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 8 ( 2 0 1 3 ) 7 7 7 e7 8 4

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Poly(acrylamide-co-vinyl sulfonic acid) p(AAm-co-VSA)

hydrogel templates for Co and Ni metal nanoparticle
preparation and their use in hydrogen production

Fahriye Seven a, Nurettin Sahiner a,b,*

a
Canakkale Onsekiz Mart University, Faculty of Sciences and Arts, Chemistry Department, Terzioglu Campus, 17100 Canakkale, Turkey
b
Nanoscience and Technology Research and Application Center (NANORAC), Terzioglu Campus, 17100 Canakkale, Turkey

article info abstract

Article history: P(AAM-co-VSA) hydrogel was prepared at different mole ratios form the corresponding
Received 24 September 2012 monomers and used in absorption of metal ions such as Co and Ni from aqueous envi-
Received in revised form ronments. Then, these bound metal ions within the hydrogel matrices were reduced to
19 October 2012 their metal nanoparticles by aqueous NaBH4 treatment. Finally, p(AAm-co-VSA)eM (M: Co
Accepted 20 October 2012 or Ni) composites were used as reactor in the hydrolysis of NaBH4 for hydrogen generation.
Available online 11 November 2012 The amounts of metal ions before and after metal nanoparticle formation were determined
by Atomic Absorption Spectroscopy (AAS). P(AAm-VSA) hydrogel showed greater absorp-
Keywords: tion tendency for Ni(II) ions than Co(II) ions, and the metal ion binding capacity of these
Hydrogen production hydrogels was increased with an increase in the amount of VSA in the copolymeric
Polymer composites hydrogel. It was also found that although the amount of Ni ions loaded into the hydrogel
Hydrogel matrices were more than Co ions, Co metal nanoparticle-containing hydrogel produced
Metal nanoparticle-embedded poly- hydrogen faster than Ni metal nanoparticle-containing hydrogel composites. The activa-
meric system tion energy for the Co nanoparticle-embedded p(AAm-co-VSA) was found as
34.505 kJ mol
1k
1, and other thermodynamic parameters were also calculated. The
p(AAm-co-VSA)eCo hydrogel can be used up to 5 times repetitively without any loss of
yield but with 55% of catalytic activity.
Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction (covalent) and secondary interactions (van der Waal, electro-

static, hydrogen bonding etc.) [5,6]. In hydrogen production,
Due to the decrease in the source of fossil fuels, and environ- generally a metal hydride, such as Ca2H, LiH, MgH2, LiAlH4,
mental concerns, the search for renewable and alternative KBH4, NaAlH4, NaBH4 and H3NBH3 was used as hydrogen carrier
energy sources has become mainstream [1e4]. Versatile mate- [8e12]. Amongst these hydrogen storage materials, NaBH4 is
rials, such as hydrogels for in situ metal nanoparticle prepara- most widely used as it has high hydrogen storage capacity,
tion and use as soft reactor, are momentous for hydrogen stability, and readily availability [13e22]. According to the
production especially for hydrogen generation in aquatic hydrolysis reaction shown below, the produced hydrogen is
environments. Hydrogels are water swollen hydrophilic poly- twice the hydrogen content of NaBH4 implying that half of the
mer chains connected to each other via primary bonds produced hydrogen is coming from water [16e19].

* Corresponding author. Canakkale Onsekiz Mart University, Faculty of Sciences and Arts, Chemistry Department, Terzioglu Campus,
17100 Canakkale, Turkey. Tel.: þ90 2862180018 2041; fax: þ90 2862181948.
E-mail address: [email protected] (N. Sahiner).
0360-3199/$ e see front matter Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2012.10.072
778 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 8 ( 2 0 1 3 ) 7 7 7 e7 8 4

