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Ai-Jen Hunga, Shing-Fen Tsaib, Ya-Yi Hsub, Jie-Ren Kub, Yih-Hang Chenc,
Cheng-Ching Yua,*
a
Department of Chemical Engineering, National Taiwan University, Taipei 106-17, Taiwan
b
Energy and Environment Research Laboratories (EEL), Industrial Technology Research Institute (ITRI), Hsinchu 310, Taiwan
c
Department of Process Engineering, CTCI Corporation, Taipei 106, Taiwan
Article history: In this work, a ruthenium catalyst was prepared for hydrogen generation from the
Received 13 March 2008 hydrolysis reaction of an alkaline sodium borohydride solution. The reactions were carried
Received in revised form out in a batch reactor at temperatures of 10, 30, 40 and 60 C for at least 70% conversion or
29 July 2008 500 min, whichever came first. The experimental data was fitted to the following three
Accepted 29 July 2008 kinetic models: zero-order, first-order, and Langmuir–Hinshelwood. The results indicate
Available online 11 September 2008 that the Langmuir–Hinshelwood model gives a reasonable description of the hydrogen
generation rate over the entire temperature range studied as well as the time spans of the
Keywords: experiments. The zero-order model gives good behavior description only at relatively low
Kinetics temperature, i.e. 10 C. The first-order model works fairly well for a temperature range up
Sodium borohydride to 30 C.
Hydrolysis reaction ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
Hydrogen generation reserved.
Other authors have used a first-order model. Ozkar and Ref. [12] and the activity of Pd on the hydrolysis reaction was
Zahmakiran [4,5] used a water-dispersible Ru(0) nanocluster investigated in Ref. [10].
catalyst to increase activity. Shang and Chen [6] explored the Finally, at least one author has used a Langmuir–Hin-
effect of a concentrated NaBH4 solution on hydrogen genera- shelwood model. Zhang et al. [7] used the commercial
tion rates. The performance and reliability of carbon nano- catalyst Ru to analyze the effects of different substrates,
tubes (CNT) as the catalyst for the hydrolysis reaction were the catalyst sizes, the stirring speed and the reaction
investigated in Ref. [19]. The synthesis and characterization of temperature on the hydrogen generation rate. Table 1
a water-dispersible Ni(0) nanocluster catalyst was explored in summarizes published investigations of the kinetics of the
Table 1 – Kinetic models for different catalysts, initial concentration of NaBH4(aq), temperature ranges, activation energy
and time spans
Catalyst/support Initial concentration Kinetic Temp. Activation Time Reference
of NaBH4(aq) model range (oC) energy span
(kJ/mol) (min)
Ru(5 wt%)/IRA-400 20 wt% NaBH4 þ 10 wt% NaOH Zero-order 25–55 47.0 27 Amendola et al. [1]
Ru(5 wt%)/IRA-400 7.5 wt% NaBH4 þ 1 wt% NaOH Zero-order 0–40 56.0 42 Amendola et al. [2]
Ru(1 wt%)/IR-120 5 wt% NaBH4 þ 1 wt% NaOH Zero-order 5–55 49.7 60 Hsueh et al. [3]
