Journal of Environmental Chemical Engineering 9 (2021) 105924

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Journal of Environmental Chemical Engineering

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Research Paper

Co/Fe co-doped porous graphite carbon derived from metal organic

framework for microelectrolysis-Fenton catalytic degradation of
Rhodamine B
Peng Liu a, Dengjie Zhong a, *, Yunlan Xu a, Nianbing Zhong b, Guangjun He a
a
School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054, China
b
School of Electrical and Electronic Engineering, Chongqing University of Technology, Chongqing 400054, China

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

Editor: Dr. Zhang Xiwang Co/Fe co-doped porous graphite carbon (Co/Fe-PGC) nanocomposites were successfully prepared by one-step
pyrolysis with CoFe-MOF, in which the Co/Fe nanoparticles were uniformly coated on porous graphite carbon
Keywords: derived from MOF. It was used to microelectrolysis-Fenton degrade rhodamine B through the main active sub­
Microelectrolysis-Fenton stance ∙OH. The color and TOC removal rate of 100 mg/L rhodamine B reached 99.41% and 64.6%, respectively,
Co/Fe-PGC
for 30 min. Rhodamine B was degraded into small molecular organic acids, alcohols and lipids by N-demethy­
Cladding structure
lation and chromophore cleavage, until it was finally degraded into CO2 and H2O, and no new colored organics
Rhodamine B
were produced in the degradation process. The degradation process follows the first-order reaction kinetics, and
its rate constant is much higher than that of the previous similar studies. The excellent catalytic performance of
Co/Fe-PGC catalyst is attributed to the coupling effect of micro-electrolysis and Fenton reaction, and the ac­
celeration of cobalt on electron transport and Fe2+ reduction. Co0/Fe0 undergoes galvanic corrosion to generate
Co2+/Fe2+ and H2O2, and then these products undergo Fenton reaction to generate Co3+/Fe3+ and ∙OH, thus
forming a circulating system of Co3+/Fe3+ and Co2+/Fe2+, enhancing the activation of H2O2 and ensuring the
efficient degradation of RhB.

1. Introduction
Zero-valent iron activated carbon (Fe-C) internal micro-electrolysis
(IME) was a wastewater treatment technology developed in 1970s,
and it has been widely used in various industrial wastewater treatment
[1–3]. In the solution, when zero-valent iron particles and activated
carbon are mixed, many miniature primary cells will be formed between
the particles. At the anode, Fe0 loses electrons and releases Fe2+ into the
solution, while the cathode carbon accepts electrons and transfers them
to protons, oxygen or pollutants to accelerate the reduction [4]. How­
ever, the oxidation ability of active substances produced in IME reaction
and the in-situ generation efficiency of H2O2 are relatively low, which
leads to the low degradation efficiency of refractory organic pollutants
by Fe-C IME technology [5].
In recent years, the combination of Fe-C IME and Fenton reaction has
attracted wide attention to improve the efficiency of wastewater treat­
ment [6,7]. It is found that the generation of Fe2+ will trigger Fenton
reaction, and the addition of H2O2 will improve the removal efficiency
of pollutants [8]. Traditional Fe-C IME is usually carried out under acidic
conditions in order to meet the high degradation efficiency. However,
with the consumption of H+, the pH value of the solution increases,
which leads to the precipitation of iron mud, which subsequently hin­
ders the electron transfer between Fe0 and activated carbon, and finally
leads to the inactivation of Fe0 surface and the termination of IME [9].
In order to solve this problem, Fe0 particles are usually combined
with carbon materials to form nanocomposites. Adequate and firm
contact between Fe0 and carbon can ensure effective electron transfer
from Fe0 anode to carbon cathode [10]. In recent years, with the rapid
development of new materials technology, metal-organic frameworks
(MOFs) have gradually become the research focus in the field of catalysis
[11]. MOFs, which are composed of metal ions and organic ligands, are a
kind of expandable hybrid porous materials [12], which can be trans­
formed into porous metal NPs@carbon heterostructure by pyrolysis in
N2 atmosphere. Therefore, taking the Fe-C composite material as an IME
material, due to the protection of the carbon coating, the erosion of
oxygen on Fe0 is reduced during the pollutant degradation process,

* Corresponding author.
E-mail address: djzhong@cqut.edu.cn (D. Zhong).

