ChemBioEng Reviews - 2019 - BL Ker - Characterization of Activated Carbon Adsorbents State of The Art and Novel

Characterization of Activated Carbon Adsorbents –
State of the Art and Novel Approaches

Christian Bläker[1],*, Johanna Muthmann[1], Christoph Pasel[1], Dieter Bathen[1,2]
Abstract
Activated carbons are widely used as commercial probe molecule method was developed. For charac-
adsorbents. Thermal or chemical activation creates terization of surface chemistry, methods such as IR
a pore system and functional groups on the inner spectroscopy, temperature-programmed desorption,
surface which may significantly change adsorption and Boehm titration are subject of research. Novel
properties. Therefore, in addition to knowledge of methods were developed such as measuring of
the structural properties, a sound understanding of excess isotherms and calorimetric measurement of
surface chemistry is indispensable. This paper sum- heat of adsorption, which are presented and dis-
marizes the state of art as well as new developments cussed in greater detail in this paper. As each single
in both fields. Standardized methods for character- method can only provide limited information, a
izing structural properties are volumetric measure- better description of surface chemistry requires
ments and mercury porosimetry. To get a more combination and careful interpretation of comple-
detailed insight into the region of micropores, a mentary information from different methods.
Keywords: Activated carbon, Adsorptive properties, Characterization methods, Structural properties, Surface chemistry
Received: March 28, 2019; revised: June 28, 2019; accepted: July 02, 2019
DOI: 10.1002/cben.201900008
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium,
provided the original work is properly cited.
1 Introduction smaller the sample, the larger is the impact of material hetero-
geneity. To obtain representative activated carbon samples
Activated carbons are non-transparent porous materials. from a bulk, a sample divider should be used. Anyway, replicate
Fundamental knowledge of their adsorption properties is measurements are highly recommended to verify the results.
essential for designing technical adsorption processes as well as Most measurement methods require careful sample prepara-
for scientific research on adsorption. Today, a variety of stand- tion by heating under well-defined conditions to remove
ards and standardized methods is available to determine physi- adsorbed humidity and other gases.
cal, physical-chemical, surface-chemical, structural, and ad-
sorptive properties.
Development and application of characterization methods for 2.1 Physical and Physico-Chemical Properties
carbonaceous adsorbents is a large field of research. While for
chemically synthesized adsorbents many structural and chemical The characterization of physical and physico-chemical proper-
properties are known and controlled by the synthesis method, ties of activated carbons has been standardized by the Ameri-
activated carbons differ considerably due to heterogeneity of the can Society for Testing and Materials (ASTM). The standards
raw materials and different activation processes [1, 2]. are summarized in Tab. 1.
In the first part of this paper, an overview of established and
standardized methods is given and related assumptions and
limits of application are discussed. In the second part, the view —————
is extended to novel methods to describe pore structure and [1]
Dr.-Ing. Christian Bläker (corresponding author), Johanna Muth-
surface chemistry in greater detail. mann, Dr. Christoph Pasel, Prof. Dr.-Ing. Dieter Bathen
University of Duisburg-Essen, Chair of Thermal Process Engineer-
ing, Lotharstrasse 1, 47057 Duisburg, Germany.
2 Characterization of Activated Carbons E-Mail: Christian.blaeker@uni-due.de
[2]
Prof. Dr.-Ing. Dieter Bathen
The experimental accuracy of activated carbon characterization Institute of Energy and Environmental Technology IUTA e.V.,
mainly depends on sampling and sample preparation. The Bliersheimer Strasse 60, 47229 Duisburg, Germany.
www.ChemBioEngRev.de ª 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA ChemBioEng Rev 2019, 6, No. 4, 119–138 119
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Table 1. Standards for characterization of physical and physico- the micropores, mesopores, and macropores ranging up to
chemical properties of activated carbons. 400 nm by a single measurement proves to be particularly
advantageous [9].
Property Standard Limitation While the volumetric measuring instruments for the record-
Apparent density ASTM D 2854-09 ing of gas adsorption isotherms are technically mature, inter-
pretation of the measured data is still subject of current
Total ash content ASTM D 2866-11 research [7, 10, 11].
Moisture ASTM D 2867-17 Some qualitative information about the pore size distribution
is already available from the shape of the adsorption isotherm.
Ball-pan hardness ASTM D 3802-16 Depending on the pore structure of the adsorbent and the
pH-value ASTM D 3838-05 influence of adsorpt-adsorpt interactions, different isotherm
shapes can occur in physisorptive processes. The isotherm
Electrical conductivity ASTM D 1125-14 shapes and the shapes of possible hysteresis loops were classi-
Water soluble components ASTM D 5029-98 fied into six types by the International Union of Pure and
Applied Chemistry (IUPAC) in 1985 [12]. To date, however,
Volatile matter content ASTM D 5832-98
other characteristic isotherm shapes have been identified, fur-
Acid extractable content ASTM D 6385-99 ther refining the original IUPAC classification [13]. The
updated classification of isotherm shapes is shown in Fig. 1.
Particle size distribution ASTM D 2862-16 granular activated
carbon
ASTM D 5158-98 powdered activated

carbon
Ignition temperature ASTM D 3466-06 granular activated

carbon
Dusting attrition ASTM D 5159-04 granular activated

carbon
2.2 Structural Properties
On the structural properties side, the inner surface, the total

pore volume, the micro- and mesopore volume as well as the
pore size distribution are of particular interest. While the
pore size determines whether adsorptive molecules can pene-
trate into the pore system and adsorb there, the size of the
surface and the pore volume influence the maximum number
of molecules that can adsorb. Since the structural properties
of activated carbons cannot be investigated by optical meas-
urement methods, information on pore structure must be
obtained by indirect measurement methods and simplifying
model concepts.
In most cases, the structural properties of activated carbons
are determined by volumetric measurements and mercury po-
rosimetry measurements. In addition, the probe molecule
method can be used to determine the pore size distribution.
2.2.1 Volumetric Characterization
In the characterization of nanoporous structures by volumetric

