J Polym Environ
DOI 10.1007/s10924-017-1072-8
ORIGINAL PAPER
A Biomass Cationic Adsorbent Prepared From Corn Stalk: Low-
Cost Material and High Adsorption Capacity
Xue Wen1 · Chunjie Yan1,2 · Na Sun1 · Tiantian Luo1 · Shilai Zhou1 · Wenjun Luo1
© Springer Science+Business Media, LLC 2017
Abstract  In this research, corn stalk fibers (CSF) grafted
polyacrylic acid (PAA) on their surfaces (CSF-g-PAA)
were successfully prepared via heterogeneous esterifica-
tion in the case of maintaining inherent fiber framework
and shape. It can be used to removal cationic contaminants
from aqueous solution. Four dyes and three metal ions were
employed as models of cationic adsorbates to survey its
adsorption performance. All of them showed high adsorp-
tion capacities, even the lowest RhB reached 179  mg/g.
The CSF-g-PAA not only has a high adsorption capacity
but also maintains inherent fiber framework, showing fea-
tures of easy separation. The adsorption capacity reached
370  mg/g for methylene blue (MB), which was signifi-
cantly far higher than that of original CSF (<30  mg/g).
MB adsorption followed pseudo-second-order kinetic and
the Langmuir isotherm model. The adsorbent can be sepa-
rated easily and rapidly from wastewater through a sieve of
200 mesh. Adsorption and desorption were also evaluated.
The CSF-g-PAA might be used as a promising adsorbent
for practical application because of its low cost and high
performance.
Electronic supplementary material  The online version of this
article (doi:10.1007/s10924-017-1072-8) contains supplementary
material, which is available to authorized users.
* Wenjun Luo
luowj@cug.edu.cn
1 is about twice as many as corn [8]. Hence, it can be used
Faculty of Material and Chemistry, China University
of Geosciences, Wuhan 430074, China
2 tages of cornstalk’s environmental friendliness and low
Engineering Research Center of Nano‑Geomaterials
of Education Ministry, China University of Geosciences,
Wuhan 430074, China
 
Keywords  Corn stalk fiber · Grafting modification ·
Heterogeneous esterification · Sulfuric acid catalysis ·
Removal cationic contaminants
Introduction
In the last decade, research on various adsorbing materials
has been in ascendant because they play important roles in
sorption [1–3]. More and more excellent adsorbents were
developed and reported in research papers, especially for
those adsorbents based on nano-powder materials [4–6].
However, problems and pitfalls such as inconvenient use
and complex process limited their practical application.
Therefore, absorbents with practical value should and
must be cheap, efficient and easy to use [7]. First of all,
the adsorbent substrate should have the following proper-
ties: (1) environmental friendliness, the substrate itself
should be innocuous and can be biodegraded in nature; (2)
Source is sustained, rich and without consuming petroleum
resources. Secondly, material must be very cheap and easy
to get and can be modified to become a high performance
adsorbents. Beyond these, adsorbent must be easy to use, in
particular, must be separated easily and rapidly from waste
liquid for solid–liquid adsorption.
Corn stalk is the main byproduct in corn production. As
corn is a main grain crop, the annual yield of corn stalk is
huge. According to the Food and Agriculture Organiza-
tion, from 2011 to 2014, the average annual yield of corn
was 1.16 billion tons in the world. The yield of corn stalk
as an abundant raw material. More importantly, the advan-
cost are what we desire.
13
Vol.:(0123456789)

