Separation and Purification Technology 143 (2015) 19–26

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Separation and Purification Technology

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

Activated carbon fiber as heterogeneous catalyst of peroxymonosulfate

activation for efficient degradation of Acid Orange 7 in aqueous solution
Shiying Yang ⇑, Tuo Xiao, Jun Zhang, Youyuan Chen, Lei Li
Key Laboratory of Marine Environment and Ecology, Ministry of Education, Qingdao 266100, China
College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100, China

a r t i c l e i n f o a b s t r a c t

Article history: Increasing attention has been paid to environmental friendly activation method of peroxymonosulfate
Received 10 September 2014 (PMS) in the field of advanced oxidation processes (AOPs). In this work, activated carbon fiber (ACF)
Received in revised form 14 January 2015 was utilized as an effective and green catalyst to activate peroxymonosulfate (PMS) for degradation of
Accepted 17 January 2015
aqueous organic pollutant. As results indicated, a very low dosage of ACF (0.3 g L 1) could efficiently acti-
Available online 22 January 2015
vate PMS to eliminate Acid Orange 7 (AO7), a probe compound, and the degradation of AO7 followed first
order kinetics. Surface chemistry analyses of ACF samples, including BET specific surface area, pH at the
Keywords:
point of zero charge, Boehm titration and FTIR spectroscopy, suggested that the basic sites on ACF surface
Activated carbon fiber
Peroxymonosulfate activation
were likely to be the active sites inducing the decomposition of PMS and the generation of radicals.
Catalytic activity Quenching studies confirmed that sulfate radicals (SO4 ) and hydroxyl radicals (HO), which formed on
Dye degradation the surface of ACF, were the primary oxidizing species. A possible pathway for AO7 degradation was pro-
Reaction mechanism posed by monitoring the temporal evolution of intermediates in the solution, with the use of GC–MS and
ionic chromatography (IC). It is suggested that the degradation process of AO7 was initiated by cleavage
of azo linkage and further undergoes ring-opening reactions.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction the electron-transfer mediator, resulting in decomposition of

Advanced oxidation processes (AOPs) are considered as one of
the most effective methods to degrade organic contaminants due
to the generation of powerful oxidizing species. AOPs based on
the hydroxyl radical (HO), which has a redox potential of 1.8–
2.7 V vs. NHE (normal hydrogen electrode) [1], have been widely
studied and used in water or wastewater treatment [2–4]. In recent
years, increasing attention has been paid to the sulfate radical
(SO4 ). Compared to HO, SO4 demonstrated the same or even a
higher redox potential of 2.5–3.1 V vs. NHE [5] and has a great
ability to oxidize organic pollutants. Persulfate (PS) and peroxy-
monosulfate (PMS) is an oxidant which has been widely studied
to generate SO4 with activators including UV [6], heat [7], base
[8] and transition metals [9,10].
Porous carbon materials are excellent adsorbents and have been
used since many years ago. Nowadays, the catalytic ability of acti-
vated carbon (AC) has attracted much scientific interests in the
field of wastewater treatment. AC has many oxygen-containing
functional groups on the surface, which may act as active sites of
⇑ Corresponding author at: College of Environmental Science and Engineering,
Ocean University of China, Qingdao 266100, China. Tel.: +86 532 66782780.
E-mail address: shiningpup@hotmail.com (S. Yang).
hydrogen peroxide (H2O2) [11] and PS [12]. Researchers have
found that contaminants can be successfully degraded in the AC/
H2O2 system [13–16] or in the AC/PS system [17]. Our group pre-
viously confirmed that granular activated carbon (GAC) can also
catalyze PMS to produce radicals for degradation of azo dye Acid
Orange 7 (AO7) [18].
In the current work, we explore the application of activated car-
bon fiber (ACF), which has higher adsorption rates in the gas or
liquid phase [19]. For a long time, ACF was exclusively used in
waste water treatment based on its function as adsorption materi-
als [20,21], and in recent years it was also studied as catalyst sup-
ports [22,23]. However, to the best of our knowledge, there are no
previous studies on the application of ACF for directly catalytic
PMS oxidation, although catalytic ozonation or Fenton oxidation
with ACF has been studied [4,24].
The objectives of this present study are, (a) to demonstrate the
feasibility of ACF as a catalyst to activate PMS for degradation an
azo dye Acid Orange 7 (AO7), which has commonly been used as
a model compound for HO or SO4 based AOPs [2,4,17]; (b) to
investigate the reaction kinetics involving the influence of the con-
centration of PMS and the dosage of ACF; (c) to find the active sites
on ACF surface which are responsible for the decomposition of
PMS; (d) to identify the dominating oxidizing species generating

