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J Mol Model (2017) 23:238
DOI 10.1007/s00894-017-3402-0
ORIGINAL PAPER
An evaluation of the reliability of the characterization
of the porous structure of activated carbons based on incomplete
nitrogen adsorption isotherms
Mirosaw Kwiatkowski 1 & Bassim H. Hameed 2
Received: 24 April 2017 / Accepted: 27 June 2017
# Springer-Verlag GmbH Germany 2017
Abstract The paper presents the results of research devoted
to reliability evaluation of the analysis of results of the porous
structure of activated carbons based on incomplete nitrogen
adsorption isotherms using the BET, t-plot, and NLDFT
methods, as well as the LBET method comprising the unique
numerical fast multivariant procedure of adsorption system
identification. The research involved the application of the
nitrogen adsorption isotherms obtained for five samples of
activated carbons produced from waste materials of organic
origin by way of chemical activation with potassium hydrox-
ide, sodium hydroxide, and potassium carbonate with the use
of microwave heating. The analyses performed pointed to a
good correlation between the results obtained using the BET,
t-plot, NLDFT, and LBET methods. Moreover, the parameters
of the porous structure determined using these methods based
on incomplete adsorption isotherms of nitrogen are in fact as
reliable as these methods allow.
Keywords Adsorption . Activated carbon . Characterization .
Microporous structure
* Mirosaw Kwiatkowski
kwiatkow@agh.edu.pl
Bassim H. Hameed
chbassim@usm.my
1
Faculty of Energy and Fuels, AGH University of Science and
Technology, al. A. Mickiewicza 30, 30-059 Krakow, Poland
2
School of Chemical Engineering, Engineering Campus, Universiti
Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
Introduction
A particular interest in the processes of chemical activation
has been observed in recent years in connection with new
areas of application of activated carbons, including the pres-
surized adsorption of natural gas as fuel for the engines of
motor vehicles. The processes of adsorption-based storage of
natural gas in carbonaceous adsorbent beds have been consid-
ered as an alternative to current methods of storage based on
high-pressure compression [13]. Particularly distinguishable
among the available adsorbents are microporous activated car-
bons, especially those obtained by way of activation of KOH,
as they definitely offer the best characteristics of natural gas
adsorption at moderate pressure and, as such, have been con-
sidered for practical use.
The use of carbonaceous adsorbents of very high quality is
also required in the process of hydrogen electrosorption in the
controlled electrolysis of water at ambient temperature and
atmospheric pressure [4]. Concluding from the research re-
sults obtained so far, the efficiency of energy storage by means
of the said method can exceed that offered by high-pressure or
cryogenic systems. However, a precondition of putting this
method of energy storage into practice is to use a material with
very large micropore capacity and good electrical conduction.
Since a dozen or so years ago, porous carbonaceous mate-
rials have been considered for use as electrodes in electro-
chemical condensers in which electric charge is stored on
the surface of a polarized carbon electrode [5, 6]. Work is
underway to use such systems to enhance the performance
of fuel cells in electrically powered vehicles. The high maxi-
mum power of electric current obtained from the condenser
allows for the effective compensation of temporary surges in
power drawn by the powertrain, which helps reduce power
reserves in the main power source. Carbons activated with
chemical compounds, characterized by large specific surface
238 Page 2 of 7
area and pore distribution adjusted to the given electrolyte,
may prove suitable for that purpose.
Even though the use of alkali metal hydroxides, including
KOH and NaOH, as the activating agents in the production of
activated carbons helps yield microporous materials of sub-
stantial pore uniformity, large adsorptive capacity, and large
specific surface area, alkali metal hydroxides are corrosive,
dangerous, and harmful to the environment [7, 8]. Therefore,
these compounds can be replaced with alkali metal carbon-
ates, such as K2CO3, which have proved themselves to be
very good substitutes for the said hydroxides [9, 10].
Considering the increasingly high requirements for carbo-
naceous adsorbents in connection with new fields of applica-
tion, and the demand for adsorption methods to compete with
other solutions, improvements in adsorbent production tech-
nology must be an ongoing process. Numerous modifications
of conventional methods of producing activated carbons by
chemical activation have been put forward in recent years,
with a particularly promising trend being the application of
microwave radiation for this purpose [1115].
