Advanced Materials Research Submitted: 2014-09-22

ISSN: 1662-8985, Vol. 1113, pp 631-636 Revised: 2014-12-02

doi:10.4028/www.scientific.net/AMR.1113.631 Accepted: 2015-03-13
© 2015 Trans Tech Publications, Switzerland Online: 2015-07-13

Hydrogen Storage in Modified Kenaf

Farahhin N. J., Kamarudin K.S.N.*

Faculty of Petroleum and Renewable Energy Engineering,
Universiti Teknologi Malaysia, 81310 Skudai,
Johor, Malaysia

*E-mail address: sozana@petroleum.utm.my

Keywords: Adsorption, Storage, Hydrogen, Kenaf.

Abstract. Kenaf fiber has been recognized as a new material for adsorption based on its porous
structure. However, previous studies have proved that modified kenaf could give better interaction
towards adsorbates than the raw kenaf during the adsorption. In this study, kenaf core fiber has been
modified using Nickel metal (Ni-metal). Different concentration of Nickel nitrate, Ni(NO3)2 (0.01
M and 1 M) have been used to observe the effect of Ni-metal for hydrogen adsorption. Initially, raw
kenaf sample has been grinded and sieved into 500 µm in size. Then, the sample was heated to
remove the moisture and Ni(NO3)2 has been added into the dried kenaf. Based on this study,
modified kenaf with 0.1 M Ni(NO3)2 and 1 M Ni(NO3)2 has adsorbed more hydrogen compared to
the raw kenaf. The result has provided a fundamental knowledge of kenaf as hydrogen storage
material.

Introduction

Hibiscus cannabinus L. or kenaf is a potential industrial fiber crop that has been widely used
for various applications. The application provides a value-added to bio-based products and increase
crop demand and thus prices that benefits farmers. This product will reduce consumption of non-
renewable resources and leads to the use of green products. The more crop-derived product used,
the more lifestyle will be sustain. However, these crops require industrial processing before it can
be utilised in any application. Kenaf is a plant that originated from South Africa could growth
between fourth to sixth months until its maturity and could rise until 3.5 m to 4.5 m of height.
Kenaf crops comprised of two types of fibers which are bast and core. Both fibers are bounded
together with lignin. Bast fiber contain one-third of kenaf stalk and brown in colour. As for the core,
it is an inner white fiber and usually uses as adsorptive material. Previously, kenaf fiber was mainly
used for rope, paper and coarse cloth. However, nowadays kenaf fiber has been received wide
attention for other application such as supplement in glass fiber composites. This is due its special
characteristics that could replace conventional synthetic fibers.
It was also reported that kenaf has been used as medium to remove undesired chemical for
waste treatment. The ability of kenaf to adsorb has become well-known worldwide and can be used
for other adsorption processes. It was reported that residual of methylene blue dye used in textile
industry that could harm health and cause water pollution has been absorbed by using kenaf core
[1]. This bio-based material gives large impact towards green technology since it prevent any use of
harmful material or adsorbent and more environmental friendly. Kenaf core fiber contains highly
porous structure with superior morphologies and large surface area. Based on its porous structure, it
provides large surface area and able to trap the gas within its pores [2]. Hence, based on this unique
characteristic, kenaf core could also be used as adsorptive material for hydrogen storage.
At present, hydrogen is a clean energy source, an ideal fuel and a versatile energy carrier
[3]. U.S. Department of Energy (DOE) has set a target of 9 wt % to develop and use on-board
hydrogen storage system by 2015 [4]. In fuel technology, storing hydrogen as pressurized gas or