http://dx.doi.org/10.1016/j.seppur.2015.01.022
1383-5866/Ó 2015 Elsevier B.V. All rights reserved.
20 S. Yang et al. / Separation and Purification Technology 143 (2015) 19–26

from PMS decomposition and resulting in AO7 decay; and (e) to concentrated to 1.0 mL on a rotatory evaporator, and was kept at
give the possible pathway of AO7 degradation. 4 °C prior to GC analysis. The concentrated sample in CH2Cl2
(1 lL) was injected into a 6890 N/5975 GC/MS system for analysis.
DB-5MS capillary column with an inner diameter of 0.250 mm and
2. Material and methods
a length of 30 m was adopted in the separation system. The GC col-
umn was operated in a temperature programmed mode by main-
2.1. Materials
taining the temperature at 40 °C for 5 min, then increasing to
290 °C with an increment of 3 °C min 1 and finally holding at
Peroxymonosulfate (PMS), which is available as a triple salt of
290 °C for 10 min. Electron impact (EI) mode at 70 eV was used
sulfate commercially known as oxone (2KHSO5
KHSO4
K2SO4),
and the mass range scanned was 0–500 m/z. The substance analy-
was purchased from Shanghai Ansin Chemical Company, China.
sis was undertaken with reference to the software of NIST MS
AO7 and other chemicals were purchased from Shanghai Chemical
search 2.0.
Reagent Company and used without purification. Commercial acti-
The concentration of NH+4, NO2 , CH3COO and HCOO was per-
vated carbons (granular, about 2 mm in diameter and 4 mm in
formed with ionic chromatography (ICS-3000) and equipped with
length, SBET = 1050 m2 g 1, Vtotal = 0.49 cm3 g 1 and Vmicro = 0.26
cation exchange column of IonPac CS11-HC and anion exchange
cm3 g 1) were supplied by Shanxi Xinhua Chemical Plant.
column of IonPac AS12A.
Commercially viscose-based activated carbon fibers (felty, 10–20 lm
in diameter and 3–4 mm in thickness, SBET = 1080 m2 g 1,
Vtotal = 0.52 cm3 g 1 and Vmicro = 0.50 cm3 g 1) were obtained from 3. Results and discussion
Sutong Carbon Fiber Company, China. Before use they were both
washed with distilled water and subsequently dried at 105 °C for 3.1. Catalytic activity of ACF
24 h. The dried GAC and ACF samples were then kept in a desicca-
tor for later use and labelled as GAC0 and ACF0. Fig. 1a shows AO7 removal by PMS oxidation, GAC or ACF
adsorption, and GAC or ACF catalytic PMS oxidation. In 120 min,
2.2. Reactor and procedure the decolorization ratios of AO7 were 6%, 56% and 100% in the sys-
tem of PMS, ACF0 and the ACF0/PMS combined system, respec-
The experiments of AO7 removal by GAC or ACF adsorption, tively. Activation is necessary for application since PMS has a low
PMS oxidation, and GAC or ACF catalytic PMS oxidation were all reactivity. Obviously, there existed a synergistic effect in the
carried out in 500 mL flasks containing 250 mL of AO7 solution ACF0 and PMS combined system. That is to say, ACF has a great cat-
with an initial concentration of 100 mg L 1. The flasks were par- alytic activity of PMS activation for AO7 degradation.
tially immersed in a water bath fitted with a temperature control- Besides, it should also be noticed that the AO7 elimination rate
ler. The reaction mixture was stirred constantly at 25 ± 1 °C. Unless in the ACF0/PMS system is much higher than that in the GAC0/PMS
otherwise specified, the dosage of GAC or ACF was 0.3 g L 1, and system, in which only about 11% AO7 was removed in 120 min.
the mole ratio of PMS to AO7 was 20/1. The initial pH was adjusted This phenomenon may be attributed to the fact that ACF had a
to 5 by using 1 M NaOH or 1 M H2SO4. At a fixed interval, samples higher adsorption rate for AO7 (Fig. 1a). It is due to pore volume
were withdrawn and filtered before to be analyzed. and uniform microporosity [28] and a higher catalytic activity of
In the special experiments involving ACF pretreatment by PMS,
0.3 g L 1 ACF was immersed in 250 mL PMS solution of which the
initial concentration is 5.71 mM. The concentration was as same as
general oxidation experiments, and the reaction mixture was stir-
red constantly at 25 ± 1 °C. After specific time, ACF samples were
filtered out and washed with distilled water alternately for several
times, thereafter were dried at 105 °C for 3 h. After that these PMS-
oxidized ACF samples were also stored in a desiccator. It should be
noted that the experimental results labelled as ACF15, ACF30 and
ACF60 were the products of ACF pretreated with a PMS solution
(5.71 mM) for 15 min, 30 min and 60 min, respectively.

