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Separation and Purification Technology 58 (2007) 219–223

Hydrogen storage in platelet graphite nanofibers

Chao-Wei Huang, Hung-Chih Wu, Yuan-Yao Li ∗
Department of Chemical Engineering, National Chung Cheng University, Chia-Yi 62102, Taiwan, ROC

Abstract
Platelet graphite nanofibers (PGNFs) were synthesized by thermal decomposition from a mixture containing polymer and catalyst. The hydrogen
storage capacity of the material was measured using the volumetric method carried out at 298 K at a pressure up to 4.83 MPa. The results show
that the PGNF possess a 3.3 wt.% hydrogen storage capacity. The gaseous molecules were adsorbed between two graphene planes in the PGNFs
and residual amounts of hydrogen were possession within PGNFs while pressure decreased to ambient conditions. X-ray diffraction was used to
understand the PGNF structural modifications before and after hydrogen uptake. We found that the PGNF interlayer undergoes expansion and
returns back to the initial value before and after hydrogen uptake.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Platelet graphite nanofibers; Hydrogen storage; X-ray diffraction

1. Introduction
Since the discovery of fullerene [1] and carbon nanotubes
(CNTs) [2], these materials have been intensively studied
because of their small size and extraordinary properties. Numer-
ous carbon nano-structures have been synthesized by changing
the preparation conditions, including carbon nano-onions [3],
carbon nanocapsules [4,5], carbon discs [6], carbon nanorods
[7], graphite nanofiber (GNF) [8], etc. These materials have
been intensively studied and used in advanced devices such as
single electron transistors [9], quantum wires [10], flat panel dis-
plays [11–13], nano-forceps [14], scanning probe microscopes
[15–17] and energy storage (hydrogen, methane) [18–20]. The
fabrication strategies are based on arc-discharge [2,4], laser abla-
tion [21], chemical vapor deposition (CVD) [8,22], flame [5],
templated synthesis [23], and high-pressure experiments [24].
GNF is a novel form of filamentous graphite obtained and
investigated by Murayama and Maeda in 1990 [25]. In fact,
it was first reported in 1973 [26], but the microstructure was
not thoroughly studied due to the limitations of the analyti-
cal instruments at that time. GNF is classified into four types:
(a) platelet graphite nanofibers (PGNF) in which graphene lay-
ers are perpendicular to the fiber axis; (b) herringbone graphite
nanofibers (HBGNF) in which graphene layers tilt at an angle
to the fiber axis; (c) tubular graphite nanofibers (TGNF) in
∗ Corresponding author. Tel.: +886 5 2720411x33403; fax: +886 5 2721206.
E-mail address: chmyyl@ccu.edu.tw (Y.-Y. Li).
which graphene layers are parallel to the fiber axis [also called
multi-walled carbon nanotubes (MWCNT)] [8]; (d) cup-stacked
graphite nanofibers in which the graphene layers tilt and truncate
conically along the fiber length [27]. A variety of GNFs, in terms
of diameter, length, and graphene layer arrangement can be
controlled by synthesis conditions using various hydrocarbons,
metal catalysts [8,28,29], and temperature [30,31].
Because ever-stricter environmental regulations put great
pressure on energy companies and automobile manufacturers
to develop cleaner burning fuels and cleaner running vehicles,
various environmentally friendly fuels and related technologies
are being developed to replace fossil fuels. For example, numer-
ous studies have been carried out on hydrogen applications as
clean energy fuels. The development of hydrogen storage mate-
rials capable of meeting the U.S. Department of Energy (DOE)
storage target of 6.5 wt.% could reduce the dependence on fossil
fuels. The GNFs is one of the candidates as a hydrogen storage
material because of its unique structure, which exhibits virtu-
ally open edges and an interlayer spacing between the graphene
platelet (≥3.35 Å), acting like a slit-shaped pore hence possess-
ing the ideal configuration for use in hydrogen storage, whose
kinetic diameter is only 2.89 Å [18]. Gupta et al. reported [32] the
lateral expansion of graphene layers and increasing of the inter-
layer spacing during hydrogen storage process. Theoretically,
hydrogen can be adsorbed onto the surface and then incorpo-
rated/intercalated between GNF graphene layers or hydrogen
dissociation onto graphite edge sites [33]. Browing et al. [19]
have also noted that the graphite edge sites in the GNF struc-
ture may play a role in the dissociation of hydrogen leading to

1383-5866/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2007.07.032
220 C.-W. Huang et al. / Separation and Purification Technology 58 (2007) 219–223
Fig. 1. Schematic diagram of the P–C–T isothermal system: an automatic gas reaction controller.
