Chemosphere 303 (2022) 135123

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Controlled carbonization of microplastics loaded nano zero-valent iron for

catalytic degradation of tetracycline
Ruirui Sun, Jiapeng Yang, Rong Huang, Chongqing Wang *
School of Chemical Engineering, Zhengzhou University, Zhengzhou, 450001, 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

• Carbon substrate was fabricated by

controlled carbonization of
microplastic.
• Nano zero-valent iron loaded porous
carbon was used as heterogeneous Fen­
ton catalyst.
• Effectively degrading tetracycline was
proved by high rate constant and low
activation energy.
• Degradation of POPs including Rhoda­
mine B, p-nitrophenol, and butylxan­
thate was verified.
• Catalytic mechanism was revealed
associated with multiple characteriza­
tions and analysis.

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

Handling Editor: Yasser Vasseghian Nano zero-valent iron loaded porous carbon derived from microplastics was designed as heterogeneous catalyst
for degradation of persistent organic pollutants. Controlled carbonization of microplastics with molten salt was
Keywords: conducted to tune the morphology of carbon product. Controlled carbonization induces higher carbon yield
Advanced oxidation processes (from 17.73% to 52.24%) and larger surface area (from 403.72 m2/g to 601.82 m2/g). The catalyst (Fe/MMPC)
Carbonization
was characterized by Raman, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron
Persistent organic pollutants
spectroscopy, and scanning electron microscope. Loading nano zero-valent iron onto porous carbon are verified
Microplastics
Nano zero-valent iron in the catalyst. The process factors including Fe/MMPC dosage, H2O2, pH, anions, and temperature were studied
to estimate the catalytic performance. Tetracycline degradation (81.8% within 10 min) is effectively obtained in
the Fe/MMPC and H2O2 system. The apparent rate constant is 0.1311–0.2999 min− 1 under different tempera­
ture, and the activation energy of catalytic process is 22 kJ/mol. Pollutants including rhodamine B, p-nitro­
phenol, and butylxanthate are efficiently degraded in the catalytic system. The predominant species of catalytic
reactions are hydroxyl radicals, which are mainly produced from H2O2 activation enhanced by zero-valent iron
in Fe/MMPC. This work offers an innovative strategy for microplastic management and wastewater treatment.

1. Introduction various environments and attract increasing global attention (Saeed

et al., 2020). The concept of microplastics was first proposed by
Microplastics, as emerging pollutants, have been widely detected in Thompson et al. (2004). Plastic fibers, particles, or films with a particle

* Corresponding author.
E-mail address: zilangwang@126.com (C. Wang).

https://doi.org/10.1016/j.chemosphere.2022.135123
Received 1 March 2022; Received in revised form 24 April 2022; Accepted 23 May 2022
Available online 25 May 2022
0045-6535/© 2022 Elsevier Ltd. All rights reserved.
R. Sun et al.
size of less than 5 mm are regarded as microplastics (González-Soto
et al., 2019). Microplastics ranging micrometer to nanometer level are
invisible to the naked eye. Microplastics include primary microplastics
and secondary microplastics. The former refers to microscopical plastic
particles produced for special applications. The latter represents plastic
particles that are fragmented or smashed from macroscopic plastics
through physical, chemical, or biological processes (Auta et al., 2017).
The inherent polymers and additives in microplastics are toxic, and
microplastics enriched pollutants due to large surface area increase the
threats. Microplastics can be easily taken in or swallowed by fish and
aquatic organisms, and eventually accumulated in the human body
through the food chain (Schirinzi et al., 2017). Microplastic removal is
imperative from environment, and various physical techniques have
been proposed to address the problem (Zhang et al., 2021). How to
dispose of the collected or separated microplastics becomes an emerging
problem. Conversion of microplastics into value-added products is
promising for microplastic management.