Materials and methods
A series of previous publications has presented comprehen-
sive results of studies on preparing carbonaceous adsorbents
from waste biomass by microwave-assisted chemical activa-
tion [1620]. The research in question consisted of the pro-
duction of activated carbons obtained from coconut husk
(CHAC) by activation with potassium hydroxide KOH [16],
from jackfruit peel (JPAC) [17], from pomelo skin (PSAC)
[18] with sodium hydroxide NaOH as the activating agent,
as well as from orange peel (OPAC), citrus processing bio-
mass [19], and wood sawdust (WSAC) by activation with
potassium carbonate K2CO3 [20].
The porous structure of the resultant microporous activated
carbon was analyzed based on nitrogen adsorption isotherms
obtained at the temperature of 77.15 K. The specific surface
area was calculated using the Brunauer-Emmett-Teller (BET)
equation [21]. The total pore volume was estimated as the
liquid volume of nitrogen at a relative pressure of 0.98, while
the micropore volume and the micropore surface area were
predicted using the t-plot method [22]. The pore size distribu-
tion of the activated carbons was obtained using a method
based on non-local density functional theory (NLDFT)
[2325].
The nitrogen adsorption isotherms used as the basis for the
analysis of the porous structure of activated carbons obtained
during the chemical activation were determined in the range of
0.051 p/p0; consequently, part of the isotherm that covers the
range of micropores is missing [1620]. Therefore the ques-
tion arose, to what extent could this affect the reliability of the
results obtained using BET [21], t-plot [22] and NLDFT
J Mol Model (2017) 23:238
[2325] methods. In order to answer this question, we decided
to carry out a new series of studies devoted to assessing the
reliability of the results obtained regarding analysis of the
porous structure. The studies were based on nitrogen adsorp-
tion isotherms, i.e., those determined in the range from 0.05 to
1 p/p0.
In these calculations, the BET [21], t-plot [22] and NLDFT
[2325] methods were supplemented with the original LBET
method, including the new mathematical models of the mul-
tilayer adsorption on heterogeneous surfaces and the unique
numerical fast multivariant procedure of adsorption system
identification [2635]. The results obtained as part of this
research were compared with those obtained previously
[1620].
The LBET method is based on the original adsorption
models, which provide information on the porous structure
and capacity on the basis of the adsorption isotherms of small
molecules [2635]. The LBET class models involve five pa-
rameters: the volume of space accessible for the first adsorp-
tion layer VhA, the dimensionless parameter of the porous
structure that determines the height of clusters of molecules
of adsorbate (01). A value of = 0 means that only
individual molecules are present in pores of the analyzed ma-
terial. In turn, larger values of indicate that the clusters of
adsorbate molecules formed in the pores of the analyzed ma-
terial are of higher order proportionally to an increase in the
value of the parameter. Of the remaining parameters of the
LBET class models are: the average number of sites provided
by (n 1)th layer for the nth layer , the maximum value of
the adsorption energy on the first layer QAmax/RT and the
energy parameter for the layer above the first one BC [2635].
The LBET class models parameters can be adjusted by
fitting the theoretical adsorption isotherms to the empirical
adsorption data, with a chosen variant of the surface energy
distribution function [2635]. The values of the identifiability
index wid (01) indices offer some insight into the reliability
of adsorption systems identification. More specifically, they
provide information on the reliability with which the LBET
model variant selected by the fast multivariant procedure of
adsorption systems identification is the optimal variant, mean-
ing the one that describes the analyzed structure with maxi-
mum reliability; the closer the wid value is to 1, the better the
identifiability of the adsorption system.
Compared with other applied methods, the numerical pro-
cedure fitting the fast multivariant of the variants group of the
new LBET class models to the empirical adsorption is less
vulnerable to the absence of any information concerning the
initial part of the adsorption isotherm. This issue had to be
dealt with as part of this research, which was feasible owing
to, among other things, an analysis of the adsorption isotherm
in the whole range of relative pressures and the predictive
properties of the LBET method [2635], i.e., the possibility
to predict the missing fragment of the isotherm.
