Analytical Methods in Environmental Chemistry Journal Vol 1(2018) 29-38

Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

Investigation of Adsorption of Cobalt-phthalocyanine from

Aqueous Waste Stream Using UVM-7/Ag

Amir Vahid^a*, Majid Abdous^b, and Shahnaz Nayyeri^b

^a Research institute of petroleum industry, Tehran, Iran.

^b Faculty of chemistry, Amirkabir University of Technology, Tehran, Iran.

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

A B S T R A C T

Received 21 Aug 2018

The effect

adsorption

cobalt-phthalocyanine-3,4’,4”,4”’-

tetrasulfonicacid tetrasodium salt

[Co(tsPc)^-4•4Na⁺] onto UVM-7/Ag

Revised form 12 Nov 2018

mesoporous material was investigated. In addition, X-ray diffraction

Accepted 19 Nov 2018

(XRD), scanning electron microscopy (SEM), and nitrogen adsorption-

Available online 30 Dec 2018

desorption measurement were used to examine the morphology and the

microstructure of the obtained composite. Various parameters including

solution adsorbent dosage, contact time, initial dye concentration and

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

temperature were systematically studied. Equilibrium data fitted well

the Langmuir models; moreover, the fitness suggests that the adsorption

Keywords:

be monolayer and physical in nature. Kinetic studies showed that the

Adsorption

adsorption process could be better described by the Lagergren pseudo-

Aqueous

second-order models. Thermodynamic constant values (∆G < 0, ∆H<

0 and ∆S< 0) demonstrated that the adsorption reactions of Co(tspc)^-4

Dye

onto UVM-7/Ag were feasible, spontaneous, and exothermic under the

Isotherm

examined conditions.

Mesoporous silica

Kinetics

1. Introduction

at the center [5, 6].

Mercaptan and sulfur compounds present in the

One of the most important applications of MPCS has

crude oil and petroleum cuts cause corrosion of

been in catalysis, including large-scale industrial

pipes and different environmental pollutions[1].

processes. For instance, the Merox process,

There are various methods to remove mercaptan

referred to as

“sweetening” in the petroleum

but the major one is the catalytic oxidation in the

refining industry, involves catalytic oxidation of

presence of caustic solution and air. phthalocyanine

mercaptans in the presence of sulfonated cobalt

are effective catalysts for thiol and hydrosulfide

phthalocyanines to remove a major part of sulfur

oxidation by dioxygen[2-4]. Metal phthalocyanines

from petrol [7]. The catalytic properties of MPCS

(MPCS) are two dimensional (2D) organic macro

depend on the metal and complex structure and can

cyclic molecular catalysts (MN4) with metal atoms

be tuned by appropriate structural modifications

[8, 9]. This is the basis of the redox mechanism of

*Corresponding Author Email: avahid753@gmail.com

https://doi.org/10.24200/amecj.v1.i01.34

catalytic oxidation of sulfur-containing compound.

Analytical Methods in Environmental Chemistry Journal; Vol. 1 (2018)

Fig. 1. Schematic representation of Merox unit.

These catalysts have found wide application in the

as shown if Figure 2, makes this derivative easily

catalytic oxidation of mercaptans in oil fraction as

soluble in aqueous solution. sulfonated metal

shown if Figure 1 [10].

phthalocyanine (MSPC) complexes, highly water-

In many systems using transition metal compounds

soluble molecule and very well recognized for its

as catalysts, the mechanism suggested by Wallace

unique physicochemical properties and wide range

et al.[11] is:

of applications ranging from catalysis to sensing

and photocatalysis .

RSH + NaOH → RS^- + H₂O

The Merox catalyst is a heterogeneous blue powder

RS^- + CO⁺³ → CO⁺² + RS^●

dissolved in water.

2RS^● → RSSR

Merox catalyst of caustic solution creates problems

O _{2_2}+ H₂O → 2OH^- + 1/2 O₂

that in this work, co (II) tetra sulfophthalo cyanine

CoPC has a low solubility in water , the substitution of

Co(TSPc)^-4 catalyst removal from caustic solutions

CoPc with hydrophilic sulfonic groups [Co(tsPc)^-4]

by using meso porous silica UVM-7 is studied.