Ni 0.9 wt% NaBH4 þ 10 wt% NaOH Zero-order 10–50 62.7 150 Liu et al. [11]
Co Zero-order 10–50 41.9 30
Raney Ni Zero-order 10–30 50.7 50
Raney Co Zero-order 10–30 53.7 50
Raney Ni50Co50 Zero-order 10–30 52.5 30
Co–B 20 wt% NaBH4 þ 5 wt% NaOH Zero-order 10–30 64.9 40 Jeong et al. [15]
Co–B 0.7wt% NaBH4 þ 4 wt% NaOH Zero-order 25–40 57.8 14 Zhao et al. [16]
Co/g-Al2O3 5 wt% NaBH4 þ 5 wt% NaOH Zero-order 30–50 32.6 80 Ye et al. [13]
NixB 1.5 wt% NaBH4 þ 10 wt% NaOH Zero-order 20–60 56.0 35 Dong et al. [17]
Ni–Co–B 4.7 wt% NaBH4 þ 15 wt% NaOH Zero-order 8–27 62.0 50 Ingersoll et al. [18]
Ru(0) nanoclusters 0.5 wt% NaBH4 First-order 30–45 28.5 5 Ozkar and Zahmakiran [4]
Ru(0) nanoclusters 0.5 wt% NaBH4 þ 10 wt% NaOH First-order 25–55 41.0 6 Zahmakiran and Ozkar [5]
Ru/C 5 wt% NaBH4 þ 5 wt% NaOH First-order 42–60 37.3 35 Shang and Chen [6]
Carbon nanotubes (CNT) 1 wt% NaBH4 First-order 29–59 19.0 120 Pena-Alonso et al. [19]
Ni(0) nanoclusters 0.5 wt% NaBH4 First-order 25–45 54.0 100 Metin and Ozkar [12]
Pd/C 0.5 wt% NaBH4 First-order 10–55 28.0 20 Patel et al. [10]
Ru/C 0.8 wt% NaBH4 þ 3 wt% NaOH Langmuir– 25–85 67.0 14 Zhang et al. [7]
Hinshelwood
Ru/g-Al2O3 12 wt% NaBH4 þ 1 wt% NaOH Zero-order 10–60 54.9 500 This work
Ru/g-Al2O3 12 wt% NaBH4 þ 1 wt% NaOH First-order 10–60 55.7 500 This work
Ru/g-Al2O3 12 wt% NaBH4 þ 1 wt% NaOH Langmuir– 10–60 55.4 500 This work
Hinshelwood
international journal of hydrogen energy 33 (2008) 6205–6215 6207
Tsp (Reactor)
NaBH4(aq)+NaOH(aq)
Flow Steam H2 TT TC
meter trap
Coolant out
Thermocouple
Coolant in
Tsp (Water bath)
TT TC
Fig. 1 – Experimental setup for hydrogen generation from the hydrolysis reaction of an alkaline NaBH4 solution.
hydrolysis of NaBH4, including the kinetic models for utilizing the kinetic model to design a hydrogen generation
different catalysts, initial concentration of the alkaline device, a model capable of describing the hydrogen gener-
NaBH4 solution, temperature ranges, activation energy and ation rate over the entire batch reactor operation is
time spans. As shown in Table 1, the models are mostly preferred. The objective of this work is to determine an
zero-order or first-order with the exception of the work of appropriate kinetic model of this hydrolysis reaction in
Ref. [7]. Furthermore, the time spans of the experiments a batch reactor based on experiments at four different
range from 5 to 150 min. Because we are interested in temperatures.
8 8
1 wt% NaBH4 1 wt% NaOH
5 wt% NaOH
7 12 wt% NaBH4 7
10 wt% NaOH
13 wt% NaBH4
6 31 wt% NaBH4 6
Hydrogen generated (L)
Hydrogen generated (L)
5 5
4 4
3 3
2 2
1 1
0 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
time (min) time (min)
Fig. 2 – Hydrogen generation volume with respect to time Fig. 3 – Hydrogen generation volume with respect to time
at the concentration of NaBH4 of 1, 12, 13 and 31 wt% at at the concentration of NaOH of 1, 5 and 10 wt% at 30 8C
30 8C with the concentration of NaOH at a constant 1 wt%. with the concentration of NaBH4 at a constant 12 wt%.