J Mol Model (2017) 23:238
In addition, the LBET method, which was used as part of
this research, takes into account surface heterogeneity and
different types of restrictions in forming the clusters of mole-
cules of the adsorbent. Also, it enables determination of the
shape of the adsorption energy distribution on the surface of
the test material, thus giving much more information on the
porous structure of activated carbons being analyzed along
with an assessment of how reliably they were determined
[2635].
Results and discussion
The results of analysis of adsorption of nitrogen isotherms on
activated carbons produced by way of chemical activation
using microwave heating are compiled in Table 1 and in
Figs. 1, 2 and 3. However, an interpretation of the results
should be preceded by an analysis of the factors that influence
reliability of the results obtained, including the value of the
individual parameters and the shape of distributions associated
with the missing part of the adsorption isotherm that is respon-
sible for the area of micropores and a relatively small number
of measuring points. In addition, it is recommended to deter-
mine which parameters have been obtained as most reliable in
order to use them subsequently to evaluate how reliable the
remaining information is.
The values of the specific surface SBET area calculated from
the BET equation [21] are characterized by substantial reliabil-
ity, since this equation is valid within the extent from 0.05 to
0.35 p/p0, so the relevant information can be obtained based
on adsorption isotherms determined for the activated carbons
subject to the analysis. Moreover, the BET equation is correct
when calculating the specific surface for the adsorbents where
pores with the size of the adsorbed molecules do not occur.
In the case of the analyzed activated carbons, the propor-
tion of mesopores is significant, as evidenced by the compar-
ison between the volume of micropores Vmicro, and the volume
of mesopores Vmeso, and the average pore size D (see Table 1).
Moreover, as can be seen in Fig. 2, featuring the pore size
distributions obtained via the NLDFT method for all the acti-
vated carbons subject to the analysis, there are no pores of a
size comparable to the size of the nitrogen molecule.
Considering the above, it can be assumed that the specific
surface areas SBET of the analyzed activated carbons were
calculated with a large dose of reliability. However, the ana-
lyzed activated carbons were characterized by surfaces having
significant and different heterogeneity degrees, as evidenced
by the use of LBET class models. The values of the total pore
volumes estimated as the liquid volume of nitrogen at a rela-
tive pressure of 0.98 were also determined with high accuracy.
Therefore, they can be used successfully as reference data and
to assess how reliable the other parameters are.
Page 3 of 7 238
The micropore volume Vmicro and micropore surface
area Smicro calculated using the t-plot method were also
determined with high reliability. This method assumes
that the micropores are already filled-up, while the ad-
sorption in larger pores occurs according to a certain sim-
ple equation, typical of a large class of adsorbents [22].
The t-plot method should approximate adsorption in
mesopores and macropores in a narrow pressure range just
above the whole filling of micropores but below vapour
condensation in mesopores [22]. This assumption may be
applicable if micropores are small and super-micropores
are not present, which is the case with all the activated
carbons subject to analysis here.
Certain doubts with regard to pore size distributions obtain-
ed for all activated carbons analyzed by means of NLDFT
arise is associated with the fact that the isotherms used in order
to determine the pore size distribution were not only those
outwith the initial range of 00.05 p/p0, but also those with a
relatively small number of measurement points. As a result,
the resolution of distributions determined is low, which is
shown clearly in Fig. 2.
Moreover, the NLDFT method is based on a model of
independent slit-shaped pores with ideal graphitic walls, and
is recommended rather for characterization of ordered silica
materials [2325] due to the fact that the NLDFT model has a
significant drawback in the case of the analysis of carbon
materials with heterogeneous surfaces. More specifically, the
layering steps on the theoretical adsorption isotherms result in
artificial gaps in pore size distributions [2325]. This problem
is especially evident in the case of activated carbon adsorbents
with a broad pore size distribution.
In the case of the activated carbons analyzed here, no sig-
nificant artefacts in the diagrams of pore volume distributions
in the function of their diameter were observed (see Fig. 2),
and very broad pore size distributions were not present. This
implies that the said distributions can be considered accept-
able if approached as a certain representation of reality.
