Journal of Alloys and Compounds 415 (2006) 288–293

Nickel- and cobalt-based catalysts for hydrogen generation

by hydrolysis of borohydride
Bin Hong Liu a,∗ , Zhou Peng Li b , S. Suda a
a Department of Environment and Chemical Engineering, Kogakuin University, 2665-1 Nakano-cho, Hachioji,
Tokyo 192-0015, Japan
b Department of Chemical and Biochemical Engineering, Zhejiang University,

Hangzhou 310027, PR China

Received 21 July 2005; received in revised form 9 August 2005; accepted 10 August 2005
Available online 19 September 2005

Abstract
Borohydrides, a group of compounds with large hydrogen contents, can generate hydrogen readily by their hydrolysis reaction. In this study
catalysts based on nickel and cobalt were developed to accelerate the hydrolysis reaction for hydrogen generation. Catalysts in four forms were
tested for each metal: fine metal powder, metal salt, metal boride and Raney metal. It was found that the hydrolysis reaction was primary a zero-order
reaction under the catalysis of these catalysts. Although cobalt showed higher catalytic activity than nickel in most cases, Raney Ni exhibited
almost the same activity as the Raney Co. Among four chemical forms for nickel, Raney Ni demonstrated the best performance. Moreover, Raney
catalysts made from alloys of nickel and cobalt showed even higher activity. The reaction on Raney metals was also characterized by a slowdown
in hydrogen generation rate at low borohydride concentrations because of a mass transfer limitation.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Hydrogen; Borohydride; Hydrolysis; Catalyst; Raney metals

1. Introduction
With growing concerns for energy and environment prob-
lems, fuel cells are attracting more and more attentions as clean
and efficient power generation devices. However, their commer-
cialization is still lagging behind, mainly due to their high cost
and a lack of hydrogen infrastructure. As the current technolo-
gies for hydrogen generation by reforming hydrocarbons are
still not satisfactory considering the response time and the pres-
ence of carbon monoxide in hydrogen, hydrogen storage and
supply is now more preferred by the industries, especially for
mobile applications. Hydrogen storages in high-pressure ves-
sels and in metal hydrides are being considered as two viable
ways. However, their storage densities are not sufficient for the
requirements. On this background, chemical hydrides such as
sodium borohydride emerged as convenient hydrogen sources
for on-board hydrogen generation [7–9]. Hydrogen generation
by borohydride is especially suitable for portable applications
∗ Corresponding author.
E-mail address: bq97002@ns.kogakuin.ac.jp (B.H. Liu).
of fuel cells as other hydrogen storage methods are too bulky or
inconvenient [7,8].
Sodium borohydride can generate a large amount of hydrogen
by the catalyzed hydrolysis reaction as follows:
NaBH4 + 2H2 O = NaBO2 + 4H2 (1)
About 10.8 wt.% hydrogen can be obtained from the stoichio-
metric ratio of the reactants. In the early 50 s, Schlesinger et
al. [1] made a detailed study on the hydrolysis reaction of
sodium borohydride for hydrogen generation. They found that
the hydrolysis reaction proceeded at a very slow rate if the solu-
tion was unbuffered or in the absence of catalysts. However, the
reaction can be significantly accelerated by addition of acids
or some catalysts like metals and their salts. Many inorganic
and organic acids were found to be effective in accelerating
the hydrolysis reaction, however the reaction usually became
uncontrollable. On the other side, solid-state catalysts such as
transition metals and their salts were found to be effective and
hydrogen generation rate was easy to control. Also these cat-
alysts would be reusable. Thus, they were considered more
advantageous over acids in a practical sense [6]. Among them

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 B.H. Liu et al. / Journal of Alloys and Compounds 415 (2006) 288–293 289

