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Accepted Manuscript

Title: Adsorption of hexavalent chromium by metal organic


frameworks from aqueous solution

Author: Afshin Maleki Bagher Hayati Maryam Naghizadeh


Sang W. Joo

PII: S1226-086X(15)00066-0
DOI: http://dx.doi.org/doi:10.1016/j.jiec.2015.02.016
Reference: JIEC 2425

To appear in:

Received date: 21-12-2014


Revised date: 19-1-2015
Accepted date: 12-2-2015

Please cite this article as: A. Maleki, B. Hayati, M. Naghizadeh, S.W.


Joo, Adsorption of hexavalent chromium by metal organic frameworks from
aqueous solution, Journal of Industrial and Engineering Chemistry (2015),
http://dx.doi.org/10.1016/j.jiec.2015.02.016

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Adsorption of hexavalent chromium by metal organic frameworks from

a q u e o u s solution

Afshin Maleki 1, Bagher Hayati 1, Maryam Naghizadeh 1, Sang W. Joo2, *


1
Kurdistan Environmental Health Research Center, Kurdistan University of Medical Sciences,

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Sanandaj, Iran

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2
School of Mechanical Engineering, Yeungnam University, Gyeongsan 712-749, Korea

*swjoo@yu.ac.kr

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Abstract

A metal–organic frameworks (MOFs) based on copper-benzenetricarboxylates is


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applied to the adsorption of hexavalent chromium from aqueous solution.

Characterization of Cu-BTC was achieved by XR D, SEM micrographs, nitrogen


d

adsorption–desorption analysis and FT-IR spectra. The kinetic characteristics and


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thermodynamic parameters are also analyzed. The experimental isotherm data are

analyzed using Langmuir and Freundlich isotherm equations. Thermodynamic


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parameters are calculated by the Gibbs free energy function, confirming that the

adsorption process was spontaneous and accompanied by exothermic. The


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maximum removal has been achieved at pH = 7.0. Possible mechanism and

adsorption behavior of hexavalent chromium onto Cu-BTC are investigated.

Keywords: Metal organic frameworks; Adsorption; chromium wastewater; Cu-

BTC; Kinetic model; Langmuir isotherm

Page 1 of 18
1. Introduction

The extensive use of chromium in leather tanning, metallurgy, electroplating and other industries has

resulted in the release of aqueous chromium to the subsurface at numerous sites[1-3]. Chromium can

occur at several different oxidation states ranging from –2 to 6. Out of which only Cr (III) and Cr

(VI) are the stable forms in the natural environments. However, Cr (VI) is rarely naturally occurring,

t
ip
relatively soluble in aqueous systems and is readily transformed in groundwater[4]. Exposure to Cr

cr
(VI) poses an acute health risk because it is highly toxic and chronic exposure can lead to

mutagenesis and carcinogenesis. On the contrary Cr (III) is naturally occurring, is much less toxic

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and even essential to human glucidic metabolism, contributing to the glucose tolerance factor

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necessary for insulin-regulated metabolism[5-7].

Adsorption is the procedure of choice, which being the widely used physicochemical
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method for heavy metal removal because adsorption does not need a high operation

temperature and several materials can be removed simultaneously. Recently, a


d

variety of adsorbents have received much more attention for the removal of metal
te

ions. The use of more metal adsorbent is the granular activated carbon, active
p

diatomaceous earth and resins [8-11]. Activated carbon adsorption method is a


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method applied earlier, and this method is very effective for the removal of heavy

metal, However, it is more difficult to regenerate, and the processing cost is higher,
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so the application is narrow[12].