subsequent interacalation. This involves the initial dissociation
of hydrogen, believed to be catalyzed by carbon edge sites, which
constitute the majority of the nanofiber surface, a property which
is probably an important contributory factor toward their high
hydrogen storage capacities.
The hydrogen storage capacity of GNFs can be measured
by volumetric [18,19,32,34–39], gravimetric (TG) [40,41], and
thermal desorption spectroscopy (TDS) [42,43]. Chambers et
al. [18] reported that GNFs are capable of sorbing and retain-
ing in excess of 20 L (STP) of hydrogen per gram (∼67 wt.%)
when the GNFs are exposed to the gas at pressures of 120 atm
at 293 K. Park et al. [34] reported that adequate GNF pretreat-
ment to remove chemisorbed gases and allow hydrogen access
to the GNF pores is a critical step in obtaining high GNF storage
capacity (up to 40 wt.%). These two reports remain contested, as
several other laboratories have not been able to reproduce these
results [35–37,40]. Nonetheless, in recent years, the hydrogen
storage capacity reported in the literature for GNFs continues to
emerge showing less than 1 wt.% up to 15 wt.% [19,32,39,41].
To date, the reported hydrogen storage capacities have been dif-
ferent with a lack of reproducibility. Therefore, further studies
are needed to better understand the factors that influence the
hydrogen storage capacity (as well as the measurements) and
mechanisms for hydrogen storage within GNFs.
In this study, we have attempted to realize the hydrogen
storage capacity of PGNFs synthesized using thermal decompo-
sition of poly(ethylene glycol) (PEG) containing catalyst under
a nitrogen atmosphere [44] and to understand the structural
modifications in the PGNFs before and after hydrogen uptake.
The PGNFs were characterized using high-resolution transmis-
sion electron microscopy (HR-TEM), field-emission scanning
electron microscopy (FE-SEM), X-ray diffraction (XRD) and
hydrogen uptake measurements using the volumetric method.
2. Experiment
PGNFs were prepared by thermal decomposition from a mix-
ture containing PEG and nickel chloride (NiCl2 ) at 1023 K
under a nitrogen atmosphere. The PGNF preparation process
details were described in our previous work [44]. The samples
were observed using FE-SEM (HITACHI S-4800) for mor-
phology analysis while HR-TEM (PHILIPS Tecnai F20) was
employed to understand the structure and crystal forms. Nitro-
gen adsorption was performed using an ASAP 2020 system at
77 K. The sample was degassed in a vacuum at 473 K for 4 h
prior to the measurements. Surface area was calculated using
the Brunauer–Emmett–Teller (BET) equation [45]. The PGNF
structural modifications were measured using XRD (Shimadzu,
XRD-6000) used Cu K␣ radiation from a rotating anode X-ray
source.
The hydrogen storage capacity was measured using a pressure
composition temperature (P–C–T) isothermal system manufac-
tured by the Advanced Materials Corporation. Fig. 1 shows a
simplified sketch of this apparatus. During a typical experiment,
approximately 100 mg of PGNFs were initially loaded into the
sample chamber while heating under vacuum at 423 K for 4 h,
removing any physisorbed water. Following this the system was
allowed to cool to room temperature, after which hydrogen was
admitted and uptake determined. Initial testing included a blank
experiment, without sample, which showed that the stainless
steel vessel did not give rise to hydrogen adsorption, while also
ensuring that the instrument was leak free. Hydrogen was then
introduced into the reservoir container and subsequently allowed
access to the sample chamber for interaction with the nanofibers.
The system pressure was increased from an initial value up to
4.83 MPa at 298 K and measured at regular intervals. The PGNF
hydrogen storage capacity was calculated from the changes in
pressure following material interaction with the gas.
