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Canakkale Onsekiz Mart University, Faculty of Sciences and Arts, Chemistry Department, Terzioglu Campus, 17020, Canakkale, Turkey
Gazi University, Institute of Science and Technology, Mechanical Engineering Department, 06500, Ankara, Turkey
c
Yuzuncu Yil University, Faculty of Engineering, Chemical Engineering Department, 65080, Van, Turkey
d
Nanoscience and Technology Research and Application Center (NTRAC), Terzioglu Campus, 17020, Canakkale, Turkey
b
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abstract
Article history:
absorbed Co (II), Cu (II) and Ni (II) ions inside hydrogel networks prepared from 2-acryl-
9 April 2011
affecting the hydrolysis reaction such as the type of the metal, the amount of catalyst, the
initial concentration of AB, and temperature, were investigated. The activation energy
values in the hydrolysis reaction of AB solution in the presence p(AMPS)-Co, p(AMPS)-Cu
Keywords:
and p(AMPS)-Ni catalyst systems were calculated as Ea 47.7 kJ mol1, 48.8 kJ mol1 and
Hydrogen generation
52.8 kJ mol1, respectively. Thus, the catalytic activity of the metal nanoparticles prepared
Ammonia borane
inside the same hydrogel matrix was found to be Ni < Cu < Co.
Hydrogel nanoreactor
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
Catalysis
Hydrolysis
Hydrogel composites
1.
Introduction
(1)
AB releases hydrogen gas in the presence of a suitable
catalyst at room temperature according to the equation above
(Eq. (1)) [17e20]. Recently, numerous transition metal catalyst
systems such as: intrazeolite palladium(0) [17]; Co(0) [18], Rh(0)
[15,21] and Cu(0) nanoclusters [22]; water soluble polymer
stabilized Ni(0) [1], Rh(0) [16], Ru(0) [19,23] and Pd(0) [23]
nanoclusters; Cu/Co3O4 nanoparticles [2], hollow NieSiO2
* Corresponding author. Canakkale Onsekiz Mart University, Faculty of Sciences and Arts, Chemistry Department, Terzioglu Campus,
17020, Canakkale, Turkey.
E-mail address: sahiner71@gmail.com (N. Sahiner).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.04.140
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nanospheres [3], CoeB thin film [5], electroplated CoeP catalyst [6], magnetically recyclable Au@Co core-shell nanoparticles [9], PtxNi1-x nanoparticles [13], Co nanoparticles [24],
Pt- and Ni-based alloy catalysts [25]; monodispersed Ni
nanoparticles [26], SiO2 supported monodispersed Ni nanoparticles [27], Co nanospheres [28] and bimetallic AueNi
nanoparticles [29]; magnetically recyclable hollow CoeB
nanospindles [30] and montmorillonite immobilized Ru
nanoparticles [31] have been reported for use in the hydrolysis
reaction of AB. Direct utilization of metal nanoparticles as
catalyst is somewhat restricted due to aggregation and
destabilization [32,33]. To prepare a catalyst with better catalytic activities and to prevent aggregation generally supporting materials such as silicates [3,27e29], clays [31], zeolites
[15,17,18,21,22] and most recently hydrogels, have been
utilized [7,8,32e35]. Amongst these materials hydrogels
attract special attention due to characteristics such as
different functional groups in three-dimensional waterswollen, crosslinked hydrophilic polymeric networks
providing a unique environment for the preparation and
protection of metal nanoparticles. The anionic functional
groups eSO3 and eCOO in the hydrogel networks readily
form negative charges in aqueous environments to absorb
metal ions via electrostatic interactions and then reduce these
hydrogel bound metal ions to form metal nanoparticles.
Taking advantage of the flexible (swelling and shrinking
ability) advantages of hydrogel networks, various metal
nanoparticles or nanoclusters can be prepared in situ by
reduction of absorbed metal ions with suitable reducing
agents such as NaBH4 [7,8,32e35], providing an expanded
range of applications from environmental remediation to
biomedical applications [36e38].
