Chemical Engineering Journal 365 (2019) 175–182

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Chemical Engineering Journal

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

A facile method to modify activated carbon fibers for drinking water T

purification
⁎ ⁎
Qi Zuoa,b,1, Yu Zhanga,b,1, Hong Zhenga, , Pengyi Zhangb, , Hongwei Yangb, Jie Yub, Jie Tangc,
Yuedong Zhengc, Jiajie Maic
a
Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and
Technology, China University of Geosciences, Beijing 100083, China
b
State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China
c
Midea Group Kitchen & Water Heater Application Division, Foshan 528311, China

H I GH L IG H T S

• AEffects
method via flushing followed by calcination in humid N was used to modify ACF.
2

• Possibleofmechanism
modification parameters on pH change of sanitary soak were investigated.
• Modified ACFs underofoptimized
reducing pH change of soaking solution was clarified.
• This method can efficiently reduceconditions meet sanitary standards for drinking water.
• soaking pH change and improve COD removal.

A R T I C LE I N FO A B S T R A C T

Keywords: The safety of drinking water plays a vital role in human health. Activated carbon fibers (ACF) have been widely
Activated carbon fiber used in the field of water purification. However, current filter elements of water purifier made by ACF have an
Surface modification unqualified pH change which fails to meet sanitary soak standard and low COD removal rate. Considering the
Sanitary soak perspective of converting surface functional groups and adjusting composition of ACF, a facile method via
pH change
flushing followed by calcination in humid nitrogen atmosphere was used to modify ACF. The effects of some
COD removal
parameters including washing method, type of flushing water, flushing time, water content of calcined sample,
Drinking water purification
calcination temperature and time were investigated, and possible mechanism of reducing pH change of soaking
solution was clarified by characterizing the ACF samples before and after flushing and calcinations using Boehm
titration, XPS, TG/DTA-MS, BET, FTIR and IC analysis. The results show that some ions and fire retardants in
ACF were effectively removed and surface functional groups were converted from acidic to basic ones by this
method. Water in ACF was found to play an important role in promoting the release of gases and facilitating the
conversion of functional groups in the calcination process. The pH changes of all the modified ACF (M-ACF) and
filter elements of water purifier made by the M-ACF under optimized modification conditions met sanitary soak
standard and COD removal rate obviously increased. This economical and practical modification method for
solving unqualified soaking pH change and low COD removal problems of ACF filter elements of water purifier
has great significance in the field of drinking water purification.

1. Introduction
As an important natural resource and strategic economic resource,
water is a basic element for human survival and a basic safeguard for
social and economic development. The health and safety of drinking
water plays a vital role in human health. Water cleaning is a milestone
nowadays, not only for standard environmental issues, but also for the
emerging uses of water in the current technology field. For example,
dye-sensitized solar cells are currently developed with aqueous (or
water-based) electrolytes [1,2]. However, with the rapid development

⁎
Corresponding authors.
E-mail addresses: zhengh@cugb.edu.cn (H. Zheng), zpy@tsinghua.edu.cn (P. Zhang).
1
The first coauthors.

