Chemical Engineering Journal 405 (2021) 126895

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Chemical Engineering Journal

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Sugarcane biochar as novel catalyst for highly efficient oxidative removal of T

organic compounds in water
Lingzhi He, Zairan Liu, Jiafeng Hu, Chuanyu Qin, Lan Yao, Yu Zhang, Yunxian Piao
⁎

Key Laboratory of Groundwater Resources and Environment (Jilin University), Ministry of Education, Jilin Provincial Key Laboratory of Water Resources and Environment,
Jilin University, Changchun 130021, China

HIGHLIGHTS

• AThenovel PMS based AOPs method was developed with SugBC900 as catalyst.
• HighSugBC900 is easy to prepare and highly cost effective.
• O and 2
sp carbon content, surface area and electron transfer ability are key features.
• It can effectively
1
O •−
are dominant oxidative species instead of SO and OH. •− •

•
2 2 4
degrade BPA at broad pHs (1–11) and temperatures (10–45 °C).

ARTICLE INFO ABSTRACT

Keywords: Cost effective and environmental friendly biochar catalyst (SugBC900) with high catalytic activity toward
Biochar peroxymonosulfate (PMS) was prepared by simple pyrolysis of sugarcane waste, and utilized for efficient de-
Peroxymonosulfate activation gradation of organic pollutants. Taking advantages of high sp2 hybrid carbon content, large surface area and
Bisphenol A excellent electron transfer ability, the SugBC900 coupled with PMS presented far greater catalytic degradation
Organic pollutant
ability toward bisphenol A (BPA) as model pollutant when compared to the SugBC700, SugBC800 and other
carbonaceous catalysts. The oxidative species of 1O2 and O2•− were demonstrated to be dominant for catalytic
degradation, and the role of SO4•− and •OH was minor. 20 mg/mL of BPA could be completely degraded with less
than 60 min at pHs of 5.0–11.0, and at temperatures of 25–45 °C. And at the extremely acidic (pH of 1.0) or low
temperature (10 °C) conditions, the degradation efficiencies could still reach more than 90%. The SugBC900 was
also successfully utilized for the efficiently catalytic degradation of BPA and other organic pollutants in various
real environmental water. Because of simple preparation by impregnating none of external elements, extremely
low cost property, and robustness characteristic by having broad working conditions, the SugBC900 would have
potential to be a good alternative to the conventional catalysts.

1. Introduction
Environmental contamination by organic pollutants such as phe-
nolic compounds and organic dyes can cause serious threat to human
heath and the ecosystem [1]. These organic matters are toxic and dif-
ficult to be degraded by the traditional biological treatment processes in
the wastewater treatment plants [2]. So it is of great significance and
desired to explore highly efficient treating method to meet the re-
quirements.
Up to now, various methods including adsorption [3], biodegrada-
tion [4], and catalytic degradation [5] have been used to treat such
organic pollutants. Among them, catalytic methods including advanced
oxidation process (AOPs) and reduction are attractive owing to their
cost-effectiveness and robustness property. AOPs mainly uses catalyst to
activate oxidant to produce active species with high oxidation ability to
attack pollutant molecules and achieve mineralization [6]. The reduc-
tion reaction is the process of promoting the reducing agent to form the
reducing structures and functional groups on the material surface, or
enhancing the electron transfer between the reducing agent and pol-
lutant, and enable degradation of the pollutant [7]. Peroxymonosulfate
(PMS) based AOPs was known to be effective for degradation of organic
compounds [8]. PMS can be usually activated via UV light, heat, base,
metal oxide or carbonaceous materials [9]. The sulfate radicals (SO4•−)
and hydroxyl radicals (•OH) are the main active species in the activation

⁎
Corresponding author.
E-mail address: yxpiao@jlu.edu.cn (Y. Piao).

