Chemical Engineering Journal 373 (2019) 1329–1337

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Chemical Engineering Journal

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

Enhanced degradation of paracetamol in water using sulfate radical-based T

advanced oxidation processes catalyzed by 3-dimensional Co3O4 nanoflower
Wan-Chu Yuna, Kun-Yi Andrew Lina, , Wai-Chi Tonga, Yi-Feng Linb, , Yunchen Duc,
⁎ ⁎ ⁎

a
Department of Environmental Engineering, National Chung Hsing University, 250 Kuo-Kuang Road, Taichung, Taiwan
b
Department of Chemical Engineering and R&D Center for Membrane Technology, Chung Yuan Christian University, 200 Chung Pei Rd., Chungli, Taoyuan, Taiwan
c
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, China

HIGHLIGHTS GRAPHICAL ABSTRACT

• Adeveloped
facile but convenient protocol is
to prepare a Co O nano-
3 4
flower (CNF).
• CNF, with needle-like petals, exhibits
tremendous higher surface area and
pore volume.
• CNF shows significantly higher cata-
lytic activities than the commercial
Co3O4 NPs.
• APAP degradation is confirmed to in-
volve with sulfate radicals via EPR
analysis.
• The APAP degradation pathway by
this CNF-activated Oxone is also in-
vestigated.

ARTICLE INFO ABSTRACT

Keywords: Paracetamol (APAP) represents a critical emerging contaminant in various water bodies and sulfate radical
Paracetamol (SO4%−)-involved Advanced Oxidation Processes (AOPs) using Oxone are proven as promising approaches for
Cobalt degrading APAP. While Co3O4 is the benchmark catalyst for activating Oxone, Co3O4 nanoparticles are usually
Oxone found to aggregate severely, losing their catalytic activities. In this study, a facile but convenient protocol is
Sulfate radical
developed to prepare a unique Co3O4 material, which exhibits a morphology of nanoflower. More importantly,
Nanoflower
the flower petals of this Co3O4 nanoflower (CNF) are needle-shaped and comprised of numerous fine Co3O4
particles which are separated, enabling this CNF to exhibit high surface areas and large pore volumes. CNF also
shows significantly higher catalytic activities than the commercial Co3O4 NPs for activating Oxone to degrade
APAP. APAP degradation is confirmed to involve with sulfate radicals via examining effects of radical probe
reagents and EPR analysis. CNF is reusable over several continuous cycles. The APAP degradation pathway is
also investigated according to the degradation products determined using LC-MS/MS. The findings of this study
are valuable to advance treatments of APAP in water by sulfate-radical-based processes, and also insightful to
determine catalytic characteristics of Co3O4 with such a unique morphology of nanoflower.

⁎
Corresponding authors.
E-mail addresses: linky@nchu.edu.tw (K.-Y.A. Lin), yflin@cycu.edu.tw (Y.-F. Lin), yunchendu@hit.edu.cn (Y. Du).

https://doi.org/10.1016/j.cej.2019.05.142
Received 10 January 2019; Received in revised form 22 April 2019; Accepted 21 May 2019
Available online 22 May 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
W.-C. Yun, et al.
1. Introduction
Paracetamol (also known as APAP) is considered as one of the most
consumed non-prescription medicines to treat pain and fever [1], and
thus APAP has been extensively detected in various water bodies as
listed in Table S1 (see the supporting information), including influents
and effluents of wastewater treatment plants, hospital effluents,
groundwater, surface water and so on, ranged from 10 to 134,000 ng/L
[2–7]. Even though removal of APAP from water bodies is crucial, ty-
pical water and wastewater treatments seem impotent for degrading
APAP [8]. Accordingly, several advanced techniques have been devel-
oped to degrade APAP, including Fenton’s reactions [9–11], ozonation
[12], and UV irradiation [13]. Apart from these approaches, recently
SO4%−-involved techniques receive increasing attention for degrading
APAP, as SO4%− possesses several merits, such as high oxidation po-
tentials (i.e., 2.5–3.1 V), high selectivities for unsaturated and aromatic
structures [14,15], and long half-life (∼40 μs) [14,16].