Persistent organic pollutants (POPs) in aquatic environment result in
significant environmental pollution. Advanced oxidation processes
(AOPs) are regarded as promising technique for removing POPs due to
complete mineralization, high efficiency, and simple operation (Rana
et al., 2022). To overcome the drawbacks of conventional Fenton pro­
cess, heterogeneous AOPs receive more and more attention (Wang et al.,
2021a). Heterogeneous AOPs are currently limited by the development
of effective catalysts. Zero-valent iron (ZVI) is cheap, reactive, and
environmentally benign, and it has been proven to be effect catalyst for
degradation of different POPs (Minella et al., 2019; Jiang et al., 2020).
However, the oxidation and agglomeration of ZVI particles because of
high surface energy and magnetic interaction significantly limit the
potential application. Supporting ZVI onto porous carbonaceous mate­
rials is an effective strategy for improving the catalytic performance. ZVI
loaded on activated carbon cloth (Raji et al., 2021), biochar (Deng et al.,
2018), and graphene (Yang et al., 2019) has been proven for effective
degradation of POPs. Due to high carbon content, microplastics are
promising carbon source for fabricating carbon materials. Trans­
formation of microplastics into carbon-based catalyst realizes efficient
management of separated microplastics, and also favors high-value
recycling. To the best of our knowledge, ZVI loaded on carbon support
derived from microplastics is rarely reported.
It is hypothesized that ZVI loaded on carbon support derived from
microplastics can be catalyst for efficient degradation of POPs.
Controlled carbonization of microplastics was innovatively conducted to
tune the morphology of carbon product. ZVI supporting on porous car­
bon was designed for as heterogeneous catalyst. Antibiotics receive
special attention due to potential threats, such as acute and chronic
inhibitory impacts on microbial activities and ecosystems (Liu et al.,
2020a). Tetracycline (TC), one of the representative antibiotics, was
chosen as target pollutant. The aims of this work are (i) to fabricate
porous carbon by controlled carbonization of microplastics, (ii) to syn­
thesize novel carbon-based catalyst of ZVI supported by porous carbon,
(iii) to investigate the physicochemical properties of catalyst, (iv) to
assess the catalytic ability for pollutant degradation, and (v) to uncover
the reaction mechanism.
2. Materials and methods
The detailed information of chemical and materials used in this study
are described in this section. Controlled carbonization of microplastic
samples is depicted to fabricate porous carbon support. ZVI loaded on
carbon support is designed as catalyst for catalytic degradation of pol­
lutants. The degradation experiment to evaluate catalyst performance is
demonstrated. Multiple characterizations are conducted to examine the
characteristics of as-prepared catalyst.
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Chemosphere 303 (2022) 135123
2.1. Chemicals and materials
Microplastics samples (plastic pieces less than 5 mm) were obtained
from waste polyethylene terephthalate (PET) originated from used
beverage bottles (as shown in Fig. S1). Potassium borohydride (NaBH4,
98%) and ferrous chloride tetrahydrate (FeCl2⋅4H2O, 99%) were ob­
tained from the Sinopharm Chemical Reagent (China). Calcein
(C30H26N2O13; CA, > 90%), isopropyl alcohol (C3H8O; IPA, > 99%),
tert-butanol (C4H10O; TBA, > 99%), and o-phenylenediamine (C6H8N2;
OPD, 98%) were provided by the Aladdin Bio-Chem Technology
(China). Rhodamine B (C28H31ClN2O3; RhB, > 95%), p-nitrophenol
(C6H5NO3; PNP, 98%), and butylxanthate (C5H11OS2; BXT, > 95%),
were provided by the Tianjin Dehua Chemical Reagents (China).
Tetracycline (C22H24N2O8; TC, 96%) was achieved from the Rhawn
Chemicals (China). Basic information of RhB, PNP, BXT, and TC is
shown in Table S1. All chemicals are analytically pure.