Metal–organic frameworks (MOFs), known as metal organic coordination

polymers, commonly recognized as soft analogues of zeolites, is a new class of porous

structures composed of different varieties transition metal ions (or clusters) and

rigid-rod-like organic linkers[13]. This type structure not only provides MOFs with

tunable options, organic functionality, high thermal and mechanical stability, open

metal sites in the skeleton, large pore sizes, and high surface areas, but also can be

easily prepared in a one pot[14]. Metal–organic frameworks constitute an important


Page 2 of 18
family receiving prominence for their many potential applications in a lot of

industrially important areas[15]. To date, MOFs have exhibited numerous properties

such as gas adsorption, separations, catalysis, sensors, photocatalysis and drug

delivery. Besides, the adsorptive removal of toxic compounds has also been

studied using MOFs. For examples, adsorption of thiophene derivatives were

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carried out on MOF-5 and MOF-235 has been used for the removal of harmful

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dyes anionic dye methyl orange (MO) and cationic dye methylene blue (MB) from

contaminated water via adsorption[16].

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The applications of MOF-101 (Cr) for the removal of xylenol orange (XO) from aqueous

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solution have also been reported[17].

Cu-BTC was used as an example of MOFs due to its attractive features as a sorbent for
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the extraction of pollutants in aqueous solution, such as high surface area, uniform

pore size, accessible coordinative unsaturated sites, and excellent chemical and
d

solvent stability[18]. As is the case with several other MOFs, most of the
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experimental studies so far on Cu-BTC focused on the gas adsorption.


p

In the present work, we describe the synthesis of Cu-BTC MOFs by solvothermal reaction,
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characteristics of Cu-BTC and its adsorption properties such as adsorption equilibrium, kinetics,

thermodynamics, adsorption mechanism, were investigated. Remarkably, the Cu-BTC is


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demonstrated to exhibit significantly fast adsorption kinetics for chromium removal. In addition, the

material can be reused at least three times after washing with ethanol.

2. Experiment

2.1. Materials

Copper (II) nitrate trihydrate (Cu(NO3)2_3H2O), 1,3,5-benzenetricarboxylic acid (H3BTC), N,N-

dimethylformamide (DMF), ethanol, potassium dichromate were used as obtained from commercial

sources and used without further purification.

2.2. Synthesis procedure Page 3 of 18


The Cu-BTC MOFs was synthesized by a hydrothermal method as reported by Liu et al and it was a

modification of previous works by Rowsell and Yaghi [19, 20]. Two solutions prepared separately

by dissolving 1,3,5-benzenetricarboxylic acid (1.50 g) in 45 mL of a 1:1 mixture of ethanol/N,N-

dimethylformamide (DMF) and copper(II)nitrate trihydrate (3.114 g) in 22.5 mL deionized water

were mixed and stirred at ambient temperature for 10 min. Subsequently, they were then loaded into

t
ip
a Teflon-lined stainless steel autoclave of 100 mL capacity and heated at 373 K for 10 h. The

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resulting blue microcrystals were isolated by filtration and washed with methanol several times. The

obtained products were dried under vacuum at 333 K overnight and used for further experiments.

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2.3. Adsorption experiments

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Batch adsorption experiments were carried out by allowing a weighed amount of Cu-BTC to reach

equilibrium with the chromium solution of known concentration. To obtain the adsorption capacity,
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5.0 mg of Cu-BTC was dispersed in 10 mL of chromium solutions at different concentrations (from

10- 40 mg/L), then the solutions were stewing in a thermostatically controlled water bath and the
d

desired time at constant temperatures of 298 K, 308 K and 318 K, respectively. At the end of the
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desired equilibrium period, the solution was centrifuged for 3.0 min, and atomic adsorption
p

spectroscopy was used to analyze the residual concentrations of chromium. Batch kinetic studies
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were identical to the adsorption experiments, and the aqueous samples were taken at prespecified

time intervals. The equilibrium adsorption capacity qe (mg/g) was calculated according to Eq. (1):
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qe =[(C0-Ce)v]/m (1)

Where C0 and Ce (mg/L) were the initial and final concentrations of chromium, respectively. V (L)

was the volume of the solution, and m (g) was the mass of sorbent. The effect of pH on the removal

of chromium was studied by batch mode experiment. To study the effect of pH on the removal of

chromium from aqueous solutions, 5.0 mg of Cu-BTC was dispersed in 10 ml of solution containing

chromium (20 mg/L), adjusted the solution pH to 2.0, 4.0, 6.0, 8.0, using a certain amount of dilute

HCl or NaOH solution. After stewing in the thermostatic water bath for 20 min at 298 K, the

Page 4 of 18
supernatant fluid was obtained through the high-speed centrifuge. Ultraviolet spectroscopy was used

to analyze the remanent concentrations of chromium.