catalyst (NaBH4, 96%, Merck) was used. NaOH (97%) and HCl (37.5%)
NaBH4 þ 2H2 O/NaBO2 þ 4H2
were used for acidic and basic solutions respectively.
This exothermic reaction can be carried out over a wide Throughout this investigation 18.3 MU cm DI water was used.
range of temperatures in the presence of various metal cata-
lysts [14,15]. It is well known that, surfactants, alumina, 2.2. Preparation of p(AAm-Co-VSA) hydrogel and
zeolites, clays and finally polymeric support materials have swelling studies
been widely employed for different metal nanoparticles
preparations [4,23e31]. Amongst the polymers, hydrogels Copolymeric hydrogels at various mole ratios of AAm to VSA
known as 3-D crosslinked polymer networks attract special (AAm:VSA); 4:1, 1:1.5, 1:1, 1:0.6, and 1:0.2; were prepared using
attentions. Due to the lavish number of metal-binding func- 0.5 mol% crosslinker (MBA) and 1 mol% initiator (APS) based
tional groups in the hydrogel networks, such as eSO3H, eOH
, on the total amounts of monomers. The precursor solution
eCOOH, eSH, and NH2, and the ability to tune the hydro- containing monomer, crosslinker, and accelerator was mixed
phillicity, and the porosity, hydrogel networks from different with APS just before placing in plastic straws. For simulta-
polymers have been intensively investigated for in situ metal neous polymerization and crosslinking reactions in the straw,
nanoparticle preparation [5e7,14,16,24e26]. As hydrogel can the reaction was continued for 8 h. After this time, the p(AAm-
uptake different metal ions from aquatic environments and co-VSA) hydrogels were cut to about 5 mm in length and
fix these metal ions within the hydrogel matrices, it is possible washed for 3 days with DI water by changing the wash water
to reduce them the corresponding metal nanoparticles with every 12 h to remove impurities. The cleaned p(AAm-co-VSA)
suitable reducing agents [5,7,25]. Moreover, the hydrogel hydrogels were dried at 60  C in an oven and stored in zip lock
template can have also additional characteristics such as bags for further use.
biocompatibility, environmental sensitivity and friendly, and To investigate the swellings in DI water, a certain weight of
have applications as drug delivery materials, in cosmetics, 0.5% crosslinker 1:1 and 1:1.5 mole ratio of p(AAm-co-VSA)
tissue engineering, and even separation of toxic species from hydrogels were placed in 50 ml DI water, and the weight
water for purification purpose [16,24,25]. increase with time was recorded by removing the swollen
In the current investigation, a novel copolymeric hydrogel hydrogel piece at certain time intervals, and weighing and
based on AAm and VSA was prepared at different mole ratios then placing back to swelling medium. These weight increase
as p(AAm-co-VSA). Earlier our group demonstrated the use of measurements were continued until no more the mass
homopolymeric hydrogels such as p(AMPS), p(SPM) and increase was reached. The percent swelling ratio S% was
p(AAGA) hydrogel use in metal nanoparticle preparation and determined using the following equation.
use in catalysis of various reactions [5,6,27,28,31]. Here, the
purpose of this investigation is to develop a copolymeric S% ¼ ðMt
Md Þ=Md  100 (1)
hydrogel as versatile tools for metal nanoparticle preparation where Mt and Md are the weight of hydrogel at time t and
and then efficient hydrogen generation from the hydrolysis of initial dried weight, respectively.
NaBH4. Hydrogels based on not metal ion-binding AAm and
metal ion-binding VSA were prepared in copolymeric form 2.3. Synthesis of cobalt and nickel nanoparticles inside
with different mole ratios. Then, the metal ions, such as Co(II) hydrogel network
and Ni(II) were loaded into the hydrogels by absorption from
metal salts solution and these metal ion loaded hydrogels The preparation of Co and Ni nanoparticles within the
were treated with NaBH4 to reduce these bind ions to metallic hydrogel network structure was reported previously
forms. Finally, the hydrogelemetal composites were used as [5,6,24,25,30]. To load the hydrogel with metal ions, about 0.1 g
catalyst in hydrogen generation from hydrolysis of NaBH4. It dried p(AAm-co-VSA) hydrogels were placed in 100 ml
was found that p(AAm-co-VSA)eCo catalyst system was more 500 ppm metal ion solutions e.g., Co(II) for about 24 h. The
effective than p(AAm-co-VSA)eNi for NaBH4 hydrolysis. metal ion loaded hydrogels were washed with DI for 3 h to
Various parameters affecting the reaction kinetics were remove the unbound metal ions inside the hydrogels and the
determined. bound metal ions were reduced to metallic forms by placing
them in 100 ml 0.2 M NaBH4 solution for 3 h. Upon completion
of reduction, the metal nanoparticle-containing hydrogels
2. Experimental were washed with DI again for 3 h. Finally, these metal
nanoparticle-containing hydrogels were used in the hydro-
2.1. Reagent lysis of NaBH4.