https://doi.org/10.1016/j.cej.2020.126895
Received 20 May 2020; Received in revised form 18 August 2020; Accepted 31 August 2020
Available online 06 September 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
L. He, et al.
process of PMS [10–13], but singlet oxygen and superoxide radicals
(O2−•) can also be produced when metal and carbonaceous catalysts are
used as catalysts [14–16]. The dominant oxidative species responsible
for pollutant degradation is varied depending on the properties of
catalysts and greatly affect the removal performances. Also, the pollu-
tant removal performance is greatly affected by PMS activation ability
of the catalysts [17]. The metallic catalysts (such as Cu, Fe and Co)
having excellent PMS activation ability are considered to be highly
effective for pollutant removal, but the limitation of working conditions
and the shortcomings of easily causing secondary pollution had hin-
dered their application in practice [18–20]. The carbonaceous materials
including activated carbon, graphene, carbon nanotube and their var-
iously modified forms are promising alternatives to the conventional
metallic catalysts for their high catalytic activity and eco-friendliness
[21].
Recently, biochar as newly emerging carbonaceous material might
be attractive for use as catalyst due to the unique advantages of ex-
tremely low cost and environmental friendly nature. Biochar usually
can be obtained by simple pyrolysis of waste biomass in anaerobic
condition. It has the features of large surface area and abundant func-
tional groups, and till now, it was widely applied for soil adaptation and
adsorption of pollutants [22–25], and there are also a few reports on its
usage as fuel cell and sensor [26–28]. Lately, the applications of bio-
chars as the catalysts for activating sulfate to degrade organic com-
pounds were intensively studied [9,29]. The modification could en-
hance the catalytic activation ability of the biochar compared to the
pristine one, but it is complicated and may increase the expense in the
preparation process, also the working conditions tend to be limited by
leaching of the modified components, and sometimes causing sec-
ondary pollution.
From the point of cost effectiveness, simplicity and stability, the
development of pristine biochar with high catalytic oxidation ability
without introducing external reagents was greatly desired, but such
research was not much accessed in detail. The source of biochar is
ubiquitous and the physicochemical properties of biochar are varied
correspondingly depending on the sources [30–32]. Also the biochar
may have the diverse physicochemical characteristics such as the sur-
face area, carbonization, and electron transfer rate via changing of
preparation methods, as reported previously [3,25,33,34]. In this sense,
the high catalytic oxidation property of biochar could be anticipated by
proper control of the synthesis process. And the application of pristine
biochar directly for catalytic oxidation degradation of pollutant with
comparable or improved quality to the conventional catalysts are
challenging and valuable for robust and low cost treatment of en-
vironmental water.
In this research, the biochar catalyst with high catalytic activation
ability toward PMS was obtained via simple pyrolysis of the sugarcane
waste and utilized for efficient degradation of organic pollutant in
water. By modulation of the pyrolysis temperature, three kinds of the
sugarcane derived biochars (SugBC) were prepared, and their catalytic
degradation abilities toward bisphenol A (BPA) as model pollutant were
investigated. The SugBC obtained at 900 °C (SugBC900) presented
highly efficient BPA degradation ability. The degradation mechanism,
and the broad working capabilities at various pHs and temperature
conditions were pursued. Taking unique advantages of the sugarcane
biochar, the potential usability of SugBC900 for various organic pol-
lutants degradation in real environmental water in alternative to the
conventional carbonaceous and metal catalysts, and other biochars was
also demonstrated.
2. Experimental
2.1. Materials and apparatus
The feedstock of sugarcane waste was obtained from the local
market, washed by deionized (DI) water to remove the impurities, then
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Chemical Engineering Journal 405 (2021) 126895
dried in an oven at 105 °C for 24 h prior to use. Bisphenol A (BPA),
Phenol, Humic acid, 5,5-Dimethyl-1-Pyrroline-N-Oxide (DMPO) and
2,2,6,6-tetramethylpiperidine (TEMP) were purchased from Sigma-
Aldrich (Shanghai, China). Chromatographic purity of methanol and
acetonitrile were obtained from Fisher (USA). Peroxymonosulfate
(PMS), nitrotetrazolium blue chloride (NBT, ≥ 98.0 wt%), Rhodamine
B dye (RhB) and Methyl orange (MO) were purchased from Aladdin
Chemistry Co., Ltd. Multi-walled carbon nanotubes (MWCNT, 100 m2/
g) and graphene oxide (GO, 42 m2/g) were obtained from Nanjing
Xianfeng Nano Material Technology Co., Ltd. Other chemicals were
purchased from Sinopharm Chemical Reagent Co., Ltd. Unless other-
wise stated, chemical reagents are of analytical grade and used without
further purification.
The X-ray diffraction (XRD) patterns were obtained on a D8-
Advanecd X-ray diffractometer (Brucker, Germany) with Cu Kα radia-
tion (λ = 1.5418 Å) over the 2θ range of 10 − 80°. The surface
functional groups of different biochar samples were determined by
Fourier transform infrared spectroscopy (FTIR) (Thermo Fisher, USA).
The size property of biochar samples was investigated by a laser dif-
fraction particle size analyzer (Bettersize 2000, China). Zeta potential is
recorded on Zeta potentiometer (Nano Z, Shangguang Microscope
Factory, Shanghai, China) by dispersing samples in ultrapure water
with different pH values. The scanning electron microscopy (SEM)
images were obtained by a scanning electron microscope (Zeiss EVO
MA10, Germany). Raman spectra were recorded on a dispersive Raman
spectrometer (Tokyo Instruments Inc. Nanofinder, Japan) with an
argon ion laser (514 nm). Transmission electron microscopy images
(TEM) were recorded on a transmission electron microscope (JEOL Ltd.,
Tokyo, Japan). A nitrogen adsorption–desorption apparatus (ASAP
2020 HD88, USA) was used to determine the surface area and pore size
distribution. The elemental analyser (Elementar, Germany) was used to
estimate the elemental composition. X-ray photoelectron spectroscopy
(XPS) was conducted using an X-ray photoelectron spectrometer
(Thermo Fisher, USA). The electron paramagnetic resonance (EPR)
spectra were obtained using an EPR spectroscopy (Bruker Biospin
ELEXSYS II E500) in continuous wave X-band mode. The by-products
from the catalytic reaction were identified using the Gas
Chromatography and Mass Spectrometry (GC–MS) (Agilent, USA).
Total organic carbon (TOC) was analyzed by a TOC Analyzer
(Shimadzu, TOC-5000).
2.2. Synthesis of catalysts
Three types of biochars (BCs) were obtained by pyrolysis of su-
garcane waste under different pyrolysis conditions in a tubular furnace
(OTF-1200X, Hefeikejing materials technology Co., Ltd. China) with
continuous injection of nitrogen gas. The pyrolysis temperatures were
set to 700, 800, and 900 °C, individually, and the heating rate and
maintenance time were 7 °C/min and 1 h, respectively. The produced
materials were naturally cooled to room temperature under nitrogen
protection, and then they were grinded with a grinder for 4 h to pro-
duce fine particle sized SugBCs. The SugBCs obtained at pyrolysis
temperature of 700, 800, and 900 °C were denoted as SugBC700,
SugBC800, and SugBC900, respectively. Biochars derived from corn
husks (CHBC900) and pine needles (PNBC900) were obtained by pyr-
olysis at 900 °C using the same method.
The cobalt oxide (Co3O4) powders were prepared by thermal de-
composition of Co(NO3)2 at 500 °C for 2 h [35], and the Fe3O4 magnetic
particles were obtained by coprecipitation method according to the
previous reports [36]. Magnetic biochar (Mag-SugBC900) was prepared
according to our previous study [25].
2.3. Catalytic removal of organic pollutants
For degradation of BPA, 50 mg of SugBCs were suspended in a
100 mL of BPA (20 mg/L in ultrapure water) solution, and then 100 mg
L. He, et al.
Fig. 1. (A) SEM, (B) Size distribution and (C) TEM images of (a) SugBC700, (b) SugBC800 and (c) SugBC900, respectively.
of PMS was added to initiate the reaction. The reacting solution was
incubated in a full-temperature air bath shaking incubator with shaking
speed of 200 rpm.
At specific time intervals, 0.5 mL of the reaction solution was
sampled and the reaction was stopped by immediately addition of
0.5 mL of methanol as the quenching agent. And then it was filtered
using a 0.45 μm cut-off sized filter membrane for the following quan-
titative analysis.
To reuse the catalyst, the catalyst was collected by centrifugation of
the reacting solution at 10000 rpm for 3 min, followed by thorough
washing with deionized water and drying in a vacuum oven.
For real environmental water treatment, the tap water (TW) from
our laboratory, lake water (LW) from the vicinity of the South Lake
(Changchun, China) and municipal wastewater (MW) from the sewage
treatment plant (Songyuan, China) without any pretreatment were
spiked with 20 mg/L of BPA, 20 mg/L of phenol, 100 mg/L of MO and
10 mg/L of RhB, individually. And they were treated by the SugBC900
and PMS. All experiments were performed in triplicate to ensure the
accuracy.
2.4. Analytical methods