2.4. Characterization

The structure of the crystal was verified by X-ray powder diffraction (XRD). In this work, X-ray

diffraction (XRD) patterns of the samples were collected on a D/max-RA X-ray diffractometer

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(Rigaku, Japan), with Ni-filtrated Cu-Ka radiation (40 kV, 200 mA) over the 2h range of 5.0–55°

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At a scanning rate of 5.0°min-1. The shapes and morphologies of synthesized samples were

characterized by scanning electron microscope. Cu-BTC MOFs surface areas and pore size

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distributions were measured by nitrogen adsorption and desorption at 77 K using either a

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Micromeritics ASAP 2420 or ASAP 2020 volumetric adsorption analyzer. Surface areas of the

samples were determined by the Brunauer-Emmett-Teller (BET) method, pore size distributions and
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pore volumes were analyzed by the Barrett-Joyner-Halenda (BJH). Samples were degassed at 393 K

for 15 h under vacuum (10–5 bar) before analysis. FT-IR spectra of the Cu-BTC samples were
d

obtained between 4000– 400 cm with a FTIR spectrometer (AVATAR 360Madison, Nicolet). A
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minimum of 32 scans was signal-averaged the 4000–400 cm-1 ranges


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3. Results and discussion


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3.1. X-ray diffraction (XRD) analysis

In order to substantiate the phase purity of the complexes, powder XRD was performed before the
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other tests were measured. As shown in Fig. 1, samples showed diffraction patterns identical to those

of the simulated one, indicating that the structure of Cu-BTC was well preserved and the complexes

was pure powder. [21, 22].

3.2. SEM electron microscopy

The Cu-BTC synthesized was characterized by using SEM. Fig. 2 showed the SEM images of as-

prepared Cu-BTC samples. The octahedral shape of the Cu-BTC crystals was clearly seen in the

figure. The crystal sizes of the Cu-BTC samples were in the range of 10–20 lm without any

Page 5 of 18
aggregation. The morphology of as-prepared Cu-BTC samples was consistent with other SEM

images published for this material[23, 24]

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Fig. 1. XRD patterns of simulated one, (A) the as-synthesized (B) and fourth regenerated (C).

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Fig. 2. SEM micrographs of Cu-BTC products.


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3.3. The BET surface areas and pore volumes

To further characterize the porosity of Cu-BTC MOFs, nitrogen adsorption experiments were
Ac

performed at 77 K. The nitrogen adsorption-desorption isotherms of Cu-BTC and the corresponding

pore size distributions were reported in Fig. 3. The data of the surface area pore volume and pore

size were listed in Table 1. As could be seen from Fig. 3, the as-synthesized Cu-BTC samples

showed similar type-IV adsorption desorption isotherms, clearly, demonstrating their typical

mesoporous network. Furthermore, the type-H4 hysteresis loops in the partial pressure range from

0.4 to 1.0, which indicated a homogeneous pore size distribution. The pore size distributions of as-

prepared Cu-BTC samples was calculated from the adsorption branch of N2 isotherm by using the
Page 6 of 18
Barrett-Joy-ner-Halenda (BJH) model [25],which were shown in insets of Fig. 3. It should be noted
that the Cu-BTC samples showed a uniform, narrow pore size distributions centered at about 3.8 nm.

As could be seen in Table 1, all the materials were mesoporous (mean pore diameter = 2.95 nm) and

the BET specific surface area of Cu-BTC MOFs measured from the nitrogen isotherms was 279 m2

g_1.