https://doi.org/10.1016/j.cej.2019.02.047
Received 12 November 2018; Received in revised form 1 February 2019; Accepted 7 February 2019
Available online 07 February 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
Q. Zuo et al.
of economy, various industrial enterprises have been increasing, and
the pollution of water source area has been becoming more and more
serious. It is difficult to effectively remove the pollutants in the water
source by the traditional purification process for drinking water, so the
safety of drinking water has received more and more attention. More-
over, with the continuous improvement of living standards, people
gradually improve their requirements for quality of life and pay more
attention to health, so their demand for healthy drinking water is in-
creasingly strong and it has become a routine concept to solve the
healthy problem of household drinking water. Many efforts have been
focused on the removal of algal-derived taste, odor compounds [3] and
Escherichia coli in drinking water [4]. In recent years, in order to obtain
qualified drinking water, people have begun to use domestic water
purifiers to purify the tap water coming from municipal pipe network
[5,6] and more and more families have accepted water purifier. At
present, the commonly used household water purification equipment
on the market include water purifier with polypropylene filter ele-
ments, composite sintered activated carbon water purifier, reverse os-
mosis water purifier, ultrafiltration membrane water purifier, ceramic
filter water purifier, water softener, etc. Research shows that domestic
water purifiers are effective in removing pollutants from water [7,8].
However, there are many problems such as high cost of purification,
short life of materials and unsatisfactory purification effect [9].
ACF has abundant pore structure, high specific surface area, large
adsorption capacity, fast adsorption, easy and rapid regeneration, and
long life [10,11], and it will not produce similar risk to combustion and
explosion caused by the heat accumulation of the granular activated
carbon or the honeycomb activated carbon adsorption device, and even
has high performance in chlorine removal. Moreover, due to particular
fiber structure, ACF can be processed into various fabrics such as cloth,
felt and paper, etc., and cylinder like honeycomb. Thus it has good
shape stability even if it is used for a long time. Since the water pur-
ification equipment with ACF as adsorption material not only has high
purification efficiency and large treatment capacity, but also does not
produce black powder, it shows great application potential in the field
of water purification [12–14]. What’s more, various modification
methods have been adopted to further improve its purification ability
[15–18]. However, the current filter elements of water purifier made by
the ACF have a large pH value change which exceeds allowable 0.5
units during sanitary soak and fail to meet Sanitary Standards for
Drinking Water Quality (2001) and still no an effective method to solve
this problem by far. Moreover, COD removal rate is also low. Usually,
the pH value of human body fluids is between 7.35 and 7.45. Drinking
acidic or alkaline and high COD water for a long time will destroy the
internal pH balance of the human body and seriously endanger human
health [19]. Therefore, it is necessary to find an economical and
practical modification method for solving unqualified soaking pH
change and low COD removal problems of ACF filter elements of water
purifier.
In this paper, ACF was modified using a simple flushing followed by
calcination in humid nitrogen atmosphere method. The effects of
washing method, the type of flushing water, flushing time, water con-
tent of calcined sample, calcination temperature and time on soaking
pH change were investigated and optimized modification conditions
were obtained. For the first time, the unqualified soaking pH change
and low COD removal problems of ACF filter elements of water purifier
were solved by an economical and practical modification method. The
effects of flushing on the removal of ions and fire retardants in ACF and
calcination in humid nitrogen atmosphere on the type and content of
ACF functional groups were investigated. Possible mechanism was
clarified by characterizing the ACF samples before and after flushing
and calcination using Boehm titration, X-ray photoelectron spectro-
scopy (XPS), simultaneous thermogravimetric/differential thermal
analysis and mass (TG/DTA-MS), Brunauer-Emmett-Teller (BET) spe-
cific surface area analysis, Fourier transform infrared spectroscopy
(FTIR) and ion chromatography (IC).
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Chemical Engineering Journal 365 (2019) 175–182
2. Materials and methods
2.1. Materials
Original ACF (O-ACF) used in the experiment was obtained from
Jiangsu Sutong Carbon Fiber Co., Ltd (China). All chemicals used in this
experiment were of analytical grade and were used without any further
purification.
2.2. ACF modification
O-ACF was modified using a facile flushing followed by calcination
in humid nitrogen atmosphere method as reported in our patent [20].
Typically, a piece of O-ACF with the size of 202 * 90 mm2 was flushed
with flowing deionized water at flow rate of 50 mL/min for a certain
period of time, then the water in the sample was squeezed out and the
sample was placed in a horizontal tubular furnace (OTF-1200X-S). After
the air in the tube was completely extruded by nitrogen gas at the flow
rate of 150 mL/min, the O-ACF was heated from room temperature to
certain activation temperature at a heating rate of 10 °C/min and the
same nitrogen flow rate and kept for a certain period of time. After that,
the sample was cooled to ambient temperature in nitrogen atmosphere
with the same flow rate and noted as M-ACF. Similarly, a piece of ACF
with the larger size was also modified to evaluate the soaking pH
change of M-ACF as filter elements of water purifier (Supplementary
Material).
To investigate the necessity of flushing with flowing water, the
immersing method was also used to wash O-ACF (Supplementary
Material).
2.3. Characterization of the samples
The amount of surface acidic and basic functional groups of the
samples was determined by Boehm titration [21]. The thermal stability
and the produced gases during the heating process for O-ACF and ACF
dried by squeezing after flushed by deionized water (F-ACF-S) were
analyzed using a simultaneous TG/DTA-MS apparatus containing an
STD 2960 simultaneous TG/DTA (TA Instruments Inc.) thermal ana-
lyzer and a Thermostar GSD 300 (Balzers Instruments) quadrupole mass
spectrometer. The surface functional groups of the samples were ana-
lyzed by Fourier transform infrared spectrometer (Thermo Fisher
NEXUS870). Surface elements and surface functional groups changes
before and after flushing and calcination were investigated by X-ray
photoelectron spectroscopy (XPS, PHI-5300, ESCA). The Brunauer-
Emmett-Teller (BET) specific surface area was determined using a Mi-
cromeritics ASAP 2020 HD88 adsorption apparatus. To determine the
ion content in flushing solution, the O-ACF was flushed with deionized
water for 5 min, and various ions in the flushing solution were detected
by ion chromatography (ICS-2000). Detailed conditions can be found in
Supplementary Material.
2.4. Sanitary soak of the samples
The standard soaking solution with pH of 8, hardness of 100 mg/L,
and effective chlorine of 2 mg/L was prepared and the samples were
soaked according to Standard for Hygienic Safety Evaluation of
Equipment Protective Materials in Drinking Water (GBT 172) [22].
Typically, the sample was soaked as follows. Firstly, a piece of
sample was flushed with flowing deionized water at flow rate of 2 L/
min for 30 min. Then, after the water was removed from the sample by
squeezing, the sample was placed in a conical flask with stopper, and a
small amount of the soaking solution was added and the sample was
washed for three times. Finally, the soaking solution was added until
the sample was completely soaked and no air existed in the flask (the
ratio of the surface area of the sample contacting the soaking solution to
the volume of the soaking solution should be greater than or equal to
Q. Zuo et al. Chemical Engineering Journal 365 (2019) 175–182

