Professional Documents
Culture Documents
A soft hydrogel reactor for cobalt nanoparticle preparation and use in the
reduction of nitrophenols
Nurettin Sahiner a,b, , Hava Ozay a , Ozgur Ozay a , Nahit Aktas c
a
b
c
Canakkale Onsekiz Mart University, Faculty of Sciences and Arts, Chemistry Department, Terzioglu Campus, 17020 Canakkale, Turkey
Nanoscience and Technology Research and Application Center (NANORAC), Terzioglu Campus, 17020 Canakkale, Turkey
Yuzuncu Yil University, Faculty of Engineering, Chemical Engineering Department, 65080 Van, Turkey
a r t i c l e
i n f o
Article history:
Received 14 July 2010
Received in revised form 1 September 2010
Accepted 11 September 2010
Available online 20 October 2010
Keywords:
Hydrogel-templates
Flexible hydrogel-reactor
In situ nanoparticle formation
Hydrogel-reaction vessel
Hydrogel-nanocomposites
Co nanoparticles
a b s t r a c t
Bulk poly(2-acrylamido-2-methyl-1-propansulfonic acid) (p(AMPS)) hydrogels were prepared by irradiation of an aqueous solution of AMPS in the presence of crosslinker and photoinitiator. These p(AMPS)
hydrogel networks were utilized for in situ cobalt nanoparticle synthesis by reduction of metal ions
absorbed into the hydrogel network with a reducing agent, i.e., NaBH4 . TEM images conrmed that Co
particles are about 100 nm in size. The hydrogel network with embedded Co nanoparticles was utilized
as a catalyst in the reduction of 4-nitrophenol (4-NP) and 2-nitrophenol (2-NP) in aqueous media in the
presence of an excess amount of NaBH4 . The kinetics of the reduction reaction under different reaction
conditions was investigated to determine the activation parameters. Activation energies are 27.8 kJ mol1
and 39.3 kJ mol1 for 4-NP and 2-NP, respectively. It was found that hydrogelCo composites were 99%
active after 5 days storage.
2010 Elsevier B.V. All rights reserved.
1. Introduction
The increased use of metal nanoparticles in many advanceddesign devices in the elds of optics, microelectronics, sensors,
information storage, catalysts and nanoelectronics urge the
researcher to seek out new approaches to their synthesis [15].
There is a high demand for metal nanoparticles or nanoclusters that
are versatile in size, shape and morphology and that surmount the
main issues in the use of bare metal nanoparticles as a catalyst.
To overcome these major problems such as aggregation, oxidation and inactivation of metal nanoparticles, numerous preventive
measures have been employed. The utilization of supports such
as polymers, silicates, resins, alumina and zeolites is amongst the
some of the measures taken in the use of metal nanoparticles or
nanoclusters as catalysts [1,410].
Hydrogels as three-dimensional hydrophilic polymeric networks can provide unique environments for the preparation
and protection of metal nanoparticles. That hydrogels are threedimensional, water-swollen, crosslinked, hydrophilic polymer
chains makes them especially suitable. The polymer chains in the
138
139
Fig. 1. p(AMPS) hydrogel network and its digital camera images (a) in DI water, and (b) Co(II) ion-absorbed p(AMPS) hydrogel network, and (c) Co(II) absorption isotherm.
In the rst method, the metal ion absorption was determined from
the solution (Fig. 1(c)) and found to be 128.1 mg Co(II) absorbed
per gram dry p(AMPS) hydrogel. The amount of absorbed Co(II)
ion was calculated by subtracting the amount of Co(II) remaining in solution after absorption from the initial concentration of
Co(II) ions determined by ICP-AES measurements. In the second
method, the prepared p(AMPS)Co composite system was treated
with 100 mL 5 M HCl three times to dissolve Co metal particles,
and the amount of the Co(II) ion was determined as 124.3 mg/g
dry p(AMPS) hydrogel. Both methods gave good correlation. Moreover, the amount of Co metal particles was also determined with
themogravimetric measurements by comparing empty p(AMPS)
hydrogel with p(AMPS)Co hydrogel composite systems. Thermograms were taken under nitrogen ow to avoid oxidation on
heating up to 1200 C. As illustrated in Fig. 3, the amount of metal
nanoparticles in p(AMPS) hydrogel is about 22.7% (0.5) by weight.
It is possible that this weight may not be completely pure Co
140
Fig. 2. Representation of Co nanoparticle formation inside p(AMPS) hydrogel network (a) digital camera, and (b) TEM images of p(AMPS)Co composites.
100.0
p(AMPS)
80.0
p(AMPS)-Co
TG %
40.0
22.7 %
20.0
0.0
200
400
600
800
1000
Temp Cel
Fig. 3. TG thermogram of p(AMPS) and p(AMPS)Co composites.
