Anal. Method Environ. Chem. J. 4 (1) (2021) 46-57

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

Simultaneous adsorption of cationic and anionic dyes using a

novel multifunctional mesoporous silica

Amir Vahid ^a,*, Majid Abdouss ^b, Shahnaz Nayeri ^b, Aliakbar Miran Beigi ^a

^aResearch institute of petroleum industry, Tehran, Iran

^bFaculty of chemistry, Amirkabir University of Technology, Tehran, Iran

A R T I C L E I N F O :

Received 17 Nov 2020

Revised form 22 Jan 2021

Accepted 15 Feb 2021

A B S T R A C T

In the present work a multifunctional nanoadsorbent was synthesized

via a well-designed stepwise route, led to the grafting of an amine

group on the interior and acidic sites on the exterior of bimodal

mesoporous silica nanoparticles (UVM-7). First, amine and thiol

groups were grafted on the interior and exterior pores of silica

through co-condensation and post synthesis treatment, respectively.

Then, the oxidation of thiol on UVM-7 caused to create sulfonic

acid and the subsequent template extraction was carried out to obtain

the NH₂/UVM-7/SO₃H. The results of XRD, the nitrogen sorption,

SEM, TEM, FT-IR and elemental analysis revealed the presence

of both types of functional groups on UVM-7. Then, simultaneous

adsorption of anionic and cationic dyes (Methylene Blue [MB] and

Direct Red 23 [Dr]) using NH₂/UVM-7/SO₃H was investigated. UV-

Vis spectrophotometry was utilized for the determination of dyes in

single and binary solutions. Langmuir and Freundlich models were

used for the ﬁtting of obtained experimental adsorption data and the

constants of both isotherms were calculated for MB and Dr. Morover,

the calculation of thermodynamic parameters revealed that the

adsorption of MB and Dr on NH₂/UVM-7/SO₃H was endothermic

and spontaneous. Furthermore, the simultaneous adsorption of both

dyes regardless of their different electrostatic charge is the main

characteristics of NH₂/UVM-7/SO₃H which was specially used for

treatment of industrial wastewater.

Available online 29 Mar 2021

------------------------

Keywords:

Adsorption,

Multi-Functional,

Dye,

Mesoporous silica,

Synthesis.

Methylene Blue (MB) and Direct red (Dr) as the

1. Introduction

cationic and anionic dyes have harmful effects on

human life and environment. Acute exposure to

MB causes many health effect such as increased

heart rate and cyanosis jaundice quadriplegia in

mammals [2,3]. Up to now, the dye adsorption

studies have focused on solutions containing single

dye and mixture of dyes [4-6]. The most industrial

efﬂuents include a mixture of several dyes, so it

is necessary to study the simultaneous adsorption

of two or more dyes from aqueous solutions [7,8].

However, the dyes are resistance to biodegradation

due to their aromatic structure [9]. Many industrial

Dyes as a important raw material were used in

different industries including cloth, plastics,

tanning, cosmetics and food [1]. Additionally, the

dyes are one of the most problematic groups as a

results of their environmental impact. Furthermore,

the industrial efﬂuents containing dyes may be

have a carcinogenic effect in humans when,

discharge to waters without any proper treatment.

*Corresponding Author: Amir Vahid

Email: avahid753@gmail.com & vahida@ripi.ir

https://doi.org/10.24200/amecj.v4.i01.127

Adsorption of dyes by multifunctional mesoporous silica

Amir Vahid et al

47

technologies, including chemical oxidation [10],

adsorption [11], the coagulation/ﬂocculation [12],

the membrane separation and ion exchange [13]

was used for the adsorption of dyes from industrial

efﬂuents. Among them, adsorption has been

known as one of the practical physical processes

for the treatment and cleaning of wastewaters,

because it is cost effective and very effective. The

main problem of this technology is the synthesis of

low cost adsorbent possesses with high adsorption

capacity [14]. In multi-dye adsorption, the

interference of one dye on the other dyes is very

important [15]. The liquid chromatography [16],

the capillary electrophoresis [17], the spectrometry

[18] and the electrochemistry methods [19] are

used for the analysis of dyes. Due to advantages

of UV–Vis spectrophotometry such as accuracy

of results, sensitivity, low cost, easy operation

and reproducibility, it was used for analysis of

colored samples [20]. The main drawback of this

technique is the overlap and interference of broad

absorption peaks. So, the simultaneous analysis of

mixture dyes could be carried out using derivative

spectrophotometry [21]. It was determined based

on the derivative values of interest compound

while other components have zero value [22].