However, corn stalk unmodified has a low level of
adsorption capacity owing to the limited surface adsorption
sites [9, 10]. Increasing the adsorption sites is an impor-
tant way to improve the adsorption capacity. The main
component of corn stalk is cellulose which is accounted for
36.9–41.43% [11]. Cellulose is rich in hydroxyl, which is
the premise that many chemical reactions of cellulose can
occur.
Grafting is an effective and common method for modi-
fication of cellulose. Grafting techniques include three
method, “grafting to”, “grafting through” and “grafting
from” methods [12].
At present, “grafting from” method is the main means
of grafting. This method is based on chain initiation, chain
growth, chain transfer and chain termination. Because of
the existence of chain transfer reaction, active sites may
transfer to monomers, and the self-polymerization (means
polymerization of a single kind of monomer and failing to
graft) of monomers couldn’t be avoided in theory. In fact,
the most common is that the initiator is easy to act on the
monomers, causing the self-polymerization. A large num-
ber of self-polymers result in the waste of raw materi-
als and the increase of the cost. In this work, in order to
avoid this shortcoming, we changed the method of grafting,
using “grafting to” method to graft polyacrylic acid (PAA)
to cellulose (cellulose-g-PAA) by esterification reac-
tion. Thus, PAA has become a reactant, rather than a by-
product from the “grafting from”. The carboxylic groups
of PAA can be bound to corn stalk fibers (CSF) surfaces,
and also have electrostatic affinity to cationic pollutants,
which is expected to synergistically enhance the adsorption
performance.
In this work, the CSF-g-PPA, which satisfied all the
requirements mentioned above, was prepared by a simple
and low-cost method. As is known to all, alkali treatment
is a traditional method to obtain more pure cellulose, hav-
ing been widely used in textile and papermaking. CSF were
gotten from corn stalk by alkali treatment. Though the most
adopted approaches for cellulose modification call upon
reactions carried out in homogeneous conditions because
of the higher reactivity, the heterogeneous modification is
the most appropriate procedure to maintain the size of the
adsorbent considering its application [13]. So this esterifi-
cation is a solid–liquid heterogeneous reaction. However,
in solid state, there are hydrogen bonds between cellulose
molecules, which leads to the crystallization of cellulose.
General reagents cannot enter the crystal area and react [14,
15]. Concentrated sulfuric acid ­(H2SO4) was employed as
catalyzer, promoting the esterification reaction between
cellulose and PAA. ­H2SO4 has the ability to enter the crys-
tal area of cellulose [16, 17], increasing its reactivity.
In order to evaluate the adsorption performance, the
adsorption capacities of several cationic dyes and metal
13
J Polym Environ
ions were measured. Among them, methylene blue (MB)
was chosen to study the effect of pH value, adsorption equi-
librium, thermodynamics, kinetics and desorption due to its
