Carbohydrate Polymers 273 (2021) 118548

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Co-MOF-74 based Co3O4/cellulose derivative membrane as dual-functional

catalyst for colorimetric detection and degradation of phenol
Chen Hou a, *, Linhui Fu a, Yang Wang a, *, Wenqiang Chen a, Fang Chen a, Sufeng Zhang a, *,
Jianzhi Wang b
a
College of Bioresources Chemical and Materials Engineering, Shaanxi University of Science and Technology, Shaanxi Provincial Key Laboratory of Papermaking
Technology and Specialty Paper Development, Key Laboratory of Paper Based Functional Materials of China National Light Industry, National Demonstration Center for
Experimental Light Chemistry Engineering Education, Xi'an 710021, China
b
Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205,
China

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

Keywords: Smart nanomaterials that can simultaneously detect and eliminate contaminants in water environment are sig­
Co-MOF-74 derived Co3O4 nificant for health protection. To achieve such goal, Co-MOF-74 was in-situ assembled on regenerated cellulose
Regenerated cellulose membrane membranes followed by calcination process, thus achieving dual-functional Co3O4/cellulose derivative mem­
Mimic enzyme
brane (Co3O4/CDM) catalyst. The Co3O4 morphology was readily controlled by further recrystallization of the
Colorimetric detection
Advanced oxidation processes
deposited MOF precursor. Combining the high enrichment ability of cellulose membrane and outstanding
peroxidase-active of Co3O4, the fast color reaction for phenol was accomplished within 10 min by Co3O4/CDM
with the assistance of H2O2 and 4-aminoantipyrine (4-AAP). Moreover, the Co3O4/CDM also portrayed an
excellent degradation property for phenol elimination via sulfate radical-advanced oxidation processes (SR-
AOPs). The degradation efficiency of phenol reached 93% in 20 min, and the possible mineralization mechanism
was proposed based on the XPS and LC-MS analysis. Thus, Co-MOF-74 derived Co3O4/CDM shows excellent
properties in aiding the colorimetric detection and degradation of phenol in aqueous solutions.

1. Introduction processes (SR-AOPs), utilizing the activation of the peroxymonosulfate

(PMS) to generate reactive oxygen species to remove pollutants, are
As the common water contaminants, phenolic compounds are of high considered as one of the most efficient methods for the removal of
toxicity and difficulty to be degraded in natural conditions, which has phenol. It can degrade refractory contaminants into nontoxic com­
seriously threatened human health. Phenol is a representative substance pounds such as CO2, H2O and inorganic salts without secondary pollu­
of phenolic pollutants and widely derived from different industries tion (Giannakis, Andrew Lin, & Ghanbari, 2021). Thus, it is meaningful
including coal chemical industry, plastics, textile, dyes and other fields. to synthesize bi-functional catalyst materials which can be both applied
Even at low concentrations, phenol can result in damage to the lungs and for the colorimetric detection and degradation of phenol.
kidney (Babich & Davis, 1981). Therefore, it is very vital to effectively Due to the merits of highly activity, stability and low-cost, nano­
detect and degrade phenol in wastewater. Compared with other con­ materials mimic enzymes have received intensive research interests in
ventional and advanced techniques for phenol detection (Andrey, the chromogenic reaction. Especially, transition metal oxide (TMO)
Svetlana, & Andrey, 2020; Liu, Piao, Choi, & Seo, 2013; Wang et al., nanomaterials such as MnO2 (Zhao, Liu, Lu, Guan, & Liu, 2021), Co3O4
2020), colorimetric detection based on naked eye has offered unique (Zhu et al., 2018) and V2O5 (Cao et al., 2021) have been found to possess
superiority including on-spot operation, fast response, high selectivity unexpected enzyme-like activity and been applied in colorimetric
and low cost (Wu, Guo, Xu, Pan, & Niu, 2020). The detection is achieved detection of phenol and H2O2. Excitingly, some TMO nanomaterials
basing on the oxidative coupling reaction of the phenol and 4-aminoan­ mimic enzymes are also proved effective in activating PMS for
tipyrine (4-AAP) to form a colored quinoneimine with the help of H2O2 contaminant degradation (Zhang et al., 2020a). However, its catalytic
and catalysts. On the other hand, sulfate radical-advanced oxidation activity is greatly affected by the particle size, which is difficult to

* Corresponding authors.
E-mail addresses: houchen@sust.edu.cn (C. Hou), wangyang@sust.edu.cn (Y. Wang), sufengzhang@126.com (S. Zhang).

https://doi.org/10.1016/j.carbpol.2021.118548
Received 9 May 2021; Received in revised form 24 July 2021; Accepted 8 August 2021
Available online 11 August 2021
0144-8617/© 2021 Elsevier Ltd. All rights reserved.
C. Hou et al. Carbohydrate Polymers 273 (2021) 118548

Scheme 1. Schematic representation of the synthesis of Co3O4/CDM.