The monomers, acrylamide (AAm, 98%, Fluka) and vinyl 2.4. The determination of the amount of sulfur in hydrogels
sulfonic acid (VSA, 25%, SigmaeAldrich), the crosslinker, N,N0 - and nickel and cobalt nanoparticles in p(AAm-co-VSA)eM
methylenebisacrylamide (MBA, 99%, Acros), the initiator, composites
ammonium persulfate (APS, 99%, SigmaeAldrich), and the
accelerator, N,N,N0 ,N0 -tetraethylmethylenediamine (TEMED, The amount of sulfur (S) in dried p(AAm-co-VSA) hydrogels
98% Acros) were used in hydrogel preparation as received. were as wt% determined using an elemental analysis instru-
NiCl2.6H2O (97%, SigmaeAldrich) and CoCl2.6H2O (99%, Sig- ment (Leco SC-144DR).
maeAldrich) were used as metal ion sources. For the reaction To determine the thermal behavior and the amount of
of metal ions and hydrolysis reaction, sodium borohyride inorganic parts in the composite hydrogel, thermogravimetric
 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 8 ( 2 0 1 3 ) 7 7 7 e7 8 4 779

analysis (TGA) was carried out using a thermogravimetric ability to absorb metal ions. As illustrated in Fig. 1(a), a dried
analyzer (TGA/DTA-SII, 6300). In addition, for exact determi- hydrogel can swell in water as the sulfonyl groups can readily
nation of the amounts of metal ions Atomic Absorption develop negative charges by ionization (a strong acid) due to
Spectrophotometer (AAS, Thermo, ICA 3500 AA SPECTRO) was the chargeecharge repulsion on hydrogel network extensive
used. For TGA analysis, dried metal nanoparticle-containing swelling was attained. The degree of swelling is mainly gov-
hydrogel composites weighing about 3 mg were placed in erned by the amount of crosslinker used during synthesis and
the TGA pan and then heated up to 1200  C under N2 atmo- with the extent of functional groups depending upon the
sphere with a heating rate of 10  C/min. The weight loss swelling media. As the hydrogels were placed in different
against temperature was recorded and compared with that of metal ion solutions, they get the color of the metal ions (b) as
bare p(AAm-co-VSA) hydrogels. To determine the metal ion an indication of intake of that metal ion, and upon treatment
content via AAS measurements, certain amounts of metal with reducing agents; the corresponding metal nanoparticles
nanoparticle-containing hydrogels were treated with 50 ml are formed within the hydrogel matrices (c). As illustrated in
5 M HCl for 8 h three times and the elution solution was Fig. 2, the hydrogel p(AAm-co-VSA) (1:1.5) swells 27,000%
diluted 1/200 with DI, and the metal ions within these solu- much more than the hydrogel with (1:1) ratio which swelled
tions were determined by AAS. Each measurement was per- about 10,500% in DI, confirming that the greater the number of
formed using three different samples and results were eSO3H functional groups in the hydrogel network the more
determined as average values with standard deviations. the S% ratio. To determine the exact amounts of VSA in the
copolymeric structure, we carried out elemental analysis of
2.5. Catalysis

In hydrolysis of NaBH4, a certain weight of Co and Ni

nanoparticle-containing p(AAm-co-VSA) hydrogels were
placed in 50 ml 50 mM NaBH4 containing 5 wt% NaOH at
1000 rpm mixing rate. For example, 0.1 g p(AAm-co-VSA)eCo
hydrogel composite (containing 4.11 mg Co per g dried
hydrogel) at 30  C was chosen for NaBH4 hydrolysis reactions.
Various parameters affecting the hydrogen production such
as the amount of catalyst, the concentration of NaBH4 and the
hydrolysis reaction temperature were investigated.