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Fig. 3. N2 adsorption–desorption isotherms and BJH pore size distributions (inset) of Cu-BTC sample.
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Table 1. Some properties of Cu-BTC samples for .nitrogen adsorption experiments at 77 K.


sample SBETa (m2/g) Vpb (cm3/g) Dpc (nm)
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Cu-BTC 279 0.2064 2.95


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3.4. Fourier transform infra-red spectroscopy (FT-IR)


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The FT-IR spectra of Cu-BTC composites were measured using KBr disks and were shown in Fig. 4.

The main functional groups of the predicted structure could be observed with corresponding infrared
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absorption peaks. The absence of peaks at 1720–1680 cm_1 suggested that deprotonated had

happened in acidic COOH_. This unambiguously indicated that the carboxylate ion participates in

the complex formation. The characteristic vibration at 730 cm_1 might be attributed to Cu–O

stretching vibration, in which the oxygen atom was coordinated with Cu. Very broad peak formation

at 3100–3600 cm_1 in the complex indicated the presence of loosely bound water molecules in Cu-

BTC; The most significant things of these peaks are the stretching VC@O, VC–O and bending O–H

vibrational frequencies seen at 1644, 1373 and 1447 cm_1, respectively, indicating the presence of a

carboxylic acid group[22]. Page 7 of 18


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Fig. 4. FT-IR spectra of Cu-BTC sample.

3.5. Effect of pH

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The initial pH of the chromium solution is an important parameter, which controlled the adsorption
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process particularly the adsorption capacity. Chromium adsorption at various pH values was

measured after equilibration with Cu-BTC. In this work, the pH value effect on the adsorption was
d
te

carried out at 298 K. Select the concentration of 20 mg/L as an example. The effect of pH on the

adsorption of chromium (A) and the equilibrium pH (B) are shown in Fig. 5. The adsorbed amounts
p

increase with the increase in pH from 2.0 to 8.0. Moreover, adsorption of chromium at low pH 2.0–
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6.0 did not cause significant changes in the equilibrium pH. At lower pH, the surface charge of Cu-

BTC might get positively charged, thus making H+ ions compete with metal ions causing a decrease
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in the amount of metal adsorbed. At higher pH, the metal contains chromate anion, which is

exchanged to have a displacement reaction with NaOH to produce NaCl (aq). The salt of NaCl might

decrease the adsorption of chromium on the Cu-BTC. Maximum removal without structural

degradation of adsorbent has been achieved at the pH = 7.0. As a result, pH of 7.0 was selected for

further experiments.

Page 8 of 18
100

80

Removal (%)
60

40

20

t
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0
0 2 4 6 8 10
pH

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Fig. 5. Effect of pH on adsorptive removal of MB (A) and the equilibrium pH (B)
after adsorption of MB. (T = 298 K; m = 5.0 mg; V = 10 mL.)

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3.6. Effect of adsorbent dosage.

Fig. 6. shows the effects of adsorbent dosage on adsorption of chromium solutions using Cu-BTC.
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As shown in Figure 6, with the increase of adsorbent dosage, the removal efficiency steadily

increased. The increase in adsorption with adsorbent dosage can be attributed to increased adsorbent
d

surface and availability of more adsorption sites. However, if the adsorption capacity was expressed
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in mg adsorbed per gram of material, the capacity decreased with the increasing amount of

adsorbent. This may be attributed to overlapping or aggregation of adsorption sites resulting in a


p

decrease in total adsorbent surface area available to the metals and an increase in diffusion path
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length [26].
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100

90
Removal (%)

80

70

60

50

40
0 0.2 0.4 0.6 0.8 1
Adsorbent (g/L)

Fig. 6. Effect of Adsorbent dosage on chromium adsorption by Cu-BTC. (pH = 7, C0 = 20 mg/L, T=298 0K).
Page 9 of 18
3.7. Effect of initial chromium concentration.

