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CO2 Activation of Olive Bagasse for Hydrogen

Najoua Bader and Ouederni Abdelmottaleb
Research Laboratory: Process Engineering and Industrials Systems National School of Engineers of Gabes, University of Gabes,
St. Omar Ibn Khattab, Gabes 6029, Tunisia; (for correspondence)
Published online 31 October 2016 in Wiley Online Library ( DOI 10.1002/ep.12514

Hydrogen is considered as the most promising future fuel, important drawbacks such as low density and high pressures
as its combustion generates only water vapor besides energy. operations for compression [2], boil-off excessive energy con-
However, finding efficient, safe and low-cost storage methods sumption for liquefaction [3]. To overcome these issues,
is the basic impediment for the adoption of hydrogen as fuel. researchers have focused their attention on exploring
For this purpose, an ultramicroporous activated carbon was material-based hydrogen storage, due to their ability to
successfully synthesized from low-cost biomass residues; olive increase the density of H2 under safe operation conditions.
bagasse. The carbon material was prepared throw physical These materials are typically categorized according to hydro-
activation, using carbon dioxide as activating agent, under gen storage mechanism: (i) physisorption of molecular H2 on
controlled thermal conditions. Then, it was tested as hydro- microporous surfaces; (ii) chemisorption of atomic H2 on the
gen storage material at cryogenic and room temperature lattice framework of metal hydrides. Chemisorption is less
conditions. The textural characterizations showed a highly attractive due to relatively high temperatures required for
tailored porous texture adequate for gas adsorption. The hydrogenation and release of H2. Therefore, a lot of attention
totality of the created microporosity is of narrow range has been focused during last decades on studies of H2 physi-
(d < 0.7 nm). Interestingly, the measured median pore width sorption on different adsorbents including metal organic
was about 0.65 nm, likely the optimum pore size for hydro- framework (MOF) [4,5], Zeolites [6], and carbon-based mate-
gen adsorption. This feature accorded the AC with exception- rials [7,8]. Compared to crystalline materials (MOFs and Zeo-
al H2 storage capacity, achieving 3.34 wt % at liquid lites) carbon-based adsorbents are more advantageous. This
nitrogen temperature. It has outperformed Zeolites and is related to their low cost, good chemical, mechanical and
MOFs. V C 2016 American Institute of Chemical Engineers Environ thermal stability, easier regeneration, low densities, and wide
Prog, 36: 315–324, 2017 diversity of bulk and pore structures [9]. Among them, we
Keywords: olive bagasse, CO2 activation, microporous find activated carbons (ACs) which are the result of chemical
materials, narrow microporosity, hydrogen storage or physical activations of any carbon-rich material. They
have been intensively studied as H2 storage materials, espe-
cially after the non reproducible spectacular results of Baker
and Rodriguez [10] and Dillon et al. [11]. ACs are easy to
Hydrogen is the cleanest, sustainable and renewable ener-
obtain and their porous structure is more developed than
gy carrier, and a hydrogen energy system is expected to pro-
carbon nanotubes and carbon nanofibers. Indeed, recent
gressively replace the existing fossil fuels in the future, the
studies showed that the cryogenic hydrogen storage capaci-
latter are being depleted very fast and cause severe environ-
ties of ACs are quite promising. Yang et al. reported a stor-
mental problems. In particular, one potential use of hydro-
age capacity of 6.9 wt % at 77 K and 20 bar for a zeolite-like
gen lies in powering zero-emission vehicles via a proton
carbon material [12]. Wang et al. prepared a kind of activated
exchange membrane fuel cell to reduce atmosphere pollu-
carbons which exhibits high specific surface area and
tion. Hydrogen can be produced not only from the fossil
achieved a large hydrogen uptake of 7.08 wt % at 77 K and
fuels, such as coal and natural gas, but also from wind, solar,
20 bar [13]. However, Fierro et al. described a hydrogen stor-
thermal, hydroelectric, biomass or municipal solid wastes
age density of 6 wt % at 77 K and 40 bar for an activated car-
with no consumption of non-renewable resources and no
bon derived from a high-rank mineral coal [14]. The porous
pollution of any kinds.
texture is the main feature determining the hydrogen adsorp-
Moreover, hydrogen exhibits the highest heating value
tion capacity of ACs. Many authors have stated that ACs
per mass of all chemical fuels. However, one of the major
should have a highly developed internal surface and a large
drawback of hydrogen as energy carrier is its low energy
volume of micropores [15] with diameters in the range of
density on a volumetric basis. For example, one liter of gaso-
0.6–0.8 nm [16–18] for an efficient performance as a hydro-
line (31.7 MJ/L, 8.8 kW h/L) contains approximately six times
gen storage material at both atmospheric and high pressures.
as much energy as a liter of H2 compressed to 70 MPa (4.7
Hence tailoring pore structures of carbon’s surface is crucial.
MJ/L, 1.3 kW h/L) [1]. Hence, hydrogen storage is the bottle-
Recently, KOH activation of carbonaceous precursor has
neck that holds up the implementation of “hydrogen econo-
attracted a great attention as it has often formed porous car-
my”. The classical H2 storage technologies show some
bons with high surface areas and pore volume [19,21]. How-
ever, its main drawbacks are the price and the environmental
C 2016 American Institute of Chemical Engineers
V impact of the chemicals, which need to be eliminated after

