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Hydrogen production from ammonia borane via hydrogel


template synthesized Cu, Ni, Co composites
Ozgur Ozay a, Erk Inger b, Nahit Aktas c, Nurettin Sahiner a,d,*
a

Canakkale Onsekiz Mart University, Faculty of Sciences and Arts, Chemistry Department, Terzioglu Campus, 17020, Canakkale, Turkey
Gazi University, Institute of Science and Technology, Mechanical Engineering Department, 06500, Ankara, Turkey
c
Yuzuncu Yil University, Faculty of Engineering, Chemical Engineering Department, 65080, Van, Turkey
d
Nanoscience and Technology Research and Application Center (NTRAC), Terzioglu Campus, 17020, Canakkale, Turkey
b

article info

abstract

Article history:

In situ Co, Cu and Ni nanoparticles were synthesized by chemical reduction of the

Received 26 February 2011

absorbed Co (II), Cu (II) and Ni (II) ions inside hydrogel networks prepared from 2-acryl-

Received in revised form

amido-2-methyl-1-propansulfonic acid (AMPS) and were used as a catalyst system in the

9 April 2011

generation of hydrogen in hydrolysis of ammonia borane (AB). Several parameters

Accepted 17 April 2011

affecting the hydrolysis reaction such as the type of the metal, the amount of catalyst, the

Available online 11 May 2011

initial concentration of AB, and temperature, were investigated. The activation energy
values in the hydrolysis reaction of AB solution in the presence p(AMPS)-Co, p(AMPS)-Cu

Keywords:

and p(AMPS)-Ni catalyst systems were calculated as Ea 47.7 kJ mol1, 48.8 kJ mol1 and

Hydrogen generation

52.8 kJ mol1, respectively. Thus, the catalytic activity of the metal nanoparticles prepared

Ammonia borane

inside the same hydrogel matrix was found to be Ni < Cu < Co.

Hydrogel nanoreactor

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

Catalysis
Hydrolysis
Hydrogel composites

1.

Introduction

Because of its environmental friendliness, high energy density,


clean combustion product (only water), hydrogen is regarded as
one of the clean fuels [1e4]. Therefore, much research focuses
on hydrogen production from hydrogen storage materials such
as Ca2H, LiH, NaBH4, MgH2, LiAlH4, KBH4, NaAlH4 and H3NBH3
(ammonia borane) with superior catalyst systems [5e8]. Among
these hydrogen storage materials ammonia borane (AB) is an
attractive candidate because of its low molecular weight
(30.7 g mol1) and high hydrogen capacity (19.6 wt %) [9e11].
Furthermore, AB has high water solubility (33.6 g AB/100 g water)
[12], higher stability in aqueous solution at room temperature

[13,14], is nontoxic [15], and has an exothermic hydrolysis


reaction (DH 155.97 kjmol1) [16].

NH2 BH3 aq2H2 Ol catalyst NH
4 aqBO2 aq3H2 g
/

(1)
AB releases hydrogen gas in the presence of a suitable
catalyst at room temperature according to the equation above
(Eq. (1)) [17e20]. Recently, numerous transition metal catalyst
systems such as: intrazeolite palladium(0) [17]; Co(0) [18], Rh(0)
[15,21] and Cu(0) nanoclusters [22]; water soluble polymer
stabilized Ni(0) [1], Rh(0) [16], Ru(0) [19,23] and Pd(0) [23]
nanoclusters; Cu/Co3O4 nanoparticles [2], hollow NieSiO2

* Corresponding author. Canakkale Onsekiz Mart University, Faculty of Sciences and Arts, Chemistry Department, Terzioglu Campus,
17020, Canakkale, Turkey.
E-mail address: sahiner71@gmail.com (N. Sahiner).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.04.140

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nanospheres [3], CoeB thin film [5], electroplated CoeP catalyst [6], magnetically recyclable Au@Co core-shell nanoparticles [9], PtxNi1-x nanoparticles [13], Co nanoparticles [24],
Pt- and Ni-based alloy catalysts [25]; monodispersed Ni
nanoparticles [26], SiO2 supported monodispersed Ni nanoparticles [27], Co nanospheres [28] and bimetallic AueNi
nanoparticles [29]; magnetically recyclable hollow CoeB
nanospindles [30] and montmorillonite immobilized Ru
nanoparticles [31] have been reported for use in the hydrolysis
reaction of AB. Direct utilization of metal nanoparticles as
catalyst is somewhat restricted due to aggregation and
destabilization [32,33]. To prepare a catalyst with better catalytic activities and to prevent aggregation generally supporting materials such as silicates [3,27e29], clays [31], zeolites
[15,17,18,21,22] and most recently hydrogels, have been
utilized [7,8,32e35]. Amongst these materials hydrogels
attract special attention due to characteristics such as
different functional groups in three-dimensional waterswollen, crosslinked hydrophilic polymeric networks
providing a unique environment for the preparation and
protection of metal nanoparticles. The anionic functional
groups eSO3 and eCOO in the hydrogel networks readily
form negative charges in aqueous environments to absorb
metal ions via electrostatic interactions and then reduce these
hydrogel bound metal ions to form metal nanoparticles.
Taking advantage of the flexible (swelling and shrinking
ability) advantages of hydrogel networks, various metal
nanoparticles or nanoclusters can be prepared in situ by
reduction of absorbed metal ions with suitable reducing
agents such as NaBH4 [7,8,32e35], providing an expanded
range of applications from environmental remediation to
biomedical applications [36e38].
Previously, our group reported the synthesis of p(AMPS)
hydrogel networks and its use in the preparation of Ni, Co, Fe,
and Cu nanoparticles and utilization of these particles in the
reduction of 2- and 4-nitrophenols [32,33]. The in situ prepared
Ni and Co nanoparticles in p(AMPS) hydrogel networks used as
catalyst in the hydrolysis of NaBH4 [7,8] were also reported. In
addition to Co and Ni metal nanoparticles, we report the
preparation of Cu nanoparticles in p(AMPS) networks and their
utilization as catalyst in the hydrolysis of AB in aqueous media.
Additionally, after using the p(AMPS)-M (M: Co, Ni, Cu) catalyst
system in the generation of hydrogen, the metal catalyst can be
readily removed from the hydrogel template and it can then be
reloaded with desired metal catalysts. The reaction kinetics
were investigated under different reaction conditions and
various parameters, such as AB concentration, temperature,
catalyst amount and type, affecting the hydrolysis processes of
AB were evaluated. The reaction was carried out at five
different temperatures to calculate the activation parameters.
The activity and repetitive usage of the catalystehydrogel
system was also investigated.

