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CanakkaleOnsekiz Mart University, Chemistry Department, Faculty of Sciences and Arts, Terzioglu Campus, 17100 Canakkale, Turkey
Nanoscience and Technology Research and Application Center (NANORAC), Terzioglu Campus, 17100 Canakkale, Turkey
c
Istanbul Technical University, Chemical Engineering Department, Ayazaga Campus, 34469 Maslak, Istanbul, Turkey
b
H I G H L I G H T S
c
c
c
G R A P H I C A L
A B S T R A C T
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 14 April 2012
Received in revised form
5 July 2012
Accepted 23 July 2012
Available online 1 August 2012
A hydrogel prepared from 2-acrylamidoglycolic acid monohydrate (AAGA), denoted by p(AAGA), was
used for Co and Ni nanoparticle preparation within the hydrogel matrix. The p(AAGA)M (M: Co, Ni)
composite system was also shown to be capable of carrying out an aqueous reaction effectively, i.e., the
hydrolysis of NaBH4 for hydrogen generation. The reaction kinetics are investigated under different
reaction conditions and various parameters, such as initial NaBH4 concentration, temperature, catalyst
amounts and types, affecting the hydrolysis process of NaBH4 were evaluated. The activation energies
for the hydrolysis of NaBH4 were calculated to be 43.77 kJ mol 1 and 26.62 kJ mol 1for p(AAGA)Ni
and p(AAGA)Co catalyst systems, respectively. Even after seven repetitive uses p(AAGA)Co composite
catalyst system had 100% conversion with 95% activity. More importantly, the p(AAGA)Co system has
proven to have very good storage capacity, e.g., after 30-day storage time, p(AAGA)Co had no loss in
conversion and had 68% catalytic activity.
& 2012 Elsevier Ltd. All rights reserved.
Keywords:
Hydrogel-reactor
Microreactor
Hydrogen production
Catalysis
Catalyst support
Energy
1. Introduction
The recent progress in material science has provided materials
with unique properties and versatile applications ranging from
biomedical applications to catalysis (Ngah and Hanaah, 2008;
Arico et al., 2005; Sud et al., 2008; Moriarty, 2001; Gleiter, 2000;
Konstantatos and Sargent, 2010). Although multi-functional
n
Corresponding author at: CanakkaleOnsekiz Mart University, Chemistry
Department, Faculty of Sciences and Arts, Terzioglu Campus, 17100 Canakkale,
Turkey. Tel.: 90 286 218 0018 2041; fax: 90 286 218 1948.
E-mail address: sahiner71@gmail.com (N. Sahiner).
0009-2509/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2012.07.032
materials prepared from the combination of two or more segments provide additive advantages, a single material that is smart
and capable of multi-tasking is of great signicance. From this
aspect, hydrogels are assumed to be exible and tunable materials with their specic functionality, block topology in specic
environments (Tsitsilianis, 2010; Zeng et al., 2010; Sahiner, 2006).
The benet of smaller sizes of nanomaterials is somewhat
retarded by their known shortcomings (Ngah and Hanaah,
2008; Arico et al., 2005; Sud et al., 2008). The major concern is
to provide maximum activity while preserving stability for longer
time periods especially in industrial applications of nanomaterials
(Jiang et al., 2010; Tarascon and Armand, 2001; Wu et al., 2010;
Paek et al., 2009). Therefore, novel materials that can provide the
possibility of harvesting new sources of environmentally benign
energy from stable hydrogen storage compounds such as metal
hydrides are in demand. The search for this type of material is
increasing exponentially as oil resources are depleting (UFOP,
2008; European Union, 2006). These novel materials can be
hydrogels embedding metal nanocatalysts that can hydrolyze
metal hydrides in aqueous media. Due to environmental concerns, the research into clean energy is escalating (Hennebel et al.,
2011). Therefore, the use of hydrogel as an environmentally
friendly material for in situ metal nanoparticle preparation and
as a reactor for hydrolysis of metal hydrides for hydrogen
generation in aqueous media is appealing. Hydrogen as a clean
energy material can be obtained from resources using a variety of
materials; such as glucose (Zhang et al., 2011), glycerol (Vajani
et al., 2011), methane (Pant et al., 2011), and various hydrolysis
materials (Kim et al., 2011; Hansen et al., 2011, Ozay et al.,
2011a). In the hydrolysis of sodium borohydrides (NaBH4), metal
nanoparticles such Co, Ni, Pd and so on are generally employed
(Ozay et al., 2011b, 2011c; Sahiner, 2006; Sahiner et al.,
2011a,b,c). Hydrogel can be used for metal nanoparticle preparation providing a hydrophilic soft and exible environment, as well
as a stabilizing milieu for the metal nanoparticle. The use of
hydrogel-M catalyst systems as reaction containers also provides
easy removal of the catalyst system from the reaction medium by
simple decantation. Previously, we reported the synthesis of
p(AAGA) hydrogel networks and their use in the preparation of
Ni, Co, Cu and Ag nanoparticles and in the reduction of 4-nitrophenol (Butun and Sahiner, 2011). Here, we report the Co or Ni
embedded p(AAGA)Co and p(AAGA)Ni hydrogel composite network utilization in the hydrolysis of NaBH4 in aqueous media.