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications, www.scientific.net. (#113109460, Universiti Teknologi Malaysia UTM, Johor Bahru, Johor, Malaysia-04/03/19,03:53:20)
632 Material Science Technology and Global Sustainability

cryogenic liquid has become a common techniques. Even though both methods are well-known, but
these methods are costly and require large space and high pressure. Therefore, adsorptive storage
using porous material becomes an alternative method for hydrogen-fuelled vehicles [5]. Hydrogen
adsorption requires solid adsorbent with larger surface area in order to adsorb hydrogen gas onto
adsorbent surface to its maximum capacity with ‘safe’ pressure. Physisorption takes place when
there is Van der Waals interaction between hydrogen molecule and the surface of adsorbent. The
amount of hydrogen adsorbed is a function of the pressure, and it is reversible; the gas desorbed
when pressure decrease [6,7]. Weak interaction between hydrogen molecules and the surface will
energetically bind the molecules within the pores. In general, physical adsorption usually requires
highly porous material for adsorption. Indeed, the amount of hydrogen stored usually expressed in
weight percentage.
As stated by Cuerda-Correa et al. [8], modification could enhance the adsorption ability of
kenaf. Based on previous reports, modification of adsorbent such as activated carbon and MCM-41
increased hydrogen storage capacity [9-12]. However, study on modification of kenaf for hydrogen
storage is still new. Therefore, this paper presents adsorptive characteristics of kenaf that has been
modified using Ni(NO3)2. Part of kenaf used in this work was kenaf core fiber (inner fiber) and the
particle size used was 500 µm. Modification of kenaf core fiber was carried out by metal deposition
method. In this experiment, formaldehyde (HCHO) has been used to completely reduce the metal
precursor and ethanol (C2H6O) has been used for kenaf dispersion.

Experimental

For kenaf sample, Lembaga Kenaf dan Tembakau Negara has provided kenaf core chips. It
was further grinded and sieved to obtain 500 µm kenaf sample. The sample was heated for 24 hours
at 70 °C prior to modification. For modification of kenaf sample, it was kept in contact with
Ni(NO3)2 solution for 15 minutes at 45 °C. After off heat, Sodium hydroxide (NaOH), HCHO and
C2H6O were added into the sample and been stirred for 4 hours. Then, the sample was filtered and
dried at room temperature. The composition of solution used in metal deposition is presented in
Table 1.

Table 1. Composition for metal deposition for each sample.

Chemicals SK1 SK2 SK3

(Untreated) (0.1 M Ni-Ken) (1 M Ni-Ken)
Kenaf core (g) 10 10 10
Ni(NO3)2 0.1 M (ml) - 300 -
Ni(NO3)2 1 M (ml) - - 190
NaOH (ml) - 100 125
HCHO 37% (ml) - 30 30
C2H6O (ml) - 30 20

Hydrogen adsorption capacities of samples were measured using experimental set-up shown
in Figure 1. Hydrogen storage has been measured at 2 bars, 4 bars and 6 bars with constant
temperature, 298 K. The hydrogen storage system consists of reservoir and reactor that were
interconnected by valves. In order to prevent any undesired gases, this system has been vacuum for
5 hours before hydrogen being released into the system. After samples has been loaded into the
reactor, hydrogen gas being released for 24 hours. This pressure has been showed at PG7 and
pressure drop were calculated. The pressure drop indicates that hydrogen has been adsorbed on the
surface of adsorbent.
 Advanced Materials Research Vol. 1113 633

Figure 1. Schematic diagram of hydrogen storage system

Result and Discussion

In this study, three samples have been used to investigate the effect of metal loading on
kenaf characteristics: SK1 is a raw kenaf, SK2 is a kenaf sample modified with 0.1 M Ni(NO3)2 and
SK3 is a kenaf sample modified with 1 M Ni(NO3)2. Figure 2 shows the inner structure of kenaf for
the dispersion of nickel. The inner structure of kenaf shows that it provides potential surface for
adsorption. The macroporous structure of kenaf provides large surface area for adsorption.
However, in order to increase the adsorption ability, kenaf core sample was modified by immersing
into Ni(NO3)2 solution. During the modification, Ni-metal was directly contacted with kenaf surface
that make discrete nickel atom immediately adsorbed onto the surface. Nickel content in the kenaf
samples influenced the ability of kenaf to adsorb hydrogen since it will interact with hydrogen
molecules.