3. Results and discussion
3.1. Structural characteristics of the PGNFs
Fig. 2(a) and (b) are SEM and HR-TEM images of synthe-
sized PGNFs, respectively. It is clearly observed that the PGNFs
exhibited a diameter of about 20–40 nm and a few micrometers
in length. The as-produced GNF has a platelet structure with a
high degree of graphitization and well-ordered graphene layers
perpendicular to the fiber axis. It also shows large numbers of
nanopores, in which only edge sites are exposed, on the surface
of the PGNFs. These nanopores can act like slit-shaped pores,
hence possessing the ideal arrangement for hydrogen storage.
The selected area electron diffraction (SAED) pattern inserted
in Fig. 2(b) also shows PGNFs with high degree of graphitiza-
tion. The SAED pattern can be used to determine the spacing of
the graphene layers by measuring the distance from the center
 C.-W. Huang et al. / Separation and Purification Technology 58 (2007) 219–223
Fig. 2. (a) SEM and (b) HR-TEM images of PGNFs.
spot to the diffracted spot. The d-spacing of PGNFs was about
3.362 Å, being close to that of graphite. The BET surface area
of PGNFs was 123 m2 /g.
3.2. Hydrogen storage
PGNFs hydrogen storage was carried out using the volumet-
ric method at 298 K with the pressure up to 4.83 MPa. Fig. 3
shows the P–C–T isothermal curves of the PGNFs hydrogen
storage capacity. The result shows that the PGNFs possess a
3.3 wt.% hydrogen storage capacity. It was thought that because
of the weak (van der Waals) platelet bonding, the large number
of non-rigid wall nanopores can expand to accommodate hydro-
gen in a multilayer configuration [18]. Zuttel et al. reported that
the maximum amount of potential hydrogen adsorbed accord-
ing to the model was calculated to be 2.28 × 10−3 wt.% uptake
for each m2 of surface area for the adsorption of a mono-
layer of hydrogen at the surface [46]. This analysis requires
a flat graphene sheet and ignores the microporosity contribu-
tion. Therefore, hydrogen storage capacity only can be achieved
about 0.28 wt.% by covering the outer PGNFs surface with
221
Fig. 3. P–C–T curves of the PGNF hydrogen storage capacity.
an atomic layer. However, surface areas accessible to nitrogen
(kinetic diameter is 3.64 Å) may not necessarily be accessible
to the hydrogen molecule (kinetic diameter is 2.89 Å). Thus
hydrogen uptake does not always correlate to BET surface area,
particularly for nanocarbons [19,41,47]. Accordingly, it can be
thought that the difference between 3.3 and 0.28 wt.% might
be evidence of hydrogen intercalation within the graphene lay-
ers. Dresselhaus et al. reported that the intercalant must initially
find exposed graphene edges. These sites then provide pathways
for more intercalant to move inward, filling the space between
the basal planes [33]. Consequently, the possibility of hydrogen
atom intercalation into the graphene layers might be considered
and increase the hydrogen storage capacity.
3.3. XRD analysis
Because the amount of hydrogen desorption is less than
that which is adsorpted, it has been speculated the graphene
interlayer was expanded during the adsorption process and an
unexpectedly high hydrogen retention capacity is found within
GNFs [32–34]. To determine whether graphene layer expansion
occurs after the hydrogen uptake process, we used the XRD tech-
nique to understand the structural modifications in PGNFs. Fig. 4
Fig. 4. XRD patterns of (a) as-produced, (b) immediately after hydrogen uptake
and (c) a week after PGNF hydrogen uptake.
222 C.-W. Huang et al. / Separation and Purification Technology 58 (2007) 219–223
shows the XRD results of (a) as-produced sample, (b) imme-
diately after hydrogen uptake, and (c) a week after hydrogen
uptake. It was clearly found that hydrogen induces an expansion
of the graphene layer d-spacing from 3.362 Å (prior to adsorp-
tion and consistent with the result calculated using SAED) to
3.398 Å (immediately after hydrogen uptake) and then decrease
to 3.38 Å (a week after hydrogen uptake under ambient condi-
tions). The hydrogen uptake leads to graphene layer expansion
and an increase in the d-spacing of the structure. The PGNF
d-spacing seems to undergo an expansion and return to the ini-
tial value during and after hydrogen uptake. This may indicate
that some hydrogen still remains within the structure. Park et al.