2.2. Catalyst synthesis
Porous carbon derived from microplastics was fabricated using the
modified carbonization process reported by Zhang et al. (2019). Briefly,
microplastic sample was mixed with molten salt (ZnCl2/NaCl mass ratio:
1:1), and then carbonized in a tubular resistance furnace. Carbonization
was conducted at 280 ◦ C for 8 min and then 550 ◦ C for 10 min. Adding
NaCl to ZnCl2 reduces the melting temperature of ZnCl2 from 290 ◦ C to
~250 ◦ C, which is close to the melting temperature of PET plastic
(Zhang et al., 2019). Heating the mixtures at 280 ◦ C induce the ho­
mogenous phase and uniform mixing of plastics and molten salt. The
product was rinsed using 1 M HCl to remove the molten salt. After
washing with ultrapure water and dried at 60 ◦ C for 12 h, the product
was labeled as MMPC. Without the addition of molten salt, carbon
product was fabricated using the same process for comparison, and it
was labeled as MPC.
To improve the catalytic activity, loading ZVI onto the MMPC was
performed by liquid phase reduction method (Xiang et al., 2021). The
synthesis procedure can be shown as Fig. S2. FeCl2⋅4H2O (0.355 g) was
dissolved in 100 mL ultrapure water in a three-necked flask (250 mL).
After adding MMPC (0.4 g) to the solution, degassing using N2 was
conducted for 30 min. 0.1 mM NaBH4 was added under N2 and stirred
for 30 min for iron reduction. Vacuum filtration was performed to
separate the reaction product. After washing several times using ethanol
and ultrapure water and drying for 10 h in a vacuum oven at 60 ◦ C, the
as-prepared composite was used as catalyst (Fe/MMPC).
2.3. Degradation experiments
Degradation experiments were conducted in an Erlenmeyer flask
with 50 mL solution. Fe/MMPC (40 mg/L) was put into TC solution (40
mg/L). The solution was oscillated in a thermostatic oscillator at 150
rpm. The following factors including H2O2, Fe/MMPC dosage, initial pH,
anions, and temperature were studied by single factor experiment
(Wang et al., 2021c). At regular intervals, solution sample was taken out,
centrifuged for 1 min, and then the concentration was determined
through UV–Vis spectrometer (Ashraf et al., 2019). The change of
UV–Vis spectra of different pollutants (RhB, PNP, BXT, and TC) were
recorded (Huang et al., 2022). IPA and TBA were used as radical scav­
engers for quenching experiments (Wang et al., 2021c). CA and BPY
were employed as chelating agents to reveal the role of iron ions (Wang
et al., 2022).
2.4. Characterizations
The morphology was examined using a FEI Quanta FEG 250 scanning
electron microscope (SEM, America), and the elemental distribution was
determined by an energy dispersive spectrometer (EDS). The functional
groups were characterized by a Thermo Scientific Nicolet iS10 Fourier
R. Sun et al.
Fig. 1. (a) Pictures and N2 adsorption isotherms of MPC and MMPC, (b)
schematic diagram of controlled carbonization using ZnCl2/NaCl molten salt as
a porogen, and (c) mechanism of the controlled carbonization of PET
microplastic.
transform infrared spectrometer (FTIR, America). The specific surface
area was examined using a Micromeritics ASAP 2020 surface area
analyzer (America) through N2 adsorption/desorption. Rigaku Ultimate
IV X-ray diffraction spectrometer (XRD, Japan) was used for XRD
analysis. The surface elements were detected by a Thermo ESCALAB
250XI X-ray photoelectron spectroscopy (XPS, America). Raman spec­
trum was recorded employing a HORIBA LabRAM HR Evolution Raman
spectrometer (Japan). A zeta potential analyzer (DELSA-440SX, Coulter,
America) was used to analyze surface charge of catalyst. UV–vis spectra
of different pollutants were recorded using a Shimadzu UV-2600 spec­
troscopy (Japan). The electron spin resonance (ESR) spectrum was
measured employing a JES FA200 spectrometer (JEOL, Japan) to iden­
tify the reactive radicals in the catalytic system. An inductively coupled
plasma mass spectrometry (PerkinElmer Avio 500, America) was
employed to examine the leached iron.