2.

Experimental

2.1.

Materials

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

(MBA) as crosslinker, 2,20 -azobis(2-methylpropionamidine)


dihydrochloride (MPA) as UV initiator were used and purchased
from SigmaeAldrich and Acros Chemical Companies.
NiCl2.6H2O (Riedel de Haen), CoCl2$6H2O (Aldrich) and
CuCl2$2H2O (Aldrich) as metal ion sources and NaBH4 (Aldrich)
as reducing agent were used for in situ metal particle preparation. NH3BH3 (Aldrich) was used as hydrogen source. All the
reagents were of analytical grade or highest purity available,
used without further purification.
The 18.2 MU cm (Millipore Direct-Q3 UV) distilled water
was used for preparation, washing of hydrogels, and for
preparation of the reagents. The metal nanoparticle content of
p(AMPS) hydrogels was determined via Thermogravimetric
Analysis (SII TG/DTA 6300) and Inductively Coupled PlasmaAtomic Spectrometry (Varian Liberty II AX Sequential ICPAES) measurements. TG measurements were performed
between 50 and 1200  C with10  C/min heating rate under
100 ml/min nitrogen flow.

2.2.
Hydrogel synthesis and in situ metal particles
preparation
P(AMPS) hydrogels were synthesized according to the procedure in the literature [7,8]. Synthesis of metal nanoparticles
inside the hydrogel network was carried out by using 100 mg
dry hydrogel according to the procedure in the literature
[7,8,32e35].

2.3.

Catalytic hydrolysis and kinetic studies of AB

The catalytic activity of in situ metal nanoparticles inside


p(AMPS) hydrogels in the hydrolysis of AB was determined by
measuring the hydrogen generation rate. All the experiments
were carried out by using 50 mM 50 ml AB (0.077 g) solution
and 100 mg dried hydrogel, containing different metal nanoparticles, in a 100 ml reaction flask. The reactions were performed at 1000 rpm mixing rate at 30  C in 1 atm if not stated.
The generated amount of hydrogen gas at specified time
intervals was passed through 100 ml of concentrated H2SO4 to
remove water vapor from the gas washing bottle and the
amount of hydrogen gas was determined from the inverted
volumetric cylinder, based on the principle of substitution
(filled water was replaced by produced H2 gas). All the experiments were conducted three times and the constructed
graphs are presented with standard deviation.
In order to determine the effect of the types of catalysts,
100 mg of hydrogel containing 12.4 mg Co, 11.0 mg Cu or
11.8 mg Ni nanoparticles (determined by ICP-AES measurements) was crushed and used by placing into a reaction flask
containing aqueous solution of 50 mM 50 ml AB at 30  C for the
hydrolysis reaction.
In order to determine the effect of the amount of catalyst on
the hydrolysis reaction of AB at 30  C and 1000 rpm mixing rate,
five different amounts (50e500 mg) of Co nanoparticlecontaining hydrogels were placed into 50 mM 50 ml AB solution. The weights of the hydrogels containing Co nanoparticles
were 50 mg, 100 mg, 150 mg, 300 mg and 500 mg.
For the kinetic studies, 100 mg crushed hydrogel-Co
composites were used in hydrolysis of 50 mM 50 ml AB

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solution at five different temperatures with an increment of


10  C in the range from 30 to 70  C.
To determine the effect of initial concentration of AB on
the reaction rate and to assess the degree of reaction, 50 ml of
four different AB solutions varying the concentration of AB
from 25, 50, 100, to 200 mM were used in the hydrolysis
reactions at 30  C and 1000 rpm mixing rate.
To evaluate whether these p(AMPS)-Co composite systems
are reusable or not, 100 mg of the composite catalyst was used
5 times consecutively, rinsing with DI water between every
use, in the hydrolysis of 50 ml 50 mM AB at 30  C and 1000 rpm
mixing rate. Additionally, the shelf-life of the prepared
composite catalyst was investigated by storing freshly
prepared p(AMPS)eCo systems in DI water for 1, 3, 5 and 10
days, and using them (each one with 12.4 mg Co nanoparticles
p(AMPS)) in the hydrolysis reaction of AB under the same
reaction conditions.

