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 ) 1 5 2 5 0 e1 5 2 5 8

Available online at www.sciencedirect.com

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

The on demand generation of hydrogen from Co-Ni bimetallic

nano catalyst prepared by dual use of hydrogel: As template
and as reactor
Nurettin Sahiner a,b,*, Ozgur Ozay b, Nahit Aktas c, Erk Inger d, Jibao He e
a

Faculty of Science & Arts, Chemistry Department, Canakkale Onsekiz Mart University, Terzioglu Campus, 17100 Canakkale, Turkey
Nanoscience and Technology Research and Application Center (NANORAC), Canakkale Onsekiz Mart University, Terzioglu Campus,
17100 Canakkale, Turkey
c
Yuzuncu Yl University, Faculty of Engineering, Chemical Engineering Department, 65080, Van, Turkey
d
Gazi University, Institute of Science and Technology, Mechanical Engineering Department, 06500 Ankara, Turkey
e
Central Instrument Facilities (CIF), Tulane University, New Orleans 70118, LA, USA
b

article info

abstract

Article history:

We report the preparation of metal nanoparticles in various formulations inside

Received 26 June 2011

p(2-acrylamido-2-methyl-1-propansulfonic acid; p(AMPS)) hydrogels and their utilization

Received in revised form

as a catalyst in hydrolysis of NaBH4. The swollen, flexible p(AMPS) network was used for

19 August 2011

metal ion loading and reduction in situ for the preparation of Co:Ni nanoparticles as

Accepted 26 August 2011

bimetallic clusters in various formulation, and Co and Ni bimetallic catalysts as Co Co,

Available online 17 September 2011

Co Ni, Ni Co and Ni Ni. In addition to utilization of hydrogels as support materials,

the p(AMPS)-metal nanoparticle system was used as catalyst to generate hydrogen in the

Keywords:

hydrolysis of NaBH4 with very high yield. Various parameters for the hydrolysis reaction

Hydrogel-template

were determined and the activation parameters were calculated. For the first time, inclu-

Hydrogel-reactor

sion of ferrite magnetic particles to control hydrogen generation on demand by using an

Magnetic soft composites

externally applied magnetic field to remove the hydrogel-catalyst system from the

Hydrogen generation control

hydrolysis medium is reported.

NaBH4 hydrolysis

Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1.

Introduction

Hydrogels are water-swollen crosslinked smart polymeric

materials [1]. Due to the existence of hydrophilic groups in
their network such as -OH, -NH2, -COOH, -SO3H hydrogels can
uptake a large amount of water via hydrogen bonding, iondipole and/or polarepolar interactions [1,2]. Hydrogels are
being increasingly investigated for applications such as tissue
and bioengineering, controlled drug delivery, sensors, water
purification and separation processes due to their

environmentally friendly nature and tunable physical and

chemical characteristics [3,4]. In addition, recently it was
shown that metal particles and magnetic particles, such as
Fe3O4 or g-Fe2O3 (ferrites), can be prepared in situ within
crosslinked hydrogel networks. Additionally, the hydrogel
network can also be further exploited as a template for metal
nanocatalyst preparation and used in the catalysis; e.g.,
hydrogen production from the hydrolysis of NaBH4, the
reduction reaction of aromatic nitro compounds, the removal
of toxic metal ions from aqueous media, and the preparation

* Corresponding author. Faculty of Science & Arts, Chemistry Department, Canakkale Onsekiz Mart University, Terzioglu Campus,
17100 Canakkale, Turkey. Tel.: 90 286 2180018x2041; fax: 90 2862181948.
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.2011.08.082

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 ) 1 5 2 5 0 e1 5 2 5 8

of antimicrobial materials against gram positive and gram

negative bacteria [2,5e8].
Hydrogen is known as an environmentally clean fuel and
an alternative energy source with many challenging issues
associated with its use [9,10]. For example, the efficient and
safe storage of hydrogen is one of the most important obstacles to using hydrogen as an energy source [11e13]. Therefore,
the production of hydrogen from chemical hydrides as efficient and safe hydrogen sources have been considered seriously by many researchers. Ammonia-borane and various
other chemical hydrides such as Ca2H, LiH, NaBH4, MgH2, and
LiAlH4 are suitable materials for hydrogen storage [14e16].
Among these hydride materials, sodium borohydride (NaBH4)
is the most appropriate hydrogen source as it offers many
advantages such as a nontoxic nature, non-flammability and
high stability in air, high hydrogen storage capacity (10.8 wt
%), stability of its solution under high pH values, and so on
[17,18]. The hydrolysis of NaBH4 in the presence of a catalyst
yields two-fold more hydrogen than its hydrogen content by
producing half of the hydrogen from water used as solvent
according to the following reaction [19,20]:
Catalyst

NaBH4 2H2 O ! NaBO2 4H2 [

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used to remove the catalyst system (hydrogel-metal nanoparticles) from the reaction media.

2.

Experimental Section

2.1.

