Activated carbon as catalyst support: precursors, preparation,

modification and characterization

Melanie Iwanow1,2, Tobias Gärtner1, Volker Sieber1,3 and Burkhard König*2

Review Open Access

Address: Beilstein J. Org. Chem. 2020, 16, 1188–1202.

1Fraunhofer Institute for Interfacial Engineering and Biotechnology doi:10.3762/bjoc.16.104
IGB, Bio-, Electro- and Chemocatalysis BioCat, Straubing Branch,
Schulgasse 11a, 94315 Straubing, Germany, 2Department of Received: 10 March 2020
Chemistry and Pharmacy, University of Regensburg, Accepted: 20 May 2020
Universitätsstraße 31, 93040 Regensburg, Germany and 3Technical Published: 02 June 2020
University of Munich, Campus Straubing for Biotechnology and
Sustainability, Schulgasse 16, 94315 Straubing, Germany Associate Editor: M. Rueping

Email: © 2020 Iwanow et al.; licensee Beilstein-Institut.

Burkhard König* - Burkhard.Koenig@chemie.uni-regensburg.de License and terms: see end of document.

* Corresponding author

Keywords:
activated carbon; catalysis; characterization techniques; metal
supported on carbon catalysts; preparation methods

Abstract
The preparation of activated carbon materials is discussed along selected examples of precursor materials, of available
production and modification methods and possible characterization techniques. We evaluate the preparation methods for activated
carbon materials with respect to its use as catalyst support and identify important parameters for metal loading. The considered car-
bon sources include coal, wood, agricultural wastes or biomass as well as ionic liquids, deep eutectic solvents or precursor solu-
tions. The preparation of the activated carbon usually involves pre-treatment steps followed by physical or chemical activation and
application dependent modification. In addition, highly porous materials can also be produced by salt templating or ultrasonic spray
pyrolysis as well as by microwave irradiation. The resulting activated carbon materials are characterized by a variety of techniques
such as SEM, FTIR, nitrogen adsorption, Boehm titrations, adsorption of phenol, methylene blue and iodine, TPD, CHNS/O
elemental analysis, EDX, XPS, XRD and TGA.

Introduction
Support materials for metal catalysts allow the dispersion and compared to other support materials. The carbon surface is
stabilization of small metal particles on a surface. Compared to inert, especially in strongly acidic and basic conditions, the pore
the bulk metal, these catalyst preparations present a higher sur- size distribution and the chemical properties on the surface can
face area of catalytically active atoms [1]. The use of activated be adjusted (polarity and hydrophobicity) according to the
carbon as support for metal catalysts shows several advantages envisaged application. In addition, metal particles can be recov-