However, it must be borne in mind that the NLDFT method
in its original version assumes that the surface is homoge-
neous, while the surfaces of the analyzed activated carbons
are largely heterogeneous, as evidenced using the LBET
method.
Based on the values of the fitting error dispersion e for all
the analyzed adsorption systems presented in Table 1, it can be
concluded that the errors in the fitting of theoretical LBET
class models to the adsorption isotherms obtained for the an-
alyzed materials may be deemed negligible owing to, among
other things, reliable determination of the adsorption iso-
therms of nitrogen on all activated carbons, and the correspon-
dence between the assumptions for LBET class models re-
garding microporous structure and the processes taking place
on the surface of materials on the one hand, and the actual
conditions on the other hand.
238 Page 4 of 7 J Mol Model (2017) 23:238

Table 1 Parameters obtained

from the isotherms of N2 Active carbon CHAC [16] JPAC [17] PSAC [18] OPAC [19] WSAC [20]
adsorption on the analyzed Raw material Coconut husk Jackfruit peel Pomelo skin Orange peel Wood sawdust
activated carbons using the Activator KOH NaOH NaOH K2CO3 K2CO3
Brunauer-Emmett-Teller (BET)
equation, the t-PLOT, density SBET (m2/g) 1356.25 1286.70 1335 1104.45 1496.05
functional theory (DFT), and the Smicro (m2/g) 725.77 656.95 524 420.09 892.79
LBET methods Vmicro (m2/g) 0.392 0.356 0.29 0.247 0.470
Vmeso (m2/g) 0.388 0.408 0.48 0.368 0.394
D (nm) 2.297 2.375 2.309 2.227 2.306
LBET No. 30 7 11 12 11
QAmax/RT 7.73 5.07 4.69 6.44 5.71
BC 2.97 4.04 2.93 4.03 3.73
h 9 5 7 7 7
VhA (cm3/g) 0.647 0.624 0.653 0.544 0.705
0.16 0.14 0.10 0.06 0.13
2.00 2.00 1.61 2.00 1.89
e 0.1 0.19 0.19 0.09 0.17
wid 0.78 0.61 0.63 0.83 0.75

All in all, the fitting error dispersion values are insignificant
and have no effect whatsoever on the yielded parameters of
the microporous structure. Furthermore, as can be observed in
Table 1, the values of width for all the analyzed adsorption
systems are higher than 0.6, showing that the adsorption sys-
tems are identified with substantial reliability.
Based on the results of nitrogen adsorption isotherm anal-
yses compiled in Table 1 and presented in Figs. 1, 2 and 3, it
can be concluded that the activated carbon CHAC [16] is
characterized by a micro-mesoporous structure, as evidenced
by the obtained values of the specific surface area SBET, the
specific surface of micropores Smicro, and the volumes of mi-
cropores Vmicro and mesopores Vmeso, which are evidently
comparable. Moreover, the shape of the adsorption isotherm
(Fig. 1) and the average size of the pores, as well as the shape
of the pore size distribution, determined using the NLDFT
method (Fig. 2) confirm the above conclusion. However, it
is surprising to see that micropore volume is not taken into
30
account in the pore size distribution diagram (Fig. 2). On the
other hand, the analyses carried out using the LBET method
pointed out that the surface of the activated carbon CHAC is
strongly heterogeneous, as evidenced by the value of the pa-
rameter (h = 9). The number of the best-fitted LBET model,
namely 30, points to adsorption type two according to the
LBET theory, i.e., the process where limitations to adsorbate
molecule cluster growth are mostly geometrical in character;
the limited size of micropores impedes the expansion of ad-
sorbate molecule clusters [2635]. The volume of the first
adsorbed layer is VhA = 0.647 cm3/g, which, compared to
the micropore volume Vmicro = 0.392 cm3/g, shows that the
first adsorbed layer is also formed in the area of mesopores.
The adsorption energy distribution diagram (Fig. 3) points to a
very broad spectrum of adsorption energy on the surface of the
analyzed material, which supports the earlier conclusions.