6208 international journal of hydrogen energy 33 (2008) 6205–6215
6 Trxn=30°C
80 Trxn=40°C
Trxn=60°C
XNaBH4 (%)
60
3
40
20
0
0 100 200 300 400 500 t = 265.86 min
0
time (min) 0 100 200 300 400 500
t = 33.86 min t = 107.50 min
time (min)
Fig. 4 – Hydrogen generation volume with respect to time
at temperatures of 10, 30, 40, and 60 8C with the Fig. 5 – (A) Concentration of NaBH4 with respect to time, (B)
concentrations of NaBH4 and NaOH at 12 and 1 wt%, conversion of NaBH4 with respect to time for four
respectively. temperatures: 10 8C, 30 8C, 40 8C, and 60 8C.
international journal of hydrogen energy 33 (2008) 6205–6215 6209
A 10°C B 30°C
0.8 3.5
R2 = 0.9991 R2 = 0.9947
(CNaBH4,0-CNaBH4) (mol/L)
(CNaBH4,0-CNaBH4) (mol/L)
3
(CNaBH4,0-CNaBH4) (CNaBH4,0-CNaBH4)
0.6
=0.001455•t+0.06476 2.5 =0.006153•t
2
0.4
1.5
1
0.2
0.5
0 0
0 100 200 300 400 500 0 100 200 300 400 500
time (min) time (min)
C 40°C D 60°C
4 5
R = 0.9987
2
R2 = 0.9999
(CNaBH4,0-CNaBH4) (mol/L)
(CNaBH4,0-CNaBH4) (mol/L)
(CNaBH4,0-CNaBH4) (CNaBH4,0-CNaBH4)
4
3 =0.01486•t =0.04628•t
3
2
2
1
1
0 0
0 50 100 150 200 250 0 20 40 60 80 100
time (min) time (min)
Fig. 6 – Linear regression based on zero-order while the temperature is (A) 10 8C (B) 30 8C (C) 40 8C (D) 60 8C.
seen in Fig. 3, the hydrogen generation decreases when the For kinetic analysis, it is preferable to convert the hydrogen
NaOH concentration is increased. The reagent solution was generation rate into the reactant (sodium borohydride)
stirred by a magnet to maintain a uniform temperature. The concentration – both as functions of time. From the reaction
hydrogen that was generated exited through the third neck stoichiometry, the number of moles of NaBH4 remaining in
into a coil condenser and then passed through a steam trap in the batch reactor with respect to time can be expressed as:
order to remove the water vapor. During the experiments, the NNaBH4 ðzÞ ¼ NNaBH4 ðz 1Þ NH2 ðz 1Þ=4 (2)
hydrogen generation rates were measured by a flow meter at
the following temperatures: 10, 30, 40, and 60 C. The where N is the number of moles and z is the discrete variable.
sampling times for the temperature and flow measurements The number of moles of H2O remaining in the batch reactor
are 1.06 s. with respect to time is:
NH2 O z ¼ NH2 O z 1 NH2 z 1 2 (3)
3. Results and discussions
The number of moles of NaBO2 remaining in the batch
reactor with respect to time is:
3.1. Kinetics
NNaBO2 ðzÞ ¼ NNaBO2 ðz 1Þ þ NH2 ðz 1Þ=4 (4)
3.1.1. Data treatment
Because of the noise associated with measurements, it is The solution volume with respect to time can then be
desirable to use an exponential filter to smooth the raw data evaluated as follows:
for hydrogen generation rates. Raw data was smoothed with NNaBH4 ðzÞ$MNaBH4 NH2 O ðzÞ$MH2 O NNaBO2 ðzÞ$MNaBO2
VðzÞ ¼ þ þ
a filter with a time constant of 0.42 min. The relatively small rNaBH4 rH2 O rNaBO2
time constant will not alter the dynamic behavior of the (5)
reaction because the process time constant is much large, at
least 40 min. The Appendix shows the hydrogen generation where V is the solution volume, r denotes the density, M
rate before and after the filtering at 30 and 60 C. The accu- stands for the molecular weight. Consequently, the concen-
mulative volumetric hydrogen generation with respect to tration of NaBH4 as a function of time can be obtained from
time is shown in Fig. 4 at temperatures of 10, 30, 40, and CNaBH4 ¼ NNaBH4/V as shown in Fig. 5(A). The corresponding
60 C. conversion of NaBH4 can be calculated as shown in Fig. 5(B). In
6210 international journal of hydrogen energy 33 (2008) 6205–6215
Table 2 – Products of reaction rate constant and catalyst weight, correlation coefficients of regression and correlation
coefficients for the entire range for zero-order, first-order, Langmuir–Hinshelwood at 10, 30, 40, and 60 8C
Temp. ( C) Time span k (mol/L/min) Correlation Correlation
for regression (min) coefficient (R2) coefficient (R2)
of regression for the entire
rangea
a Full time span range: 0–500 min for 10 and 30 C, 0–250 min for 40 C, and 0–100 min for 60 C.