The BPA and phenol concentrations were determined using the high
performance liquid chromatography system equipped with UV–vis de-
tector and a Zorbax SB C18 column (150 × 4.6 mm, particle size of
5 μm, Agilent, USA). For BPA, the detection wavelength was set at
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Chemical Engineering Journal 405 (2021) 126895
280 nm, and the mobile phase was consisted of methanol and water
(65:35, v/v) at a flow rate of 1 mL/min. For phenol, the detection
wavelength was set at 270 nm, and the mobile phase was composed of
acetonitrile and water (50:50, v/v) at a flow rate of 1.0 mL/min.
The RhB and MO concentrations were determined using an UV–vis
spectrophotometer (UV-2450, Shimadzu, Japan), the detection wave-
lengths were set to 464 nm and 554 nm, respectively.
The PMS concentration during the catalytic reaction was de-
termined by an ABTS method according to previous study [37]. The
DMPO was used as spin-trapping agents for detecting SO4•−, •OH, and,
O2•−, and TEMP for detecting 1O2.
The reaction rate was fitted with a pseudo first-order-kinetic model
(Eq. (1)).
ln(C/C0) = -kt (1)
where C0, C and k correspond to the initial concentration of BPA, the
concentration of BPA at certain times, and reaction constant, respec-
tively.
2.5. Electrochemical measurements
The electrochemical property of the SugBCs was investigated with
an electrochemical workstation (Shanghai Chenhua Instrument Co.,
Ltd, China) from CH Instruments. For the preparation of working
electrodes, 2 mg of the SugBCs was dispersed in 1 mL of ultrapure water
containing 0.5 μL of HCl (1 M), and then ultrasonically dispersed for
L. He, et al.
1 min to form a suspension, then 6 μL of it was deposited on a well
polished glassy carbon electrode with a diameter of 3 mm, and in-
cubated for 40 min under an ambient condition [33]. Ag/AgCl elec-
trode and a platinum wire were used as reference and counter elec-
trodes, respectively. The linear sweep voltammetry (LSV) was
conducted at the potentials of −1.0–1.0 V with the scan rate of 50 mV/
s, and the chronoamperometry was carried out at an applied potential
of 0.0 V by using 50 mM Na2SO4 as the electrolyte. The cyclic vol-
tammetry (CV) and electrochemical impedance spectroscopy (EIS)
measurements were conducted in a 5 mM K3Fe(CN)6 solution con-
taining 0.1 M KCl.
3. Results and discussion
3.1. Physicochemical properties of SugBC catalyst
By changing the pyrolysis temperatures, three types of SugBC cat-
alysts (SugBC700, SugBC800 and SugBC900) were obtained. The cat-
alytic properties were mostly related to the characteristics of the cata-
lysts, so various physicochemical properties of the SugBCs were
investigated.
The morphology of SugBCs was analyzed by SEM. As shown in
Fig. 1A, all SugBCs were irregularly shaped, and the particle size be-
came smaller as pyrolysis temperature was increased from 700 °C to
900 °C. This should be due to that SugBC obtained at 900 °C contains a
larger amount of carbon with a graphite structure compared to the
other two samples, which could be more easily pulverized during the
same grinding process. From the size distribution obtained by the laser
diffraction particle size analyzer (Fig. 1B). it was found that the particle
size became smaller as the increment of the pyrolysis temperature. The
particle sizes in the range of 0.02–2.0 μm for SugBC700, SugBC800 and
SugBC900 were 4.12%, 50.56% and 84.35%, and average particle sizes
were 29.74, 1.96 and 0.81 μm, respectively. Smaller particle size
property would contribute to larger surface area and exposure of more
catalytic sites for efficient catalytic oxidation reaction [38].
The change of structural property was analyzed by TEM. As pre-
sented in Fig. 1C, the biochar pyrolyzed at 700 °C (SugBC700) showed
disordered carbon, while SugBC900 presented more ordered carbon
structure, indicating that with the increase of pyrolysis temperature, the
biochar structure would change from disordered channel to highly or-
dered one. This also suggested that at the higher pyrolysis temperature,
the more reversible pore structure in the SugBC could be produced due
to the presence of graphene sheets with parallel arrangement [39].
The element composition, pore size, and surface area of the SugBCs
were also analyzed. As indicated in Table 1, the C contents of three
types of SugBCs were all around 80%, indicating a high degree of
carbonization of SugBCs, and the O contents were gradually decreased
as the pyrolysis temperatures became higher. From the nitrogen ad-
sorption–desorption isotherm of SugBC900 (Fig. 2A), it was found the
type IV isotherms with H2 hysteresis loops and capillary condensation
occurred at the relative pressure (P/P0) of 0.4–0.6, suggested the
SugBC900 has the mesoporous structure, which was in accordance with
Table 1
Physicochemical properties of the obtained SugBCs.
BC types
SugBC700 SugBC800 SugBC900
C (%) 80.63 81.66 80.16
O (%) 11.12 9.45 8.64
H (%) 2.47 1.75 1.26
O/C 0.14 0.12 0.11
BET Surface Area (m2 g−1) 26.53 34.38 602.52
Pore volume (cm3 g−1) 0.050 0.056 0.274
Average pore size (nm) 6.460 7.485 1.764
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Chemical Engineering Journal 405 (2021) 126895
TEM analysis. As illustrated in Fig. 2B and Table 1, the average pore
size of SugBC900 (1.764 nm) was smallest compared to the SugBC700
(7.485 nm) and SugBC800, which was due to a relatively higher pyr-
olysis temperature could produce more narrow mouthed pores [39,40].
However, the surface area and pore volume of SugBC900 (602.52 m2
g−1, 0.274 cm3 g−1) were significantly larger than that of SugBC700
(26.53 m2 g−1, 0.050 cm3 g−1) and SugBC800 (34.38 m2 g−1,
0.056 cm3 g−1). This is related to the volatilization of more gas mole-
cules at higher carbonization temperature [41] and smaller size of
biochar could produce larger surface area. which could facilitate the
mass transfer and expose more catalytic sites to activate PMS for pol-
lutants removal. It was also found the surface area of SugBC850
(172.27 m2 g−1) was larger than SugBC800 and smaller than
SugBC900, and the surface area of SugBC700 could be greatly enlarged
to 572.36 m2 g−1 by further pyrolysis of the SugBC700 at 900 °C (Fig.
S1), suggested that the surface area of biochar was greatly affected by
the pyrolysis temperature.
The crystal structural property of the SugBCs prepared at different
pyrolysis temperatures was evaluated by the XRD analysis. As presented
in Fig. 2C, the three types of SugBCs (BC700, SugBC800 and SugBC900)
all had the broad peaks at approximately 2θ = 25° that attributed to the
(0 0 2) crystal planes of parallel stacked graphene sheet [42], suggested
that the SugBCs contain graphitized structures. There were also dif-
fraction peaks at 2θ = 43.2° that are corresponded to the (1 0 0) crystal
plane of sp2 carbon with honeycomb structure [39]. It was noticed the
peak of SugBC900 was a little sharper than that of SugBC700 and
SugBC800, meaning higher graphitization degree and more sp2 carbon
content of SugBC900 than others, by which high efficiency PMS acti-
vation for pollutant degradation could be enabled.
The graphitization property of the SugBCs was also accessed by the
Raman spectrometry. As presented in Fig. 2D, the D band at 1320 cm−1
represented the defects and heteroatoms of disordered sp2 hybrid
carbon in the graphite lattice, and the G band at 1594 cm−1 referred to
the crystalline graphite carbon in the SugBCs [35]. The ID /IG value of
SugBC900 (0.96) was higher than that of SugBC700 (0.84) and
SugBC800 (0.88), indicating more defects in carbon lattice produced
with pyrolysis temperature of 900 °C, which was consistent with the
XRD analysis. For carbon materials, the key factor determining the
heterogeneous electron transfer rate is the state of electronic density ,
which comes from the defect density of carbon materials [43]. The high
defect density property of SugBC900 would lead to higher electron
transfer rate, thus an enhanced catalytic performance would be an-
ticipated.
The functional groups of SugBCs were characterized with the FTIR.
As shown in Fig. 2E. the three types of SugBCs all presented peaks at
1574 and 1110 cm−1 corresponding to aromatic C = C (sp2 carbon)
stretching, and 3424 cm−1 to the stretching of –OH [34,39]. It was
noted that the peak intensities of aromatic C = C were increased with
the elevation of pyrolysis temperatures, suggesting higher temperature
would result in increment of the sp2 content in the final structure of
biochar, which was consistent with XRD analysis.
XPS analysis was also performed to analyze the carbon forms in
different SugBC samples. As displayed in Fig. S2, as pyrolysis tem-
peratures higher, the peak of 284.4 eV responsible for the sp2 hybrid
carbon was increased from 26.49% (SugBC700) to 47.83% (SugBC900),
and the peak of 285.0 eV responsible for sp3 hybrid carbon decreased
from 50.99% (SugBC700) to 31.03% (SugBC900), demonstrated that
pyrolysis at high temperature would improve the sp2 hybrid carbon
content, which was consistent with the former characterization results
(Fig. 2C and E). The surface charges of the SugBCs were also analyzed.
As shown in Fig. S3, surfaces of both SugBC700 and SugBC800 were
positively charged, and the potential change amplitude was small under
different pHs. Instead, the surface of BC900 was negatively charged at
pHs of 1.0–11.0.
L. He, et al.
Fig. 2. (A) Nitrogen adsorption–desorption isotherms, (B) Pore diameter distribution, (C) XRD, (D) Raman, and (E) FTIR spectra of SugBC700, SugBC800 and