Also, the value of the dimensionless parameter of the maxi-
mum adsorption energy QAmax/RT = 7.73 points to a strong
interaction between the adsorbate molecules and the surface of

25 0.02
OPAC
JPAC
20
m (mmol/g)

WSAC
dV(w)/dw (cm /nm/g)

CHAC
15 PSAC
3

OPAC/LBET 12
a

0.01
10 JPAC/LBET 7
WSAC/LBET 11
5 CHAC/LBET 30
PSAC/LBET 11
0
0 0.2 0.4 0.6 0.8 1
p/p0 0
0 1 2 3 4 5
Fig. 1 Nitrogen adsorption isotherms obtained for all activated carbons w (nm)
subject to analysis [1620], and numbers of the best-fit theoretical LBET Fig. 2 Pore size distribution obtained using the non-local density func-
class models tional theory (NLDFT) method
J Mol Model (2017) 23:238
1.2
OPAC
1 JPAC
WSAC
0.8 CHAC
f(QA/RT)
PSAC
0.6
0.4
0.2
0
8 6 4 2 0 2 4 the expansion of the neighboring clusters of adsorbate mole-
Q /RT
A cules, and not from the limited size of micropores, as was the
Fig. 3 Adsorption energy distributions on the first layer obtained using
the LBET method
the adsorbent, while the adsorption energy for the layers n > 1
as defined by the dimensionless parameter BC has a relatively
smaller value, which provides favorable conditions for the
placement of adsorbate molecules directly on the surface of
the material at the expense of the creation and expansion of
adsorbate molecule clusters. The values of the geometrical
parameters = 0.16 and = 2.00 testify that very low and
branched clusters of adsorbate molecules are formed in the
micropores, i.e., one molecule on the n layer attracts more than
molecule of the n + 1 layer.
Another activated carbon analyzed JPAC, produced from
jackfruit peel by activation with NaOH using microwave
heating [17], is characterized by an insignificantly higher pro-
portion of the mesoporous structures in the total porosity, as
evidenced by the values of the following parameters: the mi-
cropore surface Smicro = 656.95 m2/g, the specific surface area
SBET = 1286.70 m2/g, the micropore volume
V m i c r o = 0.356 cm 3 /g, and the mesopore volume
Vmeso = 0.408 cm3/g; the average pore size determined using
the NLDFT method is D = 2.375 nm. As can be seen in Fig. 2,
the shape of the pore size distribution in the function of pore
size is similar to the corresponding shape for the activated
carbon CHAC discussed above.
The results of the analyses carried out using the BET, the t-
plot, and the NLDFT methods suggest that the activated car-
bons CHAC and JPAC have evidently very similar adsorptive
properties. However, only upon an accurate analysis carried
out using the LBET method was it revealed that the activated
carbon JPAC is characterized by an evidently lower maximal
energy of adsorption on the first layer QAmax/RT = 5.07 com-
pared with the above sample of CHAC and by higher adsorp-
tion energy for the layers n > 1 (BC = 4.04). This points to the
occurrence of less powerful adsorptive interactions between
the adsorbate molecules and the surface of the activated car-
bon JPAC, as well as to stronger adsorptive interactions in the
layers n > 1 compared with the activated carbon CHAC.
Moreover, the surface of the sample of the activated carbon
JPAC is characterized by less heterogeneity compared with
the sample of the activated carbon CHAC, as evidenced by
Page 5 of 7 238
the value of the parameter h = 5. Equally noteworthy are the
insignificantly lower values of the parameter VhA, i.e., the
volume of the first adsorbed layer (VhA = 0.624 cm3/g), and
the adsorbate molecule cluster height parameter ( = 0.14).
Based on the number of the best-fitted LBET class model,
namely no. 7, it can be concluded that the limitations to the
growth of the particular adsorbate molecule clusters result
from competitive adsorption, i.e., from the favorable condi-
tions for the adsorption of individual adsorbate molecules and
case with the activated carbon CHAC.
The diagram of the adsorption energy distribution on the
first layer (Fig. 3) shows explicitly that the surface of the
activated carbon JPAC is characterized by a narrow spectrum
of adsorption energy. Consequently, in terms of energy, the
said adsorbent is the most homogeneous of all the activated
carbons subject to analysis. As was pointed out above, the
surface of the activated carbon CHAC is characterized by
the broadest spectrum of first-layer adsorption energy of all
the analyzed samples, showing that the surface of this adsor-
bent is the most heterogeneous in terms of energy.