this work, the following three kinetic models were used to the range of 50–500 min with the correlation coefficient of
describe the behavior of the hydrolysis reaction for hydrogen 0.9991. The data at temperatures of 30, 40, and 60 C could be
generation using an integral method. linearly regressed only within the cut-off time, where the
conversion of NaBH4 is 50%, as shown in Fig. 6(B–D). As can be
3.1.2. Zero-order seen from Fig. 5(A), the concentration of NaBH4 at 10 C is
If the rate of consumption of NaBH4 (CNaBH4) with respect to always higher than 2.5 (mol/L) within the whole reaction
time is equal to a reaction rate constant, the reaction has zero- time whereas the variations in the concentration of NaBH4
order kinetics (independent of any concentration). at 30, 40, and 60 C are greater. Therefore it is appropriate
dCNaBH4 to apply the zero-order model while the concentration of
¼ rNaBH4 ¼ kðTÞ (6) NaBH4 remains high. Table 2 summarizes the following
dt
where C is the concentration, r is the rate of reaction, k is the -3
reaction rate constant based on the solution volume. R2 = 0.9971
Integrating the differential Eq. (6) it then becomes: -3.5 6599.7
ln (k) = = 16.765
CNaBH4;0 CNaBH4 ¼ kt (7) T
-4
Comments
activation energy of 54.90 kJ/mol (the slope of the linear
regression) and the pre-exponential factor of 1.91 107 mol/
temperature up to 30 C.
temperature up to 60 C.
L/min (the intercept of the linear regression) could both be
determined, as shown in Table 3. Because of the gradual
deterioration of the NaBH4 concentration at higher temper-
atures toward the end of the time frame, e.g., 30, 40, and
3.1.3. First-order
Considering the case when the reaction rate is first-order in
Table 3 – Pre-exponential factors and activation energy for zero-order, first-order and Langmuir–Hinshelwood models
the concentration of NaBH4, we have:
¼ 1:96
dCNaBH4
¼ rNaBH4 ¼ kCNaBH4 (8)
dt
!
Integrating the differential Eq. (8) it then becomes:
mol
L
CNaBH4;0
ln ¼ kt (9)
and Ka
CNaBH4
55:70 a
a
Kinetic parameter
*
!
!
RTðKÞ
RTðKÞ
RTðKÞ
a straight line, the slope of which is the reaction rate constant.
54:90
55:40
!
!
Fig. 8(A) and (B) shows that plots of lnðCNaBH4;0 =CNaBH4 Þ versus
!
RTðKÞ
RTðKÞ
54:90
55:40
RTðKÞ
55:70
¼ 1:15 106 exp
time at temperatures of 10 and 30 C produce good linear
regression with correlation coefficients of 0.9999 and 0.9967.
¼ 9:53 106 exp
Nevertheless, the data at 40 and 60 C could be regressed
¼ 1:91 107 exp
!
NaBH4 on the catalyst. Table 2 summarizes the following
g cat min
g cat min
g cat min
!
!
mol
mol
regression data for a first-order model: the reaction rate
!
L
L min
L min
mol
mol
min
sion and the correlation coefficients for the entire range. The
k0
k0
k0
k
¼ k
dCNaBH4
dCNaBH4
dt
dt
dt
3.1.4. Langmuir–Hinshelwood
The Langmuir–Hinshelwood model [7,23] is commonly used to
describe reaction kinetics for catalytic reactions. Consider the
following rate expression:
.