Environmental Progress & Sustainable Energy (Vol.36, No.1) DOI 10.1002/ep January 2017 315
the treatment by thorough washing of the resulting carbon. considering slit-shaped pores and by using Horvath-Kawazoe
In contrast, the physical activation considered to be more (HK) method. Adsorption of CO2 at 273 K was used to assess
environmentally friendly, and is commonly carried out in a the narrowest micropores (pore size smaller than 0.7 nm)
two step process. The carbonaceous raw material is first [26]. Elemental analysis of olive stones, its charred and activat-
pyrolyzed in inert atmosphere, generally below 8008C, and ed samples were carried out using ELTRA elemental analyzers;
the resulting char is then partly gasified between 700 and CS-800 and ONH-2000. Scanning electron micrographs of the
10008C with an activating agent that usually consists in steam charred and the corresponding activated carbon were
and CO2 [22]. recorded by Dual Beam TM – SEM/FIB (Nova 600 NanoLab). It
As Mediterranean country, olive cultivation is particularly combines ultra-high resolution field emission scanning elec-
widespread throughout Tunisia. The mean annual olive oil tron microscopy (SEM) and precise focused ion beam (FIB).
production for the decade 2004–2014 is 180 thousand tonnes X-ray diffraction (XRD) experiment for OB-CO2 sample was
and reached 299 thousand tonnes in 2015 [23]. Therefore, performed using a Philips X’ Pert diffractometer (Co_Ka radia-
olive pomace with high olive stones content is a very abun- tion, k 5 1. 7903 A8) equipped with position sensitive detector
dant agricultural by-product in Tunisia, and many results and monochromator in the diffracted beam. XRD pattern was
obtained made clear that this lignocellulosic precursor is a recorded for 2u in the range [58;1358], under operating condi-
very adequate raw material to obtain efficient activated car- tions of 40 kV and 40 mA, at a step of 0.058 and 10 s per step.
bons [24,25].
The main goal of the present study is to prepare an AC Measurement of Hydrogen Storage Capacities
from olive stones by physical activation with CO2 for hydro- H2 storage was measured in three independent laborato-
gen storage purpose. The morphology and textural proper- ries in volumetric devices. In all experiments, high-purity H2
ties of the produced carbon material were investigated, using ( 99.9999%) was used for the uptake measurements. H2
N2 and CO2 adsorption, X-ray diffraction, and scanning elec- uptakes were calculated in gravimetric basis (wt %).
tron microscopy. Finally, its hydrogen sorption property was
performed in three different international laboratories; using At 77K and Up to 1 Bar
verified volumetric automated and laboratory-made devices Determination of H2 storage at liquid nitrogen tempera-
which ensure high reproducibility. ture and up to 1 bar was carried out at Alicante University
(Laboratory of Advanced Materials, Spain). The automated
apparatus was the one used for N2 and CO2 adsorption
measurements. In each adsorption test 100 mg of the pre-
Activated Carbons Preparation pared AC sample were degassed at 2508C under vacuum pri-
Carbon materials were prepared from olive bagasse. First, or to adsorption measurements for at least 6 h.
the raw precursor was washed abundantly with hot distilled
water to obtain grains of olive stones sized to about 1–3 mm. At Temperature Ranged from 77 K to Room Temperature and up to