[34] reported these changes can be rationalized according to the
notion that as hydrogen enters the region between the graphene
layers, a concomitant expansion of the interlayer takes place to
accommodate the gas molecules, being slowly released over a
period of time.
4. Conclusions
This study obtained high degree of graphitization and large
numbers of open edges in PGNFs prepared from the ther-
mal decomposition of a mixture containing PEG and NiCl2 .
Hydrogen storage in PGNFs, measured using the volumetric
method at 298 K and a pressure up to 4.83 MPa, possessed
a 3.3 wt.% hydrogen storage capacity. The d-spacing of the
PGNFs underwent an expansion and returned back to the ini-
tial value confirmed by XRD analysis. The graphene layer
d-spacing expansion was induced from 3.362 Å (prior to adsorp-
tion) to 3.398 Å (immediately after hydrogen uptake) and then
decreased to 3.38 Å (a week after hydrogen uptake at ambient
conditions). As a result, a residual amount of hydrogen may
remain in PGNFs, which perturbed the PGNF graphene layer
structure.
References
[1] H.W. Kroto, J.R. Heath, S.C. Obrien, R.F. Curl, R.E. Smalley, C-60-
buckminsterfullerene, Nature 318 (1985) 162–163.
[2] S. Iijima, Helical microtubules of graphitic carbon, Nature 354 (1991)
56–58.
[3] D. Ugarte, Curling and closure of graphitic networks under electronbeam
irradiation, Nature 359 (1992) 707–709.
[4] Y. Saito, K. Nishikubo, K. Kawabata, T. Matsumoto, Carbon nanocap-
sules and single-layered nanotubes produced with platinum-group metals
(Ru, Rh, Pd, Os, Ir, Pt) by arc discharge, J. Appl. Phys. 80 (1996) 3062–
3067.
[5] T.C. Liu, Y.Y. Li, Synthesis of carbon nanocapsules and carbon nanotubes
by an acetylene flame method, Carbon 44 (2006) 2045–2050.
[6] A. Krishnan, E. Dujardin, M.M.J. Treacy, J. Hugdah, S. Lynum, T.W. Ebbe-
sen, Graphitic cones and the nucleation of curved carbon surfaces, Nature
388 (1997) 451–454.
[7] Y. Gogotsi, J.A. Libera, N. Kalashnikov, M. Yoshimura, Graphite polyhe-
dral crystals, Science 290 (2000) 317–320.
[8] N.M. Rodriguez, A. Chambers, R.T.K. Baker, Catalytic engineering of
carbon nanostructures, Langmuir 11 (1995) 3862–3866.
[9] S.J. Tans, A.R.M. Verschueren, C. Dekker, Room-temperature transistor
based on a single carbon nanotube, Nature 393 (1998) 49–52.
[10] S.J. Tans, M.H. Devoret, H. Dai, A. Thess, R.E. Smalley, L.J. Geerligs, C.
Dekker, Individual single-wall carbon nanotubes as quantum wires, Nature
386 (1997) 474–477.
[11] D.W.A. Heer, A. Chatelain, D. Ugarte, A carbon nanotube field-emission
electron source, Science 270 (1995) 1179–1180.
[12] S. Fan, M.G. Chapline, N.R. Franklin, T.W. Tombler, A.M. Cassell, H. Dai,
Self oriented regular arrays of carbon nanotubes and their field emission
properties, Science 283 (1999) 512–514.
[13] N.S. Lee, D.S. Chung, I.T. Han, J.H. Kang, Y.S. Choi, H.Y. Kim, S.H. Park,
Y.W. Jin, W.K. Yi, M.J. Yun, J.E. Jung, C.J. Lee, J.H. You, S.H. Jo, C.G.
Lee, J.M. Kim, Application of carbon nanotubes to field emission displays,
Diam. Relat. Mater. 10 (2001) 265–270.