Langmuir–Hinshelwood
0:5 g cat
0:03L
dCNaBH4 Ka CNaBH4
¼ rNaBH4 ¼ k (10)
dt 1 þ Ka CNaBH4
¼k
First-order
a k0 ¼ k
1 CNaBH4;0
ln þ CNaBH4;0 CNaBH4 ¼ kt (11)
Ka CNaBH4
6212 international journal of hydrogen energy 33 (2008) 6205–6215
A 10°C B 30°C
0.3 1.2
R2 = 0.9999 R2 = 0.9967
0.25 ⎛ CNaBH4,0 ⎛ 1 ⎛ CNaBH4,0 ⎛
ln(CNaBH4,0/CNaBH4) ln ⎜⎜ ⎜⎜ = 0.0004909•t+0.01263 ln ⎜⎜ ⎜⎜ = 0.002356•t
ln(CNaBH4,0/CNaBH4)
⎝ CNaBH4 ⎝ ⎝ CNaBH4 ⎝
0.2 0.8
0.15 0.6
0.1 0.4
0.05 0.2
0 0
0 100 200 300 400 500 0 100 200 300 400 500
time (min) time (min)
C 40°C D 60°C
2.5 4
R2 = 0.9967 R2 = 0.9859
3.5
⎛ CNaBH4,0 ⎛ ⎛ CNaBH4,0 ⎛
2 ln ⎜⎜ ⎜⎜ = 0.005347•t ln ⎜⎜ ⎜⎜ = 0.01663•t
ln(CNaBH4,0/CNaBH4)
ln(CNaBH4,0/CNaBH4)
⎝ CNaBH4 ⎝ 3 ⎝ CNaBH4 ⎝
1.5 2.5
2
1 1.5
1
0.5
0.5
0 0
0 50 100 150 200 250 0 20 40 60 80 100
time (min) time (min)
Fig. 8 – Linear regression based on first-order while the temperature is (A) 10 8C (B) 30 8C (C) 40 8C (D) 60 8C.
A plot of ð1=Ka ÞlnðCNaBH4;0 =CNaBH4 Þ þ ðCNaBH4;0 CNaBH4 Þ as a func- minimizing Eq. (12) at temperatures of 40 and 60 C. In order to
tion of time should give a straight line, the slope of which is determine the reaction rate constant for Langmuir–Hinshel-
the reaction rate constant. The objective function can be wood, the optimal adsorption constant was input into the data
minimized by varying the adsorption constant using the data at temperatures of 10 and 30 C, as shown in Fig. 11(A) and (B).
at 40 and 60 C. Therefore, it can be formulated as follows: As can be seen in Fig. 11(C) and (D), the data at 40 and 60 C
could be linearly regressed within the whole time span. Table
min f ðKa Þ ¼ 1 R240 C þ 1 R260 C (12) 2 also shows the reaction rate constants, the correlation
Ka
-5 2.2
T
-5.5 2
-6
ln (k)
1.8
-6.5
1.6
-7
-7.5 1.4
Ka,opt=1. 96
-8
1.2
1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5
-8.5
3 3.1 3.2 3.3 3.4 3.5 3.6 Ka (L/mol)
1/T (1/K) x 10-3
Fig. 10 – Optimization of the adsorption constant for
Fig. 9 – Arrhenius plot for first-order. Langmuir–Hinshelwood using the data at 40 and 60 8C.
