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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3

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Effect of various CoeB catalyst synthesis conditions

on catalyst surface morphology and NaBH4
hydrolysis reaction kinetic parameters

Yih-Hang Chen*, Chuan-Yi Pan

Energy and Opto-Electronic Materials Research Center, Department of Chemical and Materials Engineering,
Tamkang University, Danshui Dist., New Taipei City 25137, Taiwan

article info abstract

Article history: The objective of this work is to study the effect of various CoeB catalyst synthesis condi-
Received 3 September 2013 tions on the catalyst surface morphology and kinetic parameters. The CoeB catalyst was
Received in revised form synthesized on IR-120/TP-207 resin surface by using ion exchange and chemical reduction
14 November 2013 method using NaBH4 as a reduction agent. The reduction conditions which were investi-
Accepted 19 November 2013 gated here were: reduction temperature, NaBH4 concentration, pH value, NaBH4 adding
Available online 19 December 2013 flowrate and different types of resins. The result shows reduction temperature gives the
most dramatic effect on surface morphology which is caused by competing reactions of
Keywords: reduction and hydrolysis. Low reduction temperature resulted in a slower CoeB reduction
CoeB catalyst rate and made the catalyst surface denser with a branched structure. This created more
NaBH4 surface area than higher reduction temperatures. Low reduction temperature catalyst had
Kinetic parameters the better performance on NaBH4 hydrolysis reaction for hydrogen generation rate. The
Hydrolysis reaction optimal reduction temperature of the CoeB/IR-120 is 25
C. The L-H model was used to
Chemical reduction method regress kinetic parameters from the experiment data. The frequency factor, activation
energy and adsorption constant are 1.17  109 mol gcat1 min1, 70.65 kJ mol1, and
6.8 L mol1 at 40
C, respectively. Finally, the TP-207 resin was used instead of IR-120. After
scanning for all catalyst synthesis conditions, the CoeB/TP-207 had the higher catalyst
loading, faster hydrogen generation rate and more stable than CoeB/IR-120.
Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

conditions and has 10.8 wt.% theoretical storage capacity.

1. Introduction
Hydrogen has shown the potential to become an energy car-
rier due to high efficiency and zero carbon emission for fuel
cells used. It can be stored in high pressure tanks, as can liquid
hydrogen, metal hydride and chemical hydride. Considering
the released hydrogen conditions and hydrogen storage ca-
pacity properties, NaBH4 can release hydrogen in ambient
However, it has some limitations during the released of
hydrogen [1,2]. One of the key issues is catalysts of NaBH4
hydrolysis reaction for hydrogen generation. The catalyst can
be made from noble (Pt, Ru, Pt.etc.) [3e8] and non-noble
metal (Ni, Co, CoeB.etc.) [9e16]. The noble metal show
good performance for hydrogen generation but are much
more expensive than non-noble. In recent years, most papers

* Corresponding author. Tel.: þ886 2 26215656x3283; fax: þ886 2 26209887.