Previously, our group reported the synthesis of p(AMPS)
hydrogel networks and its use in the preparation of Ni, Co, Fe,
and Cu nanoparticles and utilization of these particles in the
reduction of 2- and 4-nitrophenols [32,33]. The in situ prepared
Ni and Co nanoparticles in p(AMPS) hydrogel networks used as
catalyst in the hydrolysis of NaBH4 [7,8] were also reported. In
addition to Co and Ni metal nanoparticles, we report the
preparation of Cu nanoparticles in p(AMPS) networks and their
utilization as catalyst in the hydrolysis of AB in aqueous media.
Additionally, after using the p(AMPS)-M (M: Co, Ni, Cu) catalyst
system in the generation of hydrogen, the metal catalyst can be
readily removed from the hydrogel template and it can then be
reloaded with desired metal catalysts. The reaction kinetics
were investigated under different reaction conditions and
various parameters, such as AB concentration, temperature,
catalyst amount and type, affecting the hydrolysis processes of
AB were evaluated. The reaction was carried out at five
different temperatures to calculate the activation parameters.
The activity and repetitive usage of the catalystehydrogel
system was also investigated.
2.
Experimental
2.1.
Materials
2.2.
Hydrogel synthesis and in situ metal particles
preparation
P(AMPS) hydrogels were synthesized according to the procedure in the literature [7,8]. Synthesis of metal nanoparticles
inside the hydrogel network was carried out by using 100 mg
dry hydrogel according to the procedure in the literature
[7,8,32e35].
2.3.
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2.4.
3.
3.1.
Determination of the amount of metal nanoparticles
in p(AMPS) network and characterization
Previously, we reported in situ metal particle preparation in
crosslinked p(AMPS) hydrogel networks and showed that they
are highly porous visualized by cryo-SEM images (depending
on the crosslinking ratio, about 200 mm pore can be obtainable)
and the porosity of hydrogel networks can be controlled by the
amount of crosslinker used during hydrogel synthesis [34,35].
The metal nanoparticle content of p(AMPS) hydrogels was
determined via Thermogravimetric Analysis (SII TG/DTA
6300) and Inductively Coupled Plasma-Atomic Spectrometry
(Varian Liberty II AX Sequential ICP-AES) measurements
according to previously reported literature [7,8,32e35]. The
determined amount of Co (124 mg/g dry gel) and Ni (118 mg/g
dry gel) using ICP-AES according to previously reported literature was assumed in the experimental studies. To determine
the amount of metal nanoparticles inside p(AMPS) e.g., Cu,
p(AMPS)-Cu composite systems were treated with 5M 100 ml
HCl three times and the eluted Cu(II) concentration was found
to be 110 mg/g dry gel by ICP-AES according to literature
procedure. All TGA and ICP measurements are summarized in
Table 1. As can be seen in Table 1, ICP-AES always measured
metal nanoparticles lower than the TGA measurement. As
illustrated with ICP-AES measurements p(AMPS)-metal
composite systems contain some boron and sodium that
was included in the TGA measurements. As the TGA analysis
gave inorganic parts of the composites. i.e., metal, sodium and
boron, the determined amount of inorganic parts of the
composites is larger than the results obtained by ICP-AES
measurements. To further corroborate metal (Co, Cu and Ni)
particle formation, p(AMPS)-metal composites were ground
with mortar and pestle to form a powder, a drop of this
powder suspended in ethanol was placed on a formvar coated
TEM grid to microscopically visualize the metal particles in
the p(AMPS) network. According to the TEM images in previously reported literature [7,8,32,33], the obtained Co and Ni
nanoparticles are about 100 nm in size and Cu nanoparticles
have a wide variation from tens of nanometers to over
a hundredth of a nanometer. Fig. 1a shows the TEM image of
cobalt nanoparticles in p(AMPS) hydrogel network.
3.2.