https://doi.org/10.1016/j.jece.2021.105924
Received 18 April 2021; Received in revised form 6 June 2021; Accepted 22 June 2021
Available online 25 June 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
P. Liu et al.
meanwhile, the precipitation of iron ions on the surface of Fe0 is avoided
during the process, and the stability of the material is improved [13].
However, the degradation efficiency of Fe-C IME composed of single
metal is low, which seriously affects its practical application.
Bimetal (such as Fe and Co) oxides have been widely studied in the
field of wastewater treatment because of their excellent catalytic per­
formance and electron transport ability, and have shown broad pros­
pects [14,15]. In addition, due to the close interaction between iron and
cobalt, the leaching of metal ions can be effectively inhibited [16]. As we
all know, cobalt and iron ions have good catalytic properties in homo­
geneous Fenton oxidation [17]. In CoFe bimetallic system, the syner­
gistic effect of cobalt and iron ions can enhance Fenton reaction [18]. It
can be predicted that adding cobalt into Fe@C as IME-Fenton catalyst
can show excellent catalytic activity for pollutant degradation.
In this study, the Co/Fe-PGC material with cladding structure was
successfully prepared by one-step pyrolysis with bimetallic CoFe-MOF
matrix in N2 atmosphere, and used as IME-Fenton catalyst to degrade
rhodamine B (RhB). The structure and morphology of the prepared
catalyst were characterized by X-ray diffraction (XRD), scanning elec­
tron microscope (SEM), transmission electron microscope (TEM) and X-
ray photoelectron spectroscopy (XPS). The effects of different factors on
the degradation efficiency of RhB were systematically investigated. The
mechanism of degradation reaction, and the stability and reusability of
the catalyst were discussed.
2. Experimental
2.1. Chemicals
Cobalt chloride (CoCl2∙6H2O) and rhodamine B (C28H31ClN2O3)
were purchased from Chengdu kelong chemical reagent factory. N, N-
dimethylformamide (DMF), iron trichloride (FeCl3∙6H2O) and sodium
hydroxide (NaOH) were purchased from the Tansoole reagent platform.
Terephthalic acid (PTA) and tert-butyl alcohol (TBA) were purchased
from Aladdin reagent platform. Ethanol (EtOH) was obtained from
Sinopharm Chemical Reagent Co. Ltd. (China). All the chemicals are of
analytical grade without further treatment, and the water used in this
paper is deionized water.
2.2. Materials synthesis
Fig. 1 describes the synthesis process of Co/Fe-PGC material. At first,
6 mmol FeCl3∙6H2O and 2 mmol CoCl2∙6H2O were dissolved in 15 mL N,
N- dimethylformamide (DMF) to form solution A, and 4 mmol 1,4-
phthalic acid (PTA) was dissolved in 15 mL DMF to form solution B.
Next, solutions A and B were mixed and stirred for 15 min. Then, the
mixture was transferred to an autoclave lined with 100 mL Teflon, and
heated at 120 ℃ for 24 h. At last, brown product was obtained by
centrifuging the reaction solution, washed with DMF and ethanol for 3
times, and dried in vacuum at 60 ℃ overnight, which was CoFe-MOF.
Under the protection of N2, CoFe-MOF was carbonized at 700 ℃ for 3
Fig. 1. Preparation scheme diagram of Co/Fe-PGC.
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Journal of Environmental Chemical Engineering 9 (2021) 105924
h, and Co/Fe-PGC nanocomposite material was obtained. Unless
otherwise specified, the molar ratio of Co/Fe is 1:3, the calcination
temperature is 700 ℃, and the calcination time is 3 h. For comparison,
the Fe-PGC was prepared by the same steps as Co/Fe-PGC except that
CoCl2∙6H2O was not added.
2.3. Materials characterization and analytical method
The crystal structure of the catalyst was obtained by XRD (Shimadzu,
XRD-7000). The target crystal is copper (Cu Kα radiation, λ = 1.5406 Å),
the accelerating voltage is 40 kV, the current is 30 mA, the scanning rate
is 5◦ / min, and the scanning 2θ range is 10◦ –80◦ . The morphology was
observed by SEM (Apreo S HiVac) and TEM (Tecnai G2 F20). XPS was
obtained with Thermo Scientific K-Alpha. Al K characteristic X-ray line,
50 eV pass energy (energy steps 0.05 eV) and FAT mode were applied
for recording the XPS lines of Co 2p, Fe 2p, O 1s, C 1s, and binding
energy of C 1s at 284.8 eV was used as reference for charge
compensation.
The absorbance of RhB dye solution was measured using UV-Vis
spectrophotometer (UV-6100s) at λ max 554 nm. The removal per­
centage of the dye was determined using Eq. (1) [19]:
C0 − Ct A0 − At
ηRhB (%) = × 100% = × 100% (1)
C0 A0
where C0, Ct and A0, At are the concentration (mg/ L) and the absorbance
of the dye solution at the beginning (t = 0) and a certain reaction time t,
respectively. TOC was measured by TOC/TN analyzer (liquid TOC II)
(Elementar Corporation, Germany) with deionized water and 0.8% HCl
as mobile phase. In addition, a pseudo-first-order model (Eq. 2) is used
for dynamic analysis [20,21]:
( )
c0
ln = kt (2)
ct
where C0 and Ct is the concentration (mg/ L) of RhB at the reaction time
0 and t, respectively. k is the apparent first-order rate constant of RhB
degradation. The concentration of the leached metal ions in the solution
was measured by atomic absorption spectrometer (AAS, AA80, Perkin-
Elementar).
The degradation products were detected by GC-MS, with an Agilent
7890 gas chromatograph equipped with an Agilent 5975 C mass spec­
troscopy equipment. The GC system is equipped with HP-5MS capillary
column (30 m × 0.25 mm×0.25 µm). Inject 1 μL sample, and keep the
temperature of the oven at 40 ℃ for 5 min. Then, the temperature was
raised to 280 ℃ at a rate of 10 ℃/min. The products were analyzed
according to NIST11 mass spectrometry database.
2.4. Catalytic activity test
The degradation experiment of RhB was carried out in a beaker at