the maximum ratio under actual applied conditions) and the flask was Table 2
sealed with water. At the same time, the blank soaking solution in Effects of flushing time with deionized water on pH changes of soaking solu-
another conical flask with stopper was sealed with water as a control. tions.
After the sample was soaked in the dark at room temperature for Calcination Calcination ΔpH
24 ± 1 h, the pH value of the soaking solution was measured. For sa- temperature (°C) time (min)
nitary soak of filter element of water purifier, firstly, O-ACF or M-ACF Flushing for Flushing for Flushing for
5 min 10 min 30 min
with the size of 202 × 550 mm2 was encapsulated into a filter element,
and then the filter element was flushed with deionized water at flow 700 120 – – 0.45
rate of 2 L/min for 30 min. After that, the soaking solution was pumped 800 5 0.02, 0.21a 0.19, 0.10a –
into the filter element at a flow rate of 1.8 L/min to 2 L/min after water 10 – – 0.04
30 – 0.08 0.12
was drained. Two minutes later, the inlet and outlet of the filter element
60 – – 0.06
were sealed. Similarly, the filter element was soaked in the dark at 120 – – 0.04, 0.14a
room temperature for 24 ± 1 h, and then the pH value of the soaking 850 2 – 0.41 –
solution was measured. The pH value before and after soaking was 5 – – 0.48
measured using a pH meter (Thermo fisher Orion 3 star). 900 2 0.33 – –
120 – 0.41 –