2.3. Analytical methods

The decolorization of AO7 was monitored by measuring the

absorbance of samples at 484 nm (UNICO 2100 spectrophotome-
ter, UNICO (Shanghai) Instruments Co., Ltd., China) as a function
of reaction time.
The concentration of PMS was analyzed via an iodometric titra-
tion method [25]. The point of zero charge (pHpzc) for ACF was
determined according to a mass titration method [26]. The Boehm
titration method was used to determine the acidity and the basi-
city of ACF [27].
Specific surface area was determined by a ST-08A Specific Sur-
face Area Analyzer. Fourier transform infrared (FTIR) spectroscopy
analysis of the ACF was performed on a BRUKER TENSOR 27
spectrometer.
GC–MS was used to detect the organic intermediate products of
AO7 degradation. The sample at 120 min was extracted with Fig. 1. (a) The degradation of AO7 in different systems. (b) The comparison of PMS
CH2Cl2 (3 times, 20 mL each time). The extraction liquid was then decomposition ratios in the presence of ACF0 and GAC0.
 S. Yang et al. / Separation and Purification Technology 143 (2015) 19–26 21

Fig. 2. UV–vis spectra of methanol extractions from used ACF in the ACF/PMS
system.

Fig. 4. (a) Effect of ACF dosage on the degradation of AO7 in the ACF/PMS system.
(b) The degradation rates of AO7 and PMS decomposition ratios vs. ACF dosages in
the ACF/PMS system.

Fig. 3. Effect of PMS concentration on the degradation of AO7 in the ACF/PMS

Table 1
system.
Surface characteristics of ACF0 and ACF60.

Sample SBET pHzpc Total acidity Total basicity

PMS decomposition than GAC (Fig. 1b). Apparently, ACF was supe- (m2 g 1
) (lmol g 1) (lmol g 1)
rior over GAC for activating PMS to generate some active species, ACF0 1080 7.23 330 643
which will degrade aqueous organic pollutant. ACF60 904 1.75 1928 352
Although 100% decolorization of AO7 was achieved in the ACF/
PMS system, it was still uncertain whether the removal of AO7 was
mainly due to oxidation other than adsorption, because some of 10/1 to 20/1 or 30/1. Possibly, this can be explained by the limited
AO7 molecular might be adsorbed on the surface of ACF. In order amount of active sites on the surface of ACF (0.3 g L 1) relative to
to answer this question, a simple experiment was conducted as fol- the PMS concentration. In the meantime, the excessive PMS may
lows: After 120 min, the ACF sample in the ACF/PMS system was scavenge sulfate radicals.
filtered out and then methanol was employed to extract the adsor- In order to confirm this assumption, effect of ACF dosage on the
bates on the surface of ACF. The recovery AO7 of extraction from AO7 degradation and PMS decomposition were studied, and the
ACF surface of this method is close to 61.3%. The results are pre- results are depicted in Fig. 4. As shown in Fig. 4a, AO7 was
sented in Fig. 2. The negligible absorbance at 484 nm of methanol degraded more and more quickly with increased ACF dosages.
extractions indicates that there is no obvious quantity of AO7 Fig. 4b displays the pseudo first-order kinetic constants (k0,AO7)
absorbed on ACF in the ACF/PMS system. In addition, the strong and PMS decomposition ratios as a function ACF dosage. Interest-
absorbance in the UV region, especially at 225 nm, 232 nm and ingly, as observed, both k0,AO7 and PMS decomposition ratios line-
252 nm, shows intermediate products of AO7 degradation, which arly increased with ACF dosages. The relationship between PMS
may be some aromatic compounds. In conclusion, it is believed decomposition ratios and ACF dosages is similar to the phenome-
that AO7 was almost fully oxidized other than adsorbed in the non that between PS decomposition and AC dosage, which was also
ACF/PMS system. obtained by other researchers [12].