Functionalized with Ag and

, γ-Alumina was

prepared by sol-gel method and the synthesized

nanoparticle was characterized by scanning

electron microscopy (SEM) and X-ray diffraction

(XRD).

Mesoporous materials can have large adsorption

capacity, excellent selectivity and improved powder

recoverability for removal of toxic compounds

from aqueous solutions[12,

13]. The effects of

adsorbent dosage, initial Co(tspc)^-4 concentration

and contact time were studied. The adsorption was

fit to different adsorption isotherms and also to

kinetics of the adsorption was studied. Parameters

Fig. 2. Structure of the Co (II) tetra sulfophthalocyanine

affecting the removal of Co(tspc)^-4 from the

^-4.4Na⁺[ organometal.

]Co(tsPc)

aqueous solution was investigated and validated by

Adsorption of cobalt-phthalocyanine by UVM-7/Ag; Amir Vahid, et al

using three factorial Box- Behnken Design (BBD).

2. Experimental

2.1. Synthesis and characterization

The general procedure for the synthesis of UVM-

7 is the atrane route, in which the presence of the

polyalcohol is the key to balancing the hydrolysis

and condensation reaction rates [18]. In a typical

synthesis, TEOS was added to determined

amounts of TEAH₃

(tri ethanolamine). The

solution was heated up to 140ºC under vigorous

stirring. After cooling down to 90ºC, CTAB (cetyl

Fig. 3. TEM image of UVM-7/Ag.

trimethylammonium bromide) was added to this

solution. After that, water was added slowly to this

which reached to

601 m²g^-1 after doping with

solution under stirring until a white suspension

silver. These are direct and indirect evidences of

resulted. This suspension was aged for 4 hours at

formation of ordered UVM-7 which contains silver

room temperature. The solid was filtered, washed

nanoparticles.

with sufficient amounts of water and acetone

XRD pattern of the as-synthesized and calcined

and dried in an oven at 80ºC overnight. Thermo

UVM-7 are illustrated in Figure 4. As can be

calcination of the as synthesized UVM-7 was

seen, a sharp peak at low angle about 1.5×2theta

carried out under a flow of air up to 550ºC for 6

is characteristic of mesoporous materials. In case

hours with a heating rate of 1 C/min to remove both

of calcined UVM-7 higher order diffraction, i.e.

the surfactant and TEAH₃ from the as-synthesized

d₁₁₀ and d₂₀₀ are sign of better structural order

UVM-7. The final molar composition of the

which is usually seen in mesoporous materials

reactants was 1.0 TEOS : 3.5 TEAH₃ : 0.25 CTAB:

after thermocalcination and condensation of silanol

90 H₂O.

groups.

2.2. Modification of UVM-7

3.2. Adsorption studies

For the modification of UVM-7 with Ag, 1 gram of

Adsorption behavior was studied by a batch method,

calcined UVM-7 is mixed with 100 mL of distilled

which parameters that influence the adsorption

water contains 0.1 gram of AgNO₃ and stirred for 24

process such as contact time, initial concentration,

hours. The water was distilled using and automatic

adsorbent dose, surfactant template, and reaction

evaporator and calcined at 450 ºC for 5 hours.

temperature was investigated. In addition, aqueous

solutions of Co(tsPc)^-4 which its chemical structure

3. Results and Discussion

is shown in Figure 1; moreover, with concentration

3.1. Characterization UVM-7/Ag

ranging from 100 to 500 mg L^1-were prepared by

TEM image of UVM-7/Ag is displayed in Figure

dissolving Co(tsPc)^-4 in double distilled water. In

3. Mesochannels of the UVM-7 is obviously

each adsorption experiment, 10 mg adsorbent was

visible in this image. Furthermore, dark points in

added in 10 mL Co(tsPc)^-4 solutions. to study the

the image related to the higher contrast of heavy

effect of temperature the adsorption was carried

silver atoms with incident electron beam. BET

out at four different temperatures (27, 35, 40 and

surface area of the calcined UVM/7 was 838 m²g^-1

50 ⁰C) and for contact time studies the samples

Analytical Methods in Environmental Chemistry Journal; Vol. 1 (2018)

Fugire 4. XRD pattern of as-synthesized and calcined UVM-7.

