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 3 9 0 e1 3 9 7

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Chemisorption, physisorption and hysteresis

during hydrogen storage in carbon nanotubes

Seyed Hamed Barghi, Theodore T. Tsotsis, Muhammad Sahimi*

Mork Family Department of Chemical Engineering & Materials Science, University of Southern California,
Los Angeles, CA 90089-1211, United States

article info abstract

Article history: The question of chemisorption versus physisorption during hydrogen storage in carbon
Received 9 July 2013 nanotubes (CNTs) is addressed experimentally. We utilize a powerful measurement tech-
Received in revised form nique based on a magnetic suspension balance coupled with a residual gas analyzer, and
26 October 2013 report new data for hydrogen sorption at pressures of up to 100 bar at 25
C. The measured
Accepted 30 October 2013 sorption capacity is less than 0.2 wt.%, and there is hysteresis in the sorption isotherms
Available online 2 December 2013 when multi-walled CNTs are exposed to hydrogen after pretreatment at elevated tem-
peratures. The cause of the hysteresis is then studied, and is shown to be due to a com-
Keywords: bination of weak sorption e physisorption e and strong sorption e chemisorption e in the
Hydrogen storage CNTs. Analysis of the experimental data enables us to calculate separately the individual
Carbon nanotubes hydrogen physisorption and chemisorption isotherms in CNTs that, to our knowledge, are
Chemisorption reported for the first time here. The maximum measured hydrogen physisorption and
Physisorption chemisorption are 0.13 wt.% and 0.058 wt.%, respectively.
Hysteresis Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction
Hydrogen is considered a promising sustainable source of
energy, due to its high energy density, and the fact that it can
be produced from a variety of renewable sources, including
biomass (via gasification) and water electrolysis (e.g., via
renewable solar energy). Hydrogen combustion, in addition,
does not emit green-house gases to the atmosphere [1],
which justifies its classification as a clean source of energy.
To be able to use hydrogen as an energy source, its safe and
efficient storage is a key requirement, but has remained a
most challenging issue. Compressing hydrogen at room
temperature to high pressures of up to 350e700 bar, or its
liquefaction at cryogenic temperatures and lower pressures,
were the initial two methods used for hydrogen storage. The
high costs and the safety risks involved are, however, key
drawbacks of these two conventional storage techniques and
have hindered their commercial applications so far [2].
Adsorbing hydrogen on a solid adsorbent at moderate pres-
sures and ambient temperatures is another potential method
for hydrogen storage. The method is safer and requires less
expensive storage equipment than the high-pressure
compression and cryogenic systems [3]. Synthesis of adsor-
bent materials capable of adsorbing large amounts of
hydrogen at such conditions is, however, the main issue that
still needs to be addressed, in order to commercialize
hydrogen storage systems based on solid adsorbents. Metal
hydrides and carbon-based materials are the two major types
of adsorbents that have been considered to date, and have
been the subject of many studies in the field of hydrogen
storage over the past 10 years [4e8].

* Corresponding author. Tel.: þ1 (213) 740 2064; fax: þ1 (213) 740 8053.
E-mail address: moe@usc.edu (M. Sahimi).
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.2013.10.163
 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 3 9 0 e1 3 9 7
Among the various types of carbon-based adsorbents
proposed for hydrogen storage, carbon nanotubes (CNTs)
have received considerable attention in recent years, due to
their high surface area, nanometer size pores with a narrow
pore size distribution, and low mass density [9e11]. To
investigate the performance of CNTs for hydrogen storage,
it is necessary to accurately determine the equilibrium
hydrogen adsorption/desorption isotherms on such mate-
rials. In particular, the kinetics of adsorption are highly
important to determining the charging time of any practical
hydrogen storage system, as well as the method by which
such charging may be implemented. Moreover, in order to
be able to ensure that the storage system is capable of
delivering the adsorbed hydrogen to the vehicle’s engine
with an appropriate rate, the kinetics of hydrogen desorp-
tion from the CNTs must also be measured.