typicality [18, 19] and convenience.
Materials and Methods
Materials
Raw corn stalks, a total of 25  kg, were obtained from a
farm in Henan province, China. After removing the leaves
and washing with freshwater, the materials were cut into
sections about 5  cm sizes using hay cutter, then washed
deionized by water and dried at 50 °C. The dried corn stalk
was denoted as CS.
Reagents
Concentrated sulfuric acid ­(H2SO4, 98 wt%), acroleic acid
(AAc), ammonium peroxydisulfate [(NH4)2S2O8], sodium
bisulfite ­(NaHSO3) hydrochloric acid (HCl), sodium
hydroxide (NaOH), ethanol (­C2H5OH), Ce(NO3)3·6H2O,
Ni(NO3)2·6H2O and ­ CuSO4·5H2O were purchased from
Fu Chen Chemical Reagent Factory (Tianjin City, China).
MB, rhodamine B (RhB), malachite green (MG) and safra-
nine T (ST) were obtained from Xiangda Chemical Rea-
gent (Hunan, China). Deionized water was used to prepare
all solutions. All chemicals used in this study were of com-
mercially available analytical grade and used without fur-
ther purification.
Preparation of CSF
Firstly, CS was immersed in 9  wt% NaOH and stewed
for 2  h at 80 °C. Secondly, it was washed by deion-
ized water. With the removal of a large amount of lignin
and hemicellulose, the CS was looking like fiber. Then,
it was immersed in 9  wt% NaOH alcohol aqueous solu-
tion (VC2H5OH:VH2O = 1:1) for 2 h at −20 °C. Finally, it was
washed to near neutral. By this time, the preparation of
CSF were completed.
Preparation of PAA
The PAA solution was synthesized by solution polymeri-
zation at 65 °C. 30 wt% AA solution (100 g), (­NH4)2S2O8
(1.5  g) and ­NaHSO3 (0.5  g) were added together to react
for 4 h.
J Polym Environ
Preparation of CSF‑g‑PAA
The procedure used for the preparation of the CSF-g-PAA
is shown in Fig.  1. Deionized water (50  mL) and H ­ 2SO4
(20 mL, 98%) were added to a 250 mL beaker. After heat-
ing the beaker to 80 °C in a water bath, PAA (50 mL) was
rapidly added to the beaker with stirring irregularly. In
order to avoid precipitation of PAA, the irregular stirring
and rapid addition were necessary, because hydrogen bonds
of –COOH groups would increase under strong acid condi-
tions, and strong hydrogen bonds would cause that the PAA
crimpled in group and precipitated. Then, some of the CSF
were immersed in the solution. Kept reaction temperature
at 80 °C for 4  h, and stirred them every 20  min. Finally,
CSF-g-PAA was washed by 2  mol/L NaOH solution to
remove unreacted PAA and to turn –COOH to –COONa.
Fig. 1  The preparation scheme of CSF-g-PAA
Adsorption Procedures
Typical adsorption procedure was conducted as follows:
15 mg of CSF-g-PAA was added to a vial that contained
20 mL of MB solution, then the mixture was shaken by a
shaker with speed of 120 rpm. Afterward, the supernatant
liquid was determined by spectrophotometer and its value
was calculated by the following equation:
)V
(
qe = C0 − Ce
m
where qe (mg/L) is the amount of adsorbed MB at equilib-
rium, C0 and Ce (mg/L) are the initial and equilibrium con-
centrations of MB, m is the mass of CSF-g-PAA (g), and V
(L) is the volume of solution.
13