NaBH4 was investigated as hydrogen storage material over the last
years, and according to the DOE No-Go recommendation (2007)
the main deciency of the NaBH4 systems is found the hydrogen
storage capacity. DOE hydrogen target as gravimetric density was
0.045 kg H2/kg system in 2010, and ultimate gravimetric density
was 0.075 kg/kg system (Muir and Yao, 2011). Researches continued
to investigate NaBH4 and found that its solid form has shown better
hydrogen storage capacity than traditional systems. Murugesan and
Subramanian (2009) asserted that reactants-only gravimetric hydrogen storage capacity was 10 wt% with 97% NaBH4 conversion. There
are also some drawbacks of those new systems although it improves
the gravimetric and volumetric hydrogen storage targets. The new
system requires the acid or catalyst precursor; therefore, the fuel
price will increase with this method. In addition, other alternative
methods were studied in order to challenge the issue of the DOEs
hydrogen storage targets and its high price. Kojima and Haga (2003)
demonstrated a system, which NaBO2 reacts with MgH2 under high
temperatures and pressures in order to give NaBH4 and MgO, as
products, by means of Si as reducing agent. According to this
mechanism by product NaBO2 is recycled using Mg during NaBH4
hydrolysis in fuel cell vehicles. This process reduces production cost
and acts as a hydrogen storage and production system. Kojima and
Haga (2003); Suda et al. (2005); Muir and Yao, (2011). Zhang et al.
(2007) investigated 1 kWe sodium borohydride generation system
(50% fuel cell efciency) and developed a one-dimensional/homogenous catalyst distribution model in a NaBH4 hydrolysis packed
bed reactor. The numerical model is based on both heat and mass
transfer and chemical kinetics theory. According to their results, the
model is found to be useful in optimizing hydrogen storage systems
using NaBH4. After DOEs No-Go recommendation was issued,
many researchers were tried to investigate alternative system
designs such as non-catalytic systems or catalyst precursor systems
in order to supply convenient ways for NaBH4 hydrolysis. We,
therefore, investigate to nd an alternative catalyst system to
generate hydrogen by NaBH4 hydrolysis because of its signicant
115
properties which are still in interest of for other industrial application such as hydrogen powered stations/vehicles and turbines for
electricity, as gas, or as burning fuel, and as hydrogenation of
chemicals and fertilizer industry and so on.
116
P(AAGA)
P(AAGA)-M
+n
NaBH
NaBH
P(AAGA)-M
M: Co or Ni
Fig. 1. Schematic representation of in situ metal particle preparation in the
p(AAGA) hydrogel network, and their digital camera images.
reactions. Also, parameters coming from the reactor (in this case the
hydrogel network) such as the extent of crosslinker used during
hydrogel synthesis, the binding ability of the functional groups to
the metal ions, the nature of these functional groups and the
hydrophilicity of the network are the main factors in determining
the size, shape and structure of metal nanoparticles (Ozay et al.,
2011b, 2011c; Sahiner, 2006;Sahiner et al., 2011a,b
3.1. Factors affecting hydrogen generation rate
The hydrogen generation rate from hydrolysis of NaBH4 is
affected by various parameters such as the amount of NaOH in
the hydrolysis medium, the type of the metal nanoparticle, the
amounts of the catalysts, the NaBH4 concentration and reaction
temperatures. The hydrolysis reaction mechanism of NaBH4
catalyzed by hydrogelM (M: Co, Ni, Ru etc) given in Eq. (1)
NaBH4 2H2 O
Hydrogel-M
!
M:Co, Ni etc
NaBO2 4H2
p(AAGA)-Co
117
p(AAGA)-Ni
Fig. 2. TEM images of Co and Ni nanoparticles inside the p(AAGA) hydrogel network.
% 0 NaOH
% 1.0 NaOH
% 5.0 NaOH
% 10 NaOH
300
200
100
10
15
20
25
Time (min)
p(AAGA)-Co
p(AAGA)-Ni
control
300
Volume of Hydrogen (mL)
200
100
10
20
30
40
50
60
70
Time (min)
Fig. 3. (a) The effect of the amount of NaOH on the hydrolysis of NaBH4. [Reaction
conditions: 0.2 g p(AAGA)Co composite containing 18.4 mg Co nanoparticles,
50 mL 50 mM NaBH4 at 30 1C, 1000 rpm mixing rate.] (b) The effect of Co and Ni
metal nanoparticles with control on the hydrolysis of NaBH4 [Reaction conditions:
0.2 g p(AAGA)Co composite containing 18.4 mg metal nanoparticles; 50 mL
50 mM NaBH4 at 30 1C with 5 wt% NaOH, 1000 rpm mixing rate].
the gure that the H2 production rate does not change with the
increase in the amount of NaBH4. Therefore, the hydrolysis
reaction of NaBH4 is zero order with respect to NaBH4 concentration in reaction media under the investigated conditions.