[14] P. Kim, C.M. Lieber, Nanotube nanotweezers, Science 286 (1999)
2148–2150.
[15] H. Dai, J.H. Hafner, A.G. Rinzler, D.T. Colbert, R.E. Smalley, Nan-
otubes as nanoprobes in scanning probe microscopy, Nature 384 (1996)
147–150.
[16] C.L. Cheung, J.H. Hafner, T.W. Odom, K. Kim, C.M. Lieber, Growth
and fabrication with single-walled carbon nanotube probe microscopy tips,
Appl. Phys. Lett. 76 (2000) 3136–3138.
[17] C.L. Cheung, J.H. Hafner, C.M. Lieber, Carbon nanotube atomic force
microscopy tips: direct growth by chemical vapor deposition and appli-
cation to high-resolution imaging, Proc. Natl. Acad. Sci. USA 97 (2000)
3809–3813.
[18] A. Chambers, C. Park, R.T.K. Baker, N.M. Rodriguez, Hydrogen storage
in graphite nanofibers, J. Phys. Chem. B 102 (1998) 4253–4256.
[19] D.J. Browning, M.L. Gerrard, J.B. Lakeman, I.M. Mellor, R.J. Mor-
timer, M.C. Turpin, Studies into the storage of hydrogen in carbon
nanofibers: proposal of a possible reaction mechanism, Nano Lett. 2 (2002)
201–205.
[20] E. Bekyarova, K. Murata, M. Yudasaka, D. Kasuya, S. Iijima, H. Tanaka, H.
Kahoh, K. Kaneko, Single-wall nanostructured carbon for methane storage,
J. Phys. Chem. B 107 (2003) 4681–4684.
[21] A. Thess, R. Lee, P. Nikolaev, H. Dai, P. Petit, J. Robert, C. Xu, Y.H.
Lee, S.G. Kim, A.G. Rinzler, D.T. Colbert, G.E. Scuseria, D. Tománek,
J.E. Fischer, R.E. Smalley, Crystalline ropes of metallic carbon nanotubes,
Science 273 (1996) 483–487.
[22] Z.F. Ren, Z.P. Huang, J.W. Xu, J.H. Wang, P. Bush, M.P. Siegal, P.N.
Provencio, Synthesis of large arrays of well-aligned carbon nanotubes on
glass, Science 282 (1998) 1105–1107.
[23] S.H. Joo, S.J. Choi, I. Oh, J. Kwak, Z. Liu, O. Terasaki, R. Ryoo, Ordered
nanoporous arrays of carbon supporting high dispersions of platinum
nanoparticles, Nature 412 (2001) 169–172.
[24] P.F. McMillan, New materials from high-pressure experiments, Nat. Mater.
1 (2002) 19–25.
[25] H. Murayama, T. Maeda, A novel form of filamentous graphite, Nature 345
(1990) 791–793.
[26] H.P. Boehm, Carbon from carbon monoxide disproportionation on nickel
and iron catalysts: morphological studies and possible growth mechanisms,
Carbon 11 (1973) 583–590.
[27] M. Endo, Y.A. Kim, T. Hayashi, Y. Fukai, K. Oshida, M. Terrones, T.
Yanagisawa, S. Higaki, M.S. Dresselhaus, Structural characterization of
cup-stacked-type nanofibers with an entirely hollow core, Appl. Phys. Lett.
80 (2002) 1267–1269.
[28] C. Park, R.T.K. Baker, Catalytic behavior of graphite nanofiber supported
nickel particles. 2. The influence of the nanofiber structure, J. Phys. Chem.
B 102 (1998) 5168–5177.
[29] O.C. Carneiro, N.M. Rodriguez, R.T.K. Baker, Growth of carbon nanofibers
from the iron-copper catalyzed decomposition of CO/C2 H4 /H2 mixtures,
Carbon 43 (2005) 2389–2396.
[30] O.C. Carneiro, M.S. Kim, J.B. Yim, N.M. Rodriguez, R.T.K. Baker, Growth
of graphite nanofibers from the iron-copper catalyzed decomposition of
CO/H2 mixtures, J. Phys. Chem. B 107 (2003) 4237–4244.