Kinetic Studies
15  mg of CSF-g-PAA was mixed with 20  mL of MB
solution in a 25  mL vial under initial MB concentration
of 350  mg/L, and the vial was shaken in a shaker with
120  rpm for 24  h at 30 °C. There were eight identical
vials representing eight time points shown in Fig.  4A.
The concentration of MB was measured at predetermined
time by UV–Vis spectrometer.
In order to investigate the mechanism of adsorption,
nonlinearized Lagergren pseudo first-order kinetic model
and pseudo second-order kinetic model were applied
to analyze the adsorption process [20], which were
expressed as follows:
Lagergren pseudo first-order kinetic model:
qt = qe 1 − e−k1 t
( )
pseudo second-order kinetic model:
k2 q2e t
qt =
1 + k2 qe t
where qe and qt (mg/g) are the adsorption capacities at
equilibrium and at time t (h), respectively. k1 ­(h−1) and k2
[g/(mg  h)] are the equilibrium rate constants of pseudo-
first-order and pesudo-second-order models, respectively.
Adsorption Isotherms
To optimize the design of an adsorption system, it is
important to establish the most appropriate correlation
for equilibrium conditions [21]. According to different
adsorption mechanisms, there are currently several dif-
ferent adsorption isotherms used for fitting experimental
adsorption results. Among these, Langmuir and Freun-
dlich isotherms are widely used and therefore are applied
in this study [20]. The nonlinear forms of these isotherms
are given as follows:
Langmuir model [22]:
q K C
qe = ( m a e )
1 + Ka Ce
Freundlich model [23]:
qe = KF Ce1∕n
where, qe (mg/g) is the amount of MB adsorbed at equilib-
rium, Ce (mg/L) is the equilibrium concentration of MB, qm
(mg/g) is the adsorption capacity. Ka is the Langmuir bind-
ing constant which is related to the energy of adsorption.
13
J Polym Environ
KF and n are equilibrium constants indicative of adsorption
capacity and adsorption intensity respectively.
Thermodynamic Studies
In order to obtain the thermodynamic nature of the adsorp-
tion process, the adsorption equilibrium at 30, 40, 50, 60 °C
was studied. The thermodynamic parameters can be calcu-
lated according to the following three equations [24, 25].
ΔG◦ = − RT ln K0
where R is universal gas constant (8.314  J/(mol  K)), T is
the absolute temperature (K). K0 is the thermodynamic
equilibrium constant, which can be calculated by the fol-
lowing equation:
Cad,
e
K0 =
Ce
where Cad, e is the amount of MB (mg) adsorbed on the
adsorbent per liter of the solution at equilibrium and Ce is
the equilibrium concentration (mg/L) of MB in solution.
Finally, the values of ΔH° and ΔS° are obtained from
the intercept and slope of the plot of ∆G° versus T using
the following relationship:
ΔG◦ = ΔH ◦ − TΔS◦
Zeta‑Potential and pH Studies
The effect of solution pH on the adsorption efficiency was
investigated in the range of 2–11 through a similar proce-
dure described above, where the solution pH was adjusted
by adding a certain amount of 0.1 mol/L HCl or 0.1 mol/L
NaOH solution. The zeta-potential of CSF-g-PAA was
measured by Zeta-Meter 4.0 (Ankersmid Co., LTD, The
Netherlands).
Desorption and Reusability
The MB-adsorbed CSF-g-PAA was collected after typi-
cal adsorption procedure described above. The MB-loaded
adsorbent was washed gently with water to remove any
unadsorbed dye. 0.1  mol/L HCl solution was added to
MB-adsorbed CSF-g-PAA to perform desorption. Then it
was placed on the shaker for 24 h. After being filtered, the
regenerated adsorbent was activated with 2  mol/L NaOH
solution and washed with deionized water to neutralize for
the next cycle. MB-adsorbed CSF-g-PAA was desorbed
and regenerated. A total of six cycles were performed.
Characterization
The morphologies of CS, CSF and CSF-g-PAA were char-
acterized by field emission scanning electron microscope
J Polym Environ
(FE–SEM) (Hitachi SU8010, Japan) and optical micro-
scope. The surface functional groups of CSF and CSF-g-
PAA were detected by Fourier transform infrared (FT-IR)
spectroscope (FT-IR-2000, PerkinElmer), where the spectra
were performed in KBr pellets and recorded from 4000 to
400 cm−1.
Results and Discussion
Characterization of Materials
Figure 2A show the SEM images of the CS, CSF and CSF-
g-PAA. From a, we can see the flake-like structure of the
CS, because the cellulose fibers are linked by lignin, hemi-
celluloses and pectin. After alkali treatment, as is shown
Fig. 2  Morphological characterization: SEM images of CS (Aa), CSF (Ab) and CSF-g-PAA (Ac) and optical microscope photographs of CS
(Ba, b), CSF (Bc), CSF-g-PAA (Bd), CSF-g-PAA after MB (Be) and ­Cu2+ (Bf) adsorption
in the Fig.  2A(b), the corn stalk became fibers due to the
removal of the most of impurities. Comparing A(b) with
A(c), it can be seen that the fibers are further dispersed,
obtaining a larger specific area. As reported in the litera-
ture [26], “grafting to” method is relatively easy, but once
polymer chains populate the surface, it becomes hard for
succeeding polymer chains to react with the surface of the
particle, which results in relatively low grafting densities.
Therefore, the grafted PAA cannot be seen in Fig.  2A(c),
while the grafted layers in SEM images are obvious who
used the “grafting from” method [10, 23, 27].
Figure  2B is the photograph. The a, b are the cross-
section and interior side of the CS, respectively. The loose
structure illustrates that corn stalk has a natural condition
to be used as an absorbent. The B(c, d) show the appear-
ance of CSF and CSF-g-PAA, respectively. It can be seen
13

