Preparation and Adsorption Behavior of …nas1fiber.superscholar.kr/jkfs/16(9)-13.pdfPreparation and...

1925

ISSN 1229-9197 (print version)

ISSN 1875-0052 (electronic version)

Fibers and Polymers 2015, Vol.16, No.9, 1925-1934

Preparation and Adsorption Behavior of Diethylenetriamine/Polyacrylonitrile

Composite Nanofibers for a Direct Dye Removal

Arash Almasian, Mohammad Ebrahim Olya*, and Niyaz Mohammad Mahmoodi

Department of Environmental Research, Institute for Color Science and Technology, Tehran 1668814811, Iran

(Received September 3, 2014; Revised July 27, 2015; Accepted August 2, 2015)

Abstract: The diethylenetriamine (DETA)/polyacrylonitrile (PAN) composite nanofibers were prepared by usingelectrospinning technique. The surface morphology and chemical characterization of PAN/DETA composite nanofibers wereinvestigated using scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. Releasingpossibility of DETA from nanofibers was tested by total organic carbon (TOC) analysis. Results indicated that theincorporation of DETA into PAN affects the morphology of nanofibers. In order to hinder DETA releasing, this compoundwas fixed to the polymer using alkali treatment. The obtained PAN/DETA composite nanofibers were evaluated foradsorption of C.I direct red 80 (DR80). The amount of the dye adsorbed onto the PAN/DETA nanofiber mats was influencedby the initial pH, DETA amount, contact time, and the initial concentration of the dye solutions. The maximal adsorptioncapacity of the dye on the PAN/DETA nanofiber mats was calculated from the Langmuir model.

Keywords: Polyacrylonitrile, Electrospinning, Direct Red 80, Adsorption isotherm, Dye kinetic

Introduction

Nowadays, stress of water shortages is increased due to

deteriorating water quality, urbanization, and climate change

and wastewater reclamation. Water reuse is becoming a

widely endorsed strategy for augmenting freshwater resources.

In this regard, many methods such as adsorption, chemical

flocculation, chemical oxidation, froth flotation, ultra filtration,

and biological treatment technologies have been employed.

Among all, adsorption has been shown to be a highly

efficient process due to its sludge-free clean flexible operation,

simplicity of design, and complete removal of dyes from

dilute solutions. The adsorption properties of adsorbents

depend on the type and amount of functional groups of on

their surfaces. It was previously found that an adsorbent

containing nitrogen-based ligands are effective in forming

complexes with metal ions and dyes [1,2]. There are many

forms of nano adsorbents in different shapes including

cubes, spheres [3], plates [4], and fibers [5]. Nanofiber can

give an enormous surface area per unit volume, high

porosity, high gas permeability, and small interfibrous pore

size due to having diameter between tens and hundreds of

nanometer. Among the various methods reported in literatures

[6] for producing the nanosized fibers, electrospinning has

shown a great deal of attention due to simplicity, convenient,

low cost, and ability to produce ultrafine continuous fibers

from many polymeric [7] and ceramic [8] materials. One

advantage of production of nanofiber mats for application in

wastewater treatment is that they can be easily removed

from the solutions, which reduces the operation cost.

Polyacrylonitrile (PAN), a common and inexpensive

commercial polymer, has desirable chemical and thermal

properties [9] as well as good solubility in organic solvents

[10]. This polymer has extensively been studied for the

production of nanofibers by electrospinning process [9].

Since the properties of adsorbents used to remove dyes

changes with the solution conditions, the mechanism of

adsorption on the adsorbents is also changed significantly,

depending on different types of interaction between adsorbents

and dyes. Commonly, for this purpose the electrostatic

interaction has been identified as the major adsorption

mechanism for adsorption of dyes.

The combination of polymers and compounds with different

functional groups such as carboxyl and amine, enable their

utilization as effective adsorbents in dyes removed from

wastewater [11]. Previous research works stated PAN as a

desirable polymer for electrospinning and subsequent wastewater

treatment [12,13]. It is therefore of our interest to investigate

the feasibility of using a composite nanofiber mat bearing

amine groups for anionic dye removal from wastewater.

Some attempts were performed on surface modification of

PAN fibers. The amidoximated PAN nanofibers and aminated

PAN fibers were studied for ion adsorption by Saeed et al.