Fig. 2. SEM images of Fe/MMPC: (a) × 50 k magnifications, (b) × 100 k magnifications, and (c) EDS elemental mapping of iron, oxygen, and carbon.
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Chemosphere 303 (2022) 135123
3. Results and discussion
3.1. Controlled carbonization of microplastic
Catalyst is designed by loading ZVI onto carbon support derived from
microplastic. The large surface and porous structure of carbon support
are imperative, and controlled carbonization of microplastic is con­
ducted to improve the properties. Fig. 1a shows that microplastic sam­
ples are transformed into black carbon material after carbonization.
Carbon product derived from the mixture of microplastic and ZnCl2/
NaCl molten salt is very fluffy compared with that obtained from
microplastic alone. The yield of MPC and MMPC is 17.73% and 52.24%,
respectively. This suggests that the presence of ZnCl2/NaCl molten salt
promotes carbon fixation in carbonization process.
According to IUPAC classification, MPC shows the type I adsorption
isotherm (Fig. 1a), indicating the microporous structure. A sharp in­
crease in N2 adsorption is observed at low relative pressure, while
saturation adsorption appears when it reaches higher relative pressure.
The adsorption isotherm of MMPC conforms to type II isotherm, sug­
gesting the existence of mesoporous structure. As displayed in Table S2,
the surface area of MPC and MMPC is determined to be 403.72 m2/g and
601.82 m2/g, respectively. The controlled carbonization results in the
notable increase of the surface area. Additionally, the total pore volume
is increased from 1.82 cm3/g to 3.77 cm3/g.
The addition of NaCl reduces the melting temperature of ZnCl2 from
290 ◦ C to 250 ◦ C, which is close to the melting temperature of PET
plastic (Zhang et al., 2019). First step of carbonization at 280 ◦ C results
in simultaneously melting the mixtures and uniformly mixing. With
increasing temperature to 550 ◦ C, the formation of carbon frame occurs,
while the ZnCl2/NaCl molten salt as porogens produces porous struc­
ture. The mechanism of control carbonization is shown in Fig. 1b.
Molten salt promotes the decarboxylation and dehydration of micro­
plastics to produce vinyl terminal chain fragments and aromatic rings
(Fig. 1c). These intermediates build the carbon framework and further
crosslink and cyclize (Yu et al., 2016). The remaining molten salt as a
porogen to produce more pore structure.
3.2. Characteristics of catalyst
The characteristics of carbon products derived from microplastics are
characterized by multiple techniques. Fig. 2 exhibits the morphology of
Fe/MMPC, showing a porous lamellar structure. The clusters of small
particles on the surface may be the loaded nano iron species. EDS
mapping shows the uniform distribution of carbon and iron, implying
the efficient loading iron species on the carbon surface. MMPC was used
R. Sun et al.
Fig. 3. (a) XRD patterns, (b) FTIR spectra, (c) Raman spectra of MMPC and Fe/MMPC, and high-resolution XPS spectra of Fe/MMPC: (d) C 1s, (e) O 1s, and (f) Fe 2p.
as the support to load nano zero-valent iron as heterogeneous catalyst.
The successfully loaded iron onto carbon surface potentially provides
active sites for pollutant degradation.
Fig. S3 shows the II type adsorption isotherm of Fe/MMPC. The
surface area is 472.85 m2/g and the total pore volume is 3.45 cm3/g.
Compared to MMPC, the loading zero-valent iron slightly lower the
surface area and pore volume (Table S2). This can be attributed to pore
plugging by the occupation of pore structure of carbon surface by iron
particles. It is speculated that the active metal iron species are success­
fully supported on the carbon support.