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ered simply by burning the carbon support [1,2]. Thus, porous leum coke for an enhanced CO2 capture [7]. Pietrzak et al. used
carbon materials represent a large part of the supporting materi- high volatile bituminous coals, brown coals and anthracites for
als for the preparation of heterogeneous catalysts. Nevertheless, modified activated carbon preparation [5,10-12]. Lillo-Ródenas
only a small amount of the worldwide produced activated car- et al. investigated the chemical activation with sodium or potas-
bon (<1%) is used as catalyst support. A possible reason may be sium hydroxide by the use of an anthracite precursor [8,13,14].
the lack of reproducibility due to inconsistent carbon precursor
compositions [2]. Wood
Non-fossil precursors for the preparation of activated carbons
In general, activated carbon is an amorphous carbon modifica- are of great interest due to an increasing demand of these mate-
tion with a high surface area and a well-developed porosity, rials. Wood and the lignocellulosic wastes from forestry and
which can be produced from a variety of carbon sources [3]. agriculture are well-suited for this purpose [15]. Wood is
The preparation of activated carbons is already broadly covered mainly composed of cellulose (40 to 55 wt %), hemicelluloses
in the literature. Therefore, we limit our brief overview to (mostly xylan in hardwoods with 20 to 35 wt %) and lignin
selected examples. Emphasis is given to carbon precursors, (18 to 35 wt %). Cellulose maintains the structure of the cell
preparation and modification methods, characterization tech- walls of plants and is the most abundant raw material with a
niques and metal loading on the carbon materials. production of 1011–1012 tons per year, followed by lignin as
second most abundant raw material [16]. Lignin is a three-
dimensional phenolic polymer and is responsible for the cemen-
Review tation of cellulose fibres in plants [17]. Hemicelluloses, pre-
Precursor materials for activated carbon dominantly xylan, are non-cellulosic polysaccharides with a
production comparable low molecular weight [15]. Khezami et al. investi-
Many cheap raw materials with high carbon content can be used gated the preparation of activated carbon from wood and its
for the production of activated carbon [4]. Fossil and renewable main components: cellulose, xylan and lignin [15]. Suhas et al.
sources for the preparation of activated carbon are discussed in reviewed the use of cellulose as well as lignin for activated car-
this part of the review, as well as special precursor solutions or bon preparation in detail [16,17]. Hameed and co-workers pre-
ionic liquids and deep eutectic solvents as non-conventional pared high surface area AC from wood sawdust [18].
precursor materials. The properties of the resulting activated
carbon depend, in addition to the type of precursor material, on Agricultural waste/ biomass
the preparation or activation method and the modification used. The use of agricultural waste as precursor for activated carbon
materials is summarized in a variety of reviews [3,19-24]. Any
Coal low cost lignocellulosic materials with high carbon content are
In the beginning of the 1990s, 360 kilotons activated carbon of great interest as starting material [22]. An exemplary
were produced, whereby 42% were based on coal as precursor overview of agricultural byproducts and waste used for the pro-
due to the availability and low coast of coals such as brown duction of activated carbon materials is shown in Table 1.
coals, bituminous coals, petroleum cokes or anthracites. The
coals should have a low mineral matter content and thus, a low According to Ioannido et al., the composition and structure of
ash content [4,5]. Bituminous coal-based activated carbons the used raw material determines the reactivity during pyrolysis
result in a well-developed porous structure due to the presence and activation steps and thus, the resulting elemental composi-
of primary pores in the coals. However, the size of these pores tion. They concluded that pyrolysis of agricultural waste
is very small [5]. Activated carbons prepared from bituminous provides up to twice the amount of char obtained from wood.
coals are more durable compared to other coal-based carbons Different starting materials yield activated carbons with differ-
[6]. Petroleum coke as byproduct of the refinery industry, show ent ash contents or BET surface areas. Nutshells and cherry
a high carbon content, low amount of ash and is widely avail- stones show for example less ash content compared to grape
able [7]. Anthracites are very suitable precursors for activated seeds. Olive wastes and bagasse results in activated carbons
carbon (AC) preparation, since they are high-rank coals (high C with high surface areas, whereas straw is less suitable to
to H atomic ratio without carbonization) and show a non-negli- produce high surface areas [19]. Yahya et al. mentioned that the
gible volume of very fine micropores [8,9]. yields of the activated carbons prepared from these residues is
lower compared to anthracite or coal as starting materials.
Various working groups investigated the preparation of acti- Nevertheless, high volatile matter content in the biomass are ad-
vated carbons by different methods from coal precursors. Yang vantageous for the production of porous activated carbon mate-
et al. synthesized nitrogen-doped activated carbon from petro- rials as well as the low cost of the agricultural waste [22].

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Table 1: Exemplary overview of agricultural waste sources for acti-

contents are obtained depending on the composition of the deep
vated carbon production. eutectic solvents [79].

