1)

α-Fe2O3@diatomite 5 20 306 100 120 1.31 0.011 (He et al., 2018)

Fe-CS/MMTNS 10 20 68 100 120 2.94 0.024 (Zhao et al., 2020)
Fe3O4/C/Cu2O 25 100 278 50 60 0.72 0.012 (Chai et al., 2016)
α-Fe2O3@GO 100 40 15 400 80 10.67 0.133 (Liu et al., 2017)
Fe3O4@void@CdS 10 10 510 50 20 0.09 0.004 (Shi et al., 2016)
β-FeOOH@GO 100 40 14.96 400 50 10.70 0.210 (Su et al., 2019)
MCuFe MOF 5 50 17 100 40 58.82 1.471 This work

Q: the consumption of MB caused by 1 g catalyst and 1 g H2O2 (g−1); Q t: the consumption of MB caused by 1 g catalyst and 1 g H2O2 per min (g−1 min−1).

8
S. Shi, X. Han, J. Liu et al. Science of the Total Environment 795 (2021) 148883

CuFe2O4 and MIL-100(Fe, Cu) are excited and the photogenerated holes system, confirming MCuFe MOF is an excellent and universal photo-
and electrons are in their VB and CB, respectively (Eq. (5)). Due to the Fenton catalyst. Additionally, in order to visualize the excellent catalytic
photothermal effect of CuFe2O4 core, the holes and electrons can be performance of MCuFe MOF, Tables S7–10 also displays the calculated
heated to the “hot electrons” and “hot holes” by converting light energy consumption of four contaminants caused by 1 g catalyst and 1 g H2O2
to the heat. Because of the great potential difference between the per minute (g−1 min−1). Compared to the most reported materials,
conduction band of CuFe2O4 (−0.95 V vs NHE) and MIL-100(Fe, Cu) MCuFe MOF exhibits the best photo-Fenton catalytic effect. Therefore,
(0.02 V vs NHE), the photogenerated electrons have a tendency to trans- the binary homologous bimetallic heterojuncted-structured catalyst
fer from CuFe2O4 to MIL-100(Fe, Cu) and holes have a converse transfer. with the synergistic photothermal-enhanced effect is profitable for the
Such an energetic situation of the heterojunction prolongs the transfer degradation of various organic pollutants.
lifetime of the photogenerated e− and h+. Then H2O2 could be
decomposed by reacting with the photogenerated e− to produce active 3.5. Reuse of MCuFe MOF
•OH (Eq. (6)) (Cheng et al., 2019). The reduced chemical valent of ≡FeII
and ≡CuI in the MCuFe MOF could react with H2O2 to produce active Generally, degradation recyclability and structural stability are an-
•OH, along with formation of ≡FeIII and ≡CuII (Eqs. (7) and (8)). The other two important factors for evaluating the excellence of a catalyst
oxide chemical valent of ≡FeII and ≡CuI could be regenerated from the considering the economic plausibility. Therefore, the reversibility of
photogenerated e− and h+ and accelerated by the photothermal effect MCuFe MOF for the MB degradation for five cycles was performed and
of the CuFe2O4 core (Eqs. (9) and (10)). Meanwhile, the existence of the results are displayed in Fig. 5a. Over the period of 5 cycles, degrada-
≡CuI is thermodynamically favorable to react with ≡FeIII directly to accel- tion efficiency of MCuFe MOF drops negligibly and MB could still be re-
erate the generation of ≡FeII (Eq. (11)). Therefore, the ≡FeII/≡FeIII and moved completely within 40 min at the fifth cycle, indicating fantastic
≡CuII/≡CuI show lasting circulation of self-catalyzing during photo-Fenton reusability of MCuFe MOF. The photocatalytic stability of MCuFe MOF