2.6. The reusability of p(AAm-co-VSA)eCo catalyst

composites

The prepared p(AAm-co-VSA)eCo catalyst composites were

tested for reusability. For this purpose, 0.1 g p(AAm-co-VSA)e
Co (containing 4.111 mg Co) were used in hydrolysis of 50 ml
50 mM NaBH4 at 30  C, and the conversion and catalytic
activities were determined. Then, hydrogel catalyst system
washed with 500 ml water and again used in hydrolysis of
50 ml 50 mM NaBH4 at 30  C and these processes repeated five
times and every time conversion and activities were
determined.

3. Results and discussion

3.1. Characterization

As the prepared hydrogel contained different amounts of

eSO3H groups, the main group responsible for swelling, and
metal ions absorption, p(AAm-co-VSA) with different mole
ratios were employed in swelling experiments and metal ion
absorption studies. As the vinyl sulfonic acid monomer used
is very hard to polymerize separately because it contains 75 wt
% water, very dilute, the use of AAm and easy polymerizable
monomer afforded new copolymeric hydrogels. Additionally, Fig. 1 e The digital camera images of 0.5% crosslinked
the use of AAm monomer enhanced mechanical stability of p(AAM-co-VSA) hydrogels at 1:1.5 mole ratio (a) dried and
hydrogels, whereas VSA monomer provided metal loading swollen hydrogels, (b) Co and Ni ions absorption, and (c)
ability of the hydrogel. The p(AAm) hydrogel alone with the the reduction of these ions to corresponding metal
same amounts of crosslinker has low swelling ratios and no nanoparticles within hydrogel matrices.
780 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 8 ( 2 0 1 3 ) 7 7 7 e7 8 4

30000
Table 2 e The amounts of metal ions obtained by
dissolution of metal nanoparticles within p(AAm-co-
P(AAm-co-VSA) VSA) hydogela, and absorption capacity of p(AAm-co-
20000
1:1.5 VSA)b.
a
Hydrogels Mole Types of metal Amounts of metal
S%

ratio nanoparticles ions per g dried

10000
hydogels (mg/g)
P(AAm-co-VSA)
1:1 p(AAm-co-VSA) 1:1 Co 34.890  4.314
0 p(AAm-co-VSA) 1:1 Ni 41.327  2.517
0 50 100 150 200 p(AAm-co-VSA) 1:1.5 Co 41.103  2.927
Time (min) 41.383  1.863b
p(AAm-co-VSA) 1:1.5 Ni 58.215  4.126
Fig. 2 e The swelling S% of 0.5% crosslinked p(AAm-co- 58.375  0.480b
VSA) hydrogels at different mole ratios in DI water. a The results were obtained by AAS measurements, after three
times 50 ml 5 M HCl treatment.
b Metal ion absorption capacity from solution.