To date, three techniques have been used to measure
hydrogen adsorption in CNTs, namely, the Sievert method,
thermal desorption spectroscopy (TDS), and the gravimetric
method [12]. The Sievert method is a commonly-used
volumetric technique based on changes in the pressure of
the measurement vessel caused by adsorption/desorption of
the adsorptive gas. Its simplicity and the fact that it may
better approximate the conditions under which commercial
hydrogen storage systems operate are, reportedly, the key
advantages of the method. On the other hand, since in the
Sievert method the change in the pressure of the adsorption
vessel is the main means via which adsorption and/or
desorption amounts are measured, omnipresent leaks dur-
ing the experiments can (and often do) lead to erroneous
results [13]. In addition, since vessel fluid dynamics inter-
fere with measurements at short times, it is difficult to
accurately measure fast sorption kinetics and, thus, to
accurately differentiate by this method between weak e
physisorption e and strong e chemisorption e isotherms, as
we are able to do with the technique used in this study.
Another drawback of the Sievert method is the fact
that atmospheric pressure is the lowest pressure at
which desorption experiments may be conveniently carried
out [14].
The TDS method is based on measuring the hydrogen
that is adsorbed in CNTs via its desorption in high vacuum
using mass spectrometry. The high sensitivity of the
technique, allowing it to detect adsorption even by a
small amount of CNTs (as low as 1 mg), is the main
advantage of the method [15]. On the other hand, it is not
possible to use this technique for identifying adsorption
hysteresis that may occur, or to differentiate among the
various types of sorption that may take place simulta-
neously. In addition, since hydrogen desorption happens
under high vacuum, it is difficult to gauge from the iso-
therms measured by this method whether the material
studied can function as a practical storage medium in the
range of pressures (of up to 100 bar) suggested by the U.S.
Department of Energy [16].
The gravimetric method is the third technique utilized
for the analysis of hydrogen adsorption. In this method,
solid adsorbents are exposed to the adsorptive gases at
various pressures, while the gravimetric balance monitors
the weight change of the adsorbent that is caused by
1391
adsorption. The advantage of this method, compared to the
TDS, is that one can independently determine both the
adsorption and desorption isotherms, as we do in this study
and, thus, detect the presence of hysteresis, In addition, one
is able to study fast dynamics and, thus, to discriminate
among various types of sorption phenomena occurring
either simultaneously or at distinct time scales. Compared
to the Sievert method, the advantage of the gravimetric
method is that it is not affected by the often inevitable gas
leaks that develop in the measurement cell [12]. Though the
technique cannot, by itself, distinguish the various gases
adsorbed (a key requirement for studying multi-component
adsorption), coupling the gravimetric balance equipment to
a sensitive mass analyzer (as is the case with the experi-
mental system used in this study) overcomes this main
drawback [13].
The hydrogen uptake capacities of carbon nanomaterials
published in the literature are remarkably scattered. Geng et al.
[17] reported, for example, that CNTs are capable of adsorbing
0.1 wt.% hydrogen at 293 K and 10 MPa, whereas Chambers et al.
[18] claimed that tubular graphite nanofibers adsorb 11.26 wt.%
hydrogen at 298 K and 11.35 MPa. Other experimental data,
which are in variance with the two aforementioned studies,
have been reported as well [19]. Such inconsistent results have
been a matter of controversy in the area of hydrogen storage
using carbon nanomaterials. To resolve the controversy, Tib-
betts et al. [20] examined hydrogen sorption in nine carbon
materials, including graphite particles, activated carbon,
graphitized PYROGRAF vapor-grown carbon fibers (VGCF), CO
and air-etched PYROGRAF fibers, Showa-Denko VGCF, carbon
filaments, and nanotubes from the MER Corp. and Rice Univer-
sity. Sorption experiments were carried out at temperatures
between 80
C and 500
C and at pressures of up to 11 MPa. The
maximum hydrogen uptake for the nine carbon materials at
room temperature was 0.1 wt.%. According to Tibbetts et al., the
hydrogen adsorption capacity of a number of the carbon mate-
rials at room temperature is so low that, without doing careful
calibration, it is impossible to even detect it with a reliable ac-
curacy. These findings can potentially cast doubt on the prior
experimental work that has claimed hydrogen uptake capacities
higher than 1 wt.% for carbon materials at room temperature.