international journal of hydrogen energy 33 (2008) 6205–6215 6213
A 1
10°C B 4
30°C
2
R = 0.9993 R2 = 0.9971
1/Ka*ln(CNaBH4,0/CNaBH4)
1/Ka*ln(CNaBH4,0/CNaBH4)
1 ⎛CNaBH4,0 ⎛ 1 ⎛CNaBH4,0 ⎛
0.8 ln ⎜ ln ⎜
⎜C ⎜ + (CNaBH4,0 - CNaBH4) ⎜C ⎜+(CNaBH4,0 - CNaBH4)
+(CNaBH4,0-CNaBH4)
+(CNaBH4,0-CNaBH4)
1.96 ⎝ NaBH4 ⎝ 3 1.96 ⎝ NaBH4 ⎝
= 0.001705•t + 0.07120 = 0.007287•t
0.6
2
0.4
1
0.2
0 0
0 100 200 300 400 500 0 100 200 300 400 500
time (min) time (min)
C 5
40°C D 6
60°C
R2 = 0.9990 R2 = 0.9997
1/Ka*ln(CNaBH4,0/CNaBH4)
1/Ka*ln(CNaBH4,0/CNaBH4)
4 1 ⎛CNaBH4,0 ⎛ 5 1 ⎛CNaBH4,0 ⎛
ln ⎜ ln ⎜
+(CNaBH4,0-CNaBH4)
(C -C ) (C -C )
⎜+ NaBH4,0 NaBH4 ⎜+ NaBH4,0 NaBH4
+(CNaBH4,0-CNaBH4)
⎜C ⎜C
1.96 ⎝ NaBH4 ⎝ 1.96 ⎝ NaBH4 ⎝
4
3 = 0.01729•t = 0.05659•t
3
2
2
1
1
0 0
0 50 100 150 200 250 0 20 40 60 80 100
time (min) time (min)
Fig. 11 – Linear regression based on Langmuir–Hinshelwood with the temperature set at (A) 10 8C (B) 30 8C (C) 40 8C (D) 60 8C.
coefficients of both regression and the entire range for Lang- 3.2. Batch reactor model
muir–Hinshelwood. Therefore from the Arrhenius plot of ln(k)
versus 1/T as shown in Fig. 12, the activation energy and the With the kinetic models available, a constant-pressure batch
pre-exponential factor could be determined to be 55.40 kJ/mol reactor model can be constructed. From the mole balance and
and 2.82 107 mol/L/min. The reaction rate constants based
on the solution volume and the catalyst weight for zero-order,
first-order, and Langmuir–Hinshelwood are summarized in 9
Table 3. Exp. data (Trxn = 60°C)
Zero-order
First-order
-2.5 Langmuir-Hinshelwood
Hydrogen generated (L)
-3 R2 = 0.9979 6
6667.3
-3.5 ln (k) = - + 17.155
T
-4
-4.5
ln (k)
3
-5
-5.5
-6
-6.5 0
0 20 40 60 80 100
time (min)
-7
3 3.1 3.2 3.3 3.4 3.5 3.6
x 10-3 Fig. 13 – Model predictions for zero-order, first-order, and
1/T (1/K)
Langmuir–Hinshelwood with the experimental data at
Fig. 12 – Arrhenius plot for Langmuir–Hinshelwood. 60 8C.
6214 international journal of hydrogen energy 33 (2008) 6205–6215
60
constant reaction temperature, the energy balance equa-
tions are negligible in this system. Eqs. (13)–(15) can be
solved by using the Euler method, the code is programmed 40
in FORTRAN.
90
4. Conclusions
60
In this study, the catalyst Ru/g-Al2O3 was prepared by the
impregnation–reduction method for the hydrogen generation
from the hydrolysis reaction of an alkaline NaBH4 solution. 30
Next, the reaction was carried out in a batch reactor at 10, 30,
40 and 60 C, respectively, until at least 70% conversion was 0
0 20 40 60 80 100
achieved, except for the case of 10 C when the reaction was time (min)
terminated at 500 min. The results indicate that the zero-
order model can only be applied for low conversion, e.g., Fig. A1 – Raw data and filtered data at (A) 30 8C and (B) 60 8C.
x < 50%, and/or low temperature, e.g., 10 C. The first-order
model shows somewhat better applicability and gives
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