XRD patterns of MMPC and Fe/MMPC are shown in Fig. 3a. The
broad peak at around 19.2◦ in XRD spectrum of MMPC is attributed to
carbon. As to Fe/MMPC, the peak at 2θ of 44.7◦ is attributed to the plane
of (110) crystal Fe0 (JCPDS PDF Card #65–4899) (Luo et al., 2020). The
peaks at 2θ of 35.5◦ and 56.8◦ may be ascribed to Fe3O4 (JCPDS PDF
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Chemosphere 303 (2022) 135123
Card #65–3107) (Sahadevan et al., 2021). The appearance of Fe3O4 may
be resulted from partial oxidation of Fe0 in the fabrication process. Iron
loading onto MMPC is verified by XRD analysis.
Fig. 3b shows the FTIR spectrum of Fe/MMPC and MMPC. A wide
peak of about 3320 cm− 1 is derived from –OH vibration in adsorbed
water molecules (Wang and Wang, 2018). The peak located at 1610
cm− 1 is resulted from C– – O vibration (Wang et al., 2016), while the
absorbance peak at 1340 cm− 1 is assigned to the C–H stretching of
benzene structure. The slight shift of the peak at 1340 cm− 1 after iron
loading indicates the variation of benzene structure, agreeing with the
carbon fixation in the carbonization process. The new peak at 1080
cm− 1 suggests the appearance of C–O group after iron loading (Wang
et al., 2018).
Raman spectra of MMPC and Fe/MMPC are shown in Fig. 3c. The
broad peaks appeared at approximate 1350 cm− 1 and 1600 cm− 1 are
R. Sun et al. Chemosphere 303 (2022) 135123

Fig. 4. Effect of (a) catalyst dosage, (b) H2O2 concentration, (c) pH level, (d) anions, (e) temperature on TC degradation, and (f) kinetic fitting. (Experimental
conditions: H2O2 2.0 mM, Fe/MMPC 40 mg/L, TC 40 mg/L, pH level 4.0, and temperature 25 ◦ C).

assigned to D band and G band of carbon materials (Wang et al., 2020).
D band represents the disorganized sp3 carbon, while G band reveals the
hybrid sp2 carbon in the graphite structure. The defect degree of carbon
materials can be characterized by the D band and G band ratio (ID/IG)
(Dissanayake et al., 2020). The calculated ID/IG value of MMPC and
Fe/MMPC is 0.81 and 0.85, suggesting that iron loading slightly in­
creases defect degree. The defective carbon may be favorable for cata­
lytic reaction (Wang et al., 2021b).
Fig. 3d displays the signals of C 1s XPS peak. The fitted peaks at
284.8 eV, 286.6 eV, and 289.8 eV reveal the C–C/C– – C, C–O, and C– –O
groups, respectively (Sun et al., 2021). This suggests the existence of
oxygen-containing groups on MMPC surface, which is consistent with
FTIR analysis. The O 1s spectra manifest the fitted peaks at 532.9, 531.6,
and 530.2 eV (Fig. 3e), assigning to the hydroxyl oxygen, surface
oxygen, and lattice oxygen (Wei et al., 2019). Fig. 3f displays the fitted
peaks of iron. The presence of ferrous iron (Fe2+) is proved by the peaks
at binding energy of 711.0 and 724.7 eV, and the fitted peaks at 712.9
and 726.8 eV are attributed to ferric iron (Fe3+) (Wang et al., 2022). The
minor peak at 707.1 eV is ascribed to Fe0. XPS analysis is consistent with
XRD results, proving the existence of Fe0 and Fe3O4 in Fe/MMPC.