Figure 2. Inner kenaf structure

In metal deposition baths, Ni-metal has been used as metal precursor with HCHO as
reducing agent and C2H6O has been used as dispersant agent. Both of these chemicals play
important roles to ensure that Ni-metal would be deposited onto kenaf surfaces. Figure 3 shows the
amount of hydrogen that has been adsorbed after 6 hours. The initial pressure of the reactor kept at
2 bars. It shows that the modification of kenaf enhanced the adsorption capacity of kenaf. The
untreated kenaf exhibits an insignificant adsorption even after 6 hours of contact with hydrogen gas.
634 Material Science Technology and Global Sustainability

Based on the result, modified kenaf, 0.1 M Ni-Ken (SK2) can adsorb more hydrogen than raw kenaf
(SK1) after Ni(NO3)2 was added to sample. Modified kenaf (SK2) can adsorb up to 6.89 mmol/g of
hydrogen and the value remains constant after 24 hours indicates desorption did not occur.
The result shows that presence of Ni-metal on the surface of the adsorbent (SK2) has
increased the active sites that allow better interactions between the adsorbate and adsorbent thus
leads to higher adsorption capacity of kenaf. However, at higher concentration of Ni(NO3)2 (1 M),
SK3 only able to adsorb 2.33 mmol/g of hydrogen. As reported by Yi et al [12] that excessive of
amount of modifier could block the pores in the kenaf and thus reduce the adsorption of hydrogen
in the kenaf porous structure. Meanwhile, less hydrogen adsorbed into SK1 sample (0.089 mmol/g)
indicates less interaction between hydrogen molecules and kenaf surface. By comparing to Jimenez
et al [9], using carbon nanofibers (CNFs) also require Ni-metal as modifier in order to improve the
hydrogen adsorption capacity. This shows Ni-metal as promising modifier for improvement in
hydrogen adsorption capacity.

8
7
Hydrogen Adsorbed (mmol/g)

6
5
4
3
2
1
0
SK1 SK2 SK3
Sample

Figure 3. Hydrogen adsorbed at 2 bars.

However, adsorption at higher pressure (4 bars) shows that SK3 sample adsorbed more
hydrogen than SK1 and SK2 samples. This result indicates that even though kenaf has porous
structure, but the interaction between adsorbate (hydrogen gas) and the surface is very low. As
shown in Figure 4, SK1 adsorption increased from 0.089 mmol/g to 2.2 mmol/g of kenaf as the
initial pressure in the reactor increased from 2 bars into 4 bars. Hence, minimum number of
hydrogen molecule has been trapped in the kenaf structure. As the kenaf has been modified with
Ni(NO3)2, the adsorption process successfully increased.
In this study, Ni-metal loading gives high impact towards the hydrogen adsorption capacity.
This result indicates there was chemisorption characteristic instead of physisorption process. Higher
hydrogen capacity in adsorption could be featured since the oxygen functional groups contain in
Ni(NO3)2 work as an efficient hydrogen atom receptors [12]. Therefore, kenaf sample with 1 M
Ni(NO3)2 shows higher hydrogen adsorption after 6 hours. The concentration of Ni-metal used for
SK3 was higher than SK2. Figure 4 shows SK1 has the lowest adsorption capacity with 2.2 mmol/g
adsorbed. SK2 adsorbed 5.76 mmol/g and SK3 adsorbed 10.41 mmol/g.
 Advanced Materials Research Vol. 1113 635

12

Hydrogen Adsrobed (mmol/g)

10

0
SK1 SK2 SK3
Sample

Figure 4. Hydrogen adsorbed at 4 bar.

