CHEMOSPHERE

 Effcient adsorption removal of anionic dyes by an imidazolium-based

mesoporous poly(ionic liquid) including the continuous column
adsorption-desorption process

ARTICLE INFO
Article history:
Received 13 December 2020
Received in revised form
31 December 2020
Accepted 9 January 2021
Available online 13 January 2021
 SECTIONS
1. Introduction
2. Materials and methods
2.1 Materials
2.2 Characterization
2.3 Batch adsorption process
2.4 Column adsorption and desorption process
3. Results and discussions
3.1 Characterization roperties of PDVIm-Cl
3.2 Adsorption kinetics
3.3 Adsorption isotherms
3.4 Effect of H on adsorption
3.5 Column adsorption-desorption studies
3.6 Adsorption mechanism
4. Conclusions
1. Introduction

Nowadays, multifarious dyes have been widely used in many industrials.

The presence of dyes in water has detrimental impacts on human beings and ecosystem, such
as being toxic owing to harmful organic groups like azo, anthraquinone .
 
Therefore, it is highly necessary to develop efficient methods for the removal of dyes before
their discharging into the environment.

At present, there have been many methods including adsorption, oxidation, electrochemical
process and membrane separation employed in treatment of dye wastewater.

Among them, the adsorption process is considered as one of the most promising and effective
methods because of its easy-operation, low-cost and no other harmful substances producing.
2. Materials and Methods
2.1 – Materials

IL monomer N,N0 methylene-bis chloride was prepared from the quaternization reaction
of dichloromethane and 1-vinyl-1H imidazole in tetrahydrofura.

The molar ratio of DCM and VIm was used as 3:4.

Then, the PDVIm-Cl was prepared by the polymerization of DVIm-Cl induced by 2,20
azobis in the mixed solvents and subsequently treated by supercritical carbon dioxide
drying to obtain mesoporous structure.
2.2 – Characterization

The FT-IR spectra were recorded on a Nicolet 330 infrared spectrometer and used to
analyze the functional groups of PDVIm-Cl before and after adsorption.

The Zeta potential of the adsorbent was measured by Malvern Zetasizer with
electrophoretic light scattering.

Liquid Ultravioletevisible spectroscopic analysis of dyes solution was performed on a UV-

Vis spectrophotometer.

The specific surface area, pore volume and pore size distribution of the adsorbent were
tested on the physical adsorption instrument.

The morphology of the prepared PIL was analyzed using a Zeiss SIGMA microscope.
2.3 - Batch Adsorption Process

Batch adsorption experiments were operated to explore the adsorption kinetics, isotherms
and effect of pH.

A typical procedure is as follows: a certain amount of adsorbent was added into a solution of
SY, and the mixture was magnetically stirred; after that, suspension from the mixture was
sampled and filtered.

To obtain the adsorption kinetics of PIL for different anionic dyes, fixed concentration of
dye solution and the adsorbent were mixed and stirred.

The UV-Vis analysis was used to analyze the filtered sample solution with drawn at regular
intervals.

The adsorption kinetic curves were plotted by fitting the experimental data with the pseudo
first-order and second-order model.
 
To get the maximum equilibrium adsorption capacities of PIL for different dyes, removal
of dyes with different initial concentrations was performed via the batch process at room
temperature respectively. The data obtained were used to determine the adsorption
isotherms.
 
To explore the effect of pH on the dyes adsorption, the initial pH values of dyes solution
were adjusted by using HCl or NaOH.
 
The adsorption experiments under different pH were also performed according to the
batch process of dye solution and keeping stirring for 3 h at room temperature.
2.4 - Column Adsorption and Desorption Process

PDVIm-Cl and silica sand were mixed and introduced into a glass column.
No adsorption capacity for dyes was found from the sand.

Taking SY as an example, the column adsorption procedure is as follows: the orange-

yellow solution flowed through the column from the top and the colorless effluent
from the bottom of the column was collected until SY was detected by the UV-Vis
analysis.

In the same way, the column desorption was performed by washing the column with a
solution of saturated NaCl until there was no SY detected in the effluent.
3.1 Characterization properties of PDVIm-Cl

The porous structure properties of PDVIm-Cl were characterized by SEM and N 2

adsorption-desorption isotherm analyses.

The adsorbent displayed a mesoporous structure with pore size ranging from a few
nanometers to tens of nanometers, and the N2 adsorption-desorption isotherm further
demonstrated that the adsorbent possessed abundant mesoporous structure.

Calculated by the Barret-Joyner-Halenda (BJH) method.

3.2. Adsorption Kinetics

Adsorption kinetics of PDVIm-Cl for each anionic dye was explored with 137 mg L -1 adsorbent and
fixed initial dye concentration without adjusting the pH at room temperature respectively.

All the data were fitted by the pseudo second-order (Fig. 2) and pseudo first-order model (Fig. S3)
respectively.
 