E-mail address: yihhang@mail.tku.edu.tw (Y.-H. Chen).
0360-3199/$ e see front matter Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2013.11.067
 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3
[17e21] have focused on enhancement of catalyst perfor-
mance on non-noble metal in order to attain commercializa-
tion. Oronzio et al. [22] mentioned that Co metal with
magnetism has potential to become a NaBH4 hydrolysis re-
action catalyst due to low cost and easy recycle. Schlesinger
et al. [23] used chemical reduction method for synthesis
catalyst powders under ambient conditions. Due to loss of
catalyst powders from the reactor during NaBH4 hydrolysis
reaction for hydrogen generation, Amendola et al. [3] used
different types of resins as a support to exchange Ru ion into
resin surface. Liu et al. [24] used IR-120 resin as a support to
exchange Co2þ and then reduced Co metal on resin surface.
Liu et al. [24] and Zhu et al. [25] mentioned that the grain size,
porosity, and surface area of catalysts were affected by
reduction conditions. But there is a lack of further study of
performance improvement and stability of catalysts. The
quantitative performance index of catalysts is kinetic pa-
rameters. In the kinetic model of NaBH4 hydrolysis reaction
for hydrogen generation, it can be cataloged into zero-order
[3e5], first-order [8,9,11,13] and LangmuireHinshelwood
[6,14,16,18,26e28]. Hung et al. [26] has mentioned that Lang-
muireHinshelwood kinetic model provided the largest oper-
ating temperature range for describing whole hydrogen
generation profile. The relationship between catalyst synthe-
sis conditions, surface morphology and kinetic parameters
were not discussed.
In this work, the effect of various CoeB catalyst synthesis
conditions on the catalyst surface morphology and kinetic
parameters have been addressed. In section 2, experiments
of the catalyst synthesis and the NaBH4 hydrolysis reaction
for hydrogen generation were set-up. In section 3, five
catalyst synthesis variables which affected catalyst surface
morphology were investigated. In section 4, NaBH4 hydro-
lysis reactions for hydrogen generation with different CoeB
catalysts present were used to assess catalysts performance
and evaluate kinetic parameters of catalysts. Finally, a
catalyst stability test was done to assess the operating
performance.
2. Experiment set-up
The experiments of this research included two stages. One
was CoeB catalyst synthesis. The CoeB catalyst was made by
using ion exchange and chemical reduction method. The
other was CoeB catalyst performance of NaBH4 hydrolysis
reaction for hydrogen generation.
2.1. Material
Cobalt(II) chloride hexahydrate, produced by Alfa Aesar
which had a purity of 98%, was a precursor and was dissolved
in de-ionized water and formed Co2þ. Amberlite IR-120 and
Lewatit TP-207 resins which were used as catalyst supports
were bought from SigmaeAldrich. The functions of Sodium
borohydride were as a reduction agent of catalyst synthesis
and a reactant of hydrolysis reaction. The NaBH4 was pro-
duced by Uniregion bio-tech with a purity of 98%. Sodium
hydroxide was used to adjust the pH value of catalyst
1649
synthesis and was manufactured by SHIMAKYU’S Co. with
98% purity.
2.2. CoeB catalyst synthesis
The CoeB catalyst was made by using ion exchange and
chemical reduction methods [24]. The individual experi-
mental procedures are listed below.
2.2.1. Ion exchange method
Co2þ replaced the protons of the ion exchange resins (IR-120/
TP-207). The detail procedures are shown below:
(1) 4 g of each resin (IR-120 or TP-207) were washed by using
de-ionized water for purification and water was then
drained out through a stainless net.
(2) When IR-120 resin was used, 1.1 g of CoCl2$6H2O and
13.2 g of de-ionized water (7.7 wt.% CoCl2) were mixed
until completely dissolved. (When TP-207 resin was
used, 1.5 g of CoCl2$6H2O and 18 g of de-ionized water
(7.7 wt.% CoCl2) were mixed until completely dissolved.)
The ion exchange conditions were changed because of
differing ion exchange resins saturation conditions
with a constant concentration of Co2þ.
(3) 4 g of resin was placed into the CoCl2 solution and
stirred for 1 h at 100 rpm Co2þ ion exchange occurred.
(4) At the conclusion of the ion exchange, de-ionized water
was used to wash out the excess and un-exchanged
Co2þ until the solution became colorless. (Note: Co2þ
solution is pink.)
(5) Further washing was carried out using de-ionized water
in a sonication bath, this de-ionized water was replaced
every 5 min and repeated three times.
(6) The trace amount of Co2þ in the exchanged resin was
removed by continuous stirring for one day.
2.2.2. Reduction of CoeB catalyst
After exchanging Co2þ on the ion exchange resin surface, the
Co2þ needed to be further reduced to Co metal. The pro-
cedures are shown as follows:
(1) The NaBH4 concentration and injection flowrate were
set at the desired reduction conditions.
(2) The container was placed in thermostat and set at the
desired reduction temperature.
(3) 50 ml of NaBH4 solution was used as a reduction agent
and was added into the exchanged resin container to
start the reduction of Co2þ to Co metal on the resin
surface with a constant 350 rpm stirring rate.
(4) The reduction reaction was finished when no hydrogen
generated from the container.
(5) Washing was carried out using de-ionized water in a
sonication bath, this de-ionized water was replaced
every 5 min and repeated until the solution became
colorless.
(6) The CoeB/resin catalyst was dried at 80
C with vacuum
continuously for 1 day.
(7) The weight difference between dry resins and CoeB/
resin catalyst were recorded.
1650 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3
Fig. 1 e Experiment scheme of the NaBH4 hydrolysis reaction for hydrogen generation.
2.3. Characterization of CoeB/resin catalyst
The prepared CoeB/resin catalyst microstructure
analyzed by using SEM/EDS, ICP-MS and BET.
2.3.1. Inductively Coupled Plasma Mass Spectrometer (ICP-
MS)
0.5 g of CoeB/resin catalysts was dissolved in 15 mL of 70 wt.%
nitric acid for one day. ADVANTEC No. 1 with 6 mm average
pore size was used to filter out the solution from un-dissolved
resins. Co and B element of the solution were quantitatively
identified by using ICP-MS (SCIEX ELAN 5000).
2.3.2. Field scanning electron microscope (FESEM)
The surface morphology of CoeB catalysts was photoed by
using a LEO-1530 Zeiss Field scanning electron microscope
(FESEM). The compositions on catalyst surface were analyzed
with energy dispersive spectra (EDS) which installed on the
FESEM.
2.3.3. BrunauereEmmetteTeller (BET)
The specific surface area of CoeB catalysts and resin supports
was measured with a Micromeritics ASAP 2020 surface area.
2.3.4. NaBH4 hydrolysis reaction
NaBH4 hydrolysis reaction for hydrogen generation was used
to test the catalyst performance and using the experiment
data to regress the kinetic parameters. The NaBH4 hydrolysis
reaction for hydrogen generation took place in a batch reactor
isothermally. 0.0333 g of CoeB/resin catalyst was placed into
the batch reactor and desired temperature was attained.
When the hydrolysis reaction started, 2.67 ml of 12.5 wt.%
NaBH4(aq) was immediately injected into the reactor.
Hydrogen was generated from the batch reactor and stored in
a bottle via a tube. The water in the bottle was rejected by
hydrogen and sent to balance. Water weight change on the
balance was measured by using “Water Displacement
was Method”. The reaction temperature and hydrogen flowrate
was transferred and recorded in the computer. The experi-
ment scheme of the NaBH4 hydrolysis reaction for hydrogen
generation is shown in Fig. 1.
3. Catalyst synthesis variables
In the previous section, we discussed the CoeB catalyst syn-
thesis experiments which included ion exchange and reduc-
tion reaction steps. The catalyst synthesis variables
investigated here are ion exchange time, different types of
resins, reduction temperature, reduction concentration,
reduction pH value and reduction agent injection flowrate. In
this section, we introduce how the catalyst synthesis variables
affected the surface morphology and composition of catalysts.
3.1. Ion exchange time
The precursor CoCl2 dissolved in the de-ionized water and
ionized to form Co2þ. The ion exchange reactions functional
group on resins and Co2þ are shown as follows [29]:
2R  SO3 H þ Co2þ /ðR  SO3 Þ2 Co þ 2Hþ (1)
R  NðCH2 COOHÞ2 þ Co2þ /R  NðCH2 COOÞ2 Co þ 2Hþ (2)
2þ
The Co exchanged to the resin amounts can be evaluated
by measuring the concentration of Co2þ or Hþ. The objective of
ion exchange step is to reach the equilibrium saturated ca-
pacity of Co2þ on the resin surface. The proton concentration
was chosen for measuring using the on-line method with a pH
meter. The ion exchanged times of IR-120 and TP-207 resins
 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3 1651

Table 1 e Effect of reduction variables on CoeB/IR-120 catalyst kinetic information.