Materials

For hydrogel synthesis, 2-acrylamido-2-methyl-1-propansulfonic acid as monomer, N,N0 -methylenebisacrylamide (MBA)

as crosslinker, 2,20 -azobis(2-methylpropionamidine) dihydrochloride as UV-initiator were purchased from Aldrich and
Acros Chemical Companies. NiCl2.6H2O (Riedel de Haen) and
CoCl2.6H2O (Sigma) were used as metal ion sources and NaBH4
(98%) (Aldrich) as reducing agent was used for in situ metal
nanoparticle preparation. All the reagents were of analytical
grade or highest purity available, and used without further
purification. The 18.2 MU cm (Millipore Direct-Q3 UV) purified
water was used for preparation and washing of hydrogels and
in all reactions.

2.2.

Synthesis of p(AMPS) networks

(1)

Metal particles and nanoclusters such as Ru [12,13,16,21e24],

Ni-Ru [25], Rh [14], Pd [12], Pt [26], Ni [20], Co [15,27,28], Co-B
[18,29,30], Co-Fe-B [17], Co-Fe-B/Ni [19], Co-P-B [31], Co-Ni-P-B
[32] are some of the developed catalysts investigated rigorously for hydrogen production from metal hydrides or ammonia
borane [33e35]. Due to their strong tendency to aggregate during
direct utilization of metal nanoparticles as catalyst, a support
material is necessary [7,8,21,22]. Thus, as an efficient way of
preventing aggregation, metallic nanoparticles are generally
prepared in solid supporting materials such as zeolite [14],
polymer [16], graphite [21], actived carbon [15,22,26,28], attapulgite clays [29] and so on. Recently, we proposed the utilization of hydrogel networks as soft and flexible support materials
in the preparation of metallic particles [5e8]. Previously, the in
situ metal nanoparticle preparation of nickel and cobalt in 2methyl-1-acrylamido-2-propansulfonic acid (AMPS) hydrogel
[5] and their use as catalyst for the catalytic reduction of
aromatic nitro compounds [7,8] and the hydrolysis of sodium
borohydride was reported [36,37]. Co has high catalytic performances but it has low stability in comparison to Ni nanoparticles. And Ni nanoparticles shows better stability against
oxidation and is relatively cheaper.
Therefore, in this study, p(AMPS) hydrogels were loaded with
nickel (II) and cobalt (II) ions via electrostatic interactions
between eSO
3 groups of p(AMPS) and Ni (II) and Co (II) ions in
solution, and then these ions held in position inside the
hydrogels were reduced with NaBH4 to produce Ni:Co (0)
bimetallic cluster nanoparticles at room temperature. Additionally, bimetallic catalyst of Co (II) and Ni (II) was also prepared
by sequential absorption and reduction inside p(AMPS) hydrogels as Co Co, Co Ni, Ni Co, and Ni Ni. It was found that
these hydrogel-Co:Ni composites are very effective catalysts
and a novel reactor. Additionally, Co:Ni nanoparticles were also
prepared in magnetically functionalized hydrogel networks for
the first time and it is reported that the reaction can be stopped
or restarted on demand by an externally applied magnetic field

The crosslinked p(AMPS) hydrogel was prepared as reported

earlier [2,5,36,37]. In brief, 0.5 mol % MBA was dissolved in
50 wt % of aqueous AMPS and 0.5 mol % (with respect to
monomer) UV-initiator was added to this mixture and placed
in plastic straws. The straws were irradiated in a photo reactor
((LUZCHEM, 420 nm, Canada) for 2 h. The obtained hydrogels
were placed in purified water and washed for 24 h to remove
unreacted species and dried in an oven. They were stored for
use in metal particle preparation and the catalysis reactions.

2.3.

Synthesis of the magnetic p(AMPS) hydrogels

The magnetic particle preparation procedure was carried out

by modifying the reported procedure in the literature [2,5]. To
prepare magnetic particles (ferrites) in situ inside hydrogel
matrices, p(AMPS) hydrogels were loaded with iron ions up to
their maximum capacity. Briefly, a cleaned and known
amount of dried hydrogel was placed in 0.5 M Fe (II) and Fe (III)
ion aqueous solution (Fe (II): Fe (III) mole ratio 1:2) for 12 h to
load the hydrogel. Then they underwent a cleaning period in
which iron ion-loaded hydrogels were kept in purified water
for 24 h to remove unbound and/or physically bound metal
ions. After cleaning, iron ion (Fe (II) and Fe (III)) -loaded
hydrogels were transferred into 0.5 M of sodium hydroxide
solution and the reaction proceeded for 5 h in a water shaker
bath at ambient temperature. Finally, the obtained magnetic
hydrogels were cleaned by washing with purified water for
another 12 h and dried in a vacuum oven at 40  C.