gas adsorption, isothermal adsorption equilibria of an unpolar
or weakly polar gas on the adsorbent are investigated. For the Figure 1. Classification of isotherm shapes [13].
analysis mainly nitrogen (N2) at 77 K, argon (Ar) at 77 or 87 K,
krypton (Kr) at 77 K, or carbon dioxide (CO2) at 273 or 298 K Isotherms of Typ I (a) occur in microporous adsorbents with
are used. Several authors compare the effects arising from dif- mostly narrow micropores (diameter <1 nm). As a result of
ferent size and chemical nature of the gases [3–8]. strong adsorpt-adsorbent interactions in small micropores an
Besides the economic efficiency and the high degree of auto- almost linear slope occurs in the lowest partial pressure range.
mation of this method, the possibility to completely capture After complete filling of the micropores a plateau is reached,
which can be interpreted as the maximum load. In contrast Several theories exist to account for hysteresis loops. On the
Type I (b) isotherms are to be found for adsorbents with a one hand, smaller menisci may occur during desorption due to
broader pore size distribution including wide micropores and occupied pore walls [15]. On the other hand, network effects
potentially narrow mesopores (diameter< 2.5 nm). and forms of pore blocking are discussed [14, 15]. Another
Isotherms of Type II result from physisorption of gases on effect proposed for cylindrical open-ended pores is the meta-
non- or mesoporous adsorbents. A sharp bend at point B indi- stability of an adsorbed multilayer and the hindered nucleation
cates the formation of a complete monolayer. With increasing of liquid bridges, which results in delayed condensation
relative pressure multilayer adsorption in mesopores and mac- [14, 16]. In such pores the adsorption branch is not in thermo-
ropores as well as on the outer surface results in an increasing dynamic equilibrium. Hysteresis of type H1 (Fig. 2) can be seen
isotherm slope. On multilayer adsorption the strength of for adsorbents with uniform mesopores in a narrow pore size
adsorpt-adsorbent interactions drops with increasing number area and is mostly attributed to delayed condensation [13]. H2
of layers formed, so that at high layer thicknesses adsorpt- hysteresis results from porous structures in which network
adsorpt interactions dominate. effects affect desorption.An example is the bottleneck effect.
Formation of Type III and V isotherms appears if the inter- The wide body of the bottle remains filled until the narrower
action between adsorpt and adsorbent is very weak. Because necks are emptied. If the radius of the bottlenecks is smaller
adsorpt-adsorpt interactions dominate, creation of clusters at than the adsorptive- and temperature-specific critical radius,
the energetically most favorable adsorption sites occurs [14]. desorption takes place through cavity formation or spontane-
While Type-III isotherms are formed on non- or macroporous ous formation of bubbles in the pore. The bottleneck remains
adsorbents, Type V isotherms are characteristic for mesoporous filled while the bottle body empties. Pores with a larger radius
adsorbents. These isotherms develop a hysteresis between the are subject of pore blocking. A steep desorption curve (H2 (a)),
adsorption and desorption branch due to capillary condensa- results from bottlenecks with a narrow pore size distribution.
tion. The adsorption branch shows that the bottle bodies have differ-
Isotherms of Type IV show a hysteresis as a result of capil- ent radii. H2 (b) hysteresis, on the other hand, indicates a
lary condensation which indicates the existence of mesopores. broader pore size distribution of the bottlenecks. In case of
The marked slope at low relative pressures denotes additional hysteresis of type H3, which shows no limitation of adsorption
micropores. In comparison to Typ IV(a), isotherms of Type at high relative pressures, the adsorption branch is based on a
IV(b) possess no hysteresis, because the radius of the meso- type II isotherm. It occurs in slit-shaped pore systems [13]. The
pores is smaller than the critical radius for the occurrence of a adsorption branch of H4 hysteresis is based on type I and II
hysteresis. The critical radius depends on the adsorptive and isotherms. Compared to type H3, H4 hysteresis has a more
the temperature. Type VI isotherms are indicative of multilayer pronounced increase in the range of low relative pressures due
adsorption on a uniform surface, where individual layers to the micropore filling. Due to the lower proportion of meso-
strictly develop one after another. pores, H4 hysteresis is more horizontal than an H3 hysteresis.
The hysteresis loops of type IV (a) and type V isotherms can The shape of type H5 hysteresis results from a combination of
exhibit different forms. While the IUPAC classifications from blocked pores, as in H2 hysteresis, and open pores. Therefore,
1985 makes a distinction between four shapes of hysteresis H5 hysteresis features two stages in the desorption branch. The
loops, currently 6 main types are distinguished (Fig. 2) [13]. types H3, H4, and H5 show a steep decrease in the desorption
branch due to cavitation in pores with
necks below the critical radius.
In addition to the qualitative discus-
sion of pore structure using the shape
of isotherms and hysteresis loops,
structural properties can also be de-
scribed quantitatively. For this purpose,
equilibrium data are evaluated using
physical structure models. Simplifying
assumptions are made, e.g., about the
geometry of the pores and the adsorp-
tive molecules or the type of interaction
with the surface and between the
adsorbate molecules. In the following,
the most important physical models for
determining the structural properties
(Tab. 2) are presented and discussed.
2.2.1.1 BET Method
The specific surface area, which is

Figure 2. Classification of the shapes of hysteresis loops [13]. the most frequently used structural
Table 2. Evaluation methods of volumetric measurements to determine structural properties.
Method Structural properties Type of isotherm
BET Method Specific surface area SBET (I), II, IV
Gurvich Rule Pore volume VP all
DR-Plot, DA-plot Micropore volume Vmicro I
t-Plot, aS-plot Specific surface area S, micropore volume Vmicro I, II, IV
BJH Method Mesopore volume Vmeso, mesopore surface Ameso, mesopore distribution peak dmeso IV (a) with hysteresis
H1, H2 (a), H2 (b) and H5
HK-Plot Pore size distribution of micropores I
NLDFT and GCMC method Pore size distribution all
property in the comparison of adsorbents, can be determined regard to the range of application is the BET constant C. Since
using the BET method developed by Brunauer, Emmett, and in many cases the adsorption enthalpy EAds is larger than the
Teller according to DIN ISO 9277 [17, 18]. Inert probe mole- evaporation enthalpy EV, the BET constant C can be calculated
cules should be used which predominantly form dispersion using the ideal gas constant R and the temperature T, must
interactions with the adsorbent surface. In this case, it can be have a positive value:
assumed that the specific surface of the adsorptive molecule is
approximately identical on different adsorbents. The BET EAds EV
C ¼ exp (3)
equation describes the volumetrically determined load RT
VA [cm3(STP) g–1] as a function of the relative pressure p/p0,
the BET constant C and the monolayer volume Vm. The BET The most reliable evaluation of the BET method is obtained
equation is based on the assumption that all binding sites on from type II or IV adsorption isotherms which are dominated
the adsorbent surface are energetically equal, freely accessible, by meso- and macropores [9, 19].
and can only be occupied by one molecule at a time. In addi- Caution should be exercised when interpreting type I iso-
tion, the classical BET equation assumes that an infinite num- therms or composite isotherms (i.e., combinations of I and II
ber of adsorbate layers can form. To calculate the BET surface or I and IV). In type I isotherms, the presence of micropores
area SBET, the classical BET equation is linearized: significantly shifts the linear BET range to lower relative pres-
p p
sures as the monolayer is completed at lower pressures. In
1 ðC 1Þ order to apply the BET method also to microporous adsorbents
p0 ¼ þ
p0
(1) with type I isotherms, Rouquerol et al. [20] suggested a proce-
p Vm C Vm C
VA 1 dure that is based on two criteria. The BET constant C must
p0
have a positive value and the application of the BET equation
When the isotherm is transferred to the BET diagram, must be limited to the range where the term VA(1–p/p0) contin-
(p/p0)/[VA(1–p/p0)] is plotted versus the relative pressure p/p0. uously increases with p/p0. Due to the deviations from the
For type II and type IV isotherms, a linear regression line is above-mentioned assumptions of the BET method, the deter-
drawn in the relative pressure range from 0.05 to 0.3–0.35. The mined specific surface area of microporous adsorbents does
BET constant C and the monolayer volume Vm are determined not represent a ‘‘true’’ surface area but has the character of a
from the slope (C–1)/(VmC) and the y-axis intersection ‘‘characteristic or equivalent BET surface’’. Since the linearity
1/(VmC). Then SBET can be calculated using the molar standard range depends on the adsorbent, the selected linearity range
volume VN, Avogadro’s constant NA and the specific surface should always be documented in this evaluation.
area of the adsorptive molecule A: Despite the limitation regarding the characterization of
microporous materials, the BET method is still most com-
Vm monly used to determine the specific inner surface area.
SBET ¼ N A (2)
VN A
The selected relative pressure range between 0.05 and 0.3– 2.2.1.2 Gurvich Rule
0.35 results from the underlying assumptions. Below a relative
pressure of 0.05, mainly micropores are filled, whereby mono- The Gurvich rule can be used to calculate the total pore volume
and multilayer adsorption can be superimposed by the micro- VP of an adsorbent. It is based on the assumption that close to
pore-filling process, which can lead to a deviation from linear- saturation (at p/p0»1) all pores are completely filled with ad-
ity in the BET diagram. The upper limit for the relative pres- sorbed molecules. The adsorbate is in a liquid-like state. From
sure was set at 0.3–0.35, since capillary condensation can occur the volumetrically determined load VA at a relative pressure of
at higher relative pressures, leading to a sharp increase in load 0.98, the pore volume Vp can be determined using is the molar
and also to a deviation from linearity. A further limitation with mass M and the liquid density rL of the adsorptive molecules:
VA M method assumes flat surfaces during multilayer adsorption and
VP ¼ (4) a sequential micropore filling and capillary condensation.
VN rL
The t-method by Lippens and de Boer [30] and the aS-meth-
The drawback of this method is the use of the liquid density od further developed by Sing [31] convert the loading of the
to approximate the density of the adsorbate. Especially in the reference material into a layer thickness. In the t-plot, the load-
first layers the density is significant higher compared to the ing of the adsorbent is now plotted versus layer thickness t at
liquid state. Therefore, the pore volume of microporous the respective relative pressure. This method linearizes the iso-
adsorbents is often underestimated [21]. therm of the reference material (Fig. 3). In the case of adsorp-
tion in macropores, the curve of the adsorbent is congruent
with the line of the reference material. However, if adsorption
2.2.1.3 DR-Plot and DA-Plot takes place in other pores, the plots deviate from each other. In
the standard developed by Schull et al. [32], the layer thickness
The DR-plot for determining the micropore volume Vmicro, as t is calculated using the load, the monolayer, and the mono-
standardized according to DIN 66135-3 [22] and published by layer thickness tm of the adsorptive used:
Dubinin and Radushkevich [23, 24], is based on the assump-
tion that adsorption in micropores is a volume filling. This VA
t¼ t (8)
assumption is justified if the diameter of the adsorptive mole- Vm m
cule is in the order of the pore diameter and therefore a model
with successive adsorption layers is not applicable [25]. The
theory developed by Dubinin and Radushkevich is based on
the potential theory of Polanyi [26]. Each system of adsorbent
and adsorptive has a characteristic adsorption potential E de-
pending on partial pressure and temperature. This corresponds
to the energy required to transfer an adsorptive molecule from
the adsorbate phase into the gas phase. Dubinin describes the
volumetrically determined load empirically as a function of a
characteristic energy constant E0, the affinity coefficient b, rela-
tive pressure and temperature:
2
RT p0
ln
VA ¼ Vmicro e bE0 p
(5)
The representation of the Dubinin isotherm derives from the