Then, dried olive stones were activated through physical 25 Bar
process. First, the carbonization of the above solid was car- At these conditions, the measurements were performed at
ried out in a quartz tubular reactor with a length of 115 cm Max Planck Institute for Intelligent Systems in Stuttgart
using nitrogen as the sweep gas. The reactor was heated (Hydrogen Storage Group, Germany). During the adsorption
externally by a horizontal electrical furnace, whose tempera- tests a commercial Sieverts type apparatus (PCT Pro 2000
ture is controlled using a thermocouple feedback installed with microdoser, HyEnergy) was used. This apparatus mea-
inside the reactor. The temperature was maintained at 6008C sures automatically adsorption and desorption isotherms in a
for 2 h, while the heating rate was 108C min21 under nitro- sample volume of 1.3 mL. Before each measurement, the
gen flow (100 cm3.min21). Activation of the resultant char sample (about 100 mg) was heated under vacuum at 2008C
was, then, conducted in the same tubular furnace, under a for 24 h. the relative excess uptake in wt % is calculated by:
CO2 flow of 100 cm3 min21. The temperature of activation
was set at 9008C for 8 h, under heating rate of 108C min21. nexc 3M
The granular carbon material was denoted as OB-CO2. One exc:uptake51003 (1)
nexc 3M1m
other activated carbon was prepared for comparison pur-
pose. The carbonization step is the same as described above. M denotes the molar mass of hydrogen (M 5 2.01588 g.
However, the activating gas was water steam under a flow of mol21); m denotes sample mass.
100 cm3 min21, and was left for 2 h at 7008C. The resultant The absolute hydrogen adsorption is calculated by the
material was also in granular form and labeled as OB-H2O. multiplication of a correction factor:
Material Characterization !
The textural properties of activated carbon were deter- P3M
nabsolute 5nexc 3 11 (2)
mined by N2 and CO2 sorption at 77K and 273K, respective- Z3R3qliq 3T
ly, using an automated manometric system ASAP2020
(Micromeritics Instrument Corporation). Before each mea- qliq : hydrogen liquid density(assumed to 0.07 g mL21); R:
surement, about 100 mg of the sample were degassed for ideal gas constant(8.314472 J K21 mol21); Z: correction factor
24 h at 2508C and 10 26Torr. From N2 adsorption isotherm, for the non ideal gas given by Ref. 27; P in bar and T in K.
the specific surface area was estimated by applying the Bru-
nauer, Emmett and Teller (BET) within the range of relative A 77 K and Room Temperature and up to 200 Bar
pressure (P/P8) from 0.01 to 0.10. The total pore volume was These measurements were carried out with a laboratory-
determined from the amount of nitrogen adsorbed at P/P85 built volumetric device at Institut de Recherche sur l’Hydro-
0.99. While, t-plot method was applied to measure the total gène (Universite de Quebec a Trois Rivières, Canada). Before
micropore area (Sinternal) and total micropore volume (pore measurements, the carbon sample was outgassed for 12 h at
size smaller than 2 nm). Moreover, the total micropore vol- 2508C. The apparatus consists of calibrated reference cell
ume was determined by the application of Dubinin Radush- which was attached to sample cell via Swagelok quick con-
kivish (DR) equation, and the pore size distributions (PSD) nect. The volume of the reference cell measured at ambient
were calculated by density functional theory (DFT) temperature was found to be 6.60 mL. Once the sample was

