Journal of Cleaner Production 171 (2018) 482e490

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Journal of Cleaner Production

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

Mesoporous activated carbon fibers synthesized from denim fabric

waste: Efficient adsorbents for removal of textile dye from aqueous
solutions
Taís L. Silva a, b, Andre
L. Cazetta a, Patrícia S.C. Souza a, Tao Zhang c, Tewodros Asefa c, d,
a, *
Vitor C. Almeida
a
Laboratory of Environmental and Agrochemistry, Department of Chemistry, State University of Maringa
, Av. Colombo 5790, CEP 87020-900 Maringa

,
Parana
, Brazil
b
, 635 Marcílio Dias Street, Apucarana, Parana
Federal University of Technology e Parana
, Brazil
c
Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, NJ 08854, USA
d
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road, Piscataway, NJ 08854, USA

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

Article history: Denim fabric waste was used as a carbon precursor, and chemically activated with phosphoric acid in the
Received 24 June 2017 ratio of 1:1 (v:m) under a slow pyrolysis process to obtain activated carbon fibers (ACFs). The chemical
Received in revised form and physical properties of the ACFs were investigated from the thermogravimetric analysis (TGA), N2
6 September 2017
porosimetry, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray
Accepted 4 October 2017
diffraction (XRD), Raman and Fourier transform infrared spectroscopy (FTIR), Boehm titration method,
Available online 5 October 2017
and point of zero charge (pHPZC). The obtained ACFs showed high yield (53%), BET surface area of
^ as de
Handling Editor: Cecilia Maria Villas Bo 1582 m2 g
1, mesoporous features (average pore diameter of 3.60 nm), and surface acidic properties
Almeida (pHPZC value of 2.13 and 1.13 mmol g
1 of acidic groups). The ACFs were applied in the removal of textile
dye, Remazol Brilliant Blue R (RBBR), from aqueous solution. The adsorption isotherm and kinetic studies
Keywords: showed that adsorption of RBBR on the ACFs were better described by the pseudo-second order kinetic
Activated carbon fiber model and the Freundlich equilibrium model. The maximum adsorption capacity of the ACFS for RBBR
Denim waste was determined to be 292 mg g
1, which is higher than other adsorbent materials reported in the
Adsorption
literature. The adsorption thermodynamic parameters indicated that adsorption process is spontaneous
Dye
and exothermic.
Remazol Brilliant Blue R
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction environment, which in turn leads to a decrease in photosynthetic

Dyes are chemical compounds widely used in the food, paper
and clothing industries. The textile industries, in particular, use a
variety of synthetic dyes that have chemical affinity with textile
fibers for the purpose of dying cloths. These industries are
responsible for the daily generation of large volumes of wastewater,
containing dyes, which whether not properly treated can lead to
environmental and public health issues (Kumar et al., 2011). Many
of the dyes used in these industries are potentially carcinogenic,
mutagenic and toxic to human and aquatic species (Hazzaa and
Hussein, 2015). Among their environmental impacts, the main
issue is related to the reduction of light into the aquatic
* Corresponding author.
activity (Reife and Freeman, 1996). In addition to environmental
concerns involving the wastewaters, the textile industries produce
a large amount of solid wastes, among which fabric pieces
composed of different types of fibers stand out (Bommel and
Goorhuis, 2014). Cotton fiber is the main precursor of denim fab-
ric, which is used to produce jeans products that are widely used by
consumers all over the world. The solid residues typically generated
by the jeans industries consist of fabric remnants left over after the
production of the clothes. Most of these residues are often disposed
in landfills or subjected to incineration or composting (Wang,
2010), while the wastewaters generated by these industries are
usually treated from processes involving coagulation, flocculation,
biodegradation, oxidation, and adsorption (Vargas et al., 2011).
Activated carbon fibers (ACFs) are amorphous carbonized fibers
that contain high surface areas and functionalized surfaces (Yang