SugBC900, respectively.
3.2. Catalytic degradation of BPA by SugBC
The ability of the three types of SugBCs for activating PMS for de-
gradation of BPA was investigated by treating BPA (20 mg/L) with the
SugBCs (0.5 g/L) and PMS (1.0 g/L) in ultrapure water (pH 7.0) at
25 °C. As indicated in Fig. 3A, the BPA removal efficiency by only PMS
was very low (5.4% in 180 min). When the BPA was treated using PMS
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Chemical Engineering Journal 405 (2021) 126895
together with the SugBCs, the removal ability was greatly improved,
suggested that PMS alone could not effectively degrade BPA, but it may
catalytically be activated by the SugBCs and benefit to the fast and
efficient BPA degradation. It was interestingly found that, with the
SugBC700 and SugBC800 the BPA degradation efficiencies in 180 min
of reaction were 18.5% and 28.7%, respectively, however, with the
SugBC900, the degradation efficiency reached to 93.7% in 30 min, and
L. He, et al.
Fig. 3. (A) BPA removal and (B) PMS decomposition by SugBC700, SugBC800 and SugBC900. Reaction conditions: [SugBCs] = 0.5 g/L, [PMS] = 1.0 g/L,
[BPA]0 = 20 mg/L, [pH] = 7.0, [Temperature] = 25 °C.
100% in 60 min. These results demonstrated that the three kinds of
SugBCs coupled with PMS all can degrade BPA, and among them
SugBC900 have the highest activation ability.
To realize whether the adsorption can contribute to the removal of
BPA, the BPA was treated with the same amounts of only SugBCs, and
found that the removal efficiencies by SugBC700, SugBC800, and
SugBC900 were 9.52%, 3.92%, and 3.55% in 60 min, respectively (Fig.
S4), suggested very low or neglectable adsorption removal abilities of
the SugBCs toward BPA.
The activation ability of SugBCs toward PMS was also investigated
by treating PMS with SugBCs for 180 min at 25 °C, and measuring the
residual amounts of PMS. As presented in Fig. 3B, the PMS could be
decomposed by the SugBC900 with the decomposition efficiency of
58.7%, which was much higher than by SugBC700 (8.1%) and
SugBC800 (17.5%). The abilities of three kinds of SugBCs for PMS de-
composition were consistent with that of BPA degradation. This result
suggested the SugBC900 presenting far greater BPA degradation ability
is due to its higher catalytic activation effect toward the PMS by su-
perior characteristics of the SugBC900 such as the high leveled gra-
phitization degree, more sp2 carbon content, and significantly large
surface area (Fig. 2C, Table 1).
3.3. Factors affecting catalytic reaction of SugBC900
The catalytic activity of SugBC900 toward PMS for BPA degradation
can be affected by various factors. So BPA degradation profiles at var-
ious conditions including concentrations of BPA, PMS, and SugBC900,
reaction temperature and pH, were investigated.
3.3.1. Influence of BPA concentration
As shown in Fig. S5A and B, the BPA degradation efficiencies were
varied depending on the concentrations of BPA. When initial con-
centration of BPA was 20 mg/L, 100% of BPA could be removed within
60 min, while the removal efficiencies reached 68.2% and 39.1% for
the BPA concentrations of 40 mg/L and 60 mg/L, respectively. And the
reaction rate constants were 0.126, 0.056, and 0.026 min−1 for BPA
concentrations of 20, 40, and 60 mg/L, respectively.The reduced de-
gradation rate should be due to that high concentration of BPA solution
may occupy the catalytic active sites of the SugBC900, and block the
contact with the sulfate oxidant, resulting in reduction of the oxidized
species in the reaction solution.
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Chemical Engineering Journal 405 (2021) 126895
3.3.2. Influence of PMS concentration
As presented in Fig. S5C and D, the performance of BPA (20 mg/L)
degradation was also affected by PMS concentrations. When the PMS
concentrations were changed from 0.4 to 0.7, 1.0 and 1.3 g/L, the re-
action rate constants became higher from 0.096 to 0.106, 0.126 and
0.137 min−1, respectively, indicating the SugBC900 possesses abun-
dant catalytic active sites. Also suggested that the higher concentration
of PMS will lead to production of more amounts of oxidized active
species resulting in the faster degradation of target pollutant. When
1.0 g/L of PMS was used, the BPA removal efficiency could reach 100%
in 60 min (Fig. S5C), so this concentration was used in the following
experiments.
3.3.3. Influence of SugBC900 concentration
The profile of BPA degradation depending on the change of
SugBC900 dosage was investigated. As shown in Fig. S5E and F, the
BPA (20 mg/L) removal efficiency reached 46.26%, 85.01%, and 100%
in 60 min by using 0.1, 0.3, and 0.5 g/L of SugBC900, respectively, and
efficiency of 100% was achieved in 15 min with 0.7 g/L of SugBC900,
suggesting BPA removal ability was improved as increment of the
SugBC900 dosage. The reaction rate constants were also elevated from
0.022 to 0.345 min−1 as the increment of the SugBC900 concentrations
from 0.1 to 0.7 g/L, which is because more amounts of the SugBC900 in
the solution could provide more catalytic sites for PMS activation and
enable more fast and efficient degradation of BPA. Although 0.7 g/L of
SugBC900 presented faster reaction rate than that of using 0.5 g/L,
since both two could completely degrade BPA in short time, the con-
centration of 0.5 g/L was used in the following study.
3.3.4. Temperature effect
The BPA degradation profiles at various temperature conditions
were accessed by treating 20 mg/L of BPA with 0.5 g/L of SugBC900
and 1.0 mg/L of PMS at pH of 7.0. As shown in Fig. 4A, the BPA could
be efficiently degraded at various temperature conditions. When the
temperatures were 25 °C, 35 °C and 45 °C, the BPA removal efficiencies
could all reach 100% in 60 min of reaction. And even at the low tem-
perature of 10 °C, the removal efficiency could reach 94.7%. The re-
action rate constants were found to be increased from 0.060 to
0.150 min−1 as the temperatures became higher from 10 to 45 °C
(Fig. 4B) that is related to the activation capacity of heat treatment
[44]. The activation energy (Ea) of BPA degradation by SugBC900 and
PMS was 38.49 kJ/mol as calculated by the Arrhenius equation with the
linear regression coefficient of 0.995 between ln(K) and 1/T. This was
L. He, et al.
Fig. 4. Effects of (A, B) reaction temperature and (C, D) initial pH values on BPA removal.
lower than that of other catalysts coupled with PMS for BPA degrada-
tion (Table S1), suggesting that SugBC900 has an excellent ability to
activate PMS for pollutants degradation. Overall, the ability of BPA
degradation at such broad temperature conditions, especially even at
the low temperature, is beneficial for the in-situ water remediation in
field.
3.3.5. pH effect
The profile of BPA degradation depending on the various pH con-
ditions was accessed by treating 20 mg/L of BPA with the SugBC900
(0.5 mg/L) and PMS (1.0 g/L) at room temperature. As illustrated in
Fig. 4C, after 60 min reaction, the BPA degradation efficiency could
reach 95.2% when pH was 3.0, and when the pHs were 5.0, 7.0, and
9.0, 100% of BPA could be degraded within 60, 50, and 40 min. Even at
the strong acidic (pH = 1.0) and alkali (pH = 11.0) conditions, the
BPA could be effectively degraded with efficiencies of 91.7% in 60 min
and 100% in 15 min respectively. This suggested SugBC900 together
with PMS could effectively degrade BPA at all range of pHs from 1.0 to
11.0, such robustness property is significantly advantageous in treat-
ment of complicated wastewater.
From Fig. 4D, it was also noted that the BPA degradation rates be-
came faster (0.086 to 0.238 min−1) as the pH values became higher.
This is because higher leveled hydroxide ions in the alkali solution can
activate PMS for BPA degradation [45], and the higher concentration of
hydrogen ions in the acidic solution can remove oxidative species in-
cluding sulfate and hydroxyl radicals [17]. In addition, because the
surface of SugBC900 is negatively charged according to zeta potential
analysis (Fig. S3), and the pHzpc of BPA is 9.73 [29], so the hydrogen
ions and the plus charged BPA might competitively adsorb to surface of
7
Chemical Engineering Journal 405 (2021) 126895
the negative charged SugBC900 catalyst, occupying the active sites and
reducing the degradation rate.
3.4. Catalytic mechanism
3.4.1. Characterization of oxidizing species
In PMS catalyzed reaction, the sulfate (SO4•−) and hydroxyl radical
•
( OH) are usually the major oxidizing species that degrade pollutants,
and the singlet oxygen (1O2) and the superoxide radical (O2−•) may also
play important roles in the activation of PMS by non-metallic carbo-
naceous catalysts. To confirm the main oxidizing species generated by
the SugBC900 and PMS during BPA degradation, the EPR analysis was
performed by using the DMPO and TEMP as the chemical scavengers to
trap the oxidizing species.
As presented in Fig. 5A, the presence of DMPO adducts at weak
strength, suggested that SO4•− and •OH were generated. When the
DMPO capture experiment was performed in a methanol solution, the
DMPO-O2−• adduct signal also appeared in the EPR spectrum. To fur-
ther prove the generation of O2−•, NBT was used as the qualitative
indicator as it could be reduced by O2−• (k = 5.88 × 104 M−1 s−1),
and the existence of O2−• could be verified by the absorbance change of
NBT at 259 nm [46]. As shown in Fig. S6, the typical absorption peak of
NBT in the catalytic reaction system was decreased in 60 min, which