316 January 2017 Environmental Progress & Sustainable Energy (Vol.36, No.1) DOI 10.1002/ep
Table 1. Elemental analysis of the stones, the charred and
the resultant activated carbon sample.

Materials C H O S N
Stones 47.5 4.36 35.3 0.83 2.02
char 89.6 2.38 6.48 0.00 ca 0.33
OB-CO2 90.2 0.48 6.25 0.00 ca 0.48

Figure 1. N2 adsorption-desorption isotherms at 77K of CO2

and steam activated carbons.
Figure 2. PSD using DFT method of CO2 and steam activat-
ed samples (a); H-K pore size distribution of OB-CO2 sample
loaded on the system, it was typically left for 24 h outgassing (b).
at room temperature using the turbomolecular pump. For
the measurements at 77 K, the sample cell was immersed
into liquid nitrogen dewar flask to a predetermined height. contents. The carbonization of the stones followed by CO2
In order to maintain isothermal conditions, entire Sievert’s activation increase the carbon content up to 90% (wt/wt),
system is placed inside a thermostated laboratory whose decrease the hydrogen and oxygen contents and eliminate
temperature is maintained constant within 60.58C. The rela- sulphur from the carbon matrix. The nitrogen content
tive excess uptake in wt % was calculated by: remains almost unaltered during the activation process which
can be indicative of the inclusion of nitrogen into the aro-
Hydrogen uptake5 3100 (3) matic structure and not in functional groups on the layer
madsorbent edges.
The N2 adsorption desorption isotherms of OB-CO2 and
OB-H2O are shown in Figure 1. One can conclude that both
Isosteric Heat of Adsorption Measurements the activating agents generate microporous activated carbons,
In cryogenic hydrogen storage applications, the heat of because of the Type I characteristic of the isotherms [28].
adsorption is a very important characteristic and has to be However, the main difference lays in the N2 adsorption
identified because hydrogen uptake at the low pressure capacity revealing the difference on the created surface area.
range is strongly governed by this value. The apparent isos- On the other hand, by observing the PSD (Figure 2a) of the
teric enthalpy of adsorption of hydrogen into the carbon two samples one can note that CO2 activation is more effec-
pores, DHads, can be estimated for different surface coverage tive on microporosity creation than water steam. Moreover,
using Vant’ Hoff’s equation: the figure shows a heterogeneous PSD after water steam acti-
! vation by the creation of mesoporosity (two broad peaks at
oðlnPÞ DHads d > 2 nm). In contrast, CO2 activation leads to highly micro-
  5 (4) porous activated carbons with well controlled porosity cen-
o T1 R
u tered in narrow range as demonstrated by Figure 2b. The
plot is perfectly mono-modal with one maximum centered
where P: pressure in bar; T in K; R: molar gas constant and h on 0.65 nm. Recently, Nabais et al. [29] also stated that CO2
is the surface coverage. For calculations we used adsorption activation of lignocellulosic precursor (coffee endocarp)
isotherms at 77 K (liquid nitrogen) and 87 K (liquid argon) leads to samples with higher BET surface areas and pore vol-
and up to 25 bar. umes when compared with samples produced by steam acti-
vation and with similar burn-off values. The different textural
RESULTS AND DISCUSSION parameters deduced from N2 and CO2 adsorption at 77K and
273K, respectively are gathered in Table 2. For the charred
Surface Chemistry and Porosity Development During sample the nitrogen sorption measurement was also per-
Activations formed but no data were collected, indicative of diffusion
As can be seen from the chemical analyses presented in restrictions on the adsorption of N2 at 77 K. However, at a
Table 1, the raw biomass shows high carbon and low sulfur much temperature carbon dioxide can penetrate due to an

Environmental Progress & Sustainable Energy (Vol.36, No.1) DOI 10.1002/ep January 2017 317
Table 2. Textural parameters of char, CO2 and steam-activated olive stones deduced from N2 and CO2 adsorption isotherms.

SBET Sinternal VT pore VDR-N2 Vmeso VDR-CO2 DHK

Materials (m2/g) (m2/g) (cm3/g) (cm3/g) (cm3/g) % micro (cm3/g) (nm)
Char 296* – – 0.03 – – 0.17 –
OP-CO2 1185 1078 0.52 0.43 0.09 83 0.47 0.65
OP-H2O 351 – 0.18 0.15 0.03 83 0.15 –

*Measured with CO2 adsorption isotherm at 273 K; DHK: median pore width calculated by HK method; % micro 5 VDR-N2/VT pore.