In another work, Zuttel et al. [21] investigated the hydrogen
storage capacity of a number of carbon materials, including
multi-walled CNTs (MWCNTs) fabricated by the pyrolysis of
acetylene. Their experiments yielded hydrogen storage ca-
pacities, at room temperature and at a pressure of 10 MPa, not
greater than 0.6% (on a per mass basis). Zuttel et al. suggested
that the early reports of extraordinary large hydrogen
adsorption capacities of CNTs must, therefore, be viewed with
skepticism. In addition to the aforementioned experimental
studies, molecular simulations have also indicated relatively
low hydrogen adsorption capacities for CNTs. Dodziuk and
Dolgonos [22] used molecular mechanics calculations and
molecular dynamics simulations, for example, to study the
ability of individual armchair, zigzag, chiral, and bundles of
nanotubes to function as hydrogen storage media, suing the
consistent-valence force field (CVFF) and the extensible sys-
tematic force field (ESFF) in their simulations. Their results
suggested that high hydrogen storage in CNTs cannot be
achieved through physisorption alone.
1392 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 3 9 0 e1 3 9 7
Hydrogen adsorption/desorption hysteresis in CNTs has
been reported previously in studies that used the conven-
tional Sievert method to measure the sorption isotherms
[14,23,24]. It has been hypothesized that the reason for
observing the hysteresis may be the formation of some type
of chemical bonding between hydrogen and the metal
catalyst residues or the amorphous carbon in CNTs. Previ-
ous studies have not, however, been able to perform quan-
titative experiments in order to confirm the hypothesis. For
example, one cannot exclude conclusively that the observed
differences between the adsorption and desorption
isotherm branches are not simply due to the experimental
difficulties associated with leaks in the Sievert measure-
ment vessel [12]. Another possible scenario is that the hys-
teresis may have been a result of chemisorption of hydrogen
on CNTs, which has been reported [25] as an adsorption
mechanism in CNTs. Thus, it is crucial to be able to clearly
distinguish between hydrogen chemisorption from phys-
isorption occurring in CNTs.
In this paper, we specifically address the question of
hysteresis during hydrogen sorption in CNTs, as well as
whether chemisorption or physisorption occurs in such
nanostructured materials. Another motivation for the pre-
sent work is the need for high-precision experiments, so
that one can potentially identify the reason for the scattered
hydrogen adsorption uptake data in the literature. We
report here new measurements of hydrogen sorption in
CNTs, using a precise measurement technique that enables
us to measure separately the contributions of chemisorption
and physisorption to the overall storage capacity of CNTs. In
contrast, most measurement techniques used in the past
[26] cannot readily differentiate between physisorption and
chemisorptions. To carry out the experiments, we use a
high-pressure gravimetric instrument, coupled with a
highly-sensitive mass analyzer system for measuring
hydrogen sorption isotherms of MWCNTs. To our knowl-
edge, the technique we use has not been utilized before in
such studies, and there have been no previous studies that
could unequivocally distinguish between chemisorption
and physisorption of hydrogen occurring on MWCNTs at
room temperature. This has been made possible in this
study by the combination of the gravimetric and mass
spectrometry techniques because,
(i) Hydrogen adsorption and desorption isotherms are
measured accurately and simultaneously with the
same experimental method. This is not possible with
the TDS method, whereas the Sievert method is sen-
sitive to system leaks [27e30]. Therefore, since the
two methods are distinct with their own inherent
experimental errors, a quantitative comparison be-
tween the results obtained with these two methods is
not reliable.
(ii) With our experimental technique, the presence of po-
tential impurities in the adsorptive gas or the desorp-
tion of volatile impurities from the solid sample can be
detected with the residual gas analyzer that is con-
nected to the gravimetric equipment. This then distin-
guishes the method from the gravimetric method used
alone, or from the conventional Sievert method.