3. Results and discussion
3.1. Effects of calcination temperature and time on soaking pH change
For O-ACF, the pH value of the soaking solution reduced from 7.82
before soaking to 6.38 after soaking, which decreased by 1.44 pH units,
and the pH change exceeded allowable 0.5 pH units and failed to meet
Sanitary Standards for Drinking Water Quality (2001). Considering that
basic surface functional groups can be formed by calcining carbon fiber
at high temperature and in inert atmosphere and oxygen-containing
functional groups can be removed by thermal treatment under ultra-
high vacuum or in inert atmosphere [23], O-ACF was first calcined at
800 °C and in nitrogen atmosphere for 30 min so that the pH change
could be reduced. However, although the pH value of the solution after
soaking increased to 6.72, the change of 1.1 pH units was found to still
exceed allowable 0.5 pH units. Therefore, a modified method via
flushing followed by calcination in humid nitrogen atmosphere was
used to modify ACF. The effects of the calcination temperature and time
on pH changes of soaking solutions are shown in Table 1. It can be seen
that at the same calcination time, with the increase of calcination
temperature, the pH value after soaking gradually increased and was
close to the blank value, accordingly the pH change gradually de-
creased; while at the same calcination temperature, with the pro-
longation of calcination time, no obvious pH change was observed. All
the samples calcined at 800 °C (M-ACF-800) showed the smaller pH
difference from the blank pH value and met Sanitary Standards for
Drinking Water Quality (2001). The possible reason was attributed to
the sufficient conversion of surface functional groups of O-ACF from
acidic to basic ones at the calcination temperature of 800 °C, which is
confirmed by the results of Boehm titration and XPS analysis in sub-
sequent possible mechanism of reducing pH change. The unqualified
samples appeared when the samples were calcined at a temperature of
650 °C or lower.
a
The repeated experimental results under the same conditions.
3.2. Effects of flushing time on soaking pH change
As we all know, short flushing time can help us to save the cost. The
effects of flushing time with deionized water on pH change are shown
in Table 2. It can be seen that all the pH changes of soaking solutions
met Sanitary Standards for Drinking Water Quality (2001) when
flushing time was more than 5 min and calcination temperature was
above 700 °C. Usually, fire retardant such as phosphate is added to
prevent carbon fiber from burning when carbon fiber was activated at
high temperature to prepare activated carbon fiber (ACF). Therefore,
some fire retardant can remain in ACF after the carbon fiber is acti-
vated. To clarify the role of flushing, the ions and C contents in flushing
solution (flushing for 5 min) were detected and displayed in Table S1. It
can be seen that some ions including Na+, PO43−, Ca2+, K+, NO3−,
Cl− and Mg2+ can be flushed out from O-ACF and no TC, IC and SO42−
were detected. The reduction of PO43− in the sample could reduce not
only the release of PO43− from the modified sample during the sanitary
soak, but also the adsorption of Ca2+ in the soaking solution, thereby
the influence on the pH value of the soaking solution could be reduced.
However, unqualified samples appeared when flushing time was less
than 2 min. The possible reason was attributed to less removal of PO43−
in short flushing time.
3.3. Effects of flushing water on soaking pH change
It will be advantageous to save the cost if deionized water can be
replaced by tap water. The pH changes were compared and are shown
in Table 3 when the samples were flushed with deionized water and tap
water, respectively. We can see that with the increase of calcination
temperature, the pH value after soaking gradually increased and the pH
changes gradually decreased when the sample was flushed with tap
water, which is similar to that with deionized water. However, the pH

Table 1
Effects of calcination temperature and time on pH changes of soaking solutions.
Calcination time (min) Calcination temperature (°C)

600 650 700 800 850

2 – – – – 7.99a/7.58b
5 – – – – 7.77a/8.25b
10 – – – 7.89a/7.82b –
30 – – – 7.97a/7.72b 7.78a/7.70b
60 – – – 7.97a/7.78b –
120 7.75a/7.08b 7.75a/7.24b 7.82a/7.37b 7.87a/7.65b –

Experimental conditions: flushing water, deionized water; flushing time, 30 min; water content of calcined sample, no less than 10%;
a
The pH value of the blank soaking solution after soaking.
b
The pH value of the soaking solution for the samples after soaking.

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Q. Zuo et al. Chemical Engineering Journal 365 (2019) 175–182

Table 3
Effects of flushing water on pH changes of soaking solutions.
Flushing time Calcination ΔpH
(min) temperature (°C)a
Tap water Deionized water

5 600 0.98 –
700 0.68 0.45
800 0.08 0.02, 0.21b
10 600 1.24 –
700 0.73 –
800 0.42, 0.56b, 0.19
0.59b, 0.44b

a
Calcination time, 5 min.
b
The repeated experimental results under the same conditions.

Fig. 2. Effects of water content of calcined sample on pH changes of soaking

solutions (flushing time, 5 min; calcination temperature, 800 °C; calcination
time, 5 min).

can be flushed with tap water for a period of time, and then flushed
with deionized water for less than 2 min.

3.4. Effects of washing method on soaking pH change

To investigate the necessity of flushing with flowing water, im-

mersing method was carried out and the results are shown in Fig. 1. It
can be seen that although the immersing method could decrease the pH
change of soaking solution to some extent, it did not make the pH
change to meet the Sanitary Standards for Drinking Water Quality
(2001). The possible reason was attributed to less removal of PO43−
coming from poorer cleaning ability by immersing method than
flushing with flowing water.