linearization of Eq. (5), in which all constants are combined in
a Dubinin constant D:
2
p
lnðVA Þ ¼ lnðVmicro Þ D ln 0 (6)
p
Using data from the medium pressure range (10–4 < p/p0 < 0.1)
ln(VA) is plotted versus (ln(p/p0))2. The plot shows a straight line
with the slope D. The micropore volume Vmicro can also be calcu-
lated from the intersection with the ordinate. Figure 3. Isotherms (at the top) and converted diagrams (at the
bottom) of non-porous (A), mesoporous (B) and microporous (C)
The DA equation developed by Dubinin and Astakhov [27]
materials.
represents an extension of the DR plot:
n

RT
ln
p0 The monolayer thickness of nitrogen amounts to 3.54 Å. The
VA ¼ Vmicro e bE0 p
(7) monolayer volume may be determined by the BET method.
The as-method, in contrast, defines a reference pressure
The DA exponent n is varied between 1 and 3 to optimize (p/p0 = 0.4) where monolayer adsorption is assumed to be
the regression line. This procedure improves the fit mainly in complete while no capillary condensation has yet occurred.
case of narrow micropores [28]. The reduced adsorption is determined from the ratio of the
measured load and the load at the reference pressure of 0.4
according to:
2.2.1.4 as-Plot and t-Plot
VA
as ¼ (9)
The as- and the t-method according to DIN 66135-2 [29] VA0:4
are based on the comparison of adsorption isotherms of a
porous adsorbent with a reference isotherm of a chemically Accordingly, the as-value at p/p0 = 0.4 is one. The diagrams
similar, ideally non-porous material. The method is used to are constructed in analogy to the t-plot. Both variants yield the
determine micropore volumes and specific surface areas. The same shape with different scaling of the axes.
Fig. 3 compares the plots of a non-porous sample (A), a mes-
oporous sample (B), and a microporous sample (C). In linear
sections of t- or as-plots, undisturbed multilayer adsorption on
the sample to be analyzed takes place like on the non-porous
reference sample. However, a curvature indicates that the
adsorbent has pores where adsorption differs from multilayer ad-
sorption on the non-porous material. Evaluating the extension of
linear and curved sections, the size of the corresponding pores
can be estimated semi-quantitatively. If a straight line is fitted to
the linear range, the specific surface area S can be calculated
from its slope b using the slope of the reference isotherm bRef
as well as the surface area of the reference material SRef:
Figure 4. Desorption of condensate from mesopores.
SRef
S¼b (10)
bRef relative pressure close to saturation, the related Kelvin radius is
calculated for each desorption step by Eq. (11) along with the
For microporous materials, it is also assumed that the micro- layer thickness of the adsorbate layer. The pore radii are calcu-
pore volume Vmicro corresponds to the liquid volume, which lated using Eq. (12) from the sum of rk and t.
can be calculated from the ordinate section of the straight line To calculate the pore volume distribution, for each equili-
(Fig. 3) with Eq. (4).The as-method and the t-method can be brium step m it is assumed that the measured desorbed volume
applied to a variety of materials. Since no pore models are used, DVm arises from capillary emptying of the core pores with a ra-
the evaluation is independent of the pore geometry. If Vm, tm dius resulting from the Kelvin equation and from reducing the
and A are known, also other adsorptives except nitrogen can be adsorbate layer thickness on the walls of larger pores which
used. have already empty cores (Fig. 5). Taking geometric considera-
tions into account, the volume of the pores with cores emptied
in step m, Vp,m, is calculated from the difference between the
2.2.1.5 BJH Method total desorbed volume DVm and the volume desorbed from the
surface of pores which cores emptied in previous steps
The BJH method according to DIN 66134 is based on the prin- (Eq. (13)) [33]. The volume desorbed from the pore surface is
ciple of stepwise pore emptying of condensed adsorptive. The determined from the reduction of the adsorbate layer thickness
method was developed by Barrett, Joyner, and Halenda [33, 34] in step m, Dtm, and the specific pore surface Sp,m. The quantity
for cylindrical pores and allows the determination of volume Rm is the ratio of total pore volume to pore volume desorbed in
Vmeso, surface area Ameso, and pore volume distribution of mes- step m.
oporous materials using the desorption isotherm in a relative
pressure range of 0.99 to 0.3. Type IV (a) isotherms with hyste-
resis forms H1, H2 (a), H2 (b), and H5 are suitable for the eval-
uation. The method cannot be used for the forms H3 and H4
because no finite value for the saturation capacity is found. At
given gas phase pressure, all pores are filled up to a maximum
radius. This Kelvin radius rk can be calculated for cylindrical
pores using the following Kelvin equation as a function of sur-
face tension g, contact angle q, molar volume, temperature, and
relative pressure:
p 2gVm cosðqÞ
ln ¼ (11)
p0 rk T
As shown in Fig. 4, an adsorbate layer remains on the pore

wall when emptying pores fill with condensate. Hence, the pore
radius rp results from the addition of the layer thickness of the
adsorbate t and the Kelvin radius of the empty core.
rp ¼ rk þ t (12)
The layer thickness can be calculated using the t-plot meth-

od, the Harkins Jura isotherm, or the Halsey isotherm. Further
layer thickness equations are also given in literature [35–38].
The pore volume distribution can be calculated from desorp-
tion measurements by plotting the specific sorbate volumes Figure 5. Pore core emptying and desorption from the pore
against the corresponding pore radius. Starting with the highest wall.
X
m 1
rp;j tj ous extensions for the HK plot, such as the SF plot for cylin-
Vp;m ¼ Rm DVm Rm Dtm Sp;j (13) drical pores developed by Saito and Foley [41] or the CY plot
j¼1
rp;j
for spherical pores developed by Cheng and Yang [42]. Since
cylindrical and spherical pore geometries are not assumed for
The total mesopore volume Vmeso is obtained by summing activated carbons, these two methods are not discussed in
up the pore volumes Vp,m of all desorption steps. The specific detail.
surface areas Sp,m can be calculated from the pore volumes
Vp,m using the cylinder geometry. By summing up the specific
surface areas of all desorption steps, the cumulative mesopore 2.2.1.7 DFT and GCMC
surface area Smeso is obtained. Since the BJH method was devel-
oped for cylindrical pores, errors may occur in the evaluation Modern approaches for the determination of pore size distribu-
of activated carbons with slit-shaped pores. tion are based on the density functional theory (DFT) [43] or
on Grand Canonical Monte Carlo simulations (GCMC)
[44, 45]. These methods take into account the interactions
2.2.1.6 HK-plot between adsorptive molecules in the fluid phase of an ideal
pore model as well as the solid-fluid interactions of the adsorp-
In 1983 Horvath and Kawazoe [39] developed a method for tive with the surface atoms. Using potential energy functions,
calculating the micropore distribution of slit-shaped pores of these methods simulate the theoretical equilibrium isotherm
carbon molecular sieves using potential functions to describe for a pore system with a uniform radius. These theoretical
the interaction between the adsorbent and an adsorpt molecule. equilibrium isotherms are called kernels. The pore wall dis-
Based on the Lennard-Jones potential, Everett and Powl [40] tance is varied in discrete steps from 0.4 to 300 nm. A set of
developed a relationship for an adsorbate molecule between isotherms for various radii is then used to recursively search
two parallel walls. The potential energy e(z) is defined as a for a pore size distribution that best replicates the measured
function of the pore width L, the distance between a gas atom isotherm. This numerical evaluation represents a so-called ‘‘ill-
and the surface at zero interaction energy s, the Avogadro’s posed problem’’, which allows more than one solution for a
constant, the minimum of the potential energy e*, and the dis- finite number of measuring points. This leads to results which
tance z between molecule and wall [25]: depend significantly on the choice of the evaluation parameters
[46, 47]. Simulation artifacts in the pore size distribution may