Reduction agent Reduction pH Injection Catalyst K0 Ea DH0 DS0
NaBH4(aq) 50 ml temperature (
C) flowrate loading (mol gcat1 min1) (kJ mol1) (kJ mol1) (kJ mol1 K1)
wt.%
I-1 10 wt.%NaBH4 0
C 10.45 50 ml 10.1 2:55  108 66.32 19.09 0.055
Impulse
I-2 10 wt.%NaBH4 25
C 10.45 50 ml 9.6 1:17  109 70.65 52.26 0.151
Impulse
I-3 10 wt.%NaBH4 40
C 10.45 50 ml 7.9 2:85  109 73.79 60.90 0.170
Impulse
I-4 10 wt.%NaBH4 80
C 10.45 50 ml 6.5 5:30  1010 81.72 90.89 0.263
Impulse
I-5 5 wt.%NaBH4 25
C 10.01 50 ml 9.3 3:32  109 74.28 46.03 0.127
Impulse
I-6 15 wt.%NaBH4 25
C 10.51 50 ml 9.6 2:14  109 72.38 44.44 0.129
Impulse
I-7 10 wt.%NaBH4 25
C 12.96 50 ml 11.2 3:54  1010 80.00 67.47 0.199
þ5 wt.%NaOH Impulse
I-8 10 wt.%NaBH4 25
C 10.45 20 ml min1 7.5 1:04  1010 76.87 68.24 0.196
I-9 10 wt.%NaBH4 25
C 10.45 5 ml min1 5.3 4:75  109 75.17 79.69 0.227

which reached equilibrium saturated capacity are 20 and
40 min, respectively. The ion exchange times of the two cases
are set at 1 h in order to achieve the saturated Co2þ exchanged
capacity.
3.2. Reduction of CoeB catalyst on resin surface
Sodium borohydride was used as a reduction agent to reduce
the Co2þ into CoeB metal and can be operated at moderate
temperature conditions. And its side reaction was NaBH4 hy-
drolysis reaction. The reduction and hydrolysis reactions are
shown in Eqs. (3)e(5) [30] and Eq. (6):
2CoCl2 þ 4NaBH4 þ 9H2 O/Co2 B þ 4NaCl þ 12:5H2 þ 3BðOHÞ3
4Co2 B þ 3O2 /8CoðsÞ þ 2B2 O3
B2 O3 þ 3H2 O/2BðOHÞ3
NaBH4 þ 2H2 O/NaBO2 þ 4H2
Grain size, porosity, and surface area of CoeB catalysts
were affected by reduction conditions. The reduction tem-
perature, BH4/Co2þ mole ratio, reduction pH value and
reduction agent injection flowrate were investigated here.
The base case values of the reduction conditions are 25
C
(reduction temperature), 10 wt.% (reduction agent concen-
tration), 10.45 (pH value) and 50 ml one time (reduction
agent injection flowrate). The detail analysis for each
reduction variable is shown in a later section based on IR-
120 resin.
3.2.1. Reduction temperature
When the Co2þ reduced on the IR-120 resin surface, the
reduction Eqs. (3)e(5) and hydrolysis reaction Eq. (6) took place
simultaneously. In our experiment, four reduction tempera-
tures are used and investigated: 0 (Ie3), 25(Ie3), 40(Ie3),
80
C(Ie4).
Steady state analysis of reduction/hydrolysis competing
reactions: Higher reduction temperature caused faster
reduction/hydrolysis reaction. From a steady state view
point, the more hydrolysis reaction which took place; the
less Co metal reduced on the IR-120 surface when a
limiting 50 ml NaBH4(aq) reduction agent was used. The
catalyst synthesis conditions (Ie1 w Ie4) and catalyst
loading are shown in Table 1. Higher reduction tempera-
ture from 0 to 80
C; Lower catalyst loading from 10.1 to
6.5 wt. % caused smaller amounts of NaBH4 to be used in
reduction reaction.
Dynamic analysis of reduction/hydrolysis competing
reactions: The SEM surface morphology of CoB/IR-120 cat-
alysts for different operating temperatures are shown in
(3) Fig. 2. From SEM, lowering the reduction temperature
induced a “branch like” surface structure and lower
(4) porosity (Fig. 2(a)); raising the reduction temperature
caused a “sheet like” surface structure and higher porosity
(5) (Fig. 2(d)). The reasons for these phenomena are as follows.
Firstly, lowering the reduction temperature reduced the
(6) reduction rate and the Co metal arranged more dense (low
porosity). Also lowering the reduction temperature
decreased the hydrogen generation from the catalyst sur-
face which caused the hydrogen leaving channels to be
necessarily smaller. Therefore, the Co metal grew on the IR-
120 surface in a more branched and broader form. The
opposite occurred when the reduction temperature was
raised.
3.2.2. Reduction concentration
From the reduction reaction of CoeB/IR-120 catalyst in Eq.
(3), the BH4/Co2þ mole ratio should be in excess of 2 in
order to reduce Co2þ to Co metal on the IR-120 resin surface.
The catalyst loadings of 5, 10, and 15 wt.% of NaBH4 solu-
tion concentrations are shown in Table 1. When the NaBH4
solution concentration changed from 0.5, 1, 2, 5, 10 to
15 wt.%, the CoeB/IR-120 catalyst loadings are 5.8, 8.5, 8.9,
9.3, 9.6, 9.6 wt. %. Theoretically, the BH4/Co2þ mole ratio
1652 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3
Fig. 2 e The SEM image catalyst surface morphology at CoeB/IR-120 reduction temperatures of (a) 0
C, (b) 25
C, (c) 40
C, (d)
80
C.
equals 2 which corresponded to 1 wt.% of NaBH4(aq) con-
centration. From the experiment data, the result shows
CoeB/IR-120 catalyst loadings reached a maximum and
stable value at 9.6 wt.% when NaBH4(aq) concentration
exceeded 10 wt.%. The NaBH4(aq) concentration was set at
10 wt.% in the succeeding studies. The SEM of catalyst
surface morphology at different NaBH4(aq) concentrations
are shown in Fig. 3.
3.2.3. pH value
Reduction agent NaBH4 can stabilize in an alkaline solution to
prevent the hydrolysis reaction taking place [31]. Ie2 and Ie7
in Table 1 show the reduction conditions. The difference be-
tween Ie2 and Ie7 in Table 1 are 10 wt.% NaBH4(aq) with and
without 5 wt.%NaOH. The pH values and catalyst loadings of I-
2 and I-7 are 10.45, 12.96 and 9.6 wt.%, 11.2 wt.%. The pH value
of reduction solution influenced the catalyst loading due to
the following reasons.
(1) From steady state view point for reduction/hydrolysis
competing reactions, the reduction and hydrolysis re-
action rate kept constant at the same reduction tem-
perature. Higher pH values (from 10.45 to 12.96)
inhibited the hydrolysis reaction which meant more Co
reduction took place (9.6e11.2 wt.% catalyst loading).
The result is shown in Table 1.
(2) From dynamic view point for reduction/hydrolysis
competing reactions, the total hydrogen generation rate
from the catalyst surface of NaBH4 reduction and
hydrolysis reactions (Eqs. (3)e(6)) was reduced due to
inhibiting hydrolysis reaction by adding NaOH. The less
hydrogen flowrate that left the catalyst surface; the
narrower the hydrogen flow channel size. This means a
reduced porosity of CoeB catalyst surface structure. The
result is shown in Fig. 4. The Co metal grew on the IR-
120 surface and became “branch like” with NaOH pre-
sent (see Fig. 4(b)).
3.2.4. Reduction agent NaBH4 injection flowrate
To initiate the Co2þ reduction, a reduction agent, NaBH4, was
injected into a glass vat at a flowrate controlled by a rotary
pump and stirred at a rate of 350 rpm. This caused a dramatic
change in the catalyst loading. Table 1 shows catalyst loadings
decreased from 9.6 wt.%, 7.5 wt.% to 5.3 wt.%, when NaBH4
adding flowrates changed from 50 ml one time(Ie2),
20 ml min1(I-8) to 5 ml min1(I-9). Although there was stirring
in the reduction reaction vat, the reduction of Co metal on IR-
120 catalyst surface shows non-uniformity of Co metal dis-
tribution while the injection flowrate decreased. (Some cata-
lysts were black; but some catalysts were deep amber which is
IR-120 resin raw material color). This is caused by non-
uniformity NaBH4 concentration in the reduction vat. When
Co2þ reduced on IR-120 surface, the remaining NaBH4 con-
centration in local areas was exhausted due to hydrolysis re-
action. Most of the reduction agent was used to hydrolyze
instead of reduce. This resulted less CoeB/IR-120 catalyst
loading.
 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3 1653