3.2. Catalytic activity of the p(AAGA)Co catalyst systems
For industrial applications, catalytic systems are required to
meet certain criteria in terms of selectivity, quality, time, storage,
durability, environmental safety and so on. Therefore, the
118
Conversion
Activity
100
80
200
60
9.2 mg
300
18.4 mg
100
40
36.8 mg
20
55.2 mg
73.6 mg
10
20
30
Conversion
100
150 mM
800
Activity
80
600
60
40
400
20
200
0
0
10
20
30
Initial
40
Time (min)
Fig. 4. (a) The effect of the amount of catalyst on the hydrolysis of NaBH4.
[Reaction conditions: p(AAGA)Co composite containing 9.273.6 mg Co nanoparticles; 50 mL50 mM NaBH4 at 30 1C with 5 wt% NaOH, 1000 rpm mixing rate.]
(b) The effect of NaBH4 on the hydrolysis of NaBH4. [Reaction conditions: 0.2 g
p(AAGA)Co composite containing 18.4 mg Co nanoparticles; 50 mL 50150 mM
NaBH4 at 30 1C with 5 wt% NaOH, 1000 rpm mixing rate.]
10
20
30
Number of days
Fig. 5. (a) Repetitive use of p(AAGA)Co catalyst in hydrolysis of NaBH4, and (b)
the change in the activity and conversion of the catalyst with time [reaction
conditions: 0.2 g p(AAGA)Co composite containing 18.4 mg Co nanoparticles;
50 mL 50 mM NaBH4 at 30 1C with 5 wt% NaOH, 1000 rpm mixing rate].
300
Volume of Hydrogen (mL)
100 mM
Number of usage
Time (min)
50 mM
40
200
30C
40C
50C
100
60C
70C
10
15
20
Time (min)
Fig. 6. The effect of temperature on the hydrolysis of NaBH4 [reaction conditions:
0.2 g p(AAGA)Co containing 18.4 mg Co nanoparticles; 50 mL 50 mM NaBH4 at
30 1C with 5 wt% NaOH, 1000 rpm mixing rate].
0.06
30 0C
C (mol/L)
40 0C
0.04
50 0C
60 0C
70 0C
0.02
0
0
12
16
Time (min)
-3
y = -3201.9x + 5.1618
R = 0.9794
ln k
-4
-5
-6
0.0028
0.003
0.0032
0.0034
1/T
-9.5
Table 1
The activation parameters and rate constants at different temperatures for the
hydrolysis of NaBH4 by hydrogel metal composite catalysts.
Compound
y = -2879.8x - 1.614
R = 0.9749
-10
ln (k/T)
119
-10.5
0.003
0.0032
0.0034
1/T
Fig. 7. (a) The effect of temperature on the hydrolysis of NaBH4, (b)
lnkvs1=T(Arrhenius equation), and (c) ln (k/T) vs 1/T (Eyring equation). [Reaction
conditions: p(AAGA)Co containing 18.4 mg Co nanoparticles; 50 mL 50 mM
NaBH4 at 30 1C with 5 wt% NaOH, 1000 rpm mixing rate.]
DS#
R2
(J mol 1 K 1)
P(AAGA)
Ni
30
40
50
60
70
0.0011
0.0015
0.0037
0.0052
0.0074
43.77
41.09
166.45
0.9921
0.9907
0.9939
0.9971
0.9982
P(AAGA)
Co
30
40
50
60
70
0.0048
0.0056
0.0090
0.0116
0.0156
26.62
23.94
210.96
0.9918
0.9931
0.9880
0.9890
0.9908
-11
-11.5
0.0028
k
Ea
DH#
T
1
1
1
(1C) (min ) (kJ mol ) (kJ mol )
120
4. Conclusion
It was shown with investigation that p(AAGA) hydrogel can be
used as a template to prepare Co and Ni nanoparticles within the
hydrogel network by loading these metal ions from aqueous
solutions followed by reduction with NaBH4 in situ. The prepared
p(AAGA)-Co and p(AAGA)Ni composite systems were shown to
be very effective in the hydrolysis of NaBH4 to produce hydrogen
from aqueous media. It was found that the hydrolysis reaction is
zero order with respect to NaBH4 concentration and rst order
with respect to catalyst amount for both catalyst systems. By
comparing the activation parameters for the hydrolysis of NaBH4
for both catalysts, it was found that Co-containing catalyst is
faster than Ni catalyst systems between 30 and 70 1C. As the
reusability of these materials in terms of catalytic performance
and storage capacities are important parameters for industrial
applications, the hydrogelM catalyst systems were found to be
very effective, and even after the 7th use, 100% conversion and
95% activity were obtained. Moreover, after 30 day storage time,
p(AAGA)Co catalyst system showed no loss in conversion and
68% catalytic activity. Therefore, the use of hydrogel p(AAGA)
matrices to prepare different catalysts is promising and offers
great potential for the next generation of catalyst systems for
synthesis, storage and different purposes, e.g., for the generation
of hydrogen energy and in other aquatic reactions.
Acknowledgments
This work is supported by The Scientic and Technological
Research Council of Turkey (110T649). N. Sahiner greatly acknowledges to the Turkish Academy of Science for the partial support
under 2008 TUBA-GEBIP program and National Boron Research
Institutes of Turkey.
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