demonstrated the existence of O2−•. The presence of singlet oxygen in
the catalytic reaction was evaluated with TEMP as the spin capture
reagent. As shown in Fig. 5B, there generated strong signals with the
relative intensity ratio of 1: 1: 1 in the EPR spectra, which corresponded
to the TEMP-1O2 adduct. These results suggested that 1O2 and O2−•
were produced during the process of catalytic reaction.
L. He, et al.
Fig. 5. EPR spectra obtained using (A) DMPO and (B) TEMP as spin-trapping agent, (C) BPA removal and (D) reaction rate by using SugBC900/PMS system in the
presence of different scavengers. Reaction conditions: [SugBC900] = 0.5 g/L, [PMS] = 1.0 g/L, [BPA] = 20 mg/L, [Temperature] = 25 °C, [EtOH] = 100 mM, [p-
BQ] = [L-his] = 24 mM, [DMPO] = [TEMP] = 80 mM, [pH] = 7.0. The control experiment was conducted without the addition of scavenger.
To realize main contributions of the different kinds of oxidative
species in the catalytic reaction for BPA degradation, the quenching
assay was performed by using ethanol (EtOH), L-histidine (L-his), and
p-benzoquinone (p-BQ) as the quenchers for SO4•− and •OH, 1O2, and
O2−•, respectively [46]. As shown in Fig. 5C and D, after treating with
quenchers the BPA degradation abilities were all lowered than the
control. In response to the EtOH, L-his, and p-BQ, the degradation ef-
ficiencies in 60 min were dropped to 92.7%, 51.9%, and 49.2%, and the
reaction rate constants also decreased to 0.065, 0.036, and 0.032 min-1,
respectively. This indicated that L-his and p-BQ had relatively stronger
inhibitory effect on the degradation of BPA (Fig. S6), while the influ-
ence of EtOH was weaker, this suggested SO4•−, •OH, 1O2, and O2−• are
all responsible for catalytic degradation, and among them, contribu-
tions by 1O2 and O2−• are dominant.
3.4.2. Electrochemical property analysis
Generally, the ability of catalyst for degradation of pollutants by
PMS activation are usually related to the electrochemical property of
the catalyst [47], this is because the catalytic reaction involves the
electron transfer between catalyst, PMS and target pollutants. There-
fore, the electrocatalytic properties of the sugarcane derived biochars
were evaluated by measuring CV, EIS in 5 mM K3Fe(CN)6 and 0.1 M KCl
solution.
As shown in the CV (Fig. 6A), the redox peak at around 0.27 V with
the SugBC900 (81.0 μA) modified electrode was much higher than that
of SugBC700 (46.83 μA) and SugBC800 (30.7 μA). The resistance
8
Chemical Engineering Journal 405 (2021) 126895
property of the SugBC was also accessed by EIS (Fig. 6B), in which, the
obtained Nyquist diagram showed a semicircle in the high frequency
region and a linearity in the low frequency region, which corresponded
to the electron transfer resistance (RCT) and the diffusion limit process
The RCT for SugBC900 was 22 Ω that was 13.5 and 5.6 times lower than
that of SugBC700 (297 Ω) and SugBC800 (124 Ω), respectively. These
results suggested that SugBC900 has superior conductivity and electron
transferring ability than the others, which would contribute to sig-
nificantly promoting the performance of PMS activation for efficient
pollutant degradation.
The charge transfer property between PMS and SugBCs was in-
vestigated by monitoring chronoamperometric responses of the su-
garcane SugBC electrode after sequential addition of PMS (1.0 g/L) and
BPA (20 mg/L) to the Na2SO4 solution. As shown in Fig. 6C, after ad-
dition of PMS, the currents were abruptly changed, suggesting that the
surfaces of PMS and SugBCs are likely to undergo electron transfer
through the formation of charge transfer complexes while SugBC may
serve as the mediator [1]. The current shift for SugBC900 (60.5 μA) was
much larger than that of SugBC700 (3.6 μA) and SugBC800 (32.54 μA),
that is due to the superior electron transfer ability of the SugBC900
enabled more efficient activation reaction between SugBC and PMS.
Subsequently, after addition of BPA, another current shift was observed
by SugBC900 electrode that should be due to the electron transfer from
BPA to the complex of SugBC and PMS. The current shift in response to
BPA were none or lower with SugBC700 and SugBC800 electrodes,
respectively, that is because of the lower electron transfer ability.
L. He, et al.
Fig. 6. (A) Cyclic voltammetric and (B) electrochemical impedance spectro-
metric profiles, and (C) i-t profiles of SugBC700, SugBC800 and SugBC900
modified GCE.
According to the LSV analysis in the Na2SO4 solution (Fig. S7), with
the elevation of PMS concentrations from 1.0 to 10.0 g/L, the current
responses by the SugBCs were all increased, and current response by
SugBC900 was greatly higher than by SugBC700 and SugBC800, which
was consistent with the previous results (Fig. 6C), and demonstrated
excellent catalytic activity of SugBC900 to PMS. It was concluded that
SugBC900 with higher electron transfer ability and catalytic activity
can be used as a super effective PMS activator, thus significantly im-
proving the catalytic performance in degradation of organic pollutants.
9
Chemical Engineering Journal 405 (2021) 126895
3.4.3. The main active structure for PMS activation
The catalytic performance of the biochar should be greatly related
to the structural properties of the biochar. To investigate relation be-
tween the structural properties and the catalytic degradation perfor-
mance of the SugBC900, the change of various physical and chemical
properties of SugBC900 after first time use for BPA degradation was
pursued.
From the FTIR analysis shown in Fig. S8A, after the first use, the
characteristic peak intensity of the aromatic C = C (sp2 carbon) func-
tional groups at 1574 and 1110 cm−1 were significantly weakened
compared to that of the fresh SugBC900, indicating that it may act as an
effective activation structure for PMS activation. As illustrated in the
C1s spectra of XPS (Fig. 7A and B), after the first time use, the peak of
284.4 eV responsible for the sp2 hybrid carbon was decreased from
47.83% (fresh SugBC900) to 40.62%, and the peak of 285.0 eV re-
sponsible for sp3 hybrid carbon increased from 31.03% (fresh
SugBC900) to 39.79%. This suggested that the portion of sp2 hybrid
carbon structure in the biochar would be responsible for high catalytic
activity of the SugBC900 catalyst, which can effectively activate PMS
and produce oxidation active species to degrade BPA. It is known that
the contents of sp2 hybrid carbon and sp3 hybrid carbon in the biochar
correspond to contents of the graphite carbon and the disordered
carbon, respectively [47]. The decrease of sp2 hybrid carbon content
represents the decrease of graphitization degree of biochar, which
makes it difficult to transfer electrons, and the ability of activating PMS
to produce oxidized species for BPA degradation would be also reduced.
The decrease of graphitization degree was also analyzed by Raman
spectroscopy. As illustrated in Fig. S8B, the relative intensity ratios of D
and G bands (ID/IG) were 0.96 and 0.91 for fresh SugBC900 and the
used SugBC900, respectively, suggested that the graphitization degree
of biochar decreased after the catalytic reaction, which was consistent
with XPS analysis.
From the BET analysis presented in Fig. S8C, the surface area of the
used Sug900 has decreased from 602.52 m2 g−1 to 133.25 m2 g−1. This
is possibility due to the adsorption of the intermediate products pro-
duced in the system to the surface of the biochar, that would result in
decrease of the available catalytic sites.
According to the above results, the catalytic mechanism of BPA
degradation using SugBC900 together with PMS can be realized
(Scheme 1). There should be two pathways coexist in the SugBC900
based catalytic reaction. One is the radical reaction that was mediated
by SO4•−, •OH and O2−•, and the other one is the non-radical catalytic
pathway mediated by 1O2. The oxidation reaction of 1O2 and O2−•
generation is the prevailing pathway, while the formation of SO4•− and
•
OH is the recessive pathway. It has been reported that the catalytic
performance of carbon materials is closely related to the surface func-
tional groups such as hydroxyl and carboxyl groups [48]. BC and sur-
face oxygen-containing functional groups can act as electron transfer
media and activation sites [49], react with PMS to produce sulfate ra-
dical, which then reacts with water molecules to form hydroxyl radical
[50]. In this study, the oxygen content of SugBC900 was only 8.64%
(Table 1), indicating that most of the oxygen containing functional
groups were removed at high temperature. At the same time, FTIR also
confirmed that there were only a small amount of hydroxyl functional
groups. Therefore, less sulfate radical and hydroxyl radical would be
produced.
Combined with quenching experiment and EPR analysis, superoxide
radical and singlet oxygen play a leading role in BPA degradation,
which indicates that SugBC900 may react with dissolved oxygen in
solution and transform to superoxide radical. As the reaction solution is
acidic (pH nearly 4.0) after adding PMS, superoxide radical will react
with hydrogen ion to form singlet oxygen (Eqs. (2)–(4)). Also, the an-
ionic radicals of PMS (SO5•−) may be generated by electron transfer
from PMS to SugBC900, and then SO5•− react with water molecules to
form singlet oxygen (Eqs. (5)–(6)). Moreover, sp2 hybrid carbon
structure was likely to be the main active site participating in the
L. He, et al. Chemical Engineering Journal 405 (2021) 126895