https://doi.org/10.1016/j.jclepro.2017.10.034
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
 T.L. Silva et al. / Journal of Cleaner Production 171 (2018) 482e490
et al., 2011). Owing to their porous and fibrous structures, they have
been used in adsorption processes, electrochemical applications
and as platforms in the synthesis of heterogeneous catalysts
(Huang et al., 2015; Aber et al., 2009; Du et al., 2013). ACFs are
synthetized mainly from viscose and lignocellulose fibers such as
linen and acrylic fibers (Suzuki, 1994; Zhao et al., 2016). More
recently, researchers have explored the synthesis of ACFs from
biomasses and/or agricultural wastes, e.g., bamboo (Zhao et al.,
2015), kenaf fibers (Shamsuddin et al., 2016), cocoons of the silk-
worm (Li et al., 2015) and hemp stalks (Yang et al., 2011), in order to
produce more sustainable ACFs. Zheng et al. (2014) reported the
synthesis of ACFs from the woven and physical-chemical activation
process, using H3PO4/(NH4)2HPO4 and CO2 as activators, and they
obtained ACFs with high microporosity and a surface area of
789 m2 g
1. Chiu and Ng (2012) synthesized cotton-derived ACFs
using ZnCl2 as an activating agent, and the resulting fibers also
showed microporosity and high surface area (2060 m2 g
1). Thus,
most of these and other ACFs reported in the literature have mainly
microporous features, which make these materials to have limited
applications for adsorption of large molecules in aqueous medium
(Prajapati et al., 2016).
The aim of this work was to synthetize ACFs of high surface area
and mesoporous features, using the denim fabric waste as raw
material, for adsorption of Remazol Brilliant Blue R (RBBR) textile
dye from the aqueous solution. The ACFs’ synthesis was carried out,
employing a chemical activation procedure with H3PO4 and slow
pyrolysis. Several analytical techniques (TGA, XRD, SEM, Raman,
TEM and FTIR) were used to investigate the physical and chemical
properties of the obtained ACFs. Additionally, the RBBR adsorption
onto ACFs were evaluated from the adsorption thermodynamic,
kinetic and equilibrium studies.
2. Materials and methods
2.1. Precursor of ACFs
The denim fabric waste was obtained from a clothing industry in
the city of Maring
a, Parana
, Brazil, which producing pants and
jackets from the denim of higher engraving (mass in grams per
square meter) without any washing procedure. The collected
denim fabric waste is composed of 100% cotton. Initially, the
collected sample was dried in oven at 60  C for 24 h, then, it was cut
into smaller pieces with sizes of about 1 cm2 and stored in a
desiccator to further analyses. The contents of moisture, ash and
fixed carbon in the precursor were determined according to ASTM
D1762 (1984).
2.2. Preparation of ACFs
The ACFs were prepared by chemical activation using H3PO4
(Sigma-Aldrich, 85%) as activating agent in a ratio of 1:1 (H3PO4:
raw material, v:m). Typically, 3.00 g of denim fabric waste was
introduced in a vertical stainless-steel reactor that has diameter of
3.0 cm, height of 6 cm, internal volume of 42 cm3, and removable
lid with holes for inlet and outlet of gases. Then, 3.0 mL of H3PO4
(85%) was added, and the reactor containing the precursor and the
acid was kept in an oven at 60  C for 24 h, obtaining an acid-
impregnated material. After, the acid-impregnated material was
submitted to slow pyrolysis process of three steps, using furnace
(EDG-S equipment EDG3P 7000), under a N2 flow of 100 mL min
1
and heating rate of 5  C min
1. In the first step, the material was
heated from room temperature to 300  C and kept at 300  C for 2 h.
In the second step, the temperature was raised to 500  C and kept at
that temperature for 1 h. In the third step, the furnace was let to
483
cool down from 500 to 100  C. The resulting material was ground
into powder and washed one time with 0.1 mol L
1 NaOH solution,
followed with distilled water until the solution's pH reaches ~6.0.
The material was then dried in oven at 100  C for 24 h and properly
storaged for further studies. The yield of the material was deter-
mined by gravimetry, based on the initial mass of the precursor and