2.4.

Reloading of the catalyst particles

To reload p(AMPS) hydrogel with metal nanoparticles


p(AMPS)eCo composite system was treated with 5 M HCl to
dissolve Co metal particles after performing their task and
then, as mentioned in section 2.2, Co or other metal ions can
be reloaded by absorption from their corresponding solution
and reduced by NaBH4 inside this hydrogel matrix.
For the determination of the effect of metal loading number,
two different types of p(AMPS)-Co catalyst systems were used
in the hydrolysis reaction of 50 mM 50 ml AB at 30  C with
1000 rpm mixing rate. In the first loading the catalyst system
had 24.8 mg Co in 200 mg p(AMPS) hydrogel and in the second
the catalyst system had 20.6 mg Co in p(AMPS) after two
consecutive metal ion loadings and reductions.
In order to determine the effect on hydrogen production
rate, hydrolysis of AB or NaBH4 (50 ml 50 mM) was carried out
by using 100 mg p(AMPS)-Co catalyst system at 30  C and
1000 rpm mixing rate.

3.

Result and discussion

3.1.
Determination of the amount of metal nanoparticles
in p(AMPS) network and characterization
Previously, we reported in situ metal particle preparation in
crosslinked p(AMPS) hydrogel networks and showed that they
are highly porous visualized by cryo-SEM images (depending
on the crosslinking ratio, about 200 mm pore can be obtainable)
and the porosity of hydrogel networks can be controlled by the
amount of crosslinker used during hydrogel synthesis [34,35].
The metal nanoparticle content of p(AMPS) hydrogels was
determined via Thermogravimetric Analysis (SII TG/DTA
6300) and Inductively Coupled Plasma-Atomic Spectrometry
(Varian Liberty II AX Sequential ICP-AES) measurements
according to previously reported literature [7,8,32e35]. The
determined amount of Co (124 mg/g dry gel) and Ni (118 mg/g
dry gel) using ICP-AES according to previously reported literature was assumed in the experimental studies. To determine
the amount of metal nanoparticles inside p(AMPS) e.g., Cu,
p(AMPS)-Cu composite systems were treated with 5M 100 ml

HCl three times and the eluted Cu(II) concentration was found
to be 110 mg/g dry gel by ICP-AES according to literature
procedure. All TGA and ICP measurements are summarized in
Table 1. As can be seen in Table 1, ICP-AES always measured
metal nanoparticles lower than the TGA measurement. As
illustrated with ICP-AES measurements p(AMPS)-metal
composite systems contain some boron and sodium that
was included in the TGA measurements. As the TGA analysis
gave inorganic parts of the composites. i.e., metal, sodium and
boron, the determined amount of inorganic parts of the
composites is larger than the results obtained by ICP-AES
measurements. To further corroborate metal (Co, Cu and Ni)
particle formation, p(AMPS)-metal composites were ground
with mortar and pestle to form a powder, a drop of this
powder suspended in ethanol was placed on a formvar coated
TEM grid to microscopically visualize the metal particles in
the p(AMPS) network. According to the TEM images in previously reported literature [7,8,32,33], the obtained Co and Ni
nanoparticles are about 100 nm in size and Cu nanoparticles
have a wide variation from tens of nanometers to over
a hundredth of a nanometer. Fig. 1a shows the TEM image of
cobalt nanoparticles in p(AMPS) hydrogel network.

3.2.
The effect of metal species on the hydrogen
generation rate
In situ Co, Cu and Ni nanoparticles in p(AMPS) hydrogel
networks were used as catalyst in the hydrolysis reaction of
AB. For this purpose, 100 mg p(AMPS) hydrogel containing any
metal nanoparticle e.g., Co (12.4 mg), Cu (11.0 mg) or Ni
(11.8 mg), was used in the hydrolysis of 50 ml 50 mM AB at
30  C and 1000 rpm mixing rate. As shown in Fig. 1b, 186 ml
hydrogen gas was produced with p(AMPS)-Co composite
systems in approximately 25 min, whereas when p(AMPS)-Cu
and p(AMPS)-Ni were used they produced the same amount of
hydrogen in 65 min and 75 min, respectively. The reaction
rates relating to hydrolysis of AB were 637 (ml H2) (min)1 (g of
Co)1 for Co, 287 (ml H2) (min)1 (g of Cu)1 for Cu and 242 (ml
H2) (min)1 (g of Ni)1. Additionally, the total turnover
frequencies (TOF) were calculated for all p(AMPS)-metal
composites and were 1.43, 0.72 and 0.54 mol H2 (mol catalyst. min)1 for Co, Cu and Ni, respectively. In this investigation, the prepared p(AMPS)-Co composite showed better
catalytic activity in comparison with Cu and Ni particles
prepared by the same methods. Therefore, p(AMPS)-Co

Table 1 e The metal content of hydrogel in metal catalyst


systems.
Hydrogel
-composite

p(AMPS)-Co
p(AMPS)-Cu
p(AMPS)-Ni

124.3  4.6
110.0  3.4
118.3  3.9

Catalyst
(mg)

B (mg)

22.5  3.7
24.9  3.2
23.3  4.1

Na (mg)

49.6  5.9
36.5  2.1
27.3  4.7

b
TG
Residue
(mg)

227  9
187  7
174  5

a The amount of catalyst were calculated per gram of hydrogel.


b Inorganic parts of the composites (Metal nanoparticle (Co, Cu or
Ni) B Na).