Carbon source References

Precursor solutions
straw [25-29] Xu et al. used energy-rich carbon precursors for the spherical
rice husk [23,30-33] carbon preparation via ultrasonic spray pyrolysis. Lithium, sodi-
bagasse [30,34-37] um or potassium propiolates are one class of such energy rich
miscanthus [38,39] materials and exhibit leaving groups such as CO, CO2 or C2H2
bamboo [40-42] eliminated by decarbonylation or decarboxylation. Poly(propio-
cotton residues [43,44] late) salts are formed by polymerization of the starting materi-
nut shells [45-49] als after heating. The different cations of the propiolates cause
fruit pits [49-53] changes in the thermal behavior of the starting materials since
fruit seeds [54-56] different temperatures are required for the decomposition or dif-
fruit peels [57-59] ferent amounts of gases are released. Alkali salts of acetylene
coconut shells [60-63]
dicarboxylic acid can also be used as precursor for the prepara-
olive stones [64-66]
tion of carbon spheres. The structure and morphology of the
sunflower seed oil residues [67,68]
carbon spheres can be influenced by the used alkali salts [80].
coffee residue [69,70]
corn cobs [71,72]
oil palm residues [73-75]
Activated carbon preparation
rotten strawberries [76]
The following chapter summarizes the different preparation
methods for activated carbon materials. Depending on the car-
bon source, different pre-treatment steps are required before the
Ionic liquids and deep eutectic solvents carbonization/pyrolysis and activation of the precursor materi-
Zhang et al. demonstrated the preparation of carbon materials als can be performed. In addition to the most widely used
with high surface areas from protic ionic liquids and salts. The method of physical or chemical activation, specialized methods
precursors have low-molecular weights, are available and such as salt templating and ultrasonic spray pyrolysis are
cheap. Preparation of the carbon materials is simple: Neutraliza- presented.
tion of the nitrogen-containing bases, e.g., phenanthroline or
3-cyanopyridine with sulfuric acid and subsequent removal of Pre-treatment
the solvent leads to the desired protic ionic liquids and salts. Different pre-treatment steps are necessary before carboniza-
Carbonization at 1000 °C results in the final carbon materials tion or activation of the carbonaceous precursors. The use of
with high nitrogen content without further modification. The biomass as carbon precursor requires often additional washing
basic components of the protic ionic liquids influence the yield steps to remove impurities [30]. Drying at ≈100 °C for a defined
of the materials. Thermally stable benzene moieties increase time removes the free moisture in the material, which could
significantly the amount of carbon material produced, whereas affect the carbonization step [81]. A defined and standardized
mixtures based on amines or heterocycles decrease the yields starting material size of the raw materials is also essential for
[77]. The salt templating method developed of Antonietti and the activated carbon production process and is obtained by
co-workers produces carbon materials with high surface areas milling and sieving of the carbon precursors [30,45,81,82].
from ionic liquids. A defined salt mixture was added to the
ionic liquids 1-butyl-3-methylpyridinium dicyanamide (Bmp- De-ashing/demineralization
dca, N-doped materials) or 1-ethyl-3-methylimidazolium tetra- Activated carbons contain different ash contents due to mineral
cyanoborate (Emim-tcb, N- and B-doped materials) and the components in the raw materials, which affect the chemical
mixture was heated under nitrogen atmosphere. Removal of the properties of the prepared materials. For catalytic applications,
salt by immersing in water for several hours, filtration and only activated carbons with the lowest possible ash contents can
drying in vacuum leads to the final carbon material [78]. be used. Prior to the production of activated carbons from the
Iwanow et al. investigated deep eutectic solvents as raw materi- precursor materials, the amount of ash and minerals in the mate-
als for activated carbon production. They dissolved the metal rials is reduced by leaching with acidic or basic solutions [83].
salts already in the low melting mixtures before pyrolysis and Samples are mostly demineralized by concentrated hydro-
prepared carbon-supported metal catalysts in one-step. Never- chloric and hydrofluoric acids according to the Radmacher and
theless, the surface area of these materials is much lower com- Mohrhauer method [10]. Dofour et al. described the procedure
pared to the conventional activated carbons, but high nitrogen in detail. The stepwise treatment with hydrochloric acid, hydro-