Fig. 7. C1s XPS of (A) fresh SugBC900 and (B) 1st used SugBC900.

activation process of PMS according to the XPS and FTIR analysis, including p-Isopropenylphenol, 2,4-ditert-butylphenol, benzoquinone,
combined with large surface area and high electron transfer property of hydroquinone and phenol were identified. On this basis, two pathways
SugBC900, enhanced reaction rate and high performance of BPA de- for BPA degradation were proposed (Fig. S9). On the one hand, BPA is
gradation could be endowed. attacked by reactive species via breaking C–C bond, and leading to
formation of p-Isopropenylphenol and phenol, then the p-Iso-
O2 + SugBC900 → SugBC900+ + O2−• (2)
propenylphenol is further oxidized to p-hydroquinone through the hy-
2H +
+ O2−• + O2−• 1
→H2O2 + O2 (3) droxylation process. Subsequently, benzoquinone is generated through
−• • + 1 −
the oxidation of phenol and p-hydroquinone. On the other hand, the
O2 + OH + 2H → O2 + OH (4) BPA is firstly oxidized by the reactive oxygen species, generating iso-
HSO5− + SugBC900 → SO5•− +H +
(5) propenylphenol radicals, which would couple with BPA and further
decompose into 2,4-ditert-butylphenol and phenol, and phenol would
2SO5•− + H2O → 2HSO4− + 1.5 O21
(6) be transformed into benzoquinone. In addition, ring-opened inter-
mediates, such as oxalic acid, formic acid, acetic acid and alkane may
also produce and could be mineralized into CO2 and H2O.
3.5. Intermediates and pathway of BPA degradation