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Fig. 2 e The effect of hydrogel-Co composite amount on AB


hydrolysis (50 mM 50 ml AB, 30  C, 1000 rpm).

However, this fairly good linear correlation indicates that the


hydrolysis reaction is first order with respect to the catalyst
amount. Therefore, the amount of p(AMPS)-Co was chosen as
100 mg for subsequent experiments.

3.4.
Fig. 1 e (a). The TEM image of hydrogel supported Co
nanoparticles. (b) The effect of metal species on AB
hydrolysis (50 mM 50 ml AB, 100 mg hydrogel-metal
composite (containing 12.4 mg Co0; 11.0 mg Cu0 and
11.8 mg Ni0), 30  C, 1000 rpm).

composite catalyst was used in order to investigate the effect


of parameters such as temperature, catalyst amount, and AB
concentration on hydrolysis of AB.

3.3.
The effect of the amount of catalyst on the
hydrolysis reaction of AB
To examine the effect of the catalyst on AB hydrolysis,
different amounts of Co nanoparticle-containing p(AMPS)-Co
composites weighing 50, 100, 150, 300 and 500 mg (containing
6.2, 12.4, 18.6, 37.2, 62.0 mg Co (0), respectively) were used in
the hydrolysis of 50 mM 50 ml AB at 30  C and 1000 rpm mixing
rate. As illustrated in Fig. 2, the plots of the hydrogen generation volume versus time, and hydrogen production rate with
amount of catalyst (the inset) show there is a almost linear
relationship between them. It is apparent from Fig. 2 that
186 ml hydrogen with 50 mg p(AMPS)-Co (containing 6.2 mg
Co) was produced in 42.5 min; on the other hand, the same
reaction took 5 min with 500 mg p(AMPS)-Co composite. A
tenfold increase in the amount of catalyst speeds the reaction
8.5 fold. The hydrogen production rates were 405, 637, 967,
1774 and 2921 (ml H2) (min)1 (g of Co)1 for 6.2, 12.4, 18.6, 37.2,
62.0 mg Co (0), respectively. Therefore, the increase in the
amount of catalyst increases the rate of hydrogen production
almost linearly for all the reactions performed under the same
conditions. The slight deviation from linear behavior could be
due to the interaction of the catalysts with each other, which
may hinder the reaction when used in larger amounts.

The effect of temperature on the hydrolysis of AB

To inspect the effect of temperature on the hydrolysis reaction, the temperature range was chosen as 30e70  C with 10  C
increments. The temperature was fixed at the desired level in
an oil bath for 30 min, then the hydrolysis reaction was carried
out with 50 ml 50 mM AB using 100 mg p(AMPS)-Co composite.
All the reactions performed at the five temperatures
(30e70  C), generated an average of 186 ml H2 gas at each
temperature. As illustrated in Fig. 3, at 30  C the reaction was
completed in 27.5 min, whereas at 70  C the hydrolysis reaction was completed in about 3 min, almost 9 times faster than
the reaction at 30  C. The hydrogen production rates were
found in the range of 673e5878 (ml H2) (min)1 (g of Co)1 for
the temperatures between 30 and 70  C which is comparable
with the literature [18,39e41]. Similar experiments were also
carried out by using p(AMPS)-Cu and p(AMPS)-Ni catalyst
systems (data are not shown). The activation parameters for
the hydrolysis reactions of AB with p(AMPS)-Co, p(AMPS)-Cu
and p(AMPS)-Ni composite catalyst systems were calculated

Fig. 3 e The effect of temperature on AB hydrolysis (50 mM


50 ml AB, 100 mg hydrogel-Co composite (containing
12.4 mg Co0), 1000 rpm).

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using the well-known Arrhenius and Eyring equations and the


constructed ln k versus 1/T graph is shown in the inset of Fig. 3
for p(AMPS)-Co composite catalyst. The activation energy
values for the hydrolysis reaction of AB solution were calculated as Ea 47.7 kJ mol1 for p(AMPS)-Co catalyst system,
48.8 kJ mol1for p(AMPS)-Cu catalyst system, and 52.8 kJ mol1
for p(AMPS)-Ni catalyst system. The other activation parameters for the hydrolysis reaction of AB using p(AMPS)-Co,
p(AMPS)-Cu and p(AMPS)-Ni composite catalysts are given in
Table 2. As seen p(AMPS)-Co catalyst provides lower activation energy than p(AMPS)-Cu and p(AMPS)-Ni catalyst
systems in AB hydrolysis. Therefore, for the metal nanoparticles prepared in the same p(AMPS) matrix the catalytic
activity order is Ni < Cu < Co. The comparison of other catalyst systems with this investigation in terms of activation
energies for the hydrolysis reaction of AB solution are listed in
Table 3. As shown in the table, apart from the nanoparticleassembled CoeB thin film [5], cobalt-molybdenum-boron/
nickel foam [12], PtxNi1-x nanoparticles [13], SiO2 supported
monodispersed nickel nanoparticles [27]; p(AMPS)-metal
composite catalyst provides the lowest activation energy in
the catalytic hydrolysis of AB solution with additional favorable characteristics. Due to their flexibility hydrogel networks
have the ability to swell/shrink in response to external stimuli
providing additional functionality.