2.4.
The in situ preparation and characterization of
cobalt, nickel and cobalt:nickel nanoparticles in the hydrogel
network structure
Single metal nanoparticle synthesis inside hydrogels were
reported earlier [2,5,7,8]. For bimetallic cluster nanoparticle
preparation, the cleaned and dried 0.2 g p(AMPS) and
magnetic p(AMPS) hydrogels were placed in a mixture of

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100 mL of 0.1 M Co (II) and 0.1 M Ni (II) (1:1 M ratio of Co:Ni).

The hydrogels were kept in the metal ion solution for 24 h in
a water shaker bath for the loading procedure. To prepare
bimetallic clusters in different mole ratios e.g., 2:1, 1:1, and 1:2
for Co:Ni nanoparticles, the corresponding metal ion solutions were prepared in these molar ratios and the hydrogels
were placed in these metal ion solutions for loading procedures under constant shaking. The absorbed amount of Co (II)
and Ni (II) were determined from the metal ion solutions using
ICP-AES (Inductive Coupled Plasma-Atomic Spectrometry
(Varian Liberty II AX Sequential). Again, after metal ion loadings, the hydrogels were transferred to purified water for
cleaning for another 24 h. Then, the metal ions inside the
hydrogels were reduced by transferring these metal ionloaded hydrogels into 100 mL 0.5 M NaBH4 solution. The
reduction period continued for 5 h in a water shaker bath
followed by washing procedure in purified water for 12 h. The
black-colored hydrogel-metal nanoparticle composites were
broken into smaller pieces and used as catalyst media on the
same day.
For characterization, the hydrogels and hydrogel-metal
composites were ground and dried in a vacuum oven at
40  C. All the experiments performed in this investigation
were in triplicate, and purified water used was exposed to
10 min N2 passage to remove the dissolved oxygen. All the
metal nanoparticle-containing hydrogels to be tested for
activity and conversion experiments were stored in N2
bubbled purified water in the dark at ambient temperature.
In order to determine the inorganic material amount in Co,
Ni, and Co:Ni bimetallic clusters, bare hydrogels and their
corresponding metal nanoparticle-containing composites
TGA was carried out using a thermal analyzer (SII TG:DTA
6300) by heating between 50 and 1200  C with 10  C/min under
nitrogen flow of 100 mL/min. Additionally, to determine the
exact amount of metal ions inside the hydrogel matrices, the
metal nanoparticles were dissolved with concentrated acid
treatment (three times with 5 M HCl) and their quantification
was done with ICP-AES measurements.
To get information about the metal nanoparticles embedded
inside p(AMPS) matrices Transmission Electron Microscopy
(JEOL 2010) was employed.

2.5.
Utilization of p(AMPS)-Co:Ni and magnetic
composites in the hydrolysis of sodium borohydride
In the utilization of metal nanoparticles stabilized by hydrogel
matrices, there are several parameters affecting the hydrolysis of NaBH4. In this investigation, the effects of the
concentration of NaOH, the amount of NaBH4, the ratio of
Co:Ni in the preparation of the metallic bimetallic cluster
nanoparticles, and the temperature on the hydrolysis of
NaBH4 were investigated. 0.2 g p(AMPS) or magnetic p(AMPS)
containing Co-Ni nanoparticles at different molar ratios were
smashed into smaller pieces and placed in flasks containing
50 mL 50 mM (0.095 g) NaBH4 with various amounts of NaOH
0e10 wt % at 30  C. To investigate the effect of the catalyst
amounts on the hydrolysis of NaBH4, various amounts of
hydrogel-composites at six different concentrations: 0.1, 0.2,
0.4, 0.75, 1.0 and 1.5 g were placed in 50 mL 50 mM (0.095 g)
NaBH4 containing 5 wt % NaOH at 30  C. To observe the initial