room temperature to evaluate the performance of the prepared catalyst.
P. Liu et al.
Generally, 0.01 g catalyst was added and fully diffused into 100 mL of
RhB solution, then, 0.1 mmol of H2O2 oxidant was added to trigger the
degradation reaction, and the reaction time was started at the same
time. 1 mL of the reaction solution was extracted at a specified time
interval, immediately quenched with 1 mL EtOH, filtered with filter
membrane, and the absorbance of the obtained filtrate was detected. In
the cycle experiment, the catalyst was recovered after each operation,
washed with distilled water and ethanol for 3 times, and dried overnight
in a vacuum drying oven at 60 ℃. Unless specified, the experimental
conditions were at pH value of 3.0, 1.0 mM H2O2, 0.1 g/L catalyst
dosage and 100 mg/L RhB. All experiments were conducted at least
three times.
3. Results and discussion
3.1. Characterization of Co/Fe-PGC
3.1.1. XRD
XRD was used to characterize the crystal structure of Fe-MOF, CoFe-
MOF, Co/Fe-PGC and Fe-PGC. Fig. 2a shows XRD patterns of Fe-MOFs
and CoFe-MOF. Fe-MOFs give clearly characteristic diffraction peaks,
which are in well consistent with previous reports [22–24], indicating
well crystallized MOF structure forms and Fe-MOF has been successfully
prepared. The XRD patterns of CoFe-MOF is basically consistent with
that of Fe-MOF, indicating that Co doping has little effect on the struc­
ture of Fe-MOF. The XRD patterns of Fe-PGC and Co/Fe-PGC are shown
in Fig. 2b. In the spectrum of Co/Fe-PGC, the peaks at 30.1◦ , 35.5◦ ,
43.7◦ , 53.4◦ , 57.0◦ and 62.6◦ correspond to the (220), (311), (400),
(422), (511) and (440) crystal planes of CoFe2O4 (JCPDS No.22-1086),
respectively. The peaks at 44.6◦ and 65.0◦ correspond to the (110) and
(200) crystal planes of CoFe alloy (JCPDS No.44-1433), respectively
[25], which are present at the same location as those of Fe0 peaks of
Fe-PGC (JCPDS No.06-0696). Peaks at 36.0◦ , 41.9◦ , 60.7◦ , 72.7◦ and
76.5◦ respectively represent the (111), (200), (220), (311) and (222)
crystal planes of FeO. In addition, an obvious graphitic carbon peak at
26.3◦ corresponding to (002) crystal plane (JCPDS No. 41-1487) is
found, which clearly shows that amorphous carbon is transferred into
graphite carbon in the carbonization process of CoFe-MOF [26]. In
summary the catalyst Co/Fe-PGC has been successfully synthesized.
3.1.2. XPS
XPS was used to elucidate the surface composition and chemical state
of Co/Fe-PGC. From spectrum of C1s in Fig. 3a, three peaks at 284.8,
286.0 and 288.5 eV can be observed, which are assigned to the vibration
of C–C, C–O and O– – C–O, respectively [27,28]. Fig. 3b shows XPS
Fig. 2. XRD patterns of (a) Fe-MOF and CoFe-MOF, (b) Fe-PGC and Co/Fe-PGC.
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Journal of Environmental Chemical Engineering 9 (2021) 105924
spectra of O1s, the peak appears at 529.4 eV is due to iron oxides,
attributing to lattice oxygen (O-2) [29]. The binding energy at 531.2 eV is
related to the surface adsorption of oxygen (OH‾). In addition, the peak
at 532.7 eV may be attributed to the oxygen-binding species of C–O
[30]. Fig. 3c shows the XPS spectra of Fe2p. The peak separation results
show that the characteristic peaks at 706.3, 710.3 and 713.1 eV repre­
sent Fe0, Fe2+ and Fe3+ of Fe2p3/2, respectively. The characteristic peaks
at 723.0 and 725.7 eV are the spin separation peaks of Fe2p1/2, which
represent Fe2+ and Fe3+, respectively [31,32]. In addition, the two peaks
at 718.6 and 730.8 eV are the vibration satellite peaks of Fe3+ [25].
Fig. 3d shows the spectra of Co2p. As shown in the figure, peaks at
776.4, 780.1 and 782.7 eV represent Co0, Co3+ and Co2+ of Co2p3/2,
respectively [33]. Peaks at 785.7 and 790.0 eV are the vibration satellite
peaks of Co3+ and Co2+ at Co2p3/2, respectively [34]. Peaks at 794.8 and
798.3 eV are spin separation peaks of Co2p1/2, representing Co3+ and
Co2+ respectively, while peak at 805.5 eV represents the spin vibration
satellite peak of Co3+ [35]. The appearance of Fe0 and Co0 peaks in­
dicates that the iron oxide is reduced during the calcination process,
which is consistent with the XRD results (Fig. 2). The above results
confirm the fact that Co/Fe-PGC has been successfully synthesized.
3.1.3. SEM and TEM
The morphology of the Co/Fe-PGC was observed by SEM and TEM.
Fig. 4a and b show the SEM images of CoFe-MOF. The obvious spindle
shape can be observed, which is consistent with other reports [36].
Fig. 4c and d exhibit the SEM images of pristine Co/Fe-PGC. The
structure of Co/Fe-PGC (CoFe-MOF after calcination) has changed
greatly compared with that before calcination. This may be due to the
thermal decomposition of the organic ligands during the calcination
process, which led to the combustion of ligand molecules, resulting in
the framework structure of MOF and the breakdown of the partial
connection [37]. The spindle shape can still be observed in Fig. 4d,
which indicates that the prepared catalyst has certain thermal stability.
Fig. 4e and f exhibit the TEM images of pristine Co/Fe-PGC. It can be
observed that the catalyst presents obvious spindle structure, this is
because the doping of cobalt improves the stability of the structure [38].
From Fig. 4f, it can be observed that CoFe nanoparticles cover in the
carbon layer, indicating that the catalyst has been successfully prepared.
3.2. Catalytic performance of Co/Fe-PGC
In order to evaluate the degradation performance of Co/Fe-PGC, the
degradation efficiency of different materials (Co/Fe-PGC and Fe-PGC) in
different processes (with and without H2O2) was investigated. The
corresponding processes are called Co/Fe-PGC/H2O2, Co/Fe-PGC, Fe-
P. Liu et al. Journal of Environmental Chemical Engineering 9 (2021) 105924