the final mass of the material obtained after the washing procedure.
The fibrous carbonaceous material was labeled as ACFs.
2.3. Characterization
The thermal properties of the denim fabric and H3PO4-
impregnated denim fabric were investigated by thermogravimetric
analysis (TGA) using a thermogravimetric analyzer (Netzsch STA
409 PC). The samples were heated from the room temperature to
850  C, under N2 flow of 100 mL min
1 and heating rate of 10  C
min
1. The ACFs were characterized by N2 porosimetry, using
Quantachrome model NOVA 1200e gas adsorption instrument. The
BET surface area (SBET) of the material was calculated by equation of
Brunauer-Emmett-Teller (BET) in relative pressure range (p/pº) of
0.0503e0.183. The total pore volume (VT) of the material was
determined at relative pressure of 0.995, and the micropore volume
(Vm) by the deBoer method (Schneider, 1995). The average pore
diameter (DP) of the material was determined by using the equation
4VT/SBET, and the pore size distribution and mesoporous volume
were deduced by the Barrett-Joyner-Halenda method (BJH) (Barrett
et al., 1951). The morphology of the ACFs was investigated by
scanning electronic microscopy (SEM) with a SEM microscope
(Shimadzu, Model SS 550) and Transmission electron microscopy,
with FEI Tecnai T-12 t. The crystallinity of the material was evalu-
ated using an X-ray diffractometer (Shimadzu, Model XRD-7000),
operating with a Cu Ka radiation source (l ¼ 1.540598 Å) in a 2q
diffraction angle range of 5e80 with a step of 0.02 min
1 (data
shown in Supplementary Information section). Raman spectrum of
the ACFs was recorded in the range of 2500e500 cm
1, using a
Brüker dispersive micro Raman spectrometer (Senterra) operating
with 532 nm laser having a power of 2 mW. In the measurements
were employed resolution of 9e15 cm
1, slit of 25  1000 mm,
acquisition rate of 10 scans min
1 and integration time of 5 s
(Supplementary Information section). The surface functional
groups on the ACFs were evaluated with the Boehm titration
method (Boehm, 1994) and Fourier transform infrared spectros-
copy (FT-IR), using the ATR mode. The latter was performed using
Nicole IZ10 FT-IR spectrometer, and the spectra were collected in a
range of 4000 to 600 cm
1 with a resolution of 4 cm
1 and an
acquisition rate of 20 scan min
1. The pHPZC value of the ACFs was
determined according to the methodology reported by Prahas et al.
(2008).
2.4. Adsorption studies
Adsorption studies on the ACFs were carried out in two trials,
using the textile dye RBBR as adsorbate, which was purchased from
Sigma-Aldrich. The dye has a molecular formula of
C22H16N2Na2O11S3 and a molecular mass of 626.54 g mol
1. Its
molecular structure is shown in Fig. S1 (Supplementary
Information section).
For adsorption studies, a stock solution of 1000 mg L
1 dye was
prepared by dissolving 1000 mg of RBBR in 1000 mL of distilled
water. Working solutions were prepared by diluting the stock so-
lution and adjusting the solution pH values were performed using
HCl (0.1 mol L
1) or NaOH (0.1 mol L
1) solutions.
Batch adsorption experiments were performed in 50.0 mL
polypropylene tubes, in each of which 25.0 mL of the RBBR solution
484
and 20.0 mg of ACFs were placed. The solutions were shaken using
a thermostatic shaker incubator (200 rpm) for determined times
(2.5e240 min) at 25  C. Then, they were filtrated, using Millipore
HA membranes (pore size of 0.45 mm), and the concentration of the
remaining RBBR in the filtrates were determined with UVeVis
spectrophotometer (PerkimElmer Lambda 25) by monitoring the
intensity of the peaks at wavelength of 591 nm, and comparing the
values with those in the calibration curve.
The effect of pH was investigated using RBBR solutions of
200 mg L
1 with pH values ranging between 2.0 and 9.0. Into each
solution was added ACFs (20.0 mg), which were shaken for
240 min at 25  C. The concentrations of the remaining RBBR in the
solutions, after filtration, were determined with a UVeVis spec-
trophotometer, and the adsorption capacity of the material (qm)
was calculated with Eq. (1) below:


C0
Cf V
qm ¼
m
where C0 and Cf are the initial and the final concentrations (mg L
1)
of RBBR, respectively, V is the volume (L) of the solution and m is
mass (g) of the ACFs.
Kinetics studies were carried using RBBR solutions (25.0 mL)
with concentrations of 100, 200 and 300 mg L
1 at pH 2.0. These
solutions were placed in contact with ACFs (20.0 mg) and shaken
for times ranging between 2.5 and 240 min at 25  C. Adsorption
equilibrium studies were performed using RBBR solutions with
concentrations ranging from 25 to 500 mg L
1 at pH 2.0 (25.0 mL).
The solutions containing ACFs (20.0 mg) were shaken for
240 min at 25  C. The concentrations of RBBR in the solutions after
filtration were determined, and the amounts of RBBR adsorbed on
the material at time t (qt) and at equilibrium (qe) were calculated
using Eq. (2) below:


C0
Cf V
qe;t ¼
m
where, C0 is the initial concentration (mg L
1) of RBBR in the so-
lution, Ct is the concentration (mg L
1) of remaining RBBR in the
solution at time t, Ce is concentration of RBBR in the solution at
equilibrium, V (L) is the solution volume of the solution and m (g) is
the mass of ACFs.
The kinetic models of pseudo first order (Lagergren, 1898) and
pseudo second order (Ho, 2006; Ho and Mc Kay, 1999), and the
isotherm models of Langmuir (1916), Freundlich (1906) and Dubi-
nin Radushvick (Dabrowski, 2001) (Table S1) were fitted to the
experimental data, using Origin 9.1 software. The parameters were
used to determine the maximum adsorption capacity of the ma-
terial as well as to understand the mechanism and dynamic of
adsorption of the RBBR dye molecules on the ACFs. The model fits
were evaluated based on the values of the normalized standard
deviation and the coefficient of determination (R2). The values of
Dqe (%) were calculated using Eq. (3).
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uPh
.
u
t qe;exp
qe;cal qe;exp
Dqe ð%Þ ¼ 100
N
1
where qe,exp and qe,cal represent the calculated and experimental
adsorption capacity values, respectively, and N is the number of
data points.
2.4.1. Thermodynamic studies
In order to evaluate the effect of temperature on the adsorption
T.L. Silva et al. / Journal of Cleaner Production 171 (2018) 482e490
of RBBR on ACFs, thermodynamic study was performed in duplicate
at temperatures of 303, 313 and 323 K. In a typical procedure, ali-
quots of RBBR (25.0 mL, 500 mg L
1) and 20.0 mg of ACFs were
placed in polypropylene tubes, and the solutions were shaken for
4 h in a thermo-shaker. After then, the solutions were filtered and
the remaining concentrations of the dye were determined spec-
trophotometrically (same procedure of 2.4 above). The adsorption
capacities of the ACFs at the equilibrium (qe) for each temperature
were calculated using Eq. (2), while the thermodynamic parame-
ters; Gibbs free energy change (DG), enthalpy change (DH) and
entropy change (DS), were calculated from equations listed in
Table S1.
3. Results and discussion
3.1. Proximate analysis of denim fabric waste and yield of synthesis
(1) The proximate analysis of denim fabric waste revealed that it
has 5.93% moisture, 0.83% ash, 90.8% volatile matter and 2.43% fixed
carbon. The synthesis yield of ACFs obtained from the denim fabric
was 53%. Despite its low content of fixed carbon and high content of
volatile materials, the precursor provided a high yield of ACFs. This
can be attributed to the fact that H3PO4 restricts the release of
volatile materials or helps with the retention of carbon during the
carbonization process (Benadjemia et al., 2011).
Cotton fibers contain about 97e98% of cellulose (Perepelkin,
2004) and of 2e3% of pectins, waxes, fattys and mineral salts.
During the ACFs synthesis procedure, it is believed that H3PO4 re-
acts with cellulose, forming ester linkages with its eOH groups at
temperatures below 200  C, helping to crosslink the polymer
chains. The acid also stabilizes the cellulose structure, inhibiting the
formation of levoglucosan (volatile compound), which offers a
route to its degradation through decomposition to volatile prod-
ucts. Additional reactions can occur at high temperatures as cycli-
zation and condensation, leading to an increase in aromaticity and
(2) the size of the polyaromatic units, enabled by the scission of PeOeC
bonds, and followed by continued cleavage of crosslinks, which
promotes a growth in the size of the aromatic units (Jagtoyen and
Derbyshire, 1993, 1998; Molina-Sabio et al., 1995).
3.2. Thermogravimetric analysis (TGA)
Fig. 1 shows the TG curves of denim fabric waste (raw material)
and H3PO4-impregnated denim fabric. It can be seen from the TG
i2
(3)
Fig. 1. TG curves of denim and H3PO4-impregnated denim.
 T.L. Silva et al. / Journal of Cleaner Production 171 (2018) 482e490 485

curves that both materials have three distinct stages of weight

losses. The first stage of TG curves of both materials, at 130  C (I),
corresponds to weight loss caused by removal of physisorbed water
(Burhenne et al., 2013).
By evaluating the TG curve of denim fabric, it can be seen a
significant weight loss of about 70% (second stage - II), which is
related to degradation processes such as dehydration, decomposi-
tion and depolymerization of cyclic rings glucose (Roman and
Winter 2004). Additionally, the third stage (III) is associated with
the degradation and removal of relatively more stable volatile
species from the material (Rosas et al., 2009).
In the case of the TG curve of the H3PO4-impregnated denim
fabric, a weight loss of approximately 20% in the temperature range
between 200  C and 600  C (second stage - II) was observed. In this
temperature interval, a reaction between the activating agent and
denim fabric waste occurs, promoting the formation of phosphate
esters and the development of micropores (up to 350  C) and
mesopores (up to 550  C), besides causing the elimination of H3PO4
and the gradual reduction in the pore volume of the material. In the
third stage (III), the reaction between the denim fabric and H3PO4,
followed by the final oxidation of carbon, the decomposition of the
phosphate bridging groups formed in the material, and the gradual
reduction in the micropore volume of the material, take place (Xu
et al., 2014). The TG curves further show that the H3PO4-impreg-
nated denim fabric has a greater thermal stability than the denim
fabric (raw material). In addition, it was observed a residual weight
of 62% at 500  C for H3PO4-impregnated denim fabric, which is
close to the yield value found for ACFs.