3.2. Reaction kinetics of AO7 removal 3.3. Active sites of ACF

The first-order loss of AO7 in solutions with a range of PMS/AO7
molar ratios is illustrated in Fig. 3. When PMS/AO7 molar ratio
increased from 5/1 to 10/1, there was an obvious enhancement
in the AO7 removal. However, the decay rate of AO7 can hardly
have an improvement when PMS/AO7 molar ratio increased from
In order to explore how PMS oxidation caused the change of
ACF catalytic ability, surface textural and chemical properties of
different ACF samples were characterized. Data of specific surface
area, pHpzc, total acidity and total basicity are summarized in
Table 1. Additionally, the FTIR spectrums of different ACF and
22 S. Yang et al. / Separation and Purification Technology 143 (2015) 19–26
Fig. 5. (a) FTIR spectra for ACF0, ACF-Used, GAC-0. (b) FTIR spectra for ACF0, ACF15,
ACF30 and ACF60.
GAC samples are also monitored as presented in Fig. 5. Major
absorption differences in the spectrums of samples are in five posi-
tions: 3430 cm 1, 1710 cm 1, 1558 cm 1, 1400 cm 1 and
1111 cm 1. The absorption of 1558 cm 1 can be ascribed to stretch
vibration of C@O [29], and 3430 cm 1 can be assigned to hydrogen-
bonded OH [30]. The absorption in 1710 cm 1 and 1400 cm 1 was
due to the existence of COOH and C@OH stretching molds in phe-
nolic groups respectively. The peak at 1111 cm 1 indicated the
involvement of OH or COC [31]. Fig. 5a showed that the hydro-
gen-bonded OH of used ACF and GAC were poor while C@O and
CAOH increased compared to ACF-0. Furthermore, the FITR spec-
trum of ACF-Used demonstrated that there were no sign of AO7
on the surface, which was consistent with the extraction
experiment.
After pre-oxidation by PMS, Fig. 6 showed that the treatment
has restrained the catalytic activity of ACF. The degradation rates
of ACF0, ACF15, ACF30, ACF60 are 5.8  10 2, 5.4  10 2,
4.9  10 2, and 3.7  10 2 min 1 respectively. In a word, the
longer pretreat time is, the more obvious inhibitory effect would
emerge.
In order to further understand the deep reasons of the restrain
effect, we try to explore from the perspective of material proper-
ties. ACF exhibited the decrease of pHpzc from 7.23 to 1.75 and
the sextuple increase of the total acidity, which possibly a reflec-
tion of the increase in acidic functional groups. The analysis of
functional constituents by FTIR (Fig. 5b) proved this speculation.
In contrast to ACF0, the OH absorptions of ACF15, ACF30 and
ACF60 at 3430 cm 1 only slightly decreased, and absorption at
Fig. 6. (a) Effect of PMS pretreatment on ACF catalytic ability. (b) Pseudo first-order
kinetics of AO7 removal by ACF catalytic PMS oxidation ([AO7]0 = 100 mg/L, ACF
dosage = 0.3 g/L, PMS/AO7 molar ratio = 20/1).
1558 cm 1 and 1111 cm 1 of them had pronounced increases. It
may be due to the formation or increase of lactone groups, which
have bands of both COC and C@O. From the above results, PMS pre-
treatment caused the increase of carboxyl and lactone on ACF sur-
face, which are both acidic groups. The result of FTIR analysis was
consistent with the measurement of the total acidity.
Although it is difficult to find information about basic oxygen-
containing groups in FTIR spectrums of ACF samples, an obvious
decrease of the total basicity from ACF0 to ACF60 can be observed
from Table 1. It should be noted that the delocalized p-electrons of
the basal planes were also assumed to have a basic nature [32].
Above all, PMS pre-oxidation rendered ACF the increase of
acidic sites and the decrease of basic sites. The basic sites on the
surface of ACF were possible active sites provoking the decomposi-
tion of PMS and thereby the generation of radicals.
3.4. Radical identification
To identify the dominating oxidizing species responsible for
AO7 decay in the ACF/PMS system, methanol (MA) and tert-butyl
alcohol (TBA) were initially selected to perform quenching studies.
MA is widely used as the scavenger of HO and SO4 , while TBA is an
effective quenching agent for HO [33]. As depicted in Fig. 7, the
addition of either MA or TBA caused no effective decrease of AO7
removal even with a high mole ratio to AO7 of 1000/1. Actually,
prior to this study, similar results had been found in the GAC/PS
system [17]. It can be explained by the same fact that MA and
TBA as hydrophilic compounds are assumed not to be able to accu-
mulate near or on the surface of GAC or ACF to a significant extent.
However, the oxidizing species in the ACF/PMS system may be
 S. Yang et al. / Separation and Purification Technology 143 (2015) 19–26 23

Fig. 7. The degradation of AO7 in the ACF/PMS system in the presence of different
radical scavengers. (MA/AO7 molar ratio = 1000/1, TBA/AO7 molar ratio = 1000/1,
phenol/AO7 molar ratio = 50/1, NB/AO7 molar ratio = 50/1).