concentration effect of NaBH4 and to see its effect on the

reaction rate and the conversion, three different concentrations of NaBH4 (25, 50 and 150 mM) were used each containing
0.2 g hydrogel-composite catalyst in the presence of 5 wt %
NaOH. Similarly, to understand the effect of the volume of
solution on hydrolysis rate of NaBH4 and the conversion, the
solution volume was changed between 20 and 100 mL, each
containing 0.095 g NaBH4 with 5 wt % NaOH using 0.2 g
hydrogel-Co-Ni nanoparticles.
To determine the effect of metal composition in hydrolysis
of the NaBH4, the hydrogel matrix stabilized Co:Ni bimetallic
clusters at different mole ratios: 1:0, 2:1, 1:1, 1:2 and 0:1 were
used in the same reaction conditions: 0.2 g hydrogelcomposites, 50 mL 50 mM (0.095 g NaBH4 with 5 wt % NaOH
at 30  C).
It is known that the eSO3 functional groups are responsible
for metal ion absorption in the p(AMPS) structure. Once they are
loaded with metal ions they are connected or linked to the metal
ions, upon reduction of these seized metal ions with NaBH4,
these functional groups are freed and can be used potentially for
reloading with the same or different metal ions. Therefore,
initially Co or Ni nanoparticles or nanoclusters are formed
inside p(AMPS) hydrogels and later these metal nanoparticlecontaining hydrogels were reloaded with Co (II) or Ni (II) ions
by absorption from their corresponding metal ion solutions.
Again reducing with NaBH4 generated Co Co, Co Ni, Ni Ni
and Ni Co bimetallic nanoparticles embedded in p(AMPS) and
the formed bimetallic catalyst systems were also tested in the
hydrolysis of NaBH4 (50 mL 30  C in 50 mL 50 mM (0.095 g NaBH4
with 5 wt % NaOH)).
To determine the activity and the conversion, two types of
experiments were performed. Firstly, 0.2 g hydrogel containing bimetallic cluster catalysts (Co-Ni) were used 5 times
sequentially in a day at the standard reaction conditions (30  C
in 50 mL 50 mM (0.095 g NaBH4 with 5 wt % NaOH)). Secondly,
to see the storage capacity of the hydrogel-metal catalyst
systems, after their synthesis, they were stored in purified
water for 1, 5, 10 and 15 days and then tested for their catalytic
performances.
In the kinetic studies of the hydrolysis reaction, the
temperature was scanned with 10  C increments from 30 to
70  C with the standard reaction conditions. The reduced
amount of NaBH4 was determined with the production rate of
hydrogen via the ideal gas equation. All the experiments were
performed at 1500 rpm mixing rate and the produced
hydrogen amount was measured at specific times via a digital
flow-meter (Alicat Scientific, Alicat M Series). To remove the
water vapor (as reactions were carried out in an aqueous
solution of NaBH4), the produced H2 gas was passed through
100 mL H2SO4 via a gas washing set up. Additionally, the
experimental set up was arranged in a way that, after the gas
passed through the flow-meter, it was also sent to an inverted
water-filled graded cylinder using the principle that the
produced gas replaces the liquid to confirm the flow-meter
results were correct. For all the experiments, the room
temperature was set at 30  C  3 and the atmospheric pressure
was taken as 1 atm as the lab is situated 50 m above sea level.
All the experiments in this investigation were repeated three
times and the standard deviation are given in the constructed
graphs.

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100

Results and discussion

To load metal ions e.g., Co (II) and Ni (II), into the hydrogel
network via the electrostatic interaction with the functional
groups of the hydrogel (-SO3H) and the metal ions, a certain
amount 0.2 g of p(AMPS) hydrogels were placed in 0.1 M Co (II)
and 0.1 M Ni (II), with Co:Ni ions at 1:1 molar ratios, for 24 h
under constant shaking at ambient temperature. The absorbed
amount of metal ions was determined by ICP-AES measurements. The metal ion-loaded hydrogels were also washed with
purified water for 24 h to extract the unbound metal ions and
this was taken into considerations in the ICP-AES measurements. Upon reducing the metal ions inside p(AMPS) hydrogels
with 0.5 M 100 mL NaBH4, thermogravimetric analysis was also
performed on bare and p(AMPS)-metal nanoparticle composites, each weighing w3 mg with a 10  C/min heating rate under
N2 100 mL/min flow rate by heating up to 1200  C from 50  C.
The determined amount of metal using both methods is
summarized in Table 1. As demonstrated, in the TG analysis of
hydrogel-composite systems, the amount of inorganic parts
varied between 17.4  0.5e22.7  0.9 wt %, mostly as metal
particles depending on the mole ratios used to load hydrogels
(1:0; 2:1; 1:1; 1:2; 0:1). TGA gives the amount of inorganic parts of
the material that also contain metal oxides in addition to boron
and sodium. The inorganic part is not necessarily metal
particles as was demonstrated by ICP-AES measurements after
dissolving the metal particles inside hydrogels by 5 M HCl
treatments three times. It was found that Co:Ni (1:1) metal
particle-containing p(AMPS) hydrogel contains 20.8  2.6 mg
boron and 34.3  2.9 mg sodium per gram of hydrogels. As can
be seen from Table 1, the TGA values are higher than the ICPAES results due to the oxidation of metal particles inside
hydrogels. Because of the acid functional groups on the
hydrogel backbone and due to heating during TGA measurements, it is possible to form metal oxides. The TGA thermogram shown in Fig. 1 also reveals that bare p(AMPS) starts to
degrade above 200  C, and upon introduction of metal nanoparticles the degradation temperature rises to over 400  C, this
a significant increase in which the prepared hydrogel-metal
nanocatalyst system can be used for reactions that may
require higher temperatures.
To illustrate that the amount of metal nanoparticle in the
hydrogels can be increased by sequentially loading (absorption)
and reducing inside hydrogels, after one loading-reducing
procedure, the hydrogels were loaded with metal ions again
and reduced. This allows one to control the amount of catalyst
and also provides an opportunity to prepare multiple catalysts

80

TG %

3.

