Chemical Engineering Science 82 (2012) 114120

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

p(AAGA) hydrogel reactor for in situ Co and Ni nanoparticle preparation and

use in hydrogen generation from the hydrolysis of sodium borohydride
Nurettin Sahiner a,b,n, Sultan Butun a, Tugce Turhan b,c
a

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

Polymeric hydrogel template and

reactor.
Soft catalyst for hydrogen generation.
NaBH4 hydrolsis via p(AAGA)Co and
p(AAGA)Ni composites.

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;

N. Sahiner et al. / Chemical Engineering Science 82 (2012) 114120

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.

2. Materials and methods

2.1. Materials
2-Acrylamidoglycolic acid monohydrate (AAGA) (96%, Aldrich)
as monomer; N,N-methylenebisacrylamide (MBA, 99%, Acros) as
cross-linker; and 2,2-Azobis(2-methylpropionamidine) dihydrochloride (98%, Acros) as UV-initiator were used in p(AAGA)
hydrogel synthesis. Nickel (II) chloride hexahydrate (NiCI2  6H2O,

97%, Riedel-de Haen)

and cobalt (II) chloride hexahydrate
(CoCI2  6H2O, 99%, SigmaAldrich) were used as metal ion sources
and NaBH4 (96%, Merck) as reducing agent and as hydrolysis
material was also used. Distilled water (Millipore Direct-Q3 UV)
was used throughout the experiments. The metal amounts of
p(AAGA)M (M: Co, and Ni) were determined by using Atomic
Absorption Spectroscopy (AAS) (Thermo, ICA 3500 AA SPECTRO)
and via thermal measurements (SII TG/DTA 6300). The samples
were heated under constant nitrogen ow over 50800 1C temperature range at the rate of 10 1C min  1 as described earlier.
2.2. p(AAGA)Co and p(AAGA)Ni within hydrogel network
The preparation of p(AAGA) hydrogels and their metal nanoparticle containing composites were reported earlier (Butun and
Sahiner, 2011). Briey, 100 mg of the cleaned and dried p(AAGA)
hydrogels were placed in 100 mL 500 ppm aqueous metal (Ni2 ,
Co2 ) solution under constant stirring for 24 h. Following a
washing procedure with DI water for another 12 h, these metal
ion-loaded hydrogels were transferred into a 100 mL 0.4 M NaBH4
solution in a beaker and allowed to react for 4 h under constant
stirring (400 rpm) at room temperature. The metal ions (Ni2 ,
Co2 ) were reduced to their corresponding metal nanoparticles
(Ni0, Co0). Again, the metal nanoparticle-containing composites
were washed with DI for 12 h and kept in DI water in a closed
container at ambient temperature for hydrolysis reactions.
2.3. Characterization of the metal catalyst
Dried Ni and Co particle-containing hydrogels were ground
with mortar and pestle for imaging by transmission electron
microscopy (TEM, JEOL2010) and for thermal analysis. The inorganic parts of the composite were determined by comparing the
blank hydrogel and metal nanoparticle-containing hydrogel composites using a thermal analyzer. The amounts of Ni and Co
within the p(AAGA) hydrogel matrix were determined by heating
from 50 to 1000 1C with 10 1C/min heating rate and under
nitrogen ow of 100 mL/min. After dissolution of the metal
nanoparticles by three 100 mL 6 M HCl treatments, the amount
of nickel and cobalt ions was determined by ame-atomic
absorption spectroscopy (F-AAS).
2.4. Hydrolysis of sodium borohydride by Co and Ni
nanoparticle-loaded hydrogels
Certain amounts of p(AAGA) hydrogel composites (containing,
e.g., catalyst 18.4 mg metal nanoparticle) were crushed into
smaller pieces and put in 50 ml of DI water at 30 1C. This was
mixed with 50 mL 50 mM (0.095 g) aqueous NaBH4. All the
hydrogen production experiments were performed with rigorous
mixing at 1000 rpm. As soon as the hydrogelM catalyst system

116

N. Sahiner et al. / Chemical Engineering Science 82 (2012) 114120

was placed in the hydrolysis medium, a gas evolution was observed.