To obtain SO4%−, Oxone reagent is frequently-adopted as Oxone is
environmentally benign [17]. Nonetheless, Oxone requires “activation”
to facilitate generation of SO4%− from Oxone as Oxone is difficult to
self-decompose. While numerous approaches have been proposed to
“activate” Oxone, utilization of metal catalysts for activating Oxone has
been deemed as practical and efficient approaches [18–20]. Hence,
several transition metals have been studied for activating Oxone to
degrade APAP, such as Mn [21,22], Co [22] and Fe [8], etc.
Despite the fact that Mn and Fe are able to activate Oxone, Co has
been validated as the most effective transition metal to activate Oxone
[23,24]. Thus, many efforts have been made to develop Co-based cat-
alysts, especially heterogeneous ones, for activating Oxone to degrade
APAP. To date, Co3O4 has been a longstanding popular Co-based het-
erogeneous catalyst for Oxone activation [18,25]. Many studies even
fabricated Co3O4 nanoparticles (NPs) and anticipated that Co3O4 NPs
may exhibit enhanced catalytic activities for Oxone activation owing to
the nanoscale dimensions of Co3O4 NPs [26,27]. Unfortunately, NPs
agglomerate severely, especially in water, losing their contacting sur-
faces and diminishing catalytic activities [26]. Therefore, it is critical to
develop Co3O4 NPs-based catalysts, which, however, exhibit high sur-
faces and porosities for enhancing their catalytic activities. While Co3O4
can be fabricated into various configurations to achieve high surface
areas and pore volumes, many techniques involve complicated proto-
cols and reagents, such as electrospinning [28], hard-templated and
soft-templated methods [29,30], etc. Thus, it would be even more ad-
vantageous to employ simple processes and reagents to prepare such
Co3O4 materials.
Fig. 1. The preparation scheme for 3-D Co3O4 nanoflower (CNF).
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Chemical Engineering Journal 373 (2019) 1329–1337
In this study, we particularly propose a facile but convenient pro-
tocol to prepare a Co3O4 material, which exhibits a unique morphology
of nanoflower. More importantly, the flower petals of this Co3O4 na-
noflower (CNF) are needle-shaped and comprise of numerous fine
Co3O4 particles which are specially configured to be separated rather
than being aggregated, enabling this CNF to exhibit high surface areas
and large pore volumes. Therefore, CNF should be a promising and
advantageous Co3O4-based heterogeneous catalyst for activating Oxone
to degrade APAP. Especially, as no similar materials have been reported
for APAP degradation, investigation of this study would be valuable to
advance treatments of APAP, and also insightful to probe into catalytic
characteristics of Co3O4 with such a unique morphology of nanoflower.
Additionally, commercial Co3O4 NPs are directly used here for
comparisons with CNF for activating Oxone to degrade APAP, and the
mechanism of APAP degradation by Oxone activated by CNF is in-
vestigated and the corresponding degradation pathway is also de-
termined.
2. Experimental
2.1. Materials
All chemicals in this study were purchased from fine chemical
suppliers and used directly without purification. Paracetamol (APAP),
cobalt sulfate (Co(SO4)2), Oxone, tert-butyl alcohol (TBA) and 5,5-di-
methyl-1-pyrroline N-oxide (DMPO) were received from Sigma-Aldrich
(USA). Co3O4 nanoparticles (50–80 nm) and urea were purchased from
Alfa Aesar (USA). Ethanol and methanol were obtained from Echo
Chemicals (Taiwan). Deionized (DI) water was prepared to less than
18 MΩ-cm.
2.2. Preparation and characterization of CNF
The fabrication of CNF can be illustrated as Fig. 1. A precursor
mixture was firstly prepared by mixing 30 mmol of Co(SO4)2 and
150 mmol of urea in 150 mL of DI water. Next, the mixture was trans-
ferred to a Teflon-lined stainless steel autoclave for a hydrothermal
process at 100 °C for 12 h. The resulting precipitate was then collected
and washed thoroughly with ethanol and DI water, and dried at 65 °C
for 12 h, followed by calcination at 300 °C for 5 h at a heating rate of
1 °C/min to afford CNF.