control because they are also easy to aggregate. To alleviate this prob­ enrichment, detection, and degradation. Therefore, it can be reasonably
lem, adopting metal-organic frameworks (MOFs) as TMO precursor is inferred that exploration of a rationally synthesized and recycled MOFs-
regarded as an effective strategy. derivated TMO/cellulose membrane will achieve superior effect in
MOFs composed of metal nodes and organic linkers have flexible colorimetric catalysis and PMS activation.
structures and customizable chemistry and thus can be applied as In this work, the dual-functional Co-MOF-74 based Co3O4 assembled
promising templates to obtain TMO nanomaterials with controllable size on regenerated cellulose derivative membrane (Co3O4/CDM) was syn­
(Lu et al., 2020). In detail, MOFs-derived TMO nanomaterials can thesized via a novel strategy, which is proposed for phenol detection and
maintain the high specific surface area and ordered pore structure of degradation. It is hypothesized that the dispensability of nanoparticles
MOFs materials, endowing them regular morphology and excellent can be improved with a hydrothermal recrystallization approach on
catalytic performance. MOF-74 emerged as an ideal TMO precursor membrane. Moreover, the cellulose membrane can not only provide
because it has developed porous nature, superior thermal stability, and more convenience in operation, but also is applied to enrich the phenol
abundant coordination unsaturated metal sites (Rosi et al., 2005). to enhance the detection and degradation ability. Besides, MOFs-derived
Moreover, researchers found that an amorphous MOFs-mediated TMO based nanocomposites will effectively refrain from metal ion
recrystallization approach (AMMRA) via hydrothermal method could spillage rate. Various characterization and analytical methods will be
make Co-MOF-74 NPs arrayed spontaneously in certain dimensions. discussed to explore the structure and properties of the as-prepared
After calcining, the obtained Co3O4 can preserve the intrinsic Co3O4/CDM. This strategy may provide a new prospect for the con­
morphology (Zou, Hou, Liu, Pang, & Xu, 2018). Hence, we propose the struction of both visual detection and removal of organic pollutants in
recrystallization of in-situ synthesized amorphous MOF-74 to increase wastewater.
the dispersion of the ultimate TMO particle and improve its catalytic
performance. 2. Experimental section
Anchoring MOFs-derived TMO on the matrix is another way to
further control their growth precisely and improve the monodispersity 2.1. Chemicals and materials
and functionality of the dual-role catalyst. Biopolymers have been
widely utilized as supporting materials owning to their affinity with Cotton cellulose (cotton linter pulp, DP = 600) was provided by
nanoparticles, high mechanical strength and non-toxic (Kalantari, Zhongchao Paper Co., Ltd. (Tianjin, China). Cobalt (II) acetate tetra­
Khalilzadeh, Zareyee, & Shokouhimehr, 2020; Khalilzadeh, Sadeghifar, hydrate (Co(CH3COO)2⋅4H2O) 2,5-dihydroxyterephthalic acid (C8H6O6)
& Venditti, 2019; Seyednejhad, Khalilzadeh, Zareyee, Sadeghifar, & were purchased from Aladdin chemicals Co. Ltd. (China). CH3COONa
Venditti, 2019). Among the various biopolymers for immobilization, (NaAc), CH3COOH (HAc), o-phenylenediamine (OPD), H2O2 (30%), 4-
cellulose fibers were used as the ideal matrix for MOFs and MOFs- aminoantipyrine (4-AAP), Phenol, and other chemicals and reagents
derived TMO immobilization. Increased reports have reported ZIF-67 were purchased from Sinopharm Chemical Reagent Co. Ltd. (Xi'an,
or bimetallic ZIF-8/67 and their pyrolyzed metal/metal oxide based China). Peroxymonosulfate (PMS) was obtained from Macklin
cellulose composite materials exhibited enhanced performance in elec­ Biochemical Technology Co. Ltd. (China).
trochemistry and pollutant removal (Lee, Yoo, Choi, & Ahn, 2020; Wu
et al., 2021; Zhang et al., 2020c; Zhang, Zhao, Li, Hou, & Du, 2021). 2.2. Synthesis of regenerated cellulose membrane and Co-MOF-74/
Furthermore, the regenerated cellulose membrane using non- cellulose composite membrane
derivatizing organic or inorganic solvents can decrease the hydrogen
interaction between cellulosic fibers thus in favor of nucleation for The regenerated cellulose membrane was conducted according to a
nanoparticle. Its three-dimensional network structure can provide typical method (Zhang et al., 2020b). Firstly, NaOH, urea, thiourea and
anchoring sites to immobilize nanoparticles even during cellulose H2O were mixed at a weight ratio of 8:6:8:78, and subsequently was pre-
calcination (Liu et al., 2016). Moreover, due to the pivotal role of cooled at − 12.5 ◦ C for 2 h to prepare the solution used for cellulose
membrane separation and enrichment technology in water treatment, dissolution. Next, 2.0 g dried cotton pulp fiber was dissolved in the
cellulose membrane would exhibit versatile functions such as above mentioned solution, and vigorously stirred at room temperature

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C. Hou et al. Carbohydrate Polymers 273 (2021) 118548

Fig. 1. SEM images of the (a, b) regenerated cellulose membrane; (c, d) Co-MOF-74/CCM; (e, f) R-Co-MOF-74/CCM; (g, h) Co3O4/CDM.