The volume of the produced hydrogen gas with time was determined in an experimental setup based on the principle that the
generated gas replaces the water in an upside down graded cylinder
and by passing the hydrogen gas through a washing bottle to
remove water vapor. All the experiments were carried out in the lab
with set temperature at 30 1C and 1 atm pressure as the laboratory
is about 50 m above sea level. In order to determine the effect of the
amount of catalyst, various amounts of catalyst ranging from 9.2 to
73.6 mg metal nanoparticle were used. Also, to investigate the
effect of metal hydride initial concentration, 50150 mM aqueous
NaBH4 solutions were used. For the effect of temperature on the
hydrolysis reaction rate, the hydrolysis reaction temperature ranged between 30 and 70 1C. The catalytic activities, reusability and
shelf-life experiments were also carried out.

P(AAGA)

P(AAGA)-M

+n

3. Results and discussion

Synthesis and characterization of p(AAGA) hydrogel were reported
in a previous study (Butun and Sahiner, 2011), and this hydrogel was
used as a template for the in situ Co and Ni metal nanoparticle
preparation and as a reaction media in the reduction of nitrophenols.
Here, we further demonstrate the use of these p(AAGA)-M composites as reactors in the hydrolysis of NaBH4. Other hydrogel networks,
such as p(2-acrylamido-2-methyl-1-peopansulfonic acid) p(AMPS),
were used as a template for the preparation of various hydrogel
networks such as Co, Ni, Cu, Fe and Ru and used for the catalysis of
different reactions in addition to the hydrolysis of NaBH4 and
ammonia borane, another hydrogen storage material (Ozay et al.,
2011b, 2011c; Sahiner, 2006; Sahiner et al., 2011a,b).
The functional groups such as OH and COOH that exist on the
p(AAGA) hydrogel network are responsible for metal ion absorption
from their solutions. As all the sites are lled with these ions on the
hydrogel network, the polymer network is also physically woven
via M(II)OOC electrostatic interactions between the metal ions
and the COO and OH groups. Upon contacting these metal ionloaded hydrogels with a reducing agent such as NaBH4 the
corresponding metal nanoparticles can be formed in situ within
the hydrogel. The utilization of the hydrogel as a template also
provides a stabilizing effect on the produced metal nanoparticles.
Fig. 1 illustrates the schematic presentation of metal loading onto
the p(AAGA) hydrogel and their reduction within the hydrogel
matrices along with digital camera images.
From the TGA analysis, the thermogram of p(AAGA)Co and
p(AAGA)Ni composite hydrogels contain 31 wt% Co and 36 wt% Ni
nanoparticles upon comparison with bare p(AAGA) weight losses at
800 1C (Butun and Sahiner, 2011). As the used reducing agent is
NaBH4, the metal nanoparticles contain some boron and sodium
elements with some oxygen in the Co and Ni nanoparticles as the
hydrogel contains carboxylic acid groups that can oxidize the metal
nanoparticles. To determine the exact amount of metal, about
100 mg p(AAGA)M composite hydrogel system was treated with
100 mL 6 M HCl solution three times to dissolve the metal nanoparticles, and the amount of M ions were determined by using
Atomic Absorption Spectroscopy. The AAS results revealed that
each p(AAGA)M composite has 93 mg Co and 103 mg Ni for each
gram of p(AAGA)M. Fig. 2 illustrates the TEM images of p(AAGA)Co and p(AAGA)Ni composites. As can be seen from the TEM
images the sizes of the nanoparticles are between 80 and 200 nm, a
broad size distribution. Although, the size of the particles have great
effect on the catalysis reactions, e.g., in the hydrolysis reactions,
different parameters also effect the hydrolysis of NaBH4. Depending
on the reaction conditions such as the amount of the loaded metal
ions and their corresponding particle, the nature of the metal
nanoparticle and/or the electronic structures inuence the catalysis