cobalt and nickel borides were the most investigated catalysts cific surface areas of powders were measured on Shimadzu
[1–6]. Salts like CoCl2 was reduced spontaneously by borohy- FLOWSORB II 2300.
dride to form metal borides like Co2 B that showed excellent
catalytic activity on the hydrolysis reaction. Recently, Amen- 3. Results and discussion
dola et al. [7] reported that they employed Ru supported in ion
exchange resin beads as the catalyst for hydrogen generation of 3.1. Ni and Co powder
sodium borohydride. Also Pt supported on LiCoO2 was devel-
oped [9]. In a previous paper we studied the catalytic properties Metal borides prepared by reducing metal salts with borohy-
of an intermetallic compound Mg2 Ni and its hydride [8]. dride solutions are the most studied catalysts for the borohydride
In the present paper, we examined the properties and per- hydrolysis [1–6]. However, few have reported the catalytic prop-
formance of cobalt- and nickel-based catalysts in four different erties of these metals prepared by other methods. In this study,
forms in an effort to develop inexpensive but effective catalysts we first examined the catalytic properties of commercially avail-
for hydrogen generation from borohydride. Factors influencing able fine Ni and Co powders. Fig. 1 shows the relations of
hydrogen generation rate such as fuel concentrations are also generated hydrogen volume with time at different temperatures.
surveyed. It clearly shows that the reaction was a zero-order reaction in
which the hydrogen generation rate was independent of the boro-
2. Experimental details hydride concentration in the solution. The result of zero-order
kinetics is similar as the observations on metal borides [5,6].
2.1. Preparation of catalysts By comparing the powder size and specific surface area of Ni
and Co power, it seems that Co showed higher catalytic activity
Commercially available fine nickel powder Inco type Ni210 than Ni. According to the calculated rate constants at different
(0.5–1 ␮m) from Inco Ltd. and fine Co powder (1–2 ␮m) from
Soekawa Rikagaku Co., Japan were examined as the catalysts for
borohydride hydrolysis. The catalytic properties of metal salts
were measured by using hydrated metal salts like CoCl2 ·6H2 O,
NiCl2 ·6H2 O and NiF2 ·4H2 O in solid states. Also metal borides
were prepared by adding alkaline borohydride solutions (boro-
hydride in 10 wt.% NaOH) into the solutions of CoCl2 and
NiCl2 . The formed black precipitates were separated from the
solution, washed and dried in a vacuum desiccator at room tem-
perature. Raney Ni or Raney alloys were prepared as follows: the
precursor alloys Ni1−x Cox Al3 (x = 0, 0.05, 0.1, 0.25.0.5, 0.75,
1.0) were prepared by arc-melting the pure constituent metals in
a water-cooled copper hearth in an argon atmosphere. The alloy
ingots were remelted three to four times to ensure homogeneous
compositions. The alloys were then pulverized to a size of less
than 75 ␮m and reacted with a 20 wt.% NaOH solution to leach
the aluminum out at about 70 ◦ C for several hours and then kept
in the alkaline solution for use.

2.2. Kinetics measurement of hydrogen generation

Sodium borohydride with a purity of 97% was from Rohm

and Haas Company, USA. No further purification was under-
taken. Borohydride solutions were prepared by dissolving
sodium borohydride into a 10 wt.% NaOH solution. The hydrol-
ysis reaction experiments were carried out in a three-neck flask
(200 ml). The central neck was connected to a funnel (100 ml)
with a borohydride solution. Catalysts were initially put at the
bottom of the flask. The hydrolysis reaction was initiated by
opening the valve of the funnel and introducing the solution into
the flask. The volume of evolved hydrogen gas was measured by
a water displacement method or a gas flow meter and was trans-
formed to the value in standard temperature and pressure (STP).
Fig. 1. (a) Hydrogen generation kinetics at various temperatures under the catal-
The flask was immersed in a water bath to stabilize the temper- ysis of Inco Ni210 powder (Ni: 0.5 g, solution: 0.2 g NaBH4 in 20 ml 10 wt.%
ature. No stirring was employed in the flask. X-ray diffraction NaOH). (b) Relation of hydrogen generation kinetics with the temperature for the
(XRD) analyses were carried out on a Rigaku RINT-1200. Spe- Co powder catalyst (Co: 0.5 g, solution: 0.2 gNaBH4 in 20 ml 20 wt.% NaOH).
290 B.H. Liu et al. / Journal of Alloys and Compounds 415 (2006) 288–293

Table 1
Properties and performance of the catalysts
Catalyst Powder size (␮m) Specific surface area (m2 /g) Hydrogen generation rate Activation energy (kJ/mol)
(ml/min/g catalyst)

Ni powder 0.5–1 1.98 19.5 (293 K) −62.7

Co powder 1–2 1.15 126.2 (293 K) −41.9
NiCl2 ·6H2 O Granule 9.8 (293 K)
NiF2 ·4H2 O Granule 34.7 (323 K)
CoCl2 ·6H2 O Granule 570.0 (283 K)
Ni2 B 18.3 (293 K)
Co2 B 468.3 (293 K)
Raney Ni 228.5 (293 K) −50.7
Raney Co 267.5 (293 K) −53.7
Raney Ni50 Co50 648.2 (293 K) −52.5