3.3. TC degradation in different systems
The catalytic ability of Fe/MMPC is evaluated associated with H2O2
for degradation of target TC. Fig. S4 shows the comparison of TC
removal under Fe/MMPC alone, H2O2 alone, or Fe/MMPC and H2O2
system. The effect of Fe/MMPC or H2O2 alone on TC removal is negli­
gible, while significant decline of TC is seen in the presence of Fe/MMPC

5
R. Sun et al.
Fig. 5. Degradation of (a) TC, (b) PNP, (c) BXT, and (d) RhB in the catalytic system. (Experimental conditions: Fe/MMPC 40 mg/L, H2O2 2.0 mM, and tempera­
ture 25 ◦ C).
and H2O2. The H2O2 oxidation or adsorption effect by Fe/MMPC results
in minor TC removal, while Fe/MMPC effectively activates H2O2 for TC
degradation (81.8% within 10 min). Fig. S5 shows the zeta potential of
Fe/MMPC as a function of pH. The point of zero charge (pHpzc) of Fe/
MMPC is approximate 5.1, and Fe/MMPC is positively charged at pH
below pHpzc. TC molecule in solution occurs as cations (pH < 3.3),
zwitterions (pH = 3.3–7.7) and anions (pH > 7.7) (Qi et al., 2018).
Electrostatic repulsion may occur between Fe/MMPC and TC molecule
at low pH, agreeing well with low TC adsorption onto Fe/MMPC.
Solid catalysts in heterogeneous Fenton system are indispensable for
H2O2 activation (Wang et al., 2019). It is necessary to determine the
suitable dosage since it affects the catalytic performance and operating
costs. Fig. 4a manifests the effect of Fe/MMPC on TC degradation. When
the dosage of Fe/MMPC increases from 0 to 80 mg/L, TC degradation is
improved significantly. The improved catalytic performance associated
with catalyst dosage are in accordance with previous studies (Chu et al.,
2020; Xie et al., 2020). The addition of Fe/MMPC provides more cata­
lytic sites for H2O2 activation. When the dosage of Fe/MMPC increases
from 40 to 80 mg/L, the improvement of degradation efficiency is
slightly weakened. Excessive catalyst may undesirably consume reactive
radicals. Fe/MMPC of 40 mg/L was chosen for subsequent experiments.
Fig. 4b shows TC degradation as a function of H2O2 concentration.
TC removal is highly limited in absence of H2O2. TC degradation grad­
ually improves when the concentration of H2O2 increases from 0 to 4
mM. The formation of reactive radicals such as ⋅OH depends on H2O2.
Increasing H2O2 concentration can improve the generation of ⋅OH in
heterogeneous Fenton system (Xin et al., 2021). TC degradation is
almost unchanged by increasing H2O2 from 2 to 4 mM. This can be
ascribed to self-decomposition of hydrogen peroxide (Eq. (1)) and
scavenging effect of excessive H2O2 (Eqs. 2-3) (Liu et al., 2020b).
6
Chemosphere 303 (2022) 135123
2H2O2 → O2 + 2H2O (1)
H2O2 + ⋅OH → ⋅OOH + H2O (2)
⋅OOH + ⋅OH → O2 + 2H2O (3)
Solution pH is an important factor in heterogeneous Fenton system.
Fig. 4c exhibits the impact of pH on TC degradation. TC degradation is
efficiently gained at pH 3.0. Gradual decline of TC degradation occurs
with increasing solution pH to 9.0. When pH is larger than 6.0, it is
difficult to achieve TC degradation. The decline in TC degradation
associated with pH variation agrees with previous reports (Li et al.,
2020; Wang et al., 2021c). The optimal pH of the Fenton reaction be­
tween Fe2+ and H2O2 is 2.5–4.0. Low pH induces dissolved metal ions
instead of forming hydroxide precipitation (He et al., 2020; Yu et al.,
2019). The high oxidation potential of active radicals at low pH also
contributes to high TC degradation. At higher pH, the weakened TC
degradation can be ascribed to H2O2 decomposition and the formation
of insoluble ferric hydroxide. Fig. 4d manifests the effect of co-existing
ions. The presence of Cl− ion causes slight increase of TC degradation,
while SO2−4 ion shows negligible effect on TC degradation. HCO3 ion
−
significantly lowers TC degradation, and this can be attributed to the
increased pH.