2. Experimental
2.1. Characterization of carbon nanotubes
The hydrogen used in the experiments was ultrahigh pure
grade (99.999%) from Gilmore. The MWCNTs with a purity of
97.46 wt.% were purchased from Nanostructure and Amorphous
Materials, Inc. (the manufacturer reports the following other
elements as impurities: Al, 0.19 wt.%; Cl, 1.02 wt.%; Co, 1.09 wt.%,
and S, 0.24 wt.%). The MWCNTs are produced by natural gas
catalytic decomposition over a Co-based catalyst. The inner and
outer diameters of the nanotubes are approximately 5 and 8 nm.
Specific surface area, average pore diameter, and pore volume of
the MWCNTs sample were determined by us via nitrogen
adsorption at its normal boiling temperature using an ASAP 2010
BET instrument. The crystalline structure of MWCNTs was
examined with the aid of a Rigaku XRD equipment.
2.2. Monitoring the gas composition
The composition of hydrogen gas used in the experiments was
monitored with a residual gas analyzer (RGA200), manufac-
tured by Stanford Research Systems (SRS), Inc. The RGA sys-
tem was equipped with an electron multiplier that makes it
possible to measure partial pressures of species as low as
1014 Torr. The effect of the background noise on the mass
analysis results was corrected by running the RGA200 system
without injecting any gases. In the first step, the composition
of the ultrahigh pure hydrogen was determined prior to
injecting the gas into the system, in order to ensure that there
were no unexpected impurities in the hydrogen feed. In the
next step the gas stream leaving the adsorption vessel was
analyzed to check that there was no source of contamination
in the system, and that MWCNTs do not contain any unstable
contaminations. The aim of this step was to guarantee that
the data represent solely hydrogen adsorption, and that
possible adsorption of other gasses or desorption of impurities
from MWCNs do not cause experimental errors.
2.3. Effect of the drift
The gravimetric hydrogen uptake of MWCNTs was measured
using a magnetic suspension balance (MSB), manufactured by
Rubotherm, by monitoring the changes in the weight of the
MWCNTs sample due to hydrogen adsorption. Therefore, in
order to make definitive estimates of the change in the sam-
ple’s weight during the experiments, it is necessary to
consider the drift of the MSB over time, which is the error in
the weight measurement by the MSB that may happen during
the experiments. Since no adsorption or desorption would
occur when there is no sample in the container, measuring
over time the weight of the empty stainless steel sample
container is the most accurate way of observing the effect of
the drift on the accuracy of the data.
2.4. Stability of the MWCNT sample
Before starting the experiments, it is important to remove the
potential adsorbed impurities (e.g., water, CO2, and various
 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 3 9 0 e1 3 9 7
Fig. 1 e (a) Analysis of the gas streams entering and leaving
the adsorption vessel using the residual gas analyzer. (b)
Weight of the empty sample container and the fresh
sample’s weight vs. time under dynamic vacuum at
pressures of 10L5 bar. (c) Plot of Eqn. 1 for the MWCNTs for
various pressures of Helium gas.
hydrocarbons) from the MWCNTs surface. This was done by
heating-up the sample at 120
C for 5 h under dynamic vac-
uum. The sample’s weight was subsequently recorded under
vacuum at 25
C. The goal was to ensure that there is no
desorption of possible adsorbed impurities from the MWCNTs
sample during the hydrogen adsorption experiments. This
step is important because desorption of any impurities from
the sample during the hydrogen adsorption experiments
1393
would lead to misleading estimates of the hydrogen uptake
capacity of MWCNTs.