Fig. 10. (a) Concentration of NO2 and NH+4 (b) concentrations of formic acid and
acetic acid during AO7 degradation by the ACF/PMS system.
Fig. 8. UV–vis spectra change during the process of AO7 degradation.

As seen from Fig. 7, the addition of phenol or NB (with a mole

formed on the surface of ACF, as HO is formed on the surface of the
GAC in the GAC/H2O2 system [14]. It was assumed that phenol and
nitrobenzene (NB) could move close to the surface of ACF because
of the interaction between the delocalized p electrons of the oxy-
gen-free Lewis basic sites and the free electrons of the dye mole-
cule present in the aromatic rings. As a result, these two radical
inhibitors, phenol and NB, were also utilized to conduct quenching
experiments.
ratio to AO7 of 50/1) significantly inhibited the performance of
the ACF/PMS system with AO7 removal decreased from 100% to
36% and 65% in 120 min, respectively. Because phenol can react
with both SO4 and HO with high rates (kSO4 /phenol = 8.8  109
M 1 s 1, kHO /phenol = 6.6  109 M 1 s 1) [34,35], and that NB has
different reaction rate constants with SO4 and HO (kSO4 /NB < 106
M 1 s 1, kHO /NB = 3.0  109 M 1 s 1) [36,37], the involvement of
both SO4 and HO was therefore confirmed. In others words, SO4

Fig. 9. GC–MS identified reaction intermediates during AO7 degradation by the ACF/PMS system.
24 S. Yang et al. / Separation and Purification Technology 143 (2015) 19–26
Fig. 11. Possible pathway of AO7 degradation in the ACF/PMS system.
and HO may share the responsibility for AO7 degradation. Further-
more, it is concluded that the degradation of AO7 does not occur in
the bulk aqueous phase, but near or on the surface of ACF, since SO-4