Also, many applications were used by UVM-

7 in different sciences [23-26]. In this work, the

synthesis of a multifunctional mesoporous silica

contains both acidic and basic functional groups

were reported. At the second step, the adsorption

of MB / Dr from aqueous solution was carried out

simultaneously and the adsorption phenomenon

was studied.

2. Experimental

2.1. Reagents and materials

All reagents with ultra-trace analytical grade such

as; lead nitrate salt, acids and base solutions were

purchased from Merck (Darmstadt, Germany). The

structure of MB and Dr are shown in Figure 1.

Ultrapure water has been obtained from Millipore

continental water system (Bedford, USA).

Tetraethyl orthosilicate (TEOS, (C₂H₅O)₄Si,

CAS N: 78-10-4, Sigma), triethanolamine

(TEAH_3,C₆H₁₅NO₃, CAS N: 102-71-6, Sigma),

cetyltrimethylammonium

bromide

(CTAB,

C₁₉H₄₂BrN, CAS N: 57-09-0, Merck) and other

reagents with analytical grade were prepared from

Merck or Sigma Aldrich, Darmstadt, Germany.

The pH adjustments were made using appropriate

buffer solutions (Merck, Germany).

Fig.1. The structure of MB(a) and Dr(b)

Anal. Method Environ. Chem. J. 4 (1) (2021) 46-57

48

2.2. Synthesis of UVM-7

spectrophotometer at 502 and 664 nm for Dr and

MB, respectively. In binary solution, the best

wavelength for each dye was ﬁnd out utilizing ﬁrst-

order derivative spectrometry.

UVM-7wassynthesizedviawell-knownatraneroute

in which triethanol amine (TEAH3), has effect on

the rate of hydrolysis and condensation of teraethyl

orthosilicate (TEOS). In a typical synthesis, mixture

of TEOS and TEAH3 heated up to 120 °C and then

CTAB (cetyltrimethylammonium bromide) was

added when the temperature of the solution reached

to 70°C. After addition of water a suspension was

formed and aged for 4 hours at ambient temperature.

The ﬁnal molar composition of the synthesis mixture

was 1.0 TEOS : 3.5 TEAH3 : 0.25 CTAB : 90 H₂O.

The product was ﬁltered, washed with water and

acetone and dried in an oven at 80°C overnight and

calcined at 550°C for 6 hours.

The adsorption percentage (R%) and adsorption

capacity of each dye q_e, (mg dye/g adsorbent) was

calculated according to the following equations

(Eq.1 and Eq.2):

(

−

V

C₀C_e⁾

=

q

e

M

(Eq. 1)

(

−

C₀C_e⁾

R% =

×100

C₀

2.3. Synthesis of NH₂- /UVM-7/SO₃H

(Eq. 2)

First, 1.0 g of aminopropyle triethoxysilane

(APTES) was added to the aqueous solution of

CTAB and after 5 minutes, mixture of TEOS and

TEAOH, was added to the micellar solution. The

reactants molar ratio was 1.0 TEOS: 3.5 TEAH3

: 0.25 CTAB : 90 H₂O: 0.20 APTES. After aging,

the white suspension was ﬁltered and washed

thoroughly with water and acetone. The white

precipitate dried in oven over night at 80 °C. At the

second step, 1.0 g of the as-synthesized NH₂/UVM-

7 and 1.0 g of triethoxysilane propanethiol (TPTES)

was reﬂuxed in 50 mL of toluene for 12 hours and

then, the mixture ﬁltered and dried in oven again.

Then, thiol groups grafted on the external surface

of the sample was oxidized in 15% H₂O₂and 1

molar solution of H₂SO₄. Then, CTAB of the as-

synthesized NH₂/UVM-7/SO₃H was removed by

reﬂux in 1 molar ethanolic solution of HCL for 24

hours to get access to the internal pores and amine

groups. The ﬁnal product was dried in oven at 80

°C in vacuum oven overnight.