To realize the process of BPA degradation by SugBC900 and PMS, 3.6. Reusability of SugBC900 for catalytic degradation of BPA
the intermediates produced during degradation reaction were analyzed
by the GC–MS. After 60 min of catalytic reaction, the byproducts It is meaningful for the catalyst to have good reusability in terms of

Scheme 1. Schematic illustration of the synthesis of SugBC900 and proposed mechanism of BPA degradation by SugBC900 and PMS.

10
L. He, et al. Chemical Engineering Journal 405 (2021) 126895

Fig. 8. (A) Degradation kinetic (inset: reaction rate profile) and (B) removal efficiency of phenol (20 mg/L), MO (100 mg/L) and RhB (10 mg/L) using SugBC900/
PMS system in different types of water samples. Reaction conditions: [SugBC900] = 0.5 g/L, [PMS] = 1.0 g/L, [BPA]0 = 20 mg/L, [Temperature] = 25 °C. (C)
Degradation kinetic and (D) reaction rate of SugBC900-catalyzed oxidation of BPA in comparison to MWCNT, GO, CHBC900 and PNBC900. Reaction conditions:
[cata] = 0.5 g/L, [PMS] = 1.0 g/L, [BPA]0 = 20 mg/L, [pH] = 7.0, [Time] = 60 min, [Temperature] = 25 °C.

reducing cost. The reusability of the SugBC900 catalyst was in-
vestigated by repeated treating of BPA (20 mg/L) with SugBC900
(0.5 g/L) and PMS (1.0 g/L). As shown in Fig. S10, at the first time use
of SugBC900, the BPA could be completely degraded within 60 min,
and at the second and third time usages, the removal efficiencies were
81.58%, 57.63%, respectively. At the fourth and fifth times usages, the
removal efficiencies (38.53% and 10.11%) were less than 50%. The
decrease in BPA removal efficiency may be due to decrement of the sp2
hybrid carbon, and increment of the sp3 hybrid carbon that can not
produce enough oxidizing species and it may also be due to the ad-
sorption of by products on the catalyst and the reduction of effective
active centers for PMS activation [51].
The regeneration ability of the biochar catalyst was evaluated by
anaerobic heat treatment (900 °C) of the catalyst after fifth reuse. And
found the BPA degradation efficiency by the regenerated SugBC900
could recovered to more than 89%, which would be due to the partial
recovery of carbonization and removal of possible impurities attached
on the catalyst surface at high temperature.
3.7. The effect of anions and natural organic matters on catalytic
degradation of BPA
humic acid are the typical inhibitors that may possess the ability of
radical trapping and competitive adsorption [52], so influences of such
reagents were investigated.
As illustrated in Fig. S11, when 20 mM of SO42−, H2PO4−, HCO3−,
Cl− and 20 mg/L of humic acid were coexisted with 20 mg/L of BPA,
the BPA degradation efficiencies were 100%, 97.23%, 87.64%, 99.39%,
and 93.96%, respectively. This indicated that the influences by SO42−,
H2PO4−, and Cl− were negligible. Although the Cl− was reported to
react with SO4•− and •OH (Eq. (7) and (8)) and inhibit relating catalytic
reaction [53], but in the SugBC900 based catalytic reaction, the role of
SO4•− and •OH are minor, instead 1O2 and O2−• are the major oxidizing
species (Fig. 5), so the BPA degradation was rarely effected by the Cl−.
However, with the presence of HCO3− the BPA degradation efficiency
dropped 12.36% than the control (100%) that is due to the reaction of
HCO3− with the SO4•− and •OH and producing H+, which may gen-
erate radical scavenging effect and make the pH of solution lowered
(Eq. (9) and (10)). The lower pH would result in reduced BPA de-
gradation efficiency (Fig. 4C and D). The humic acid as a typical natural
organic materials resulted in about 6% drop of BPA degradation effi-
ciency that is because of the competitive reaction with the reactive
species, this is similar with the results reported previously [54].

Cl− + SO4•− ↔ Cl• + SO42− (7)

Considering the complexity of environmental water, the effect of
− • •−
some typical anions and natural organic matters on catalytic degrada- Cl + OH ↔ ClOH (8)
tion of BPA should be concerned. SO42−, H2PO4−, HCO3−, Cl− and

11
L. He, et al. Chemical Engineering Journal 405 (2021) 126895

HCO3− + SO4•− → SO42− + CO3•− + H+ (9) Table 2

Structural and electrochemical properties of various catalyst.
HCO3− •
+ OH → H2O + CO3•− (10)
Samples Ipa (μA) Rctb (Ω) ID/IGc Surface aread (m2 g−1) sp2 contente

SugBC900 81.0 22 0.96 602.52 47.83%

3.8. BPA degradation in real environmental water PNBC900 49.9 89 0.92 182.19 40.26%
CHBC900 31.8 102 0.90 121.68 34.64%
The performance of BPA degradation in real environmental water MWCNT 52.1 64 1.01 100 38.08%
was conducted by spiking tap water (TW), lake water (LW) and muni- GO 30.4 135 0.82 42 28.88%