3.5. Effects of water in the calcinations process on soaking pH change

Fig. 1. Effects of washing method on pH changes of soaking solutions (ΔpH of To investigate the necessity of water during calcinations, F-ACF was
O-ACF is 1.44; washing water, deionized water; flushing time, 30 min; water dried by different ways and the results are shown in Table 4. It was
content of calcined samples, no less than 10%). found that the presence of water in the calcination process had an
obvious effect on the pH changes of soaking solutions. Although all the
pH changes met the Sanitary Standards for Drinking Water Quality
Table 4
Effects of water in the calcinations process on pH changes of soaking solutions. (2001) when the samples were calcined at 800 °C in humid and dry
nitrogen atmosphere, the pH change was much larger when the sample
Flushing time Calcination Calcination time ΔpH
was calcined in dry nitrogen atmosphere than that in humid one. Fur-
(min) temperature (°C) (min)
Dry N2 Humid N2 thermore, although the pH change was still acceptable when the sample
was calcined at 900 °C in humid nitrogen atmosphere for 2 min, it was
30 800 10 0.39 0.07 unqualified when the sample was calcined at 900 °C in dry nitrogen
2 900 2 0.6 0.15
atmosphere for 2 min. Therefore, the presence of water during calci-
nation is advantageous to reducing the pH change. However, the pH
change was found to be unqualified (ΔpH = 0.56) when the O-ACF was
change was unstable due to the existence of other ions introduced by
soaked in 500 mL of deionized water for 5 min and calcined at 800 °C in
tap water. From the repeated pH change results under the same con-
humid nitrogen atmosphere for 10 min. The possible reason was at-
ditions which was flushed by tap water for 10 min and calcined at
tributed to the role of water in promoting the release of gases and fa-
800 °C for 5 min (average value is 0.50, standard deviation is 0.085), we
cilitating the conversion of functional groups in the calcination process,
can see that some unqualified samples appeared. Moreover, with the
which is proved by the results of TG/DTA-MS and FTIR analysis in
prolongation of flushing time, larger pH change was found. What’s
subsequent possible mechanism of reducing pH change. Therefore, both
more, the longer the flushing time was, the greater the effects on pH
the presence of water in the calcination process and enough flushing
change were. Since the water quality of the tap water varies from place
time are essential to lower the pH change of soaking solution.
to place, deionized water was proposed to deep purification of actual
To obtain the appropriate water content, effects of water content of
drinking water. Certainly, the pH change also met the Sanitary Stan-
calcined sample on the pH change were investigated, in which water
dards for Drinking Water Quality (2001) when the sample was flushed
content was controlled by heating flushed sample to ensure uniform
with tap water for 10 min, followed by being flushed with deionized
distribution of water in the sample. The results are shown in Fig. 2. It
water for less than 2 min (heat-treated at 800 °C for 5 min,
can be seen that with the decrease of water content, the pH change
ΔpH = 0.10). Therefore, considering the cost of deep purification, it
increased. However, as long as a small amount of water remained in the