2.5. Determining the volume of the MWCNTs sample
Buoyancy forces have a small but non-negligible effect on the
sample’s weight, particularly at the higher pressures. To ac-
count for their impact, one must first measure the sample’s
true solid volume, otherwise, known as the skeletal volume
that excludes the pore volume. For gravimetric measure-
ments, this is typically accomplished by measuring the sam-
ple’s (apparent) weight, mP , at various pressures of He and by
correlating to the sample’s true weight (and also its apparent
weight under vacuum conditions) m0 according to the simple
Archimedes formula
m0 ¼ mP þ Vs rg (1)
where Vs is the sample’s true (skeletal) volume, and rg is the
density of He. He was used as a test gas because it is
considered to be inert, non-adsorbing and the lightest among
the noble gases. In the experiments, its bulk gas density, rg ,
was measured directly by weighing a reference stainless
steel insert of known volume at various pressures. Plotting
ðm0  mP Þ vs. the gas density, rg , yields a straight line
[Fig. 1(c)] with its slope being the sample’s true volume,Vs .
Once the skeletal volume is known, and the hydrogen den-
sity is measured at various pressures, the true sample weight
during adsorption/desorption is calculated by adding to the
apparent weight the buoyancy correction term. The
measured hydrogen density is 0.007625 g/cm3 at 100 bar,
0.000801 g/cm3 at 10 bar and 0.0000813 g/cm3 at 1 bar (the
calculated densities using the Peng Robinson equation of
state [31] at 100, 10, and 1 bar are 0.00783 g/cm3, 0.00081 g/
cm3, and 0.0000813 g/cm3, respectively) and, thus, the total
buoyancy term corresponds to 0.354 wt.% at 100 bar,
0.0372 wt.% at 10 bar, and 0.00378 wt.% at 1 bar. During the
sorption calculations the assumption was made, due to the
small amounts of hydrogen adsorbed (particularly the
strongly adsorbed hydrogen that occupies less than 5% of the
BET surface area), that no significant changes in the sample’s
skeletal volume take place. Relaxing that assumption and
assuming a 5% volume change would correspond to an error
of 0.0177% at 100 bar, 0.00186% at 10 bar, and 0.000189% at
1 bar, and would, in no way, change any of the conclusions
about adsorption hysteresis and the presence of strong and
weak adsorption occurring in MWCNT.
2.6. Hydrogen adsorption isotherms
The hydrogen uptake of the MWCNTs sample was determined
by weighing the sample at various hydrogen pressures in the
measurement vessel. The effect of the buoyancy forces on the
results was taken into account in the calculations using Eq. (1).
After reaching the equilibrium state at each pressure, a back-
pressure controller increased the system’s pressure to the
next higher pressure. After hydrogen adsorption was
measured at 100 bar, the system’s pressure was decreased
step by step to measure the desorption isotherm, which rep-
resents the first hydrogen adsorption/desorption cycle.
1394 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 3 9 0 e1 3 9 7
At the end of the first hydrogen sorption cycle, the hydrogen
uptake of the MWCNTs sample was measured again, repre-
senting the second hydrogen adsorption/desorption cycle. The
difference between the first and the second cycles was in the
initial preparation of the MWCNTs samples. For the first cycle,
the MWCNTs were first degased at elevated temperature of
120
C. For the second cycle the MWCNTs were not degased at
the elevated temperatures and, therefore, the hydrogen
remaining on the surface from the first cycle was still adsorbed
on the MWCNTs at the beginning of the second cycle.
3. Results and discussion
The surface area and pore structure characteristics of the
MWCNTs sample were measured using the BET technique.
The specific surface area is 441.3 m2/g, the average tube
diameter is 7.4 nm, while the pore volume is 0.82 cm3/g. The X-
ray diffraction (XRD) analysis of the MWCNTs produces two
sharp peaks for the carbon layers that are characteristic of the
C(002) and C(100), which are the typical XRD peaks for carbon
reported for MWCNTs, but detects no other crystalline phases
[32]. The mass-spectrometric analyzer (RGA200, coupled with
an electron multiplier), was used to analyze the compositions
(in the range of 1e64 amu) of the gas streams entering and
leaving the sorption measurement system. The results of the
analysis are reported in Fig. 1(a) and they show only the
presence of molecular hydrogen (a sharp peak at 2 amu); there
are no other impurities (analytical detection limit of
<0.1 ppmv) in the gas phase that could have resulted in
experimental uncertainties.