for 30 min to obtain the homogeneous solution. Then, 4.8 g cellulose the in-situ growth at room temperature followed by the recrystallization
solution was cast on a petri dish and dried in vacuum oven at 80 ◦ C for 1 via hydrothermal method (Xiong et al., 2020). 2.0 mmol Co
h, the obtained product was washed with deionized water for removing (CH3COO)2⋅4H2O was dissolved in 50 mL methanol solution and then
impurities. After freeze-drying for 2 h, pure regenerated cellulose sonicated for 5 min until fully dissolved. 0.08 g fabricated pure regen­
membrane was prepared. erated cellulose membrane was initially soaked in the per-mixture so­
The synthesis of Co-MOF-74-loaded cellulose membrane involved in lution and was oscillated in the shaking bath for 1 h at room temperature

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C. Hou et al. Carbohydrate Polymers 273 (2021) 118548

Fig. 2. (a) XRD patterns, (b) FT-IR spectra of regenerated cellulose membrane, R-Co-MOF-74/CCM, Co-MOF-74, Co3O4/CDM and Co3O4.

Fig. 3. (a) The UV–vis spectra of different systems. Phenol concentration: 90 μM; catalyst dosage: 4 mg; 4-AAP concentration: 7 mM; H2O2 concentration: 60 mM; (b)
UV–vis absorption spectra of 4-AAP solutions containing Co3O4/CDM upon the addition of 0.5–300 μM phenol; (c) the plot of A 525 versus phenol concentration; (d)
colorimetric change of 4-AAP solutions containing Co3O4/CDM upon the addition of 0.5–300 μM phenol.

to adsorb cobalt ions. Subsequently, 25 mL methanol solution contain­ room temperature, the recrystallized Co-MOF-74/CCM (R-Co-MOF-74/
ing 0.1486 g 2,5-dihydroxyterephthalic acid was added dropwise in the CCM) was washed with methanol and deionized water, then dried under
above solution under magnetic stirring at room temperature. The ob­ vacuum at 60 ◦ C for 6 h. Co-MOF-74 NPs was also obtained by the same
tained mixture containing cellulose membrane was further oscillated for procedure without cellulose membrane.
about 2 h. Finally, the yellow Co-MOF-74/cellulose composite mem­
brane (Co-MOF-74/CCM) was washed with methanol and deionized
water alternately and dried in vacuum oven at 60 ◦ C for 6 h. The as- 2.3. Synthesis of Co3O4/cellulose derivative membrane
prepared dried Co-MOF-74/CCM was transferred into a Teflon-lined
reaction kettle and reacted at 175 ◦ C for 12 h. After cooling down to The as-prepared R-Co-MOF-74/CCM and Co-MOF-74 NPs were
annealed at 300 ◦ C for 2 h with a heating rate of 5 ◦ C min− 1 under air

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Scheme 2. Illustration of the reaction of phenol, 4-AAP and H2O2 catalyzed by Co3O4/CDM.

3. Results and discussion

3.1. Characterization of catalyst

SEM image in Fig. 1(a) and (b) showed the regenerated cellulose
membrane featured an interweave fibrous network, the cellulose fibers
were smooth with a mean diameter of about 18 μm. After in-situ syn­
thesis, the surface of cellulose fibers became rough obviously with the
growth of Co-MOF-74 NPs (Fig. 1(c) and (d)). Compared with Co-MOF-
74/CCM, the R-Co-MOF-74/CCM presented a more regular morphology
and the recrystallized Co-MOF-74 NPs with rice-granule structure were
uniformly distributed on cellulose fiber (Fig. 1(e) and (f)). The
morphology of the Co3O4 NPs did not change basically after calcining
due to the porous structure of MOFs were retained as seen in Fig. 1(h).
Moreover, it can be seen from Fig. 1(g) that the interconnected 3D
porous network structure of the cellulose membrane was retained and
Co3O4 NPs didn't aggregate after calcination.
The crystal structure of prepared samples was confirmed by XRD
patterns (Fig. 2(a)). For the regenerated cellulose membrane, the main
( )
peaks at 11.9◦ , 20.3◦ and 21.9◦ can be attributed to the 110 , (110)
Fig. 4. Value at 525 nm of the solutions containing 70 μM phenol or and (200) planes of cellulose II crystalline allomorph, respectively (Jiao
various species. et al., 2018). Compared to the XRD pattern of in-situ synthesized Co-
MOF-74/CCM, R-Co-MOF-74/CCM appeared two new and sharp char­
atmosphere in a tube furnace. After calcination treatment, the black acteristic peak of R-Co-MOF-74 NPs at 6.8◦ and 11.7◦ , evidencing its
Co3O4/cellulose derivative membrane (Co3O4/CDM) and Co3O4 NPs good crystallinity after recrystallization process. After calcination,
were obtained respectively. diffraction peaks clearly appeared at approximately 18.9◦ , 31.3◦ , 36.8◦ ,
44.8◦ , 59.4◦ , and 65.2◦ for the Co3O4/CDM matched well with the (111),
2.4. Characterization and analytical methods (220), (311), (400), (511), and (440) Co3O4 planes (JCPDS no. 74-
2120). Besides, the diffraction peaks at 11.9◦ , 20.3◦ and 21.9◦ became
Different techniques for the characterization and analytical methods broad and very weak, indicating a gradual decrease in cellulose crys­
of the nanocomposites were discussed in the supporting information tallinity as the temperature increased up to 300 ◦ C. The change of these
(SI). peaks suggested the underlying cleavage of the H-bonds or the scission
of glycoside bonds and pyran ring during calcination. The cellulose
derivative membrane configured a three-dimensional network polymer
2.5. Peroxidase-like catalytic activity of Co3O4/CDM
in the form of crystalline to immobilize nanoparticles (Xin et al., 2015).
FT-IR measurement was further obtained to investigate the chemical
Peroxidase-like catalytic activity of Co3O4/CDM was examined by
structure of these materials (Fig. 2(b)). For the regenerated cellulose
analyzing the oxidation of OPD in the presence of H2O2 (detailed dis­
membrane, the wide and strong peak at 3000–3600 cm− 1 was ascribed
cussion was shown in the SI).
to the O–H stretching vibration in hydroxyl groups (Jiao et al., 2018).
Besides, the absorbance bands at 2910 cm− 1 was observed due to the
2.6. Colorimetric detection of phenol
asymmetric of methylene (–CH2–) groups in long alkyl chain, and a
characteristic peak at 1639 cm− 1 attributed to the C– – O stretching vi­
The colorimetric detection of phenol was measured and discussed in
bration in the carboxyl and carbonyl groups. The absorbance bands
the SI.
assigned to at 1432 and 1012 cm− 1 corresponding to glycosidic bond
and glucose unit. The characteristic peaks of Co-MOF-74 at 1630 cm− 1
2.7. PMS activation over Co3O4/CDM for efficient phenol degradation existed in the spectra of R-Co-MOF-74/CCM indicated that Co-MOF-74
NPs successfully loaded on the regenerated cellulose membrane. With
Experiment was carried out by using Co3O4/CDM as catalyst for PMS further hydrothermal process and calcination, the decreased in the in­
activation to generate SO4•–, which was efficiently for phenol degrada­ tensity of the band in 3000–3600 cm− 1 demonstrated that hydroxyl
tion (Scheme 1). The details experimental procedure was discussed in groups were easily degraded to intermediate products at a high
the SI.