[11] and Shin et al. [14] respectively. However, no research

was reported to investigate the dye removal efficiency of the

polyacrylonitrile/diethylenetriamine (PAN/DETA) composite

nanofibers.

In the present work, PAN/DETA composite nanofiber mat

was synthesized and characterized by Fourier transform

infrared spectroscopy (FT-IR) and scanning electron microscopy

(SEM). The effect of the amount of DETA, the pH, the

contact time, and initial dye concentration on the adsorption

capacity of a direct dye was examined using a UV-vis

spectrophotometer.

*Corresponding author: [email protected]

DOI 10.1007/s12221-015-4624-3

1926 Fibers and Polymers 2015, Vol.16, No.9 Arash Almasian et al.

Experimental

Materials

Polyacrylonitrile copolymer (93.7 % acrylonitrile and

6.3 % vinylacetate with Mw=100.000 g /mol) was purchased

from Isfahan Polyacryl Inc. (Iran). N,N-dimethylformamide

(DMF), potassium carbonate, and diethylenetriamine (DETA;

~99 % purity) were used as received from Merck. DR80 was

supplied by Alvan Sabet Co. Iran. The chemical structure of

the dye is shown in Figure 1.

Preparation of PAN/DETA Composite Nanofibers

Electrospinning solution was prepared by 10 w/w% PAN

dissolved in DMF. Mechanical stirring was applied for 12 h

at room temperature in order to obtain homogeneous PAN

solution. The mixture of PAN/DETA solutions were then

prepared by adding a 10, 20, and 40 w/w% of DETA into

10 w/w% PAN solution, respectively. The mixtures were

stirred on a magnetic stirrer, and the reactions were allowed

to proceed at 95 oC for 240 min. The as-prepared solutions

were then electrospun under a fixed electric field of 15, 17,

and 19 kV, using a Gamma High Voltage Research RR60

power supply, onto aluminum (Al) sheet which was used as

the collector. The distance from the tip to the collector was

15 cm and the feeding rate of the polymer solution was

1.2 ml/h. The electrospun composite nanofiber mats were

placed at a vacuum oven (65 oC, 5 h) to ensure evaporation

of the solvent.

Composite Nanofibers Fixation Process

In order to provide bonding between DETA and PAN with

nanofiber, the mats were immersed in a distilled water batch

containing 100 % (w/w) potassium carbonate at 80 oC for

2 h. Finally, composite nanofibers were dried at an oven

(60 oC, 3 h).

Characterization

The FTIR spectra of pure PAN and PAN/DETA composite

nanofibers were examined by the FTIR spectroscopy

(ThermoNicolet NEXUS 870 FTIR from Nicolet Instrument

Corp., USA). The surface morphology of pure PAN and

PAN/DETA nanofibers were investigated using a scanning

electron microscope (SEM, LEO1455VP, and ENGLAND).

The releasing amount of DETA from composites was tested

by a TOC analyzer (TOC-L, Shimadzu).

Adsorption Studies

DR80 was selected as a dye to evaluate the adsorption

capacity of the membranes. For this purpose, 0.004 g of the

adsorbents were added to 90 ml of the dye solutions with

concentration of 40 mg/l. The pH of each solution was

adjusted to the desired value using HCl or NaOH solution. A

single-beam UV spectrophotometer (CECIL CE2021) is used

for adsorption measurements. The amounts of decolorization

from solutions were determined as a function of time

according to the following equation:

(1)

where A0 and A are dye concentration at t=0 and t,

respectively.

Results and Discussion

FTIR of PAN/DETA Composite Nanofibers

FTIR spectra were recorded for pure PAN and various

composites before and after the fixation process and results

are shown in the spectral range of 4000-450 cm-1 in Figure 2.

The PAN spectrum (curve a) exhibited the absorption peaks

of stretching vibrations at 3446 cm-1 (OH), 2242 cm-1 (C≡N)

[15], 1737 cm-1 (C=O) [9,16], 2966 cm-1 (CH stretching in

CH, CH2, and CH3 groups) [16,17] and 1200-300 cm-1 (C-

O) [18-20], which suggests that PAN is a copolymer

containing both of acrylonitrile and vinylacetate polymers.