and HO are formed on ACF surface and their half-lives are so
short that they cannot move to bulk aqueous phase.
3.5. AO7 degradation pathway
To clarify the changes of molecular and structural characteris-
tics of AO7 during the oxidation process in ACF-activated PMS oxi-
dation, samples were taken at time intervals of 0, 20, 40 and
80 min and representative UV–vis spectra changes as a function
of reaction time were observed. The corresponding spectra are
shown in Fig. 8. The azo dye, AO7, basically consists of an azo link-
age (AN@NA), a benzene ring and naphthalene ring, all of which
exhibit different absorbance peaks. The maximum absorption
wavelength for AO7 was determined to be 484 nm, which accounts
for the orange color of solution and can be attributed to the azo
linkage. The two other bands in the ultraviolet region located at
229 and 310 nm are related to the naphthalene and benzene rings,
respectively [38,39]. As the reaction proceeded, the visible band
remarkably disappeared and this was mainly due to the fragmen-
tation of the azo links by oxidation. In addition, the decay of the
absorbance at 229 and 310 nm was considered as evidence of aro-
matic fragment degradation in the dye molecule and its intermedi-
ates [40].
To further identify the intermediate products, GC–MS analysis
was employed and the products identified are shown in Fig. 9.
And the concentration of NH+4, NO2 , CH3COO and HCOO as a
function of reaction time was also determined by IC as shown in
Fig. 10. As the result of Fig. 10, these four kinds of intermediate
products wiped out in 120 min and NO3 was not detected in the
experiments. In order to verify the inferences that ACF can adsorb
the intermediate products which generated by AO7, the experi-
ments of adsorption of NO3 , CH3COO and HCOO by ACF were
proceeded. As Fig. S1 indicated that the ACF can adsorb low con-
centration of nitrate rapidly. In addition, the ACF can also adsorb
CH3COO and HCOO (Fig. S2).
Based on these results, a possible pathway for AO7 degradation
in the ACF/PMS system is proposed in Fig. 11. It is assumed that the
degradation process is initiated by the separation of azo links due
to the oxidative attack of SO4 and HO that generated from PMS by
the activation of ACF [41–44]. The free radicals render the forma-
tion of sulfanilic acid and 1-amino-2-naphtol [45]. As sulfanilic
acid has high thermal stability, it can easily dissolve in water.
And the 1-amino-2-naphtol is sensitive to oxygen, so it can be
 S. Yang et al. / Separation and Purification Technology 143 (2015) 19–26
oxidized in the air [46]. For these reasons, the GC–MS had not
detected these two products. Then they are further oxidized, the
desulfurization lead sulfanilic acid to form 1,4-benzoquinone
[47]. At the same time the further oxidation of 1-amino-2-naphtol
can product 1,2-naphthalenedione, 2H-1-benzopyran-2-one and
phthalic anhydride [48]. And the oxidation process of sulfanilic
acid and 1-amino-2-naphtol can generate NH+4, NO2 . As proposed
in Fig. 9a, in the reaction the concentration of NH+4 is well above
that of NO2 , and NO3 was not detected from the samples. We
can deduce that in the AO7 degradation process the N is mainly
transformed to NH+4. Then, all the organics of intermediate prod-
ucts undergo ring-opening reactions and lead to the formation of
short-chain aliphatic acids such as CH3COO and HCOO . Finally,
these organics are mineralized into CO2 and H2O [45]. From
Fig. 9b, both the concentration of CH3COO and HCOO increased
firstly and then decreased. It can be interpreted that as the reaction
went on, AO7 decolorizing reaction was nearly completed. The
degradation of intermediate products would be the main reaction,
so formic acid and acetic acid began to be degraded into CO2 and
H2O. Besides part of formic acid and acetic acid would be adsorbed
on the surface of ACF.
4. Conclusions
ACF was successfully used to activate PMS to generate oxidizing
species to efficiently degrade AO7 in aqueous phase at ambient
temperature. In the ACF/PMS system, catalytic oxidation made
the major contribution to the total AO7 removal rather than
adsorption. Basic sites on the surface of ACF were possible active
sites for PMS decomposition with radicals generated. SO4 and
HO, formed on the surface of ACF, were mainly responsible for
AO7 degradation. Under the attack of radicals, the degradation pro-
cess of AO7 is initiated by cleavage of azo linkage and further
undergoes ring-opening reactions to cause mineralization. It is
practical significance of ACF, an environment-friendly catalyst, dis-
plays efficient catalytic activity of PMS activation.
