Journal of Environmental Chemical Engineering 6 (2018) 1995–2002

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Journal of Environmental Chemical Engineering

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CO2 capture using N-containing nanoporous activated carbon obtained from T

argan fruit shells
Ouassim Boujibara,b, Ahmed Souiknya, Fouad Ghamoussb, Ouafae Achaka, Mouad Dahbic,
⁎
Tarik Chafika,
a
Laboratory LGCVR-UAE/L01FST, Faculty of Sciences and Techniques, University Abdelmalek Essaadi, Tangier, Morocco
b
PCM2E, EA 6299 Université François Rabelais de Tours, Parc de Grandmont, 37200 Tours, France
c
Materials Science and Nano-Engineering Department, Mohammed VI Polytechnic University, 43150, Ben Guerir, Morocco

A R T I C LE I N FO A B S T R A C T

Keywords: The present work investigates the CO2 capture by activated carbons prepared from Argan fruits shells. The
CO2 capture protocol consist on carbonization followed by activation using wet impregnation or dry physical mixing with
Argan shells activating agents such as KOH or NaOH. The as-prepared samples have been subjected to textural investigations
Activated carbon and comprehensive characterizations using scanning electron microscopy, energy dispersive X-ray diffraction,
Nitrogen-containing
Raman and FTIR spectroscopy. Values of specific surface areas and pore volume up to 2251 m2/g and 1.04 cm3/
Nanoporous
g, respectively, were extracted from adsorption isotherms that allow, also, determination of pores sizes and
surface energy distributions. Of interest, the chemical composition given by EDX revealing significant N content
up to 13.90 wt% and approved by FTIR spectroscopy. Moreover, the CO2 isotherms measured, under 1 bar and
25 °C, show uptake capacity reaching 5.63 mmol/g. This values is likely attributed to CO2 adsorption by the
prepared activated carbon combining large surface area, narrow micropores and the N containing surface
functionalities.

1. Introduction regeneration by electrical swing adsorption (ESA) [6] or pressure swing

adsorption (PSA) and thermal swing adsorption (TSA) processes [7].
Global warming took on a much more worrying dimension due to These adsorption facilities make use of appropriate porous materials
the continuous increase in greenhouse gases (GHGs) emissions. Man- such as activated carbons, zeolites and metal-organic frameworks re-
made CO2 is one of the major contributors to global warming as a result garding their large surface areaper unit of mass as well as suitable pore
of the staggering amounts that are being released into the atmosphere size distribution [8–10]. In general, activated carbons are preferentially
on a daily basis [1]. In the past decades, considerable effort has been used considering their relatively low cost and availability, especially
put into developing new technologies to reduce excessive CO2 emission when obtained from low-cost biomass/waste precursors [11,12]. Acti-
and mitigate its long-term effects on climate change [2]. The main vated carbons also show good stability when operated under moist
treatment technologies used to capture CO2 from flue gas streams are environments due to their hydrophobic character, and can be readily
absorption, adsorption and membrane separation [3]. Generally, liquid- regenerated thermally or by evacuation with lower energy require-
phase absorption is the most commonly used method for CO2 capture ments [13]. Recently, biomass wastes have attracted considerable at-
because of its higher efficiency. However, this process presents several tention as efficient precursors for the preparation of activated carbons
drawbacks, such as high energy consumption and serious concerns re- with a well-developed porous network [14,15]. Bio-wastes are largely
lated to solvents useand waste management [4]. Hence, adsorption abundant, inexpensive and naturally occurring materials usually rich
emerges as a promising contender technology, as it allows achieving lignocellulosic compounds and can be directly transformed into porous
high CO2 uptake capacities while maintaining high thermal stability, carbons through carbonization followed by activation [16,17]. Basi-
which is a prerequisite for operating under high-temperature conditions cally, the activation step can be conducted by employing a physical or a
such as those involved in post-combustion power plants [5]. Another chemical process [18]. In physical activation, the precursor is first
major advantage offered by the adsorption is the possibility to restore carbonized, then activated using steam or carbon dioxide [19,20].
the initial performance of the used solid adsorbent through Whereas for chemical activation, the precursor is mixed with a