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

According to the ideal hydrolysis reaction stoichiometry which

is rst noted by Schlesinger et al. (1953), 1 g of fully hydrolyzed
NaBH4 produces 2.37 L of hydrogen gas at standard temperature
and pressure. However, the hydrolysis of NaBH4 gives mixtures of
hydrated sodium metaborate as by products. In this situation, the
reaction is limited by excess water requirement x, which is given
in Eq. (2). NaBH4 and sodium metaborate by-products give low
solubility in water which are 55 g NaBH4/100 g H2O at 25 1C
(James and Wallbridge, 1970) and 28 g NaBO2/100 g H2O at 25 1C
(Kojima et al., 2004), respectively.
NaBH4 s 2 xH2 Ol!4H2 g NaBO2 UxH2 Os heat

Although the hydrolysis of NaBH4 can be initiated without the

addition of any base in the reaction medium, the hydrogen

N. Sahiner et al. / Chemical Engineering Science 82 (2012) 114120

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

Volume of Hydrogen (mL)

300

200

100

10

15

20

25

Time (min)
p(AAGA)-Co

p(AAGA)-Ni

control

300
Volume of Hydrogen (mL)

production is faster in the presence of NaOH. As illustrated in

Fig. 3(a), after 5 wt% addition of NaOH there is no signicant
increase in the hydrogen production rate, therefore, all the
hydrolysis reactions in this investigation were carried out using
5 wt% NaOH. The nature of the metal nanoparticle also has
another signicant effect on the hydrogen production rate. Therefore, the in situ prepared Co and Ni nanoparticles within p(AAGA)
matrices catalytic performances were compared and graphed in
Fig. 3(b). Without any catalyst the p(AAGA) network cannot
catalyze the hydrolysis of NaBH4. On the other hand, as shown
in Fig. 3(b), p(AAGA)Co catalyst produces the same amount of
hydrogen (250 mL) at least four times faster than the p(AAGA)Ni
system under the same reaction conditions using 50 mL 50 mM
NaBH4 and 18.4 mg Co or Ni metal catalysts at 30 1C, 1000 rpm
mixing rate. This is very important in certain applications where
fast hydrogen generation is required. All types of the metal
nanocatalyst performed at over 99% yield. It is also important to
note that in addition to the almost complete hydrolysis of NaBH4,
half of the produced hydrogen comes from the water in the
reaction media even at room temperature. This is another
advantage of this system as otherwise to obtain hydrogen from
water dissociation requires high energy input. The reaction rates
relating to hydrolysis of NaBH4 were 799 (mL H2) (min)  1 (g of
Co)  1 for Co, 245 (mL H2) (min)  1 (g of Ni)  1 for Ni. The total
turnover frequencies (TOF) were calculated for composite systems, and they were found that 1.88 mol H2 (mol catalyst.min)  1,
0.53 mol H2 (mol catalyst.min)  1 for p(AAGA)Co and p(AAGA)
Ni, respectively.
To investigate the effect of the used amount of catalyst on the
hydrolysis of NaBH4, the reaction was performed with ve
different catalyst amounts; 9.2, 18.4, 36.8, 55.2, and 73.6 mg Co
nanoparticles in p(AAGA)M composite. As shown in Fig. 4(a), the
amount of H2 gas produced did not change with the increase in
amount of catalyst. However, the time to produce the same
amount of H2 gas changed considerably. For example, by using
73.6 mg Co, 250 mL H2 can be produced in about 4.5 min whereas
the same amount of H2 can be produced in about 36 min upon
using 9.2 mg Co under the same reaction conditions. The reaction
rates relating to hydrolysis of NaBH4 were 754 (mL H2) (min)  1
(g of Co)  1 for containing 73.6 mg Co, and 754 (mL H2) (min)  1
(g of Co)  1 for containing 9.2 mg Co.
To determine the effect of the initial concentration of NaBH4
on the hydrolysis mechanism, the hydrolysis of NaBH4 was
performed using 18.4 mg Co catalyst, 5 wt% NaOH, and ve
different NaBH4 concentrations; 50, 100, 150 mM and 50 mL
volumes at 30 1C. In Fig. 4(b), the H2 production with time for
different NaBH4 initial concentrations is shown. It is clear from