temperatures, the activation energies of Ni and Co are shown
in Table 1.
3.2. Cobalt and nickel salts and their reduction products
Cobalt salt CoCl2 and its reduction product Co2 B from
borohydride solution are well-known catalysts for borohydride
hydrolysis since Schlesinger et al. reported their excellent cat-
alytic activities [1]. In this work, we also examined the catalytic
properties of cobalt and nickel salts as well as their reduction
products from borohydride solution. Granules of the hydrated
salts were used in the present study. Fig. 2 shows the hydro-
gen generation rates when using CoCl2 ·6H2 O, NiCl2 ·6H2 O and
NiF2 ·4H2 O. It was observed that the cobalt salt-induced violent
reaction and fast hydrogen generation even at lower tempera-
tures while the nickel salts only led to slow hydrogen release. In
all cases, black precipitates formed spontaneously when the salts
met with the borohydride solution. It was reported that the black
precipitates are metal–boron compounds. In the case of cobalt
and nickel, Co2 B and Ni2 B would be formed [1,3–5]. Accord-
ing to Kaufman and Sen [6], metal salt-catalyzed borohydride
hydrolysis is a successive reaction of a reduction of metal salts
by borohydride and then the hydrolysis under the catalysis of
the formed metal borides. The overall hydrogen generation in
the presence of metal salts is simultaneously metal and acid cat-
alyzed.
As described in Ref. [4], the reduction reaction of metal salts
proceeds as follows:
CoCl2 + 2NaBH4 + 3H2 O = 6.25H2 + 0.5Co2 B
+ 2NaCl + 1.5HBO2 (2)
According to (2), 0.5 g CoCl2 ·6H2 O containing 0.123 g Co will
need 0.159 g NaBH4 to finish the above reaction. As the solution
contained 0.2 g NaBH4 in this experiment, NaBH4 was in excess
for reaction (2). The mole ratio for NaBH4 and H2 in (2) will
be 1:3.1, rather than 1:4. However, we did not observe such
a large decrease in hydrogen volume. The released hydrogen
was still near the stoichiometric value in (1). The same result
was observed for the nickel salts. It suggests that the actual
reaction mechanism may be other than (2). More accurate and
detailed study is necessary to elucidate the reaction mechanism
considering the complicated nature of the system in which many
reactions take place in parallel.
Fig. 3 demonstrates the catalytic properties of metal borides.
Similar as the results shown in Fig. 2, the cobalt boride shows

Fig. 2. Catalytic performance of some cobalt and nickel salts (hydrated salts: Fig. 3. Comparison of catalytic properties between cobalt and nickel boride
0.5 g, solution: 0.2 g NaBH4 in 20 ml 10 wt.% NaOH). (cobalt or nickel boride: 0.5 g, solution: 0.2 g NaBH4 in 20 ml 10 wt.% NaOH).
 B.H. Liu et al. / Journal of Alloys and Compounds 415 (2006) 288–293 291

Fig. 4. XRD patterns for Ni powder and Raney Ni.

much higher catalytic activity than the nickel borides. It was

reported that the catalytic activity of nickel borides was only
a little inferior to that of cobalt boride [1,5,6]. The discrepancy
between our results and the others may originate from the prepa-
ration conditions of the metal borides. In our experiment, metal
borides were prepared by reacting salt solution with strong alka-
line solution of borohydrde (NaBH4 in 10 wt.% NaOH), while
other authors used solid NaBH4 powder [1] or NaBH4 dissolved
in water [6]. It was reported by Paul et al. [3] that the catalytic
activity of nickel boride was strongly dependent on the pH dur-
ing its formation, and nickel boride prepared in alkaline solution
showed much lower activity than the ones prepared in acidic or
neutral conditions. Therefore, it needs further investigation to
find out the differences in composition or surface structure for
nickel borides prepared in different pH conditions and to relate
them with catalytic activities.
Fig. 5. Hydrogen generation kinetics under the catalysis of Raney Ni and Raney
Co (Raney Ni or Co: 0.5 g, solution: 1 g NaBH4 in 100 ml 10 wt.% NaOH).
3.3.2. Raney Ni–Co alloys
Although Raney Ni and Raney Co already offered very high
catalytic activities, their alloys exhibited even better perfor-
mance. Fig. 6 shows the XRD patterns of the precursor alloys
Ni1−x Cox Al3 . The hydrogen generation kinetics of the Raney
alloys is illustrated in Fig. 7. It can be seen that the alloys led
to faster hydrogen generation rates than the pure metals. It was
also found by Doren [10] that addition of some Fe in Raney Ni
improved the hydrolysis kinetics. This kind of phenomenon is
very interesting from a practical as well as academic point of
view. Further investigation is being carried out to understand
the mechanism.
3.4. Effects of NaBH4 and NaOH concentrations