⁎
Corresponding author.
E-mail address: t.chafi[email protected] (T. Chafik).

https://doi.org/10.1016/j.jece.2018.03.005
Received 10 December 2017; Received in revised form 13 February 2018; Accepted 5 March 2018
Available online 06 March 2018
2213-3437/ © 2018 Published by Elsevier Ltd.
O. Boujibar et al. Journal of Environmental Chemical Engineering 6 (2018) 1995–2002

chemical reagent and followed by a heating under inert atmosphere carbonized product is denoted as ARG-C.
[21]. Compared to physical activation, chemical processing has been
advantageous due to its ability to be performed in only one step at 2.3. Chemical activation
relatively low temperatures, leading to greater yields [22].
Besides, the nature of biomass used as a precursor, is considered as The ARG-C precursor was crushed and sieved in order to retain
key parameter governing the production of high quality activated car- particles size fraction between 500 and 1000 μm. Chemical activation
bons [23]. In Morocco, the agricultural activity related to the produc- was carried out using sodium hydroxide (NaOH) or potassium hydro-
tion of Argan fruit (Argania Spinosa) for oil extraction is rapidly emer- xide (KOH), following two different methods namely impregnation (Im)
ging because of worldwide growing interest regarding its uses for and physical mixing (PM). In the case of impregnation method, an
culinary and cosmetic purposes. So far, the increased popularity of amount of 4 g of ARG-C precursor was impregnated in a solution con-
Argan oil has prompted an annual production up to 4000 tons by taining 16 g of KOH or NaOH dissolved in 50 ml of distilled water. The
Morocco, which leaves behind about 80.000 tons of hard shells [24]. solution was kept under vigorous stirring for 2 h at 60 °C. The resulting
The latter is currently considered as an agriculture by-product without slurry was dried overnight in an oven at 110 °C. The resulting samples
any significant economic value and mainly used by the local population denoted ARG-K-Im and ARG-N-Im, respectively, for the carbon acti-
as domestic combustible [25]. Even more interesting, Argan shells are vated using impregnation with KOH and NaOH. For the physical mixing
well known by rich lignocellulosic content [26], allowing high potential activation, 16 g of NaOH or KOH beads were physically mixed with 4 g
for use as raw material for the production of activated carbons. Indeed, of the carbonized ARG-C sample at room temperature. It is to be noticed
we previously reported successful production of nanoporous activated that this process was performed in the absence of water. The obtained
carbon made out of Argan shells, using optimal preparation conditions samples using KOH or NaOH were denoted ARG-K-PM and ARG-N-PM,
following empirical approach [27]. The aim of the present work is to respectively.
improve the surface area and the prosity of the activated carbons fol- After impregnation and physical mixing processes, the resulting
lowing the traditional protocole based on carbonization followed by samples were heat-treated under 600 cm3/min of N2 flow in a tem-
activation. It is established that the carbonization step is carried out in perature programmable oven, following the sequence below:
order to ensure removal of moisture and the conversion of organic
matter into elemental carbon. Note that appropriate carbonisation i) Heating from room temperature to 850 °C at a rate of 5 °C.min−1;
temperature is needed in order to avoid char yield decrease through ii) Holding at 850 °C for one-hour;
further decomposition and release of gaseous and condensable products iii) Cooling to room temperature.
[28]. Subsequent activation step permits the development of prosity
through the diffusion of activating agent into the charcoal. This step After the heat treatment, all the samples were washed with HCl
depend on several parameters such as the ratio char/reactant, the (5 M) solution, rinsed with distilled water until reaching neutral pH
temperature and chemical nature of the activating agent. Recent works then dried at 110 °C overnight.