Fig. 3 e The SEM image catalyst surface morphology at CoeB/IR-120 reduction concentrations of (a) 0.5 wt.%, (b) 5 wt.%, (c)
10 wt.%, (d) 15 wt.%.

3.2.5. Catalyst support: TP-207 resin
The effect of reduction temperature, reduction concentration,
pH value and injection flowrate on TP-207 catalyst surface
loading are shown in Table 2. (Te1 w Te4) and (Te2, Te5,
Te6), (Te2, Te7) and (Te2, Te8, Te9) are the experiment re-
sults of reduction temperature, reduction concentration, pH
value and injection flowrate change. In our reduction condi-
tion range (Te1 w Te7), the result shows no significant change
on catalyst loading (around 14 wt.%). The SEM of these
reduction conditions are shown in Fig. 5. The injection flow-
rate changed from 50 ml one time to 5 ml min1, the catalyst
loading decreased from 14.2 to 12.7 wt.%. The result is the
same as CoeB/IR-120 catalyst; which is non-uniformity NaBH4
concentration in the reduction vat.
3.3. Characterization of CoeB/IR-120 and CoeB/TP-207
catalysts
In order to compare the support effect, I-2 and T-2 catalysts
under the same reduction conditions are listed in Tables 1 and
2. The detailed physical properties of these resins are shown
in Table 3. The IR-120 and TP-207 stand for strongly acidic and

Fig. 4 e The SEM image catalyst surface morphology at CoeB/IR-120 reduction pH values of (a) 10.45, (b) 12.91.
1654 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3

Table 2 e Effect of reduction variables on CoeB/TP-207 catalyst kinetic information.

Reduction agent Reduction pH Injection Catalyst K0 Ea DH0 DS0
NaBH4(aq) 50 ml temperature (
C) flowrate loading (mol gcat1 min1) (kJ mol1) (kJ mol1) (kJ mol1 K1)
wt.%
T-1 10 wt.%NaBH4 0
C 10.45 50 ml 14.3 2:30  108 64.50 52.49 0.155
Impulse
T-2 10 wt.%NaBH4 25
C 10.45 50 ml 14.2 2:10  108 64.45 46.42 0.136
Impulse
T-3 10 wt.%NaBH4 40
C 10.45 50 ml 14.6 2:50  108 65.00 49.24 0.144
Impulse
T-4 10 wt.%NaBH4 80
C 10.45 50 ml 14.4 2:64  108 65.08 47.61 0.141
Impulse
T-5 5 wt.%NaBH4 25
C 10.01 50 ml 14.2 8:89  108 68.17 47.82 0.141
Impulse
T-6 15 wt.%NaBH4 25
C 10.51 50 ml 14.9 3:46  108 65.73 44.29 0.130
Impulse
T-7 10 wt.%NaBH4 25
C 12.96 50 ml 14.4 4:56  108 65.95 51.88 0.155
þ5 wt.%NaOH Impulse
T-8 10 wt.%NaBH4 25
C 10.45 20 ml min1 13.0 5:28  108 66.27 50.81 0.152
T-9 10 wt.%NaBH4 25
C 10.45 5 ml min1 12.7 5:14  108 66.04 45.06 0.136