[31] A. Tanaka, S.H. Yoon, I. Mochida, Preparation of highly crystalline
nanofibers on Fe and Fe–Ni catalysts with a variety of graphene plane
alignments, Carbon 42 (2004) 591–597.
[32] B.K. Gupta, O.N. Srivastava, Further studies on microstructural characteri-
zation and hydrogenation behavior of graphitic nanofibres, Int. J. Hydrogen
Energy 26 (2001) 857–862.
[33] M.S. Dresselhaus, G. Dresselhaus, Intercalation compounds of graphite,
Adv. Phys. 30 (1981) 139–326.
 C.-W. Huang et al. / Separation and Purification Technology 58 (2007) 219–223
[34] C. Park, P.E. Anderson, A. Chambers, C.D. Tan, R. Hidalgo, N.M.
Rodriguez, Further studies of the interaction of hydrogen with graphite
nanofibers, J. Phys. Chem. B 103 (1999) 10572–10581.
[35] C.C. Ahn, Y. Ye, B.V. Ratnakumar, C. Witham, R.C. Bowman, B. Fultz,
Hydrogen desorption and adsorption measurements on graphite nanofibers,
Appl. Phys. Lett. 73 (1998) 3378–3380.
[36] M. Rzepka, E. Bauer, G. Reichenauer, T. Schliermann, B. Bernhardt, K.
Bohmhammel, E. Henneberg, U. Knoll, H.E. Maneck, W. Braue, Hydrogen
storage capacity of catalytically grown carbon nanofibers, J. Phys. Chem.
B 109 (2005) 14979–14989.
[37] G.G. Tibbetts, G.P. Meisner, C.H. Olk, Hydrogen storage capacity of
carbon nanotubes, filaments, and vapor-grown fibers, Carbon 39 (2001)
2291–2301.
[38] E. Poirier, R. Chahine, T.K. Bose, Hydrogen adsorption in carbon nanos-
tructures, Int. J. Hydrogen Energy 26 (2001) 831–835.
[39] Y.Y. Fan, B. Liao, M. Liu, Y.L. Wei, M.Q. Lu, H.M. Cheng, Hydrogen
uptake in vapor-grown carbon nanofibers, Carbon 37 (1999) 1649–1652.
[40] R. Ströbel, L. Jörissen, T. Schliermann, V. Trapp, W. Schütz, K. Bohmham-
mel, G. Wolf, J. Garche, Hydrogen adsorption on carbon materials, J. Power
Sources 84 (1999) 221–224.
223
[41] A.D. Lueking, L. Pan, D.L. Narayanan, C.E.B. Clifford, Effect of expanded
graphite lattice in exfoliated graphite nanofibers on hydrogen storage, J.
Phys. Chem. B 109 (2005) 12710–12717.
[42] A.C. Dillon, K.M. Jones, T.A. Bekkedahl, C.H. Kiang, D.S. Bethune, M.J.
Heben, Storage of hydrogen in single-walled carbon nanotubes, Nature 386
(1997) 377–379.
[43] K. Shindo, T. Kondo, M. Arakawa, Y. Sakurai, Hydrogen adsorp-
tion/desorption properties of mechanically milled activated carbon, J. Alloy
Compd. 359 (2003) 267–271.
[44] C.W. Huang, Y.Y. Li, In situ synthesis of platelet graphite nanofibers from
thermal decomposition of poly(ethylene glycol), J. Phys. Chem. B 10
(2006) 23242–23246.
[45] S. Brunauer, P.H. Emmett, E. Teller, Adsorption of gases in multimolecular
layers, J. Am. Chem. Soc. 60 (1938) 309–319.
[46] A. Zuttel, P. Sudan, P. Mauron, P. Wenger, Model for the hydrogen
adsorption on carbon nanostructures, Appl. Phys. A: Mater. 78 (2004)
941–946.
[47] A.D. Lueking, R.T. Yang, N.M. Rodriguez, R.T.K. Baker, Hydrogen stor-
age in graphite nanofibers: effect of synthesis catalyst and pretreatment
conditions, Langmuir 20 (2004) 714–721.