Adsorption metal is a mass transfer process that can generally be defined as the accumulation of

metal at the interface between two phases. For this reason, the influence of initial metal

t
concentration was investigated as a separately parameter. The influence of varying the initial metal

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concentration (10, 20, 30 and 40 mg/L) was assessed and the other parameters were kept constant in

cr
optimization values (Fig. 7). It is obvious that the higher the initial metal concentration, the lower

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the percentage of metal adsorbed. The adsorption values are acceptable in concentration 20 mg/L of

chromium and concentration of chromium equals to 20 mg/L was chosen the optimum value for

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metal removal[27]. M
110

100
Removal (%)

90
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80

70
p

60
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0 10 20 30 40 50
Adsorbate (mg/L)
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Fig. 7. Effect of initial metal on chromium adsorption by Cu-BTC. (pH = 7, C0 = 20 mg/L, T=298 0K).

3.8. Isotherm studies

Biosorption isotherm indicates the relation between the mass of metal adsorbed at constant

temperature per unit mass of biosorbent and liquid phase metal concentration at equilibrium. In

addition, it presents how metal can be distributed between the liquid and solid phases at various

equilibrium concentrations and how efficiently a given biosorbent interacts with adsorbate. Several
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factors such as the number of compounds in the solution, their relative adsorbabilities, initial
concentration of adsorbate in the solution, and the degree of competition among solutes for

biosorption sites determine the shape of isotherm [28].

The Langmuir equation often describes by monolayer biosorption. This model assumes a

uniform energy of biosorption and a single layer of adsorbed solute at a constant temperature. The

Langmuir model is the most frequently employed model and given by as follows [29]:

t
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qe = Q0KLCe / (1 + KLCe) (2)

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Where qe, Ce, Q0, and KL are the amount of solute adsorbed at equilibrium (mg/g), the concentration

of adsorbate at equilibrium (mg/L), maximum biosorption capacity (mg/g), and Langmuir constant

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(L/mg), respectively. The linear form of Langmuir equation is Eq. (3) [30] :

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Ce 1 C
  e (3)
qe K L Q0 Q0

To study the applicability of the Langmuir isotherm for the chromium biosorption onto Cu-BTC,
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linear plot of Ce/qe against Ce was plotted and the values of Q0, KL, RL, and R2 (correlation
d

coefficient) are shown in Table 2.


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The essential characteristics of the Langmuir isotherm can be expressed by a dimensionless constant

called equilibrium parameter, RL, which is defined by the following equation [22]:
p

RL =1 / (1+ KLC0) (4)


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The nature of the biosorption process to be either unfavorable (RL > 1), linear (RL =1), favorable (0 <
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RL < 1), or irreversible (RL = 0). Values of RL were indicated that the biosorption processes were

favorable (Table 2).

Table 2. linearised isotherm coefficient for chromium biosorption onto Cu-BTC


Langmuir isotherm Freundlich isotherm
Metal Q0 KL KF
RL R2 N R2
(mg/g) (L/g) (L/g)

Cr 48 0.984 0.326 0.989 156 2.610 0790

The Freundlich equation is another well-known model for biosorption. It is an empirical

equation used to describe the distribution of solute between solid and aqueous phases at a point of
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saturation. The basic assumption of this model is that there is an exponential variation in site

energies of biosorbent and surface biosorption is not rate limiting step [31]. The Freundlich isotherm

is derived by assuming a heterogeneous surface with a nonuniform distribution of heat of biosorption

over the surface. Freundlich isotherm can be expressed by as follows [32-35]:

qe = KF Ce1/n (5)

t
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Where KF is biosorption capacity at unit concentration and 1/n is biosorption intensity. 1/n values

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indicate the type of isotherm to be irreversible (1/n = 0), favorable (0 < 1/n < 1), unfavorable (1/n >

1) [36]. Equation (5) can be rearranged to a linear form as follows:

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log qe = log KF + 1/n log Ce (6)

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To investigate the applicability of the Freundlich isotherm for the chromium biosorption onto Cu-

BTC, linear plot of log qe versus log Ce was plotted and the values of KF, n, and R2 are shown in
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Table 2.

As illustrated in Table 2, the correlation coefficients, R2, for the Langmuir isotherm model
d

were greater than 0.989. The results revealed that the number of biosorption sites on Cu-BTC was
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limited and metal molecules formed a monomolecular layer on the biosorbent at saturation. The
p

plots of the total amount of metal adsorbed against the total equilibrium metal concentration were
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fitted by the Langmuir equation (Table 2).