The morphology of CNF was measured by scanning and transmis-
sion electronic microscopies (SEM/TEM) (JEOL, Japan), whereas the
chemical composition of CNF was determined using Energy-dispersive
W.-C. Yun, et al.
Fig. 2. The morphology of CNF: (a) SEM; (b) and (c) TEM images and (d) HRTEM.
X-ray spectroscopy (EDS) (Oxford Instrument, UK). The crystalline
structure of CNF was characterized by an X-ray diffractometer (Bruker,
USA). The surface chemistry of CNF was then analyzed using X-ray
photoelectron spectroscopy (XPS) (PHI 5000, ULVAC-PHI, Japan).
Textural properties of CNF and the commercial Co3O4 NPs were mea-
sured by a volumetric gas adsorption analyzer (Quantachrome Auto IQ,
USA).
2.3. Degradation of paracetamol (APAP) by Oxone activated using CNF
Degradation of APAP using Oxone activated by CNF was in-
vestigated by batch-type degradation experiments. In a typical experi-
ment, Oxone (e.g., 40 mg) was firstly dissolved in 0.2 L of APAP solu-
tion with an initial concentration C0 of 5 mg/L at a desired temperature
(e.g., 30 °C). Subsequently, CNF (e.g., 10 mg) was immediately added to
the APAP solution. At a pre-set time, a sample aliquot was filtrated
through a PVDF syringe filter to separate CNF from the APAP solution.
The filtrate was then analyzed by a UV–Vis spectrophotometer (Jasco
V670, Japan) at 243 nm to determine the remaining concentration of
APAP (Ct). Furthermore, electron paramagnetic resonance (EPR)
(Bruker EMX-P, Germany) was employed to specify radical species
generated from CNF-activated Oxone using DMPO as a radical-trapping
agent. The recyclability of CNF for activating Oxone to degrade APAP
was evaluated by reusing CNF over multiple cycles of APAP degrada-
tion experiments. The used CNF was collected by centrifugation and
washed thoroughly by ethanol and water to remove impurities and
residues, followed by drying before reuse. The resulting CNF was then
used as the pristine CNF in the new batch of APAP solution with Oxone
for a new experiment of APAP degradation. Degradation products of
APAP were then identified by liquid chromatography tandem-mass
spectrometry (Thermo TSQ Quantum, USA). The concentration of Co
ion in solutions were analyzed by inductively coupled plasma-optical
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Chemical Engineering Journal 373 (2019) 1329–1337
emission spectrometry (ICP-OES) (Perkin Elmer Optima, USA).
3. Results and discussion
3.1. Characterization of CNF
The morphology of CNF was first visualized using SEM in Fig. 2(a),
in which several flower-shaped spheres were bundled together, vali-
dating that the resulting CNF certainly exhibited the flower-shaped
appearance. The size of single CNF was ranging from 1 to 3 µm. On the
other hand, Fig. 2(b) shows the TEM image of the edge of CNF, re-
vealing that CNF had very fine and thin flower petals. A closer view
(Fig. 2(c)) further validates that these petals of CNFs exhibited the
needle-shaped morphology and, more interestingly, these petals were
comprised of nanoscale spherical particles. Fig. 2(d) further displays a
HRTEM image of the needle-shaped petals of CNF and the observed
lattice spacing of 0.244 nm and 0.286 nm, corresponding to the (3 1 1)
and (2 2 2) planes of Co3O4, confirming that CNF was assuredly com-
prised of Co3O4.