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Fig. 5. (a) Degradation efficiency of phenol in different reaction systems within 21 min; (b) effect of PMS dosage; (c) effect of pH; (d) effect of temperature.

temperature. Similar trends were also observed in 900–1500 cm− 1 hydroxyl radicals, which can catalyze the reaction of phenol and 4-AAP
corresponding to glycosidic bond and glucose pyran ring. The peak at to form a pink quinone imine (Xiong et al., 2015).
1593 cm− 1 revealed that condensed C– – C groups were present in Co3O4/ Under the optimal conditions (shown in SI), colorimetric detection of
CDM, and the adsorption band at 1680 cm− 1 corresponded to the phenol was developed and a typical phenol concentration response
carboxylate groups. These results testified that dehydration and curve was obtained. A gradual enhancement in the absorbance at 525
aromatization occurred during the hydrothermal method and carbon­ nm was witnessed with the increased addition of phenol, which was
ization. In this process, cellulose was gradually depolymerized into ol­ displayed in Fig. 3(b). Correspondingly, it was further found that a linear
igosaccharides followed by the cleavage of the glycosidic bond to plot of the absorbance at 525 nm with the concentration ranging from
produce D-glucopyranose and finally formed levoglucosan (Liu, Jiang, & 0.5 to 300 μM (R2 = 0.9947), and the detection limit was estimated to be
Yu, 2015). What's more, two strong absorption bands at 665 and 570 about 1.02 μM (Fig. 3(c)). As well as by visual observation in Fig. 3(d),
cm− 1 confirmed the existence of Co3O4 in the composite membrane. the red color intensified along with the concentration of phenol. The
The stress-strain curves, BET analysis, TG curves and XPS analysis for result implied that the as-prepared Co3O4/CDM was a good artificial
the samples were discussed in SI. These characterizations provided enzyme for the potential application in environmental monitoring.
supportive evidence for the triumphant fabrication of Co3O4/CDM. Moreover, in comparison with previously reported methods for phenol
determination, the Co3O4/CDM exhibited a good detection limited of
3.2. Colorimetric detection of phenol 1.02 μM towards phenol (Table S1).
The selectivity of this colorimetric assay was further explored by
Identically, a facile colorimetric platform of phenol had been con­ monitoring the absorbance change with the addition of phenol and other
structed due to the excellent peroxidase-like activity indicated above. control molecules (Fig. 4). Only the presence of phenol in solution can
The assay was proceeded by oxidation of phenol and 4-AAP in acetate induce rapid and naked eye color change of it from colorless to pink,
buffer (0.2 M, pH = 4.0) to generate a pink quinoid type dye (Wu, Guo, indicating the high selectivity of this developed colorimetric method.
Xu, Pan, & Niu, 2020), which exhibited a characteristic absorption peak Additionally, the resulted colorimetric approach provided a facile, high-
at 525 nm. As depicted in Fig. 3(a), the combination of 4-AAP and selectivity and sensitivity detection platform for phenol rapid moni­
phenol didn't trigger any obvious changes, while a weak pink color was toring without cumbersome instrument and complex pretreatment,
given with the addition of H2O2. By comparison, the 4-AAP + phenol + decreasing the detection cost to some extent.
H2O2 + Co3O4/CDM system led to a notable color reaction in only about
10 min. Meanwhile, it gave a dramatic increase in the absorbance at 525 3.3. Degradation of phenol by Co3O4/CDM activated PMS
nm than that of Co3O4 NPs and Co-MOF-74/CCM. This phenomenon
indicated the excellent peroxidase-like activity of Co3O4/CDM, which Together with the efficient colorimetric detection of phenol, the
can be ascribed to the good dispensability and the crystal structure of degradation of phenol in wastewater was also important. The Co3O4/
nanoparticles. Thus, the possible underlying mechanism for the phe­ CDM, which exhibited peroxidase-like activity, can also been utilized as
nomenon we speculated was shown in Scheme 2. In brief, under the AOPs catalyst to activate PMS. The degradation efficiency of phenol
catalysis of Co3O4/CDM, H2O2 was firstly decomposed to generate using different catalytic system was shown in Fig. 5(a). In the absence of