Fig. 3. XPS spectra of (a) C 1s, (b) O 1s, (c) Fe 2p and (d) Co 2p for Co/Fe-PGC.

Fig. 4. (a) and (b) SEM images of CoFe-MOF, (c) and (d) SEM images of Co/Fe-PGC, (e) and (f) TEM images of Co/Fe-PGC.

4
P. Liu et al.
Fig. 5. Removal effect of RhB by different processes.
PGC/H2O2 and Fe-PGC, respectively. The degradation effect results of
these processes are shown in Fig. 5. The order of degradation efficiency
of RhB is: Co/Fe-PGC/H2O2 > Co/Fe-PGC > Fe-PGC/H2O2 > Fe-PGC,
and the corresponding values are 90.50%, 47.41%, 21.57% and 14.21%,
respectively. The results show that Co/Fe-PGC /H2O2 obtains the
highest degradation efficiency, which is 43.09%, 68.93% and 76.29%
higher than that of Co/Fe-PGC, Fe-PGC/H2O2 and Fe-PGC. On the one
hand, the degradation efficiency of Co-doped material process (Co/Fe-
Fig. 6. The influence of (a) calcination temperature, (b) calcination time, and (c) Co/Fe molar ratio.
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Journal of Environmental Chemical Engineering 9 (2021) 105924
PGC /H2O2 or Co/Fe-PGC) is much higher than that of non-Co-doped
material process (Fe-PGC/H2O2 or Fe-PGC), whether in the process
with or without H2O2. The result suggests that Co doping can effectively
promote the degradation of RhB. This is because Co doping can accel­
erate the transmission of electrons, thus promoting the effective reduc­
tion of Fe2+, and finally enhancing the degradation of pollutants. In
addition, the degradation efficiency of Co/Fe-PGC /H2O2 is 43.09%
higher than that of Co/Fe-PGC, while the degradation efficiency of Fe-
PGC/H2O2 is 7.36% higher than that of Fe-PGC, indicating Co2+ can
participates in the activation of H2O2 [39], or cobalt and iron may have
synergistic effect [40] on activating H2O2. On the other hand, the
degradation efficiency of the process with H2O2 (Co/Fe-PGC /H2O2 or
Fe-PGC/H2O2) is much higher than that of the process (Co/Fe-PGC or
Fe-PGC), whether for the materials with or without Co doping. This is
because in the absence of H2O2, the degradation of RhB is mainly caused
by the IME reaction of Fe0/Co0 and carbon micro galvanic cells. How­
ever, the H2O2 in-situ produced by IME is not sufficient to meet the
degradation requirements of pollutants, so the degradation efficiency is
low. Therefore, adding H2O2 to the system can make up for this defi­
ciency. Therefore, the process with H2O2 (Co/Fe-PGC /H2O2 or Fe-PG­
C/H2O2) has higher degradation efficiency than that of the process
without H2O2 (Co/Fe-PGC or Fe-PGC). Among the above processes, the
Co/Fe-PGC /H2O2 process obtains the highest degradation efficiency
and it has the most research value.
P. Liu et al.
3.3. Influencing factors of catalytic efficiency of Co/Fe-PGC /H2O2
3.3.1. Influence of catalyst preparation conditions
The effect of catalyst preparation conditions on the degradation of
RhB was systematically investigated. The results are shown in Fig. 6.
Fig. 6a and b show the effects of calcination temperature and time on
RhB degradation, respectively. It can be clearly observed that with the
increase of calcination temperature and time, the degradation efficiency
of RhB first increases and then decreases. When calcination temperature
and time are 700 ◦ C and 3 h, the degradation efficiency of the catalyst is
the highest. This is because the graphitization crystallinity of the cata­
lyst gradually increases with the increase of calcination temperature and
time [41], and graphitization is beneficial to the reduction of metal ions
[37], thus increasing the content of active components of the catalyst,
which is beneficial to the degradation of RhB. However, When the
calcination temperature is too high and the calcination time is too long,
the decomposition of organic ligands may be accelerated, which leads to
the breakdown of the internal structure of MOF [42,43], thus reducing
the degradation efficiency.
The results of the influence of Co/Fe molar ratio (adjusted by
changing the dosage of iron and cobalt) are shown in Fig. 6c. The effect
of Co/Fe molar ratio is similar to that of calcination temperature and