The effect of metal species on the hydrogen
generation rate
In situ Co, Cu and Ni nanoparticles in p(AMPS) hydrogel
networks were used as catalyst in the hydrolysis reaction of
AB. For this purpose, 100 mg p(AMPS) hydrogel containing any
metal nanoparticle e.g., Co (12.4 mg), Cu (11.0 mg) or Ni
(11.8 mg), was used in the hydrolysis of 50 ml 50 mM AB at
30 C and 1000 rpm mixing rate. As shown in Fig. 1b, 186 ml
hydrogen gas was produced with p(AMPS)-Co composite
systems in approximately 25 min, whereas when p(AMPS)-Cu
and p(AMPS)-Ni were used they produced the same amount of
hydrogen in 65 min and 75 min, respectively. The reaction
rates relating to hydrolysis of AB were 637 (ml H2) (min)1 (g of
Co)1 for Co, 287 (ml H2) (min)1 (g of Cu)1 for Cu and 242 (ml
H2) (min)1 (g of Ni)1. Additionally, the total turnover
frequencies (TOF) were calculated for all p(AMPS)-metal
composites and were 1.43, 0.72 and 0.54 mol H2 (mol catalyst. min)1 for Co, Cu and Ni, respectively. In this investigation, the prepared p(AMPS)-Co composite showed better
catalytic activity in comparison with Cu and Ni particles
prepared by the same methods. Therefore, p(AMPS)-Co
p(AMPS)-Co
p(AMPS)-Cu
p(AMPS)-Ni
124.3 4.6
110.0 3.4
118.3 3.9
Catalyst
(mg)
B (mg)
22.5 3.7
24.9 3.2
23.3 4.1
Na (mg)
49.6 5.9
36.5 2.1
27.3 4.7
b
TG
Residue
(mg)
227 9
187 7
174 5
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3.4.
Fig. 1 e (a). The TEM image of hydrogel supported Co
nanoparticles. (b) The effect of metal species on AB
hydrolysis (50 mM 50 ml AB, 100 mg hydrogel-metal
composite (containing 12.4 mg Co0; 11.0 mg Cu0 and
11.8 mg Ni0), 30 C, 1000 rpm).
3.3.
The effect of the amount of catalyst on the
hydrolysis reaction of AB
To examine the effect of the catalyst on AB hydrolysis,
different amounts of Co nanoparticle-containing p(AMPS)-Co
composites weighing 50, 100, 150, 300 and 500 mg (containing
6.2, 12.4, 18.6, 37.2, 62.0 mg Co (0), respectively) were used in
the hydrolysis of 50 mM 50 ml AB at 30 C and 1000 rpm mixing
rate. As illustrated in Fig. 2, the plots of the hydrogen generation volume versus time, and hydrogen production rate with
amount of catalyst (the inset) show there is a almost linear
relationship between them. It is apparent from Fig. 2 that
186 ml hydrogen with 50 mg p(AMPS)-Co (containing 6.2 mg
Co) was produced in 42.5 min; on the other hand, the same
reaction took 5 min with 500 mg p(AMPS)-Co composite. A
tenfold increase in the amount of catalyst speeds the reaction
8.5 fold. The hydrogen production rates were 405, 637, 967,
1774 and 2921 (ml H2) (min)1 (g of Co)1 for 6.2, 12.4, 18.6, 37.2,
62.0 mg Co (0), respectively. Therefore, the increase in the
amount of catalyst increases the rate of hydrogen production
almost linearly for all the reactions performed under the same
conditions. The slight deviation from linear behavior could be
due to the interaction of the catalysts with each other, which
may hinder the reaction when used in larger amounts.
To inspect the effect of temperature on the hydrolysis reaction, the temperature range was chosen as 30e70 C with 10 C
increments. The temperature was fixed at the desired level in
an oil bath for 30 min, then the hydrolysis reaction was carried
out with 50 ml 50 mM AB using 100 mg p(AMPS)-Co composite.