Table 3. Comparison of our results with previous works on CO2 activation of different raw materials.

N2 pyrolysis CO2 activation SBET VT pore Vmicro VDR-CO2

Precursors conditions conditions (m2/g) (cm3/g) (cm3/g) (cm3/g) References
Eucalyptus T 5 8008C T 5 8008C 1190 0.52 0.48 0.35 Tancredi et al.
wood t52 h Flow rate 5 200 mL/min 1996 [30]
Flow rate 5 100 mL/min T rate 5 10 K/min
T rate 5 10 K/min
Furnace 5 horizantal
Bituminous T 5 7508C T 5 9008C 754 – 0.31 – Ahmadpour
coal t52 h Flow rate 5 150 mL/min et al. 1995 [32]
Flow rate 5 100 mL/min T rate 5 158C/min
T rate 5 38C/min Furnace 5 vertical
Furnace 5 vertical
Olive-mill T 5 3008C; 8008C T 5 8408C 793 – – 0.26 Moreno Castilla
waste t 5 3 h; t 5 2h Flow rate 5 300 mL/min et al. 2001[33]
Flow rate 5 300 mL/min
T rate 5 108C/min
Quercus T 5 4508C T 5 8408C 1201 0.67 0.51 0.011 Sanchez et al.
agrifolia t52 h t52 h 2001 [31]
wood T rate 5 208C/min Flow rate 5 500 mL/min
Furnace 5 horizantal
Olive stones T 5 6008C T 5 8508C 778 1.4 0.4 – Roman et al.
t51 h t52 h 2008 [34]
Flow rate 5 150 mL/min Flow rate 5 40 mL/min
Coffee T 5 6008C T 5 7008C 1287 0.64 0.53 – Nabais et al.
endocarp t51 h Flow rate 5 85 mL/min 2008 [29]
Flow rate 5 85 mL/min
T rate 5 108C/min
Olive stones T 5 6008C T 58008C 909 0.44 – 0.29 Plaza et al.
2009 [35]
Flow rate 5 10 mL/min
oak Intermediate pyrolysis T 5 9008C 724 0.32 0.27 – Jung and Kim
(pyrolysis plant) t 51h 2014 [36]
Flow rate 5 10 NL/min flow rate 510 NL/min
T rate 5 108C/min
Olive stones T 5 6008C T 5 9008C 1185 0.52 0.42 0.47 This study
t52 h t58 h
Flow rate 5 100 mL/min Flow rate 5 100 mL/min
T rate 5 108C/min T rate 5 108C/min
Furnace 5 horizantal Furnace 5 horizantal

T: temperature, t: time, T rate: temperature rate: furnace: conception of the used furnace.

activated adsorption process and BET surface area and the dehydration of lignin and cellulose, thus leading to a char
micropore volume were measured. Consequently, the with a rudimentary pore structure, and other products such
carbonized material must be essentially microporous, with as tar and volatile liquids and gas. After steam and CO2 gasi-
surface area of about 300 m2/g basically in microporosity fication this porosity will be more accessible to N2 and
only slightly larger than the carbon dioxide diameter. almost all the textural parameters are measured. These two
Actually, carbonization of lignocellulosic materials implies a agents extract carbon atom from the structure of the porous
set of reactions such as depolymerization, cracking, and carbon according to the following stoichiometric equations

318 January 2017 Environmental Progress & Sustainable Energy (Vol.36, No.1) DOI 10.1002/ep
Figure 3. SEM micrographs of the outer surface (a, b) and transverse sections (c, d) of the activated carbon OB-CO2.