Furthermore, EDS was employed to characterize CNF as shown in
Fig. 3(a) and only Co and O were detected, confirming that these
needle-shaped petals and CNF were certainly made of cobalt oxide.
Fig. 3(b) also validates that CNF was made of Co3O4 as its crystalline
structure could be well-indexed to the typical XRD pattern of Co3O4
based on JCPDS #43-1003.
Moreover, the surface chemistry of CNF was analyzed using XPS and
its full-spectrum survey can be seen in Fig. 4(a), in which only Co and O
signals can be detected, validating no other significant elements in CNF.
Fig. 4(b) further reveals the Co2p core-level spectrum of CNF, which
was deconvoluted to display several noticeable peaks. The peaks at
780.2 and 795.1 eV were derived from Co3+, whereas the peaks at
781.8 and 796.9 eV could be corresponding to Co2+. These specific Co
W.-C. Yun, et al.
Fig. 3. Characteristics of CNF (a) EDS and (b) XPS pattern.
species were attributed to Co3O4 [31], confirming the content of Co3O4
in CNF.
Since textural properties are crucial parameters for catalytic reac-
tions, N2 sorption/desorption isotherms of CNF were then analyzed
(Fig. 5(a)). The isotherm of CNF appeared to be a combination of the
IUPAC type III and IV isotherms, suggesting that CNF was a porous
material. Fig. 5(b) confirms that CNF was comprised of pores (ranging
from 2 to 150 nm) with a high pore volume of 0.41 cm3/g and the
surface area was determined as 121 m2/g. In this study, the commercial
Co3O4 NPs were employed for comparisons with CNF; thus the textural
properties of Co3O4 NPs were then characterized and shown in
Fig. 5(a). However, the N2 adsorption amount to the Co3O4 NPs seemed
very low and the corresponding pores were also very few, leading to a
significantly small pore volume of 0.007 cm3/g and a very low surface
area of 2.8 m2/g. These comparisons indicate that CNF was significantly
more porous than the commercial Co3O4 NPs. This is probably because
the Co3O4 NPs, even though their size was a few tens nanometers,
tended to aggregate as shown in Fig. S1. On the contrary, those Co3O4
particles of CNF were specially arranged and separated owing to the
needle-shaped floral configuration, thus leading to the much higher
pore volume and surface area.
Fig. 4. XPS analyses of CNF: (a) Full-survey spectrum; (b) Co2p core-level spectrum.
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Chemical Engineering Journal 373 (2019) 1329–1337
3.2. Paracetamol degradation by Oxone activated using CNF
Prior to evaluating APAP degradation by Oxone activated using
CNF, it was essential to examine whether APAP could be removed due
to adsorption to CNF. Fig. 6 displays that the concentration of APAP
remained almost the same after 30 min, demonstrating that CNF was
unable to remove APAP via adsorption. On the other hand, Oxone alone
was also examined for APAP degradation; however APAP was only
slightly eliminated after 30 min. This indicates that Oxone (without
activation) could not efficiently degrade APAP. However, when CNF
and Oxone were both added to the APAP solution, the concentration of
APAP rapidly diminished and Ct/C0 approached zero in 30 min,
showing that CNF combined with Oxone could degrade APAP. Fig. S2
also demonstrates that APAP was certainly mineralized by the combi-
nation of CNF and Oxone, validating that APAP was decomposed. As
CNF and Oxone were unable to degrade APAP individually, this effec-
tive degradation of APAP by CNF and Oxone demonstrated that Oxone
was activated by CNF.
Since CNF consisted of cobaltic species of Co2+ and Co3+ from
Co3O4, these Co species can react with Oxone for generating SO4%− as
follows [32,33]:
Co2+@CNF + HSO5− → Co3+@CNF + SO4%− + OH− (1)
3+ 2+
Co @ CNF → Co @CNF + SO5%− + H+ (2)
W.-C. Yun, et al.