reaction, insuring the rapid regeneration of ≡FeII and high-efficient produc- was then tested after reaction by examining the leaching of metal
tion of ·OH (Yao et al., 2015) (Li et al., 2019). Overall, the photothermal en- amount from the solid to aqueous phase. As shown in Fig. 5b, the
hanced MCuFe MOF heterojunction can not only accelerate the generation metal leaching ratios of Fe and Cu after each reaction were below
and separation of photogenerated e− and h+, but also improve the contin- 0.022% and 0.051%, respectively. To exclude the effect of leached ions,
uous and efficient circulation of ≡FeIII/≡FeII and ≡CuII/≡CuI binary redox the experiment using the leached solution in the absence of catalyst
couples, leading to enhanced photo-Fenton reactivity and reduced H2O2 was carried out and the result was shown as Fig. S12, which demon-
dosage. On the other hand, direct solid phase reduction of ≡FeIII and ≡CuII strates negligible ability of Fe and Cu ions to degrade MB. To further ex-
by electrons can enhance the structural stability of the binary homologous amine the stability of the catalyst, the structural stability and surface
bimetallic MCuFe MOF heterojunction and broaden the pH range. properties of MCuFe MOF before and after reaction were examined
by FT-IR. The surface functional groups were also like the pristine
þ
MCuFe MOF þ hv ! eCB − þ hVB ð5Þ sample (Fig. 5c), further suggesting the cyclic stability of its
structure.
H2 O2 þ e− ! OH− þ OH ð6Þ
4. Conclusion
≡FeII þ H2 O2 ! ≡FeIII þ OH− þ OH ð7Þ
In summary, we have prepared a binary bimetallic magnetic
≡CuI þ H2 O2 ! ≡CuII þ OH− þ OH ð8Þ heterojunction with homologous bimetals via an in-situ derivation
strategy for comprehensively enhanced photocatalytic degradation of
≡FeIII þ e− ! ≡FeII ð9Þ organic pollutants over a wide pH value (3.0–10.0). The unique struc-
ture and composition promise the MCuFe MOF with excellent light-
≡CuII þ e− ! ≡CuI ð10Þ harvesting capability, mass and charge transfer ability, and the rapid
regeneration of FeII. The photothermal-enhanced effect of catalyst for
≡CuI þ ≡FeIII ! ≡CuII þ ≡FeII ð11Þ photo-Fenton degradation of organic pollutants was disclosed for the
first time. As results, the as-prepared MCuFe MOF realized remarkable
To further verify the excellent photo-Fenton performance and uni- degradation efficiency for various organic pollutants and worked effi-
versality of MCuFe MOF towards organic pollutant degradation, ciently under a wide range of pH conditions. Additionally, MCuFe MOF
photo-Fenton experiments are also conducted with several other com- showed high durability for organic pollutant degradation by showing
mon organic pollutants, such as RhB, TC, PNP and 2, 4–D at concentra- almost no activity decrease and negligible metal leaching after five suc-
tions of 100 ppm. As shown in Fig. 4f-i, the degradation efficiencies all cessive catalytic. The possible photo-Fenton reaction mechanism re-
achieve above 95% by the MCuFe MOF-induced photo-Fenton reaction vealed that the photothermal property, heterojunction structure and

Fig. 5. (a) Relative concentration changes (Ct / C0) of MB over five cycles of reuse (b) Related Fe and Cu ions leaching from MCuFe MOF in the reaction solution over five cycles. (c) FT-IR
spectras of MCuFe MOF before and after five cycles.