3.5.
The effect of AB concentration on the catalytic
hydrolysis reaction
In order to determine AB concentration effect on the hydrolysis rate, a series of experiments were carried out by using
four different AB concentrations, 25 mM, 50 mM, 100 mM, and
200 mM each with 50 ml volume using 100 mg p(AMPS)-Co
composite catalyst at 30  C. The produced H2 with time for
each AB concentration is shown in Fig. 4. As shown in the
figure, the amount of produced hydrogen gas changed
between 93 and 744 ml with p(AMPS)-Co composite systems in
approximately 12e80 min, whereas the hydrolysis rate did not
change. This indicates that the H2 production rate is independent from the concentration of AB. Therefore, the hydrolysis reaction is zero order with respect to the initial
concentration of AB.

3.6.
The reusability and shelf-life of p(AMPS)-Co catalyst
in the hydrolysis reaction of AB

Table 3 e The comparison of activation energies in the


hydrolysis of AB catalyzed by various catalyst systems.
Catalyst
Nanoparticle-assembled
Co-B thin film
Cobalt-molybdenum
-boron/nickel foam
PtxNi1-xnanoparticles
Intrazeolite cobalt(0)
nanoclusters
Zeolite confined
copper(0)nanoclusters
SiO2 supported monodispers
nickel nanoparticles
Bulk nickel
PVP-stabilized Co(0) nanoclusters
Zeolite stabilized
nickel(0) nanoparticles
Hydrogel supported
Ni (0) nanoparticles
Hydrogel supported
Cu (0) nanoparticles
Hydrogel supported
Co (0) nanoparticles

Activation
Reference
Energy (kj mol-1)
34

44.3

12

39
56

13
18

51.8

22

34

27

70
63
54.4

39
40
41

52.8

This study

48.8

This study

47.7

This study

times in the reduction reactions of 50 mM 50 ml AB at 30  C


with 1000 rpm mixing rate. The conversion percentage
remained unchanged as shown in Fig. 5 whereas the activity
of the catalysts reduced to 92% at the fifth usage and the
reaction was completed in 27.5 min. The decrease after reuse
can be attributed to the poising of cobalt catalyst via oxidation
or catalyst inactivation inside the hydrogel network.
Furthermore, to determine the shelf-life of these systems,
hydrogel-metal nanocomposites (100 mg p(AMPS)-Co) were
placed in DI water under nitrogen stored for 1, 3, 5 and 10 days
at ambient temperature. After these time periods, 12.4 mg
cobalt nanoparticle-containing hydrogel-composite catalysts
were used in the hydrolysis reaction of 50 mM 50 ml AB at
30  C with 1000 rpm mixing rate. The conversion and the
activities are calculated and summarized in Table 4. The
activity is calculated considering initial H2 production rate to
the production rate of the samples stored at different times.
As shown in the table, the conversion percentage remained
unchanged whereas the activity of the catalysts reduced to
93% with ten days of storage time.

To determine the reusability of the catalyst systems, the same


catalyst (100 mg p(AMPS)-Co) was utilized repeatedly up to five

Table 2 e The activation parameters for the hydrolysis of


AB by hydrogelemetal composites catalyst.
Catalyst
p(AMPS)-Co
p(AMPS)-Cu
p(AMPS)-Ni

Ea(kJ mol1) DH# (kJ mol1) DS# (J mol1 K1)


47.7
48.8
52.8

45.0
46.0
50.1

146.7
151.2
140.3

Reaction conditions: 50 mM 50 ml AB, 100 mg hydrogelemetal


composite (containing 12.4 mg Co0; 11.0 mg Cu0 and 11.8 mg Ni0),
30e70 C, 1000 rpm

Fig. 4 e The concentration effect of AB on the hydrolysis of


AB hydrolysis (50 ml volumes each with 100 mg hydrogelCo composite (containing 12.4 mg Co0), 30  C, 1000 rpm).

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Table 4 e The shelf-life measurements of hydrogeleCo


catalyst systems at different storage time intervals.
Days

%Conversion
%Activity

Initial (0)

10

100
100

100
100

100
98

100
96

100
93

Reaction conditions: 50 mM 50 ml AB, 100 mg hydrogelemetal


composite (containing 12.4 mg Co0), 30  C, 1000 rpm.

Fig. 5 e The comparison of hydrogen production rate of the


hydrogel-Co composite catalyst in the hydrolysis AB
(50 mM 50 ml AB, 100 mg hydrogel-Co composite
(containing 12.4 mg Co0), 30  C, 1000 rpm).

3.7.
The reusability of p(AMPS) hydrogel networks and
reloading ability
One of the most important advantages of the used hydrogel
network in the preparation of metal nanoparticles is their
insolubility in harsh basic and acidic media. Therefore, these
hydrogel networks can be used repeatedly to prepare new
metal nanocatalysts after removing the first one from the
hydrogel network that has lost its catalytic activity for some
reason [7,8]. Fig. 6 summarizes the repreparation of the metal
nanocatalyst inside the same hydrogel network as the
continual usage of any catalyst system with time causes loss
of activity, a new catalyst of the same or different metal can be
prepared in the same network. Firstly, metal nanoparticles
can be dissolved from the hydrogel network with a suitable
acid without harming the hydrogel structure and reused for
the preparation of metal nanoparticles. As shown in Table 3,
after 10 days storage time p(AMPS)-Co catalyst system shows
93% catalytic activity. So this p(AMPS)-Co composite hydrogel
was treated with 5 M HCl and reused for Co nanoparticle
preparation. This reloaded Co nanoparticle hydrogel showed
100% catalytic activity and 100% conversion on first use. The
preparation of Co, Ni and Cu nanoparticles is very simple and
economically feasible. In addition, the method presented here
is very important when using expensive catalyst systems such
as Ru, Rh, Pt, Ag, or Au. The loss of catalytic activity can be
regained after reloading them from the same matrices.
Therefore, it could be possible to use a catalyst many times