3.9. Kinetic studies


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Kinetic data provide information regarding the mechanism of biosorption that is important for the

efficiency of the process. It is important to know the rate of biosorption during removing

contaminants from wastewater to optimize the design parameters because kinetic of system controls

the adsorbate residence time and reactor dimension. As a result, predicting the rate at which

biosorption takes place for a given system is probably the most important factor in biosorption

system design [37].

Pseudo first order equation is generally represented as follows [38, 39]:

dqt/dt = k1 (qe - qt) (7)


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Where k1 is the equilibrium rate constant of pseudo first order kinetics (1/min). After integration and

applying conditions, qt = 0 at t = 0 and qt = qt at t = t, then eq. (9) becomes

Log(qe - qt) = log (qe) - k1 / 2.303t (8)

The straight-line plots of log (qe - qt) versus t for the biosorption of chromium biosorption onto Cu-

BTC have been tested to obtain the rate parameters. The k1, the experimental qe and correlation

t
ip
coefficients (R2) under different metal concentrations values were calculated and given in Table 3.

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Table 3. Kinetic constant for pseudo-first and pseudo-second order and intraparticle diffusion model
Pseudo-first order Pseudo-second order
Metal (qe)Exp
(20 mg/L) (mg/g) (qe)Cal. k1 (qe)Cal. k2
R2 R2
(mg/g) (1/min) (mg/g) (g/mg.min)

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Cr 48 170 M0.057 0.856 50 0.015 0.999

Data were applied to the pseudo second order kinetic rate equation which is expressed as

follows : [36, 40]


d

dqt / dt = k(qe – qt) (9)


te

Where k2 is the equilibrium rate constant of pseudo second order (g/mg min) On integrating the

eq.(11), eq. (12) is obtained.


p

t/qt = 1/k2qe2 + (1/qe)t (10)


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To understand the applicability of the model, linear plots of t/qt versus t for chromium biosorption
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onto Cu-BTC were drown. The k2, the experimental qe and correlation coefficients (R2) were

calculated from these plots and given in Table 3.

The linear fit between the t/qt versus contact time (t) and calculated correlation coefficients

(R2) for pseudo second order kinetics model show that the chromium removals kinetic using Cu-

BTC can be approximated as pseudo second order kinetic (Table 3).

3.10. Thermodynamic studies

Thermodynamic parameters including the Gibbs energy (∆G), enthalpy (∆H), and entropy (∆S) are

the actual indicators for practical application of a biosorption process. According to the values of
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these parameters, what process will occur spontaneously can be determined. The thermodynamic

parameters were determined using the following equations : [34]

∆G = ∆H - T ∆S (11)

Kc = qe/Ce (12)

ln Kc = ∆S/R - ∆H/RT (13)

t
ip
Where Kc , R, and T are the equilibrium constant, the amount of metal adsorbed on the adsorbent of

cr
the solution at equilibrium (mol/L), the equilibrium concentration of metal in the solution (mol/L),

the gas constant (8.314 J/mol K), and the absolute temperature (K), respectively. By plotting a graph

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of ln Kc versus 1/T, the values ∆H and ∆S can be estimated from the slopes and intercepts. The

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obtained thermodynamic parameters were given in Table 4. Positive ∆H suggests endothermic

reaction. The positive value of ∆S suggests the increased randomness at the solid/solution interface
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during the biosorption of chromium onto Cu-BTC. The negative values of ∆G imply the spontaneous

nature of the biosorption process. Furthermore, the decrease in the values of ∆G with the increasing
d

temperature indicates the biosorption is more spontaneous at higher temperatures. Generally, the
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change in free energy for physisorption is between -20 and 0 kJ/ mol, but chemisorption is in a range
p

of -80 to -400 kJ/mol [41]. The values of ∆G obtained in this study are within the ranges of the
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physisorption mechanism.
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Table 4. Thermodynamic constant for chromium biosorption onto Cu-BTC