were taken at predetermined time intervals (10, 20,

determined according to the following equation:

30, 40, 60, 80 and 100 min). After equilibrium,

(

)

⁻c

the concentration of the adsorbate in the residual

×100

solution was analyzed by a UV-spectrophotometer

at λ max of 661 nm. The amount of Co(tsPc)^-4

adsorbed per unit mass of UVM-7/Ag the qe (mg

3.2.1. Effect of adsorbent dosage

g^-1) was calculated by the following equation:

The effect of adsorbent dosage (m) on the amount

of Co(tsPc)^-4 adsorbed at equilibrium

(qe, mg

(

−

)

g^-1), was investigated by adding different weights

of adsorbent UVM-7/Ag into 10 ml of solution

where q_e is the adsorption capacity (mg g^-1) of the

500 mg l^-1 Co(tsPc)^-4 and shaking the mixture

adsorbent at equilibrium; C₀ and C_e are the initial

for 60 min at ambient temperature. It is evident

and equilibrium concentrations of solute (mg L^-1)

from figure 5، qe increases by increasing m, can

respectively. Also, V is the volume of the aqueous

be attributed to the availability of greater surface

solution (L). and W is the mass (g) of adsorbent

area and more adsorption sites. that adsorption

used in the experiments.

capacity of Co(tspc)^-4 increased when UVM-7/Ag

The adsorptive removal efficiency

(R) was

dosage varied from 2 mg to 10 mg. However, the

Figure 5. .Effect of adsorbent dosage on the adsorption of Co(tsPc)^-4 by UVM-7/Ag.

Adsorption of cobalt-phthalocyanine by UVM-7/Ag; Amir Vahid, et al

adsorption capacity slowly as the adsorbent dosage

adsorption is

60 min. The adsorption rate was

increased from 10 mg to 15 mg. Thus 10 mg was

related to the content of the active adsorption sites

chosen as the optimal UVM-7/Ag dosage in this

on the matrix of the adsorbent[15].

study[14].

3.2.3. Effect of temperature

3.2.2. Effect of contact time

The effect of temperature on the adsorption of

It is visible from Figure 6, that the amount of the

Co(tsPc)^-4 onto UVM-7/Ag was investigated by

adsorbed Co(tsPc)^-4 increases with time and then

adding 10 mg of the adsorbent into 10 mL of solution

reaches a constant value. At this point, the amount

500mg L^-1 Co(tsPc)^-4 and shaking the mixture for

of Co(tsPc)^-4desorbing from the adsorbent is in a

60 min at different temperatures of 27, 35, 40 and

state of dynamic equilibrium with the amount of

50 ^◦C in a water bath. The results indicated that the

Co(tsPc)^-4 being adsorbed onto the mesoporous.

equilibrium adsorption amount (q_e) decreases with

The time required to attain this state of equilibrium

increasing temperature (Figure 7), indicating that

is termed equilibrium time. estimate equilibration

the adsorption process is exothermic in nature[16].

time for Calculation maximum adsorption

In order to understand the effect of temperature on

Capacity and to know the kinetics of the adsorption

the adsorption process, thermodynamic parameters

It is seen that the rate of uptake is rapid.Required

should be determined at various temperatures. For

at the beginning, and time required for equilibrium

this reason, three basic thermodynamic parameters

Fig. 6. .Effect of contact time on the adsorption of Co(tsPc)^-4 by UVM-7/Ag

Fig. 7 .Effect temperature on the adsorption of Co(tsPc)^-4 by UVM-7/Ag

Analytical Methods in Environmental Chemistry Journal; Vol. 1 (2018)

were studied: the Gibbs free energy of adsorption

Therefore the optimal reaction temperature was

(∆G), the enthalpy change (∆H), and the entropy

300 K.

change (∆S).The Gibbs free energy change of the

adsorption process is related to the equilibrium

3.2.4. Effect of initial dye concentration

constant

(K_c). The thermodynamic parameters

The effect of initial Co(tsPc)^-4 concentration on

∆G, ∆S and ∆H for this adsorption process were

adsorption behaviors was investigated in Figure

calculated from the following equations:

8. It can be seen that the majority of Co(tsPc)^-4

was removed by UVM-7/Ag in lower initial

∆G = - RT ln KC

where R is the gas constant (8.314 J mol^-1 K^-1), T is

Co(tsPc)^-4 concentration, the Co(tsPc)^-4 removal

the absolute temperature. K_c values were estimated as

efficiency decreased with increase

initial

Co(tsPc)^-4 concentration. also This effect can has

Kc = Ca /

been attributed to the ratio of surface active site to

where C_a is the equilibrium concentration of

the total Co(tsPc)^-4 ions in the solution .while The

Co(tsPc)^-4 on adsorbent

(mg L^-1), C_b is the

result reveals that the amount of capacity adsorbed

equilibrium concentration of Co(tsPc)^-4 in the

(qe) increases as the concentration increases. The

solution

(mg L^-1). the ∆H and ∆S values were

initial concentration of Co(tsPc)^-4 can serve as an

calculated from slope and intercept of the linear

essential driving force for overcoming the mass

plot of lnK_c versus 1/T[17, 18].

transfer resistance of dye molecules between the

aqueous solution and solid-phase adsorbent. As

ln Kc = -∆H/RT + ^∆S/_R

the initial concentrations of Co(tsPc)^-4 increased,

The corresponding values of thermodynamic

the driving force became higher as well, which

parameters are presented in Table 1. It shows that

facilitated more dye molecules adsorbing onto the

∆H, ∆S and ∆G are negative for all experiments.

adsorbent, contributing to better adsorptive removal

The negative value of the standard enthalpy change

performance and higher adsorption capacity[21].

for Co(tsPc)^-4

sorption indicates exothermic

nature of adsorption[19] .The values of ∆G were

3.3. Effect of presence of surfactant template

calculated to be

-6.3,

-5.4,

-4.4,

-3.7 kJ mol^-1

When the surfactants in aqueous solution are

at the temperatures of 300, 308, 313 and 323 K,

beyond the critical micelle concentrations (CMC),

respectively. The negative ∆G indicates that the

micelles are formed and they act as templates for

adsorption is a spontaneous process. The increase

preparing UVM-7 materials. The existence of

of ∆G values with rising temperature demonstrate

cationic template within the framework of UVM-

a negative influence of temperature on the

7 materials causes the change in the surface

adsorption reaction. Moreover, negative ∆S values

chemistry and porosity of the sorbate, which in turn

indicate a reduction of randomness at the solid-

affects the sorption behavior of sorbate. CTAB/

liquid interface during the adsorption process[20].

UVM-7 possesses high adsorption energy of

Table 1. Thermodynamics parameters for Co(tspc)^-4 adsorption onto UVM-7/Ag

Thermodynamics quantities

Temperature (k)

∆H(KJ mol^-1)

∆G(kj mol^-1)

∆S(kj mol^-1k^-1)

300

-21.976

-6.3

-0.099

308

-21.976

-5.4

-0.099

313

-21.976

-4.4

-0.099

323

-21.976

-3.7

-0.099

Adsorption of cobalt-phthalocyanine by UVM-7/Ag; Amir Vahid, et al

Figure 8. Effect initial concentration on the adsorption of Co(tsPc)^-4 by UVM-7/Ag.

quaternary alkyl ammonium groups (Si-C-C-C-

for the adsorption of dyes, various isotherm

[N⁺-(CH3)3]) contributed from cationic template.

equations like those of Freundlich, Langmuir and

Apparently, the surfactant template can alter the

Temkin have been used to describe the equilibrium

surface chemistry and population of sorption sites

characteristics of the adsorption. For describing

of the materials. The cationic templates improve

the relationship between the amount of adsorbate

the sorption towards those species containing

adsorbed on adsorbents at equilibrium (q_e) and the

anionic groups. It is known that hydrophobicity,

concentration cu(tspc)^-4 of the remaining in aqueous

electrostatic

interactions,

p-p interactions,

solution

(c_e). The Langmuir relation assumes

hydrogen bonding, dipole-dipole interactions,

monolayer sorption on to the homogeneous surface

steric hindrance as well as a combination of them,

with a specific number of equivalent sites. The

are among the most important interactions which

Langmuir isotherm[23] is represented by the

determine the retention behavior of substances

following linear equation:

in the absorbent. When the adsorbent is CTAB-

containing mesoporous silica, the aromatic cycles

could interact with the alkyl part of CTAB by

hydrophobicity; the sulfonic acid groups interact

where C_e (mgL⁻¹) is the equilibrium concentration,

with the positive polar heads of surfactants by

qe (mgg^-1) the amount of adsorbate adsorbed per

electrostatic interactions. It is mentioned multiple

unit mass of adsorbent, qm (mg g⁻¹) is the Langmuir

interactions which give the surfactant-containing

constant representing maximum monolayer capacity

adsorbent excellent adsorption capability. As

and b is the Langmuir constant related to the energy

shown if Figure 9, The adsorption capacity of

of adsorption. The Langmuir constants b and q_m were

‘‘calcined’’ adsorbent is weak and is generally due

calculated from this isotherm and their values are

to the van der Waals interactions present between

listed in Table 2. The Freundlich isotherm is derived

the molecules of dyes and adsorbent [22].

by assuming a heterogeneous surface with a non-

uniform distribution of heat of adsorption over the

3.4. Adsorption isotherms

surface. Finally, the Freundlich isotherm as follows:

To optimize the design of an adsorption system

Analytical Methods in Environmental Chemistry Journal; Vol. 1 (2018)

Fig. 9. Effect presence of surfactant template.

it provides information about the mechanism of

the adsorption process such as mass transfer and

log

= log

log

chemical reaction. In this context, the mechanism

where K_f is the Freundlich constant (mg g⁻¹ (mg L⁻¹)

of the adsorption of Co(tspc)^-4 ion onto adsorbents,

ⁿ) and 1/n is the heterogeneity factor. The slope 1/n

different kinetic models such as the pseudo-first-

ranging between 0 and 1 is a measure of adsorption

order and pseudo-second-order has been studied.

more intensity or surface heterogeneity, becoming

The pseudo- first-order equation can be used to

heterogeneous as its value gets closer to zero. The

determine the rate constant for the adsorption

plot of log qe versus log Ce, gives straight lines

process and describe the initial stage of the

with slope 1/n [24].

adsorption processas follows [27]:

The Temkin isotherm equation assumes that the

heat of adsorption of all the molecules in the layer

(

) +

decreases linearly with coverage due to adsorbent-

adsorbate interactions, and that the adsorption

where q_e and q_t are the amounts of adsorbed

is characterized by a uniform distribution of the

Co(tspc)^-4 at equilibrium and any time t (mg g⁻¹),

binding energies, up to some maximum binding

respectively, k₁ is the equilibrium rate constant of

energy [25, 26]. Temkin isotherm is given as:

the first-order sorption (min⁻¹).

q_e=B lnK_t+BlnC_e

The pseudo-second-order rate equation of can be

K_t is the equilibrium binding constant

(Lmg^-1)

represented in the following form [28, 29] :

corresponding to the maximum binding energy, and

constant B is related to the heat of adsorption. From

Table 2, the Langmuir isotherm model yielded the

best fit with the highest R² value (0.99) compared

where K₂ (g mg^-1 min^-1) is the rate constant of

to the other two models.

the second-order equation, qt

(mg g^-1) and qe

(mg g^-1) Co(tspc)^-4 adsorbed at time t (min) and

3.5. Adsorption kinetics

at equilibrium respectively [30]. Pseudo-second-

The study of adsorption kinetics is desirable as

order kinetics is based on the adsorption capacity,

Adsorption of cobalt-phthalocyanine by UVM-7/Ag; Amir Vahid, et al

Table 2. Isotherm parameters for Co(tspc)^-4 adsorption onto UVM-7/Ag.

Langmuir isotherm

Freundlich isotherm

Temkin isotherm

R²

K_F

R²

K_T

R²

(mg g^-1)

(L mg^-1)

(mg g^-1)

(L mg^-1)

)Lmg^-1)

188.8

0.441

0.99

77624.72

15.38

0.982

1.52

11.53

0.709

which usually gives a good description of the whole

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R²

(mg g^-1)

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(mg g^-1)

(g mg^-1min^-1)

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29.5

0.957

250

0.000149

0.982

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