with multiple dissolution and reloading procedures and this


provides significant impact in the reduction of costs for the
expensive catalyst systems. Since the hydrogel matrix, for
example p(AMPS) hydrogels, have eSO3H groups for metal ion
absorption and these groups electrostatically bind to metal
ions, for example, Co (II) ions, and then can be reduced to Co
(0) with NaBH4 leaving eSO3H free to be reabsorbed by the
same or different metal ions. P(AMPS) hydrogel was prepared
with Co (0) nanoclusters in situ according to the procedure
described above, and this hydrogel was reused in the Co (II)
absorption and reduced with NaBH4 to produce bimetallic
Co Co nanoparticles. In this case, the work of 200 mg catalysts was done by 100 mg of catalyst. As can be seen in Fig. 7,
when 200 mg p(AMPS)-Co system (containing 24.8 mg Co) was
used the reaction completed in 13 min with 100% conversion
with 611 (ml H2) (min)1 (g of Co)1 production rate. On the
other hand, 100 mg p(AMPS)-Co system (containing 20.6 mg
Co) was used two times, after metal ion loading procedure,
again 100% conversion was obtained in 16 min with 512 (ml
H2) (min)1 (g of Co)1 hydrogen production rate. Almost the
same amount of hydrogen production can be obtained by
using a lesser amount of hydrogel accommodating a tunable
catalyst amount. The same hydrogen production rate can be
obtained by the method presented providing a great advantage over conventional systems.

3.8.
The effect of hydrogen storage compound on
hydrolysis reaction
In order to compare the capacity of the storage materials,
NaBH4 and AB hydrolysis was carried out with the same
catalyst system, p(AMPS)-Co. As illustrated in Fig. 8, 50 mM
50 ml of the hydride compounds were used and NaBH4
provided much more hydrogen (246 ml) in 22 min than AB.

Fig. 6 e A schematic representation of the repreparation of metal nanoparticles in hydrogel network.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 8 2 0 9 e8 2 1 6

Fig. 7 e The effect of metal loading number on AB


hydrolysis (50 mM 50 ml AB, 1000 rpm, 30  C).

Fig. 8 e The effect of hydrogen storage compound on


hydrolysis reaction (50 mM 50 ml AB or NaBH4, 100 mg
hydrogel-Co composite (containing 12.4 mg Co0), 1000 rpm,
30  C).

This is plausible as both of these compounds provide 100%


conversion, the amount of H2 generated from NaBH4 should be
1.33 fold more than H2 generated from AB (see Eq. (1)). The
hydrogen production rate of 960 ml H2 (min)1 (g of Co)1 was
obtained with NaBH4, whereas a 673 ml H2 (min)1 (g of Co)1
rate was obtained when AB was used.

4.

Conclusion

In this work, we have reported the synthesis of Cu metal


nanoparticle preparation in addition to Co and Ni metal
nanoparticles within p(AMPS) hydrogel network [7,8,33,35]
and their use as a catalyst for the hydrolysis of AB. One of
the most important outcomes of this investigation is the
ability to dissolve the catalyst from the p(AMPS) network after
its activation capacity decreases and then reload the same
hydrogel materials with the same or a different catalyst. This
is very important outcome especially for rare or expensive
catalyst systems. In summary, this investigation presents the
following conclusions;
 The reported p(AMPS) provides a novel template matrix for
metal nanocatalyst preparation which can be used in the
hydrolysis of AB at room temperature. Amongst studied
catalyst systems, the p(AMPS)-Co composite catalyst

8215

provided highest reaction rates for the hydrolysis of AB


solution.
The kinetic studies show the catalytic hydrolysis reaction of
AB is first order with respect to catalyst amount and zero
order with respect to AB concentration for p(AMPS)-Co
composite catalyst.
The activation energies for the hydrolysis reactions of AB
with p(AMPS)-Co, p(AMPS)-Cu and p(AMPS)-Ni catalyst are
47.7, 48.8 and 52.8 kJ mol1, respectively. Hence, the catalytic activity is in the order Ni < Cu < Co for the metal
nanoparticles prepared within p(AMPS) matrix.
The p(AMPS)-Co composite catalyst can be repetitively used
up to five times with 100% conversion and 93% activity can
be obtained even with ten days storage.
Finally, it was demonstrated that after losing/decreasing its
catalytic activity for any reason, p(AMPS)-Co composite
system was treated with HCl to dissolve the deactivated Co
metal particles and then, Co nanoparticles were re-prepared
inside the p(AMPS) hydrogel matrix from its metal ion
solution and then reduced with a suitable reducing agent
e.g., NaBH4 to freshly prepare a new catalyst with higher
catalytic activity. This new catalyst system showed 100%
conversion and 100% catalytic activity.