Where C₀and C_e(mg L^-1) are the initial and

equilibrium concentration of dye, respectively. V

(L) is the volume of the solution and M (g) is the

mass of adsorbent used.

2.5. Characterization

X-ray diffraction (XRD) patterns were recorded

using a Philips 1840 diffractometer using nickel-

ﬁltered Cu Kα (1.5418˚ A) X-ray source, operating

at 35.4 kV and 28 mA. Textural properties of the

synthesized samples were measured by nitrogen

adsorption at 77 K using a BELSORP-max

apparatus after being out-gassed in vacuum at 120

°C. ElementalanalysiswascarriedoutusingCHNS-

Elementar. FT-IR spectra was recorded using a FT-

IR 70 VERTX Bruker spectrophotometer using

KBr powder. UV–Vis spectrophotometer was used

to measure the concentration of the Methylene

Blue and Direct red23 in aqueous solution. FE-

SEM images were captured using Mira TESCAN

3-XMU. Samples were sputtered with gold prior

to imaging. TEM images were recorded at 150 kV

operating voltage using a Zeiss microscope.

2.4. Batch adsorption procedure

In each test, 0.1 g of adsorbent was added to the 10

mL of a solution containing a known concentration

of each dyes while agitating at 250 rpm at 25 °C.

After 120 minutes the concentration of residual

dyes in supernatant was determined by UV–Vis

3. Results and discussion

3.1. Characterization of NH₂/UVM-7/SO₃H

XRD pattern of NH₂/UVM-7/SO₃H is shown in Figure 2.

Adsorption of dyes by multifunctional mesoporous silica

Amir Vahid et al

49

A strong and broad diffraction peak can be observed

which is characterized in bimodal meso/macroporous

material. This peak can be attributed to diffraction of

incident X ray from the d₁₀₀plane. According to the

hexagonal symmetry, two weak and broad peaks at

higher diffraction angles can be assigned to d₁₁₀and

overlap of d₂₀₀and d₂₁₀planes, respectively.

pressure, the inﬂection is not sharp. By approaching

to the saturated relative pressure, increasing of gas

uptake led to the sharp increasing of isotherm. This

can be attributed to the inter particles of UVM type

material which is also present in NH₂/UVM-7/

SO₃H after internal and external grafting of organic

moieties. The high BET surface area and pore

volume means that the pore structure/size almost

preserved after grafting. However, after grafting

of organic moieties on UVM-7, the sharpness of

these region slightly decreases. The two inﬂections

in NH₂/UVM-7/SO₃H can be attributed to the

presence of two types of pore system.