time, that is, the degradation efficiency of RhB first increases with the
increase of Co/Fe molar ratio, and then decreases. The best degradation
efficiency is obtained when the Co/Fe molar ratio is 1:3. This is because
when the concentration of cobalt increases, more cobalt ions exists at the
nodes of MOF. When the Co/Fe molar ratio is less than 1:3, the cobalt
content in the catalyst is too low, and the synergistic effect of cobalt and
Fig. 7. Effect of (a) initial pH value, (b) H2O2 concentration, (c) catalyst dosage and (d) RhB concentration on RhB degradation.
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Journal of Environmental Chemical Engineering 9 (2021) 105924
iron is weak, so the degradation efficiency increases with the increase of
Co/Fe molar ratio. When the Co/Fe molar ratio is greater than 1:3, since
the Co-O bond is weak, the Co-O bond is easier to break at the same
calcination temperature[44], which leads to the collapse of the material
structure and is not conducive to the degradation of RhB.
In summary, the best preparation conditions of Co/Fe-PGC is:
calcination temperature 700 ◦ C, calcination time 3 h and Co/Fe molar
ratio 1:3.
3.3.2. Influence of reaction conditions
The results of the effect of reaction parameters on RhB degradation
are shown in Fig. 7. The effect of solution initial pH value on RhB
degradation (Fig. 7a) shows that solution initial pH value plays a very
important role in the degradation of RhB. As the initial pH value drops
from 5.0 to 2.5, the degradation rate of RhB increases from 15.00% to
92.60%. When the pH value continues to drop to 2.0, the degradation
rate of RhB decreases slightly to 88.17%. Generally, at acid conditions,
more H+ ions are available, which is more conductive to the production
of H2O2, and then it can decompose rapidly to produce ∙OH to enhance
the RhB degradation [45]. In addition, initial pH value can affect the
release of Co2+/Fe2+ ions through the galvanic corrosion of Co0/Fe0,
while the concentration of Co2+/Fe2+ directly affects the production of
∙OH via Fenton reaction between Co2+/Fe2+ and H2O2 (Eqs. 3 and 4)
[46,47]. However, when the initial pH value is too low, the degradation
efficiency decreases because H+ can scavenge ∙OH (Eq. 5) [48].
Co0/Fe0 + O2 + 2H+ → H2O2 + Co2+/Fe2+ (3)
2+
Co /Fe 2+ + 3+
+ H2O2 + H → Co /Fe 3+
+ ∙OH + H2O (4)
P. Liu et al.
∙OH + H+ + e- → H2O (5)
Fig. 7b shows the influence of the initial concentration of H2O2 on
the degradation of RhB. The degradation rate of RhB increases from
58.16% to 99.89% with the increase of H2O2 concentration from 0 to
6.0 mM. This is because the addition of H2O2 promotes the production of
∙OH, thus accelerating the degradation of RhB. However, when the
concentration of H2O2 increases to 8.0 mM, the degradation rate of RhB
is 99.44%, which is even slightly lower than that (99.89%) of 6.0 mM.
This is because H2O2 is not only related to the production of ∙OH, but
also related to the elimination of ∙OH [49]. As shown in the reaction Eq.
(6) [50], excessive H2O2 can covert more active ∙OH to less active HO2∙.
Therefore, when the concentration of H2O2 is high enough, the degra­
dation efficiency of RhB is basically stable or even slightly decreases.
∙OH + H2O2 →HO2∙ + H2O (6)
Fig. 7c shows the influence of catalyst dosage on RhB degradation.
With the increase of catalyst dosage from 0.02 to 0.5 g/L, the degra­
dation rate of RhB increases from 68.79% to 97.27%. This is because
with the increase of catalyst dosage, the concentration of dissolved
Co2+/Fe2+ in the solution also increases, which promotes the generation
of ∙OH and thus improves the degradation rate of RhB. However, when
the dosage of catalyst exceeds 0.5 g/L, the degradation rate of RhB
basically remains stable. This is because excessive catalyst can produce
more ∙OH, but at the same time, excessive catalyst will release more
Fe2+, which can react with ∙OH through Eq. (7) and consume it.
Therefore, when the catalyst concentration is high enough, the degra­