We note that there was no drift in the measured weight of
the empty container, even after the measurement had been
carried out for 3 days [see Fig. 1(b)]. This means that the drift of
the magnetic suspension balance during the hydrogen
adsorption experiments is negligible. Fig. 1(b) also shows the
MWCNTs sample’s weight at 25
C and under dynamic vac-
uum as a function of time (prior to that the sample was
degased at 120
C for 6 h to remove water and other impurities
that might potentially had adsorbed during exposure to lab-
oratory conditions). The sample’s weight remains constant
under dynamic vacuum even after 2 days, indicating the
absence of volatile impurities on the surface of the MWCNTs.
Coupled to the findings that no other species are detected in
the gas phase [see Fig. 1(a)], one concludes that any subse-
quent weight changes detected with this particular MWCNT
sample is only a result of hydrogen adsorption/desorption,
and not due to instrument drift or potential instability of the
MWCNTs themselves.
Fig. 1(c) illustrates the results for the measurement of the
sample’s weight at various helium pressures, corresponding
to various gas densities. The linear relationship between the
sample’s weight and the helium gas density confirms the
validity of Eq. (1) for determining the MWCNTs sample’s true
volume. The true density of the MWCNTs sample, determined
using helium gas, was 2.15 g/cm3, which is virtually identical
to what has been previously reported (w2.1 g/cm3) by others
for such materials [33].
Fig. 2 shows the hydrogen adsorption in the MWCNTs as a
function of time at a pressure of 5 bar. For this experiment, the
MWCNTs were exposed to a hydrogen flow for the first time
after the sample was degased in vacuum at 120
C for 6 h; this
also represents the first hydrogen sorption step on the way to
generate the adsorption isotherm. Fig. 2 demonstrates that it
takes around 4e5 h for the system to reach equilibrium, which
is in line with the equilibration times reported in the literature
[24] for such materials. Careful examination of Fig. 2 reveals,
furthermore, that a considerable part of the hydrogen adsorbs
almost instantaneously on the MWCNTs, and that w90% of
the total amount is adsorbed within the first hour. This fast
“charging” time is an important consideration in terms of the
eventual practical application of these materials.
After the sample’s weight had equilibrated (upon raising
the pressure from vacuum to 5 bar), the pressure was raised
again in a step-wise manner in order to generate the adsorp-
tion isotherm, which is indicated as the 1st hydrogen
adsorption cycle in Fig. 3. Subsequently, the pressure was
lowered in a step-wise manner in order to obtain the
desorption branch of the cycle, which is also shown in Fig. 3.
When the pressure reached back to 5 bar, the weight of the
sample was allowed to equilibrate and, subsequently, the
vacuum pump was turned on. The change in the sample
weight is also shown in Fig. 2. Interestingly, even after the
weight of the sample levels off, it does not return to its initial
weight, and in fact the sample retains almost 35% of the total
hydrogen adsorbed on the CNTs at the end of the first
adsorption isotherm run. Keeping the sample under 105 bar
of dynamic vacuum for an additional two and a half days (the
data not shown here) did not change the sample’s weight any
further beyond what is shown in Fig. 2. The data in Fig. 3
clearly show that there is a substantial hysteresis between
the adsorption and the desorption branches of the first cycle.
Subsequently, the pressure of the sample was raised from
105 bar to 5 bar and the adsorption and desorption isotherms
were again generated, indicated as the 2nd adsorption/
Fig. 2 e (a) Hydrogen adsorption at the beginning of the 1st
adsorption/desorption cycle (step from 0 to 5 bar); (b)
Hydrogen desorption at the end of 1st hydrogen
adsorption/desorption cycle (from 5 to 0 bar). (c) Desorption
of chemisorbed hydrogen under vacuum at 120
C after the
end of the 3rd hydrogen adsorption/desorption cycle.