In the spectra of the composite nanofibers mats (curves b-d),

the band at 3436 cm-1, corresponding to the overlapping of

the stretching vibration bands of OH and NH groups is

intensified and shifted to the lower wavenumbers compared

to that at pure PAN. This clearly states that the OH groups

are generated by the hydrolysis of the ester groups in the

PAN nanofiber. Such a result is further supported by the

disappearance of the band at 2966 cm-1 (CH stretching), and

decreasing in the intensity of the band at 1734 cm-1 (C=O

stretching), confirming hydrolysis of the acetate ester

groups. The spectra of composite fibers also showed shifting

of the band at 1631 to 1663 cm-1 and appearance of a new

band at 1562 cm-1 (c,d). These changes can be assigned to

the stretching vibrations of the amidine group (N-C=N) and

the bending vibrations of the secondary amine of DETA,

respectively [21-23]. Decreasing the intensity of the carbonyl

ester peak with an increase in the amount of DETA further

confirm the reaction of PAN with DETA [23]. The peak

associated with the nitrile group of the PAN composite

nanofiber mats at 2242 cm-1 also decreased in its intensity as

the amount of DETA increased. Results obtained from FTIR

suggested, the number of converted nitrile groups to amidine

Dec%A0 A–

A0

-------------- 100×=

Figure 1. The chemical structure of Direct Red 80.

DETA/PAN Composite Nanofiber and Dye Removal Ability Fibers and Polymers 2015, Vol.16, No.9 1927

increase with increment in the amount of DETA in composite

nanofibers.

Figure 2(a-g) showed the FTIR spectra of various

composites after the fixation process with alkali solution. It

can be seen that there is not a significant change between the

spectra of composites before and after the fixation process,

except for the band intensity at 1667 cm-1 which is related to

amidine group. The peak shifting, occurred from 1631 to

1667 cm-1 related to N-C=N group in amidine groups [24].

Here we conclude that the number of converted nitrile group

to amidine group is increased after the fixation process

relating to the amount of DETA.

Morphology of PAN/DETA Composite Nanofibers

Figures 3-5 show SEM images of pure PAN and different

PAN-DETA composite nanofibers electrospun before the

fixation process at three different applied voltages: 15, 17,

and 19 kV. The SEM images in Figure 3 show that the

nanofibers obtained at 15 kV are not taut and some irregularities

and beads are present on the surfaces of the nanofibers,

especially for those with higher amount of DETA. It can also

be observed that the diameters of nanofibers with higher

amount of DETA is more varied compared with those

having lower amount due to strong interactions between

PAN and DETA causing strong viscosity of electrospinning

solution. DETA is therefore used as a strong crosslinkers for

PAN matrix through chemical reactions between the nitrile

groups of PAN and amine groups of DETA [24,25].

According to Figure 4, PAN-DETA fibers electrospun at

17 kV showed less defects and beads compared to those

electrospun at 15 kV. Such beads and non-uniformity are

also observed for PAN-DETA nanofibers electrospun at

19 kV, confirming that an optimum voltage for electrospining

of PAN-DETA composites is 17 kV.

In the electrospinning process, a balance between the

electrostatic repulsion, surface tension, and viscoelastic

force is very important [24]. When the applied voltage is

15 kV, the electric field is not strong enough to provide the

necessary electrostatic repulsion in order to balance the

surface tension and viscoelastic force, and hence the liquid

jet is not stable. On the other hand, a voltage of 19 kV is too

high for electrospinning and the balance cannot be maintained.

The voltage of 17 kV can therefore provide a balance between

the electrostatic repulsion, surface tension and viscoelastic

forces, resulting to stabilization of the liquid jet and formation

of smooth surface morphology of fibers. The SEM results

are in good agreement with FTIR spectra.

Figure 6 showed the SEM image of composite nanofibers

(20 % w/w) at magnification of 21,000×. Here we found that

the surface of the composite became much rougher after

fixation process than that of untreated. Also the diameter of

the nanofibers slightly increased. This roughness and increasing

in nanofibers diameter occurred by alkali treatment and

further diffusion within the composite matrix. This result is

also observed by other researchers [15,26].

TOC Analysis

Table 1 showed the TOC analysis result of fixed and

unfixed composite fibers after immersing in distilled water.