cipal water (MW) samples with 20 mg/L of BPA, and treating with
SugBC900 (0.5 g/L) and PMS (1.0 g/L). As illustrated in Fig. S12, after
60 min reaction in water samples of TW, LW and MW, 86.72%, 82.91%
and 65.22% of BPA removals were achieved, respectively. During the
experiment, TOC can be used to characterize the mineralization of BPA.
Fig. S11B shows the TOC removal efficiency in different water en-
vironments, As the time pass, the removal efficiency of TOC has in-
creased. After 3 h, the removal efficiency increased from 60.44% to
90.33% in DW, 54.13% to 82.52% in TW, 47.12% to 74.41% in LW, and
37.75% to 69.55% in MW, respectively. The decrease in removal effi-
ciency in the real water may be due to the presence of various anions
and organics that occupy the active sites of catalysts and react with free
radicals [55]. However, the occurrence of BPA mineralization indicates
that part of the BPA was oxidized to carbon dioxide during the ex-
periment. At the same time, the relatively high degree of mineralization
in various water environments means that the SugBC900 based PMS
activation method has a good application prospect in the restoration of
real organic polluted water bodies.
3.9. Catalytic degradation of other pollutants with SugBC900 and PMS
The catalytic degradation abilities of SugBC900 and PMS toward
other organic pollutants including phenol, methyl orange (MO) and
Rhodamine B (RhB) were accessed. As presented in Fig. 8A, phenol
(20 mg/L) and MO (100 mg/L) could be completely removed within
30 min and 60 min, the removal efficiency for RhB (10 mg/L) could
reach 92.6% in 60 min. The degradation reaction rates of phenol, MO
and RhB were 0.296, 0.235 and 0.107 min−1, accordingly. In real en-
vironmental water, satisfactory degradation performance in these or-
ganics polluted water was also achieved (Fig. 8B). It could be concluded
that the sugarcane SugBC900 and PMS based catalytic oxidation
method showed wide adaptability in the complex environments and
offered a promising prospect in the water treatment contaminated by
organic pollutants.
3.10. Comparison of the SugBC900 with other catalysts
To investigate the catalytic performances of biochar from other
types of biomass, biochars from the corn husks and pine needles were
prepared at 900 °C, and depicted as CHBC900 and PNBC900, respec-
tively. Their catalytic performances were compared with the SugBC900,
and relationship between the structural property and catalytic activity
was evaluated by several characterization methods including CV, EIS,
Raman, BET, and XPS analysis. It was found that the BPA degradation
efficiency and reaction rate using CHBC900 and PNBC900 were 29.4%
and 0.016 min−1, and 39.7% and 0.019 min−1 (Fig. 8C and D), re-
spectively, which were lower than that of using SugBC900 as the cat-
alyst (100% and 0.1259 min−1). From the results by the CV, EIS,
Raman, BET, and XPS analysis (Fig. S13, Table 2), it was noted that the
oxidation current, graphitization degree (ID/IG), surface area, and sp2
hybridized carbon content of SugBC900 (81.0 μA, 0.96, 602.52 m2 g−1,
47.83%) were all higher than that of CHBC900 (31.8 μA, 0.90,
121.68 m2 g−1, 34.64%) and PNBC900 (49.9 μA, 0.92, 182.19 m2 g−1,
40.26%). And the resistance (22 Ω) was also lower than that of
CHBC900 (102 Ω) and PNBC900 (89 Ω). These results suggested that
the catalytic performance of the biochar was greatly related to the
structural properties of the biochar, and the SugBC900 obtained from
a
Determined by CV.
b
Determined by EIS.
c
Calculated by Raman spectra.
d
Determined by BET analysis.
e
Estimated by XPS analysis.
sugarcane has the superior characteristics for the high performance of
catalytic reaction.
The catalytic activity of SugBC900 was also compared to the con-
ventional catalysts including multi-walled carbon nanotube (MWCNT)
and graphene oxide (GO). From the CV, EIS, Raman, and XPS analysis
(Fig. S14, Table 2), it is noticed that the SugBC900 has better electron
transfer ability, higher sp2 carbon content and lower resistance than
MWCNT and GO, but the ID/IG ratio of SugBC900 was lower than that
of MWCNT indicating higher defect degree of MWCNT. Under the same
conditions with the same amounts of catalyst and PMS, the BPA de-
gradation efficiencies and reaction rates with the GO and MWCNT as
the catalysts reached 14.3% and 0.007 min−1, and 64.9% and
0.070 min−1, respectively, which were much lower or slower than that
with the SugBC900 (Fig. 8C and D) that should be related to their
electron transfer abilities and the carbonic structures.
Given the high efficiency of metal catalysts based PMS activating
system, the catalytic performance of SugBC900 was compared to the
metal catalyst. As depicted in Fig. S15. with the same amount of Co3O4
and PMS, 100% of BPA removal could be achieved within 30 min, and
the reaction rate was 0.214 min−1, this enables the maximum activa-
tion of PMS due to the cobalt catalysts [6].
The BPA degradation efficiencies using the Fe3O4 and Fe3O4 mod-
ified SugBC900 (Mag-SugBC900) were 38.2% and 61.4%, and the re-
action rates were calculated to be 0.020 and 0.054 min−1, respectively
(Fig. S15). The incorporation of magnetic nanoparticles to the
SugBC900 is good to separate the catalyst from the solution, but due to
the poor catalytic property of the Fe3O4, the control of the modified
amount of the Fe3O4 is needed to favor the practical use.
Considering the economic feasibility of the catalyst, the cost of the
various catalysts were evaluated. As shown in Table S3, the unit price of
SugBC900 (0.052 $/g) was less than Mag-SugBC900, Fe3O4, Co3O4,
MWCNT and GO suggesting that SugBC900 has better economic bene-
fits than the conventional carbonaceous and metallic catalysts. Al-
though its BPA degradation efficiency is slightly lower than Co3O4, but
SugBC900 should be significantly perspective for broad application in
pollutant degradation in terms of environmental friendliness and cost
effectiveness.
In addition, the performance of catalytic oxidation reaction of
SugBC900 with PMS for BPA degradation was compared with the other
reported advanced oxidation process using modified or non-modified
biochar (Table 3). It was found the proposed SugBC900 catalyst pre-
sented wider range of working pHs (1.0–11.0) and temperatures
(10–45 °C) than other modified or non-modified biochars, suggested the
superior robustness property of the SugBC900 in catalytic degradation
of BPA. These results strongly revealed that the method of pollutant
degradation using the SugBC900 as the catalyst for PMS activation
could be a powerful approach for environmental remediation in terms
of comparable efficiency, robustness and highly cost effectiveness.

12
L. He, et al. Chemical Engineering Journal 405 (2021) 126895

Table 3
Comparison of BPA degradation performances with various biochars as catalysts.
Resource BPA concentration Catalyst and Oxidant Modification Conditions Removal efficiency References

Pine pollen 20 mg/L biochar@CoFe2O4-Ag3PO4 0.5 g/L (MBA-3) CoFe2O4-Ag3PO4 UV 300 W 91.0%, 60 min [56]
Green tea 20 mg/L BC-iron (2 g/L) Iron US 60 W, pH 3.0 97.8%, 80 min [57]
PS (3 mM)
Sawdust 20 mg/L Fe-BC-700 (0.15 g/L) Iron pH 3.0, 5.0, 7.0, 9.0 100%, 15 min [29]
PMS (0.2 g/L)
Banana peels 20 mg/L Fe2O3@BC 0.3 g/L Fe2O3 pH 6.28 100%, 20 min [58]
PS 5 mM
Sewage sludge 10 mg/L SBC-600 0.2 g/L None pH 4.0–11.0 100%, 30 min [59]
PMS 0.1 g/L
Spent coffee 5 mg/L NBC-1000 0.2 g/L Nitrogen pH 4.0 99.0%, 60 min [51]
PMS 0.3 g/L
Rice husk 22.9 mg/L MnO2/BCs 0.5 g/L MnO2 US 130 W pH 7.0 100%, 120 min [60]
H2O2 10 mM
Sugarcane waste 20 mg/L SugBC900 0.5 g/L None pH 1.0, 3.0 90% − 95%, 60 min This work
PMS 0.4–1.0 g/L pH 5.0, 7.0, 9.0, 11.0 100%, 15–60 min

4. Conclusion
A highly efficient organic pollutant degradation method was de-
veloped by using the sugarcane derived pristine biochar (SugBC900) as
the novel catalyst coupled with PMS. The SugBC900 presented excellent
features benefit to catalytic activation such as higher surface area
(602.52 m2 g−1) and sp2 hybrid carbon contents (47.83%), and greater
electron transfer ability than that of the SugBC700, SugBC800 and
other biomass derived CHBC900 and PNBC900. The quenching and EPR
test revealed that the oxidative species of 1O2 and O2•− were dominant
for the catalytic reaction, and the role of the SO4•− and •OH was minor.
The decrease of the sp2 carbon content after catalytic degradation of
BPA was also confirmed. It was likely the sp2 carbon structure of the
SugBC900 be the active site for catalyzing PMS decomposition to de-
grade pollutants. The most significant achievement is fast and highly
efficient BPA degradation ability and the broad pH (1.0–11.0) and
temperature (10–45 °C) conditions for catalytic reaction. The SugBC900
with advantages properties including extremely low cost, highly effi-
cient catalytic activation ability and broad working conditions, would
be significantly perspective for degradation of various organic pollutant
in the complicated practical environment water.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This work was funded by the National Natural Science Foundation
of China (51809111), and the open fund from the Key Lab of Eco-re-
storation of Regional Contaminated Environment (Shenyang
University), Ministry of Education of China (2019_ERRCE_K2).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2020.126895.
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