The analysis of another isotherm of adsorption on the acti-
vated carbon PSAC, produced from pomelo skin by way of
chemical activation with NaOH using microwave radiation
[18], pointed to a higher proportion of mesopores compared
with the structures of the activated carbons CHAC and JPAC
discussed above, as evidenced by the lower values of micro-
pore surface and volume (S m i c r o = 524 m 2 /g and
Vmicro = 0.29 cm3/g) and the higher value of mesopore volume
(Vmeso = 0.48 cm3/g). Based on the analyses carried out using
the LBET method, it was concluded that the surface of the
analyzed sample of activated carbon is heterogeneous (h = 7),
while adsorbate cluster growth was impeded by competitive
adsorption and the expansion of neighbouring clusters.
The values of the maximal energy of adsorption on the first
adsorbed layer and the successive layers were the lowest of all
in the analyzed samples (QAmax/RT = 4.69 and BC = 2.93).
This information permits a conclusion that the case of the
activated carbon PSAC was characterized by less favorable
conditions for adsorbate molecule adsorption and adsorbate
molecule cluster expansion compared with the activated car-
bons discussed above, as confirmed by the values of the geo-
metrical parameters and ( = 0.10 and = 1.61).
Another adsorption isotherm subject to the analysis was the
isotherm defined for the sample of the activated carbon OPAC
produced from orange peel by way of activation with K2CO3
[19]. As can be concluded from the data presented in Table 1,
the material in questionsimilar to the activated carbons
discussed aboveis characterized by micro-mesoporous
structure (see Table 1). However, particularly noteworthy is
the shape of the pore size distribution diagram (Fig. 2) laid out
using the NLDFT method; more specifically, a substantial
238 Page 6 of 7
proportion of micropore volume is noticeable. On the other
hand, the results obtained with the use of the LBET class
models permit the conclusion that the surface of the analyzed
activated carbon OPAC is heterogeneous, as evidenced by the
value of the parameter h = 7, and that exceptionally low ad-
sorbate molecule clusters are formed inside its micropores
( = 0.06). The volume of the first adsorbed layer VhA is the
lowest of all in the activated carbons subject to the analysis
(VhA = 0.544 cm3/g). As can observed in Fig. 3, the activated
carbon OPAC is characterized by a broad spectrum of the
energy of adsorption on the first adsorbed layer.
The last analyzed isotherm of nitrogen adsorption was that
obtained for the activated carbon WSAC produced from wood
sawdust by activation with K2CO3 using microwave radiation
[20]. Based on the results of the analyses compiled in Table 1
and presented in Figs. 1, 2 and 3, it can be concluded that the
material in question is micro-mesoporous and that micropores
prevail in the total specific surface area and pore volume, as
evidenced by the values of the parameters (Smicro, SBET, Vmicro
and Vmeso).
Based on the analyses carried out using the LBET class
models, it was observed that the surface of the activated car-
bon WSAC is strongly heterogeneous (h = 7), while adsorbate
molecules that adsorb in its micropores form low and
branched clusters ( = 0.13 and = 1.89). Particularly note-
worthy is the highest volume of the first adsorbed layer,
VhA = 0.705 cm3/g, compared with other analyzed materials.
Conclusions
As can be concluded from the analyses conducted, the param-
eters of the porous structure determined using the BET, t-plot,
and NLDFT methods based on incomplete adsorption iso-
therms of nitrogen are in fact reliable as much as these
methods themselves allow. However, this means that the lim-
itations of these methods resulting directly from their theoret-
ical basis and assumptions should be taken into account. The
analyses also point to a strong correlation between the results
obtained using the BET, t-plot, NLDFT, and LBET methods.
Still, one should remember that the BET, t-PLOT, and NLDFT
methods provide only an approximate and greatly simplified
picture of the porous structure and the adsorptive properties of
the material. This is particularly due to the intrinsic limitations
of these methods and the adoption of unrealistic assumptions,
including the assumption of surface homogeneity. In the case
of simple analyses, the information on pore structure obtained
by means of the BET, t-plot, and NLDFT methods is often
sufficient, yet the processes that consist of the optimization of
the technology of producing activated carbons that require
specific surface properties call for accurate and comprehen-
sive information obtained, e.g., by other advanced methods.