As can be seen for unfixed samples, with increasing the

amount of DETA in composites, the TOC values increase.

For fixed samples, much less releasing of DETA is observed

confirming successful fixation and bonding of DETA to

PAN.

Adsorption Studies

DR80 Adsorption Time Studies for PAN/DETA Composite

Fibers

Figure 7 showed the effect of duration on DR80 removal

Figure 2. FTIR spectra of (a) pure PAN, (b) PAN-DETA

composite nanofibers mat (10 % w/w), (c) PAN-DETA composite

nanofibers mat (20 % w/w), (d) PAN-DETA composite nanofibers

mat (40 % w/w) before the fixation process, (e) PAN-DETA

composite nanofibers mat (10 % w/w), (f) PAN-DETA composite

nanofibers mat (20 % w/w), and (g) PAN-DETA composite

nanofibers mat (40 % w/w) after the fixation process.


Figure 3. SEM images of (a) pure PAN, (b) PAN-DETA composite nanofibers (10 % w/w), (c) PAN-DETA composite nanofibers (20 %

w/w), and (d) PAN-DETA composite nanofibers (40 % w/w) (electrospinning voltage: 15 kV).




by PAN/DETA composite nanofibers. As it is shown in

Figure 7, the adsorption was initially quite rapid during the

first 10 min. Nearly 90 % of the ultimate adsorption occurred

within 10 min, and the adsorption then slowed down,

reached the equilibrium. The uptake of dye molecules by the

adsorbent and the time required for establishment of



Figure 6. High magnification SEM images showing the surface morphologies of (a) the composite nanofibers mat before the fixation

process and (b) the composite nanofibers mat after the fixation process.

Table 1. TOC values

Before fixation After fixation

SampleDistilled

water

PAN-10%w/w

DETA

PAN-20%w/w

DETA

PAN-40%w/w

DETA

PAN-10%w/w

DETA

PAN-20%w/w

DETA

PAN-40%w/w

DETA

TOC value

(mg/l)0.107 2.002 3.258 5.012 0.100 0.110 0.101


equilibrium suggest the effectiveness of our synthesized

nanocomposite fibers for wastewater treatment. A decrease

in the amount of dye adsorbed for more than 10 min duration

of treatment is due to aggregation of dye molecules on the

surface of adsorbents. This problem may hinder the migration

of the dye, as the adsorption sites become saturated, and

resistance to diffusion of dye molecules in the adsorbents

increased. As can be seen from the Figure 8, PAN-40 % w/w

DETA had a high adsorption capacity as compared to other

two composites. The percentages of dye removal for PAN-

20 % w/w DETA and PAN-40 % w/w DETA are higher than

PAN-10 % w/w DETA and there is negligible difference

between PAN-40 % w/w DETA and PAN-20 % w/w DETA.

In this regard, PAN-20 % w/w DETA was chosen as an

optimum sample in this study, and it was used for further

studies.

Effect of Adsorbent Dosage on Dye Removal

The effect of variation of the adsorbent dosage on the

DR80 dye removal was studied by changing the adsorbent

dosage from 0.001 to 0.006 g and results are illustrated in

Figure 8. The adsorption experiments with variation of

adsorbent doses were carried out at fixed dye concentration

of 40 mg/l. It is clear from Figure 8 that the adsorbent

dosage had a great effect on the amount of adsorbed dye by

composite fibers. The enhancement in dye adsorption with

increasing the adsorbent dosage is most probably due to the

stronger driving forces and larger surface area available for

adsorption. However, if the adsorption capacity of composite

fibers is expressed in mg of adsorbed dye per gram of

material, the adsorption capacity decreased with increasing

the amount of PAN/DETA nanofiber mat. This result is

probably attributed to overlapping or aggregation of adsorption

sites resulting in a decrease in total adsorbent surface area

available to the dye. This results to further increase in

diffusion path length [27].