the prepared hydrogels at different mole ratios. As sulfur

comes from VSA moieties, the VSA content is readily deter-
that with the increase in the amount of VSA in the copoly-
mined by elemental analysis. As illustrated in Table 1, the
meric hydrogel, the amounts of absorbed metal ions also
theoretical value of S is always higher; almost twofold more
increased regardless of the type of the metal ions. Also, it is
than the measured amounts. As the highest amounts of S was
obvious that these hydrogels can absorb Ni ions more than Co
obtained at 1:1.5 mole ratio of p(AAm-co-VSA), further inves-
ions could be due to the more complexing tendency of eSO3
tigations were done using this composition. The amounts of
groups for Ni ions than Co ions. The amounts of Co and Ni
Ni and Co ions absorbed by p(AAM-co-VSA) hydrogels at
within p(AAm-co-VSA) hydrogels were also determined by
1:1.5 mol as given in Table 2, reveals that, the binding
employing TGA analysis and AAS studies as aforementioned.
tendency of p(AAM-co-VSA) for Ni ions is greater than for Co
As illustrated in Fig. 3, the thermograms of bare, Co- and Ni-
ions. We also prepared p(AAm) hydrogels and used in Co, and
containing p(AAm-co-VSA) have similar thermal degradation
Ni ions absorption and found that no significant amounts of
temperatures. All the materials start to degrade between 150
metal ions were uptaken by pure p(AAm) hydrogels. To
and 300  C with almost the same characteristics. At about
further corroborate that sulfonyl groups are responsible for
400  C, each showed different thermal degradation pathways,
metal ion absorption, and to determine the exact amounts of
and between 400 and 600  C similar behavior and then heating
metal ions that formed the metal nanoparticles within
up to 1200  C they have different thermal degradation paths.
copolymeric hydrogels at different mole ratios, p(AAm-co-
As shown in Fig. 3, the overall difference between Co- and Ni-
VSA)eM (M: Co or Ni) were treated with concentrated HCl
containing p(AAm-co-VSA) composite and bare p(AAm-co-
(50 ml 5 M) three times to dissolve the metal ions and then the
VSA) can be attributed to the existence of Co and Ni parti-
dissolve ions were measured using AAS and are reported in
cles, respectively; and was 13.9 and 15.6% by weight in
Table 2. As can be seen, the metal ion absorption capacity is
comparison to bare p(AAm-co-VSA) with 4.23 wt% left over.
increased with the increase in the amount of VSA component
The stabilization of the nanoparticles inside the hydrogel
of copolymeric hydrogels for the same metal ions. Also, it can
could be both streric and electrostatic in nature. As the
be said that almost all the absorbed ions were converted to
particles were formed within 3-D structure of hydrogel
their corresponding particle by comparing asterisk in Table 2
matrices, the particles are entrapped inside hydrogels and
for p(AAm-co-VSA) at 1:1.5 mole ratios for Co and Ni. The
small difference could be due to the used reducing agent,
NaBH4 that can form some boron-containing compounds and
100.0
on heating up to 1200  C can cause some metal oxides to form
[4,9]. The more correct result is expected to be obtained by
dissolution of the metal nanoparticles within hydrogel 80.0
matrices and measuring the amounts with AAS. It is evident
60.0
TG %

P(AAm-co-VSA)-Ni
40.0
Table 1 e The S content of the prepared p(Aam-co-VSA) %15.6

hydrogels. P(AAm-co-VSA)-Co
%13.94
Hydrogels Mole ratio Theoretical Results obtained 20.0
P(AAm-co-VSA)
from elemental % 4.23
analysis

p(AAm-co-VSA) 1.5:1 13.512 6.274

200.0 400.0 600.0 800.0
p(AAm-co-VSA) 1:1 15.906 8.449 Temp Cel
p(AAm-co-VSA) 1:1.5 18.029 9.743
Fig. 3 e TGA thermogram of p(AA-co-VSA) hydrogels.
 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 8 ( 2 0 1 3 ) 7 7 7 e7 8 4 781

surrounded by the polymeric chains. At the same time, as the As illustrated in Fig. 5(a), the amounts of produced hydrogen
Co and Ni metal nanoparticles were prepared from their did not change with time, that is 250 ml H2 was produced at
metallic ions, the stabilization is due to the electrostatic every temperature, but the time to produce the same amount
interaction between the positively charged metal ions and of hydrogen changed greatly e.g., decreased with increased
negatively charged sulfonic acids groups on the polymeric temperature. It took 8 min at 60  C to hydrolyze the same
chain. Therefore, these interactions are also partially effective amount of NaBH4 while it took 35 min at 30  C. Using the rates
and do exist even after particle formations rendering the over of hydrolysis at different temperatures, ln k
1/T and ln
stabilization of metal nanoparticles within hydrogel network. (k/T )
1/T graphs were constructed using the very well
known Arrhenius (Eq. (2)) and Erying (Eq. (3)) equations.