3.3. Characterization

3.3.1. BET surface area and pore size distribution

Fig. 2a shows the N2 adsorption and desorption isotherms of the
ACFs. The results show that with the increase of relative pressure
occurs a rapid increase in the amount of N2 adsorbed. According to Fig. 2. N2 adsorption-desorption isotherms (a) and pore size distribution (b).
IUPAC classification, the isotherm can be classified as Type I(b) with
H4 hysteresis (Thommes et al., 2015). Type I(b) isotherm is common
Table 1
to materials with pores distributed over a broad range, including Textural properties of ACFs.
wider micropores and narrow mesopores. The hysteresis loop
shows a capillary condensation step between p/pº of 0.4e0.9, Sample SBET (m2g
1) VT (cm3g
1) Vm (cm3g
1) VM (cm3g
1) DP (nm)

indicating the presence of well-developed mesoporous structure
on the ACFs.
The pore size distribution from the BJH (Fig. 2b) showed a nar-
row pore size distribution with pores ranging from 30 to 50 Å and
the main peak centered at around 30 Å. These results clearly sug-
gest that the use of H3PO4 and the slow pyrolysis (up to tempera-
ture of 550  C) on the denim fabric waste help creating mesoporous
structure in the obtained ACFs.
The textural properties of ACFs are compiled in Table 1. Ac-
cording to the results, ACFs have high SBET value (1582 m2 g
1) and
mesopores with diameters between 30 and 40 Å. These results are
in line with other reports in the literature, which describe that: 1)
chemical activations generally result in carbon materials with high
surface areas and, 2) chemical activations with acids lead to porous
carbons with more mesoporous compared with carbon materials
prepared from chemical activation using bases and/or physical
activation methods with steam and/or CO2 (Khezami et al., 2005;
Hu et al., 2003). In addition, the ACFs showed an average pore
diameter of 3.6 nm, which can play an important role in the
adsorption properties of the carbon materials, since mesoporosity
feature of a given material allows ions and macromolecules pene-
trate easier into their porous (Hu et al., 2003).
3.3.2. Morphology
The morphologies of denim fabric (Fig. 3a) and ACFs (Fig. 3b and
ACFs 1582 1.005 0.170 0.390 3.60
SBET ¼ BET surface area; VT ¼ total pore volume; Vm ¼ micropore volume;
VM ¼ mesopore volume; DP ¼ average pore diameter.
c) were investigated by scanning electron microscopy (SEM). The
representative SEM images showed that the denim fabric has lon-
gitudinal fibers with thicknesses ranging from 5 to 15 mm. After
subjecting the denim fabric to slow pyrolysis and activation process
using H3PO4, the resulting material (ACFs) showed fibers with
thicknesses of ~10 mm. This suggests that fibrous characteristics
from the precursor were partially kept in the ACFs, which corrob-
orates with studies carried out by Barker and Hendrix (1979), who
reported about the use of phosphorus compounds as flame re-
tardants for wood and cellulose. The H3PO4 helps in the cross-
linking of the biopolymer chains, avoiding its decomposition to
volatile products (Jagtoyen and Derbyshire, 1998). The TEM
micrograph of ACFs is shown in Fig. 3d, from which it is possible to
see porous features of the material obtained.
3.4. Chemical surface characterization
FT-IR ATR spectra of denim fabric and ACFs are shown in Fig. 4.
According to results, can be seen that significant changes occurred
from the raw material (denim fabric) to ACFs. FT-IR ATR spectrum of
486 T.L. Silva et al. / Journal of Cleaner Production 171 (2018) 482e490
Fig. 3. Scanning electron microscopy (SEM) images of denim waste (a), ACFs (b and c) and TEM micrograph of ACFs (d).
Fig. 4. FT-IR ATR spectra of denim fabric and ACFs.
denim fabric showed characteristic peaks for cellulose around
1000-1200 cm
1 (CeOeC stretching at 1160 cm
1 and CeO
stretching at 1029 cm
1), and other bands attributed to cellulose
chemical structure found in cotton fabric (Nam et al., 2017; Wang
et al., 2006; Chung et al., 2004). These other bands consist of
bands at ca. 3600-3300 cm
1 that are attributed to hydrogen-
bonded OeH stretching from alcohols present in glucose chain, as