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Q. Zuo et al.
Fig. 3. XPS spectra of the samples: C1s (a, d, g), O1s (b, e, h) and N1s (c, f, i) of O-ACF, F-ACF-105, and M-ACF-800, respectively.
sample, it could work at high temperature and was enough to lower the
pH change. In actual operation, the water content can be adjusted on
the basis of the density of water vapor at the calcination temperature
and one atmospheric pressure and the volume of the experimental
tubular furnace. The water content of no less than 60% was re-
commended in order to decrease the probability of unqualified samples.
3.6. Possible mechanism of reducing pH change
To further discussed the possible mechanism of reducing pH change,
the ACF samples before and after flushing and calcination were char-
acterized by Boehm titration, XPS, TG/DTA-MS, FTIR and specific
surface area analyses.
3.6.1. Boehm titration
The results of Boehm titration are summarized in Table S2. We can
see that only slight change was found for the amount of various acidic
groups of ACF dried at 105 °C after flushed by deionized water (F-ACF-
105) and the total amount of acidic and basic surface functional groups
slightly increased compared with those of O-ACF. However, for M-ACF-
800, the amount of lactonic and phenolic groups sharply reduced from
0.3012 to 0.1067 mmol/g and from 0.3530 to 0.1052 mmol/g, respec-
tively. Meanwhile, the amount of carboxylic groups and ketonic/alde-
hydic groups also obviously decreased. As a result, the total amount of
acidic surface functional groups significantly decreased from 1.1391 to
0.5920 mmol/g, while basic surface functional groups significantly in-
creased from 0.7148 to 1.0770 mmol/g. The reduction of acidic groups
and the increase of basic groups are beneficial to improve the pH and
reduce the pH change during the sanitary soak.
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Chemical Engineering Journal 365 (2019) 175–182
3.6.2. XPS analysis
To further investigate the effects of flushing and calcinations on the
amount of surface elements and surface functional groups, XPS analysis
of the O-ACF, F-ACF-105 and M-ACF-800 was performed, and atomic
percentages of the elements in the full-spectrum scan are shown in
Table S3. It can be seen that, compared with O-ACF, the content of
element P coming from phosphate used as a fire retardant in O-ACF
after flushing obviously reduced, the C content slightly increased, and
the N content decreased, which is consistent with the detection results
of the ions and C contents in flushing solution. The reduction of P
content can reduce the effects of acidic ions on pH value. Deoxidation
occurred after calcination at 800 °C, the relative percentages of O atoms
on the surface obviously decreased from 3.63% to 2.39% [24]. The
reduction of O content can reduce the effects of acidic oxygen-con-
taining functional groups on pH change during the sanitary soak.
The high-resolution XPS spectra of the C 1s, O1s and N1s regions are
illustrated in Fig. 3. We can see that the peaks in the C 1s spectrum
(Fig. 3a, d, g) can be divided into four peaks centered at 284.8, 285.5,
288.0 and 290.0 eV, respectively, which can be assigned to the C]C,
CeOH/CeOeC, C]O and COOR, respectively [25,26]. Their percen-
tages in various samples are shown in Table S4. Compared with those in
O-ACF (44.42%, 34.31%, 5.01%, and 16.27%, respectively), almost no
changes were found in F-ACF-105 (48.60%, 30.84%, 5.57% and
14.99%, respectively), inferring that the flushing mainly removes some
ions in the sample, and has little influence on the type and content of C
functional groups. However, significant changes were found in M-ACF-
800 (60.98%, 21.48%, 9.01% and 8.53%, respectively), especially C
content combined with O significantly decreased, the decrease of C-
OH/C-O-C was nearly 40% and that of COOR was close to 50%,
Q. Zuo et al. Chemical Engineering Journal 365 (2019) 175–182

Fig. 5. The pH changes of soaking solutions for the filter elements of water
purifier made by the M-ACF.

suggesting that many surface acidic functional groups were removed by

calcination after flushing, which contributes to reducing pH change
during the sanitary soak. Similarly, the O1s spectrum also can be di-
vided into four peaks (Fig. 3b, e, h): the peak at 530.3 ± 0.3 eV as-
cribed to OH, the peak at 531.7–531.97 eV ascribed to C]O (carboxyl,
ketone and lactone), the peak at 532.3–532.9 eV ascribed to C-O (OH or
ether), and 533.2–533.6 eV ascribed to C-O (carboxyl or ester), re-
spectively [17]. Compared with their percentages in O-ACF (8.65%,
31.62%, 12.43% and 47.03%, respectively, as shown in Table S5), those
in F-ACF-105 (0.85%, 25.34%, 18.91% and 54.89%, respectively) ob-
viously changed, especially OH content significantly decreased, in-
dicating that flushing removes most of the surface hydroxyl groups.
Moreover, those in M-ACF-800 (0.17%, 23.56%, 26.66% and 49.6%,
respectively) further changed, and the contents of surface acidic func-
tional groups (eOH and C]O) were further removed by calcination at
800 °C, which is generally consistent with the results of C1s. The re-
moval of surface hydroxyl groups, surface carboxylic acids and surface
carboxyl groups is helpful to reduce the release of acid from the sample,
thereby reducing pH change during the sanitary soak. N1s can be di-
vided into four peaks corresponding to pyridine-like (N-6; peak 1,
BE = 398.7 ± 0.3 eV), pyrrolic, pyridone, amide and imide groups (N-
5; peak 2, BE = 400.4 ± 0.3 eV), protonated pyridines and/or pyrrolic
and amine salts (N-Q; peak 3, BE = 401.4 ± 0.3 eV) [27–31], and ni-
trogen oxide (N-X; peak 4, BE = 405.6 ± 0.1 eV) [18,32–34]. Their
percentages are shown in Table S6. Compared with those in O-ACF
(21.95%, 1.83%, 53.04%, 23.19%, respectively), those in F-ACF-105
and M-ACF-800 obviously changed. After flushing and calcination, N-5
significantly increased and N-Q significantly declined, indicating that
N-Q was converted to N-5 in the modification process, that is, the basic
functional groups contents increased and the acidic functional groups
contents decreased [31]. This is beneficial to improve the pH value and
reduce the pH change during the sanitary soak, which is consistent with
the Boehm titration results.