chelating ion exchange resins. The Co2þ ion exchange bond of temperature range for describing whole section of hydrogen
these two resins are electrical charge and covalent bond, and generation profile [26]. The experiment of NaBH4 hydrolysis
their saturated exchanged capacities are 1.8 meq ml1 and reaction for hydrogen generation was described in section
2.2 meq ml1 with respective to 9.6 wt.% and 14.2 wt.% catalyst 2.3.4. The hydrogen generation profiles with respect to time
loadings. for different operating temperatures with I-1 catalyst are
The SEM of I-2 and T-2 catalysts are shown in Figs. 2(b) and shown in Fig. 7. In section 4, the kinetic parameters will be
5(b). EDS surface composition and spectra of resins and cata- regressed from the experiment data. The kinetic parameters
lysts are shown in Table 4 and Fig. 6. From EDS analysis, it was of catalysts for different reduction conditions were deduced
confirmed that Co metals were reduced on the IR-120 and TP- from its surface morphology.
207 resins.
Glavee et al. [30,32], Jeong et al. [33] and Liu et al. [24] have
pointed out the possible metal forms are Co2B, Co(BO2)2, CoO, 4.1. Modeling
Co2O3, Co3O4. Jeong et al. (2007) also pointed the metal Co and
Co3O4 have very low catalytic activity than other metal form. In order to find the kinetic parameters, a mathematical model
Glavee et al. [32] was demonstrated and proofed that Co2B has was built to describe NaBH4 hydrolysis reaction in a batch
higher catalytic activity than Co(BO2)2. In order to check the reactor with a wide range of catalysts. The material balance of
metal compositions on the resin, ICP-MS was used and the NaBH4 is shown below:
result is shown in Table 5. The result shows Co and B elements
 dn
1 dnA A=
V0 dCA
were found in the catalyst compared to an absence in the raw ¼ ¼ ¼ rA (7)
V0 dt dt dt
resin materials. The Co/B ratios of CoeB/IR-120 and CoeB/TP-
120 are 6.2 and 3.02 at 25
C reduction temperature. From the where V0 is batch reactor volume (L), nA is mole of NaBH4 in
result, the Co/B ratio of CoeB/TP-120 catalysts is close to 2 the batch reactor (mol), CA denotes NaBH4 concentration in
(Co2B form). Its activity is better than CoeB/IR-120 catalysts. the reactor (mol L1), rA represents the reaction rate
The result can also proofed by hydrogen generation rate of (mol L1 min1).
NaBH4 hydrolysis reaction (section 4.5.2). The reaction rate unit was converted into ‘catalysts weight
BET was used to measure the surface areas of I-2 and T-2 based’; the Eq. (7) can be rewritten as:
catalyst. The surface area of I-2 CoeB/IR-120 catalyst

dCA
increased from 0.19 (raw IR-120 resin) to 0.95 m2 g1. And The V0 ¼ r0A Wcat (8)
dt
surface area of T-2 CoeB/TP-207 catalyst increased from 0.03
(raw TP-207 resin) to 17.65 m2 g1. From the result, T-2 has where r0A is reaction rate using catalysts weight based
much higher surface area than I-2 catalyst. (mol gcat1 min1). Wcat denotes weight of catalysts (g).
LangmuireHinshelwood model was used and is shown as
follows:

4. NaBH4 hydrolysis reaction with CoeB Ka CA

r0A ¼ kLH (9)
1 þ Ka CA
catalysts: kinetic parameters regression
where kL-H and Ka are rate constant (mol gcat1 min1) and
In this work, LangmuireHinshelwood kinetic model was adsorption constant (L mol1).
chosen, because it can provide the largest operating Substituting Eq. (9) into Eq. (8), we have:
 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3 1655

Fig. 5 e The SEM image catalyst surface morphology at CoeB/TP-207 reduction variables of (a)T-1, (b)T-2, (c)T-3, (d)T-4, (e)T-
5, (f)T-6, (g)T-7, (h)T-8, (i)T-9.
1656 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3

The regressions of kinetic parameters for different oper-

Table 3 e The detailed physical properties of IR-120 and
ating temperatures are shown in Table 6. Arrhenius equation
TP-207 resins.
(k ¼ k0exp(Ea/RT)) was used, and nature log operation was
Resin IR-120 TP-207
taken on both sides of the equation. Let X equal to 1/T and Y
Support structure Mesoporous Macroporous equal to ln(k). The least square linear regression for 1/T vs.
Resin pore diameters 0.5e20 nm 20e200 nm
ln(k) was used to fit frequency factor(k0) and activation energy
Exchange capacity 1.8 meq ml1 2.2 meq ml1
(Ea) from experiment data (shown in Table 6). The values of
Ion attraction Electrical charge Covalent bond
which are 2.55  108 mol gcat1 min1, 66.32 kJ mol1.
Adsorption constant is a function of DH0 and DS0 and can
dCA Wcat Ka CA be derived from standard Gibbs free energy (DG0 ¼ RTln(Ka)
¼ kLH (10)
dt V0 1 þ Ka CA and DG0 ¼ DH0  TDS0). And the equation is shown as follows
[6]:
Integrating Eq. (10) with initial condition of t ¼ 0, CA ¼ CA0:

 DH0 DS0
1 CA0 Wcat ln Ka ¼ þ (13)
ln þ ðCA0  CA Þ ¼ kLH t (11) RT R
Ka CA V0
where DG0, DH0 and DS0 are the changes of standard Gibbs free
Let X ¼ t and Y ¼ 1/Kaln(CA0/CA) þ(CA0  CA). The slope of the
energy (kJ mol1), enthalpy (kJ mol1) and
linear function Eq. (11) is WcatkLeH/V0. 1 1
entropy(kJ mol K ). R and T denote gas constant
(kJ mol1 K1) and operating temperature (K). Let X equal to 1/
4.2. Kinetic parameters regression procedures T and Y equal to ln(Ka). The least square linear regression for 1/
T vs. ln(Ka) was used to find DH0 and DS0 from experiment data
Before evaluating the kinetic parameters (kLeH and Ka), the (shown in Table 6). The values of which are 19.09 kJ mol1,
accumulated hydrogen generation volume ðVH2 ðtÞÞ from 0.055 kJ mol1 K1, respectively.
experiment data should convert into NaBH4 concentration
(CA). The equation is shown below:
4.3. Kinetic parameters regression for different catalysts


1  VH2 ðtÞ
CA ðtÞ ¼ CA0 (12)
VH2 ;f The reduction variables and conditions of CoeB catalysts were
investigated in section 3. The hydrogen generation profiles of
Where VH2 ðtÞ and VH2 ;f are the accumulated hydrogen volume
NaBH4 hydrolysis reactions for different operating tempera-
and total hydrogen volume completely converted from NaBH4
tures and I-1 to I-6 catalysts are shown in Fig. 9. The hydrogen
hydrolysis reaction (L).
generation profiles with Ie2, Ie7 to Ie9 catalysts are shown in
The unknown variables in Eq. (11) are kLeH and Ka. The
Fig. 10. The kinetic regression procedures were followed as in
regression procedures are listed below:
section 4.2. The kinetic parameters of CoeB/IR-120 and CoeB/
TP-207 catalysts are shown in Tables 1 and 2.
(1) Select the hydrogen generation profile ðVH2 ðtÞÞ from
experiment data at 40
C. (Note: 90% NaBH4 conversion
was taken from the experiment data). 4.4. Stability test
(2) Convert the hydrogen generation profile to NaBH4 con-
centration (CA(t)) by using Eq. (11). Most of NaBH4 hydrogen generation researches were focused
(3) Give an adsorption constant (Ka). on solid NaBH4 hydrolysis reaction. The common method was
(4) Substitute Ka, CA(t) and CA0 into Eq. (11). mixed solid NaBH4 and catalysts particles into a tablet to
(5) Use ’least square linear regression method’ to find the become a device. When hydrogen release from the device, the
slope of Eq. (11) and calculate kL-H and square of rest components of the device are solid catalyst particles and
P
errorðE ¼ ni¼1 ðyi  axi Þ2 Þ. (The result is shown in Fig. 8.) solid NaBO2 (by-product). In order to recycle the catalysts, the
(6) Change the Ka value and repeat steps (3)e(5), until the catalysts needed to be washed (clean the surface NaBO2) and
minimum square of error is found. dried which for next used.
(7) Repeat steps (1)e(6), until the values of kLeH and Ka are In order to analyst the stability of catalysts, 0.0333 g of
found at different operating temperatures between 40 CoeB/IR-120 (CoeB/TP-207) catalyst and 2.67 ml of 12.5 wt.%
and 80
C. NaBH4(aq) was placed into the batch reactor which is shown

Table 4 e EDS analysis of resins and catalysts.

Elements IR-120 resin CoeB/IR-120(cat.) TP-207 resin CoeB/TP-207(cat.)
wt.% at% wt.% at% wt.% at% wt.% at%
C 63.04 73.50 44.98 61.66 65.83 72.79 67.29 76.63
N 0 0 0 0 07.12 06.75 06.26 06.12
O 23.61 20.66 23.06 23.73 19.12 15.87 15.63 13.36
S 13.36 05.83 09.40 04.83 0 0 0 0
Na 0 0 07.95 05.70 07.93 04.58 03.80 02.26
Co 0 0 14.61 04.08 0 0 07.02 01.63
 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3 1657

Fig. 6 e EDS spectra of (a) IR-120 resin, (b) CoeB/IR-120 catalyst, (c) TP-207 resin, (d) CoeB/TP-207 catalyst.

12
TR=400C ,R2=0.991

TR=500C ,R2=0.988
Table 5 e Co and B metal composition on the resin 10
TR=600C ,R2=0.991
1/Ka *ln(CNaBH4,0/CNaBH4)

surface.
+(CNaBH4,0-CNaBH4)

TR=700C ,R2=0.992
CoeB/IR-120 Co(mg L1) B(mg L1) Co/B 8
TR=800C ,R2=0.998
25
C 1624 47.98 6.2
CoeB/TP-207 Co(mg L1) B(mg L1) Co/B 6
25
C 3153 191.0 3.02
4

800
0
0 50 100 150 200 250
700 time(min)

Fig. 8 e The regression of NaBH4 hydrolysis reaction

Hydrogen generation (mL)

600
kinetic parameters with I-1 catalyst for different operating
500
temperatures.
400
TR=400C
300
TR=500C
Table 6 e Rate constants and adsorption constants of I-1
200 TR=600C
catalysts for different operating temperatures.
TR=700C
100 Operating Rate constant Adsorption constant
TR=800C temperature kLeH(mol gcat1 min1) Ka(L mol1)
0 T (
C)
0 50 100 150 200 250
Time(min) 40 0.00232 2.08
50 0.00456 1.61
Fig. 7 e The hydrogen generation profiles of NaBH4 60 0.01063 1.51
hydrolysis reaction with I-1 catalyst at different operating 70 0.01817 1.05
80 0.04295 0.91
temperatures (TR).
1658 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3

in Fig. 1, the reactor temperature was set at 80
C. The
hydrogen generation profile is shown in Fig. 11. After the 1st
NaBH4 hydrolysis reaction test, the solid CoeB/IR-120 (CoeB/
TP-207) catalysts particle was collected and re-cleaned with
de-ionize water. Then, the CoeB/resin catalyst was dried at
80
C with vacuum continuously for 1 day and waited for next
NaBH4 hydrolysis reaction test. After five uses, hydrogen
generation rate of NaBH4 hydrolysis reactions with the CoeB/
IR-120 catalyst reduced by around half (shown in Fig. 11(a)).
But the CoeB/TP-207 shows good performance and stability