s 4 s10 s 4 s 10 be observed at pore sizes below 2 nm [48, 49]. To eliminate
eðz Þ ¼ NA e* þ þ these drawbacks, numerous studies focus on developing a more
z z Lz Lz
(14) realistic pore model by taking into account energetic inhomo-
geneity of the surface (Quenched Solid DFT, QSDFT) [50] or
finite, multidimensional pore models [51–53].
By integrating and substituting the potential energy by the
The adsorptive most commonly used for characterization of
adsorption potential, Eq. (15) is obtained, which describes the
pore size distributions of porous solids is N2 at 77 K [54–56].
relationship between L and p/p0.
When characterizing microporous activated carbons, however,
diffusion problems of the molecules within the narrow micro-
p N A þ Na Aa
RTln ¼ NA s 4 s pores (pore width <0.7 nm) may occur due to the low tempera-
p0 s ðL z Þ
ture, so that the characterization of the pore size distribution in
2 3
the micropore range is a major challenge [56–59]. To avoid
6 s4 s10 s4 s10 7 kinetic restriction, adsorption isotherms can be measured at
·4 3 9 z 3 þ z 9 5
3 ðL z Þ 9ðL zÞ 3 3 higher temperatures. To characterize micropores with pore
2 2 widths smaller than 0.7 nm CO2, adsorption isotherms at 273
(15) or 298 K are used [55, 60]. CO2 has a very similar critical diam-
eter to N2 (0.28 nm for CO2 and 0.3 nm for N2) but a higher
NS represents the number of gas atoms per unit area of sur- adsorption capacity, which is easier to measure.
face and Na the number of molecules per unit area of the adsor-
bate. As and Aa are constants specific for a pair of adsorbent +
adsorptive given by the Kirkwood-Müller, London, etc. equa- 2.2.2 Probe Molecule Method
tions [39].
Eq. (15) is used to correlate pore sizes and relative pressures. In order to deepen the understanding of adsorption in micro-
The adsorption isotherm gives the increase of the adsorbed pores, the probe molecule method can be used. The principle
amount for a step of increasing relative pressure. The pore size of the probe molecule method is based on the measurement of
distribution is obtained from a combination of the two correla- pure substance isotherms of probe adsorptive molecules of dif-
tions. ferent geometry followed by the evaluation of the pore volumes
Since the HK plot is based on the potential theory, which using the Gurvich rule. As the size of the sample molecule
takes no account of lateral interactions between adsorbed increases, the proportion of the pore system accessible to the
molecules, it is not suitable for the evaluation of mesopores adsorbent decreases. The pore volume difference reflects
where capillary condensation can take place. There are numer- exactly that part of the pore system that lies between the
smaller and the larger molecule (Fig. 6). When examining a ser- and ISO 15901-1, first the porous adsorbent and then the
ies of sample molecules of different sizes, a section of the pore liquid elemental mercury is filled into a calibrated sample ves-
size distribution is obtained which can be compared with com- sel. As mercury is a non-wetting liquid, in contrast to adsorp-
mon evaluation methods. tion measurements in the liquid phase no spontaneous filling
of the pore system occurs. The liquid mercury is only pressed
into the pores of the adsorbent by an external pressure
increase, so that filling of the pore system begins. The behavior
of non-wetting liquids towards porous materials was first
described by Washburn [66]. The linear relationship between
filled pore width L and applied pressure p results from the
Washburn equation for slit-shaped activated carbons:
Figure 6. Principle of pore accessibility for different molecular
structures. gcosðqÞ
L ¼ 2 (17)
p
Since the evaluation of the pore volume according to
Gurvich takes place at complete pore filling (p/p0 = 0.98), the At low pressures, only the interstitial volume and the macro-
saturation vapor pressure of the sample molecule method must pores are filled. With increasing pressure, more and more mes-
be within the working range of the volumetric device (up to opores of smaller pore sizes are filled. As the mechanical stress
1.2 bar). Small molecules such as methane, carbon dioxide, or on the adsorbent increases with increasing pressure, an irrever-
sulphur hexafluoride are therefore not suitable. In order to cap- sible destruction of the pore structure may occur. Therefore,
ture structural influences as far as possible, chemically similar Hg porosimetry is often carried out up to a maximum pressure
molecules of different size, such as linear, branched, and cyclic of 400 MPa. This pressure corresponds to a pore width of
alkanes, are selected as adsorptives. 1.9 nm for slit pores and 3.8 nm for cylindrical pores, so that
The use of adsorptives of different molecular size for the Hg porosimetry can only be used to investigate structural prop-
characterization of porous structures has been discussed for erties in the meso- and macropores. As pore filling should be
many years [61]. Hu et al. [62] laid the foundation for the carried out under equilibrium conditions, the rate of pressure
method by systematically increasing the size of the adsorptives build-up must be adapted to the respective adsorbent. Modern
used (CO2 < C2H6 < n-C4H10 < i-C5H12 < CCl4). For the first devices use an equilibrium-control to allow short measurement
time, Nakai et al. [63] used the method for the qualitative char- times under guaranteed equilibrium conditions.
acterization of the micropore system of activated carbons. For Because the volume of mercury intruded by the increase in
alkanes of increasing molecular size (n-butane, iso-butane, and pressure cannot be measured directly, the change in the electri-
neopentane), the accessible pore volume was determined and cal capacitance of the mercury column above the adsorbent is
related to the nitrogen volume. used as an indirect measure proportional to the intruded vol-
Helmich et al. [64, 65] measured the nitrogen isotherm at ume. The plot of the integral volume versus the impressed
77 K on each adsorbent sample in addition to the isotherm of pressure is referred to as intrusion curve (pressure build-up) or
the probe molecule to eliminate statistical scattering within the extrusion curve (pressure reduction). Intrusion and extrusion
adsorbent batch. Thus, for each activated carbon sample, the curves form a hysteresis, because during pressure reduction
pore volume accessible for nitrogen Vp,N2 can be used as a part of the intruded mercury is longer retained in the pore sys-
reference value for calculating a pore volume difference. tem, particularly in case of bottleneck pores. Furthermore,
some mercury is left in the interstitial volume, which results in
DVp ¼ Vp;N2 Vp;PM (16) part from the interstices being counted as pores. The pore size
distribution can be derived from the intrusion curve using the
The pore size distribution is calculated using Eq. (16) by sub- Washburn equation and the conversion of integral volume to
tracting the pore volume differences of the probe molecules differential volume. While the pore volume can be read directly
Vp,PM in the specific pore width according to the molecular from the intrusion curve, the specific surface area S is calcu-
diameter of the probe molecules. lated according to Rootare and Prenzlow [67]:
Since the experimental effort of the sample method increases
with the number of adsorptives used, the method is mainly ZVmax
1
suitable for the characterization of small pore size ranges where S¼ pdV (18)
gcosðqÞ
adsorption measurements of few adsorptives are sufficient. V0
V0 is the initial volume and Vmax the maximum introduced