3.6.3. TG/DTA-MS analysis

Fig. 4. TG and DTA diagram of O-ACF (a) and F-ACF-S (b) and simultaneous
detection by mass spectroscopy of H2O (c) and CO2 (d).
To investigate the effects of water on the release of the gases during
calcination, TG and DTA of O-ACF and F-ACF-S were determined and
shown in Fig. 4. From TG and DTA curves of O-ACF (Fig. 4a), two
distinct weight loss and endothermic peaks in the regions of 600–800 °C
and 800–1000 °C were observed. The smaller endothermic peak in the
region of 600–800 °C could be attributed to water loss in structure and
the release of some gases including CO, CO2 and NH3 and the weight
loss percentage was about 4.9%. The larger endothermic peak in the
region of 800–1000 °C could be ascribed to further release of gases such
as CO2 and weight loss ratio was about 6%. TG and DTA curves of F-

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Table 5
COD and effective chlorine removal by the filter elements of water purifier made by the M-ACF.
Filter element Total water volume (L) Flow rate (L/min) COD Effective chlorine

Addition (mg/L) Effluent (mg/L) Removal rate(%) Addition (mg/L) Effluent (mg/L) Removal rate (%)

O-ACF 0 4.29 2.15 0.78 63.72 1.93 0.01 99.48%

1823 4.15 2.54 0.78 69.29 2.05 0.01 99.51%
3617 3.97 3.12 1.02 67.31 2.14 0.02 99.07%
5465 3.54 2.51 0.31 87.65 2.11 0.02 99.05%
7467 3.11 2.36 0.47 80.08 1.98 0.01 99.49%

M-ACF-850 0 4.33 2.15 0.39 81.86 1.93 0.01 99.48%

1820 4.11 2.54 0.55 78.35 2.05 0.01 99.51%
3622 4.07 3.12 0.67 78.53 2.14 0.01 99.53%
5419 3.54 2.51 0.55 78.09 2.11 0.01 99.53%
7321 3.26 2.36 0.39 83.47 1.98 0.01 99.49%