(a) (b)
Hydrogen generation (mL)

Hydrogen generation (mL)

800 800
TR=400C TR=500C
600 600

400 400
I-1 I-1
I-2 I-2
200 200
I-3 I-3
I-4 I-4
0 0
0 50 100 150 200 250 0 20 40 60 80 100 120
Time(min) Time(min)
(c) (d)
Hydrogen generation (mL)

Hydrogen generation (mL)

800 800
TR=600C TR=700C
600 600

400 400
I-1 I-1
I-2 I-2
200 200
I-3 I-3
I-4 I-4
0 0
0 20 40 60 0 10 20 30 40
Time(min) Time(min)
(e) (f)
Hydrogen generation (mL)

Hydrogen generation (mL)

800 800
TR=800C TR=400C
600 600

400 400
I-1
I-2 I-5
200 200
I-3 I-2
I-4 I-6
0 0
0 5 10 15 20 0 100 200 300
Time(min) Time(min)
(g) (h)
Hydrogen generation (mL)

Hydrogen generation (mL)

800 800
TR=600C TR=800C
600 600

400 400

I-5 I-5
200 200 I-2
I-2
I-6 I-6
0 0
0 20 40 60 0 5 10 15 20
Time(min) Time(min)
Fig. 9 e Hydrogen generation profiles of NaBH4 hydrolysis reaction with I-1 to I-6 CoeB/IR-120 catalysts.
 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3 1659

(a) (b)

Hydrogen generation (mL)

Hydrogen generation (mL)

800 800
TR=400C TR=600C
600 600

400 400

200 200
I-2 I-2
I-7 I-7
0 0
0 100 200 300 0 20 40 60
Time(min) Time(min)
(c) (d)

Hydrogen generation (mL)

Hydrogen generation (mL)

800 800
TR=800C TR=400C

600 600

400 400

I-2
200 I-2 200
I-8
I-7 I-9
0 0
0 5 10 15 20 0 100 200 300
Time(min) Time(min)
(e) (f)
Hydrogen generation (mL)

Hydrogen generation (mL)

800 800
TR=600C TR=600C

600 600

400 400

I-2 I-2
200 200
I-8 I-8
I-9 I-9
0 0
0 20 40 60 80 100 0 20 40 60 80 100
Time(min) Time(min)
Fig. 10 e Hydrogen generation profiles of NaBH4 hydrolysis reaction with I-2 and I-7 to I-9 CoeB/IR-120 catalysts.

after several reuses (shown in Fig. 11(b)). CoeB/IR-120 catalyst stability reduced fast at this temperature. The phe-
lost its activity due to two reasons. nomenon did not happen in TP-207 resins because
cross-linking poly-styrene structures of TP-207 resins
(1) Characterization of resins: The SEM of IR-120 and TP- did not swell and stable in water [29].
207 resins are shown in Fig. 12. The pore sizes of IR- (2) Characterization of CoeB metal layers on the resins:
120 and TP-207 resins are meso-porous and macro- After repeated using/cleaning of catalyst, CoeB metal
porous, respectively. When CoeB/IR-120 catalyst layer flaked from the IR-120 resin surface (shown in
reused, it needed to wash and dried. When 1st NaBH4 Fig. 12(e)) due to swelling and drying of IR-120 resin. And
hydrolysis reaction for hydrogen generation test pro- also catalyst particles came into contact with each other
ceeded, the CoeB/IR-120 catalyst must deep into the during hydrogen generation. As more hydrogen was
water. This made the IR-120 resin volume increase (by generated, so more CoeB metal layer flaked from the IR-
swelling). After the test, the CoeB/IR-120 catalyst must 120 resin surface (CoeB metal layer flaked from the IR-
wash and dried. This made the IR-120 resin volume 120 resin surface did not reuse). The final weight
decrease (by drying). The repeated using/cleaning cy- percent of the catalysts after 5 times reuse is 95.2% its
cles caused CoeB/IR-120 catalyst to cleave more easily original weight (0.0333 g). This situation was acerbated
(shown in Fig. 12(g)). This is caused by the CoeB/IR-120 at 80
C than 25
C. This made small pieces of CoeB
is not stable at 80
C which is proven by TGA analysis. Its metal layer sheet flake off from the IR-120 resin surface.
1660 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3