well as NeH stretching of dye molecule on denim fabric (Zhu et al.,
2016; Cui et al., 2017). The band at 2902 cm
1 was assigned to
stretching of aliphatic CeH, which indicates the presence waxes.
The band at 1627 cm
1 was attributed to OeH bending of absorbed
water, and band at 1315 cm
1 of CeH wagging. FT-IR ATR spectrum
of ACFs showed significantly lower peak intensities when
compared to denim fabric spectrum. The broad absorption band
between 3200 and 3600 cm
1 was attributed to the stretching vi-
bration of hydrogen-bonded OeH from carboxyl, phenols or alco-
hols, and surface adsorbed water molecules present in the material,
as well as NeH stretching (Zhu et al., 2016). The ACFs spectrum did
not show peak at ca. 2900 cm
1 characteristics of the stretching
vibrations of aliphatic, indicating aromaticity of material. Addi-
tionally, can be seen, a band with maximum peak at 1570 cm
1,
which was assigned to aromatic ring stretching mode enhanced by
presence of polar groups (Sych et al., 2012). The small peak at
1696 cm
1 is characteristic of C]O absorption in carboxylic acids.
The band between 1118 and 1320 cm
1, with a maximum at
1200 cm
1 can be attributed to the stretching mode of hydrogen-
bonded P]O, OeC stretching vibrations of PeOeC (aromatic)
linkages and P]OOH (Puziy et al., 2002). The band between 1013
and 1095 cm
1 can be assigned to the linkages in the ionized forms
of PþeO- species and symmetrical vibration in PeOeP chains
(polyphosphates) (Khan et al., 2016). The peak at 862 cm
1 was
ascribable to CeH out-of-plane bending absorption in aromatic
ring. The presence of carbon, oxygen, phosphorous and nitrogen
elements on the ACFs was confirmed by EDS analysis (Fig. S4b),
which it is corroborating with the FT-IR analyses.
The Boehm titration method provides important information
regarding the surface properties of carbon materials, which in turn
can dictate the performance of the materials in adsorption pro-
cesses. The amounts of basic and acid functional groups per unit
gram of the ACFs are determined and compiled in Table 2. It can be
 T.L. Silva et al. / Journal of Cleaner Production 171 (2018) 482e490
Table 2
Surface functional groups of ACFs determined from Bohem method.
Surface functional groups (mmol g-1)
Material Acid Groups Basic Groups
Carboxylic Lactonic Phenolic Total
ACFs 0.386 0.290 0.454 1.13 0.569
seen that the total amount of acid groups (carboxylic, lactonic and
phenolic) on the material is greater in number than the total
amount of basic groups. This is in line with those obtained by FTIR
analysis, which also showed the presence of surface acid groups.
The pHPZC represents the pH at which the charge of the adsor-
bent surface is zero, whose value is extremely important to
examine the effect of solution pH on the adsorption capacity of a
given adsorbent material (Marzbali et al., 2016). The pHPZC value of
the ACFs was found to be 2.1 (Fig. S2), suggesting that the ACFs’
surface is negatively charged in solutions with pH values higher
than 2.1 and positively charged in solutions with a pH values lower
than 2.1. The pHPZC value obtained for ACFs is in line with the data
obtained from FTIR analysis and the Boehm method, both suggest
that the ACFs have acidic functional groups on their surfaces.
Similarly, a low pHPZC value (2.13) was reported by Marzbali et al.
(2016) for apricot nut shells -derived activated carbon using
H3PO4 as an activating agent.
3.5. Adsorption studies of RBBR dye onto ACFs
3.5.1. Effect of pH
The effect of the solution pH on the adsorption capacity (qm) of
ACFs is shown in Fig. 5. From the results, it can be seen that the
highest qm value was found at pH 2.0, which decreased until pH 5.0,
and then remained constant until pH 9.0. This result corroborates
with those obtained by chemical surface characterization, which
indicated the presence of surface acidic groups on the ACFs. Spe-
cifically, for solutions with pH < 2.0, the ACFs have predominance of
positive charges on their surface, while the RBBR dye molecules
have negative charges in solution from their sulfonic groups
(eSO-3). So, the higher adsorption capacity (qm) of the ACFs at pH 2.0
toward RBBR dye can be attributed to the electrostatic interactions