pointed out that chemical activation using impregnation or physical
mixing with alkaline hydroxides e.g. NaOH and KOH, allows obtaining 2.4. Characterization of the activated carbons
microporous activated carbon with larger surface area and narrow pore
size, that can be appropriate candidate for CO2 capture at ambient The carbonization temperature of the Argan shells was decided
temperature and pressure [29–31]. This approach has been adopted in based on the Thermo-gravimetric analysis using Perkin Elmer Pyris STA
the present work and yields to activated carbon with interesting pre- 6000 instrument under a nitrogen flow. The chemical composition was
sence of nitrogen without further doping with nitrogen-containing assesed with energy dispersive X-ray spectroscopy (EDX) using a Bruker
chemicals. The as-prepared activated carbons have been investigated Nano XFlash Detector 430-M. The surface functionalities were in-
with respect to the potential application as efficient CO2 adsorbent vestigated with FT-IR spectroscopy, Jasco 410. The morphology was
through the measurements of CO2 uptake under ambient conditions studied with scanning electron microscopy (SEM, Model SH–4000 M) at
(25 °C and 1 bar). The obtained CO2 adsorption capacity values were acceleration voltage of 15 kV. The crystalline structure was examined
compared to those reported in the literature, under similar conditions, by X-ray diffraction (XRD) using Brukereco D8 Advance diffractometer.
for various biomass-derived activated carbons. The objective is to help The graphitization degree was determined using LabRAM HR Raman
creating economic value through valorization of available local agri- spectrometer. The textural characteristics were studied by measing N2
culture by-product as efficient porous material for CO2 capture. adsorption isotherms at 77 K using Micromeritics ASAP 2020 apparatus.
Furthermore, CO2 adsorption isotherms measured at 273 K were used to
2. Material and methods assess the ultramicropores size distribution (pores of width < 0.7 nm).
Before adsorption experiments, all samples were outgassed for 4 h at
2.1. Raw material 523 K under high vacuum (13.3 kPa) in order to achieve surface
cleaning from moisture and others contaminants. BET surface area,
Argan hard shells collected from the southern region of Morocco SBET, was determined according to BET method [31], considering the
were first washed with distilled water and dried in an oven at 100 °C for molecular cross-sectional area of N2 at 77 K to be 0.162 nm2.The total
24 h, then crushed and sieved to retain the fraction between 1 and pore volume, VT,was obtained from the amount of N2 adsorbed at a
3 mm that were subsequently, carbonized without any prior chemical relative pressure of P/Po = 0.90. For reasons mainly related to N2
treatment. molecules diffusion inside the very narrow pores at 77 K, it is assumed
that N2 isotherms correspond to the adsorption in mesopores and mi-
2.2. Carbonization of Argan shells cropores larger than 0.7 nm. Whereas CO2 isotherms at low relative
pressure (P/Po < 0.035) are assumed to be associated with adsorption
The carbonization process was carried out with 50 g of the clean-dry in ultramicropores (0.4–0.8 nm). Thus, the Horvath–Kawazoe (H-K)
shells contained in a crucible placed in a home-made stainless steel equation [32] was applied to N2 and CO2 isotherms for the determi-
reactor, itself positioned inside a horizontal furnace. After 10 min of nation of the micropore and ultramicropore volumes denoted, respec-
purge under N2 flow, the reactor was heated under a N2 flow of tively, VHK-N2 and VHK-CO2. Mesopores volume, Vmeso, was calculated
100 cm3/min at a rate of 10 °C/min until reaching 700 °C, then main- from the difference between VT and VHK-N2 [33]. The pore size dis-
tained at this temperature for a period of 1 h. Finally, the reactor was tribution (PSD) was determined by applying density functional theory
allowed to cool down to room temperature under N2 flow. The resulting (DFT) method to N2 and CO2 adsorption isotherms data, assuming a slit