Acknowledgement
Financial support from the National Natural Science Foundation
of China (No. 21107101) is fully acknowledged.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.seppur.2015.01.
022.
References
[1] G.V. Buxton, C.L. Greenstock, W.P. Helman, A.B. Ross, Critical review of rate
constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl
radicals (OH/O) in aqueous solution, J. Phys. Chem. Ref. Data 17 (1988) 513–
886.
[2] H. Zhang, Y.L. Li, X. Zhong, X.N. Ran, Application of experimental design
methodology to the decolorization of Orange II using low iron concentration of
photoelectro-Fenton process, Water Sci. Technol. 63 (2011) 1373–1380.
[3] H. Yao, P. Sun, D. Minakata, Kinetics and modeling of degradation of ionophore
antibiotics by UV and UV/H2O2, Environ. Sci. Technol. 47 (2013) 4581–4589.
[4] L. Wang, Y. Yao, Z. Zhang, Activated carbon fibers as an excellent partner of
Fenton catalyst for dyes decolorization by combination of adsorption and
oxidation, Chem. Eng. J. 251 (2014) 348–354.
[5] P. Neta, R.E. Huie, A.B. Ross, Rate constants for reactions of inorganic radicals in
aqueous solution, J. Phys. Chem. Ref. Data 17 (1988) 1027–1284.
[6] T.K. Lau, W. Chu, N.J.D. Graham, The aqueous degradation of butylated
hydroxyanisole by UV/S2O28 : study of reaction mechanisms via dimerization
and mineralization, Environ. Sci. Technol. 41 (2007) 613–619.
[7] C. Tan, N. Gao, Y. Deng, N. An, J. Deng, Heat-activated persulfate oxidation of
diuron in water, Chem. Eng. J. 203 (2012) 294–300.
25
[8] O.S. Furman, A.L. Teel, R.J. Watts, Mechanism of base activation of persulfate,
Environ. Sci. Technol. 44 (2010) 6423–6428.
[9] G.P. Anipsitakis, D.D. Dionysiou, Radical generation by the interaction of
transition metals with common oxidants, Environ. Sci. Technol. 38 (2004)
3705–3712.
[10] S.-Y. Oh, S.-G. Kang, P.C. Chiu, Degradation of 2,4-dinitrotoluene by persulfate
activated with zero-valent iron, Sci. Total Environ. 408 (2010) 3464–3468.
[11] M. Kimura, I. Miyamoto, Discovery of the activated-carbon radical AC+ and the
novel oxidation-reactions comprising the AC/AC+ cycle as a catalyst in an
aqueous solution, Bull. Chem. Soc. Jpn. 67 (1994) 2357–2360.
[12] C.J. Liang, Y.T. Lin, W.H. Shih, Treatment of trichloroethylene by adsorption and
persulfate oxidation in batch studies, Ind. Eng. Chem. Res. 48 (2009) 8373–
8380.
[13] S. Khorramfar, N.M. Mahmoodi, M. Arami, H. Bahrami, Oxidation of dyes from
colored wastewater using activated carbon/hydrogen peroxide, Desalination
279 (2011) 183–189.
[14] G. Wang, T. Wu, Y. Li, D. Sun, Y. Wang, X. Huang, G. Zhang, R. Liu, Removal of
ampicillin sodium in solution using activated carbon adsorption integrated
with H2O2 oxidation, J. Chem. Technol. Biotechnol. 87 (2012) 623–628.
[15] C.M. Domínguez, P. Ocón, A. Quintanilla, J.A. Casas, J.J. Rodriguez, Highly
efficient application of activated carbon as catalyst for wet peroxide oxidation,
Appl. Catal. B: Environ. 140–141 (2013) 663–670.
[16] A. Anfruns, E. Garcıa-Suarezb, M. Montes-Moran, New insights into the
influence of activated carbon surface oxygen groups on H2O2 decomposition
and oxidation of pre-adsorbed volatile organic compounds, Carbon 77 (2014)
89–98.
[17] S.Y. Yang, X. Yang, X.T. Shao, R. Niu, L.L. Wang, Activated carbon catalyzed
persulfate oxidation of azo dye Acid Orange 7 at ambient temperature, J.
Hazard. Mater. 186 (2011) 659–666.
[18] J. Zhang, X.T. Shao, C. Shi, S.Y. Yang, Decolorization of Acid Orange 7 with
peroxymonosulfate oxidation catalyzed by granular activated carbon, Chem.
Eng. J. 232 (2013) 259–265.
[19] J.M. Valente Nabais, P.J.M. Carrott, M.M.L. Ribeiro Carrott, J.A. Menéndez,
Preparation and modification of activated carbon fibers by microwave heating,
Carbon 42 (2004) 1315–1320.
[20] Q.S. Liu, T. Zheng, P. Wang, J.P. Jiang, N. Li, Adsorption isotherm, kinetic and
mechanism studies of some substituted phenols on activated carbon fibers,
Chem. Eng. J. 157 (2010) 348–356.
[21] X. Ma, F. Zhang, J. Zhu, Preparation of highly developed mesoporous activated
carbon fiber from liquefied wood using wood charcoal as additive and its
adsorption of methylene blue from solution, Biores. Technol. 164 (2014) 1–6.
[22] Y.Y. Yao, L. Wang, L.J. Sun, S. Zhu, Z.F. Huang, Y.J. Mao, W.Y. Lu, W.X. Chen,
Efficient removal of dyes using heterogeneous Fenton catalysts based on
activated carbon fibers with enhanced activity, Chem. Eng. Sci. 101 (2013)
424–431.
[23] Z. Huang, H. Bao, Y. Yao, Novel green activation processes and mechanism of
peroxymonosulfate based on supported cobalt phthalocyanine catalyst, Appl.