between the adsorbent and the adsorbate (Silva et al., 2016). On the
Fig. 5. Effect of pH on the adsorption of RBBR onto ACFs. (C0 ¼ 200 mg L
1;
pH ¼ 2.0e9.0; T ¼ 25  C; shaking ¼ 200 rpm and time ¼ 240 min).
487
other hand, for pH values higher than 2.0, ACFs tend to have
negatively charged surface, and thus repel the negatively charged
adsorbate. So, for solution pH values higher than the ACFs’ pHPZC
value, the adsorption can take place via non-electrostatic interac-
tion, such as: p-p interaction, hydrogen bonding and electro donor-
acceptor complex mechanism (Moreno-Castilla, 2004).
3.5.2. Adsorption kinetics
Kinetic models of pseudo-first order and pseudo-second order
were employed to evaluate the rate of adsorption and the nature of
interactions between RBBR molecules and the ACFs surface. Fig. 6
shows the adsorption kinetics at three different initial concentra-
tions (100, 200 and 300 mg L
1). Based on the results, for the lower
concentration, the adsorption equilibrium was reached in about
90 min, indicating a rapid saturation of the adsorbent by the dye
molecules. On the other hand, for higher concentrations, adsorp-
tion equilibrium was attained over longer times. This occurs due
the occupation of the adsorption sites by a larger volume of dye
molecules, which leads to the saturation of the volume of space in
the material. The non-linear models of pseudo-first order and
pseudo-second order were then fitted to the experimental data
(Fig. 6), and the kinetic parameters associated with the adsorption
processes were calculated and compiled in Table S2
(Supplementary Information section).
The results show that for the three different concentrations of
RBBR, the model that fitted well to the experimental data was the
pseudo-second order model, which showed the highest values of
determination coefficient (R2) and the lowest values of normalized
standard deviation (Dqe). This suggests that the rate-limiting step
on the system may be chemisorption, which involves valence forces
through sharing or exchange of electrons between the adsorbent
and the adsorbate molecules (Djilani et al., 2015). In addition, the k2
values of pseudo-second order model decreased with increase in
the initial concentration of RBBR (Table S2), this can be due to
competition between higher levels of adsorbate ions for the limited
adsorption active sites (Albadarin et al., 2012).
The adsorption mechanism of ACFs-RBBR system was investi-
gated from the Weber and Morris intra-particle diffusion model,
which it was fitted to the kinetic experimental data (Fig. S6,
Table S5 and discussion in the SI). The results showed that the intra-
particle diffusion is not the rate-limiting step of the adsorption
process, suggesting that other processes plays important role in the
adsorption of RBBR toward ACFs.
3.5.3. Adsorption isotherms
Adsorption isotherm studies can provide information about the
adsorption mechanisms involved for a given system, besides that, it
allows to determine the theoretical maximum adsorption capacity
of an adsorbent to a given adsorbate (Dashamiri et al., 2017).
Several kinds of interactions, such as H-bonding, electrostatic in-
teractions and interactions between donor-receiver of electron, can
be responsible for the adsorption of RBBR molecules on the ACFs
(Lim et al., 2013).
Fig. 7 shows the experimental data and fits of the Langmuir,
Freundlich and Dubinin-Radushkevich models. The Langmuir
model assumes that the adsorption process is uniform and occurs
in monolayer, involving a limited number of identical active sites.
The Freundlich model is an empirical model that considers the
adsorption process occurs in multilayers on heterogeneous surfaces
formed by active sites with different energies (Cazetta et al., 2016).
The Dubinin-Radushkevich model is more general than the Lang-
muir model, since it does not presume a homogeneous surface or a
constant adsorption potential (Larous and Meniai, 2016).
The adsorption isothermal parameters and the values of R2 and
Dqe are displayed in Table S3. According to the results, the
488 T.L. Silva et al. / Journal of Cleaner Production 171 (2018) 482e490