9
S. Shi, X. Han, J. Liu et al. Science of the Total Environment 795 (2021) 148883

coexistence of FeIII/FeII and CuII/CuI binary redox couples are keys in Houas, A., Lachheb, H., Ksibi, M., Elaloui, E., Guillard, C., Herrmann, J.-M., 2001. Photocatalytic
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nanodots as photothermal-enhanced Fenton nanocatalysts for synergistic tumor
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CRediT authorship contribution statement
Jamieson, A.J., Malkocs, T., Piertney, S.B., Fujii, T., Zhang, Z., 2017. Bioaccumulation of per-
sistent organic pollutants in the deepest ocean fauna. Nat. Ecol. Evol. 1 (3).
Shuo Shi: Formal analysis, Methodology, Writing – original draft. Jia, Y., Wu, C., Kim, D.-H., Lee, B.W., Rhee, S.J., Park, Y.C., Kim, C.S., Wang, Q.J., Liu, C., 2018.
Ximei Han: Writing – review & editing. Jie Liu: Formal analysis, Nitrogen doped BiFeO3 with enhanced magnetic properties and photo-Fenton cata-
lytic activity for degradation of bisphenol A under visible light. Chem. Eng. J. 337,
Software. Xi Lan: Investigation. Jianxing Feng: Formal analysis, 709–721.
Conceptualization. Yuchen Li: Software. Wentao Zhang: Supervision, Kramm, U.I., Ni, L., Wagner, S., 2019. 57Fe Mössbauer spectroscopy characterization of
Writing – review & editing. Jianlong Wang: Supervision, Writing – electrocatalysts. Adv. Mater. 31 (31), 1805623.
review & editing. Li, X., Wang, Z., Zhang, B., Rykov, A.I., Ahmed, M.A., Wang, J., 2016. FexCo3−xO4
nanocages derived from nanoscale metal–organic frameworks for removal of
bisphenol A by activation of peroxymonosulfate. Appl. Catal. B Environ. 181, 788–799.
Declaration of competing interest Li, Q., Kong, H., Li, P., Shao, J., He, Y., 2019. Photo-Fenton degradation of amoxicillin via
magnetic TiO2-graphene oxide-Fe3O4 composite with a submerged magnetic sepa-
The authors declare that they have no known competing financial ration membrane photocatalytic reactor (SMSMPR). J. Hazard. Mater. 373, 437–446.
Liu, Y., Jin, W., Zhao, Y., Zhang, G., Zhang, W., 2017. Enhanced catalytic degradation of
interests or personal relationships that could have appeared to influ- methylene blue by alpha-Fe2O3/graphene oxide via heterogeneous photo-Fenton re-
ence the work reported in this paper. actions. Appl. Catal. B Environ. 206, 642–652.
Liu, Y., Fan, X., Quan, X., Fan, Y., Chen, S., Zhao, X., 2019a. Enhanced perfluorooctanoic acid
Acknowledgments degradation by electrochemical activation of sulfate solution on B/N codoped dia-
mond. Environ. Sci. Technol. 53 (9), 5195–5201.
Liu, Y., Guo, Z., Li, F., Xiao, Y., Zhang, Y., Bu, T., Jia, P., Zhe, T., Wang, L., 2019b. Multifunctional
The authors thank the National Natural Science Foundation of China magnetic copper ferrite nanoparticles as Fenton-like reaction and near-infrared
(31901794), the Shaanxi Provincial Science Fund for Distinguished photothermal agents for synergetic antibacterial therapy. ACS Appl. Mater. Interfaces
11 (35), 31649–31660.
Young Scholars (2018JC-011), the National Postdoctoral Program for
Liu, C., Li, Q., Cao, J., Zhang, Q., Man, P., Zhou, Z., Li, C., Yao, Y., 2020. Superstructured α-
Innovative Talents (BX20180263), the Young Talent Fund of University Fe2O3 nanorods as novel binder-free anodes for high-performing fiber-shaped Ni/
Association for Science and Technology in Shaanxi, China (2019-02-03), Fe battery. Sci. Bull. 65 (10), 812–819.
and the Tang Scholar by Cyrus Tang Foundation. Lu, Z., Zhou, G., Song, M., Wang, D., Huo, P., Fan, W., Dong, H., Tang, H., Yan, F., Xing, G.,
2019. Magnetic functional heterojunction reactors with 3D specific recognition for
selective photocatalysis and synergistic photodegradation in binary antibiotic solu-
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Luan, S., Qu, D., An, L., Jiang, W., Gao, X., Hua, S., Miao, X., Wen, Y., Sun, Z., 2018. Enhancing
photocatalytic performance by constructing ultrafine TiO2 nanorods/g-C3N4 nano-
Supplementary data to this article can be found online at https://doi.
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