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

N. Sahiner et al. / Chemical Engineering Science 82 (2012) 114120

Conversion

Activity

100
80

200

60

9.2 mg

Volume of Hydrogen (mL)

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.]

repetitive use of p(AAGA)Co was evaluated in the hydrolysis of

NaBH4. Percent activity was calculated taking initial ratio of the
hydrogen production rate to the following hydrolysis reaction for
each use, and the percent conversion was calculated based on
100% conversion of NaBH4 that exists in the hydrolysis medium.
As illustrated in the reaction mechanism half of the hydrogen
coming from the water in the medium is also taken into
consideration.
The p(AAGA)Co catalysts were used seven times consecutively and 95% activity was obtained as shown in Fig. 5(a). As seen
from the gure, in every use almost 100% conversion is attainable.
The p(AAGA)Co system gave better results in terms of repetitive
use in the hydrolysis of NaBH4 in comparison to the p(AMPS)Ni
or Co systems (Ozay et al., 2011a, 2011b; Sahiner et al., 2011b).
The storage capability of the catalyst system is also very important in real applications. P(AAGA)-Co hydrogel catalyst systems
catalytic performances were tested for a month for the hydrolysis
of NaBH4 and their activity and conversion vs time was constructed and is illustrated in Fig. 5(b). As can be clearly seen
almost 100% conversion is obtainable with 68% activity at end of
30 day. This clearly illustrates that this p(AAGA)Co catalyst
system can be stored over a month in DI water losing less than
half of its catalytic performance.
3.3. The effect of temperature on hydrolysis of NaBH4
by p(AAGA)-Co composite-hydrogel
To investigate the effect of temperature on hydrolysis of
NaBH4 catalyzed by p(AAGA)Co, the reaction was carried out
between 30 1C and 70 1C with 10 degree increments using 50 mM
NaBH4 and 5% NaOH in 50 mL water employing 18.4 mg Co
nanoparticle-containing p(AAGA) hydrogels. The effect of

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)

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].

temperature on the hydrolysis of NaBH4 is shown in Fig. 6. All

the reactions generated an average of 250 mL H2 gas. As clearly
seen from the gure, the temperature increase from 30 1C to 70 1C
reduces the hydrolysis time from16 min to 4.5 min. The reaction
rates relating to hydrolysis of NaBH4 were 799 (mL H2) (min)  1
(g of Co)  1 for containing 18.4 mg Co at 30 1C, and 3019 (mL H2)
(min)  1 (g of Co)  1 for containing 18.4 mg Co at 70 1C.
The hydrogen generation rates at other temperatures are
between these two limits. The reactions that were carried out
with same amount of Ni catalyst at the same temperatures
showed slightly lower generation rates. For example, as the
reaction temperature increased from 30 1C to 70 1C the reaction
time decreased from 55 min to 7.5 min (gure not shown). The
reaction rates relating to hydrolysis of NaBH4 were 245 (mL H2)
(min)  1 (g of Ni)  1 for containing 18.4 mg Ni at 30 1C, and 1812
(mL H2) (min)  1 (g of Ni)  1 for containing 18.4 mg Ni at 70 1C.

N. Sahiner et al. / Chemical Engineering Science 82 (2012) 114120

Therefore, it can be said that p(AAGA)Co catalysts can catalyze

NaBH4 hydrolysis faster than p(AAGA)-Ni catalyst systems with
its hydrogen generation rate of 799 (mL H2) (min)  1 (g of Co)  1.
For expensive catalyst in the literature, for example, Amendola
et al. (2000) studied Ru/IRA-400 found that 3772 (mL H2)(min)  1
(g of metal)  1 at 25 1C, and Zahmakiran, Ozkar (2006) studied Ru
nanoclusters and found that about 2213 (mL H2)(g)  1(g of metal)  1
at 25 1C. Although the hydrogen production rate depends on
various parameters such as the amounts NaBH4 and the catalysts
amount and types, and the amounts of used base, it can still be
assumed that p(AAGA)Co catalyst systems have fair hydrogen
production rates and shows better activity than Ru nanoclusters.
Fig. 7(a) reveals the reduction in NaBH4 concentrations with
time at different temperatures for p(AAGA)Co catalyst systems.
To determine the activation parameters for this system in the
hydrolysis reaction of NaBH4, rate constants at different tempera