Fig. 6. Adsorption kinetics of RBBR on ACFs and non-linear fits of pseudo-first order and pseudo-second order models. Initial concentrations: (a) 100 mg L
1, (b) 200 mg L
1, and (c)
300 mg L
1 (pH ¼ 2.0; T ¼ 25  C; shaking ¼ 200 rpm and times ¼ 2.5e240 min).

Table 3
Values of BET surface area (SBET) and maximum adsorption capacities of several
adsorbent materials tested for adsorption of RBBR.

Adsorbent SBET (m2 g
1) Qm (mg g
1) Reference

Activated carbon 942 135a Zhong et al. (2012)

Activated carbon 941 199a Ahmad et al. (2014a)
Activated carbon 958 204a Ahmad et al. (2014b)
Biosorbent e 48.3a Ergene et al. (2009)
Biosorbent e 9.0a Mafra et al. (2013)
Biosorvent e 42.0b Rahmat et al. (2016)
Activated carbon fibers 1582 292a This work
a
Values of experimental adsorption capacity.
b
Maximum monolayer adsorption capacity.

kinds of adsorbent materials for RBBR. It is worth noting that the

Fig. 7. Adsorption of RBBR on ACFs and non-linear fits of the models of Langmuir,
Freundlich and Dubinin-Radushkevich. (C0 ¼ 25e500 mg L
1; pH ¼ 2.0; T ¼ 25  C;
shaking ¼ 200 rpm and time ¼ 240 min).
Freundlich model showed the highest R2 value and the lowest Dqe
value, indicating that the adsorption of RBBR occurs through the
formation of multilayers. The result further suggested that the
adsorption process was favored by the mesoporous structures in
the ACFs. Given the fact that the chemical structure of RBBR (Fig. S1)
has dimensions of 1.13 nm and 1.84 nm and ACFs have an average
pore size of 3.6 nm, it is possible to propose that each pore can
accommodate more than one dye molecule. Additionally, this may
justify the difference between value of monolayer maximum
adsorption capacity determined by Langmuir model (253 mg g
1)
and value of experimental maximum adsorption capacity
(292 mg g
1). Table 3 shows the adsorption capacities of several
ACFs reported herein showed higher SBET values as well as higher
adsorption capacity for RBBR compared to many other adsorbents
and AC materials.
3.5.4. Thermodynamic studies
The thermodynamic study of the adsorption process can help
understanding the effect of temperature on the adsorption of RBBR
molecules over the ACFs. Fig. 8 shows a graph of ln Kc versus 1/K,
from which it can be seen that an increase in the temperature
causes a decrease in the value of ln Kc, as well as a decrease in the
distribution constant value (Kc). These results indicate that the
adsorption process over ACFs is more efficient at lower
temperatures.
The thermodynamic parameters for the adsorption of RBBR on
ACFs were determined, and the values are compiled in Table S4. As
can be seen, the value of the change in enthalpy (DH) was found to
be
5.19 kJ mol
1, which suggests the exothermic nature of the
adsorption process (Ahmad et al., 2014a). The Gibbs free energy
change (DG) is an important parameter that provides information
 T.L. Silva et al. / Journal of Cleaner Production 171 (2018) 482e490
Fig. 8. Linear plot of lnKe versus 1/T (K
1) for RBBR adsorption onto ACFs.
(C0 ¼ 500 mg L
1; pH ¼ 2.0; T ¼ 30, 40, and 50  C; shaking ¼ 200 rpm, and
time ¼ 240 min).
about the spontaneity of a given system, or in this case, if the
adsorption process on ACFs occurs via chemisorption or phys-
isorption. For DG values between
80 and
400 kJ mol
1, chemi-
sorption has been widely suggested to be the predominant process
during adsorption, whereas for DG values between 0 and
-20 kJ mol
1, physisorption has been suggested to be the pre-
dominant process (Zhang et al., 2015). According to the results
(Table S4), an increase in temperature leads to a decrease in the
negative values of DG, suggesting the spontaneity and feasibility of
the adsorption of RBBR on the ACFs, additionally, it is expected that
physisorption plays an important role in the adsorption process.
The negative value of DS reveals the decrease of randomness or
random distribution of sites covered by the adsorbate molecules at
the solid-liquid interface (Ahmad et al., 2014a).
4. Conclusion
Denim fabric waste and H3PO4 were subjected to a slow pyrol-
ysis process to obtain activated carbon fibers (ACFs), and which
were applied as efficient adsorbent for removal of Remazol Brilliant
Blue R dye (RBBR) from aqueous solution. The H3PO4 acted as a
protective agent for the precursor, helping it to maintain its fibrous
morphology and incorporate phosphorus-based functional groups
on the surfaces of the resulting ACFs. The ACFs showed high surface
area (1582 m2 g
1) with presence of mesoporous. The activation
procedure herein proposed provided a material with fiber features
with thickness of ~10 mm, and presence of some graphitic layers
along amorphous structure. Additionally, the procedure of acid
activation procedure led to obtaining material with surface acid
groups and low pHPZC value. Adsorption studies of RBBR onto ACFs
revealed that the kinetic model of pseudo-second order and the
adsorption isotherm model of Freundlich fitted well to the exper-
imental data. These models indicated that the adsorption process
may occurs by chemisorption and takes place via multilayer
adsorption. Adsorption equilibrium study showed high maximum
adsorption capacity of the material for RBBR, and thermodynamic
studies indicated that the adsorption process was exothermic and
spontaneous, occurring via physisorption. From the results, it can
then be concluded that both physisorption and chemisorption may
drive the adsorption process of RBBR dye over the ACFs, which may
involve strong and weak chemical bonds. The ACFs herein obtained
489
have features of N and P doped mesoporous carbon material, which
are attractive features for their application as electrocatalyst.
Acknowledgements
The authors acknowledge the financial support provided by
~o Arauca
CNPq-Brazil, CAPEs-Brazil and Fundaça
ria-Brazil.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.jclepro.2017.10.034.
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