60
40
20

(1)
(2)
(3)
(4)
(5)
(6)

(6)
(5)
(4)
(3)
(2)

p(AMPS)
p(AMPS)-Ni
p(AMPS)-Co:Ni
p(AMPS)-Co
p(AMPS)-Ni+Ni
p(AMPS)-Co+Co

(1)

0
200

400

600

800

Temp Cel
Fig. 1 e Thermogram of p(AMPS) and composite p(AMPS)
hydrogels.

in one hydrogel matrix. For example, after loading the hydrogel

with Co (II) and Ni (II) ions and reducing with NaBH4, it can
again be loaded with the same metal ions or different ones and
then reduced repeatedly allowing bimetallic or more metal
nanoparticle formation. As demonstrated in Table 2, the first
absorption of Co (II) is 128.1  5.3 mg/g, and after reducing the
second absorption by p(AMPS) is 117.7  5.7 mg/g Co (II) that is
less than the first one. After reducing in situ and dissolving this
Co Co metal nanoparticle by treatment with 100 mL 5 M HCl
three times, 241.6  6.6 mg/g Co (II) was found by ICP-AES
measurements. These results demonstrate that the multi
step loading and reducing of the metal ions is almost additive
of each loading procedure. Table 2 summarizes the hydrogelbimetallic metal nanoparticle composites metal ion content
by two time loading and reduction of the Co (II) and Ni (II) with
variations in the order.
The prepared particles are in the order of tens of nanometer to a few hundred nm as illustrated by the TEM images in
Fig. 2. The bimetallic cluster particle sizes, as shown in Fig. 2a,
are also in the same order of magnitude upon comparison of
Co and Ni nanoparticles inside p(AMPS) matrices [5,7,8]. One
of the most significant problems that should be solved is the
control of the hydrogen generation, or on demand generation
of the hydrogen, in real applications. Therefore, we introduced a magnetic responsive behavior for the first time to
metal nanoparticle catalyst-containing p(AMPS) catalyst
system by the in situ preparation technique of ferrites. The
iron ions (Fe (II); Fe (III) in 1:2 M ratio) were loaded inside the
hydrogel and precipitated with ammonia as reported earlier

Table 1 e The amount of metal ion in p(AMPS)-Co:Ni bimetallic cluster catalyst prepared at different molar feed ratios.
Co:Ni mixture
in feed

ICP-AES Absorption
Results (mg/g Hydrogel)
Co

1:0
2:1
1:1
1:2
0:1

128.1  5.3
87.2  3.8
64.7  4.2
42.6  4.7
e

Ni
e
39.5  3.1
60.4  3.4
81.4  5.7
122.6  4.6

ICP-AES Desorption
Results (mg/g Hydrogel)
Co
124.3  4.6
84.3  4.2
61.6  3.7
41.8  3.9
e

Co-Ni Alloys
TG Results (Residue %)

Ni
e
38.6  2.8
57.8  3.6
79.0  3.2
118.3  3.9

22.7
20.9
18.7
17.7
17.4







0.9
1.0
0.6
0.7
0.5

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Table 2 e The amount of metal ions inside bimetallic-p(AMPS) hydrogel-catalyst systems prepared by sequential addition
and reduction (mg/g hydrogel).
I. Ion

I. Absorption

II. Ion

II. Absorbtion

ICP-AES Desorbtion
Results (mg/g Hydrogel)
Co

Co
Co
Ni
Ni

128.1 
128.1 
122.6 
122.6 

5.3
5.3
4.6
4.6

Co
Ni
Ni
Co

117.7 
108.2 
106.3 
119.0 

5.7
4.2
5.8
6.9

[2]. As confirmed with TEM images, shown in Fig. 2b, the

prepared magnetic ferrites were 10e20 nm in dimension and
confirmed with EDS to be in a separate position from the metal
nanocatalysts in hydrogel matrices.
It is very well known that the hydrolysis of NaBH4 is
favored in a basic medium, therefore; we investigated the
optimum NaOH concentration in the hydrolysis of NaBH4 by
changing the weight ratios from 0 to 10% in the solution (0, 2.5,
5 and 10 wt %). Even without a base, the pH of the solution is 9
and as the reaction progressed the pH gets higher as the
formation of NaBO2 increases, as given in equation (1). As
illustrated in Fig. 3 in hydrolysis of NaBH4 with p(AMPS)-Co:Ni
bimetallic clusters, beyond a certain amount of NaOH, the
production rate of H2 and conversion do not change significantly and are almost the same for 5 and 10 wt % NaOH. In the
hydrolysis of NaBH4 with 5wt % NaOH at 30  C with p(AMPS)Co:Ni bimetallic cluster catalyst (12.32 mg Co 11.56 mg Ni
determined by ICP-AES), 246 mL H2 (g) was generated and the
yield was 99%. The same amount of NaOH was reported for
single metal nanocatalyst catalyzed NaBH4 hydrolysis reaction [8], therefore, for the bimetallic cluster catalysts 5 wt %
NaOH (2.5 g) was used in this investigation.
To observe the effect of the prepared metal catalysts with
various formulations on the production amount of hydrogen in
hydrolysis of NaBH4 in the same reaction conditions, volume vs
time graphs were constructed and are illustrated in Fig. 4. Upon
changing the composition of the bimetallic clusters i.e.,
increasing the amount of Co in the Co:Ni bimetallic cluster