The kinetic parameters were listed in the Table 1, the correlation coefficient (R 2) and the calculated equilibrium
adsorption capacity obtained by fitting calculation show that the pseudo second-order kinetic model is more
suitable to describe the adsorption process of these anionic dyes by PDVIm-Cl.
As shown in Fig. 2, for acid dyes SY and AO7, the adsorption process is very fast with the adsorption amount reaching more than 90% of the equilibrium
adsorption capacity in 60 min.

And the high R2 value indicates that the chemical adsorption process (ion exchange) is the rate-limiting step for acid dyes adsorption.

Contrary to acid dyes, the correlation coefficients of adsorption kinetics for CR and RB19 fitted by pseudo second-order are relatively lower.

This may be due to the ultra-high capacity which is close to or higher than the theoretical adsorption capacity calculated by ion-exchange with two Cl - for
one RB19 or CR negative bivalent anion .
 3.3 Adsorption Isotherms

The widely used and well-known Langmuir-Freundlich adsorption isotherm model was used to
analyze the adsorption isotherms obtained in-order to better understand the adsorption process and
obtain maximum adsorption capacity results. Results were presented in Fig. S4 and Table S2.

Langmuir-Freundlich (Sips) model is introduced for fitting, which manifests that the adsorption
behavior is similar to Freundlich isotherm in the low concentration range and close to Langmuir
model in the high one. The equation of Sips model is expressed as the following:
 As can be seen, the curves do not fit well with experimental points. That is
Where
  is the Sips constant, is the why the Langmuir-Freundlich (Sips) model was introduced for fitting.
heterogeneity factor, is the adsorption
amount at equilibrium concentration, and
represents the maximum adsorption
capacity.

As shown in Fig. 3 and Table 2, the

combination of Langmuir and Freundlich
model offers the best fitting of the
adsorption equilibrium data. And the
maximum adsorption capacities of some
reported materials for anionic dyes are
listed in Table S1.

For different anionic dyes the as-prepared

PDV-Cl shows much higher maximum
adsorption capacities than most reported
results. The adsorption capacity for CR of
PDV-Cl is at least twice than most of the
adsorption capacity reported so far except
for the highest adsorption capacity of
23020

Fig. 3. Fitting lines of the isotherms data with the Langmuir-Freundlich model for the adsorption of acid
dyes AO7 (a) and SY (b), reactive dye RB19 (c) and direct dye CR (d) by PDVIm-Cl.
3.4 Effect of pH on Adsorption Fig. 4. (a) Removal efficiencies of PDVIm-Cl for anionic dyes
under different pH values with initial concentration of 100 mg L1;
It is known that the initial pH value of solution could affect the removal (b) The Zeta potential of PDVIm-Cl at different pH and after.
efficiency through tuning the Zeta potential of PDVIm-Cl and the
ionization degree of dye solution. Therefore, it is important to study the
effect of pH on anionic dyes adsorption.

Fig. 4a shows the removal efficiencies of anionic dyes at different pH

values. It is observed that the removal efficiencies of acid dye SY were
near 100% when pH was between 2 and 10 but decreased sharply when
pH was 12 due to the electrostatic repulsion between the anions of SY and
negatively charged PIL (PDVIm-Cl has the point of zero charge between
pH 11 and 12, Fig. 4b).

Differently, the removal efficiencies of PIL for RB19 and CR under

higher alkaline conditions (pH = 12) were still high, indicating that there
were other strong interactions between the adsorbent and adsorbate apart
from the electrostatic interaction and ion exchange.

It was interesting to find that the CR solution changed from red to bluish
purple after adding acid and began to form blue precipitate at about pH =
2, so the applicable range of pH for CR adsorption is 4-12. These data
confirm the PIL is capable of adsorbing different anionic dyes in a wide
range of pH.
3.5. Column adsorption-desorption studies
As displayed in Fig. 5, the SY solution was decolorized after
passing through the column while the color of adsorbent in the
stationary phase changed from light yellow to orange red.
After that, the regeneration could be easily observed by washing
the column with a solution of saturated sodium chloride
(Vwater/Vethanol ¼ 1).
As showed in Fig. 6a, the adsorption and desorption volume
remained almost unchanged in the three continuous cycles, which
indicated the
adsorption column with PIL filled exhibited excellent stability and
reusability in the dye removal experiment.
Similarly, other anionic dyes can also realize the column adsorption
and desorption. As shown in Fig. 6b, it is pleasant to find that the
desorption volume is about at least 10 times less than the adsorption
volume.
Fig. 6. (a) Comparison of adsorption and desorption volume of three
consecutive adsorption-desorption processes to SY using PDVIm-Cl
column; (b) Adsorption and desorption volume of PDVIm-Cl
column for anionic dyes.
3.6. Adsorption Mechanism

In order to get insight into the adsorption nature, the

mechanism has been explored deeply by experiments
combined with quantum chemical calculations.