3.2. Nitrogen physisorption

The isotherms of UVM-7 and NH₂/UVM-7/SO₃H

is shown in Figure 3. The isotherms showed the

four type of isotherm according to the IUPAC

classiﬁcation. In both isotherms, at low relative

Fig. 2. The XRD pattern of NH₂/UVM-7/SO₃H

Fig. 3. The isotherms of UVM-7 and NH₂/UVM-7/SO₃H

Anal. Method Environ. Chem. J. 4 (1) (2021) 46-57

50

Fig.4. The SEM of NH₂/UVM-7/SO₃H

Fig.5. The TEM of NH₂/UVM-7/SO₃H

3.3. TEM and SEM

FT-IR spectra of SO₃H/UVM-7/NH₂is shown in

Figure 6. FT-IR spectroscopy was utilized to indicate

the existence of NH₂and SO₃H functional groups

on the UVM-7. Two distinct peaks around 457 cm^-1

and 1082 cm^-1is attributed to the symmetric and

asymmetric stretching bands of Si-O-Si group in the

framework of UVM-7. A broad peak at around 3451

cm^-1is assign to the silanol groups on the surface

of UVM-7. A small absorption band at 1558 cm^-1is

attributed to the bending vibration of amine group

which overlapped with symmetric bending vibrations

of O-H. A stretching mode of NH₂is also overlapped

with silanol group’s around 3451 cm^-1. This indicates

that the UVM-7 possess of NH₂groups. A shoulder,

overlapped with asymmetric stretching of Si-O-Si,

Electron microscopy is a powerful technique

provides a direct view of porous structure, particle

morphology and many other information of

porous materials at nanoscale. The SEM of NH₂/

UVM-7/SO₃H reveals the particle size, shape and

morphology of nanomaterials. Figure 4 illustrates

the SEM image of NH₂/UVM-7/SO₃H. The sample

composed of nanosize particles without presence of

large agglomerates. The shape of the nanoparticles is

almost irregular. The TEM image of the NH₂/UVM-

7/SO₃H is taken perpendicular to d₁₀₀direction of

pores and is displayed in Figure 5. Pore openings are

clearly visible. Particle size in sub-ten nanometers

and is in agreement with those seen in SEM image.

Fig. 6. The FT-IR spectra of SO₃H/UVM-7/NH₂

Adsorption of dyes by multifunctional mesoporous silica

Amir Vahid et al

51

is attributed to the SO^3-and S=O stretching mode

of sulfonic acid functional group. It cannot be seen

absorption mode of S-H group in the entire spectrum

means that thiol groups were fully oxidized to

sulfonic acid. Two small absorption peaks at 2852

cm^-1and 2926 cm^-1is characteristic of the stretching

vibration mode of methylene groups of the propyl

chain of the APTES and TPTES.

These results proof presence of amine and sulfonic

acid functional groups on NH₂/UVM-7/SO₃H.

3.4. Determination of MB and Dr in single and

binary solution

The calibration curve obtained from absorbance

spectra of MB and Dr versus concentration at λ_maxof

the corresponding dye and used for the determination

of dyes in single solution. The concentration of dyes

in binary solution of MB and Dr is obtained by ﬁrst

order derivative spectrophotometry by plotting the

change rate of absorbance against wavelength. The

obtained spectra for raw and derivative spectra are

displayed in Figure 7a and 7b.

These results approve coexistence of amine and

sulfonic acid groups on UVM-7 simultaneously.

This statement is supported by elemental analysis

of NH₂/UVM-7/SO₃H. Elemental analysis of NH₂/

UVM-7/SO₃H revealed that the sample contains

4.9% (w/w basis) of nitrogen and 5.0% of sulfur.

Fig. 7a. The Raw absorption spectra of: MB (20 mg L^-1), Dr (15 mg L^-1),

and their mixture at λ_maxof the corresponding dye

Fig. 7b. The ﬁrst derivative spectra of MB, Dr, and their mixture

by plotting the change rate of absorbance against wavelength

Anal. Method Environ. Chem. J. 4 (1) (2021) 46-57

52

The calibration curves for determination of each

dye in the presence of the other one were obtained

by measuring of ﬁrst-order derivative at the zero

crossing points of Dr (502 nm) and MB (664nm)

[27, 28]. Several standard binary mixtures of MB

and Dr were used for the validation of the method.

The regression equations and coefﬁcients of

determinations, are given in Table 1.

isotherm was higher than that of Freundlich, which

implies that suggestions of Langmuir model. The

homogenous adsorption sites, equal activation

energy and monolayer formation, is predominantly

determine the mechanism of adsorption. The

isotherm constants are presented in Table 2.

(Eq. 3)

(Eq. 4)

3.5. Equilibrium modeling

3.5.1.Single-component adsorption isotherm

Two well-known adsorption model, Langmuir and

Freundlich, were applied to the adsorption data of

single-component dye solution (Equation 3 and

4) [29, 30]. In single solution, the R²of Langmuir

3.5.2. Multi-component adsorption isotherms

In this case, competition for occupation of

adsorption sites by adsorbate molecules occur and

Table 1. Determination of MB and Dr in mixture solution using zero-derivative

and ﬁrst-derivative spectrophotometry

Solution No.

*MB(mg L^-1)

*Dr (mg L^-1)

^aRegression equations

R²

1

2

1-5

0

S = 0.008C+0.1841

B = 0.0015C+0.002

S = 0.0471C+0.021

B = 0.0001C-0.0006

0.9981

0.9890

2-20

10

3

4

0

2

1-10

0.9974

0.9963

10-25

*C is the concentration of the corresponding dye(mg L^-1)

^aS and B is the response in single and binary solution

Table 2. Parameters of Langmuir and Freundlich models in single and binary solutions.