4.5. Result and discussion
For CoeB/IR-120 catalyst, the most important reduction vari-
ables in synthesis catalysts are reduction temperature and pH
value. In a later section, we will discuss the effect of these
catalyst synthesis variables on surface morphology and ki-
netic parameters of hydrolysis reactions. Another reduction
variable, types of resins, is also discussed later.
4.5.1. Effect of various CoeB/IR-120 catalyst synthesis
conditions on catalyst surface morphology and NaBH4
hydrolysis reaction kinetic parameters
4.5.1.1. Reduction temperature. Increasing the reduction
temperature (0e80
C) caused a decrease in catalyst loading
(10.1e6.5 wt.%) which increased the activation energy of
CoeB/IR-120 catalysts (66.32e81.72 kJ mol1). This meant
higher catalyst loading provided larger effective surface area
on the CoeB/IR-120 catalysts [34]. Furthermore, NaBH4 mole-
cules were adsorbed on the active site of the catalyst and then
reacted with water to form hydrogen, resulting in hydrogen
desorbing from the active site [6]. Lowering the reduction
temperature of catalysts (80e0
C); reduced the adsorption
constant (1.47e51.38) at 25
C. The definition of adsorption
(a) 120
100
80
H2 (sccm)
constant is adsorption constant divided by desorption con-
stant. This meant that the desorption rate of hydrogen from
the catalyst surface was faster when the reduction tempera-
ture was lowered. The result can be proven from surface
morphology (shown in Fig. 2). When the reduction tempera-
ture was reduced, the branch structure CoeB metal on IR-120
surface occurred (Fig. 2(a)). The small hydrogen bubbles
accumulated on the branch part and quickly became bigger
bubbles, then left the catalyst by buoyancy. Higher reduction
temperature caused the sheet-like CoeB metal on catalyst
surface (Fig. 2(d)). Due to lack of buoyancy, it was more diffi-
cult for the small hydrogen bubbles to leave the catalyst sur-
face. Fig. 13 (a) shows the tail of the hydrogen flowrate curve is
less pronounced for Ie4 catalyst.
4.5.1.2. pH value. Increasing the pH value (10.45e12.96)
resulted in increased catalyst loading (9.6e11.2 wt.%) which
increased the activation energy of CoeB/IR-120 catalysts
(70.65e80.00 kJ mol1). The result is shown in Table 1.
Increasing the pH value inhibited the hydrolysis reaction, and
narrowed the hydrogen channel. The SEM (Fig. 4(b)) shows the
porosity of CoeB/IR-120 reduced and the branch like surface
structure was observed, which reduced the catalyst surface
area and increased the activation energy. Moreover, the small
porosity of CoeB/IR-120 made it difficult for the hydrogen to
leave the catalyst surface which caused a larger adsorption
constant. Fig. 13(b) shows the tail of the hydrogen generation
1st used
profile is less pronounced for I-7 catalyst.
2nd used
3rd used 4.5.2. Effect of resin types on catalyst surface morphology
4th used
th
and NaBH4 hydrolysis reaction kinetic parameters
5 used
On comparing the strongly acidic and chelating resins in the
same reduction conditions, CoeB/TP-207 catalyst showed

60 greater surface area, higher loading than CoeB/IR-120 and

lower Co/B ratio (Lower Co/B ratio gave larger catalyst activity
[33]. This caused the lower activation energy in CoeB/TP-207
40
catalyst. The hydrolysis reaction for hydrogen generation with
CoeB/TP-207 catalyst present was 1.4 times faster than CoeB/
20
IR-120 at 40
C. The tail of the hydrogen generation profile with
T-2 catalyst is more pronounced than with I-2 catalyst, which
0
0 5 10 15 20 25 30 35 40 meant hydrogen could easily detach from the catalyst surface.
Time (min) This led to a smaller adsorption constant.
(b) 140
1st used
2nd used
120
3rd used
5. Conclusion
4th used
100 5th used The CoeB catalyst for NaBH4 hydrolysis reaction was syn-
thesized by using ion exchange and chemical reduction
H2 (sccm)

80
method. The reduction temperature, reduction concentration,
pH value, NaBH4 injection flowrate and types of resins were
60
investigated. The ranges of reduction temperatures from 0 to
80
C and pH values from 10.45 to 12.95 of catalyst synthesis
40
conditions affected the catalyst surface morphology and ki-
20
netic parameters dramatically. Lower reduction temperature
resulted in a “branch like structure” on the CoeB catalyst
0
surface. The resultant condition caused a lower activation
0 5 10 15 20 25
energy and adsorption constant. The optimal reduction tem-
Time (min)
perature, NaBH4 concentration, pH value, and NaBH4 injection
Fig. 11- e Stability test to NaBH4 hydrolysis reaction for flowrate of CoeB/IR-120 catalyst synthesis are 25
C, 10 wt.%,
hydrogen generation with (a) I-2 catalyst, (b)T-2 catalyst. 10.45, and impulse. Finally, CoeB/TP-207 catalyst shows
 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3 1661

Fig. 12 e The SEM images of CoeB/IR-120 and CoeB/TP-207 catalysts(a) IR-120 and (b) TP-207 resin, (c) CoeB/IR-120 and (d)
CoeB/TP-207 catalysts before use, (e) CoeB/IR-120 and (f) CoeB/TP-207 catalysts after use, (g) CoeB/IR-120 and (h) CoeB/TP-
207 catalysts after multiple-uses.
1662 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 9 ( 2 0 1 4 ) 1 6 4 8 e1 6 6 3

automotive hydrogen storage. Int J Hydrogen Energy

(a) 120 2009;34:2638e45.
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100 Petillo PJ, Binder M. An ultrasafe hydrogen generator:
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ruthenium(0) nanoclusters as catalyst for hydrogen

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TR=800C Catal A Chem 2006;258:95e103.
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[5] Hsueh CL, Chen CY, Ku JR, Tsai SF, Hsu YY, Tsau F, et al.
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Simple and fast fabrication of polymer templateeRu
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Fig. 13 e Hydrogen generation flowrate profiles of NaBH4
hydrolysis reaction at 80
C with (a) Ie1 to Ie4, (b) Ie2 and
Ie7 catalysts.
greater surface area and higher catalyst loading than CoeB/IR-
120. This causes a lower activation energy and adsorption
constant in CoeB/TP-207 catalyst. From stability test of cata-
lysts, CoeB/TP-207 catalyst shows good performance and
stability after several reuses. But CoeB/IR-120 catalyst lost its
activity due to IR-120 resin particle being cleaved by swelling
and CoeB metal layer flaking from the IR-120 resin surface.
Acknowledgments
This work was supported by the National Science Council of
Taiwan under grant NSC 101-2221-E-032 -034 -MY2.
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