3.3. Raney catalysts Hydrolysis kinetics was found to be not only dependent on
catalyst performance, but also influenced by other factors. Fig. 8
3.3.1. Raney Ni and Co shows the effects of initial NaBH4 concentration on the hydrogen
Although some papers [1,6] mentioned that Raney Ni is active generation kinetics under the catalysis of fine Ni powder Ni210.
for the hydrolysis reaction, there was no detailed report on their Although the reaction showed the zero-order kinetics, change
catalytic properties. In this work, we measured the catalytic of the initial concentration of NaBH4 was still found to slightly
properties of Raney metals based on cobalt and nickel. Fig. 4 affect the hydrogen generation rate. As the changes in generation
shows the XRD patterns of the nickel powder and Raney Ni. rate happened from the initial stage of the reaction, it may be
From the broadened peaks of Raney Ni, it can be deduced that
Raney Ni was of extremely fine structure. Fig. 5 shows hydrogen
generation kinetics using Raney Ni and Raney Co as the catalyst.
It is apparent that both Raney Ni and Raney Co have very good
catalytic activity. They showed excellent response with almost
no perceivable time delay. Fig. 5 also reveals that the hydroly-
sis reaction has also zero-order kinetics under the catalysis of
Raney metals. However, it was found that the reaction slowed
down around 90% completion and it took a much longer time
to finally finish the rest reaction. In this respect, Raney metals
showed different performance with the fine metal powders as
the latter offered constant hydrogen generation rates until 100%
completion.
The Raney Ni showed almost the same catalytic activity as the
Raney Co, though in other forms Co had much better catalytic
performance than Ni. Fig. 6. XRD patterns of Ni1−x Cox Al3 (x = 0, 0.25, 0.5, 0.75, 1.0) alloys.
292 B.H. Liu et al. / Journal of Alloys and Compounds 415 (2006) 288–293

Fig. 9. Hydrogen generation kinetics influenced by the initial borohydride con-

Fig. 7. Hydrogen generation kinetics under the catalysis of Raney Ni–Co alloys centration using Raney Ni–Co catalyst (Raney Ni95 Co5 : 0.5 g, temperature:
(Raney Ni100−x Cox : 0.5 g, solution: 1 g NaBH4 in 100 ml 10 wt.% NaOH, tem- 293 K).
perature: 293 K).

due to some influence on the catalyst. Borohydride concentration

showed different effects on Raney metals. As demonstrated in
Fig. 9, hydrogen generation rate decreased when borohydride
concentration was lower than 0.2 wt.% NaBH4 while it was not
influenced at higher concentrations. As the reaction kinetics was
greatly enhanced on Raney metals, mass transfer became the
limiting factor at low borohydride concentrations. The very fine
surface structure may also increase the difficulty of mass transfer
as we found that at extremely low borohydride concentrations
the hydrogen generation rate was even lower than that on the Ni
powder.
The effect of NaOH concentration on reaction kinetics is
shown in Fig. 10. When NaOH concentration was less than
20 wt.%, there was no influence on hydrogen generation rate.
However, when NaOH concentration was increased to 30 wt.%,
hydrogen generation rate was affected. At initial stage, the Fig. 10. Influence of NaOH concentration on hydrogen generation kinetics (Ni
powder catalyst: 0.5 g, solution: 0.2 g NaBH4 in 20 ml NaOH solution, temper-
hydrogen generation rate was kept but began to divert from the ature: 293 K).
straight line. The decrease of hydrogen generation rate is sup-
posed to be caused by a decrease in water activity. The experimental results summarized in Table 1 reveal that
it is possible for us to use non-precious metals like nickel and
cobalt to achieve very high hydrogen generation rate. Hydrogen
generation from borohydride is proven to be a practically viable
way of hydrogen supply for fuel cells. Among different forms for
the metals, Raney catalysts especially Ni with small additions
of Co exhibited high catalytic activity and thus may be very
promising as low cost catalysts for hydrogen generation from
borohydride.

4. Conclusions

Catalysts for the borohydride hydrolysis have been developed

Fig. 8. Influence of initial borohydride concentration on hydrogen generation
kinetics using the Ni powder catalyst (Ni powder: 0.5 g, temperature: 293 K).
based on transition metal cobalt and nickel. Four preparation
methods were employed for each metal. Commercially available
fine powders of cobalt and nickel showed considerable catalytic
activities and the hydrolysis reaction was zero-order kinetics.
Both cobalt salt CoCl2 and its reduction product from borohy-
dride solution-induced violent reaction. However, nickel salts
and their reduction products showed much slower kinetics. On
 B.H. Liu et al. / Journal of Alloys and Compounds 415 (2006) 288–293 293

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[5] K.A. Holbrook, P.J. Twist, J. Chem. Soc. A (1971) 890.
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