 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 3 9 0 e1 3 9 7
desorption cycle in Fig. 3. Interestingly, no hysteresis was
observed between the adsorption and desorption branches of
the 2nd adsorption/desorption cycle, which are completely
indistinguishable from each other, as well as being very close
to the desorption branch from the first adsorption/desorption
cycle. Upon completion of the second adsorption/desorption
cycle, a third cycle was carried out and, again, no hysteresis
was observed (the results are not shown here because they are
very much indistinguishable from those of the 2nd cycle).
It is clear from the data in Fig. 3 that evacuation of the
sample at 25
C does not return its weight to the original value.
Since the weight difference involved is rather small (0.25 mg
or w0.07% of the original MWCNT sample weight of w300 mg
e however, as previously noted, this is a large fraction w35%
of the total amount of hydrogen adsorbed during the first
adsorption cycle), the possibility exists that it may have
resulted from dust particles in the gas atmosphere or in the
apparatus chamber being deposited on the MWCNTs sample.
To exclude such a possibility, upon the completion of the 3rd
adsorption/desorption cycle the temperature of the sample
was raised (under 105 bar of dynamic vacuum) to 120
C. The
sample weight started decreasing (see Fig. 2) and after w6 h it
returned to its original weight. During the same period the
mass analyzer did not indicate the presence of any other gas
species (in the range 1e64 amu) other than hydrogen.
In our view, the data in Fig. 3 indicate two different types of
hydrogen species on the surface, weakly adsorbed, or phys-
isorbed, hydrogen and strongly adsorbed, or chemisorbed,
hydrogen, the latter being defined here as the adsorbed species
that will not desorb from the surface under dynamic vacuum at
25
C for a period of more than two days (see Fig. 2) and which
are, thus, unlikely to desorb from the same MWCNTs during
the normal charging and discharging cycles as well. In Fig. 4 we
plot the weight change during the 1st adsorption/desorption
cycle as we transition from 20 bar to 40 bar, as well as the
corresponding weight change profile as we transition back
from 40 to 20 bar during the desorption branch of the cycle.
Shown in the same figure are the rates of change in the
Fig. 3 e The 1st and 2nd hydrogen adsorption/desorption
cycles (note that for the 2nd cycle the adsorption and
desorption branches are indistinguishable).
1395
sample’s weight, dW/dt. As already noted above, during the
adsorption step one observes a clearly sharp rise in the weight,
followed by a more gradual increase. Interestingly, in the rate of
change in the weight profiles one observes two branches with
two very distinct slopes. For the desorption step again most of
the weight loss (98%) occurs in the first 7 min. If one is to as-
sume that the strongly adsorbed species, defined here as those
that do not desorb under dynamic vacuum of 105 bar, are
unlikely to desorb either as one transitions from 40 to 20 bar in
pressure, then the desorbed amount can be fully attributed to
weakly-adsorbed or physisorbed hydrogen. Since no hysteresis
exists during adsorption/desorption from the part of the
MWCNT surface that is not covered by the strongly adsorbed
hydrogen species (see Fig. 3), one can then assume that the
amount that is desorbed during the desorption branch of the
first cycle is equal to the amount that is physisorbed during the
adsorption part of the cycle. This way one can generate an
adsorption isotherm (for the first experimental cycle) for the
weakly-adsorbed hydrogen that is shown in Fig. 5. By sub-
tracting the physisorbed isotherm from the total 1st cycle
adsorption isotherm one can, in addition, generate the chemi-
sorption isotherm, which is also shown in Fig. 5. The data
suggest that for pressures of up to 20 bar the physisorption and
chemisorption have relatively the same magnitude. But, above
20 bar physisorption becomes the primary adsorption mecha-
nism as the strongly-adsorbing sites on the surface of the
MWCNT seem to saturate rather quickly.