1996
O. Boujibar et al. Journal of Environmental Chemical Engineering 6 (2018) 1995–2002

pore geometry [34]. The surface energy distribution was determined microstructure. The chemical composition of the carbonized material
using the following Eq. (1) corresponding to the solid-fluid potential given by EDX elemental analysis as displayed in Fig. 2b. It is shown,
well depth function ξ (ϵsf/kB) [35]: mainly, the presence of Carbon (84.05 wt%) and Oxygen (11.19 wt%)
along with small amounts of Nitrogen (2.95 wt%),Potassium (1.01 wt
∈ k dS
ξ ⎛ sf ⎞ = B
⎜ ⎟ %) and Calcium (0.80 wt%). The presence of nitrogen in the carbonized
k
⎝ ⎠
B S0 d∈sf (1) Argan shells was also reported by Laila Bouqbis and al., who pointed
Where kB is Boltzmann’s constant, ϵsf is the depth of the potential well out a total nitrogen content about 150 ppm determined by Kjeldahl
of the solid-fluid interaction, S is the area of the pore wall surface method as well as 100 ppm of NaNO3 contained in the char produced by
having a solid-fluid potential well depth less than ϵsf, and S0 is the total Argan shells carbonization under nitrogen flow [37].
pore wall surface. Further SEM micrographs are shown in Fig. 3a and b, corresponding
to ARG-K-Im and ARG-K-PM samples respectively, obtained after acti-
vation with KOH using impregnation and mixing methods. The samples
2.5. CO2 capture measurements
seems to present a honeycomb-like structure with large spherical cav-
ities. Moreover, in contrast to the displayed smooth cavities of ARG-K-
The CO2 adsorption capacity of the prepared carbon samples was
PM, the surface of ARG-K-Im presents some rifts and crannies resulting
measured using the same volumetric gas adsorption apparatus
from the chemical etching during liquid phase impregnation. In the case
(Micromeritics ASAP 2020). Prior to the experiment, the samples
of activation with NaOH, the SEM images of ARG-N-PM and ARG-N-Im
(0.10 g) were first purged at 0.67 kPa and 30 °C for 20 min, then heated
samples (Fig. 3c and d, respectively), show irregular and heterogeneous
up to 350 °C at 10 °C/min under a vacuum of 13.3 kPa and kept under
surface morphology displaying pores with different sizes and shapes.
these condition for 4 h [14]. CO2 adsorption measurements were then
X-ray diffraction patterns of the activated carbons and carbonized
carried out by multiple dosing of 0.2230 mmol/g of high-purity CO2
precursor (ARG-C), are gathred in Fig. 4, for sake of comparison. The
(Oxynord, Morocco, 99.99%) at low absolute pressure (5% tolerance),
XRD profile of ARG-C sample does not reveal the presence of well-de-
until reaching equilibrium. The temperature was maintained at 25 °C
fined peaks that might be associated with any distinct mineral phase,
using ethylene glycolin and ultra-thermostatic bath (Julado F25), to
which is completely consistent with the amorphous structure expected
ensure further control and stabilization of adsorption temperature.
for this kind of carbonaceous material. However, two broad humps are
Accordingly, CO2 adsorption isotherms were obtained in the pressure
noticeably present, one at 2θ = 25.56° and the other at approximately
range between 0.01–1.0 bar.
2θ = 43.16°, that can be assigned, respectively, to (002) and (100)
graphitic planes [38]. Although these features are present in all samples
3. Results and discussion after activation, the peaks of (002) and (100) have been markedly
broadened and their intensities decreased dramatically to become