ΔG (kJ/mol)
ΔH ΔS
Metal R2 T (K)
(kJ/mol) (J/molK)
298 308 318 328 338
Cr 66 107 0.986 -4 -10 -12 -18 -21

4. Conclusion.

In this research, the preparation, characterization and chromium biosorption properties of

biocompatible adsorbent (Cu-BTC) were investigated. Cu-BTC was studied using Fourier transform

infra-red (FTIR), XRD and SEM analysis. Chromiums were used as model pollutants. It was shown

that Cu-BTC has effective biosorption capacity for the removal chromium from aqueous solutions.
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At alkaline pH, the number of negatively charged sites increased which favored adsorption of metal.
With the increase of adsorbent dosage, the removal efficiency steadily increased for three metals.

This can be attributed to increased adsorbent surface and availability of more adsorption sites. The

results showed metal adsorption on Cu-BTC is a slow process. It can be attributed that at the initial

stage of adsorption unfilled surface sites are available, and once equilibrium is attained, the

remaining unfilled sites are difficult to be full, probably caused by the repellent forces between the

t
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heavy metal molecules.

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Acknowledgement
The authors thank Kurdistan University of Medical Sciences for their guidance and support. This

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work is funded by 2014 Yeungnam University Research Grant.

References
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[1] A. Rao, A. Bankar, A.R. Kumar, S. Gosavi, S. Zinjarde, Journal of contaminant hydrology, 146 (2013): 63-73.
[2] D. Sidiras, D. Politi, F. Batzias, N. Boukos, International Journal of Environmental Science and Technology, 10
(2013): 1337-1348.
[3] S. Yokoyama, K. Okazaki, J. Sasano, M. Izaki, in: THE IRAGO CONFERENCE 2013, AIP Publishing, 2014, pp.
d

181-189.
[4] S. Khedr, M. Shouman, N. Fathy, A. Attia, ISRN Environmental Chemistry, 2014 (2014).
[5] J. Chen, X. Hong, Y. Zhao, Q. Zhang, Water Science & Technology, 70 (2014): 678-684.
te

[6] R. Khosravi, M. Fazlzadehdavil, B. Barikbin, A.A. Taghizadeh, Applied Surface Science, 292 (2014): 670-677.
[7] H. Teng, S. Xu, C. Zhao, F. Lv, H. Liu, Separation Science and Technology, 48 (2013): 1729-1737.
[8] K. Liu, J.-Y. Liu, Y.-B. Xie, J.-Q. Deng, G.-H. Huang, Plating & Finishing, 3 (2013): 015.
p

[9] Y. Sun, Q. Yue, B. Gao, Y. Gao, Q. Li, Y. Wang, Chemical Engineering Journal, 217 (2013): 240-247.
[10] K.S. Kumar, S. Roy, Development, 25 (2013): 27.
ce

[11] H. Deveci, Y. Kar, Journal of Industrial and Engineering Chemistry, 19 (2013): 190-196.
[12] A. Kundu, G. Redzwan, J.N. Sahu, S. Mukherjee, B.S. Gupta, M.A. Hashim, BioResources, 9 (2014): 1498-1518.
[13] N.A. Khan, Z. Hasan, S.H. Jhung, Journal of hazardous materials, 244 (2013): 444-456.
[14] T. Liu, J.X. Che, Y.Z. Hu, X.W. Dong, X.Y. Liu, C.M. Che, Chemistry-A European Journal, (2014).
Ac