Langmuir

MB(sin)

qe(mg g-1)

52.63

b(mg L-1)

0.226

0.0983

0.0096

0.1315

n

R2

0.987

0.996

0.876

0.977

Dr(sin)

88.33

MB(bin)

18.86

Dr(bin)

100

Frendlich

MB(sin)

Kf(mg g-1)

0.0272

3.412

3.984

2.32

0.947

0.950

0.958

0.806

Dr(sin)

23.28

MB(bin)

98.24

Dr(bin)

172.60

5.29

Extended-Langmuir

MB(bin)

qmax (mg g-1)

74.32

b1

b2

R2

0.0021

0.0043

0.0038

0.0056

0.999

0.998

Dr(bin)

106.78

Condition: 10 mL solution, pH: 4 in single and binary solutions.

Adsorption of dyes by multifunctional mesoporous silica

Amir Vahid et al

53

led to a complex adsorption model. Furthermore,

for the design of treatment/reﬁning systems,

understanding the mechanism of multi-component

adsorption is very important. Despite the difﬁculty

of obtaining of a model for adsorption of binary

widely used to explain kinetic of adsorption. The

model was described by the following Equation 6:

1

₌k₁

(Eq. 6)

q q ^{( ) +}q

t

e

mixtures,

extended-Langmuir

model

was

developed to explain equilibrium adsorption model

in such system is as Equation 5:

Where q_eand q_tare the adsorption capacities (mg g^-1)

at equilibrium and at time t, respectively. K₁is the rate

constant of pseudo-ﬁrst order adsorption (L min^-1).

The pseudo-second order rate equation of McKay and

Ho can be represented in the Equation 7.

q

_ib_ic_i

=

×100

q

(Eq. 5)

e.i

^{1+ ∑}b_jc_j

Using non-linear regression technique, parameters

of Equation 5 were obtained given in Table 2. High

regression coefﬁcients (R²: 96.98–99.86) indicate

that the extended Langmuir model has the ability

to explain the adsorption equilibrium of binary

solution of MB and Dr.

t

1

(Eq. 7)

=

t

q

⁺q

q²

k₂

t

e

Where q_eis the equilibrium adsorption capacity,

and K₂is the pseudo-second order constants

(g mg^-1.min^-1). These terms can be determined

experimentally from the slope and intercept of plot

t/q_tversus t, shown in Figure 8. The coefﬁcients

of both models are shown in Table 3. In all cases

including single and binary solutions, the pseudo-

second order model has better coefﬁcient of

determination, R², which means that kinetic of

adsorption od MB and Dr on NH₂/UVM-7/SO₃H

can be explained by The difference between two

kinetic model can be attributed to the number and

accessibility of adsorption sites, speciﬁc surface

area, pore size, nature of the functional groups of

adsorbent and chemical structure of dyes.

3.6. Adsorption kinetic

The kinetic data of adsorption was obtained with

the initial concentrations of 50 mg L^-1and 100 mg

L^-1for MB and Dr, respectively. Solutions prepare

in 25 mL ﬂask with the stirring rate of 300 rpm and

the contact time was changed in the range of 10

to 120 minutes. to evaluate if there are changes/

interferences in the adsorption process in the

presence of other dyes in the solution.

3.6.1. Pseudo-ﬁrst order model

The pseudo- ﬁrst order kinetic model has been

Table 3. Kinetics parameters values for the adsorption of MB and Dr on NH₂-SO₃H/UVM-7

in single (sin) and binary (bin) dyes solution

Pseudo-ﬁrst order

q_e(mg g^-1) K₁(min) R²

Pseudo-second order

q_e(mg g^-1) K₂(g mg^-1.min^-1)

R²

MB(sin)

Dr(sin)

40

3.7

2.43

2.142

1

0.867

0.765

0.876

0.765

50

0.0012

0.372

0.962

0.983

0.934

0.826

4.3

5.26

12.98

90.9

MB(bin)

Dr(bin)

15.87

66.66

0.082

0.00068

Anal. Method Environ. Chem. J. 4 (1) (2021) 46-57

54

Fig. 8. The effect of pretreatment pH on selective adsorption of MB (a)

and Dr (b) on NH₂-SO₃H/UVM-7 in binary solution (temperature 30◦C, 400 mgL^-1initial dye concentration).