241.6  6.6
122.5  7.3
e
114.8  6.0

Co-Ni Alloys
TG Results (Residue %)

Ni
e
104.4  7.9
223.2  8.2
116.7  5.9

35.3
29.4
27.7
30.1

 1.3
 1.2
 1.4
 1.6

nanocatalysts, the hydrogen production amount was increased

significantly and when no Ni was used the fastest hydrogen
production amount was obtained, that is 99% conversion in
about 10 min with 0.2 g p(AMPS) metal catalyst employed in 1:0
(Co:Ni) ratio. On the other hand, the same amount of conversion
and amount of hydrogen is produced for 0:1 (Co:Ni) bimetallic
cluster in about 55 min while it took 30 min for 1:1 (Co:Ni)
bimetallic cluster to obtain the same results. The rate is 5.5
times faster for Co than for Ni catalysts in hydrolysis of NaBH4
under the same reaction conditions. As revealed in Fig. 4b, when
bimetallic catalysts (obtained by sequential absorption and
reduction procedures) were employed in the hydrolysis of
NaBH4, the Co catalyst showed superior catalytic performances
than Ni catalyst. In the H2 gas production rate, the order of
Co Co > Co Ni > Ni Co > Ni Ni was obtained. It can be
inferred from this order and as shown in Fig. 4b that the Co Ni
catalyst system generates hydrogen faster than Ni Co, suggesting that some of Co particles inside p(AMPS) hydrogels were
covered with Ni metal responsible for the reduced hydrogen
generation rate under the same reaction conditions. The Ni Ni
catalyst (44.64 mg Ni) completed the reaction in 32 min whereas
Ni Co (Ni 22.96 mg; Co 23.34 mg); Co Ni (Co 24.50;
Ni 20.88 mg); Co Co (Co 48.32 mg the amounts were
determined by ICP-AES) completed in 15, 12 and 6 min,
respectively all with 99% conversion. For Co Co bimetallic
catalyst as the amount of Co was doubled, the reaction rate
increased 1.8 fold suggesting that some of the Co metals do not
completely take part in the reduction reaction.

Fig. 2 e TEM images of (a) bimetallic clusters (Co:Ni in 1:1molar ratio in feed) particles and (b) same bimetallic clusters in the
presence of magnetic ferrite particles.

15255

200
10 % NaOH
5 % NaOH
2.5 % NaOH
0 % NaOH

100

0
0

15

30

45
Time (min)

60

75

90

Fig. 3 e The effect of NaOH on the hydrolysis of NaBH4

[0.2 g p(AMPS)-Co-Ni (1:1) bimetallic cluster (containing
12.32 mg Co D 11.56 mg Ni nanoparticles); 50 mM 50 mL
[0.095 g NaBH4; 30  C; 1500 rpm].

Volume of generated hydrogen (mL)

The effect of the catalyst amount on hydrolysis is

demonstrated in Fig. 5, Co:Ni (1:1) ratio was constant but
catalyst amount was increased by using 0.1, 0.2, 0.4, 0.75, 1.0
and 1.5 g p(AMPS)-Co:Ni catalysts (the amount of metal ions
was 6.16 mg Co 5.78 mg Ni per 0.1 g hydrogel) using 5 wt %
NaOH in 50 mL 50 mM NaBH4 (0.095 g) hydrolysis. As can be
seen from Fig. 5, all the reactions produced the same amount
of hydrogen (246 mL) in different reaction times; as the
amount of catalyst increased the reaction rate also increased.
To investigate the effect of NaBH4 concentration in the
hydrolysis reaction catalyzed by p(AMPS)-Co:Ni (1:1) catalyst
system the concentration of NaBH4 was varied. As

300

200

Co:Ni
1:0
2:1
1:1
1:2
0:1

100

Volume ofgenerated hydrogen (mL)

10

20

30

40

50

60

Time (min)
300

200

Co+Co
Co+Ni
Ni+Co
Ni+Ni

100

0
0

10

15

20

25

30

35

Time (min)

Fig. 4 e The effect of metal ion ratio in feed for bimetallic

cluster (a) and bimetallic catalyst (b) on the hydrolysis of
NaBH4. [0.2 g p(AMPS) hydrogel used (for loading Co and Ni
in different molar ratios in (a) and in bimetallic catalyst
preparations in (b); 50 mM 50 mL (0.095 g) NaBH4; 30  C;
1500 rpm].