The p(AMPS)-metal composite catalyst systems reported


here are promising candidates to be employed as catalysts
thanks to their easy preparation, high stability, and high
catalytic performance for hydrogen generation from the
hydrolysis of AB and/or NaBH4 solid hydrogen storage materials. Therefore, the use of hydrogel networks as a template
and their composite-containing catalysts as reaction media
have great potential in many applications.

Acknowledgements
This work is supported by the National Boron Research Institute of Turkey under the grant: 2009C0237. N. Sahiner is also
grateful for support by the Turkish Academy of Science under
TUBA-GEBIP 2008 program.

references

[1] Umegaki T, Yan J-M, Zhang X-B, Sioyama H, Kuriyama N,


Xu Q. Preparation and catalysis of poly(N-vinyl-2pyrrolidone) (PVP) stabilized nickel catalyst for hydrolytic
dehydrogenation of ammonia borane. Int J Hydrogen Energy
2009;34:3816e22.
[2] Yamada Y, Yana K, Xu Q, Fukuzumi S. Cu/Co3O4 nanoparticles
as catalysts for hydrogen evolution from ammonia borane by
hydrolysis. J Phys Chem C 2010;114:16456e62.
[3] Umegaki T, Yan J-M, Zhang X-B, Sioyama H, Kuriyama N,
Xu Q. Hollow NieSiO2 nanosphere-catalyzed hydrolytic
dehydrogenation of ammonia borane for chemical hydrogen
storage. J Power Sources 2009;191:209e16.
[4] Graham TW, Tsang C-W, Chen X, Guo R, Jia W, Lu S-M, et al.
Catalytic solvolysis of ammonia borane. Angew Chem Int Ed
2010;49:8708e11.
[5] Patel N, Fernandes R, Guella G, Miotello A. Nanoparticleassembled CoeB thin film for the hydrolysis of ammonia

8216

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

[21]

[22]

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 8 2 0 9 e8 2 1 6

borane: a highly active catalyst for hydrogen production.


Appl Catal B 2010;95:137e43.
Eom K, Cho K, Kwon H. Hydrogen generation from hydrolysis
of NH3BH3 by an electroplated CoeP catalyst. Int J Hydrogen
Energy 2010;35:181e6.
Sahiner N, Ozay O, Inger E, Aktas N. Superabsorbent
hydrogels for cobalt nanoparticle synthesis and hydrogen
production from hydrolysis of sodium boron hydride. Appl
Catal B 2011;102:201e6.
Sahiner N, Ozay O, Inger E, Aktas N. Hydrogel assisted nickel
nanoparticle synthesis and their use in hydrogen production
from sodium boron hydride. Int J Hydrogen Energy 2011;36:
1998e2006.
Yan J-M, Zhang X-B, Akita T, Haruta M, Xu Q. One-step
seeding growth of magnetically recyclable Au@Co coreshell
nanoparticles: highly efficient catalyst for hydrolytic
dehydrogenation of ammonia borane. J Am Chem Soc 2010;
132:5326e7.
Zhao J, Shi J, Zhang X, Cheng F, Liang J, Tao Z, et al. A soft
hydrogen storage material: poly(methyl acrylate)-confined
ammonia borane with controllable dehydrogenation. Adv
Mater 2010;22:394e7.
Brockman A, Zheng Y, Gore J. A study of catalytic hydrolysis
of concentrated ammonia borane solutions. Int J Hydrogen
Energy 2010;35:7350e6.
Dai H-B, Gao L-L, Liang Y, Kang X-D, Wang P. Promoted
hydrogen generation from ammonia borane aqueous
solution using cobaltemolybdenumeboron/nickel foam
catalyst. J Power Sources 2010;195:307e12.
Yang X, Cheng F, Liang J, Tao Z, Chen J. PtxNi1x
nanoparticles as catalysts for hydrogen generation from
hydrolysis of ammonia borane. Int J Hydrogen Energy 2009;
34:8785e91.
Li Z, Zhu G, Lu G, Qiu S, Yao X. Ammonia borane confined by
a metalorganic framework for chemical hydrogen storage:
enhancing kinetics and eliminating ammonia. J Am Chem
Soc 2010;132:1490e1.
zkar S. Zeolite framework stabilized
Zahmakran M, O
rhodium(0) nanoclusters catalyst for the hydrolysis of
ammonia-borane in air: outstanding catalytic activity,
reusability and lifetime. Appl Catal B 2009;89:104e10.
zkar S. Water soluble laurateDurap F, Zahmakran M, O
stabilized rhodium(0) nanoclusters catalyst with
unprecedented catalytic lifetime in the hydrolytic
dehydrogenation of ammonia-borane. Appl Catal A 2009;369:
53e9.
zkar S. Zeolite confined palladium(0)
Rakap M, O
nanoclusters as effective and reusable catalyst for hydrogen
generation from the hydrolysis of ammonia-borane. Int J
Hydrogen Energy 2010;35:1305e12.
zkar S. Hydrogen generation from the hydrolysis
Rakap M, O
of ammonia-borane using intrazeolite cobalt(0) nanoclusters
catalyst. Int J Hydrogen Energy 2010;35:3341e6.
zkar S. Water soluble laurateDurap F, Zahmakran M, O
stabilized ruthenium(0) nanoclusters catalyst for hydrogen
generation from the hydrolysis of ammonia-borane: high
activity and long lifetime. Int J Hydrogen Energy 2009;34:
7223e30.
Chandra M, Xu Q. Room temperature hydrogen generation
from aqueous ammonia-borane using noble metal nanoclusters as highly active catalysts. J Power Sources 2007;168:
135e42.
zkar S. Zeolite confined
Calskan S, Zahmakran M, O
rhodium(0) nanoclusters as highly active, reusable, and longlived catalyst in the methanolysis of ammonia-borane. Appl
Catal B 2010;93:387e94.
zkar S. Zeolite confined copper(0)
Zahmakran M, Durap F, O
nanoclusters as cost-effective and reusable catalyst in