3.1. Thermal textural and structural investigations barely visible in the case of ARG-N-Im, ARG-K-PM and ARG-K-Im
samples, and almost disappeared for ARG-N-PM. This phenomenon is
As displayed in Fig. 1, the profile of thermal gravimetric analysis due to the destruction of the graphite crystalline structure as result of
(TGA) obtained with Argan shells clearly shows several weight loss the activation process leading to the predominance of thin-carbon
occurring as function of temperature increase. This profile is also of sheets disorderly assembled. Noteworthy is the significantly high in-
interest regarding the carbonization temperature range required for the tensity at low-angle scatter (5–15°2θ) for the activated samples sug-
char production. In agreement with the literature [36], The first weight gesting porosity development [39].
loss of 5.78%, is attributed to the released of moisture content and Fig. 5 shows the Raman spectrum of the prepared active carbons
volatile matter at temperature range between 60 °C and 190 °C. The and the carbonized precursor. For all the as-prepared carbon samples,
second decomposition stage of the profile shows a weight loss of there are two peaks located at 1350 cm−1 and 1580 cm−1, corre-
53.72% at a temperature range of 230 °C to 370 °C, is due to the de- sponding, respectively, to the D and G bands of graphitic material. The
composition of hemicellulose and cellulose. The final stage of the pro- D band is due to the vibration of disordered sp3 carbon, and G band is
file exhibited weight loss of 33.66% attributed to the decomposition of ascribed to the vibration of ordered sp2 carbon [40]. The intensity ratio
lignin at a temperature above 370 °C. Stabilization of the material was of ID/IG indicates the graphitization degree of the samples. So that,
observed above 700 °C and justify the consideration of this temperature graphitization degree has an inverse relationship to the intensity ratio
for carbonization. of ID/IG. Analysis of the spectra revealed an increase in the intensity
Fig. 2a shows the SEM image of the carbonized precursor ARG-C, ratio of the activated carbons as compared with those of ARG-C. This is,
indicating a morphology characterized by bumpy and rough apparently, associated with relative decrease in the graphitization de-
gree of activated carbons due to the destruction of the graphitic crys-
talline structure within the ARG-C as a result of the activation treat-
ment.
Textural characterization of the activated carbons was investigated
using nitrogen adsorption isotherms (measured at 77 K) shown in
Fig. 6a. These isotherms are characteristic of type I, representative of
microporous solids, according to the IUPAC classification [41]. All the
isotherms present a plateau at relative pressure values higher than P/
Po = 0.5, corresponding to monolayer accommodation and saturation
with adsorbed N2 within the accessible porosity. Details concerning
micropores filling at very low relative pressures starting at P/Po below
10−5 are highlighted in the zoomed part shown in Fig. 6b. Interestingly,
at P/Po = 5.10−4, the adsorbed amounts are already about 47%, 52%,
38% and 38% of total adsorption respectively, for, ARG-K-PM, ARG-K-
Im, ARG-N-Im and ARG-N-PM samples. Accordingly, the predominance
of microporosity suggests the need for subsequent measurements with
CO2 adsorption at 273 K, known to be rather appropriate than N2 iso-
Fig. 1. TGA curve of the Argan shells under nitrogen atmosphere.
therms for the assessment of ultramicroporosity (pores of width < 0.7