tures lnk 1=T and ln k=T  1=T graphs were constructed
using the well known Arrhenius (Eq. (2)) and Eyring (Eq. (3))
equations, respectively.
lnk lnA2Ea=RT

lnk=T lnkB =h DS# =RDH# =R1=T

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

where k is the rate constant, Ea is the activation energy, T is the

temperature, kB is the Boltzmann constant (1.381  10  23 J K  1),
h is the Planck constant (6.626  10  34 J), activation enthalpy is
DH#, DS# is the entropy of activation
and R is the gas constant


1
(8.314
J K  1 mol
). The lnk 1=T graph for Eq. (1) and the


ln k=T  1=T graph for Eq. (2) are illustrated in Fig. 7(b) and (c),
respectively. As can be seen from both graphs, Arrhenius and
Eyring equations t very well to the hydrolysis of NaBH4 by
p(AAGA)Co and p(AAGA)Ni composite catalyst systems.
Activation parameters and their values at different temperatures for the hydrolysis of NaBH4 are given in Table 1.
The activation energy, enthalpy and entropy were calculated
to be 26.62 kJ mol  1, 23.94 kJ mol  1, and  210.96 J mol  1 K  1,
respectively, for p(AAGA)Co catalyzed NaBH4 hydrolysis. The
activation energy, enthalpy and entropy were also calculated
for p(AAGA)Ni catalyst systems and were 43.77 kJ mol  1,
41.09 kJ mol  1, and 166.45 J mol  1 K  1, respectively. So it can
be said that p(AAGA)Co catalyst systems are more favorable than
p(AAGA)Ni for NaBH4 hydrolysis as Co nanoparticle catalyzes
the hydrolysis reaction faster than Ni nanoparticle. As a comparison, the activation energy reported in the literature was between
30 and70 kJ mol  1 for ammonia borane hydrolysis with Co, Ni
and Cu nanoparticles (Ozay et al., 2011a). Moreover, Ni and Co
nanoparticles used in the hydrolysis of NaBH4 in more acidic
hydrogel networks, p(AMPS) reported 42.28 and 38.14 kJ mol  1,
respectively (Ozay et al., 2011b; Sahiner et al., 2011c). These
activation energies are almost comparable for Co and more than
for Ni to this study: 43.77 kJ mol  1 and 26.62 kJ mol  1 for
p(AAGA)Ni and p(AAGA)Co catalyst systems. The use of the
p(AAGA) hydrogel network provided better % activity and conversion than other similar hydrogel networks (Ozay et al.,
2011a; Sahiner et al., 2011b, 2011c). One of the main purpose
of this investigation is to evaluate the most feasible catalysts
system in terms of the matrix materials and the metal nanoparticles; Therefore, it can be interpreted that Co and Ni metal nano
catalyst are good candidates as they are not as expensive as
Pt, Ru and Rh nanoparticle and can offer alternative catalyst
particle systems due to the economical concerns and readily
availability. Additionally, they provide good catalytic performances. The matrix materials, p(AAGA) may have also better
protection/stability capability for these metal nanoparticles as the
reusability showed that up to seven consecutive runs, 95%
catalytic activity was obtained whereas with p(AMPS)Co showed
lesser activity even up ve consecutive runs (92%) (Sahiner et al.,
2011b).

-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 )

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.