Fig. 5. CNF and the commercial Co3O4 NPs: (a) N2 sorption/desorption isotherms of CNF and (b) Pore size distributions.
Furthermore, the resulting SO5%− can evolve to SO4%− as follows:
SO5%− → 2 SO4%− + O2
Consequently, SO4%− can be continuously generated through these
catalytic cyclic reactions to degrade APAP.
Even though CNF was capable of activating Oxone to degrade APAP,
Oxone could be just activated by Co ion leached out from CNF.
Therefore, Co ion leached out from CNF was then studied. Nonetheless,
the concentration of Co ion leached out from CNF in the end of the
APAP degradation experiment was only 0.1 mg/L, which was sig-
nificantly less than the concentration of CNF (i.e., 50 mg/L) in water.
Fig. 6 also reveals APAP degradation using Oxone activated by 0.1 mg/
L of Co ion (Co2+) to evaluate homogeneous activation of Oxone for
APAP degradation. Nevertheless, the corresponding degradation extent
of APAP was very limited, demonstrating that APAP degradation by
CNF-activated Oxone was mainly attributed to heterogeneous activa-
tion of Oxone.
Although CNF was able to activate Oxone, it was crucial to compare
Fig. 6. Comparison of APAP degradation by Oxone alone, adsorption to CNF,
CNF-activated Oxone Co3O4 NP-activated Oxone and Co2+-activated Oxone
(Co2+ = 0.1 mg/L) (catalyst = 50 mg/L, APAP = 5 mg/L, Oxone = 200 mg/L,
and T = 30 °C).
Chemical Engineering Journal 373 (2019) 1329–1337
it with the Co3O4 NPs. As displayed in Fig. 6, APAP was certainly de-
graded in the presence of Co3O4 NPs and Oxone, suggesting that Co3O4
(3)
NPs were capable of activating Oxone to degrade APAP. Nevertheless,
the degradation extent was significantly lower than that by CNF. This
validates that even though Co3O4 NPs consisted of Co2+ and Co3+, the
corresponding catalytic activity was much lower than that of CNF. This
significant difference between CNF and Co3O4 NPs could be attributed
to the noticeably distinct textural properties between CNF and Co3O4
NPs. As revealed in the earlier section, CNF exhibited a tremendous
larger surface area and pore volume than the Co3O4 NPs because the
Co3O4 particles were specially-configured in the flower-like CNF. In
contrast, the conventional Co3O4 NPs were highly agglomerated, and
thus their pore volume and surface were low, leading to ineffective
activation of Oxone.
3.3. Effects of CNF and Oxone dosages on APAP degradation
Even though the combination of CNF and Oxone was capable of
degrading APAP, it was essential to determine their respective con-
tributions to APAP degradation. Thus, effects of CNF and Oxone do-
sages on APAP degradation were then distinguished. Fig. 7(a) reveals
APAP degradation by CNF at different dosages and CNF at the four
dosages degraded APAP efficiently within 30 min.
This result demonstrates that CNF should exhibit a very high cata-
lytic activity to activate Oxone as a low dosage of CNF at 25 mg/L could
still activate Oxone for almost complete degradation of APAP.
Nonetheless, the degradation kinetics seemed different at various cat-
alyst dosages. To quantitatively compare the degradation kinetics, the
pseudo first order equation, which has been extensively employed for
determining kinetics of pollutant degradation by Oxone, was then
employed as follows [34]:
Ct = C0 exp( kobs t ) (4)
where kobs is the observed pseudo first order rate constant. When CNF
increased from 25 to 50 mg/L, kobs increased from 0.050 to 0.103 min−1
(Table S2, see the Supplementary material) and further rose up to 0.127
and 0.312 min−1 at CNF = 100 and 200 mg/L, respectively. This vali-
dates that a higher CNF dosage accelerated APAP degradation by pro-
moting generation of sulfate radicals from Oxone in the presence of
more active sites.