3.2. The effect of metal type on hydrolysis of NaBH4 ln k ¼ ln A
ðEa =RTÞ (2)

The different metal nanoparticles prepared within hydrogel ln ðk=TÞ ¼ ln ðkB =hÞ þ ðDS# =RÞ
ðDH# =RÞð1=TÞ (3)
matrices were compared in terms of their catalytic perfor-
mances in the hydrolysis of NaBH4 under the same reaction here, k is the reaction rate, Ea is the activation energy, T is the
conditions. As illustrated in Fig. 4, Co nanoparticle-containing absolute temperature, kB is Boltzmann’s constant
p(AAm-co-VSA) produced the same amounts of hydrogen at (1.381  10‾23 J K
1), h is Planck’s constant (6.626  10
34 J),
least five time faster than Ni-containing p(AAm-co-VSA) activation enthalpy is DH#, DS# is the entropy of activation and
composite catalyst systems. Using the results obtained from R the gas is constant (8.314 J K
1 mol
1).
AAS, the amounts of used metal nanoparticle within hydrogel The activation parameters such as energy,
matrices were kept the same (4.11 mg each). For this purpose, Ea ¼ 34.505 kJ mol
1K
1, enthalpy, DH# ¼ 29.223 kJ mol
1K
1, and
the metal content of 1 g of each p(AAm-co-VSA) composite entropy, DS# ¼
198.34 j mol
1K
1 were found. The activation
were 41.103 mg Co and 58.215 mg Ni. So, 0.1 g p(AAm-co- energy is very well comparable with the literature, implying that
VSA)eCo (4.111 mg/g) and 0.07 g p(AAm-co-VSA)eNi
(4.111 mg/g) were used in 50 ml 50 mM NaBH4 hydrolysis with
5 wt% NaOH content at 30  C under 1000 rpm mixing rate. It a 300

took p(AAm-co-VSA)eCo composite 35 min, whereas the

same reaction was completed in about 160 min with the Ni-
Hydrogen (ml)

200
containing composite. Therefore, parameters that effect
20 oC
Volume of

catalytic performance of p(AAm-co-VSA)eCo composite 30 oC

system in NaBH4 hydrolysis were investigated. 100
40 oC
50 oC
60 oC
3.3. The effect of temperature
0
0 15 30 45
To determine the effect of the temperature on the hydrolysis Time (min)
of NaBH4, 0.1 g p(AAm-co-VSA)eCo (containing 4.111 mg/g Co)
-4
was used in the hydrolysis of 50 ml 50 mM NaBH4 (containing b y = -4150,3x + 7,4084
5 wt% NaOH, with 1000 rpm mixing rate) at different
R² = 0,899
temperatures between 20 and 60  C with 10  C increments.
-5.5
lnk
300
Volume of Hydrogen (ml)

-7
0.0029 0.0032 0.0035
200
1/T

p(AA-co-VSA)-Co
c y = -3515x - 0,1065
P(Aam-Co-VSA)-Co -10
100 R² = 0,9815
p(AA-co-VSA)-Ni
P(Aam-Co-VSA)-Ni ln(k/T)
-11
0
0 60 120 180
-12
Time (min) 0.0028 0.003 0.0032 0.0034
1/T
Fig. 4 e The hydrogen production of p(AAm-co-VSA)
hydrogels containing Co and Ni nanoparticles from the Fig. 5 e The effects of temperature on the hydrolysis of
hydrolysis of NaBH4 [50 ml 50 m MNaBH4, %wt 5 NaOH, NaBH4 (a), ln k versus 1/T (Arrhenius eq.) (b), and ln (k/T )
30  C, 1000 rpm mixing rate, 4.111 mg/g Co (in 0.1 g versus 1/T (Eyring eq.) (c). [50 ml 50 m M NaBH4, %wt 5
hydrogel composite), 4.111 mg/g Ni nanoparticles (in 0.07 g NaOH, 1000 rpm, 4.111 mg/g Co nanoparticles in 0.1 g
hydrogel composite)]. hidrojel composite].
782 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 8 ( 2 0 1 3 ) 7 7 7 e7 8 4

these p(AA-co-VSA)eCo composite catalyst system catalytic 100 Conversion

performances are as good as more expensive catalyst systems
Activity
such as Ru, Ro, and Pt [4,7,8,17]. 75