Effect of Initial Dye Concentration

Effect of initial dye concentration as a function of time

was considered and results are shown in Figure 9. For this

purpose, different concentrations of dye were used to study

adsorption of 0.004 g adsorbent including 20, 40, 60, and

100 mg/l. The amount of the dye adsorbed onto PAN/DETA

nanofiber mat increases with an increase in the initial dye

concentration of solution. If the amount of adsorbent is kept

unchanged, this is due to the increase in the driving force of

the concentration gradient with the higher initial dye

concentration. The adsorption of dye by PAN/DETA nanofiber

mat is very rapid and reaches equilibrium very quickly at

low initial concentration. At a fixed PAN/DETA composite

nanofiber mat dosage, the amount of dye adsorbed is

increased with increasing concentration of solution, but the

percentage of adsorption is decreased. In other words, the

Figure 7. Dye removal ability of the prepared composites fibers

(pH=2.1, 0.004 g, 40 mg/l).

Figure 8. The effect of adsorbent dose on dye removal at different

time intervals for PAN-20 % w/w DETA (pH=2.1, 40 mg/l).

Figure 9. The effect of initial dye concentration on dye removal at

different time intervals for PAN-20 % w/w DETA (pH=2.1, 0.004 g).


residual dye concentration will be higher for more initial dye

concentrations than 40 mg/l. In the case of lower concen-

trations, the ratio of initial number of dye molecules to the

available adsorption sites is low and subsequently the

fractional adsorption becomes independent from initial

concentration [28-31].

Effect of pH

Solution pH plays an important role in the adsorption

behavior of adsorbents. This parameter affects the surface

charge of adsorbent, degree of ionization of the dye in

solution, and separation of functional groups on the active

sites of adsorbent and solution chemistry. Adsorption

behavior of the PAN-DETA composite nanofiber mats at

different pHs was studied and the results are shown in Figure

10. Maximum adsorption of anionic dye occurred at pH=2.1.

Significant electrostatic interaction exists between the positively

charged surface of the PAN-DETA composite nanofiber mat

on one hand and dye on the other hand, due to the ionization

of functional groups of mat in water and negatively charged

anionic dye.

As the pH of the system increases, the number of positively

charged sites decreases. It does not favor the adsorption of

anionic dye due to the decreasing of electrostatic attraction

[32]. Lower adsorption of dyes at alkaline pH can be due to

the presence of excess OH− ions destabilizing anionic dyes

and competing with the dye anions for the adsorption sites.

The effective pH was 2.1 and it was used for further studies.

Adsorption Isotherms

Adsorption is the accumulation of mass transfer process

that can generally be defined at the interface between solid

and liquid phases. Equilibrium relationships between sorbent

and sorbet are described by sorption isotherms, which is the

ratio between the quantity of sorbet and that remained in

solution at a fixed temperature of equilibrium. In order to

have a suitable model of isotherm data should accurately fit

into different isotherms [33].

Langmuir, Freundlich, and Tempkin isotherm equations

were used in this work. The Langmuir equation is shown as

the following equation:

(2)

where qe is the amount of dye adsorbed on the composites at

equilibrium (mg/g), Ce is the equilibrium concentration of

dye solution (mg/l), KL is the equilibrium constant (l/g), and

Q0 is the maximum adsorption capacity (mg/g). This equation

has been successfully applied to many adsorption processes

[34,35]. The Langmuir isotherm is applied for those adsorption

processes with mono-layer coverage of the dye on the

surface of the composites.

The linear form of Langmuir equation is:

(3)

The, Isotherm data was also studied by the Freundlich

isotherm, which can be expressed by the following equation

[36,37]

(4)

where KF is the adsorption capacity at unit concentration and

1/n is the adsorption intensity.

1/n values indicate the type of isotherm to be irreversible

(1/n=0), favorable 0 < 1/n < 1), and unfavorable (1/n > 1).

Equation (4) can be rearranged to a linear form:

(5)

The Tempkin isotherm is given as:

(6)

which can be linearized as:

(7)

where

(8)

Tempkin isotherm contains a factor that explicitly takes

into the account for adsorbing of species of adsorbent. This

isotherm assumes that the heat of adsorption of all the

molecules in the layer decreases linearly with coverage due

to adsorbent—adsorbate interactions, and the adsorption is

characterized by a uniform distribution of binding energies,

up to some maximum binding energy. A plot of qe versus ln

Ce enables the determination of the isotherm constants B1

and KT from the slope and the intercept, respectively. KT is

qe

Q0KLCe

1 KLCe+--------------------=

Ce

qe

-----1

KLQ0

------------Ce

Q0

------+=

qe KFCe

1/n=

logqe logKF

1

n---+ logCe×=

qe

RT

b-------ln KTCe( )=

qe B1lnKT B1lnCe+=

B1

RT

b-------=

Figure 10. The effect of pH on dye removal at different time

intervals for PAN-20 % w/w DETA (0.004 g, 40 mg/l).


the equilibrium binding constant (l/mol) corresponding to

the maximum binding energy and constant B1 is related to

the heat of adsorption.