that the CSF-g-PAA has slightly plastic texture, owning to
grafting with PAA. The B(e, f) show appearance of CSF-g-
PAA after MB and C ­ u2+ adsorption, respectively. The abil-
2+
ity of ­Cu adsorption reflects the successful modification
of corn stalk, because the adsorption effects of unmodified
corn stalk cannot be seen.
FT-IR spectra of CSF and CSF-g-PAA are shown in
Fig. 3. All peaks are summarized in Table 1. The absorp-
tion peak of corn stalk fiber at 3428  cm−1 may be due to
the presence of –OH stretching vibrations on the surface
of CSF and N–H stretching vibrations of amino for small
amounts of protein in substrate. The bands at 2921, 1636
and 1056  cm−1 are assigned to C–H stretching vibrations,
–OH flexural vibrations and C–O–C stretching vibrations,
respectively [10]. The band at 896 cm−1 is the characteristic
of β-glycosidic C–H deformation [28]. The step-like peaks
replaced by “☆” are related to guaiacyl and syringyl of the
lignin which has not been removed [29]. The new peak at
1720 cm−1 [30] in the spectrum of CSF-g-PAA are related
to the stretching vibration of C=O of –COOH groups prov-
ing that the absorbent contains PAA chains.
Fig. 3  FT-IR spectra of CSF and CSF-g-PAA
Table 1  Characteristic FT-IR Wave number (­ cm−1)
absorption bands for CSF and
CSF-g-PAA 3428
2921
1720
1636
1262–1265
1228–1235
1127
1056
896
13
J Polym Environ
In conclusion, the PAA was successfully grafted to corn
stalk cellulose fibers. The PAA is soluble in NaOH solu-
tion. As the unreacted PAA was washed by NaOH solution
in the process of preparation, the PAA chains in CSF-g-
PAA is chemically bonded to CSF.
Adsorption Kinetics
Figure  4A shows the effect of contact time on the MB
adsorption. Table  2 lists the sorption rate constants asso-
ciated with pseudo-first-order and pseudo-second-order
kinetic model. It can be seen from Fig. 4A that MB adsorp-
tion is a slow process, about 14 h is needed to reach equi-
librium for the CSF-g-PAA. The equilibrium adsorption
capacity of MB was 338.6 mg/g. Compared to the pseudo-
first-order model, the pseudo-second-order kinetic model
had a higher correlation coefficient and closer adsorption
capacity, suggesting that the MB adsorption process is a
chemisorption rather than physisorption [31].
Adsorption Isotherms
Figure  4B shows the application of nonlinear Langmuir
and Freundlich isotherms to the MB adsorption on CSF-g-
PAA. The values of KF and qm for adsorption of MB were
reported in Table 3. It is seen that the value of qm obtained
from Langmuir plots is mainly consistent with that experi-
mentally obtained. The experimental data of MB adsorp-
tion on CSF-g-PAA are better fit to Langmuir model
than Freundlich model. And the values of ­R2 reported in
Table 3, which is a measure of the goodness-of-fit, confirm
the good representation of the experimental data by Lang-
muir model. The result indicates that the binding sites of
CSF-g-PAA are uniformly distributed on its surface, and
the MB adsorption is monolayer [31]. According to the
assumption of Langmuir model, the adsorption affinity on
the surface of the CSF-g-PAA is homogenous in terms of
surface functional groups and bonding energy, and the sur-
face contains a finite number of identical adsorption sites.
Description References
–OH and N–H stretching vibrations [10]
C–H stretching vibrations of CH, C­ H2 and ­CH3 [10]
C=O stretching vibrations of –COOH [30]
–OH flexural vibrations [10]
Guaiacyl methoxyl groups [29]
C–O stretching vibrations of syringil [29]
Contribution of C–H in a plane deformation, C=O stretching [29]
of syringyl units and secondary alcohols
C–O–C stretching vibrations of cellulose [10]
β-glycosidic C–H deformation of cellulose [28]
J Polym Environ