Volume of generated hydrogen (mL)

300

300

200

179.1 mg
119.4 mg
89.55 mg
47.76 mg
23.88 mg
11.94 mg

100

0
0

15

03

45

60

75

90

Time (min)

Fig. 5 e The effect of catalyst amount on the hydrolysis of

NaBH4 [Co:Ni (1:1), and 5 wt % NaOH; 50 mM 50 mL (0.095 g)
NaBH4; 30  C; 1500 rpm].

demonstrated in Fig. 6, the bimetallic cluster catalyst containing (12.32 mg Co and 11.56 mg Ni inside 0.2 g hydrogel) was
used in the hydrolysis of NaBH4 at three different concentrations, 25 mM, 50 mM and 150 mM, at 30  C with 5% NaOH. As
the reaction is zero order with respect to the initial concentration of NaBH4, as the concentration of NaBH4 increased, the
amount of the produced hydrogen gas also increased. When
25 mM (50 mL) NaBH4 was used, 126 mL H2 was produced in
25 min and when 150 mM (50 mL) NaBH4 was used 742 mL H2
gas was produced, a little less than 6 fold (supposed to be
756 mL), in 90 min. Also to investigate the dilution effect,
keeping all the parameters the same (NaOH concentration,
temperature, mixing rate and the amount of catalyst), we used
0.095 g NaBH4 in 20e100 mL DI, and found out that the reaction yield and the reaction time were not changed (data is not
shown). To examine the effect of temperature on the hydrolysis reaction catalyzed by p(AMPS)-Co:Ni bimetallic cluster
catalyst (12.32 mg Co 11.56 mg Ni) system using 0. 2 g
hydrogel-catalyst system for 50 mL 50 mM NaBH4 (0.095 g)
with 5% NaOH (2.5 g), hydrolysis reactions were carried out at
different temperatures with 10  C increments and the corresponding graph is shown in Fig. 7. For all the reactions run at
different temperatures, almost 246 mL H2 was obtained at
different times. For example, the reaction was completed in
30 min at 30  C, whereas the same reaction was completed
about 5 times quicker (6 min) at 70  C. The reaction rate
constants calculated at different temperatures are shown in

Volume of generated hydrogen (mL)

Volume of generated hydrogen (mL.)

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 ) 1 5 2 5 0 e1 5 2 5 8

800
600
400
150 mM NaBH4
50 mM NaBH4
25 mM NaBH 4

200
0
0

25

50
Time (min)

75

100

Fig. 6 e The effect of NaBH4 amount on the hydrolysis of

NaBH4 (Volume 50 mL, 0.2 g p(AMPS) hydrogel Co:Ni (1:1)
(containing 12.32 mg Co and 11.56 mg Ni) composite with
5 wt % NaOH; 30  C; 1500 rpm].

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 ) 1 5 2 5 0 e1 5 2 5 8

% Hydrogen Production

Volume of generated hydrogen (mL)

15256

300

200

70 C
60 C
50 C
40 C
30 C

100

105

100
95
90
85

Conversion
Activity

80
75

0
0

10

15

20

25

30

35

3
Number of Cyles

Time (min)

Table 3 e The rate constants for the hydrolysis of NaBH4

hydrolysis at different temperatures. [50 mM 50 mL
(0.095 g NaBH4; 0.2 g bimetallic-p(AMPS)-Co-Ni (1:1)
(containing 12.32 mg Co D 11.56 mg Ni) nanoparticle
composites, 5 wt % NaOH; 1500 rpm).
Temperature ( C)
30
40
50
60
70

Rate constant (mol. min-1)

0.0018
0.0029
0.0047
0.0063
0.0082

% Hydrogen Production

Table 3. As can be seen, there is an increase in the NaBH4

reduction rate with the increase in the reduction reaction
temperature. The hydrogen production rate between 30 and
70  C was found as 385e1680 mL H2(min)1(g of catalyst)1. In
the literature, a catalyst containing Co, Ni and P provided
a production rate between 850 and 2400 mL H2(min)1(g of
catalyst)1 depending on the compositions [32]. In another
study by Fernandes et al., 100e1175 mL H2(min)1(g of catalyst)1 hydrogen production rate was obtained using Co-Ni-B
catalyst with compositions [38].
Using rate constants at different temperatures in Arrhenius
and Eyring equations in NaBH4 hydrolysis catalyzed by p(AMPS)Co:Ni (1:1) bimetallic cluster systems, the activation parameters
were calculated from lnk-1/T and ln(k/T)-1/T graphs. The activation energy was 33.05 kJ mol1 and activation enthalpy and
entropy were calculated as 30.37 kJ mol1 and 196.92 J mol-1 K-1,
respectively. Also, the turnover frequency (TOF) for 30e70  C
was calculated between 49e243 mol H2(mol catalyst)1(h)1.
These are comparably good values with the values reported in
the literatures [7,8]. In the literature, zeolites were used as
support for the preparation of Co and Ni nanoclusters with
smaller sizes than the reported particle sizes here. The TOF
values for Co and Ni nanocluster in zeolites reported was higher,
880 mol H2(mol catalyst)1(h)1 for Co and 1450 mol H2 (mol
catalyst)1(h)1 [15,20]. As the catalysts, materials reported here
are much smaller than those, so these results are expected.
To measure the catalytic performance of the Co:Ni bimetallic clusters prepared in p(AMPS) hydrogel at 1:1 M ratio in
feed in the hydrolysis of NaBH4, the same p(AMPS)-Co:Ni

105

100
95
90
85

Conversion
Activity

80
75

1 day

5 day
10 day
Number of Cyles

15 day

Fig. 8 e (a) The catalytic activities of 0.2 g bimetallicp(AMPS)-Co:Ni (1:1) clusters (containing 12.32 mg
Co D 11.56 mg Ni) and their conversion during five
consecutive runs, and (b) their catalytic capabilities after
different storage times. [50 mM 50 mL (0.095 gr) NaBH4;
5 wt % NaOH; 30  C; 1500 rpm].