%
50
3.4. The effect of NaBH4 concentration and the amounts
of catalyst
25

To investigate the effect of concentration on hydrolysis,

0
NaBH4 concentrations of 25, 50, 100, and 150 mM were 1 2 3 4 5
employed using 0.1 g p(AAm-co-VSA)eCo composite (con- Run number
taining 4.111 mg/g Co) with constant parameters catalytic
Fig. 7 e The activity and conversion of the repetitive use of
parameters: 5 wt% NaOH, at 30  C and 1000 rpm mixing rate.
p(AAm-co-VSA)eCo composites in NaBH4 hydrolysis [each
As illustrated in Fig. 6(a), as the concentration of NaBH4 is
reaction conditions: 50 ml 50 mM, 30  C, 1000 rpm,
increased, the amounts of produced hydrogen increased
4.111 mg Co nanoparticle in 0.1 g hydrogel composite].
almost linearly whereas the production rate (the slope of each
curve) did not change showing the reaction does not depend
on the concentration of NaBH4. On the other hand, as ex-
pected upon the increase in the amount of metal nano- concluded that the hydrolysis reaction is independent from
catalyst, the hydrogen production rate is also increased as NaBH4 concentration.
illustrated in Fig. 6(b). The hydrolysis reaction was done using
different amounts of p(AAM-co-VSA)eCo composites, 0.05, 3.5. The reusability of p(AAm-co-VSA)eCo composites
0.1, 0.2, and 0.5 g containing 2.055, 4.111, 8.222, and 20.555 mg
Co, respectively, under the same conditions (50 ml 50 mM The prepared p(AAm-co-VSA)eCo catalyst composites were
NaBH4, 5 wt% NaOH, 30  C, 1000 rpm). The same amounts of tested for reusability. For this purpose, 0.1 g p(AAm-co-VSA)e
hydrogen were produced up to about 10 min using 20.555 mg Co (containing 4.111 mg Co) were used in hydrolysis of 50 ml
as opposed to 44 min for 2.055 mg catalyst. Overall, it is 50 mM NaBH4 at 30  C repeatedly, and the yield and catalytic
activities were tested. As shown in Fig. 7, even after five
900 repetitive uses, the conversion was 100%, however, the cata-
Volume of Hydrogen (ml)

lytic activity, calculated by taking the initial hydrogen

a production rate of the first use to the hydrogen production
600
rate of the next use, was 55% at the end of fifth use. So, the
catalytic activity of p(AAm-co-VSA)eCo composite catalyst
25 mM
system was gradually reduced after each use. The mass loss of
50 mM catalysts during catalysis reaction was not observed as the
300
100 mM metal ions amounts were determined before and after the
150 mM hydrolysis reactions did not change. However, the loss cata-
lytic activity could due to the formation NaBO2 that can reside
0
0 50 100 150
on the catalyst surface reducing the catalytic activity. Also,
oxidation of metal nanoparticles within hydrogel matrices
Time (min) can happen due to close proximity of the hydrogels’ func-
tional groups leading to the loss of catalytic active sites, and
300 reduction of the overall catalytic activity of hydrogel
b composite systems.
Volume of Hydrogen (ml)

200
0.05 g
4. Conclusion
0.1 g
100 0.2. g Here, it was demonstrated that copolymeric hydrogels of
p(AAm-co-VSA) hydrogel can be prepared at different mole
0.5 g
ratios and used in metal nanoparticle synthesis such Co and Ni.
The introduction of AAm into hydrogel network proved that
0
0 20 40 60 different functional groups containing monomers can also be
used for in situ metal nanoparticle preparation. The use of
Time (min)
copolymeric hydrogels provides new opportunities such as the
Fig. 6 e (a) The effect of NaBH4 concentration on the introduction of new functional groups (amide in this investi-
hydrolysis reaction [30  C, 1000 rpm,%wt 5 NaOH, gation) e.g., some other functional groups can also be intro-
4.111 mg/g Coin 0.1 g hydrogel composite], and (b) the duced to the hydrogel structures. Therefore, copolymeric
effect of metal nanoparticles amount on NaBH4 hydrolysis hydrogels can be specific for some other metal ions with and
[50 ml 50 mM NaBH4, %wt 5 NaOH, 30  C, 1000 rpm]. eventually the copolymeric hydrogel can become suitable
 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 8 ( 2 0 1 3 ) 7 7 7 e7 8 4 783

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This work is supported by the Scientific and Technological
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