Fig. 4  Experimental results of adsorption and desorption: A kinetic adsorption capacity of several common cationic dyes and typical
models, B isotherms, C the adsorption capacity in three stage and heavy metal cations. E effect of pH (histogram) and Zeta-potential of
adsorption capacity of CSFS (CSF after ­H2SO4 treatment), D the CSF-g-PAA at different pH (line chart), F recycling of CSF-g-PAA

Table 2  Regression parameters C0 (mg/L) qe, exp (mg/g) Pseudo-first-order model Pseudo-second-order model
by pseudo-first-order and
2
pseudo-second-order equation k1 (1/h) qe, cal, 1 (mg/g) R k2 g/(mg h) qe, cal, 2 (mg/g) R2

350 338.6 0.647 324.4 0.9315 0.0026 350.8 0.9865

13
 J Polym Environ

Table 3  Regression parameters by Langmuir, Freundlich equations Thermodynamic Study

at 30 °C
Langmuir Freundlich The values of ∆G°, ∆H°, and ∆S° were listed in Table 4.
The negative values of ∆G° indicated the spontaneous
R2 0.995 R2 0.831
adsorption of MB on CSF-g-PAA. And the increase of neg-
qm (mg/g) 354.1 KF 138.2
ative value of ∆G° with the decrease of temperature indi-
Ka 0.411 n 4.263
cated that the adsorption process was more advantageous
at lower temperatures. It is probably because the increase
of temperature enhanced the mobility of MB molecules,
Table 4  Thermodynamic study of MB adsorption which caused a lower adsorption capacity. However, we
T (K) ∆G° (kJ/mol) ∆H° (kJ/mol) ∆S° [kJ/(mol K)] R2
heated the adsorption equilibrium system (30 °C) to 60 °C,
the phenomenon of desorption was not observed. It seemed
333.15 −3.353 −21.471 −0.054 0.9949 that the adsorption was almost a chemical process because
323.15 −3.817 of no desorption under the higher temperatures.
313.15 −4.454 A negative value of ΔH (−21.471 kJ/mol) suggested that
303.15 −4.956 the MB adsorption was an exothermic process. The ΔS°
had a negative value of −54  J/(mol  K), which suggested
the randomness decreased at the solid–solution interface in
the adsorption system during the adsorption process. The
­ i2+, ­Cu2+, ­Ce3+, MB
Table 5  Size and adsorption capacity of N decrease in entropy change might be attributed to the fact
Adsorbate Ionic radius (nm) Adsorption
that the MB molecules lost at least one degree of freedom
capacity when adsorbed. The low value of ΔS° also indicates that no
(mmol/g) remarkable change on entropy occurs [33, 34].
By the way, with the decrease of the adsorption tempera-
Ni2+ 0.069 3.14
ture, the adsorption speed decreased, and the time to reach
Cu2+ 0.073 2.76
equilibrium was prolonged. At 25 °C, it was longer than
Ce3+ 0.102 1.64
24 h that the time to reach equilibrium was. So the optimal
MB a = 0.42, b = 0.8 1.27
temperature to adsorb MB is 30 °C.

Adsorption Capacity

pH and Zeta‑Potential Adsorption capacity is an important index to measure the

The pH of dye solution is of particularly importance in ana-
lyzing the adsorption procedure and exploring the adsorp-
tion ability.
As shown in Fig. 4E, it was evident that the adsorption
characteristics of the materials were highly pH-dependent,
and the adsorption capacity of CSF-g-PAA was larger at
relatively high pH values. As the pH increased from 2.0
to 11.0, the adsorption capacity increased gradually and
approached the maximum value at pH 11.0. As we dis-
cussed above, the isoelectric point of the adsorbent was
found to be about pH 3.2. It meant that the CSF-g-PAA
surface was positively charged at pH above 3.2, and thus
could capture cationic MB ions via an electrostatic interac-
tion. Besides, the amount of MB adsorbed by per unit mass
of CSF-g-PAA increased with the increase in pH because
the surface charge on the CSF-g-PAA was larger at a higher
pH value (Fig. 4E). Moreover, it is worth noting that there
was still a certain adsorption capacity even at pH below
3.2, due to the hydrogen bonding interactions between the
adsorbent and MB [32].
performance of adsorbent. The CSFS in Fig.  4C was the
CSF after H ­ 2SO4 treatment. The specific process was the
same as the preparation of CSF-g-PAA, but without add-
ing PAA. This illustrated that the increase of the adsorption
capacity was mainly the result of grafting PAA.
The adsorption of several common cationic dyes and
typical heavy metal cations onto CSF-g-PAA was shown
in Fig. 4D. It could be seen that the adsorbent had a good
adsorption performance for cations. It was suggested that
the adsorption capacity was affected by the radius and
valence of cations. When the valence of pollutants was
same, the larger ions were more difficult to be adsorbed
because of the bigger steric hindrance. In addition, it
seemed that the adsorption capacities of the low chemical
valence pollutants were higher than that of high valence.
Because the high valence ions needed more –COO− groups
to neutralize. However, there was no obvious evidence to
prove it, because there were no two ions with similar radius
and different valence in this study. It was shown in Table 5
that the adsorption capacity of ­Ni2+ was higher than ­Cu2+
­ i2+ was smaller than C
while the radius of N ­ u2+. Compared