2.2.3 Hg Porosimetry mercury volume. As the pore surface below 1.9 nm is not con-
sidered in this process, the results are not comparable with
To determine the pore size distribution in the meso- and mac- those of adsorption measurements. The calculated pore volume
ropores, Hg porosimetry is the most widely used method. In can be used to determine the porosity of the adsorbent, which
addition, this technique provides reliable information about results from the ratio of pore volume to sample volume. In
pore volume, specific surface area, porosity, apparent density, addition, the apparent density, which represents the quotient of
and true density. In Hg porosimetry according to DIN 66133 sample mass relative to the difference between sample volume
and pore volume, and the true density, which represents the however, the decrease or increase of different groups can be
ratio of sample mass to sample volume, can be calculated. detected. This offers the possibility to examine the effects of
different activation conditions or modifications on the func-
tional groups.
2.3 Surface Chemistry Since activated carbons are not suitable for direct transmis-
sion spectroscopy due to their opacity, the activated carbon
As described in the previous chapter, the capacity of activated sample is first finely ground, mixed with potassium bromide
carbons depends on their structural properties. However, litera- powder and pressed to a hard pellet. It must be considered that
ture data show that activated carbons with similar structural the spectroscopic results strongly depend on air humidity dur-
properties may have different adsorption capacities for the ing sample preparation which further complicates any quanti-
same adsorptive [68]. The reason for this difference in capacity tative analysis.
can be a different surface chemistry, which depends on the type More common measurement techniques with less complex
and number of functional groups on the surface. The latter are sample preparation are diffuse reflectance infrared Fourier
formed during the activation process with oxygen and hydro- transform spectroscopy (DRIFT) and attenuated total reflec-
gen [1, 2]. tion (ATR). Due to the better signal to noise ratio, Fourier
transform infrared spectrometers are preferred to dispersive
spectrometers. All methods are restricted to the examination of
2.3.1 Ultimate Analysis the outer carbon surface while the inner pore system is not
accessible to these techniques.
Ultimate analysis allows the quantitative determination of het-
eroatoms in activated carbons. With the help of the elementary
composition, conclusions can be drawn about surface function- 2.3.3 Temperature-Programmed Desorption
alities and the polarity of an activated carbon. The most com-
mon method is the CHNS analysis, with which the carbon, Temperature-programmed desorption (TPD) enables a qualita-
hydrogen, nitrogen, and sulphur content of a sample can be de- tive characterization of oxygen-containing functional surface
termined [1]. The sample is combusted under pure oxygen at groups. TPD is a thermally induced desorption of a loaded acti-
high temperatures, with carbon reacting to CO2, hydrogen to vated carbon in an inert carrier gas stream. The inlet tempera-
H2O, sulfur to SO2, and nitrogen to NOx. A hot copper wire ture of the gas flow is increased by means of a programmed
reduces NOx to elemental N2. Flame ionization detectors or heating rate (often linear, e.g., 5 K min–1). The desorbed mole-
thermal conductivity detectors are used to analyze the product cules can be analyzed by conventional techniques such as mass
gases. With the CHNS method, the oxygen content is not and IR spectroscopy, gas chromatography, or gravimetric anal-
measured directly, but calculated by subtracting all measured yses. The interpretation of the thermal desorption profiles is
components and the ash content from the sample weight. In based on the concentration peaks and the respective desorption
the case of samples containing phosphorus or halogen, errors temperature and provides information on the type and strength
may occur in the determination of the oxygen content. Alter- of the interactions between the gaseous species and the carbon.
natively, the oxygen contained can also be determined in a sep- In addition, oxygen-containing functional surface groups are
arate analysis together with the nitrogen content. The sample is determined from gaseous compounds that are released as tem-
heated under inert gas, whereby the volatile components react perature rises. Oxygen-containing groups decompose mainly to
with a nickel-carbon phase and CO and N2 are released. The CO, CO2 and H2O [1]. The correlation between these groups
mass fractions of the components are determined in the same and the amounts of CO and CO2 desorbed during thermal
way as for the CHNS analysis. decomposition has been the subject of many studies. Different
results were published for the allocation of TPD peaks to the
surface groups [71–79]. Presumably, there is a shift of the peak
2.3.2 Infrared Spectroscopy temperatures [80] due to different heating rates, activated car-
bon fillings, and adsorber geometries. In addition, surface
Infrared spectroscopy (IR spectroscopy) is a frequently used groups can interact with adjacent surface groups during heat-
method for the qualitative determination of the surface groups ing [2].
of activated carbons. The measuring principle is based on the Two temperature ranges are found for TPD profiles of CO2,
selective absorption of infrared radiation from various surface which are assigned to different surface groups. The low temper-
functional groups. Many functional groups of organic mole- ature peak around 500 K is mainly due to carboxylic acids and
cules show characteristic absorption bands in the IR spectrum. the CO2 liberation at high temperatures about 900 K is attrib-
The basis for the allocation of the absorption bands are IR uted to carboxylic anhydrides and lactones. In contrast, TPD
spectra of pure substances [69]. For this purpose, numerous profiles of CO mainly show maxima in the range from 900 K to
comparison spectra of different functional groups [69] and of 1100 K, which are attributed to phenols, ethers, carboxylic
activated carbons [2, 70] are available in databases. However, anhydrides, carbonyl groups, and quinones [1, 71]. In TPD
since absorption bands can overlap in complex materials such profiles of H2O, the peak at low temperatures is generally
as activated carbon, a quantitative determination of the num- attributed to the desorption of physisorbed water. At high tem-
ber of functional groups from the intensity of the absorption peratures water development may derive from H-bonded oxy-
peaks is not possible [1, 68]. By comparing different spectra, gen complexes, condensation of phenolic groups, or from de-
hydration reactions of adjacent carboxylic acid groups to car-
boxylic anhydrides [81]. Due to the overlapping decomposition
of several functional groups at the same temperature, an exact
assignment of the decomposition products to the respective
groups is only qualitatively possible.
2.3.4 Boehm Acid-Base Titration
Boehm titration is a chemical method for the quantitative