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O. Boujibar et al. Journal of Environmental Chemical Engineering 6 (2018) 1995–2002

Fig. 2. (a) SEM micrograph of ARG-C and (b) EDX analysis of the encircled region.

Fig. 3. SEM micrographs of the prepared activated carbons: (a) ARG-K-PM, (b) ARG-K-Im, (c) ARG-N-PM and (d) ARG-N-Im.

Fig. 4. X-ray diffraction patterns of the prepared active carbons and the carbonized
precursor.
Fig. 5. Raman spectra of the prepared active carbons and the carbonized precursor.

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O. Boujibar et al. Journal of Environmental Chemical Engineering 6 (2018) 1995–2002

Fig. 6. (a) Nitrogen adsorption isotherms measured at 77 K for the prepared activated
carbons (b) zoomed up inset of the low-pressure region.

nm), mainly, due to diffusional difficulties of N2 molecules inside the

very narrow pores [42].
Furthermore, applying Horvath–Kawazoeequation to N2 and CO2
isotherms allows calculation of different pore volume values; VHK-N2
and VHK-CO2, as well as the VHK-N2/VT ratio, for the estimation of mi-
cropores contribution to the total pore volume. Meanwhile, BET
equation was applied to N2 isotherms to obtain BET surface area; SBET
[43]. The obtained values corresponding to all the aforementioned
parameters are gathered in Table 1. Among the prepared activated
carbons, the largest SBET and VT values were obtained for ARG-K-PM Fig. 7. Pore size distribution determined from N2 (a) and CO2 (b) adsorption isotherms
activated by physical mixing with KOH beads (2251.04 m2/g and using DFT calculations.
1.04 cm3/g), while impregnation with an aqueous KOH solution has
yielded to a slightly reduced SBET and VT (1889.63 m2/g and 0.87 cm3/ Micropores distribution comprises three groups of ultramicropores; a
g). In addition, it can be straight forwardly concluded that these surface narrow and high-intensity peak centered at pore diameter width of 8 Å
areas are mainly derived from micropores as it is revealed by the fairly and two small peaks at 12 and 16 Å. The PSD derived from CO2 ad-
high values of Smic for both samples. Note, the largest contribution of sorption data (Fig. 7b) shows a quite similar distribution in the nano-
Smic as observed for ARG-K-Im, eventhough its smaller SBET when pore region with a maximum centered at 8.5 Å, depending on the kind
compared to ARG-K-PM. On the other hand, using NaOH as an acti- of activated carbon. Moreover, a very heterogeneous distribution is il-
vating agent, produced smaller surface areas and lower pore volumes. lustrated by ultramicropores wide distribution ranging from 4.5 to 7 Å.
On top of that, an opposite trend of the above mentioned was observed, The observed higher extent of nanopores obtained in the case of KOH
i. e. impregnation in aqueous NaOH solution created more developed activated sample as compared to those activated with NaOH. This is
texture as indicated by SBET and VT values as compared to those ob- partly attributed to partial gasification and expansion of the interlayer
tained with physical mixing method. Furthermore, although the pre- spacing between graphitic planes through consecutive intercalation and
pared activated carbons are essentially microporous, there is a minor deintercalation of K with larger radii than Na [44]. Thus, K is expected
contribution of mesopores as revealed by the calculated value of Vmeso to cause much more widening of the interlayer space and produce more
reported in Table 1. The greatest contribution of mesopores was noticed nanopores, which is in a good agreement with the observed developed
for ARG-N-Im (23.95%), while the lowest for ARG-K-Im (8.04%). porosity.
The above observations are perfectly in agreement with the pores The multi-stage feature of the adsorption isotherm implies that
size distribution (PSD) derived from DFT calculations applied to N2 and there are various adsorption sites with different surface energy, e.g.
CO2 adsorption isotherms data (Fig. 7a and b). The porosity of the adsorption sites, located on surface of different predisposed porosity;
prepared active carbons consists mostly of micropores with minor ultramicropore, micropore, and mesopore [45]. Therefore, subsequent
mesopores as depicted by the shoulder between 20 and 40 Å (Fig. 7a). relevant information about the energetic heterogeneity of adsorbent’s

Table 1
Textural parameters, CO2 adsorption capacity and chemical composition of the obtained activated carbons.

Sample Surface area (m2/g) Smic/SBET Pore volume (cm3/g) VHK-N2/VT CO2 uptake at 25 °C and 1 bar Elemental composition (wt%)
(%) (%) (mmol/g)
SBET Samic Vb T VHK-N2 VHK-CO2 Vmeso C N O

ARG-K-PM 2251.04 1834.04 81.47 1.04 0.93 0.13 0.11 89.42 5.51 85.08 9.49 5.43
ARG-K-Im 1889.63 1581.87 83.71 0.87 0.80 0.15 0.07 91.95 5.63 82.68 13.90 3.42
ARG-N-PM 1462.71 1153.80 78.88 0.74 0.58 0.09 0.16 78.37 3.64 67.74 9.07 23.19
ARG-N-Im 1826.96 1428.30 78.17 0.96 0.73 0.10 0.23 76.04 3.73 82.14 12.61 5.25

a
Calculated from the DFT equation applied to the N2 adsorption isotherms.
b
Determined at P/PO = 0.90 in the N2 adsorption isotherms.

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O. Boujibar et al. Journal of Environmental Chemical Engineering 6 (2018) 1995–2002

Table 2
Comparative survey of the CO2 capture capacity of the activated carbon in this work with
other carbon materials from different resources.