120

N. Sahiner et al. / Chemical Engineering Science 82 (2012) 114120

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.
References
Amendola, S.C., Sharp-Goldman, S.L., Saleem Janjua, M., Kelly, M.T., Petillo, P.J.,
Binder, M., 2000. An ultrasafe hydrogen generator: aqueous, alkaline borohydride solutions and Ru catalysts. J. Power Sources 85, 186189.
Arico, A.S., Bruce, P., Scrosati, B., Tarascon, J.M., Schalkwijk, W.V., 2005. Nanostructured materials for advanced energy conversion and storage devices. Nat.
Mater. 4, 366377.
Butun, S., Sahiner, N., 2011. A versatile hydrogel template for metal nanoparticle
preparation and their use in catalysis. Polymer 52, 48344840.
European Union, 2006 European Union, European Energyand TransportTrendsto
2030, Summary Energy Balances and Indicators.
Gleiter, H., 2000. Nanostructured materials: basic concepts and microstructure.
Acta Mater. 48, 129.
Hansen, N.S., Ferguson, T.E., Panels, J.E., Park, A.H.A., Joo, Y.L., 2011. Inorganic
nanobers with tailored placement of nanocatalysts for hydrogen production
via alkaline hydrolysis of glucose. Nanotechnology 22, 325302325314.
Hennebel, T., Simoen, H., Verhagen, P., Windt, W.D., Dick, J., Weise, C., Pietschner,
F., Boon, N., Verstraete, W., 2011. Biocatalyticdechlorination of hexachloro
cyclo hexane by immobilized bio-Pd in a pilot scale uidized bed reactor.
Environ. Chem. Lett. 9, 417422.
James, B.D., Wallbridge, M.G.H., 1970. Metal tetrahydroborates. Prog. Inorg. Chem.
11, 99231.
Jiang, J., Liu, J., Ding, R., Ji, X., Hu, Y., Li, X., Hu, A., Wu, F., Zhu, Z., Huang, X., 2010.
Direct synthesis of CoO porous nanowire arrays on Ti substrate and their
application as Lithium-Ion battery electrodes. J. Phys. Chem. C 114, 929932.
Kim, M.S., Lee, S.Y., Kwak, J.H., Han, G.Y., Yoon, K.J., 2011. Hydrogen production by
decomposition of ethane-containing methane over carbon black catalysts.
Korean J. Chem. Eng. 28, 18331838.
Kojima, Y., Haga, T., 2003. Recycling process of sodium metaborate to sodium
borohydride. Int. J. Hydrogen Energy 28, 989993.