[22], thus the porosity has been widened and became acces- of the volume of narrow micropores (VDR-CO2) shows that
sible to the nitrogen: OB-CO2 sample has the highest measured value. On the oth-
er hand the difference between VDR-CO2 and the micropore
C1CO2 52CO DH5 1159 kJ mol21 volume measured with N2 adsorption (indicative of porosity
homogeneity) is the lowest in this study. All these observa-
C1H2 O5CO1H2 DH5 1117 kJ mol21 tions evidence that this prepared sample has a tailored and
well ordered porosity. Therefore it is noteworthy to stat that
The two reactions are endothermic which facilitates the carbon’s porosity could be tuned via simple two-step CO2
accurate control of experimental conditions in the furnace. activation process. Actually, this well-ordered pore system of
Let’s start with CO2-activated sample. According to Table 2, it the OB-CO2 is the result of contribution of many factors.
can be seen that the prepared carbon exhibits a relatively First, it is the nature of the raw material, because Tancredi
large surface area, and the porosity is almost totally devel- et al. [30] and Sanchez et al. [31]who activated materials
oped internally (Sinternal 5 91% SBET). As expected, the carbon based on wood, found very low VDR-CO2 values even though
is highly microporous, and the microporosity represents 83% the overall created specific surface and pore volume are sim-
of the total developed porosity. ilar to our result. This means that the composition of the raw
The most surprising is the almost equality registered material is crucial factor which affect the porosity develop-
between VDR-N2 and VDR-CO2 with high values (0.47cm3/g) ment. Whereas, the results are worst with gasification of coal
which reveals a uniform PSD localized in a narrow range. [32].
This means that all the operation conditions are optimized The second reason is the use of horizontal furnace. Actu-
(gasification temperature, time, burn off degree, etc . . ..) ally, the horizontal conception limits the external mass-
even though with prolonged activation time (8 h). To show transport, and consequently, will favor the internal burning
the exceptional carbon characteristics a comparison of our of the char particle and the creation of micropores rather
results with others is presented in Table 3. The overview of than their widening. Also, we shouldn’t ignore the effect of
the table indicates that our result is among the best achieved low heating rate (108C min21) on the development of a uni-
in terms of carbon’s porosity. However a direct comparison form porosity [37]. Finally, one other important reason is the