This study proved that the amount of hydrogen adsorbed on the untreated kenaf (SK1), is
relatively low. This is due to low interaction ability between hydrogen and the surface of kenaf.
Hydrogen molecules could be easily ‘escaped’ from the porous since structure in kenaf does not
have ability to bind the hydrogen molecules. Figure 5 shows the amount of hydrogen has been
adsorbed by SK3 at higher pressure (6 bars). As the pressure increased, more hydrogen adsorbed on
modified kenaf. This study showed that, the modified kenaf could adsorb up to 13.32 mmol/g of
hydrogen for SK3 sample at pressure of 6 bars. This is due to the concentration of Ni(NO3)2 added
to SK3 which gives a better result in hydrogen adsorption process. The use of kenaf could be
improved with modification using Ni-metal.
Figure 5 also shows the effect of pressure on hydrogen adsorption after modification. It
proved that kenaf requires modification in order to increase its adsorption ability. Thus, the
presence of Ni-metal creates active sites on kenaf surface thus enhance hydrogen adsorption. At
constant temperature, SK3 showed different adsorption reaction at different pressure. This shows
that pressure also influenced the adsorption ability of kenaf.

14.00
Hydrogen Adsorbed (mmol/g)

12.00

10.00

8.00

6.00
SK3
4.00

2.00

0.00
2 4 6
Pressure (bars)

Figure 5. Hydrogen adsorbed on SK3 at different pressure.

636 Material Science Technology and Global Sustainability

Conclusion
Ni(NO3)2 able to increase the hydrogen storage capacity of kenaf core. The porous structure offers
large surface area for the dispersion of nickel on the surface. By modification, the active sites
increases thus it increase the adsorption capacity of hydrogen. The modification of kenaf using
different concentration of Ni(NO3)2 shows that Ni-metal plays an important role towards hydrogen
storage. Since the temperature was constant during the experiment, varied hydrogen pressure has
been applied into the system (2 bars, 4 bars, 6 bars). From the result, it can be conclude that higher
pressure than 2 bars improve the adsorptive storage on kenaf core.

Acknowledgment

The authors gratefully acknowledge the financial support given by Ministry of Education Malaysia
for the GUP grant vote number of R.J130000.7942.4S047, Ministry of Science, Technology and
Innovation (MOSTI) and Universiti Teknologi Malaysia. An appreciation also dedicated to National
Kenaf and Tobacco Board (NKTB), Kelantan for the material supplied and guidance on Kenaf
Plantation in Malaysia.

References
[1] D. K. Mahmoud, M.A. M. Salleh, W. A. W. A. Karim, A. Idris, Z. Z. Abidin. J. Chem. Eng.
Vol. 181-182 (2012), p. 449-457.
[2] Information on http://www.lib.ncsu.edu/resolver/1840.16/999
[3] P. Soo-jin, L. Seul-Yi. J. Colloid and Interface Sc. Vol. 346 (2010), p. 194-198.
[4] Information on http://www.eere.energy.gov/hydrogenandfuelcells/mypp/pdfs/storage.pdf
[5] B. Sakintuna, F. Lamari-Darkrim, M. Hirscher. I. J. Hydrogen Energy. Vol. 32 (2007), p.
1121- 1140.
[6] P. Barbara, H. Micheal, R. Siegmar. Carbon. Vol. 43, Issues 10 (2005), p. 2209-2214.
[7] X. Hu, F. Maohong, T. F. Brian, R. Maciej, A. B. David, P. A. Ovid. Chapter 8-Hydrogen
Adsorption and Storage. (2011), p. 157-245.
[8] E. M. Cuerda-Correa, A. Macı´as-Garcı´a, M. Angeles Dı´az Dı´ez, L. Angel, B. Ortiz.
Microporous and Mesoporous Materials. Vol. 111, Issues 1–3 (2008), p. 523–529.
[9] V. Jimenez, A. Ramirez-Lucas, P. Sanchez, J. L. Valverde, A. Romero. I. J. Hydrogen
Energy 37 (2012), p. 4144-4160.
[10] Park S. J., Lee S.Y. J. Colloid and Interface Science. Vol. 346 (2010), p. 194-198.
[11] Luis F. D’Elia, I. Gonzalez, K. Saavedra, V. Gottberg. I. J. Hydrogen Energy. Vol. 34.
(2009), p. 1958-1964.
[12] Y. Wang, W. Kean, G. Cong, H. Ziming, L. Zhisong, T. Chen, L. Jing, X.Tan, T.Y. T.
Timothy, C. Ming Li. I. J. Hydrogen Energy. Vol. 36 (2011), p. 13663-13668.