3.6.2. Selective adsorption of cationic and

anionic dyes

is temperature in Kelvin. The apparent equilibrium

constant (K_c) of the adsorption is deﬁned as

Equation 9.

Figure 8 displays that NH₂/UVM-7/SO₃H can

selectively adsorb the anionic Dr from the Dr/MB

mixture and pretreated at pH=5. While, the NH₂/

UVM-7/SO₃H can selectively adsorb the cationic

MB dye from the Dr/MB mixture and pretreated at

pH=10. This test veriﬁes with the easy, the special

treatment and selective adsorption of cationic or

anionic dyes by NH₂-SO₃H/UVM-7.

c_a

⁼c_b

(Eq. 9)

k_c

Where C_aand C_bis the equilibrium concentration

(mg L^-1) a of corresponding dye on the adsorbent

and in the solution, respectively. The K_cvalue is

used in the Equation 10 to determine the Gibbs free

energy of adsorption (ΔG).

3.6.3. Thermodynamic studies

The effect of temperature on the adsorption

of MB and Dr onto NH₂/UVM-7/SO₃H was

investigated. The obtained results indicate that

the amount of equilibrium adsorption (qe) of

MB and Dr on the NH₂/UVM-7/SO₃H slightly

increases with increasing temperature which

reveals the endothermic nature of adsorption. Main

thermodynamic parameters including standard free

energy (ΔG), enthalpy (ΔH) and entropy (ΔS) were

obtained using Equation 8.

(Eq. 10)

Furthermore, ΔH and ΔS were calculated from the

slope and intercept of the linear plot of lnKc versus

1/T, respectively. The obtained thermodynamic

parametersaresummarizedinTable4.AllΔGvalues

are negative which imply that the spontaneous

nature of adsorption. Furthermore, the value of

ΔG becomes more negative with increasing of

temperature, indicating that the adsorption process

is more favorable at higher temperature. As can be

seen in Table 4, the positive value of adsorption

enthalpy, ΔS, conﬁrms the endothermic nature the

adsorption process.

(Eq. 8)

Where R is gas constant (8.314 Jmol^-1K^-1) and T

Adsorption of dyes by multifunctional mesoporous silica

Amir Vahid et al

55

Table 4. Values of thermodynamic parameters for dye adsorption

from binary solution onto NH₂/UVM-7/SO₃H

Dye

Temp.(K)

ΔG(kJ mol^-1)

ΔH(kJ mol^-1)

ΔS(kJ mol^-1k^-1)

298

-2.95

8.1

0.038

308

318

328

298

308

318

328

-3.21

-3.43

-3.98

-4.83

-5.82

-6.98

-7.83

MB

26.3

0.106

Dr

4. Conclusions

6. References

InThis work, a novel synthesis method was developed

for the preparation of an adsorbent contains both

sulfonic acid and basic amine groups in the exterior

and interior pores of UVM-7, respectively. This

multifunctional adsorbent, NH₂/UVM-7/SO₃H, can

be used for simultaneous removal of multiple dyes

with different electrostatic charge. In real aqueous

sample and wastewater there are several dyes which

differ in their nature. Furthermore, one of the most

effective parameters in the removal of dye is its

electrostatic charge. On the other hand, large pore size

and surface area of UVM-7 can improve the diffusion

of the dye toward the adsorption sites. This improved

diffusion rate can be accompanied by small size of the

adsorbent particles, UVM-7, to improve adsorption

yield. However, it would be very useful in terms of

industrial point of view, to have a single adsorbent to

remove a variety of pollutants. The proposed method

can be applied to use a variety of adsorbents and open

us a way for treatment of wastewaters which normally

contain many types of pollutants.

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5. Acknowledgments

The authors would like to thank from Faculty of

chemistry, Amirkabir University of Technology,

Tehran, Iran.

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