J Mol Model (2017) 23:238
Being the most advanced of all the methods of analysis of
the porous structure used as part of this research, having solid
theoretical foundations, and, most importantly, offering a spe-
cific physical interpretation of each parameter of the LBET
class models, the LBET method provides the greatest range of
reliable information concerning the analyzed pore structure.
Acknowledgments The research is led within the AGH University of
Science and Technology in Krakow grant No. 11.11.210.373.
References
1. Modzik J, Srescek-Nazzal J, Narkiewicz U, Morawski AW,
Wrbel RJ, Michalkiewicz B (2016) Activated carbons from mo-
lasses as CO2 sorbents. Acta Phys Pol A 129:402404
2. Policicchio A, Maccallini E, Agostino RG, Ciuchi F, Aloise A,
Giordano G (2013) Higher methane storage at low pressure and
room temperature in new easily scalable large-scale production ac-
tivated carbon for static and vehicular applications. Fuel 104:813
821
3. Antoniou MK, Diamanti EK, Enotiadis A, Policicchio A, Dimos K,
Ciuchi F, Maccallini E, Gournis D, Agostino RG (2014) Methane
storage in zeolite-like carbon materials. Micropor Mesopor Mater
188:1622
4. Jurewicz K, Frackowiak E, Bguin F (2001) Enhancement of re-
versible hydrogen capacity into activated carbon through water
electrolysis. Electrochem Solid State Lett 4:2729
5. Kierzek K, Frackowiak E, Lota G, Gryglewicz G, Machnikowski J
(2004) Electrochemical capacitors based on highly porous carbons
prepared by KOH activation. Electrochim Acta 49:515523
6. Gryglewicz G, Machnikowski J, Lorenc-Grabowska E, Lota G,
Frackowiak E (2005) Effect of pore size distribution of coal-based
activated carbons on double layer capacitance. Electrochim Acta
50:11971206
7. Srescek-Nazzal J, Michalkiewicz B (2011) The simplex optimiza-
tion for high porous carbons preparation. Polish J Chem Technol
13:6370
8. Srescek-Nazzal J, Kamiska W, Michakiewicz B, Koren ZC
(2013) Production, characterization and methane storage potential
of KOH-activated carbon from sugarcane molasses. Ind Crop Prod
47:153159
9. Hayashi J, Horikawa T, Takeda I, Muroyama K, Ani FN (2002)
Preparing activated carbon from various nutshells by chemical ac-
tivation with K2CO3. Carbon 40:23812386
10. Kwiatkowski M, Broniek E (2013) Application of the LBET class
adsorption models to the analysis of microporous structure of the
active carbons produced from biomass by chemical activation with
the use of potassium carbonate. Colloids Surf A Physicochem Eng
Asp 427:4752
11. Yang K, Peng J, Srinivasakannan C, Zhang L, Xia H, Duan X
(2010) Preparation of high surface area activated carbon from co-
conut shells using microwave heating. Bioresour Technol 101:
61636169
12. Deng H, Li GX, Yang HB, Tang JP, Tang JY (2010) Preparation of
activated carbons from cotton stalk by microwave assisted KOH
and K2CO3 activation. Chem Eng J 163:373381
13. Zhang ZY, Qu WW, Peng JH, Zhang LB, Ma XY, Zhang ZB, Li W
(2009) Comparison between microwave and conventional thermal
reactivations of spent activated carbon generated from vinyl acetate
synthesis. Desalination 249:247252
J Mol Model (2017) 23:238
14. Wang TH, Tan SX, Liang CH (2009) Preparation and characteriza-
tion of activated carbon from wood via microwave-induced ZnCl2
activation. Carbon 47:18671885
15. Yagmur E, Ozmak M, Aktas Z (2008) A novel method for produc-
tion of activated carbon from waste tea by chemical activation with
microwave energy. Fuel 87:32783285
16. Yuen FK, Hameed BH (2012) Coconut husk derived activated car-
bon via microwave induced activation: effects of activation agents,
preparation parameters and adsorption performance. Chem Eng J
184:5765
17. Foo KY, Hameed BH (2012) Potential of jackfruit peel as precursor
for activated carbon prepared by microwave induced NaOH activa-
tion. Bioresour Technol 112:143150
18. Foo KY, Hameed BH (2011) Microwave assisted preparation of
activated carbon from pomelo skin for the removal of anionic and
cationic dyes. Chem Eng J 173:385390
19. Foo KY, Hameed BH (2012) Preparation, characterization and eval-
uation of adsorptive properties of orange peel based activated car-
bon via microwave induced K2CO3 activation. Bioresour Technol
104:679686
20. Foo KY, Hameed BH (2012) Mesoporous activated carbon from
wood sawdust by K2CO3 activation using microwave heating.