Furthermore, as CNF dosage varied and their degradation extents
were quite comparable in Fig. 7(a), their rate constants were then
normalized to surface area and thus ratios of rate constants over their
surface areas for CNF at 25, 50, 100, 200 mg/L were calculated as
0.117, 0.085, 0.052 and 0.064 min−1 m−2, respectively. This indicates
that a relatively low CNF dosage led to a higher degradation ratio per
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W.-C. Yun, et al.
Fig. 7. Effects of (a) CNF dosage (APAP = 5 mg/L), Oxone = 200 mg/L and (b) Oxone dosage (catalyst = 50 mg/L) (APAP = 5 mg/L and T = 30 °C) on APAP
degradation.
unit of surface area, possibly because the surface of CNF at a low dosage
could be more exposed to reactants, leading to a higher-degree of uti-
lization of CNF surface.
APAP degradation by Oxone at different dosages was also examined
in Fig. 7(b). When Oxone dosage increased from 200 to 400 mg/L,
APAP degradation was accelerated as kobs increased from 0.103 to
0.145 min−1. Nevertheless, as Oxone dosage decreased to 100 mg/L,
the degradation kinetics was lowered to 0.039 min−1 and more im-
portantly, the degradation extent of APAP also became 70%. This de-
monstrates that the lower dosage of Oxone led to ineffective APAP
degradation probably due to insufficient SO4%− from Oxone.
As shown in Fig. 7(a), when CNF dosage was varied, even though
degradation kinetics was altered noticeably, the degradation extent was
consistent as APAP was completely eliminated at 30 min. Nevertheless,
when Oxone dosage was changed (Fig. 7(b)), not only degradation ki-
netics was altered but also was the degradation extent. This demon-
strates that the degradation extent of APAP seemed more involved with
Oxone dosages. On the contrary, CNF should act as a catalyst to ma-
nipulate the kinetics. Several previous studies have also observed si-
milar respective contributions of catalysts and Oxone dosage to de-
gradation of pollutants [35,36].
3.4. Effects of temperature and initial pH on APAP degradation
Fig. 8(a) reveals APAP degradation by CNF-activated Oxone at 30,
Fig. 8. Effects of (a) temperature and (b) pH (T = 30 °C) on APAP degradation (catalyst = 50 mg/L, Oxone = 200 mg/L, APAP = 5 mg/L).
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Chemical Engineering Journal 373 (2019) 1329–1337
45 and 60 °C. As the solution temperature increased, the APAP de-
gradation was substantially expedited. For instance, when temperature
increased from 30 to 45 °C, kobs accordingly increased from 0.103 to
0.215 min−1 and then further changed to 0.371 min−1 at 60 °C, con-
firming that higher temperatures considerably accelerated APAP de-
gradation by CNF-activated Oxone.
As higher kobs values were acquired at higher temperatures, kobs
values were further correlated to temperatures via the following
Arrhenius equation:
Ln kobs = ln A Ea/ RT (5)
where A represents the temperature-independent factor; R denotes the
universal gas constant; Ea is the activation energy (Ea, kJ/mol) of APAP
degradation; and T means the solution temperature in Kelvin (K). Based
on Eq. (5), a plot of 1/T vs. Ln kobs was then drawn as the inset in
Fig. 8(a) and the data points were properly fit by the linear regression
with R2 = 0.997 and then the corresponding Ea was calculated as 41
kJ/mol.
In addition, since APAP degradation by CNF-activated Oxone was
an aqueous reaction, solution pH represents a critical parameter.
Fig. 8(b) displays APAP degradation by CNF-activated Oxone at dif-
ferent pH values. When pH was decreased to 5, the APAP degradation
was unfavorably affected as kobs decreased to 0.036 min−1 and Ct/C0
approached 0.38. The unfavorable effect became even more pro-
nounced when the pH was even lower to 3 as kobs diminished to 0.012
W.-C. Yun, et al.