Zeta potential tests shown in Fig. 4b exhibit that

PDVIm-Cl has a high positive Zeta potential value of
26.7 mV under the natural condition, indicating that
electrostatic interaction can be easily formed between
the anionic dyes and the PIL.(Fig.4b)

Taking CR for example, the Zeta potential value of PIL

after adsorbing CR (PDVIm-CR) decreased greatly
from 26.7 to 2.34 mV, demonstrating that some of the
dye molecules were adsorbed on the surface of PIL by FIGURE 4b
the electrostatic attraction.(Fig.4)
Then, FT-IR spectra of PDVIm-Cl before and after
adsorption were analyzed to further illustrate the
adsorption process.We analyzed the FT-IR spectra of the
CR loaded PDVIm-Cl with different adsorption
capacities.Indicating the strong p-p stacking between the
aromatic ring on dye molecule and the imidazole ring on
PIL(Fig.7)

Also, the absorption peak of sulfonic group (1065 cm1 )

significantly shifted to longer wavelength with intensity
increasing, indicating the formation of new ionic bond
(1041 cm1 ).

On the contrary, the spectrum of the adsorbent with the

lower adsorption capacity (PDVIm-CR-unsaturated)
exhibits the characteristic peaks attributed to the
imidazole ring (1640 and 1547 cm1 ) and new ionic bond
is also formed with weaker intensity, showing that ion-
exchange and electrostatic attraction took place before
forming p-p stacking in the early stage of adsorption.
(Fig.7)
 To gain insight into the adsorption mechanism, quantum chemical calculations were also employed to
study the PIL-CR system, and the computational details had been shown in Supporting Information.

Owing to the symmetric characteristic of CR, the half structure and the alkyl imidazole unit of PIL were
chosen as the theoretical models for a good compromise between reasonability and computational cost.

On the basis of the optimized structure, the QTAIM analysis was implemented and the results were listed
in (Table 3.)
 To distinguish and visualize the interactions between the PIL and CR, NCI analysis was further performed based on the
reduced density gradient (RDG) function (Johnson et al., 2010); the colorfilled scatter graph of RDG versus the sign of
the calculated second Hessian matrix eigenvalue multiplied by the electron density was plotted in (Fig. 8).

The blue region denotes the strong attractiveinteractions while the red represents the strong repulsion, and the
noncovalent interactions have been shown with green color. Apparently, there are peaks from 0.005 to 0.02 a.u., which
means the existence of hydrogen bonds between the PIL and CR. (Fig.8).

From the right corresponding threedimensional graph, it can be observed hydrogen bonds occur between the
electronegative O and N atoms of CR and H atoms of the PIL.(Fig.8).

Fig. 8. Color-flled scatter graphs (left) of RDG versus sign(l2)r and the corresponding RDG isosurfaces plots (RDG ¼ 0.50)
(right) for the PIL-CR system. The white, cyan, blue, yellow, red spheres indicate H, C, N, S, O atoms respectively. (For
interpretation of the references to color in this fgure legend, the reader is referred to the Web version of this article.)
 In addition, the green
isosurface between the two
fragments indicates p-p
interaction existence
generated by the aromatic
imidazole ring and benzene
rings of CR. The red spindle
shaped regions correspond to
the strong steric effects at the
ring centers of CR.
Furthermore, the interactions
between the PIL and CR dye were
also quantitatively calculated from
the energetic angle. The GKSEDA
method was adopted to decompose
total interaction energy into six
energy components with clear
physical significance, where the
exchange and repulsion terms have
been combined together as Pauli
repulsion energy term D.
 4. Conclusions
The adsorption kinetics and isotherms were well fitted with the pseudo secondorder model
and Langmuir-Freundlich model.
The maximum equilibrium adsorption capacities of the studied anionic dyes were higher
than the majority of reported adsorbents.
Especially for RB19, the adsorption capacity was the highest so far and was nearly twice
higher than the previously reported maximum adsorption capacity.
In addition, the PIL could efficiently adsorb anionic dyes in a wide range of pH.
 
Furthermore, the adsorption mechanism including ion exchange, electrostatic interaction,
hydrogen bond and p-p stacking was elucidated by Zeta potential tests, FT-IR spectra
combined with quantum chemical calculations.
 More significantly, it is the first time to achieve the complete column adsorption-desorption
process of PIL for a variety of anionic dyes, thereby obtaining highly concentrated
dyewastewater with greatly reduced volume.
 
Ece AKSOY 05120000159
Dilşah BAHADIR 05170000838
Murat PARMAK 05170000837
Mehmet ÖZKAN 05149992034
Berk ÖZBİLGİN 05170000250
Mert ÖZTEN 05180000259
Salih ŞANLI 05180000227