Volume of generated hydrogen (mL)

Fig. 7 e The effect of temperature on the hydrolysis of

NaBH4. [50 mL 50 mM (0.095 gr) NaBH4; 0.2 g p(AMPS)-Co:Ni
(1:1) bimetallic cluster catalyst system (containing
12.32 mg Co and 11.56 mg Ni); 5% NaOH; 1500 rpm).

300

200

100

Removal of catalyst
(under magnetic field)

Co:Ni
Mag-Co:Ni

0
0

10

20

30

40

50

Time (min)

Magnetic field

Fig. 9 e (a) The effect of magnetic hydrogel on the

hydrolysis of NaBH4. [0.2 g p(AMPS)-Co:Ni (1:1) and
magnetic p(AMPS)-Co:Ni (1:1) [containing 12.32 mg
Co D 11.56 mg Ni); 50 mM 50 mL (0.095 g) NaBH4; 30  C;
1500 rpm]. (b) digital camera images of the removal of
hydrogel-catalyst system during hydrolysis reaction.

60

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 ) 1 5 2 5 0 e1 5 2 5 8

bimetallic cluster catalysts were exposed to the same reduction

reaction in the same day five times successively. Although each
time 100% conversion was obtained, the catalytic activity was
reduced to 96% at the end of the 5th use as illustrated in Fig. 8a.
The catalytic activity was calculated by taking the ratio of the
average rate per min after every use to the initial average
reduction rate per min (first use). Furthermore, to determine
the storage capability of the prepared catalyst systems,
experiments were performed in which the hydrogel-metal
bimetallic clusters were placed for 5 min in N2 bubbled purified water before use in the reactions after storing at different
times. As illustrated in Fig. 8b, even after 15 days of storage
time, 100% conversion and 79% catalytic activity was obtained.
This is an important performance in comparison to bare metal
catalysts, which reduce their catalytic activity very fast due to
aggregation and oxidation.
In addition to the favorable characteristics such as inexpensiveness, high catalytic performance, readily obtainable,
environmentally friendly and so on, a catalyst should also be
readily removable upon completing their task. This is a very
important parameter for a catalyst system to be used in daily
life especially for the production of H2. If a catalyst system can
be designed to stop and start the reaction on demand it would
provide a significant contribution to the control of the reaction
and expand their utilization in many fields. Therefore, we
prepared hydrogel systems that make it possible to prepare
magnetic particle and metal catalyst for various reactions. As
illustrated in Fig. 9a, the hydrogen production can be stopped
by applying an external magnetic field to stop the reaction and
continued by immersion of the magnetic hydrogel catalyst
system in the reaction mixture allowing control of the
hydrogen production on demand. This can be done as many
times as desired. The digital camera images shown in Fig. 9b
are a clear visualization of how this can be done on demand.
External magnetic field is applied to the catalyst system and
the catalyst is removed from the reaction mixture and
hydrogen production stopped. This was done sequentially as
illustrated in Fig. 9a and there is no loss in the performance of
catalyst with the introduction of ferrites inside the hydrogel.
This is an important result of this research that can be
applicable to other catalyst systems for various applications.

4.

Conclusions

In this investigation, the utilization of hydrogel for in situ

metal nanocatalyst preparation in bimetallic clusters and
sequentially formed bimetallic catalyst forms were demonstrated. Furthermore, it was also shown that the magnetic
ferrite particle, together with the any metal catalyst system,
can be readily prepared and used in the hydrolysis of NaBH4
for on demand generation of hydrogen. This ability provides
a significant contribution to real applications of H2 systems
that require strict control of H2 production when used. The
most important outcomes of this investigation are the
following:
 Hydrogel with various functional groups can be used in the
preparation of catalyst in different formulations (alloys,
bimetallic and magnetic)

15257

 The hydrogel-metal catalyst system with magnetic field

responsive behavior can be successfully used in hydrolysis
of NaBH4 for on demand hydrogen production.
 p(AMPS) hydrogel network stabilizes the catalyst and
magnetic particles for a longer time providing a shelter post
use after synthesis.

Acknowledgments
This work is supported by National BOREN Institute of Turkey.
N. Sahiner is grateful to the Turkish Academy of Science for
partial support under 2008 TUBA-GEBIP program. Also, partial
support from the Scientific and Technological Research
Council of Turkey, (110T649) is greatly appreciated.

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