dation rate is basically stable with the increase of catalyst dosage.
Fe2+ + ∙OH → Fe3+ + OH- (7)
Fig. 7d shows the influence of RhB concentration on its degradation
rate. With the increase of RhB concentration, the degradation rate de­
creases. This is consistent with the research result of other scholars [51].
This is because when the Co/Fe-PGC dosage and H2O2 concentration are
fixed, the amount of ∙OH produced by the reaction is constant, and the
amount of RhB that can be degraded is also constant, which leads to the
degradation rate of RhB decrease with the increase of its concentration.
Considering the economic and efficiency factors in the actual treatment
process of dye wastewater, the concentration of RhB is selected as
100 mg/L.
In summary, the optimal reaction conditions are obtained as initial
pH 2.5, H2O2 concentration 6.0 mM, catalyst dosage 0.5 g/L and RhB
concentration 100 mg/L. Therefore, subsequent experiments were car­
ried out under these reaction conditions.
Fig. 8. Effect of adsorption, IME and Fenton on RhB (a) degradation rate and (b) TOC removal rate.
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Journal of Environmental Chemical Engineering 9 (2021) 105924
3.4. Degradation process and mechanism
3.4.1. Main ways of RhB degradation
In order to investigate the main ways of RhB degradation, the effect
of adsorption, IME and Fenton on RhB degradation rate and TOC
removal rate was discussed. Fig. 8a shows the degradation rate of
adsorption, adsorption/IME and adsorption/IME-Fenton is 19.84%,
58.16% and 99.41%, respectively. The corresponding TOC removal rate
(Fig. 8a) is 4.92%, 43.98% and 64.60%, respectively. The adsorption/
IME-Fenton obtains the best results in both degradation rate and TOC
removal rate. This is because the addition of H2O2 enhances the Fenton
reaction efficiency between H2O2 and Fe2+. Considering comprehen­
sively, the contribution of adsorption to RhB degradation and mineral­
ization is 19.84% and 4.92%, IME is 38.32% and 39.06%, Fenton
reaction is 41.25% and 20.62%, respectively. Therefore, IME and Fenton
reaction enhanced by H2O2 are the main ways of RhB degradation. In
addition, the TOC removal rate of RhB is lower than its degradation rate,
which may be due to that RhB is partially degraded into small molecular
organic matters.
3.4.2. Radical identification and degradation analysis
Scavenger was used to test the active substances in the degradation
of RhB by Co/Fe-PGC/H2O2. TBA without α hydrogen can react with ∙OH
(k = 3.8–7.6 × 108 M− 1s− 1), so it can be used as a scavenger of ∙OH
[20]. As shown in Fig. 9a and Table 1, when TBA concentration is
10 mM, 100 mM and 1 M, the degradation efficiency of RhB is 53.23%,
29.13% and 19.24%, which is 46.18%, 70.18% and 80.17% lower than
that without TBA (99.41%), respectively. In addition, the kinetic anal­
ysis results are shown in Fig. 9b and Table 1. The regression coefficient
(R2) of four cases (none, 10 mM, 100 mM and 1 M TBA) is 0.9991,
0.9383, 0.9761 and 0.9930, respectively. The results show that the ki­
netics of RhB degradation is in good agreement with the
pseudo-first-order kinetics, which is similar to the research results of
other scholars [41,52]. The corresponding reaction rate constant is
0.5519, 0.0663, 0.0390 and 0.0193 min− 1, respectively. This indicates
that ∙OH is involved in the degradation of RhB. What’s interesting is that,
when the concentration of TBA is 1 M, the degradation rate of RhB is
basically consistent with the absorption degradation rate (19.84%,
Fig. 8a). The above results prove that ∙OH is the main reactive species for
RhB degradation by Co/Fe-PGC/H2O2 system.
Fig. 9c shows the concentration change trend of Co and Fe ions in the
solution during the RhB degradation by Co/Fe-PGC/H2O2. It can be
clearly observed that Fe ions in the solution increase rapidly at the
beginning of degradation. This is because the pH value in the solution is
low at the beginning of degradation, which increases the
P. Liu et al. Journal of Environmental Chemical Engineering 9 (2021) 105924