Resource Surface area Volume of CO2 uptake at Reference

(m2/g) micropores 25 °C and 1 bar
(cm3/g) (mmol/g)

Argan shell 1889 0.87 5.63 This work

Cigarette butts 2016 0.72 3.66 [60]
Palm shell 1250 0.55 4.40 [61]
Yellow mombin fruit 1384 0.49 7.30 [62]
Pineconeshell 3135 – 4.73 [63]
Gelatin 1636 < 0.51 3.80 [64]
Sucrose (N-enriched) 1745 0.53 4.30 [65]
Chitosan (N-doped) 907 0.39 4.26 [66]
Coconut shell 1535 0.73 4.80 [67]
(N-doped)

Fig. 8. Surface energy distribution determined for the prepared active carbons. and function of surface energy (K). Accordinly, Fig. 8 indicates a wide
surface energy distribution, with four peaks being detected, suggesting
the existence of different type of adsorption sites. In agreement with the
work reported by Ustinov and Do, the peak with the high energy around
65 K could be ascribed to adsorption sites located on the pore edges,
while lower energy peaks are apparently attributed to different surface
sites located on different types of accessible porosity (i.e. ultra-
micropore, micropore and mesopore) [46].
On the other hand, the acidic character of the CO2 molecule, justify
the recent development of adsorbent doped with nitrogen-bearing
groups to endow the surface with basic sites in order to improve CO2
capture efficiency [47–50]. The data concerning chemical composition,
textural caracteritics and CO2 adsorption capacity obtained with the
prepared activated carbons are summarised in Table 1 Textural para-
meters, CO2 adsorption capacity and chemical composition of the ob-
tained activated carbons. Of interest, the increased nirtogen content
obtained with ARG-K-Im up to 13.90 wt%. This finding is approved by
FTIR spectrum recorded with ARG-K-Im sample mixed with appropriate
amount of KBr in order to help identification of the targeted IR bands
(Fig. 9). In agreement with the literature [51], the presence of IR bands
at 1190 cm−1, 1560 cm−1 and 3370 cm−1 are assigned, respectively, to
Fig. 9. FTIR spectra of ARG-K-Im sample. CeN stretching [52], NeH in-plane deformation [53] and NeH and/or
eOH stretching [54]. In this sense, the activation under nitrogen flow
using chemical agent such as KOH was reported to yield to significant
amount of cyanide as result of nitrogen integration within the carbone
of graphite lattice [55]. This may explain the increased nitrogen contain
in the samples of prepared activated in the present work, seen in
Table 1 Textural parameters, CO2 adsorption capacity and chemical
composition of the obtained activated carbons., in agreement with data
reported by E. Fuente and al. [55].

3.2. CO2 capture investigation

The aforementioned procedure for the measurement of CO2 ad-

sorption at 25 °C, was adopted and permitted to obtain the curves
shown in Fig. 10, representing the variation of the adsorbed CO2
amount (mmol/g) as a function of CO2 pressure (bar). These curves
were used for the estimation of CO2 uptake capacity values gathered in
Table 1 Textural parameters, CO2 adsorption capacity and chemical
composition of the obtained activated carbons., for different prepared
active carbons samples along with their elemental composition de-
Fig. 10. CO2 uptake as a function of absolute pressure measured for the prepared acti- termined by EDX analysis. It is clearly noticed that KOH-activated
vated carbons at 25 °C and 1 bar. samples exhibited higher CO2 uptake capacities as compared with those
of samples activated with NaOH. The highest capacity was obtained
with ARG-K-Im followed by ARG-K-PM with values corresponding, re-
surface sites can be extracted through DFT calculations using the ae- spectively, to 5.63 and 5.51 mmol/g. It is worth while noting that, al-
fromentioned isotherms data. The use of Eq (1) allows determination of though ARG-K-Im shows comparable SBET to ARG-N-Im, the resulting
surface energy distribution for different activated carbons samples CO2 capture capacity is 1.5-fold higher. Even more interesting is that
prepared in this work, expressed as differential surface area (m2/g K) despite the larger SBET and micropores volumes obtained with ARG-K-

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O. Boujibar et al. Journal of Environmental Chemical Engineering 6 (2018) 1995–2002

Table 3
Kinetic parameters associated with different models fitted to CO2 adsorption data.