13
J Polym Environ

with the valence of pollutants, the sizes could be a more
obvious influencing factor. Therefore, MB showed the low-
est adsorption capacity in Table  5. Furthermore, it was
shown in Fig.  4D that the adsorption capacity sequence
MB > MG > ST > RhB was observed. Meanwhile, the struc-
tures of four cationic dyes used were shown in Table 6. In
fact, it was obvious that the sizes sequence of four dyes was
identical with the adsorption capacity sequence.
Desorption and Reusability
Desorption of adsorbates from the adsorbents is essen-
tial to make it renewable in practice. Figure  4F showed
that the CSF-g-PAA had a good reusability. Although
there was a weak decline of adsorption capacity possibly
resulted from the reduced stability of the materials in the
strong acid, the adsorption capacity to MB still remained
263  mg/g. Moreover, desorption studies can also help
elucidating the mechanism of an adsorption process. If
the strong acids, it can be said that the attachment of the
dye onto the adsorbent is by ion exchange or electrostatic
attraction [35]. It meant the MB adsorption process was a
chemisorption.
Comparison with Other Adsorbents
Compared the adsorption capacities for cationic contami-
nants removal obtained in this work with that reported in
the literature, the adsorption capacities obtained in this
work were medium of the reported works. It could also be
seen from Table  6 that PAA and corn stalk modification
had been widely used in adsorption field. Compared with
different modification methods, esterification in this work,
which had only one step and employed cheap reagents,
might be the most cost-effective method. Therefore, CSF-g-
PAA has a potential use in cationic sorption in wastewater
(Table 7).

Table 6  Structure of common Dyes Structure Dyes Structure

cationic dyes
MB MG

ST RhB

Table 7  List of several cellulose-based or PAA-modified cationic adsorbents

Substance Modifier Supplement Adsorbate qm (mg/g) References

Graphene oxide PAA Sonication MB 118 [36]

Grapheme oxide PAA, β-cyclodextrin Sonication MB, ST 248, 175 [37]
Starch PAA, humate Hydrogels Cu2+ 180 [38]
Corn cob PAA, PAM Graft copolymerization Cu2+, ­Ni2+ 8–12 [39]
Corn stalk Acrylonitrile Graft copolymerization Cd2+ 21 [40]
Loofah fiber PAA Ultraviolet radiation graft Ce3+ etc. 359 etc. [27]
Bleached pulp Succinic acid Ball milling, esterification Cd2+, ­Pb2+ 87, 187 [15]
Corn stalk Triethylenetetramine – Cu2+, ­Pb2+ etc. 69, 192 etc. [41]
Corn stalk PAA Esterification MB etc. 370 etc. This work