Environmental Progress & Sustainable Energy (Vol.36, No.1) DOI 10.1002/ep January 2017 319
Figure 4. XRD pattern of OB-CO2 sample. Figure 5. Low-pressure excess adsorption-desorption iso-
therms of H2 on OB-CO2 and OB-H2O samples at 21968C.
[Color figure can be viewed at]
activating agent itself: carbon dioxide. This is clearly elabo-
rated after the comparison with the steam activated sample
(see Table 2). However, OB-H2O sample is very similar to temperature (9008C) leads to some edge orientation and
the char, which reveals the incomplete steam gasification reduce the concentration of nonparallel single layers.
process. Actually, this is very surprising because even though
water steam is less effective as activating agent than carbon Hydrogen Storage Capacity
dioxide, we didn’t expect such poorly developed porosity.
When the activating gas comes in contact with the char, it Cryogenic Hydrogen Storage
will react with both the exterior and the interior of the parti- Figure 5 shows the hydrogen adsorption-desorption iso-
cle, the latter requiring previous diffusion of the activating therms of CO2 and steam activated carbons at 77K and up to
gas. At the activation temperature used in the preparation of 1 bar. The two investigated carbon materials show a type I
OB-H2O, 7008C, the diffusion rate of water molecules to the adsorption isotherm with an initial steep increase of the
interior of the particle is sufficiently high to expect a devel- hydrogen uptake at low pressures and an almost horizontal
opment of the whole range of porosity, at least in the early plateau at higher pressures. This type of isotherms is charac-
stages of activation. However, the progress of the reaction teristic for monolayer adsorption on microporous solids [40].
brings about the production of CO and H2, which are inhibi- No multilayers of hydrogen are formed at 77K, because the
tors of the reaction (especially H2). The increase in the con- interaction strength between single layers is too weak at tem-
centration of inhibitors in the interior of the particle will perature higher than the critical temperature of H2 [41].
favor the reaction of steam at the exterior, with the subse- Moreover, the sorption was completely reversible, indicating
quent destruction of porosity [38]. Hence there is a widening
physisorption of hydrogen on pore walls of the carbons. As
of the microporosity, since VDR-N2 increases and VDR-CO2
expected, OB-CO2 adsorbs more than OB-H2O sample,
remains almost constant. To prevent this inhibition the tem-
thanks to its highly developed porosity. Thus, there are more
perature must be further enhanced, in order to minimize the
concentration of the inhibitors. Consequently, the creation of active sites for H2 adsorption. At 1 bar, the adsorption capac-
microporosity is maximized in the OB-CO2 sample (activa- ity of OB-CO2 sample reaches 1.69 wt %, which is a consid-
tion temperature 5 9008C). erable amount especially when compared to values reached
by non-carbonaceous porous materials, as presented in Table
Morphology Observations and Structural Analyses: SEM 4. The overview of the Table 4 reveals that at the adopted
operation conditions OB-CO2 has outperformed a large
and XRD
number of nanoporous materials such as Zeolites, polymers
Micrographs of the outer surface and transverse sections
and MOFs
of OB-CO2 sample are shown in Figure 3. As can be seen,
In addition, these materials are high cost, non sustainable
the micrographs of sections of the outer surface (Figures 3a
and their production processes are not reproducible. Surpris-
and 3b) are significantly different from their corresponding
transverse sections (Figures 3c and 3d). On the former two ingly, OB-CO2 sample has outperformed nanoporous materi-
images, except for a few cracks (Figure 3b), the surface is als with higher specific surface area [46,48,49], which reveals
plain and does not manifest any pores at this level of magni- that surface area is not the only parameter that needs to be
fication and resolution of the SEM. Therefore a transverse regarded. Even though, many investigators have shown that,
section is recommended in order to see the form of the at 77K and subatmospheic pressures, the hydrogen uptake
microporosity developed during CO2 activation. On the latter was governed by the microporosity and the specific surface
two images (Figures 3c and 3d) the pores are clearly seen as area of the tested adsorbents [13,52,53]. Actually, the only
flat and irregular holes with diameter  5mm at the level of exceptional feature of OB-CO2 sample is its ultramicroporous
magnification and resolution of the SEM used in this work. character, with a well ordered pore system centered at
The XRD pattern of the same sample is plotted in Figure 4. It 0.65 nm. This observation clearly points out that the smallest
indicates a typical amorphous carbon and shows abroad pores are much more efficient in H2 sorption due a stronger
asymmetric peaks at corresponding to 2u 258 and 2u 508. interaction with H2 molecules. Therefore, the pore size is
However, there are some sharp peaks at 2u 5 30, 35 and 458, also a key factor that governs cryogenic H2 adsorption at cer-
which proves a little high degree of graphitization. This is tain pressure conditions. On the other hand, this result justi-
due to the ordered distribution of crystallites during nitrogen fies previous works which stated the existence of an
carbonization step [39]. Subsequently, the high activation optimum pore size for H2 adsorption [16,54–56]. These

320 January 2017 Environmental Progress & Sustainable Energy (Vol.36, No.1) DOI 10.1002/ep
Table 4. Comparison of physical properties and hydrogen uptake capacities of our CO2 activated carbon with non carbona-
ceous and porous materials.

Materials SBET (m2.g21) T (K) P (bar) H2 uptakes (wt %) References

Zeolites (NaA) 725 77 15 1.54 Langmi H. et al., 2003 [42]
298 0.28
Zeolites (CaX) 669 77 15 2.19 Langmi H. et al., 2005 [43]
Prussian Blue 870 77 1 1.4 Kaye et Long, 2005 [44]
Polymers of intrinsic microporosity (PIM) 830 77 1 1.43 Neil et al., 2006 [45]
Hypercrosslinked polystyrene gel 1930 77 1.2 1.55 Germain et al., 2006 [46]
Nanoporous polymers 1043 77 60 3.7 Yuan et al., 2009 [47]
298 70 0.43
Zr-MOF 1367 77 1 1.5 Ren et al., 2014 [48]
MOF (Mil-101) 1715 77 1 1.65 Ren et al., 2014 [49]
Zr-fumarate MOF 849 77 1 1.38 Ren et al., 2015 [50]
Fly ash derived Zeolites X 404 77 1 0.7 Musoyka et al., 2015 [51]
CO2 activated olive stones (OB-CO2) 1185 77 1 1.69 This study
77 25 2.59
77 200 3.34
298 200 0.63