TC degradation is enhanced with elevating temperature from 25 to
55 ◦ C (Fig. 4e). Higher temperature may accelerate the molecular
diffusion and thermal conversion of H2O2 into radicals. Increasing
temperature is not favorable for practical application due to higher
operational costs. Pseudo-first-order (PFO) kinetic model (Eq. S1) are
commonly used to study catalytic degradation of pollutants in hetero­
geneous Fenton system. The apparent rate constant increases from
R. Sun et al.
Fig. 6. (a) Effect of scavengers on TC degradation (b) spectra of OPD-trapped •OH, (c) ESR spectra of DMPO-trapped •OH and (d) effect of BPY and CA on TC
degradation. (Experimental conditions: Fe/MMPC 40 mg/L, H2O2 2.0 mM, pH 4.0, TC 40 mg/L, and temperature 25 ◦ C).
0.1311 to 0.2999 min− 1 when increasing temperature from 25 to 55 ◦ C
(Fig. 4f). Based on the linear format of Arrhenius equation (Eq. S2), the
activation energy of catalytic process is 22 kJ/mol, which is smaller than
that of the previous reports (20–56 kJ/mol) (Wang et al., 2021c). It is
significantly lower than that of H2O2 dissociation (214 kJ/mol). The
activation energy is slightly higher than that of diffusion limiting reac­
tion (10–13 kJ/mol) (Wang et al., 2019). It is clarified that Fe/MMPC is
highly efficient for H2O2 activation toward TC degradation.
Fig. 5a shows the variation of the UV–vis spectra of TC solution. The
characteristic peak at 357 nm is attributed to phenolic-diketone reso­
nance groups (Wang et al., 2017). The peak obviously declines within
10 min, implying the decomposition of the tetracene rings. Besides an­
tibiotics, there exist various POPs in wastewater, such as dyes, phenolic
compounds, and flotation reagents. Degradation of other pollutants is
further examined by UV–vis spectra. PNP is an important industrial raw
material for p-aminophenol, pesticide, and antipyretic production.
Fig. 5b displays the rapid decrease of the characteristic peak at 320 nm,
indicating the destruction of the p-nitrophenolate in PNP molecule (Park
and Bae, 2019). BXT is one common flotation reagents for improving
mineral separation, and the residual BXT in flotation wastewater causes
environment pollution. From Fig. 5c, the maximum peak at 300 nm
assigned to the xanthate group significantly declines within 8 min,
manifesting the rapid BXT decomposition (Cui et al., 2016). Fig. 5d
demonstrates the UV–vis spectra of RhB with the characteristic peak of
N-ethyl group at 554 nm. The dramatic decline of the peak with minor
shift indicates the dominated pathway of chromophore cleavage for RhB
degradation (Wang et al., 2021b). Figs. S6, S7, and S8 shows the UV–vis
spectra of PNP, BXT and RhB in the presence of Fe/MMPC, and it is
clearly observed the minor contribution of adsorption (Balaraman et al.,
2022). Degradation of different pollutants provides that the catalytic
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Chemosphere 303 (2022) 135123
system is promising for the treatment of wastewater containing POPs.
3.4. Catalytic mechanism
Quenching tests and ESR determination are carried out to determine
active radicals. Quenching tests are commonly utilized to elucidate
radicals’ impact (Schneider et al., 2020). Hydroxyl radicals are
commonly dominant oxidant in Fenton related processes for pollutants
degradation (Dutta et al., 2021). IPA and TBA are widely employed as
scavengers of ⋅OH. Fig. 6a exhibits the obvious inhibition of TC degra­
dation after adding TBA and IPA. IPA traps ⋅OH in the solution, while
TBA can quench ⋅OH both in solution and catalyst surface (Sun et al.,
2021). The results prove that ⋅OH exists on catalyst surface and in the
solution.