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fluoric acid and again hydrochlorid acid removes the metal ties, which causes a rigid matrix. This structure is less suscep-
oxides and silica in the samples and is a comparatively soft tible to volatile loss and volume contraction during the
method for the carbon material. The treatment with HNO3 is carbonization resulting in higher activated carbon yields since
another possibility for the removal of the mineral contents; no carbon burn-off is necessary [6,85]. Additional advantages
however, this method causes the oxidation of the material and of the chemical activation are lower temperatures for pyrolysis,
thus, produces new oxygen-containing surface functionalities the formation of very high surface areas and it is possible to
[84]. control the development of microporosity, e.g., a narrow pore
size distibution can be obtained [8,15]. Various parameters in-
Physical activation fluence the formation of porosity during the chemical activa-
Physical activation of carbon materials is a two-step process. tion process. A few examples for the different preparation
After preparation of char by carbonization of the precursor ma- conditions are the choice of the activing agent (KOH, NaOH,
terials for a certain time at a defined temperature under inert gas ZnCl2, H3PO4, MgCl2, AlCl3, K2CO3, etc.), the impregnation
atmosphere, steam, air or CO2 activate the materials at higher technique used or physically mixing processes, the activation
temperatures (800–1000 °C) to form a porous structure accord- reagent to carbon precursor ratio, the flow of inert gas during
ing to the Equations 1–3 [81,85,86]. carbonization and the pyrolysis temperature and time [13,14].

(1) Highly developed pore structures are obtainded by chemical ac-

tivation of carbon precursors with hydroxides [9,14]. Song et al.
(2) investigated the activated carbon preparation by chemical acti-
vation with KOH from corn cob. They found that KOH plays a
(3) crucial role in the formation of porosity. Metallic potassium is
formed during the carbonization of the carbon precursor, which
It is necessary to eliminate a high amount of internal carbon for intercalates in the carbon structure and is responsible for further
the formation of a well-developed and highly porous carbon release of carbon dioxide, carbon monoxide and hydrogen [71].
structure [6]. In general, the physical activation of carbon mate- According to Marsh and Rodriguez-Reinoso, the activating
rials has the advantage over chemical activation to avoid impu- agent reacts with the formed char and not directly with the car-
rities or additives in the final materials from the incorporation bon precursor to form a porous structure [56,93]. Hsu et al.
of the activating substances [16]. studied the preparation of highly porous activated carbons from
bituminous coal by chemical activation with ZnCl2, H3PO4 and
Several literature reports show a higher reactivity of steam as KOH. The choice of the activating reagent influences strongly
mild oxidizing reagent compared to carbon dioxide. Neverthe- the activated carbon properties. Higher yields are obtained by
less, no clear tendencies were found regarding the pore develop- activation with ZnCl2 and H3PO4 compared to KOH, whereas
ment [87-91]. Rodríguez-Reinoso et al. and Zamora and less porosity is developed. The acidic character of the activa-
co-workers investigated the influence of the different physical tion reagents ZnCl2 and H3PO4 seems to be suitable for the de-
activation gases on the development of porosity from olive velopment of large pore structures in the carbon source [6].
stone-based chars. They concluded that activation with steam Diamadopoulos and co-workers observed also the production of
results in activated carbon materials with lower micropore smaller surface areas by H3PO4 activation of bagasse and rice
volumes and wider pore size distributions (higher amounts of husk due to a reaction of the activating reagent with the carbon
meso- and macropores are formed) compared to carbon dioxide precursor. Thereby, phosphate esters or polymerization byprod-
[64,87]. Kalderis et al. prepared activated carbons from bagasse ucts are formed, which are strongly bonded to the carbon matrix
and rice husk by physical and chemical activation. They found and are not removed by the subsequent washing step [30].
that physical activation results in significantly lower surface
areas compared to the surface obtained by chemical activation Salt templating
with zinc chloride at the same temperature [30]. Fechler et al. developed the salt templating method for the prep-
aration of highly porous functional carbon materials using ionic
Chemical activation liquids as carbon source. Inorganic non-carbonizable salts were
Chemical activation is a one-step method. Impregnation or mixed with the carbon precursor and elevated temperatures lead
mixing of the carbon precursor with the activating agent and to condensation and scaffolding of the carbon source by the
subsequent carbonization of that mixture leads to highly porous presence of the molten salt. The aim of the method is to retain
activated carbon materials [8,92]. The activation agents as long as possible the miscibility of the carbon precursor and
promote a cross-link formation due to their dehydration proper- salt melt during the reaction. After a washing step to remove the