Figure 11 showed the adsorption Isotherms of DR80 using

PAN-DETA composite nanofiber mat. The Q0, KL, R2

(correlation coefficient for Langmuir isotherm), KF, n and R2

(correlation coefficient for Freundlich isotherm), and the B1,

KT, R2 (correlation coefficient for Tempkin isotherm) are

given in Table 2. Results indicated that the correlation

coefficient of the one for Langmuir equation is better than

the fitted model for Freundlich and Tempkin equations. This

means that the adsorption of dye takes place at specific

homogeneous sites and one layer adsorbed onto the PAN-

DETA composite nanofibers mat surface.

Adsorption Kinetics

Kinetic data were analyzed with the Lagergren and Ho

equations [38]. A linear form of pseudo-first- order model

was described by Lagergren of following equation:

(9)

where qe is the amount of dye adsorbed at equilibrium (mg/

g), qt is the amount of dye adsorbed at t time (mg/g), and K1

is the equilibrium rate constant of pseudo-first-order adsorption

(min-1) [39].

According to a linear form of pseudo-second-order model

(equation (10)) [40], the values obtained with Ho equation is

illustrated in Figure 12,

(10)

In equation (10), qe is the amount of dye adsorbed at

equilibrium (mg/g) and K2 is the pseudo-second-order

equilibrium rate constant (g/mg·min).

The possibility of intra particle diffusion resistance

affecting adsorption was explored by using the intra particle

diffusion model as [41]:

(11)

where kp and I are the intra particle diffusion rate constant

and intercept, respectively.

The values of K1, R2 (correlation coefficient for pseudo-

first-order sorption kinetics), K2, R2 (correlation coefficient

for pseudo-second-order sorption kinetics), and kp, I, R2

(correlation coefficient for intra particle diffusion) were

calculated and are shown in Table 3. Results indicated that

the adsorption kinetic of dye on the PAN-DETA composite

log qe qt–( ) log qe( )K1

2.303-------------t–=

t

qt

----1

Kqe

2---------

1

qe

----t+=

qt kpt1/2

I+=

Figure 11. Adsorption isotherm of DR80; (a) Langmuir, (b)

Freundlich, and (c) Tempkin.

Table 2. Linearized isotherm coefficients for dye adsorption onto the composite nanofibers mat at different dye concentration

Langmuir Freundlich Tempkin

Q0 KL R2 KF 1/n R2 KT B1 R2

1250 0.25 0.999 724.43 0.177 0.613 92.077 775.46 0.981


nanofiber mat follows the pseudo-second-order rate expression.

Conclusion

In this paper, PAN-DETA composite nanofibes mat with

various amounts of DETA in composites were prepared and

their dye removal abilities were investigated. Direct red 80

(DR80) was used as model compound. The results indicated

that the addition of diethylenetriamine in the PAN polymer

affects the chemical and morphological structure of the

nanofibers through changing the viscosity of the spinning

solution. In order to fix and hinder DETA releasing from

fibers, an alkali treatment using potassium carbonate was

performed. It was observed that the nanofiber diameter

increased and the surface of nanofiber mats became much

rougher after the fixation process. This roughness can

increase the dye adsorption capacity. It was also found that

with increasing the amount of DETA in composites, the

number of nitrile groups converted to amidine groups

increased. The dye adsorption obeyed Langmuir isotherm

and the adsorption kinetic of dye was found to conform to

pseudo-second order model. The dye removal rate of

composite nanofibers mats in acidic solution was rapid due

to the adsorption of anionic dye onto the positively charged

composite nanofibers. It can be concluded that the PAN-

DETA composite nanofiber mat being a novel fibrous

adsorbent with high dye adsorption capacity is a suitable

alternative substrate to remove anionic dyes from the

colored aqueous solutions.

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AdsorbentConcentration

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