Kojima, Y., Suzuki, K., Fukumoto, K., Kawai, Y., Kumbara, M., Nakanishi, H., et al.,
2004. Development of 10 kW-scale hydrogen generator using chemical
hydride. J. Power Sources 125, 2226.
Konstantatos, G., Sargent, E.H., 2010. Nanostructured materials for photon detection. Nat. Nanotechnol. 5, 391400.
Moriarty, P., 2001. Nanostructured materials. Rep. Prog. Phys. 64, 297381.
Muir, S.S., Yao, X., 2011. Progress in sodium borohydride as a hydrogen storage
material: development of hydrolysis catalysyts and reaction systems. Int. J.
Hydrogen Energy 36, 59835997.
Murugesan, S., Subramanian, V., 2009. Effects of acid accelerators on hydrogen
generation form solid sodium borohydrideusing small scale devices. J. Power
Sources 187, 216223.
Ngah, W.S.W., Hanaah, M.A.K.M., 2008. Removal of heavy metal ions from
wastewater by chemically modied plant wastes as adsorbents: a review.
Biores. Technol. 99, 39353948.
Ozay, O., Inger, E., Aktas, N., Sahiner, N., 2011a. Hydrogen production from
ammonia borane via hydrogel template synthesized Cu, Ni, Co composites.
Int. J. Hydrogen Energy 36, 82098216.
Ozay, O., Aktas, N., Inger, E., Sahiner, N., 2011b. Hydrogel assisted nickel
nanoparticle synthesis and their use in hydrogen production from sodium
boron hydride. Int. J. Hydrogen Energy 36 (2011), 19982006.
Ozay, H., Kubilay, S., Aktas, N., Sahiner, N., 2011c. Utilization of environmentally
benign hydrogels and their networks as reactor media in the catalytic
reduction of nitrophenols. Int. J. Polym. Mater. 60, 163173.
Paek, S.M., Yoo, E.J., Honma, I., 2009. Enhanced cyclic performance and lithium
storage capacity of SnO2/Graphene nanoporous electrodes with three-dimensionally delaminated exible. Nano. Lett. 9, 7275.
Pant, K., Jain, R., Jain, S., 2011. Renewable hydrogen production by steam
reforming of glycerol over Ni/CeO2 catalyst prepared by precipitation deposition method. Korean J. Chem. Eng. 28, 18591866.
Sahiner, N., 2006. In situ metal particle preparation in cross-linked poly(2acrylamido-2-methyl-1-propansulfonic acid) hydrogel networks. Colloid.
Polym. Sci. 285, 283292.
Sahiner, N., Ozay, O., Inger, E., Aktas, N., 2011a. Controllable hydrogen generation
by use of smart hydrogel reactor containing Ru nano catalysts and magnetic
iron particles. J. Power Source 196, 1010510111.
Sahiner, N., Ozay, O., Aktas, N., Inger, E., 2011b. Superabsorbent hydrogels for
cobalt nanoparticle synthesis and hydrogen production from hydrolysis of
sodium boron hydride. Appl. Catal. B 102, 201206.
Sahiner, N., Ozay, O., Aktas, N., Inger, E., He, J., 2011c. The on demand generation of
hydrogen from CoNi bimetallic nano catalyst prepared by dual use of
hydrogel: as template and as reactor. Int. J. Hydrogen Energy 36,
1525015258.
Schlesinger, H.I., Brown, H.C., Finholt, A.E., Gilbreath, J.R., Hoekstra, H.R., Hyde, E.K.,
1953. Sodium borohydride, its hydrolysis and use as a reducing agent and in
the generation of hydrogen. J. Am. Chem. Soc. 75, 215219.
Sud, D., Mahajan, G., Kaur, M.P., 2008. Agricultural waste material as potential
adsorbent for sequestering heavy metal ions from aqueous solutions. Biores.
Technol. 99, 60176027.
Suda, S., Morigasaki, N., Iwase, Y., Li, Z.P., 2005. Production of sodium borohydride
by using dynamic behaviours of protide at the extreme surface of magnesium
particles. J. Alloys Compd. 404-406, 643647.
Tarascon, J., Armand, M., 2001. Issues and challenges facing rechargeable lithium
batteries. Nature 414, 359367.
Tsitsilianis, C., 2010. Responsive reversible hydrogels from associative smart
macromolecules. Soft Matter 6, 23722388.
UFOP, 2008 UFOP, Costand life- cycle analysis of biofuels, Longversion http://
www.ufop.de.
Vajani, G.N., Ng, S.L., Lund, C.R.F., 2011. Rate expression for watergas shift over a
gold/ferrochrome catalyst. Ind. Eng. Chem. Res. 50, 1049310499.
Wu, Z., Ren, W., Wen, L., Gao, L., Zhao, J., Chen, Z., Zhou, G., Li, F., Cheng, H., 2010.
Graphene anchored with Co3O4 nanoparticles as anode of lithium ion batteries
with enhanced reversible capacity and cyclic performance. ACS Nano 4,
31873194.
Zahmakiran, M., Ozkar, S., 2006. Water dispersible acetate stabilized
ruthenium(0) nanoclusters as catalyst for hydrogen generation from the
hydrolysis of sodium borohydride. J. Mol. Catal. A, Chem. 258, 95103.
Zhang, L., Champagne, P., Xu, C.C., 2011. Screening of supported transition metal
catalysts for hydrogen production from glucose via catalytic supercritical
water gasication. Int. J. Hydrogen Energ. 36, 95919601.
Zhang, J., Zheng, Y., Gore, J.P., Mudawar, Fisher, T.S., 2007. 1 kWe sodium
borohydride hydrogen generation system Part II: Reactor modeling. J. Power
Sources 170, 150159.
Zeng, X.F., Li, C., Zhu, D., Cho, H.J., Jiang, H., 2010. Tunable microlens arrays
actuated by various thermo-responsive hydrogel structures. J. Micormech.
Microeng. 20 (11), 115035, , http://dx.doi.org/10.1088/0960-1317/20/11/
115035.