13

Conclusion
In this work, the heterogeneous esterification between corn
stalk cellulose fiber (solid state) and PAA (solution) was
completed successfully. A low-cost biomass absorbent of
CSF-g-PAA was obtained. Faithfully, it would be a prom-
ising absorbent because of the low cost, straightforward
process and high adsorption capacity. A good news is that
the adsorption capacity of MB reached about 350 mg/g at
the natural conditions while it is 370 mg/g at optimal con-
ditions. The adsorption process is a chemisorption that is
consistent with our expectation. Moreover, the absorbent
is of universal applicability for plenty of cationic dyes and
heavy metal cations. In addition, the CSF-g-PAA overcame
the difficulty of separation of absorbent from solution.
Basing on the conclusions in this study, the esterification
between cellulose and other polymers might be paid more
attention. Meanwhile, more efficient catalysts are worth
studying. And corn stalk may be fully utilized to make a
contribution to solve the problem of water pollution.
Acknowledgements  This work was supported by the Public Ser-
vice Project of the Chinese Ministry of Land and Resources (No.
201311024), the Comprehensive Utilization Demonstration Base
of Ganzhou Rare Earth Resource sponsored by Chinese Ministry of
Land.
References
1. Crini G (2006) Bioresour Technol 97:1061
2. Forgacs E, Cserháti T, Oros G (2004) Environ Int 30:953
3. Luo P, Zhao Y, Zhang B, Liu J, Yang Y, Liu J (2010) Water Res
44:1489
4. Tan XF, Liu YG, Gu YL, Xu Y, Zeng GM, Hu XJ, Liu SB, Wang
X, Liu SM, Li J (2016) Bioresour Technol 212:318
5. Beyki MH, Bayat M, Shemirani F (2016) Bioresour Technol
218:326
6. Jung KW, Jeong TU, Hwang MJ, Kim K, Ahn KH (2015) Biore-
sour Technol 198:603
7. Hokkanen S, Bhatnagar A, Sillanpää M (2016) Water Res 91:156
8. FAOstat (2014) http://www.fao.org/faostat/en/#data/QC
9. Zheng L, Zhi D, Zhu C, Yi X, Hui Z, Liu C (2010) Bioresour
Technol 101:5820
10. Zhou Q, Yan C, Luo W (2016) Mater Des 97:195
11. Wang T, Yin J, Zheng Z (2012) Carbohydr Polym 87:2638
13
J Polym Environ
12. Gao B, Chen Y, Zhang Z, Gao B, Chen Y, Zhang Z (2010) Appl
Surf Sci 257:254
13. Alila S, Boufi S (2009) Ind Crops Prod 30:93
14. Sathitsuksanoh N, George A, Zhang YHP (2013) J Chem Tech-
nol Biotechnol 88:169
15. Qin X, Zhou J, Huang A, Guan J, Zhang Q, Huang Z, Hu H,
Zhang Y, Yang M, Wu J (2016) RSC Adv 6:26817
16. Driemeier C, Pimenta MTB, Rocha GJM, Oliveira MM, Mello
DB, Maziero P, Gonçalves AR (2011) Cellulose 18:1509
17. Chen L, Wang Q, Hirth K, Baez C, Agarwal UP, Zhu JY (2015)
Cellulose 22:1753
18. Feng Y, Yang F, Wang Y, Ma L, Wu Y, Kerr PG, Yang L (2011)
Bioresour Technol 102:10280
19. Ghorai S, Sarkar A, Raoufi M, Panda AB, Schönherr H, Pal S
(2014) ACS Appl Mater Interfaces 6:4766
20. Ding D, Zhao Y, Yang S, Shi W, Zhang Z, Lei Z, Yang Y (2013)
Water Res 47:2563
21. Parab H, Sudersanan M (2010) Water Res 44:854
22. Langmuir I (1918) J Am Chem Soc 40:1361
23. Li X, Yan C, Luo W, Gao Q, Zhou Q, Liu C, Zhou SH (2016)
Chem Eng J 284:333
24. Han R, Zhang J, Zou W, Jie S, Liu H (2005) J Hazard Mater
125:266
25. Hasan M, Ahmad AL, Hameed BH (2008) Chem Eng J 136:164
26. Chinthamanipeta PS, Kobukata S, Nakata H, Shipp DA (2008)
Polymer 49:5636
27. Liu C, Yan C, Luo W, Li X, Ge W, Zhou S (2015) Mater Lett
157:303
28. Lopes AMDC, João KG, Rubik DF, Bogel-Łukasik E, Duarte
LC, Andreaus J, Bogel-Łukasik R (2013) Bioresour Technol
142:198
29. Rana R, Langenfeld-Heyser R, Finkeldey R, Polle A (2010)
Wood Sci Technol 44:225
30. Said HM, Alla SGA, El-Naggar AWM (2004) React Funct
Polym 61:397
31. Gerente C, Lee VKC, Cloirec PL, McKay G (2007) Crit Rev
Environ Sci Technol 37:41
32. Li J, Zhang Q, Feng J, Yan W (2013) Chem Eng J 225:766
33. Al-Ghouti M, Khraisheh MAM, Ahmad MNM, Allen S (2005) J
Colloid Interface Sci 287:6
34. Han R, Zou W, Yu W, Cheng S, Wang Y, Jie S (2007) J Hazard
Mater 141:156
35. Wang L, Zhang J, Wang A (2008) Colloids Surf A 322:47
36. Zhang J, Azam MS, Shi C, Huang J, Yan B, Liu Q, Zeng H
(2015) RSC Adv 5:32272
37. Liu J, Liu G, Liu W (2014) Chem Eng J 257:299
38. Zheng Y, Hua S, Wang A (2010) Desalination 263:170
39. Wichaita W, Samart C, Yoosuk B, Kongparakul S (2015) Macro-
mol Symp 354:84
40. Zheng L, Zhu C, Dang Z, Zhang H, Yi X, Liu C (2012) Carbo-
hydr Polym 90:1008
41. Gurgel LVA, Gil LF (2009) Carbohydr Polym 77:142