Fig. 9. The recyclability test (catalyst = 50 mg/L, Oxone = 200 mg/L,
APAP = 5 mg/L, and T = 30 °C).
min−1 and Ct/C0 only approached 0.7. This feature was possibly due to
the fact that Oxone becomes much more stable under acidic conditions
[25]; thus Oxone becomes relatively difficult to be activated.
In contrast, when the aqueous solution became alkaline to pH = 9,
APAP degradation was slightly decreased as kobs diminished to
0.084 min−1. This adverse effect become pronounced as pH was in-
creased to 11 and the corresponding kobs decreased to 0.027 min−1.
This was because Oxone tends to decompose without generation of
SO4%− under alkaline conditions [25,37] and thus SO4%− could be not
produced rapidly to degrade APAP. In addition, as the pKa of APAP is
9.38, the strongly alkaline condition (e.g., pH = 11) caused the de-
protonation of APAP. Simultaneously, the CNF surface became even
more negatively-charged as pHzpc of CNF was 6.5 (as show in Fig. S3)
and thus the electrostatic repulsion between CNF and the resulting
deprotonated APAP (APAP−) might increase, hindering with the con-
tact between APAP and CNF. On the other hand, since the pKa of
HSO5− was 9.4 [38], HSO5− would also become SO52− under strongly
alkaline conditions and thus the electrostatic repulsion might also grow
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Chemical Engineering Journal 373 (2019) 1329–1337
more intense [8], restricting contact between CNF and SO52−. Hence,
the APAP degradation became less effective under highly alkaline
conditions.
On the other hand, when SO4%− was present under alkaline con-
ditions, it could also react with OH− to result in OH% [8,39]. Never-
theless, OH% might be scavenged by anionic by-products derived from
Oxone [39], leading to less effective degradation [8,39]. Therefore, it
was consistent to observe that APAP degradation became less effective
under highly alkaline conditions [8,39].
3.5. The recyclability of CNF to activate Oxone for APAP degradation
Since CNF was proposed to be a heterogeneous catalyst for acti-
vating Oxone to degrade APAP, it was essential to evaluate whether
CNF could be reused to activate Oxone to degrade APAP. Fig. 9 displays
that APAP was still effectively degraded using Oxone activated by used
CNF over the multiple cycles. This indicates that CNF was a reusable,
durable and efficient catalyst for activating Oxone to APAP.
Fig. S4(a) further displays a SEM image of used CNF, which still
exhibited the floral morphology with petals, and its crystalline structure
was also comparable to that of pristine CNF (Fig. S4(b)), demonstrating
that CNF remained intact without significant destruction after Oxone
activation. Besides, the surface chemistry of CNF (Fig. S4(c) and (d))
further indicates that Co species (Co2+ and Co3+) in used CNF were
consistent to those in pristine CNF. However the fractions of Co2+ and
Co3+ of used CNF seemed to slightly change in comparison to those of
pristine, suggesting that these species participated in Oxone reaction as
discussed previously.
3.6. A proposed mechanism of APAP degradation by CNF-activated Oxone
Even though CNF was proven as a promising and useful catalyst for
Oxone activation to degrade APAP, it was also important to probe into
the APAP degradation mechanism by CNF-activated Oxone. In parti-
cular, when SO4%− is present in water, it may further evolve into OH%
through the following equation [40] (Eq. (6)):
SO4%− + H2O → SO42− + OH% + H+ (6)
Hence, it was essential to determine whether these potential species
(i.e., OH% and SO4%−) contributed to APAP degradation by CNF-acti-
vated Oxone. Herein, two special radical probe reagents were adopted:
TBA and methanol. Since TBA does not contain α-hydrogen and it can
react with OH% very rapidly, TBA has been adopted as a probe reagent
Fig. 10. (a) effect of radical probe reagents
on APAP degradation (catalyst = 50 mg/L,
Oxone = 200 mg/L, APAP = 5 mg/L, TBA
= methanol = 0.5 M, and T = 30 °C); (b)
EPR spectra of Oxone alone and Oxone in
the presence of CNF (□: DMPO-OH%; ○:
DMPO- SO4%−).