Fig. 9. The effect of radical quenching on (a) RhB degradation and (b) kinetic analysis. (c) The concentration change trend of Co and Fe ions, and (d) UV–vis
adsorption spectra of RhB solution during the degradation process by Co/Fe-PGC/H2O2.

Table 1 Table 2
The effect of different concentrations of TBA on the Co/Fe-PGC/H2O2 system. Literature summary of RhB degradation by different Fenton systems.
TBA concentration Degradation rate (%) k (min− 1) R2 System RhB Cat. Time k Removal Refs.
(mg/ (g/L) (min) (min− 1) efficiency
None 99.41 0.5519 0.9991
L) (%)
10 mM 53.23 0.0663 0.9383
100 mM 29.13 0.0390 0.9761 Cu/gCN/ 50 0.8 60 — 99.2 [54]
1M 19.24 0.0193 0.9930 H2O2
β-Fe2O3/ 20 0.2 180 0.0203 94.8 [55]
H2O2/light
electrochemical corrosion of Fe in the catalyst and releases a large CuAl-LDH/ 10 0.2 60 — 93.7 [56]
number of ions into the solution, so the ion leaching rate is the fastest at H2O2
this stage. After 15 min, the leaching concentration of Fe ions MIL-96@NiP/ 20 0.2 60 0.0850 100.0 [57]
PMS
(11.32 mg/L) hardly changed, which was caused by the increase of pH, LaFeO3-HNZ/ 10 0.8 90 0.0571 99.0 [58]
that is, the decrease of H+ concentration. In addition, the leaching of Co H2O2/light
in the solution is very low (0.53 mg/L), which effectively avoids the Fe@Fe2O3/ 5 0.25 120 0.0222 92.4 [59]
secondary pollution of Co. Obviously, the leaching of Co and Fe ions PCA
CoMn2O3.5- 50 0.5 80 100.0 [60]
proves that Co and Fe participate in the degradation reaction of RhB, and
—
RGO/H2O2
Fe plays a major role. Co/Fe-PGC 100 0.5 30 0.5519 99.4 This
Fig. 9d shows the change of the UV-Vis adsorption spectra of RhB /H2O2 work
solution degraded by Co/Fe-PGC/H2O2 system. With the increase of
treatment time, the absorption peak at 554 nm gradually decreased,
slightly shifted to blue, and finally disappeared. Therefore, we assume Compared with previous systems including Fenton, Fenton-like and
that N-demethylation and chromophore cleavage occur simultaneously photo-Fenton processes, Co/Fe-PGC/H2O2 system has achieved the
[53]. However, the attenuation of absorption band is much more same degradation efficiency as the literatures [54,57,58,60] under the
obvious than blue shift, which indicates that chromophore cleavage is condition of higher RhB concentration and shorter treatment time
the main step of RhB degradation. The above results show that the (Table 2). More importantly, the rate constants obtained in this work are
degradation pathway of RhB is not only adsorption removal, but also much higher than those of other systems [55,57–59].
∙OH oxidation, and the latter is the main way.