Fig. 6b shows the UV–vis spectra of ⋅OH captured by OPD, and the
peak at near 416 nm proves the existence of ⋅OH (Fang et al., 2009). ESR
determination was further conducted for radical identification. In
Fig. 6c, the ESR spectra of ⋅OH adducts captured by DMPO show strong
four-fold 1:2:2:1 peak (Xin et al., 2021). The increase of peak intensity
indicates the generation of more ⋅OH associated with increasing reaction
time. Above analysis manifests that ⋅OH acts an important role in TC
degradation.
ZVI loads on porous carbon derived from microplastics in Fe/MMPC
catalyst. Fe0 reacts with H2O2 to form Fe2+ (Eq. (4)). Fe2+ reacts with
H2O2 to generate ⋅OH (Eq. (5)). The reaction between Fe3+ and H2O2
produce Fe2+ and ⋅OOH with lower oxidability compared with ⋅OH (Eq.
(6)). Fe2+/Fe3+ cycle is commonly limited due to the low reaction rate of
Eq. (6). The presence of Fe0 promotes Fe2+/Fe3+ cycle through Eq. (7),
thus enhancing catalytic reaction and TC degradation. CA and BPY can
be used to capture Fe3+ and Fe2+, respectively (Wang et al., 2021c).
R. Sun et al.
Fig. 7. Schematic catalytic mechanism in Fe/MMPC and H2O2 system.
Fig. 6d shows TC degradation with the addition of CA and BPY. CA
causes the slight decline of TC degradation, while BPY induces almost
complete inhibition of TC degradation. The results suggest that Fe2+ is of
high importance for TC degradation. The total Fe concentration is 0.312
mg/L after reaction for 10 min, indicating iron leaching due to low so­
lution pH. Based on above analysis, the schematic illustration of cata­
lytic mechanism can be shown in Fig. 7.
≡Fe0 + H2O2 + 2H+ → Fe2+ + 2H2O
≡Fe 2+
+ H2O2 → Fe 3+
+ ⋅OH + OH −
≡Fe3+ + H2O2 → Fe2+ + ⋅OOH + H+
≡Fe3+ + Fe0 → 2 Fe2+
4. Conclusions
(i) Controlled carbonization of microplastic improves the yield and
surface area of carbon product, making it proper catalyst support.
Loading nano ZVI onto carbon support is verified by
characterizations.
(ii) Fe/MMPC manifests significant improvement of catalyst degra­
dation of TC. TC degradation of 81.8% is obtained within 10 min.
TC degradation is promoted with increasing Fe/MMPC, H2O2,
and temperature. Lower solution pH favors TC degradation, while
co-existing ions shows different effects. The apparent rate con­
stant is 0.1311–0.2999 min− 1 under different temperature, and
the calculated activation energy is 22 kJ/mol. Different POPs
including PNP, BXT, and RhB are efficiently obtained in the
catalytic system.
(iii) The predominant role of •OH for TC degradation is proved by
quenching experiments and ESR spectra. Fe0 in Fe/MMPC is
important active sites for enhancing H2O2 activation and Fe2+/
Fe3+ cycle. The tentative mechanism is proposed based on
experimental results and characterizations.
(iv) This work offers novel insights into microplastic management
and wastewater treatment. Future studies can be conducted
considering (1) real mixed microplastics as carbon sources, (2)
integrated process of microplastics removal and catalyst fabri­
cation, and (3) treatment of real wastewater.
Chemosphere 303 (2022) 135123
Author contributions statement
Ruirui Sun led the experimental studies and the writing of the
manuscript; Jiapeng Yang and Rong Huang contributed to experimental
studies and analysis of results; Chongqing Wang led the research design
and contributed to writing and revisions of the manuscript.
(4) Declaration of competing interest
(5)
The authors declare that they have no known competing financial
(6) interests or personal relationships that could have appeared to influence
the work reported in this paper.
(7)
Acknowledgements
This work was supported by the Young Elite Scientist Sponsorship
Program by CAST (2019QNRC001), and the National Key Research and
Development Project (2020YFC1908802).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.chemosphere.2022.135123.
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