Sample Langmuir Freundlich Temkin

qm (mmol/g) KL (kPa−1) R2 KF (mmol/g) N R2 KT (kPa−1) Qm (kJ/mol) R2

ARG-K-PM 11.0249 0.009243 0.971 0.1543 1.2757 0.999 0.2451 1.5553 0.928
ARG-K-Im 9.2565 0.013697 0.976 0.2129 1.3900 0.998 0.2350 1.4541 0.953
ARG-N-PM 6.5542 0.010896 0.954 0.1256 1.3711 0.999 0.2444 2.3593 0.930
ARG-N-Im 6.8228 0.010730 0.967 0.1211 1.3381 0.999 0.2432 2.2863 0.934

qm: maximum monolayer capacity.

KL: Langmuir parameter related to the affinity of the binding sites.
KF: constant indicative of the adsorption capacity of the adsorbent.
n: empirical constant related to the magnitude of the adsorption driving force.
KT: Temkin constant related to equilibrium binding constant.
Qm: Temkin constant related to the heat of adsorption.
R: correlation coefficient.

PM as compared to ARG-K-Im, the latter enables higher CO2 capture per carbonization of Argan shells followed by chemical activation through
unit of mass. Therefore, textural properties of the prepared active car- wet impregnation or physical mixing using either KOH or NaOH.
bons do not appear to be the only parameters governing CO2 capture. Textural characteristics of the activated carbons; BET specific surface
This phenomenon can be attributed to a combination of appropriate area (SBET), pore volume (VT), pores sizes distribution (PSD) and surface
porosity and surface functions, in agreement with a recent study, energy distribution were determined using N2 (at 77 K) and CO2 (at
pointing out the crucial role of basic sites towards CO2 capture [56]. 273 K) isotherms. It was shown that both chemical agents employed in
Therfore, not only physical adsorption is involved but also chemical the activation process, enhance the surface area and porosity develop-
bonding, particularly, through interaction of CO2 molecules with sur- ment. The sample prepared via dry physical mixing with KOH beads
face functionalities containing N and O belongingto activated carbons yields to higher SBET reaching the value of 2250 m2/g. The PSD profile
[57,58]. Accordingly, and based on FTIR spectrum (Fig. 9)as well as revealed different types of microporosities for all the carbon materials,
EDX results given in Table 1, the higher CO2 uptake obtained with ARG- irrespective of their preparation route. Moreover, the existence of het-
K-Im sample seems to be partly associated with the presence of sig- erogeneous adsorption sites was also illustrated by surface energy dis-
nificant content of non-carbon elements, such as N and O within the tribution using DFT calculations. CO2 capture measurements (at 25 °C
carbon matrix [59]. and 1 bar), indicate interesting uptake capacities by the prepared active
The highest CO2 capture capacity value obtained with the active carbons. The interesting CO2 capture capacity value being 5.63 mmol/
carbon prepared in our work (i.e. ARG-K-Im) is presented in Table 2, for g, which is among the highest reported, so far, for biomass-derived
shake of comparaison with the most relevant values reported in the carbons. was attributed to a combination of large surface area, appro-
literature for several activated carbons prepared from different raw priate porosity and the presence of surface functionalities containing N
mterials, including some synthesized nitrogen-doped activated carbons. and O acting as basic sites. Hence, activated carbon obtained from this
Accordignly, the sample ARG-K-Im revealed promising potential, as abundant, and renewable agriculture-by product, may offer promissing
indicated by the up take value of 5.63 mmol/g, slightly lower than contribution to local economic value chain involving Argan shells,
7.3 mmol/g reported for activated carbon made from yellow mombin paving the way to potential application as precursor for CO2 capture.
fruit stones.
On the other hand, the CO2 adsorption isotherms obtained with the Acknowledgment
prepared activated carbons were fitted with Langmuir, Freundlich and
Temkin models [68]. Related adsorption parameters are summarised in This work was supported by the CNRST/Morocco program [Project
Table 3, and the correlation coefficients (R2) has been used to check the PPR2/CHAFIK/FSTTanger]
best fit accommodation. It was found that Freundlich model was con-
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