Due to the important application of the reduced forms of nitroaromatic compounds in pharmacy, agriculture, biomedicine and
many other industries, novel catalyst systems that can operate in
very different environments are of great signicance [17,18]. For
instance, many important analgesic and antipyretic pharmaceuticals such as paracetemol, acetanilide and phenacetin are produced
from 4-aminophenol obtained from the reduction of 4-nitrophenol
[20,21]. In this investigation we prepared Co metal nanoparticles
inside environmentally friendly hydrogels, and demonstrated the
use of these composite systems in the reduction 4-NP and 2-NP
in the presence of an excess amount of aqueous NaBH4 (20-fold
excess of NaBH4 compared to 4-NP and 2-NP). Both reagents have
adsorption maxima at 400 and 414 nm, respectively, in the reaction
mixture and the decreases in these absorption bands were tracked
by UVVis spectrophotometers. Fig. 4(a) illustrates the reduction
141
a 0.016
30 0C
40 0C
50 0C
60 0C
C (mol/l)
0.012
0.008
0.004
0
10
15
20
Time (min)
25
-4.5
35
30 0C
40 0C
50 0C
60 0C
-5.5
ln C
30
-6.5
-7.5
-8.5
k (min -1)
0.12
0.08
0.04
0.01
0.02
0.03
0.04
0.05
0.06
0.07
10
15
20
25
30
35
Time (min)
Fig. 6. (a) The change in the concentration of 4-NP with time in reduction reaction by p(AMPS)Co catalyst system in the presence of aqueous NaBH4 with
reduction, and (b) ln c vs time of the same graph. (Reaction conditions: 50 mL [4NP] = 1.44 102 mol/L, [NaBH4 ] = 2.88 101 mol/L, 6.22 mg catalyst, 750 rpm.)
when more than 20-fold excess of NaBH4 is used, there is no significant change in the rate constants observed. Fig. 6(a) illustrates the
decrease in the concentration of 4-NP at different temperatures,
and the constructed ln Ct graph is shown in Fig. 6(b). A good linear
correlation, as seen in Fig. 6(b), conrms that the reduction reactions comply with rst order reaction kinetics. Similar results were
also obtained for 2-NP with p(AMPS)Co catalyst systems (data are
not shown). The total turnover frequency (TOF) was calculated for
4-NP based on Fig. 6 between 30 and 60 C and found between 0.213
and 0.568 mol 4-NP/mol Co.min that is comparable to the silver
nanoshell-coated cationic polystyrene beads used as solid phase
catalyst for the reduction of 4-NP [26].
The pseudo-rst order rate constants (k) for the reactions of
4-NP and 2-NP were calculated and are listed in Table 1. The
activation parameters for both reduction reactions with the synthesized p(AMPS)Co catalyst systems were calculated using the
well-known Arrhenius (Eq. (1)) and Eyring equations (Eq. (2)) as
shown, and their individual constructed ln k vs 1/T, and ln(k/T) vs
1/T, graphs are shown in Fig. 7(a) and (b), respectively.
ln k = ln A
ln
0.16
k
= ln
T
E
a
RT
k
B
S #
H #
R
R
(1)
1
T
(2)
142
Table 1
The change in the reduction rate constants of 4-NP and 2-NP with different temperatures and activation parameters in catalysis with p(AMPS)Co composites.
Compound
4-Nitrophenol
2-Nitrophenol
Temperature ( C)
k (min1 )
30
40
50
60
30
40
50
60
0.12
0.16
0.23
0.31
0.06
0.11
0.16
0.25
Ea (kJ mol1 )
S# (J mol1 K1 )
27.8
25.1
180.2
39.3
36.7
147.2
Reaction conditions: 50 mL [4-NP] and [2-NP] = 1.44 102 mol/L, 6.22 mg catalyst, 750 rpm.
Table 2
The change in the conversion and activity with repetitive use of p(AMPS)Co composite catalyst system in sequential reactions.
-1
4-NP
2-NP
-1.5
ln k
Use #
-2
% conversion
% activity
-2.5
-3
2.900E-03
3.000E-03
3.100E-03
3.200E-03
3.300E-03
3.400E-03
100
100
98
94
98
91
97
83
97
78
Reaction conditions: 50 mL [4-NP] = 1.44 102 mol/L, [NaBH4 ] = 2.88 101 mol/L,
6.22 mg catalyst, 750 rpm, 30 C.
1/T
ln (k/T)
-6
4-NP
2-NP
-6.5
-7
-7.5
-8
-8.5
-9
2.900E-03
3.000E-03
3.100E-03
3.200E-03
3.300E-03
3.400E-03
1/T
Fig. 7. (a) ln k1/T graphs for 4-NP and 2-NP (Arrhenius Eq. (1)), and (b) ln(k/T)1/T
graphs (Erying Eq. (2)) by p(AMPS)Co composites. (Reaction conditions: 50 mL [4NP] = 1.44 102 mol/L, 6.22 mg catalyst, 750 rpm, 30 C.)
To determine whether the amount of catalyst affected the reduction rates or not, the amount of catalyst varied by reducing the
amount of 4-NP used with 20-fold excess NaBH4 at 30 C. The
amount of Co nanoparticles inside the used p(AMPS) hydrogels was
3.11, 6.22, 9.33 and 12.44 mg, and the plotted graphs for the reduction rate constant of 4-NP vs the amount of catalyst are illustrated in
Fig. 8. The reduction reactions were also performed in the absence
of p(AMPS)Co catalyst system. No reaction was observed as no
change at 400 nm was detected for 4-NP in the UVVis absorption
spectrum. This is in accordance with the literature which states
that without a catalyst, the reduction of 4-NP is thermodynamically
0.24
k (min-1)
0.2
0.16
0.12
Table 3
The shelf-life measurements of the same p(AMPS)Co catalyst systems at different
storage time intervals.
0.08
0.04
Days
0
0
10
12
14
Initial (0)
% conversion
% activity
100
100
1
100
100
10
99
98
93
91
15
90
79
Reaction conditions: 50 mL [4-NP] = 1.44 102 mol/L, [NaBH4 ] = 2.88 101 mol/L,
6.22 mg catalyst, 750 rpm, 30 C.
143