All the reactions performed at the five temperatures
(30e70 C), generated an average of 186 ml H2 gas at each
temperature. As illustrated in Fig. 3, at 30 C the reaction was
completed in 27.5 min, whereas at 70 C the hydrolysis reaction was completed in about 3 min, almost 9 times faster than
the reaction at 30 C. The hydrogen production rates were
found in the range of 673e5878 (ml H2) (min)1 (g of Co)1 for
the temperatures between 30 and 70 C which is comparable
with the literature [18,39e41]. Similar experiments were also
carried out by using p(AMPS)-Cu and p(AMPS)-Ni catalyst
systems (data are not shown). The activation parameters for
the hydrolysis reactions of AB with p(AMPS)-Co, p(AMPS)-Cu
and p(AMPS)-Ni composite catalyst systems were calculated
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3.5.
The effect of AB concentration on the catalytic
hydrolysis reaction
In order to determine AB concentration effect on the hydrolysis rate, a series of experiments were carried out by using
four different AB concentrations, 25 mM, 50 mM, 100 mM, and
200 mM each with 50 ml volume using 100 mg p(AMPS)-Co
composite catalyst at 30 C. The produced H2 with time for
each AB concentration is shown in Fig. 4. As shown in the
figure, the amount of produced hydrogen gas changed
between 93 and 744 ml with p(AMPS)-Co composite systems in
approximately 12e80 min, whereas the hydrolysis rate did not
change. This indicates that the H2 production rate is independent from the concentration of AB. Therefore, the hydrolysis reaction is zero order with respect to the initial
concentration of AB.
3.6.
The reusability and shelf-life of p(AMPS)-Co catalyst
in the hydrolysis reaction of AB
Activation
Reference
Energy (kj mol-1)
34
44.3
12
39
56
13
18
51.8
22
34
27
70
63
54.4
39
40
41
52.8
This study
48.8
This study
47.7
This study
45.0
46.0
50.1
146.7
151.2
140.3
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%Conversion
%Activity
Initial (0)
10
100
100
100
100
100
98
100
96
100
93
3.7.
The reusability of p(AMPS) hydrogel networks and
reloading ability
One of the most important advantages of the used hydrogel
network in the preparation of metal nanoparticles is their
insolubility in harsh basic and acidic media. Therefore, these
hydrogel networks can be used repeatedly to prepare new
metal nanocatalysts after removing the first one from the
hydrogel network that has lost its catalytic activity for some
reason [7,8]. Fig. 6 summarizes the repreparation of the metal
nanocatalyst inside the same hydrogel network as the
continual usage of any catalyst system with time causes loss
of activity, a new catalyst of the same or different metal can be
prepared in the same network. Firstly, metal nanoparticles
can be dissolved from the hydrogel network with a suitable
acid without harming the hydrogel structure and reused for
the preparation of metal nanoparticles. As shown in Table 3,
after 10 days storage time p(AMPS)-Co catalyst system shows
93% catalytic activity. So this p(AMPS)-Co composite hydrogel
was treated with 5 M HCl and reused for Co nanoparticle
preparation. This reloaded Co nanoparticle hydrogel showed
100% catalytic activity and 100% conversion on first use. The
preparation of Co, Ni and Cu nanoparticles is very simple and
economically feasible. In addition, the method presented here
is very important when using expensive catalyst systems such
as Ru, Rh, Pt, Ag, or Au. The loss of catalytic activity can be
regained after reloading them from the same matrices.
Therefore, it could be possible to use a catalyst many times
3.8.
The effect of hydrogen storage compound on
hydrolysis reaction
In order to compare the capacity of the storage materials,
NaBH4 and AB hydrolysis was carried out with the same
catalyst system, p(AMPS)-Co. As illustrated in Fig. 8, 50 mM
50 ml of the hydride compounds were used and NaBH4
provided much more hydrogen (246 ml) in 22 min than AB.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 8 2 0 9 e8 2 1 6
4.
Conclusion
8215
Acknowledgements
This work is supported by the National Boron Research Institute of Turkey under the grant: 2009C0237. N. Sahiner is also
grateful for support by the Turkish Academy of Science under
TUBA-GEBIP 2008 program.
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