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Fig. 6. (a) EPR spectra obtained from the Co3O4/CDM catalyzed AOPs system in the presence of DMPO. Reaction conditions: [phenol] = 20 mg L− 1, [PMS] = 7 mM,
[catalyst] = 4 mg, [pH] = 4, [Scavenger] = 0.88 M; (b) effect of scavengers (TBA, MeOH and NaN3) on phenol degradation; the high-resolution XPS spectrums for O
1s (c) and Co 2p (d).

PMS, 9% of phenol was adsorbed on the surface of Co3O4/CDM. Without degradation ratio of phenol (Gong et al., 2018). It was found that
Co3O4/CDM, only 5% of the phenol was removed in 20 min, confirming particularly at pH 8.0, 93.1% of phenol was removed within 20 min,
that PMS itself can produce free radicals (Yang Wu et al., 2019). When indicating the Co3O4/CDM exhibited better degradation performance
PMS coexisted with Co3O4/CDM, the phenol stared to decompose under alkalescent conditions. Meanwhile, as the temperature increased
rapidly. Approximately 92.1% of phenol was removed after 20 min in from 20 to 40 ◦ C, the phenol degradation rate changed remarkably and
the presence of Co3O4/CDM and PMS, therefore the Co3O4/CDM reached a maximum of about 93.3% at 35 ◦ C (Fig. 5(d)).
possessed high catalytic activity for PMS activation. This result also
HSO5 – + SO⋅−4 →HSO4 − + SO⋅−5 (1)
confirmed that phenol removal was not simple adsorption by the cata­
lyst but the oxidative degradation. The superior phenol degradation
SO⋅−4 + SO⋅−4 →S2 O2−8 (2)
performance of the Co3O4/CDM can be ascribed to the good dispens­
ability of nanoparticles on the cellulose membrane, maximizing
numbers of active sites exposure. Additionally, the mass transfer of the 3.4. Possible mechanism for activation of PMS by Co3O4/CDM
reactants during the PMS activation was significantly favored because of
the porous fibrous morphology and the reticulated 3D structure of cel­ In order to evaluate the reactive species as well as the dominant
lulose membrane. These results were consistent with the analysis of radicals during the phenol degradation process, quenching tests com­
SEM. bined with EPR techniques were applied to identify the reactive oxidized
Other parameters such as the concentrations of PMS, pH and the species (ROS).
reaction temperature played a crucial role in the PMS activation process. The result of EPR test exhibited in Fig. 6(a), and DMPO was selected
As shown in Fig. 5(b), the degradation ratio of phenol was elevated as the trapping agent to prove whether SO4•− and •OH were generated
remarkably from 37.6% to 90.8% with the dosage of PMS increased from from the reaction. No peaks were identified for the PMS + DMPO sys­
0.2 to 0.8 mM. However, the degradation ratio was decreased with tem, while the typical pattern with the DMPO-•OH and DMPO-SO4•−
higher amount of PMS concentration, because the fact that sulfate rad­ signals was obtained for the PMS + DMPO +Co3O4/CDM system. It
icals could be scavenged by excessive PMS and reduce reactive SO5•− revealed that both •OH and SO4•− were generated at the initial stage of
production. Besides, excessive sulfate radicals made self-scavenging the catalytic reaction and the more amount of radicals were produced in
reaction occur, resulting in a slower degradation ratio of phenol (Eqs. this system when reaction time was extended to 12 min. In addition,
(1)–(2)) (Oh, Dong, & Lim, 2016). The initial pH of the solution was non-radical path for phenol degradation via singlet oxygen (1O2) had
studied for the phenol degradation in Fig. 5(c). HSO5− was the dominant also been studied (Liu et al., 2020). The characteristic triplet signals with
PMS species at pH 2, while SO52− was the main form at pH > 9.4. At the the intensity ratio of 1:1:1 of TEMPO were sighted, demonstrating the
acid solution, the PMS was so stable that it cannot conducive to the generation of 1O2 during PMS activation Fig. S7(a). Radical quenching
generation of corresponding reactive species, resulting in low experiments were further conducted in detail to uncover the ROS in
phenol degradation (Fig. 6(b)). Generally, MeOH was taken as both

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Fig. 7. Possible phenol degradation pathways after the activation of PMS by Co3O4/CDM.