[23]

[24]

[25]

[26]

[27]

[28]

[29]

[30]

[31]

[32]

[33]

[34]

[35]

[36]
[37]

[38]

[39]

[40]

[41]

hydrogen generation from the hydrolysis of ammoniaborane. Int J Hydrogen Energy 2010;35:187e97.
, Sahin S, O
zkar S. Water-soluble poly(4Metin O
styrenesulfonic acid-co-maleic acid) stabilized ruthenium(0)
and palladium(0) nanoclusters as highly active catalysts in
hydrogen generation from the hydrolysis of
ammoniaeborane. Int J Hydrogen Energy 2009;34:6304e13.
Yan J-M, Zhang X-B, Shioyama H, Xu Q. Room temperature
hydrolytic dehydrogenation of ammonia borane catalyzed by
Co nanoparticles. J Power Sources 2010;195:1091e4.
Yao CF, Zhuang L, Cao YL, Ai XP, Yang HX. Hydrogen release
from hydrolysis of borazane on Pt- and Ni-based alloy
catalysts. Int J Hydrogen Energy 2008;33:2462e7.
, Mazumder V, O
zkar S, Sun S. Monodisperse nickel
Metin O
nanoparticles and their catalysis in hydrolytic dehydrogenation
of ammonia borane. J Am Chem Soc 2010;132:1468e9.
O
zkar S, Sun S. Monodisperse nickel nanoparticles
Metin O
supported on SiO2 as an effective catalyst for the hydrolysis
of ammonia-borane. Nano Res 2010;3:676e84.
Umegaki T, Yan J-M, Zhang X-B, Shioyama H, Kuriyama N,
Xu Q. CoeSiO2 nanosphere-catalyzed hydrolytic
dehydrogenation of ammonia borane for chemical hydrogen
storage. J Power Sources 2010;195:8209e14.
Jiang H-L, Umegaki T, Akita T, Zhang X-B, Haruta M, Xu Q.
Bimetallic AueNi nanoparticles embedded in SiO2 nanospheres:
synergetic catalysis in hydrolytic dehydrogenation of ammonia
borane. Chem Eur J 2010;16:3132e7.
Tong DG, Zeng XL, Chu W, Wang D, Wu P. Magnetically
recyclable hollow CoeB nanospindles as catalysts for hydrogen
generation from ammonia borane. J Mater Sci 2010;45:2862e7.
Dai H-B, Kang X-D, Wang P. Ruthenium nanoparticles
immobilized in montmorillonite used as catalyst for
methanolysis of ammonia borane. Int J Hydrogen Energy
2010;35:10317e23.
Sahiner N, Ozay H, Ozay O, Aktas N. A soft hydrogel reactor
for cobalt nanoparticle preparation and use in the reduction
of nitrophenols. Appl Catal B 2010;101:137e43.
Sahiner N, Ozay H, Ozay O, Aktas N. New catalytic route:
hydrogels as templates and reactors for in situ Ni
nanoparticle synthesis and usage in the reduction of 2- and
4-nitrophenols. Appl Catal A 2010;385:201e7.
zay H, Kubilay S, Aktas N, Sahiner N. Utilization of
O
environmentally benign hydrogels and their networks as
reactor media in the catalytic reduction of nitrophenols. Int J
Polym Mater 2011;60:163e73.
Sahiner N. In situ metal particle preparation in cross-linked
poly(2-acrylamido-2-methyl-1-propansulfonic acid) hydrogel
networks. Colloid Polym Sci 2006;285:283e92.
Ozay O, Ekici S, Baran Y, Aktas N, Sahiner N. Removal of toxic
metal ions with magnetic hydrogels. Water Res 2009;43:4403e11.
OzayO,EkiciS,BaranY,KubilayS,AktasN,SahinerN.Utilization
of magnetic hydrogels in the separation of toxic metal ions from
aqueous environments. Desalination 2010;260:57e64.
Ozay O, Akcali A, Otkun MT, Silan C, Aktas N, Sahiner N. P(4VP) based nanoparticles and composites with dual action as
antimicrobial materials. Colloids Surf B 2010;79:460e6.
Kalindi SB, Indirani M, Jagirdar BR. First row transition metal
ion-assisted ammoniaborane hydrolysis for hydrogen
generation. Inorg Chem 2008;47:7424e9.
, O
zkar S. Hydrogen generation from the hydrolysis
Metin O
of ammonia-borane and sodium borohydride using watersoluble polymer-stabilized cobalt(0) nanoclusters catalyst.
Energy Fuels 2009;23:3517e26.
Zahmakran M, Ayval T, Akbayrak S, C
alskan S, C
elik D,
zkar S. Zeolite framework stabilized nickel(0) nanoparticles:
O
active and long-lived catalyst for hydrogen generation from
the hydrolysis of ammonia-borane and sodium borohydride.
Catal Today; 2010. doi:10.1016/j.cattod.2010.09.022.