The assumption that the amount desorbed at each pressure
step during the desorption branch of the 1st cycle is only due to
weakly-adsorbed hydrogen and by subtracting that amount
from the total adsorption isotherm one can correctly generate
the chemisorption isotherm, entails the fundamental
assumption that there are two distinctly different types of sites
on the MWCNT, one on which exclusively weak adsorption
occurs, and another on which preferential strong adsorption
takes place. If that is indeed the case, and one subtracts from
the total adsorption isotherm during the 2nd (and 3rd) cycle the
amount that remains irreversibly adsorbed under dynamic
vacuum at 25
C, one should be able to generate the phys-
isorption isotherm of Fig. 5. To prove that this is indeed the
case, all three (the physisorption isotherm of Fig. 5 and the
Fig. 4 e Hydrogen uptake (w) and absolute value of
hydrogen uptake change rate (dw/dt).
1396 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 3 9 0 e1 3 9 7
Fig. 5 e The calculated sorption isotherms in the MWCNTs
at 25
C.
estimated physisorption isotherms for cycles 2 and 3) are
shown in Fig. 6. The three lines nearly coincide, thus lending
credence to the above hypothesis. This, then, means that
hydrogen sorption hysteresis during the first cycle is a conse-
quence of hydrogen chemisorption on the MWCNTs. The
chemisorbed hydrogen atoms do not leave the MWCNTs when
the system’s pressure decreases during the desorption experi-
ments. Therefore, the accumulation of chemisorbed hydrogen
at various pressures during adsorption gives rise to the
observed hysteresis during desorption. For practical applica-
tions, these results validate the idea that only physisorption is
involved during the charging and discharging parts of the cycle.
Despite the fast rates of physisorption and the apparent
strong chemisorption affinities between hydrogen and
Fig. 6 e The amount of hydrogen physisorption on the
MWCNTs during the first sorption cycle and the
equilibrium hydrogen values during the second and third
hydrogen sorption cycles (the amount of the strongly
sorbed hydrogen after the 1st cycle is subtracted).
MWCNT surface, the fraction of the BET surface area of
MWCNT covered by adsorbed hydrogen at the end of
adsorption branch is rather small, w9.2% for the physisorbed
hydrogen and w4% for the chemisorbed hydrogen, since it is
unclear, at this point, what kind of surface species are
involved in these two different types of adsorption, or
whether it even makes good sense to compare the surface
area based on liquid nitrogen adsorption to the area occupied
by hydrogen, these estimates are based on the simple idea
that the adsorbed hydrogen molecule occupies an area on the
BET surface of MWCNTequivalent to a circle with a diameter
equal to its Lennard-Jones diameter. This is a likely to be a
good assumption for the physisorbed hydrogen, but less so for
the chemisorbed one, though any differences that may exist
are unlikely to be substantial. Such small coverages are in line
with prior modeling investigations [34].
4. Conclusions
Precise measurements by a new technique have demon-
strated that hydrogen adsorption in multi-walled carbon
nanotubes at room temperature is a combination of reversible
physisorption and irreversible chemisorption. The adsorption
measurements unveil and confirm that it is the chemisorption
part that gives rise to hysteresis in hydrogen adsorption/
desorption isotherms. For instance, while the chemisorbed
hydrogen was still on the surface of the MWCNTs, the sample
was once more exposed to hydrogen and the adsorption/
desorption isotherms were measured again. No hysteresis
was detected for the new cycle, implying that no chemisorp-
tion happened during the second cycle. The equilibrium
values of the new hydrogenation cycle are different from
those of the first cycle. Our calculations confirmed that, by
subtracting the chemisorbed values from the equilibrium data
of the first cycle, the adsorption and desorption branches of
the first hydrogenation cycle and the equilibrium data of the
second cycle take on the same values. This supports the
conclusion that the reversible hydrogen adsorption on
MWCNTs during practical conditions is completely due to
physisorption. The technique used in this work is a practical
method for determining separately hydrogen physisorption
and chemisorption in carbon nanotubes and other nano-
structured porous materials.
Acknowledgments
SB is grateful for the support from a Provost’s Fellowship at the
University of Southern California. The support of the U.S.
Department of Energy (DE-SC0003586) and the National Science
Foundation (CBET-0854427) is also gratefully acknowledged.
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