SO4•− and •OH radical quencher while TBA as •OH quencher. The results of classical quenching tests, the nonradical pathway (1O2) and
removal rate of phenol decreased from 93.13% to 84.29% with the the radicals (SO4•− and •OH) both contributed to the phenol
addition of TBA, whereas to 51.67% after MeOH was added. It meant degradation.
that both •OH and SO4•− radicals contribute to the removal of phenol in To better understand the PMS activation mechanism, XPS of Co3O4/
the AOPs and SO4•− was the dominant radicals in the reaction. Besides, CDM before and after degradation reaction were further performed.
NaN3 can effectively quench 1O2, •OH and SO4•− , and its addition nearly Fig. 6(c) demonstrated the high-resolution O 1 s spectrum. The char­
inhibited the degradation process, which suggested the existence of 1O2 acteristic peak located at 530.08, 531.31 and 533.36 eV can be ascribed
in the system. By combination of the EPR spectra variation and the to the typical metal‑oxygen bond in Co3O4 (Co–O), the surface

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Fig. 8. (a) TOC removal of phenol degradation; (b) the concentration of Co leaching in phenol degradation; (c) removal efficiencies of phenol after each cycle. Phenol
concentration = 20 mg L − 1, PMS concentration = 7 mM, initial pH = 4.0, catalyst dose = 4 mg.

absorbed oxygen species (–OH) and the absorbed molecular water at the
≡ Co(II) + SO•−5 ↔ ≡ Co(III) + SO2−4 + 1 O2 (4)
surface region, respectively. For the high-resolution spectrum of C 1s
(Fig. S7(b)), three characteristic peaks with binding energy of 284.80,
HSO−5 + SO2−5 ↔ HSO−4 + SO2−5 + 1 O2 (5)
286.36 and 288.41 eV were corresponding to C–C, C–O and C– – O,
respectively. For the Co 2p spectrum, the binding energies located at 796 1
O2 + C6 H5 OH→other intermediates + CO2 + H2 O (6)
and 780 eV (Fig. 6(d)) were attributed to Co 2p1/2 and Co 2p3/2,
respectively. Furthermore, the peaks at 780.0 (Co 2p3/2) and 795.0 eV
SO⋅−4 + OH− →SO2−4 + ⋅ OH (7)
(Co 2p1/2) can be attributed to Co3+. While those at 781.6 (Co 2p3/2) and
796.5 eV (Co 2p1/2) belong to Co2+. After catalytic reaction, the decline
SO⋅−4 + H2 O→HSO−4 + ⋅ OH (8)
of the lattice oxygen content (from 35.7% to 30.07%) and C– – O content
(from 21.22% to 15.96%) demonstrated that it was involved in the re­ •
OH + SO⋅−4 (dominant) + C6 H5 OH→several steps→CO2 + H2 O + SO2−4
action to form 1O2 (Liu et al., 2020). Furthermore, the content of Co (III)
(9)
decreased from 25% to 19.64%, while that of Co (II) increased from
74.99% to 80.9%. The result could be due to the coexisting oxidation
and reduction reactions in the solution (Zhang, Chen, & Zhu, 2016). 3.5. Possible degradation pathway of phenol by Co3O4/CDM activated
Based on these experimental results, the mechanisms of PMS acti­ PMS system
vation on Co3O4/CDM for phenol degradation might be proposed as
follows. Co3+ firstly combined with PMS to generate SO5•− (Eq. (3)), A possible pathway for phenol degradation in the catalytic system
increasing the content of Co2+ in the catalyst after the reaction. Ac­ was schematically proposed based on LC-MS results (Fig. S8 and
cording the literature, Co2+ acted as the main active sites and react with Table S3) and was consistent with other literature work (Gao, Liu, Xia,
SO5•− to produce 1O2 through Eq. (4) (Liu et al., 2020). Moreover, 1O2 Wang, & Dong, 2018; Othman, Zain, Haija, & Banat, 2020) (Fig. 7).
might also come from the self-decomposition of PMS (Liang et al., 2017). Initially SO4•− , •OH and 1O2 could attack the aromatic ring of phenol
Consequently, phenol was efficiently decomposed by 1O2 according to effectively. The first step was through oxidative hydroxylation of the
Eqs. (5)–(6). During this process, some SO4•− could also react with OH− aromatic ring to form hydroxybenzoic acid, hydroxyquinone, hydro­
or H2O to produce •OH (Eqs. (7)–(8) (Hamideh et al., 2018). Both SO4•− quinone and hydroxybenzoic aldehyde. Hydroxybenzoic aldehyde pre­
and •OH could decompose or even mineralize the phenol molecules sented in the present LC-MS spectra, and was oxidized to benzoquinon
enriched on the surface of Co3O4/CDM (Eq. (9)). The balance among and 4,4′ -dihydroxybiphenyl. On the second step, ring-opening of
Co2+/Co3+, O2− /O2 and PMS catalyzed in the water ensured the Hydroksyquinone gave rise to succinic acid, which further degraded to
continuous generation of SO4•− , •OH and 1O2. CO2 and H2O. Benzoquinon and 4,4′ -dihydroxybiphenyl were trans­
formed to muconic acid. Then muconic acid would be further break
≡ Co(III) + HSO−5 →Co(II) + SO⋅−5 + H+ (3)
down into simpler acids in the third step, and ultimately was complete