Catal. B: Environ. 154–155 (2014) 36–43.
[24] X.F. Qu, J.T. Zheng, Y.Z. Zhang, Catalytic ozonation of phenolic wastewater with
activated carbon fiber in a fluid bed reactor, J. Colloid Interf. Sci. 309 (2007)
429–434.
[25] I.M. Kolthoff, I.K. Miller, The chemistry of persulfate. I. The kinetics and
mechanism of the decomposition of the persulfate ion in aqueous medium, J.
Am. Chem. Soc. 73 (1951) 3055–3059.
[26] J.P. Reymond, F. Kolenda, Estimation of the point of zero charge of simple and
mixed oxides by mass titration, Powder Technol. 103 (1999) 30–36.
[27] H.P. Boehm, Some aspects of the surface chemistry of carbon blacks and other
carbons, Carbon 32 (1994) 759–769.
[28] J. Yang, P. Juan, Z. Shen, Removal of carbon disulfide (CS2) from water via
adsorption on active carbon fiber (ACF), Carbon 44 (2006) 1367–1375.
[29] G. Socrates, Infrared Characteristic Group Frequencies, second ed., Wiley,
Chichester, 1994.
[30] J.M. O’Reilly, R.A. Mosher, Functional groups in carbon black by FTIR
spectroscopy, Carbon 21 (1983) 47–51.
[31] M.S. Solum, R.J. Pugmire, M. Jagtoyen, F. Derbyshire, Evolution of carbon
structure in chemically activated wood, Carbon 33 (1995) 1247–1254.
[32] M.A. Montes-Morán, D. Suárez, J.A. Menéndez, E. Fuente, On the nature of basic
sites on carbon surfaces: an overview, Carbon 42 (2004) 1219–1224.
[33] J.Y. Zhao, Y.B. Zhang, X. Quan, S. Chen, Enhanced oxidation of 4-chlorophenol
using sulfate radicals generated from zero-valent iron and peroxydisulfate at
ambient temperature, Sep. Purif. Technol. 71 (2010) 302–307.
[34] M.E. Lindsey, M.A. Tarr, Inhibition of hydroxyl radical reaction with aromatics
by dissolved natural organic matter, Environ. Sci. Technol. 34 (2000) 444–449.
[35] J. Ziajka, W. Pasiuk-Bronikowska, Rate constants for atmospheric trace
organics scavenging SO4 in the Fe-catalysed autoxidation of S(IV), Atmos.
Environ. 39 (2005) 1431–1438.
[36] P. Neta, V. Madhavan, H. Zemel, R. Fessenden, Rate constants and mechanism
of reaction of SO4 with aromatic compounds, J. Am. Chem. Soc. 99 (1977)
163–164.
[37] R.G. Zepp, Nitrate-induced photooxidation of trace organic chemicals in water,
Environ. Sci. Technol. 21 (1987) 443–450.
[38] A. Azam, A. Hamid, Effects of gap size and UV dosage on decolorization of C.I.
Acid Orange 7 by UV/H2O2 process, J. Hazard. Mater. 133 (2006) 133–167.
[39] X. Zhang, Y. Wang, G. Li, J. Qu, Oxidative decomposition of azo dye C.I. Acid
Orange 7 (AO7) under microwave electrodeless lamp irradiation in the
presence of H2O2, J. Hazard. Mater. 134 (2006) 183–189.
26 S. Yang et al. / Separation and Purification Technology 143 (2015) 19–26
[40] H. Li, Y. Gong, Q. Huang, H. Zhang, Degradation of Orange II by UV-assisted
advanced Fenton process: response surface approach, degradation pathway,
and biodegradability, Chem. Res. 52 (2013) 15560–15567.
[41] S. Zhang, H. Yu, Y. Zhao, Kinetic modeling of the radiolytic degradation of Acid
Orange 7 in aqueous solutions, Water. Res. 39 (2005) 839–846.
[42] R. Yuan, S.N. Ramjaun, Z. Wang, J. Liu, Effects of chloride ion on degradation of
Acid Orange 7 by sulfate radical-based advanced oxidation process:
implications for formation of chlorinated aromatic compounds, J. Hazard.
Mater. 196 (2011) 173–179.
[43] D. Zhou, L. Chen b, C. Zhang, A novel photochemical system of ferrous sulfite
complex: kinetics and mechanisms of rapid decolorization of Acid Orange 7 in
aqueous solutions, Water. Res. 57 (2014) 87–95.
[44] H.V. Lutze, N. Kerlin, T.C. Schmidt, Sulfate radical-based water treatment in
presence of chloride: Formation of chlorate, inter-conversion of sulfate
radicals into hydroxyl radicals and influence of bicarbonate, Water. Res., in
press. http://dx.doi.org/10.1016/j.watres.2014.10.006.
[45] H. Zhao, Y. Sun, L. Xu, J. Ni, Removal of Acid Orange 7 in simulated wastewater
using a three-dimensional electrode reactor: removal mechanisms and dye
degradation pathway, Chemosphere 78 (2010) 46–51.
[46] M. Kudlich, M.J. Hetheridge, H.J. Knackmuss, A. Stolz, Autoxidation reactions of
different aromatic o-aminohydroxynaphthalenes that are formed during the
anaerobic reduction of sulfonated azo dyes, Environ. Sci. Technol. 33 (1999)
896–901.
[47] X. Zhong, L. Xiang, S. Royer, S. Valange, V. Barrault, H. Zhang, Degradation of
C.I. Acid Orange 7 by heterogeneous Fenton oxidation in combination with
ultrasonic irradiation, J. Chem. Technol. Biotechnol. 86 (2011) 970–977.
[48] X. Chen, X. Wang, H. Xiao, C. Hong, F. Zhu, Y. Yao, Z. Xue, Accelerated TiO2
photocatalytic degradation of Acid Orange 7 under visible light mediated by
peroxymonosulfate, Chem. Eng. J. 193–194 (2012) 290–295.