Figure 6. Excess hydrogen adsorption-desorption isotherms

of OB-CO2 samples at 77K and up to 25 bar.
Figure 7. Excess and absolute H2 adsorption isotherms of
OB-CO2 at 77K and high pressures. [Color figure can be
viewed at]
optimum values can hold two layers of adsorbed hydrogen
into slit pores.
Figure 6 plots the excess H2 adsorption-desorption iso-
therms of OB-CO2 sample at higher pressure (up to 25 bar). also calculated using Eq. (2), because it quantifies the
The type I isotherm is more pronounced than in Figure 4, as amount of hydrogen present in the adsorbed layer and in
at higher pressure the adsorption sites are more fully saturat- the adsorbent pores. It is crucial measurement for the design
ed. At 25 bar the H2 adsorption capacity of the carbon of storage system tanks. As shown in Figure 7 the absolute
reaches 2.59 wt %. The enhancement on H2 adsorption after adsorption isotherm exhibits Type I or Langmuirian shape.
the increase of pressures from 1 to 25 bar is about 53% The difference between excess and absolute adsorption
which is a moderate improvement. This is probably related become more significant at high pressure (from 60 bar),
to the very narrow microporosity of this sample, which satu- because there is compression contribution and the benefit of
rate at very low pressure. This is the case of carbide derived adsorption is lost [59]. At 200 bar, the absolute adsorption
carbons which have shown an exceptional H2 adsorption amount of our lab-made carbon reaches 3.34 wt %, that is a
capacity but they have been saturated at only 1 bar [57]. considerable amount. These data highlight that hydrogen
The high-pressure excess and absolute adsorption iso- storage on our biomass-based carbon can be an interesting
therms at 77K for OB-CO2 sample are illustrated by Figure 7. option, especially in wind and solar hybrid systems, wherein
With the increase of testing pressure, excess adsorption weight and volume are not limiting factors. Noting that at
reached the maximum value (2.84 wt %) at approximately 30 200 bar we still working on safe conditions and the H2 stor-
bar and then decreased step by step, which is totally differ- age system is controllable.
ent from absolute hydrogen storage. Theoretically, when the
gas densities in the pore and the bulk gas are increasing at Room Temperature Hydrogen Storage
the same rate with respect to pressure, the excess adsorption The Figure 8 illustrates the H2 adsorption-desorption iso-
will achieve a maximum value. Consequently, continuous therms of OB-CO2 at room temperature (298K). In contrast
increase in pressure has no positive effect upon the amount to low temperature measurements, at room temperature the
adsorbed. At higher pressure over the critical point, the gas adsorption isotherm is far from saturation and is described
density in the sample pores remains unchanged while the with a linear equation, according to the Henry-type behavior.
bulk gas density keeps increasing, resulting in a negative Only fractional coverage takes place and the adsorbed mole-
gain in the excess adsorption [58]. Absolute adsorption was cules behave like two-dimensional ideal gas. The overall

Environmental Progress & Sustainable Energy (Vol.36, No.1) DOI 10.1002/ep January 2017 321
conditions. Moreover, it was clearly shown that under 1 bar
only the narrow micropores contribute to H2 adsorption.

The authors gratefully acknowledge Dr. F. Reinoso-
Rodriguez (University of Alicante, Spain), Dr. R. Chahine
(IRH, Universite du Quebec a Trois Rivière, Canada) and Dr.
M. Hirscher (Max Planck Inst. for Intelligent Systems, Stutt-
gart, Germany) for accepting the research internship of Miss
N. Bader and University of Gabes for funding.

BET Brunauer, Emmett and Teller
DFT Density functional theory
Figure 8. High pressure adsorption-desorption isotherms of DR Dubinin Radushkivish
H2 on OB-CO2 at room temperature (298K). FIB Focused ion beam
HK Horvath-Kawazoe
MOF Metal organic framework
PSD Pore size distributions
SEM Scanning electron microscopy
XRD X-ray diffraction

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