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C. Hou et al. Carbohydrate Polymers 273 (2021) 118548

mineralized to CO2 and H2O. The result was furthermore testified by Cao, P. J., Gui, X. G., Pawar, D., Han, S., Xu, W. Y., Fang, M., et al. (2021). Highly
ordered mesoporous V2O5 nanospheres utilized chemiresistive sensors for selective
TOC analysis revealing about 62% mineralization of phenol (Fig. 8(a)).
detection of xylene. Materials Science and Engineering B, 265.
Gao, J., Liu, Y., Xia, X., Wang, L., & Dong, W. (2018). Fe1− xZnxS ternary solid solution as
3.6. Catalyst reusability and stability an efficient Fenton-like catalyst for ultrafast degradation of phenol. Journal of
Hazardous Materials, 353, 393–400.
Giannakis, S., Andrew Lin, K. Y., & Ghanbari, F. (2021). A review of the recent advances
The reusability and stability of Co3O4/CDM were studied and the on the treatment of industrial wastewaters by Sulfate Radical-based Advanced
results were shown in Fig. 8(c). The phenol degradation in Co3O4/CDM Oxidation Processes (SR-AOPs). Chemical Engineering Journal, 406.
Gong, Y., Zhao, X., Zhang, H., Yang, B., Xiao, K., Guo, T., et al. (2018). MOF-derived
activated PMS system was not apparently abated by sextic loop opera­
nitrogen doped carbon modified g-C3N4 heterostructure composite with enhanced
tions. However, in sextic run test, the phenol removal decreased from photocatalytic activity for bisphenol A degradation with peroxymonosulfate under
93% to 84% at 20 min, which can be attributed to the loss in the surface visible light irradiation. Applied Catalysis B: Environmental, 233, 35–45.
Hamideh, B., Akbar, E., Ramin, N., Mohseni-Bandpi, A., Anvar, A., et al. (2018).
active sites of the catalyst. Besides, ICP was applied to evaluate the
Degradation of trichloroethylene by sonophotolytic-activated persulfate processes:
release amount of cobalt after degradation (Fig. 8(b)), and the leaching Optimization using response surface methodology. Journal of Cleaner Production,
content of cobalt was 0.8 mg L− 1, which was lower than the limited of 198, 1210–1218.
Chinese National Standard (GB 25467-2010). Finally, the Co3O4/CDM Jiao, Y., Wan, C. C., Bao, W. H., Gao, H., Liang, D. X., & Li, J. (2018). Facile
hydrothermal synthesis of Fe3O4@cellulose aerogel nanocomposite and its
could be easily taken out from the solution without any complex treat­ application in Fenton-like degradation of Rhodamine B. Carbohydrate Polymers, 189,
ment. Therefore, the fabricated Co3O4/CDM is a promising catalyst for 371–378.
the degradation of phenol. Kalantari, E., Khalilzadeh, M. A., Zareyee, D., & Shokouhimehr, M. (2020). Catalytic
degradation of organic dyes using green synthesized Fe3O4-cellulose-copper
nanocomposites. Journal of Molecular Structure, 1218.
4. Conclusions Khalilzadeh, M. A., Sadeghifar, H., & Venditti, R. (2019). Natural clinoptilolite/KOH: An
efficient heterogeneous catalyst for carboxymethylation of hemicellulose. Industrial
& Engineering Chemistry Research, 58(27), 11680–11688.
In short, Co3O4 NPs-decorated cellulose derivative membrane Lee, Y.-R., Yoo, H., Choi, J., & Ahn, W.-S. (2020). Electrocatalytic oxygen reduction over
(Co3O4/CDM) was synthesized by simple in-situ method and calcination Co@Co3O4/N-doped porous carbon derived from pyrolysis of ZIF-8/67 on cellulose
process. It was proved that further recrystallization of Co-MOF-74/ nanofibers. Cellulose, 27(5), 2723–2735.
Liang, P., Zhang, C., Duan, X., Sun, H., Liu, S., Tade, M. O., et al. (2017). An insight into
cellulose composite membrane can improve the dispensability of metal organic framework derived N-doped graphene for the oxidative degradation of
Co3O4 NPs. Besides, cellulose derivative membrane used as matrix was persistent contaminants: Formation mechanism and generation of singlet oxygen
also beneficial for catalyst recycle. Basing on the excellent peroxidase- from peroxymonosulfate. Environmental Science: Nano, 4(2), 315–324.
Liu, F., Piao, Y. X., Choi, J. S., & Seo, T. S. (2013). Three-dimensional graphene
like activity and high affinity to the substrates, the dual-functional
micropillar based electrochemical sensor for phenol detection. Biosensors and
Co3O4/CDM was successfully applied both for fast colorimetric detec­ Bioelectronics, 50, 387–392.
tion and degradation of phenol in water samples. It was concluded that Liu, L., Li, Y., Li, W., Zhong, R., Lan, Y., & Guo, J. (2020). The efficient degradation of