determination of acidic oxidic surface groups on carbon-based
adsorbents [1, 82, 83]. These include the carbonyl group, the
phenol group, the lactone group, the lactol group, and the car-
boxyl group (Fig. 7).
Boehm titration is based on the selective neutralization of
functional groups with bases of different acidity [1]. With
sodium hydrogen carbonate (NaHCO3) as the weakest base,
only carboxyl groups as the strongest acid group can be neu- Figure 8. Boehm bases and assigned surface groups.
tralized. Sodium carbonate (Na2CO3) additionally neutralizes
lactone and lactol groups. Additional phenolic groups can be butane activity, iodine number and methylene blue number are
neutralized with low concentrated NaOH (0.05 M) and carbon- frequently used in the literature.
yl groups with concentrated NaOH (from 0.25 M) or sodium The CCl4 activity according to ASTM D 3467-09 indicates
ethanolate (NaOEt) [1, 83, 84]. Thus, the amount of surface the loading of activated carbon with carbon tetrachloride (in
groups according to Fig. 8 can be correlated with the respective weight percent of activated carbon) at concentrations close to
base consumptions. saturation in the gas phase. The method delivers a measure of
The base consumptions are determined from a back titration the pore volume of activated carbon and serves mainly as a
of the unreacted base with HCl. In the case of activated carbons quality test in the production of activated carbon. CCl4 activity
with a high proportion of ash containing basic components, has been replaced by butane activity under ASTM D 5742-16
this can lead to an underestimation of the acid groups, because due to the ban on carbon tetrachloride. The CCl4 activity corre-
these also react with HCl. In addition, the presence of carbon sponds to 2.55 times the value of butane activity.
dioxide influences the number of surface groups determined. In the liquid phase, the iodine number standardized accord-
Therefore, CO2 must be removed and kept away from all ing to ASTM D 4607-14 describes the amount of iodine
liquids and from the surface of the activated carbon. adsorbed from a prescribed volume of a 0.1 N iodine solution
Although Boehm titration is a common method, there is no by one gram of activated carbon until a residual concentration
procedure defined by national or international standards. It is of 0.02 N is reached in the filtrate. According to the quoted
carried out in a large number of variants with reference to guideline it is assumed that at a residual concentration of
Boehm’s publications [83, 85], can hardly be automated, and 0.02 N a monomolecular layer of iodine molecules has formed
requires great experimental care. Goertzen et al. and Oickle on the adsorbent surface and provides an indication of the
et al. [86, 87] provided for the first time an approach for the inner surface of the activated carbon. Own investigations
standardization of experimental parameters such as CO2 expul- showed that this equilibrium concentration is not yet in the
sion, endpoint determination of titration, and choice of sam- range of saturation for many coals [88]. It was also found that
ple-base ratio. there is only a small difference between the iodine numbers of
different activated carbons, which makes it difficult to evaluate
the adsorption properties.
2.4 Adsorptive Properties The methylene blue number is a decolorization test for acti-
vated carbons in aqueous solutions which delivers the volume
To determine the adsorptive properties of activated carbons, of a standard methylene blue solution decolorized by 0.1 g dry
standardized characteristic quantities and standardized num- activated carbon. For activated carbons with pore diameters
bers such as carbon tetrachloride activity (CCl4 activity), larger than 1.5 nm, methylene blue adsorption can be used to
Figure 7. Surface groups in descending acidity: (1) carbonyl, (2) phenol, (3) lactone, (4) lactol, (5) carboxyl group.
determine the surface or adsorption behavior. In own investi- tion changes due to evaporation. A more detailed description
gations, however, no correlation of the methylene blue number of the experiment is given by Treese et al. [90].
with the inner surface and the total pore volume could be pro- The reduced surface excess of the adsorbing components Gei
ven, even if the coals were classified according to raw materials is referred to the mass of activated carbon mAC. It can be calcu-
or activation process. lated from the total amount of the binary mixture n0, the mass
Despite the fact that some of tests are internationally of activated carbon and the difference of the initial mole frac-
standardized, they do not appear to be suitable for a more tion of component i in the bulk phase x0i as well as the mole
in-depth characterization of activated carbons. In order to fraction of component i in the bulk phase in equilibrium xbi.
gain a deeper understanding of the adsorptive properties on The first part of the Eq. (19) describes the reduced surface
activated carbons, further measurement methods have been excess assuming Gibbs dividing plane [91, 92]. The correlation
developed in recent years. In particular, excess isotherms, in between Gei and the total amount of substance in the adsorbed
which competitive adsorption of two different solvents in the phase GS is given by the Ostwald-de Izaguirre equation assum-
liquid phase is investigated, as well as adsorption enthalpies, ing the formation of a concrete surface layer [93, 94]. The equa-
which enable an energetic characterization of the type and tion can be derived, free of any assumption, from the mass bal-
strength of interactions in gas phase adsorption, represent ance [94]. Thus, the reduced surface excess of the adsorbing
promising methods for the detailed characterization of the components also results from the total amount of substance in
adsorptive properties. the adsorbed phase and the difference of the mole fraction of
component i in the bulk phase xbi as well as in the adsorbed
phase xsi in equilibrium:
2.4.1 Excess Isotherms
n0 0
Gei;exp ¼ x xib ¼ Gs xis xib (19)
Excess isotherms are measured from binary mixtures of mAC i
selected probe molecules from the liquid phase. They reflect
the adsorption preference in a system of two competing The reduced surface excess is plotted versus the equilibrium
adsorptives. The isotherm shape allows conclusions about the mole fraction. For graphical representation, a Bi-Langmuir
chemical nature of adsorption sites. function, a Redlich-Kister polynomial or a Kind function may
Different methods are available to measure excess isotherms be used [95]. The determination of adsorbed amounts in liquid
[89]. This paper focuses on the immersion method. The ad- phase adsorption requires a physical idea of the adsorbate
sorbent is immersed in a binary liquid mixture in a shaking geometry.
flask. The mole fractions range from 0 to 1. The samples are To enable the interpretation of excess isotherms, assump-
shaken at constant temperature until equilibrium is reached. A tions on the adsorption mechanism are necessary. This is illus-
sample of supernatant liquid is withdrawn and analyzed to trated for a system with an ideal excess isotherm in Fig. 9. The
detect the change in concentration in the bulk phase. adsorbent has only two types of surface groups. Each compo-
In own measurements, the activated carbon is heated for nent of the binary mixture is selectively adsorbed to one type
24 h at 175 C in an oven to eliminate preload and residual of groups (Fig. 9 a). The resulting excess isotherm is displayed
moisture content. Additionally, stock solutions of binary mix- in Fig. 9 b along with the mole fraction of component 1 in the
tures are prepared gravimetrically. A portion of the stock solu- adsorbed phase.
tion is added to the activated carbon sample. From the remain- Component 1 will be completely depleted from the initial
ing stock solution, a blank sample is prepared and is treated in binary mixture until all sites selective for 1 are occupied and
the same way as the experimental samples. The blank sample is the mole fraction of component 1 is zero. This idealized
used to detect systematic experimental errors like concentra- assumption implies a distribution coefficient of infinity. As
Figure 9. Composition of bulk and surface phase for an ideal adsorption excess (a) and ideal excess isotherm of a binary liquid mixture
and mole fractions of component 1 in the adsorbed phase (b).
soon as all sites of component 1 are occupied (point A), no Fig. 10 gives an example how different surface characteristics
more adsorption of 1 takes place as the sites are selective for manifest in excess isotherms and shows the reduced surface
component 2. Increasing the initial concentration x01 results in excess of toluene in the system toluene-acetone on the acti-
an increase of xb1. As adsorption is strictly selective, x1s and x2s vated carbons GAC 830 and C-Gran (Cabot Corporation). The
remain constant as long as the number of moles of 1 and 2 is experimental data were measured by a GC-FID according to
enough to saturate their sites. The composition of the adsorbed Treese et al. [90] and fitted to a Redlich-Kister polynomial. The
phase can be read from the intersection with the x-axis (point measuring error using the Gaussian error propagation is
B), which is referred to as the azeotropic point of adsorption. < 0.13 mmol g–1. Both isotherms exhibit an s-shaped pattern
At point B, the concentrations in the bulk and on the surface with a linear region between 0.3 <xbToluene<0.75. In this region
are equal and the excess is zero. At point D, only component 1 it is assumed that the isotherms determined experimentally
is left in the bulk in equilibrium, which is complementary to behave like ideal excess isotherms and that the adsorbate phase
case A. has a constant composition. The slope of the linear section is
According to Eq. (19), reduction of component 1 in the bulk mainly influenced by the structural properties since a larger
phase in equilibrium x1b compared to the initial concentration surface area results in a larger interfacial layer and a steeper
leads to a positive excess (region A–B) while reduction of com- slope. The activated carbon GAC-830 shows a more pro-
ponent 2 leads to a negative excess (region B–D). nounced toluene excess and an azeotropic point at
Treese et al. [96] modeled the surface chemistry of activated xbToluene=0.74. This means that the adsorbate phase also con-
carbons with 3 types of groups, namely aromatic surface sists of 74 % toluene and 26 % acetone.Since aromatic interac-
groups, aliphatic polar surface groups formed by heteroatoms, tions dominate, a largely aromatic or non-polar activated carbon
and aliphatic non-polar carbon surface groups. The amount of surface is assumed according to the distribution rules in Tab. 3 In
surface groups was determined from the adsorption of probe contrast, activated carbon C-Gran shows a more pronounced
molecules (of similar size to avoid sterical effects), which are acetone excess and an azeotropic point at xbToluene = 0.37. Here
assumed to adsorb preferentially to one of the three types of polar interactions predominate, so that an activated carbon
surface groups. As probe molecules, toluene was chosen as the surface consisting mainly of polar groups is assumed. These
aromatic component, acetone as the polar component, and assumptions are supported by the oxygen content determined
methylcyclohexane as the non-polar component. by an ultimate analysis. With a value of 22 wt %, the activated
The experimental excess isotherms did not follow the course carbon C-Gran has a significantly higher oxygen content than
of an idealized adsorption isotherm, but they showed linear the GAC 830 with 4.3 wt %. This indicates that there are more
sections within limited concentration ranges including the polar oxidic groups on the surface of the C-Gran, and thus, a
azeotropic point [90]. It was assumed that within this limited larger number of polar adsorption sites. The results demon-
range, the experimental adsorption isotherm behaves like an strate that surface chemistry plays a decisive role for the posi-
idealized adsorption isotherm, and the analysis of the isotherm tion of the azeotropic point. Excess isotherms are very sensitive
shape (e.g., the position of the azeotropic point B) yields the to differences in surface chemistry, since it is a competitive
mole fractions in the adsorbed phase according to the findings adsorption of two chemically different molecules and each
about idealized adsorption isotherms (Fig. 9).To infer from the adsorption site is occupied only by the molecule that can form
mole fractions of the components in the adsorbed phase to the stronger interactions.
mole fractions of the functional groups on the surface, it is
assumed that the probe molecules adsorb in compliance with
plausible distribution rules. Tab. 3 gives an example. In the
binary system toluene-methylcyclohexane, toluene is assumed
to adsorb on all kinds of sites. In case of acetone-methylcyclo-
hexane, the acetone adsorbs selectively on aromatic and polar
sites while the methylcyclohexane occupies the non-polar sites.
In the system acetone-toluene, the toluene adsorbs on the aro-
matic and the non-polar sites and the acetone on the polar
sites.
Besides these simple distribution rules, a multitude of com-
plex rules is possible where both components occupy a site
with different weights [90].
Table 3. Exemplary distribution rules [90]. Figure 10. Excess isotherms of activated carbons GAC 830 and
C-Gran in the system toluene-acetone (symbols: experimental
Binary system xSG1 xSG2 data, lines: fitted Redlich-Kister polynomial).
Toluene (1) + methylcyclohexane (2) p + p + np –
The measurement of excess isotherms is useful to determine
Acetone (1) + methylcyclohexane (2) p+p np adsorption properties. However, caution should be taken in the
Toluene (1) + acetone (2) p + np p choice of sample molecules. Sample molecules should have
approximately the same kinetic diameter in order to avoid ster-
ic size exclusion. The ratio of the binding sites can only be od [105–107]. The initial gradients of isotherms are plotted
determined correctly from excess isotherms if the pore system versus the inverse temperature at different temperatures. If
is equally accessible for both adsorptives. In addition, the space these points are connected, a straight line results. The slope of
requirement of the molecules on the surface should be similar this line is then inserted into the Clausius-Clapeyron equation.
in order to obtain the correct ratio of binding sites. If very dif- This method is mainly used for Henry and Langmuir iso-
ferent molecule sizes are used, the larger molecules can occupy therms, since the slope in the initial range of both isotherms is
several adsorption sites. This would result in an incorrect ratio load-independent and therefore constant.
of binding sites. Using the potential theory of Polanyi, a potential density func-
tion is assumed so that the loading can be described as a function
of temperature-dependent parameters [24, 108]. These parame-
2.4.2 Heat of Adsorption ters can be determined by fitting the isotherm equation to
adsorption data at different temperatures. Then the isotherm
The heat of adsorption allows an energetic characterization of equation is inserted into the Clausius-Clapeyron equation
the strength of interactions during adsorption processes. Inter- (Eq. (20)) to determine the heat of adsorption. The temperature-
actions can occur between adsorbed molecules and the surface dependent fit of the isotherm parameters has the advantage that
of the activated carbon as well as laterally between adsorbed the heat of adsorption can be described as a function of both load
molecules. The strength of interactions depends on both struc- and temperature [109]. The accuracy of this method depends sig-