Bioresour Technol 111:425432
21. Brunauer S, Emmett PH, Teller E (1938) Adsorption of gases in
multimolecular layers. J Am Chem Soc 60:309319
22. Storck S, Bretinger H, Maier WF (1998) Characterization of micro-
and mesoporous solids by physisorption methods and pore-size
analysis. Appl Catal A Gen 174:137146
23. Seaton NA, Walton JPRB, Quirke N (1989) A new analysis method
for the determination of the pore size distribution of porous carbons
from nitrogen adsorption measurements. Carbon 27:853861
24. Lastoskie C, Gubbins KE, Quirke N (1993) Pore size heterogeneity
and the carbon slit pore: a density functional theory model.
Langmuir 9:26932702
25. Ravikovitch PI, Neimark AV (2006) Density functional theory
model of adsorption on amorphous and microporous silica mate-
rials. Langmuir 22:1117111179
26. Duda JT, Kwiatkowski M, Milewska-Duda J (2005) Computer
modeling and analysis of heterogeneous structures of microporous
carbonaceous materials. J Mol Model 11:416430
View publication stats
Page 7 of 7 238
27. Kwiatkowski M (2007) Computer analysis of microporous struc-
ture by employing the LBET class models with various variants of
the adsorption energy distribution in comparison to the classical
equations. Langmuir 23:25692581
28. Kwiatkowski M (2008) Computer analyses of new numerical
methods for the description of adsorption process and the reliability
of identification of microporous structure parameters. J Mol Model
14:183200
29. Kwiatkowski M (2008) Application of fast multivariant identifica-
tion technique of adsorption systems to analyze influence of pro-
duction process conditions on obtained microporous structure pa-
rameters of carbonaceous adsorbents. Micropor Mesopor Mater
115:314331
30. Kwiatkowski M (2009) Use of fast multivariant identification of the
parameters of adsorption systems to study the impact of activating
agent on microporous structure formation during activation. J
Colloid Interface Sci 340:17
31. Kwiatkowski M (2011) Analysis of relative pressure range influ-
ence on the identification quality during computer identification of
adsorption system parameters by employing the new multilayer
adsorption models. Appl Surf Sci 257:89128922
32. Kwiatkowski M, Policicchio A, Seredych M, Bandosz TJ (2016)
Evaluation of CO2 interactions with S-doped nanoporous carbon
and its composites with a reduced GO: effect of surface features
on an apparent physical adsorption mechanism. Carbon 98:250
258
33. Kwiatkowski M, Kalderis D, Diamadopoulos E (2017) Numerical
analysis of the influence of the impregnation ratio on the micropo-
rous structure formation of activated carbons, prepared by chemical
activation of waste biomass with phosphoric acid. J Phys Chem
Solids 105:8185
34. Kwiatkowski M, Fierro V, Celzard A (2017) Numerical studies of
the effects of process conditions on the development of the porous
structure of adsorbents prepared by chemical activation of lignin
with alkali hydroxides J Colloid Interface Sci 486:277286
35. Kwiatkowski M, Srescek-Nazzal J, Michalkiewicz B (2017) An
analysis of the effect of the additional activation process on the
formation of the porous structure and pore size distribution of the
commercial activated carbon WG-12. Adsorption 23:551561