[15] J. Gaur, S. Jain, R. Bhatia, A. Lal, N.K. Kaushik, Journal of thermal analysis and calorimetry, 112 (2013): 1137-
1143.
[16] E. Haque, J.W. Jun, S.H. Jhung, Journal of hazardous materials, 185 (2011): 507-511.
[17] X.-X. Huang, L.-G. Qiu, W. Zhang, Y.-P. Yuan, X. Jiang, A.-J. Xie, Y.-H. Shen, J.-F. Zhu, CrystEngComm, 14
(2012): 1613-1617.
[18] M. Carboni, C.W. Abney, S. Liu, W. Lin, Chemical Science, 4 (2013): 2396-2402.
[19] H. Li, M. Eddaoudi, M. O'Keeffe, O.M. Yaghi, Nature, 402 (1999): 276-279.
[20] T. Düren, Y.-S. Bae, R.Q. Snurr, Chemical Society Reviews, 38 (2009): 1237-1247.
[21] R. El Osta, M. Feyand, N. Stock, F. Millange, R.I. Walton, Powder Diffraction, 28 (2013): S256-S275.
[22] A. Puškarić, I. Halasz, J. Kontrec, J. Bronić, in: 5th Serbian-Croatian-Slovenian Symposium on Zeolites, 2013.
[23] Y. Yue, A.J. Binder, R. Song, Y. Cui, J. Chen, D.K. Hensley, S. Dai, Dalton Transactions, (2014).
[24] A.M. Fracaroli, H. Furukawa, M. Suzuki, M. Dodd, S. Okajima, F. Gándara, J.A. Reimer, O.M. Yaghi, Journal of
the American Chemical Society, 136 (2014): 8863-8866.
[25] C. Brozek, M. Dincă, american Chemical Society, 135 (2013): 12886-12891.
[26] N. Zhang, X. Yang, X. Yu, Y. Jia, J. Wang, L. Kong, Z. Jin, B. Sun, T. Luo, J. Liu, Chemical Engineering Journal,
252 (2014): 220-229.
[27] X. Li, L. Zheng, L. Huang, O. Zheng, Z. Lin, L. Guo, B. Qiu, G. Chen, Journal of Applied Polymer Science, 129
(2013): 2857-2864.
[28] C. Ng, J.N. Losso, W.E. Marshall, R.M. Rao, Bioresource technology, 85 (2002): 131-135. Page 15 of 18
[29] R.L. McRae, R.L. Phillips, I.B. Kim, U.H.F. Bunz, C.J. Fahrni, Journal of the American Chemical Society, 130
(2008): 7851-7853.
[30] S.K. Das, J. Bhowal, A.R. Das, A.K. Guha, Langmuir, 22 (2006): 7265-7272.
[31] K.K.H. Choy, J.F. Porter, G. Mckay, Chemical Engineering Journal, 103 (2004): 133-145.
[32] Q.Y. Cai, C.H. Mo, Q.T. Wu, Q.Y. Zeng, A. Katsoyiannis, J.F. Férard, Journal of hazardous materials, 142 (2007):
535-542.
[33] N.M. Mahmoodi, Journal of Chemical & Engineering Data, 56 (2011): 2802-2811.
[34] N.M. Mahmoodi, B. Hayati, H. Bahrami, M. Arami, Journal of Applied Polymer Science, 122 (2011): 1489-1499.
[35] Woodard, I. Curran, Industrial waste treatment handbook, Butterworth-Heinemann, 2006.
[36] E.R. Alley, Water quality control handbook, McGraw-Hill, 2007.

t
[37] C. Quintelas, E. Sousa, F. Silva, S. Neto, T. Tavares, Process Biochemistry, 41 (2006): 2087-2091.

ip
[38] Y. Ho, C. Chiang, Adsorption, 7 (2001): 139-147.
[39] H. Yuh-Shan, Scientometrics, 59 (2004): 171-177.
[40] Y.S. Ho, G. McKay, Water Research, 34 (2000): 735-742.

cr
[41] Ö. Gerçel, A. Özcan, A.S. Özcan, H.F. Gerçel, Applied surface science, 253 (2007): 4843-4852.

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Cu-BTC metal-organic frameworks (MOFs) prepared, characterized, and tested for chromium removal

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Graphical Abstract

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Highlights

 Cu-BTC Metal-organic frameworks prepared for treatment of chromium waste water


 Kinetic and thermodynamic analyses performed experimentally and analytically
 Mechanism for chromium adsorption onto Cu-BTC investigated
 Reusability of Cu-BTC for chromium removal reported

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