W.-C. Yun, et al.
Fig. 11. A possible degradation pathway of APAP by CNF-activated Oxone.
for OH%. Fig. 10(a) reveals that APAP degradation by CNF-activated
Oxone in the presence of TBA was slightly affected. This suggests that
OH% might participate in APAP degradation. On the other hand, another
radical probe reagent, methanol, was also adopted as methanol, con-
taining α-hydrogen, is able to react with both SO4%− and OH% at
comparable rates [41]. Fig. 10(a) shows that APAP degradation was
noticeably hindered in the presence of methanol, demonstrating that
APAP degradation was certainly attributed to SO4%−.
To further identify radical species generated from CNF-activated
Oxone, EPR analyses were performed as displayed in Fig. 10(b). When
DMPO was used as a spin-trapping agent, there was almost no signal
present in the presence of Oxone alone, indicating that no significant
amounts of radicals were produced from Oxone without activation.
Nevertheless, as CNF was used to activate Oxone, a distinct signal of the
triplet pattern was detected and ascribed to the hyperfine splitting of
oxidation adduct products of DMPO-SO4 and DMPO-OH [42–46]. This
suggests that APAP degradation was attributed to both SO4%− and OH%,
generated from Oxone activated by CNF.
3.7. A potential degradation pathway for APAP by CNF-activated Oxone
While APAP was efficiently degraded by CNF-activated Oxone, it
was important to probe into the degradation pathway of APAP. Fig. S5
displays spectra of degradation intermediate products determined by
LC-MS/MS. In view of these detected intermediate compounds from C1
to C6, a potential decomposition route of APAP by CNF-activated
Oxone can be illustrated in Fig. 11 [47,48].
Initially, APAP could be oxidized, leading to the formation of a
product, C1 [48], which was then oxidized to generate C2. Next, APAP,
C1 and C2 might be further oxidized to result in C3 [47], which might
evolve into C4 and C5. Subsequently, C4 and C5 might further trans-
formed to analogues of C6 [47]. The relatively simple aromatic pro-
ducts (C6) could be continuously oxidized to open rings and decom-
posed, leading to low-molecular weight compounds.
4. Conclusions
In this study, a unique cobalt oxide nanoflower (CNF), consisting of
fine rounded Co3O4 particles, was facilely fabricated via a simple hy-
drothermal process. In comparison to commercial Co3O4 NPs, which are
highly aggregated, Co3O4 particles were configured as the needle-
1336
Chemical Engineering Journal 373 (2019) 1329–1337
shaped petals, enabling Co3O4 particles separated. As a result, CNF
exhibited the tremendous higher surface area and pore volume than the
commercial Co3O4 NPs. CNF also showed significantly higher catalytic
activities than the commercial Co3O4 NPs for activating Oxone to de-
grade APAP. CNF was also reusable for activating Oxone to degrade
APAP over several continuous cycles. The APAP degradation pathway
by this CNF-activated Oxone was also investigated according to the
degradation products determined using LC-MS/MS. The findings of this
study validate that CNF is a promising and advantageous heterogeneous
catalyst for effectively activating Oxone to degrade APAP.
Acknowledgements
This work is supported by the Ministry of Science and Technology
(MOST), Taiwan, and financially supported by the “Innovation and
Development Center of Sustainable Agriculture” from The Featured
Areas Research Center Program within the framework of the Higher
Education Sprout Project by the Ministry of Education (MOE), Taiwan.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.05.142.
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