ACF-S are shown in Fig. 4b. The sample mass quickly lowered with the
increase of temperature due to evaporation of a great of water in the
region of 100–120 °C and a large weight loss and endothermic peak
were observed. From the inset of Fig. 4b, we can see that different from
those of O-ACF, a larger weight loss accompanied with larger en-
dothermic peak in the region of 600–850 °C occurred and the weight
loss percentage was about 8%. After that, a smaller weight loss ac-
companied with smaller endothermic peak in the region of 850–1000 °C
occurred and the weight loss percentage was about 2.1%. Therefore, it
is inferred that the water in ACF could promote the release of gases at a
lower temperature in the calcination process. Fig. 4(c) and (d) show the
simultaneous detection by mass spectroscopy of H2O and CO2. It can be
seen that for O-ACF, lots of gaseous water began to release at 100 °C,
then the release mass gradually reduced. When the temperature
reached 800 °C, the release mass increased again. Conversely, released
CO2 gradually increased with the increase of temperature, and reached
maximum at about 850 °C. However, for F-ACF-S, a large amount of
gaseous water was released with the increase of temperature until
500 °C, then the release mass obviously reduced. Conversely, released
CO2 also gradually increased with the increase of temperature, and
reached maximum at about 850 °C, which is much more than that of O-
ACF. So, it is further inferred that the water in ACF could not only
promote the release of gases at a lower temperature in the calcination
process, but also promote the release of more gases, thus facilitating the
conversion of functional groups.
3.6.4. FTIR analysis
To further investigate the surface functional groups, FTIR spectra of
ACFs treated under different conditions were compared and are shown
in Fig. S1. A broad band at 3427 cm−1 was assigned to the stretching
vibration of hydroxyl [35,36], the characteristic bands at around
3004 cm−1 were ascribed to the aromatic CH stretching vibration, the
weak bands at 2950 cm−1 and 1384 cm−1 were likely to be caused by
asymmetric stretching and bending vibration of aliphatic methyl, in-
dicating the existence of some methyl groups in the structure of the
ACF. The weak bands at 2923 cm−1 were attributed to asymmetric
stretching vibration of aliphatic methylene [35]. The peak at
1608 cm−1 was ascribed to stretching vibration of C]C in benzene
rings. The peak at 1075 cm−1 corresponded to CeO in benzyl hydroxyl
[35]. Compared with O-ACF and F-ACF-105, the band intensity of hy-
droxyl at 3427 cm−1 in M-ACF-800 became obvious weaker, indicating
the amount of acidic functional groups in M-ACF-800 obviously re-
duced, and then the pH change during the sanitary soak reduced.
Moreover, FTIR spectrum of ACF calcined at 800 °C after flushed by
deionized water and dried at 105 °C (F-ACD-105–800) was also com-
pared and no reduction of hydroxyl intensity was found, further in-
dicating the water in ACF is vital to the conversion of functional groups.
These results are consistent with the results of Boehm titration and XPS.
3.6.5. Specific surface area analysis
The specific surface area is an important indicator for evaluating the
adsorption performance. ACF has abundant micropores and a small
number of mesopores [37]. To investigate the effects of flushing and
calcination on the specific surface area of ACF, BET surface areas of
ACFs treated under different conditions were determined and listed in
Table S7. Compared with BET surface area of O-ACF, that of F-ACF-105
increased from 1260 to 1358 m2/g. The possible reason was attributed
to the reduction of impurities adsorbed in the holes by flushing. Al-
though BET surface area of M-ACF-800 reduced, it still increased
compared with that of O-ACF, indicating that the modification not only
facilitates the conversion of functional groups, but also keeps a large
specific surface area of ACF.
3.7. The sanitary soak and COD removal of the filter element of water
purifier made by the M-ACF
To examine the actual effect of the M-ACF as drinking water pur-
ification material, M-ACF with the size of 202 × 550 mm2 were en-
capsulated into a filter element, and then subjected to sanitary soak.
The results are shown in Fig. 5. It can be seen that compared with O-
ACF, the pH changes of soaking solutions for the filter elements of water
purifier made by M-ACF-800 and M-ACF-850 obviously reduced from
0.78 to 0.10, which did not exceed allowable 0.5 units and met the
Sanitary Standards for Drinking Water Quality (2001), indicating the
modification method is an effective and feasible method.
Moreover, the filter element of water purifier made by M-ACF-850
was also used to remove COD and effective chlorine, and the results are
shown in Table 5. It can be seen that the COD removal rate by the M-
ACF-850 filter element is above 78%, which is about 10–20% higher
than that by O-ACF and effective chlorine removal rate still keeps as
high as that by O-ACF (above 99%). All the results indicate that the
modification method of flushing followed by calcinations in humid
nitrogen atmosphere can not only reduce pH change during the sanitary
soak, but also improve COD removal. So it is a promising modification
method of ACF.
4. Conclusions
The ACF was modified by a facile method via flushing followed by
calcination in humid nitrogen atmosphere. Some parameters including
washing method, the type of flushing water, flushing time, water con-
tent of calcined sample, calcination temperature and time were opti-
mized. The results show that flushing time and calcination temperature
in humid nitrogen atmosphere are two major influencing factors. The
pH changes of all the M-ACF and the filter elements of water purifier
made by the M-ACF can meet the Sanitary Standards for Drinking Water
Quality (2001) and the COD removal rate increases when deionized
water or pure water is used as flushing water, flushing time is no less

181
Q. Zuo et al.
than 2 min, water content of calcined sample is no less than 10%, cal-
cination temperature is 700–1000 °C and calcination time is no less
than 2 min. The possible mechanism was attributed to the removal of
some ions and fire retardants in the ACF by flushing and the conversion
of surface functional groups from acidic to basic functional groups by
calcination in humid nitrogen atmosphere. The water in ACF plays an
important role in promoting the release of gases at a lower temperature
in the calcination process and facilitating the conversion of functional
groups. This economical and practical modification method is a pro-
mising method for solving unqualified soaking pH change and low COD
removal problems of ACF filter elements of water purifier. The M-ACF
used as qualified filter elements of water purifier shows significant
potential application in the field of household drinking water pur-
ification.
Acknowledgment
The authors are grateful to Midea Group for financial support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.02.047.
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