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salt from the carbon materials, high specific surface areas are Spherical carbons
obtained with pore sizes corresponding to the salt clusters and The preparation of spherical mesoporous carbon particles as
salt percolation structures. The polarizability can be adjusted by catalyst support with high surface areas, controllable particle
selection of the cation size and counterion, which influences the sizes and large uniform pores received much attention [97,98].
pore size and the miscibility during the production process One possibility to prepare such carbon spheres with defined
[78,94]. particle sizes and pore structures is the nanocasting strategy
using silica scaffolds as shown by Fuertes [99]. Nevertheless,
Ultrasonic spray pyrolysis (USP) due to the complex and high-cost preparation of these carbon
The USP method for continuous preparation of meso- and materials (preparation of the solid scaffolds, pyrolysis of the
macroporous carbon spheres was used by Skrabalak et al. Ultra- carbon precursors in these templates and finally, the selective
sonically nebulization of a precursor solution (carbon source removal of the silica template) and the risk of structure and
and inorganic salts) by a humidifier results in a mist of micron- morphology defects by the harsh carbonization and template
sized droplets. These droplets are transported into a furnace by removal processes, this method is industrially infeasible [97].
an inert gas stream, where the solvent evaporates and the pre-
cursor decomposes. The formed carbon sphere/salt composites Carbon spheres are also prepared by hydrothermal treatment of
are collected in water bubblers. The salt is dissolved in the aqueous low cost biomass, such as lignocellulosic materials, or
collection solvent and byproducts either remain in the solvent or carbohydrate precursor solutions at defined temperatures in
were removed by the gas stream resulting in the desired porous closed systems [100,101]. The proposed mechanism of the for-
carbon spheres (Figure 1) [95]. mation of carbon spheres seems conform to the LaMer model
and starts with a polymerization step of the carbohydrate mono-
mers and followed by a carbonization step when the nucleation
is caused by the supersaturation of the solution. The resulting
nuclei grow uniformly until the final size is obtained depending
on the growth parameters [102]. Linares-Solano and co-workers
activated the resulting carbon spheres to develop different
textural properties by maintaining the morphology. Surface
areas higher than 3100 m2 g−1 could be synthesized [98].

Yan et al. presented another method for the preparation of

spherical carbon materials by aerosol-assisted self-assembly
using amphiphilic triblock copolymers as template and low-mo-
Figure 1: Experimental setup of ultrasonic spray pyrolysis. Reprinted lecular weight soluble phenol resin as carbon source. The
with permission from [95], copyright 2006 The American Chemical amphiphilic surfactant influences the pore size and mesostruc-
Society.
ture of the resulting spherical carbons. Finally, the template is
removed by calcination [97].
Suslick and co-workers used the USP process for the prepara-
tion of well-dispersed iron impregnated porous carbon micro- Comparison of conventional and microwave heating
spheres. An iron source (FeCl3 or Fe(NO3)3 is already added to Conventional heating for physical or chemical activation of the
the precursor solution consisting of sucrose as carbon source precursor materials has several drawbacks such as the non-
and NaCl or NaNO3 as inorganic salt. The pyrolysis of the pre- uniform heating of the samples or a high energy demand due to
cursor solution leads to dehydration of carbon as well as iron long carbonization and activation times at high temperatures
salt conversion to crystalline or non-crystalline iron species [103,104]. Microwave irradiation is a promising alternative
depending on the production conditions. The porosity of the with some advantages. In contrast to conventional heating,
carbon spheres is induced by either aromatization of carbon which is based on the convection mechanism involving conduc-
around an in situ template, in situ chemical activation or gasifi- tion and radiation, the sample can be heated uniformly and
cation of carbon [96]. Xu et al. found that the morphology of contactless by the heat generated from electromagnetic energy,
the porous carbon materials prepared from propiolate salts with resulting in significant time reduction and therefore energy
USP are dependent on the choice of starting materials. The ther- savings [103]. The major problem of microwave heating is that
mal decomposition behavior of the precursors, and thus the re- the carbon sources are poor receptors for the irradiation, thus
sulting morphology of the carbon materials is influenced by the activation agents are necessary as heat carriers and for promo-
propiolate cations [80]. tion of porosity [104].