tural properties and surface chemistry. Comparing heats of nificantly on the validity of the assumed potential function and
adsorption of different adsorptives on an activated carbon, the experimental accuracy in determining the temperature-
whose structural properties and surface chemistry are known, dependent variables. The latter can be improved by using a high-
allows detecting and separating the effects of both properties. er number of isotherms, which increases the measurement effort.
Heats of adsorption can be determined by different methods If the heat of adsorption is determined using the Grand
which can be distinguished regarding accuracy and effort. Esti- Canonical Monte Carlo simulation [110, 111], some assump-
mates of heats of adsorption as a multiple of the evaporation tions must be made. First, a molecular model to describe the
enthalpy are given by Ruthven et al. [97] or by v. Gemmingen adsorbed molecules and a pore model to describe the adsorbent
et al. [98]. These rough approximations cannot be used for a must be developed in order to calculate a potential field. If the
detailed discussion of adsorptive properties. Evaporation potential field is implemented in a standard GCMC simulation
enthalpies only consider lateral interactions of adsorbed mole- box [110], adsorption equilibria can be simulated at different
cules, but not the interactions between adsorbed molecules and equilibrium concentrations. For each equilibrium step, the
adsorbent surface. number of adsorbed molecules and simulation steps must be
The heat of adsorption as a function of the load can be deter- transferred to the system. From the configuration energy and
mined by thermodynamic relations such as the isosteric meth- the number of molecules in the pores, the heat of adsorption
od, the method using the van’t Hoff equation, the potential for each equilibrium step can be calculated with the fluctuation
theory of Polanyi and the Grand Canonical Monte Carlo meth- theory [112]. Especially the selection of a suitable potential field
od (GCMC). The most common calculation method is the is decisive for the validity of the simulated heats of adsorption.
isosteric method based on the equation of Clausius-Clapeyron Direct calorimetric measurements are a time-saving alterna-
[19, 99–102]. Several isotherms are measured at different tem- tive to mathematical evaluations of temperature-dependent
peratures and equilibrium points of equal loading are plotted equilibrium data. The calorimetric measuring principle most
in the isosteric diagram (logarithmic pressure ln(p) versus frequently used in literature is the Tian-Calvet microcalorime-
inverse temperature 1/T). ter developed in 1932 by Calvet et al. [113]. Based on this work,
Assuming that the heat of adsorption is temperature-inde- the measurement setup has been continuously extended by var-
pendent, the heat of adsorption DhAds can be determined using ious research groups [101, 103, 114–117].
the Clausius-Clapeyron equation from the slope of the iso- The symmetrical measuring and reference cells of Tian-Cal-
steres: vet microcalorimeters are located in a tempered aluminum or
stainless steel block. During adsorption, the released heat leads
dð lnð pÞÞ Dh to an increase in temperature in the adsorption cell and causes
¼ Ads (20)
d
1 R a heat flow from the adsorption cell into the surrounding metal
T block. To determine the released heat, resistance temperature
sensors are embedded in the interface between the adsorption
For a load-dependent description of the heat of adsorption cell and the metal block with which the change in temperature
isosteres can be evaluated at different loads. However, large is measured. The temperature sensors are connected in series.
errors often occur in the region of low loads, since the differen- The total resistance can be calculated from the individual resis-
ces between the isotherms are very small at different tempera- tances. The thermoelectric voltage that drops above the total
tures. As a result, the measurement errors have a large influ- resistance is measured as a function of time. This serves as an
ence on the slope of the isosteres and, thus, on the heat of indirect variable for calculating the average temperature of all
adsorption. In addition, the calculation is more difficult if the temperature sensors and is proportional to the heat flow. Since
isosteres are curved, due to a pronounced temperature depend- the temperature is a locally measured variable, the measure-
ence of the heat of adsorption [19, 103, 104]. The method using ment of the mean temperature may show inaccuracies which
the Van’t-Hoff equation is a modification of the isosteric meth- lead to errors in the determination of heats of adsorption.
Rouquerol and Llewellyn use a high-precision setup [118]. due to the limited symmetry of both sensor gas volumes, fluc-
Approximately 1000 temperature sensors are arranged around tuating environmental conditions influence the pressure differ-
the adsorption cell to measure the temperature profile. In addi- ence and can lead to errors in the evaluation of the heat of
tion, the adsorption cell is located in a continuous helium flow, adsorption.
which ensures optimum heat distribution. Due to the large Bläker et al. [120] used the same measuring principle but a
number of temperature sensors and the good distribution of modified experimental setup. The authors improved the sensor
heat, the temperature profile can be measured with high accu- gas calorimeter by using a strictly symmetrical setup and by
racy and high resolution, which significantly reduces the errors reducing the size of the sensor gas volumes (Fig. 11) The sam-
in the determination of heat of adsorption. ple vessel consists of a twin arrangement of measuring and
To minimize the high experimental effort required for Tian- reference cell. Both cells have an internal volume and an exter-
Calvet microcalorimeters, Zimmermann and Keller designed a nal sensor gas volume. The two interconnected inner volumes
sensor gas calorimeter consisting of a volumetric measuring form the adsorption cell and are connected to the volumetric
device and a calorimetric measuring setup with a newly devel- measuring apparatus. While the adsorbent is located in the
oped sample vessel [119]. measuring cell, the reference cell is filled with inert glass beads
The measurement of the spatial and temporal temperature to ensure greatest possible symmetry without causing adsorp-
profile of the Tian-Calvet microcalorimeter was replaced by a tion in the reference cell. The two outer sensor gas volumes are
time-dependent pressure difference measurement between two completely decoupled from each other, filled with air, and con-
sensor gas volumes. While one sensor gas volume surrounds nect to a pressure sensor. From the difference of the absolute
the measuring cell, the second sensor gas volume acts as a pressures of both sensor gas volumes, the pressure difference
reference cell. During adsorption, heat is released in the meas- can be calculated, which acts as a measuring signal. During the
uring cell, which induces a heat flow through the sensor gas entire measurement, the sample vessel is completely immersed
into the surrounding water bath and leads to a change in tem- in a tempered water bath. Thus, the influence of external dis-
perature and pressure in the sensor gas volume. Since a con- turbing factors is almost completely eliminated by permanent
stant pressure prevails in the reference cell over the entire temperature control along with high geometric symmetry. Due
measuring period, the released adsorption heat can be deter- to the miniaturized sensor gas volumes, the measured signal is
mined from the resulting pressure difference. Unfortunately, larger. The heat of adsorption DhAds,m for equilibrium step m
Figure 11. Sample vessel in twin arrangement with miniaturized calorimeter cell (a) and the experimental setup with
sample vessel in twin arrangement with miniaturized calorimeter cell (b).
can be determined from the respective area below the pressure chemistry and structural properties can each influence the
difference curve Am, a calibration factor Kf, the change of load strength and nature of the interactions during adsorption, a
Dna,m, and the mass of adsorbent material mAds: superposition of both effects occurs. Thus, a difference in the
heat of adsorption cannot be clearly assigned to one of the two
Am Kf effects without further knowledge.
DhAds;m ¼ (21)
Dna;m mAds An interpretation of the results of two activated carbons,
which differ both in their structural properties and their surface
The calibration factor has to be determined in an additional chemistry, is therefore only possible by combining different
calibration experiment. The measuring error of the heat of ad- measuring methods. Based on the knowledge of structural
sorption using the Gaussian error propagation is 1–2 kJ mol–1. A properties (volumetric characterization, probe molecule meth-
detailed description of the experimental procedure, evaluation, od) and surface chemistry (ultimate analysis, IR spectroscopy,
and error analysis as well as a comparison with literature data is TPD, and Boehm acid-base titration), adsorption mechanisms
given by Bläker et al. [120]. A methodical comparison and a dis- can be analyzed using excess isotherms and load-dependent
cussion of the measurement limits for the determination of load- heats of adsorption. Since the excess isotherms are very sensi-
dependent adsorption enthalpy with the Clausius-Clapeyron tive to differences in surface chemistry, the ratio of binding
equation, the potential theory according to Polanyi and the sen- sites (polar, non-polar, aromatic) can be determined for each
sor gas calorimeter were carried out by Berg et al. [109]. activated carbon based on the azeotropic point and the chosen
The characterization of adsorptive properties using load-de- distribution rules. The ratio of binding sites and number of
pendent heat of adsorption is presented for the adsorption of acidic oxidic surface groups (Boehm titration) can be used to
acetone and toluene on activated carbon GAC 830 (Cabot determine the dominant interactions. If this is taken into
Corporation) at 25C (Fig. 12). To eliminate preload and account in the analysis of the load-dependent heats of adsorp-
residual moisture content, the activated carbons were heated tion, a qualitative discussion of the influences of structural
before measuring under vacuum with the BELPREP-vac II properties and surface chemistry on the strength and type of
(BEL JAPAN, Inc.) for 6 h at 175 C. The heat of adsorption of interactions during adsorption should be possible. This
acetone decreases continuously with increasing load. The heat approach is currently being tested based on a systematic study
of adsorption of toluene initially increases and only decreases in which surface chemistry and structural properties of acti-
at higher loads. In addition, the heat of adsorption of toluene vated carbons are individually varied and the influence, in par-
exhibits higher values over the entire loading range. The differ- ticular on excess isotherms and the load-dependent heat of
ences in the heats of adsorption are not due to the structural adsorption, are investigated.
properties, since the smallest possible cross sections of both
molecules, which are decisive for pore accessibility in slit-
shaped pores and the strength of the interactions, are each 3 Summary and Conclusion
0.41 nm. The different adsorptive properties of acetone and
toluene therefore result from surface chemistry. The lower heat The characterization of activated carbons mainly addresses
of adsorption of the polar acetone compared to the aromatic porous structure and surface chemistry. The variety of pre-
toluene indicates that the surface of GAC 830 contains more sented methods proves the importance of this field of research.
aromatic than polar functional surface groups. Many methods to describe structural properties, like volumet-
If heats of adsorption from two measurements using the ric measurements and mercury porosity, are well-established
and standardized for quantitative analysis. In contrast, nearly
all methods to characterize surface chemistry are still subject of
research and deliver only qualitative results requiring careful
interpretation. Recent developments relate to surface chemistry
characterization by adsorption experiments with selected probe
molecules. The measurement of excess isotherms in the liquid
phase and adsorption enthalpies in the gas phase are promising
methods. For a comprehensive elucidation of adsorption-
relevant properties the results of different methods must be
combined as each method only allows a limited insight.
Acknowledgment
This work was supported by the German Research Foundation
(DFG) within the DFG project BA2012/9-1. Open access fund-
Figure 12. Load-dependent heat of adsorption of toluene and ing enabled and organized by Projekt DEAL. [Correction
acetone on activated carbon GAC 830 at 25 C. added on November 17, 2020, after first online publication:
Projekt Deal funding statement has been added.]
same adsorptive but different adsorbents are compared, an
interpretation of the results is more complex. Since surface The authors have declared no conflict of interest.
Christian Bläker studied Me- Dieter Bathen holds the chair
chanical Engineering with a of Thermal Process Engineer-
focus on Energy and Process ing at the University of
Engineering at University of Duisburg-Essen and is scientif-
Duisburg-Essen from 2008– ic director of the Institute of
2013. In 2018, he completed Energy and Environmental
his Ph.D. thesis at the Chair of Technology IUTA. He is
Thermal Process Engineering. chairman of the ProcessNet
Today, he leads the group working group Adsorption
Characterization at the Chair (VDI/DECHEMA) and chairs
of Thermal Process Engineer- various VDI guidelines on
ing at the University of Duis- adsorption. After his studies
burg-Essen. and obtaining a Ph.D. in
Chemical Engineering/Process
Engineering from the University of Dortmund, he held var-
Johanna Muthmann is re- ious functions in the Degussa Group (now Evonik AG)
search assistant at the chair of before moving to his present position in 2007.
Thermal Process Engineering
at the University of Duisburg-
Essen. Before starting her
Ph.D. thesis in the field of
Symbols used
characterization of activated
A [m3] specific surface area of a
carbon in 2017, she studied
molecule
Chemistry at Ruhr University
A a, A s [–] constant
of Bochum.
Am [kg m–1s–1] area below the pressure
difference curve of equilibrium
step m
b [m3kg–1] slope of the isotherm in the
comparison diagram
Christoph Pasel studied C [–] BET constant
Chemistry at Ruhr University D [–] Dubinin constant
of Bochum from 1985–1990 E [kg m2s–2mol–1] adsorption potential
and completed his Ph.D. thesis E [kg m2s–2mol–1] enthalpy
in 1993. Today he works as a E0 [kg m2s–2mol–1] characteristic energy constant
senior engineer in the field of i [–] component of binary mixture
adsorption technologies at the Kf [m3s–1] calibration factor
Chair of Thermal Process L [m] pore width
Engineering at the University M [kg mol–1] molar mass
of Duisburg-Essen. m [–] equilibrium step
m [kg] mass
NA [mol–1] Avogadro’s constant
N [–] number of molecules per unit
area
n [–] DA exponent
n0 [mol] total amount of binary mixture
p [kg m–1s–2] pressure
R [kg m2s–2mol–1K–1] ideal gas constant
rk [m] Kelvin radius
Rm [–] ratio of total pore volume to
pore volume desorbed in step m
rp [m] pore radius
S [m2kg–1] specific surface area
T [K] temperature
t [m] layer thickness
VA [m3kg–1] load
Vmax [m3] maximum introduced mercury
volume
VN [m3kg–1] molar volume
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ChemBioEng Reviews - 2019 - BL Ker - Characterization of Activated Carbon Adsorbents State of The Art and Novel