the as-prepared exhibited a wide linear range, low detection limit and sulfisoxazole by singlet oxygen (1O2) derived from activated peroxymonosulfate
(PMS) with Co3O4-SnO2/RSBC. Environmental Research, 187, Article 109665.
high selectivity in phenol detection. Additionally, the Co3O4/CDM Liu, T., Guo, Y. F., Yan, Y. M., Wang, F., Deng, C., Rooney, D., et al. (2016). CoO
achieved good catalytic activity towards PMS and can remove phenol nanoparticles embedded in three-dimensional nitrogen/sulfur co-doped carbon
with more than 90% degradation efficiency after 20 min. The possible nanofiber networks as a bifunctional catalyst for oxygen reduction/evolution
reactions. Carbon, 106, 84–92.
degradation mechanism was proposed based on the valence state Liu, W. J., Jiang, H., & Yu, H. Q. (2015). Development of biochar-based functional
changes of catalytic sites and the intermediate by the LC-MS and XPS materials: Toward a sustainable platform carbon material. Chemical Reviews, 115
analysis, respectively. This work exhibited great prospect of Co3O4/ (22), 12251–12285.
Lu, J. Y., Yuan, Y. R., Hu, X., Liu, W. J., Li, C. X., Liu, H. Q., et al. (2020). MOF-derived
CDM in organic contaminants detection and elimination. Fe2O3/nitrogen/carbon composite as a stable heterogeneous electro-Fenton catalyst.
Industrial & Engineering Chemistry Research, 59(5), 1800–1808.
CRediT authorship contribution statement Oh, W. D., Dong, Z. L., & Lim, T. T. (2016). Generation of sulfate radical through
heterogeneous catalysis for organic contaminants removal: Current development,
challenges and prospects. Applied Catalysis B: Environmental, 194, 169–201.
Chen Hou: Conceptualization, Methodology, Writing – review & Othman, I., Zain, J. H., Haija, M. A., & Banat, F. (2020). Catalytic activation of
editing. Linhui Fu: Data curation, Writing – original draft, Investiga­ peroxymonosulfate using CeVO4 for phenol degradation: An insight into the reaction
pathway. Applied Catalysis B: Environmental, 266.
tion, Software. Yang Wang: Methodology, Writing – review & editing,
Rosi, N. L., Kim, J., Eddaoudi, M., Chen, B. L., O’Keeffe, M., & Yaghi, O. M. (2005). Rod
Supervision. Wenqiang Chen: Visualization, Investigation. Fang Chen: packings and metal-organic frameworks constructed from rod-shaped secondary
Visualization, Software. Sufeng Zhang: Conceptualization, Supervision, building units. Journal of the American Chemical Society, 127, 1504–1518.
Seyednejhad, S., Khalilzadeh, M. A., Zareyee, D., Sadeghifar, H., & Venditti, R. (2019).
Validation. Jianzhi Wang: Investigation, Resources.
Cellulose nanocrystal supported palladium as a novel recyclable catalyst for Ullmann
coupling reactions. Cellulose, 26(8), 5015–5031.
Acknowledgments Wang, C., Chen, Y. Q., Snizhko, D., Du, F. X., Ma, X. G., Lou, B. H., et al. (2020).
Development of luminol-fluorescamine-PVP chemiluminescence system and its
application to sensitive tyrosinase determination. Talanta, 218.
This work was supported by the National Natural Science Foundation Wu, S. W., Guo, D., Xu, X. C., Pan, J. M., & Niu, X. H. (2020). Colorimetric quantification
of China (No. 21806096), the China Postdoctoral Science Foundation and discrimination of phenolic pollutants based on peroxidase-like Fe3O4
(2020M683412), the Natural Science Basic Research Plan in Shaanxi nanoparticles. Sensors and Actuators. B, Chemical, 303.
Wu, Y., Wang, Y., Lin, Z. Q., Wang, Y. Y., Li, Y., Liu, S. W., et al. (2019). Three-
Province (2021JQ-529) and the Special Research Program of Shaanxi dimensional α-Fe2O3/amino-functionalization carbon nanotube sponge for
Provincial Department of Education (20JK0541). adsorption and oxidative removal of tetrabromobisphenol A. Separation and
Purification Technology, 211, 359–367.
Wu, Y., Xu, G., Zhang, W., Song, C., Wang, L., Fang, X., et al. (2021). Construction of
Appendix A. Supplementary data ZIF@electrospun cellulose nanofiber derived N doped metallic cobalt embedded
carbon nanofiber composite as binder-free supercapacitance electrode. Carbohydrate
Supplementary data to this article can be found online at https://doi. Polymers, 267, Article 118166.
Xin, S. Z., Yang, H. P., Chen, Y. Q., Yang, M. F., Chen, L., Wang, X. H., et al. (2015).
org/10.1016/j.carbpol.2021.118548. Chemical structure evolution of char during the pyrolysis of cellulose. Journal of
Analytical and Applied Pyrolysis, 116, 263–271.
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