8
P. Liu et al. Journal of Environmental Chemical Engineering 9 (2021) 105924

Table 3 RhB degradation by Co/Fe-PGC/H2O2 system, as shown in Fig. 10. First,

GC-MS data analysis results. RhB molecules were adsorbed on the surface of Co/Fe-PGC, and then
Retentiontime / Name Molecular structure m/ they were oxidized and degraded through three steps. The first step was
min z electric corrosion. The micro galvanic cells were formed because cobalt
15.88 N-(2- 205 and iron particles were coated in the carbon layer. Co0/Fe0 was the
Carboxyethyl) anode of the galvanic cell, and graphite carbon was the cathode. Under
iminodiacetic acid acidic conditions, the anode Co0/Fe0 undergoes galvanic corrosion to
release Co2+/Fe2+ and electrons. The electrons were captured by O2
molecules adsorbed on the carbon cathode to generate H2O2. The spe­
cific reactions are shown in Eqs. (8 and 9) [61–63]. The second step was
16.24 Butanoic acid 88
Fenton reaction stage. The released Co2+/Fe2+ and the generated H2O2
could generate Fe3+/Co3+ and ∙OH by Fenton reaction. Fe3+/Co3+ were
reduced to Co2+/Fe2+ by electrons on the surface of the carbon layer,
thus realizing the circulation of Co2+/Fe2+ and Fe3+/Co3+, and
15.98 Butyric alcohol 76
improving the degradation efficiency and service life of the catalyst. The
17.04 Propanoic acid, 2- 154 specific reactions are shown in Eqs. (10 and 11) [18,64]. The third step
methyl-, butyl was the oxidative degradation of RhB by ∙OH. RhB molecules adsorbed
ester
on the surface of the catalyst reacted with ∙OH, decomposed into small
molecular organic matter under the action of N-demethylation and
30.10 Phthalic acid 166 chromophore cracking, and finally mineralized into CO2 and H2O.

Co0/Fe0-2e-→Co2+/Fe2+ (8)
-
O2+2e +2H →H2O2 +
(9)
2+ 2+ 3+
Co /Fe +H2O2→Co /Fe +∙OH+OH 3+ -
(10)
30.27 Diethyl Phthalate 222 3+ 3+ -
Co /Fe +e →Co /Fe 2+ 2+
(11)

3.5. Stability of catalyst

3.4.3. Identification of RhB intermediate products
GC-MS was used to identify the intermediate products produced by
RhB degradation to analyze the actual degradation process of RhB.
Compared with NIST database, the products in Table 3 are obtained. The
results show the degradation intermediates of RhB mainly include
organic acids, alcohols and lipids, indicating the degradation process
starts with the decomposition of RhB molecules into small organic
compounds, and then continues to be further oxidized into CO2 and H2O,
which also proves that the mineralization rate of RhB will be lower than
its degradation rate.
3.4.4. Degradation mechanism
Through the above analysis, we proposed the possible mechanism of
The stability of the catalyst is an important index to evaluate its
performance. As shown in Fig. 11a, after the catalyst was used for 5
times, the degradation rate of RhB decreased to 86.4%. This is because
that, with the increase of repetition times, the iron in the catalyst is
continuously consumed, resulting in a gradual decrease in its content,
which not only weakens the IME oxidation process, but also reduces the
leaching amount of iron to result in an adverse impact on Fenton reac­
tion. This can be verified by the variation trend of leaching concentra­
tion of cobalt and iron in the solution during the repeated process
(Fig. 11b). With the increase of repetition times, the leaching concen­
tration of cobalt and iron in the solution gradually decreases, which will
weaken the Fenton reaction and reduce the degradation rate of RhB.
This proves the above conjecture. Therefore, we can speculate that the
degradation rate of RhB will continue to decrease with the increase of

Fig. 10. Schematic illustration of possible degradation mechanism of RhB by Co/Fe-PGC/H2O2 system.

9
P. Liu et al.
Fig. 11. RhB degradation (a) and ion leaching concentration (b) for repeated use time of Co/Fe-PGC.
repeated times, which indicates that the catalyst has not long-term
stability.
4. Conclusions
In this study, Co/Fe-PGC was successfully synthesized by an easy
carbonization with CoFe-MOF precursor, and employed as IME-Fenton
catalyst for RhB degradation. Cobalt doping and H2O2 addition can
effectively promoted the degradation and mineralization of RhB. ∙OH
was the main RhB degradation active substance and the addition of
H2O2 effectively enhanced the oxidation ability of IME. The high activity
of the catalyst is due to the incorporation of Co which enhances the
electron transfer and promotes the effective reduction of Fe2+. The
degradation rate of Co/Fe-PGC is 86.4% after repeated use for 5 times,
but it has no long-term stability.
CRediT authorship contribution statement
Peng Liu: Conceptualization, Formal analysis, Investigation, Meth­
odology, Software, Validation, Writing - original draft. Dengjie Zhong:
Funding acquisition, Project administration, Resources, Supervision.
Yunlan Xu: Formal analysis, Supervision, Validation, Visualization,
Writing - review & editing. Nianbing Zhong: Project administration,
Resources, Supervision. Guangjun He: Experimental method guidance,
Data verification.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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