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ChemBioEng Reviews - 2019 - BL Ker - Characterization of Activated Carbon Adsorbents State of The Art and Novel

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Characterization of Activated Carbon Adsorbents –

State of the Art and Novel Approaches

ASTM D 5158-98 powdered activated

Ignition temperature ASTM D 3466-06 granular activated

Dusting attrition ASTM D 5159-04 granular activated

2.2 Structural Properties

On the structural properties side, the inner surface, the total

2.2.1 Volumetric Characterization

In the characterization of nanoporous structures by volumetric

2.2.1.1 BET Method

The specific surface area, which is

Method Structural properties Type of isotherm

BET Method Specific surface area SBET (I), II, IV

Gurvich Rule Pore volume VP all

DR-Plot, DA-plot Micropore volume Vmicro I

t-Plot, aS-plot Specific surface area S, micropore volume Vmicro I, II, IV

HK-Plot Pore size distribution of micropores I

NLDFT and GCMC method Pore size distribution all

The representation of the Dubinin isotherm derives from the

As shown in Fig. 4, an adsorbate layer remains on the pore

The layer thickness can be calculated using the t-plot meth-

V0 is the initial volume and Vmax the maximum introduced

2.3.4 Boehm Acid-Base Titration

Boehm titration is a chemical method for the quantitative

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