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Wang et al. prepared activated carbons with high surface areas Chemical surface properties
by microwave-induced ZnCl2 activation within minutes. The The chemical properties of the carbon surface influence the
porosity of the materials can be tailored by the carbon precur- acid–base and hydrophilic character and thus can affect the
sor to ZnCl2 ratio and the microwave irradiation time [104]. preparation of carbon-supported catalysts. Different types of
Foo et al. investigated the activated carbon preparation by active phase–support interactions can be induced by the intro-
microwave heating with K2CO3 activation from wood sawdust. duction of heteroatoms on the carbon surface, which is only
They obtained highly porous activated carbons by varying the marginally possible in other catalyst supports, e.g., silica or
impregnation ratio, microwave power and irradiation time. alumina [2]. Depending on the application of the carbon-sup-
They concluded that the high surface areas are formed due to ported catalysts, different possibilies are available for the modi-
opening of previously inaccessibly pores and the additional fication of the properties on the surface of the activated carbon
creation of new pores by the interior and volumetric heating of materials.
microwave radiation [18]. Lin and co-workers compared the
activated carbon preparation with KOH activation by conven- Oxygen-containing surface groups: The amount and composi-
tional and microwave heating. The microwave-induced materi- tion of oxygen-containing surface groups can be influenced by
als showed higher surface areas compared to those prepared by treatment with different oxidants such as H2O2, HNO3, oxygen/
conventional heating using the same precursor to activating air, ozone or NaOCl. Thereby, the acidic or basic behavior and
agent ratio [105]. the resulting surface chemistry of the activated carbons are de-
termined.
Activated carbon modification
Depending on the starting materials or preparation methods Jaramillo et al. investigated the influence of different oxidizing
used, various modification treatments can be performed to func- reagents on the activated carbon materials prepared from cherry
tionalize the surface of the activated carbons according to the stones. Different amounts of oxygen functional groups were
subsequent use of the materials. found on the surface of the materials depending on the
oxidizing agents used: HNO3 > O3 > H2O2 > O2 (air). Mostly
Surface area and porosity carboxyl groups were formed by the oxidative treatments with
In general, a high surface area and well-developed porosity of HNO3 and ozone. However, HNO3 also causes a decrease of
activated carbons are beneficial for the use as catalyst supports microporosity and of the basic sites on the carbon materials
to obtain a highly dispersed loading of metal particles on the compared to ozone modification, thus O3 is the most promising
surface. The size of the pores is also important. Highly porous reagent for the formation of oxygen functional groups [108].
activated carbons with narrow micropores can block active Han et al. investigated activated carbons with similar porosity,
centers being not available for the reactants [2]. The surface but different amounts of oxygen groups on the surface. They
area and development of porosity (amount of porosity, pore size observed a decrease of the hydrophobicity of the carbon sur-
and shape) of the activated carbons can be influenced by the face due to formation of acidic groups by oxidization with
preparation conditions. H2O2. This property change based on the increase of oxygen
surface groups made the surface more accessible for the
Lyubchik et al. used different chemical (HClO4 or Mg(ClO4)2) aqueous metal solution during the impregnation process and
and physical (CO2) activation methods for the modification of results in a better platinum dispersion. Nevertheless, less acidic
the porosity of anthracite-based activated carbons. The final and more thermally stable surface groups avoid the sintering of
pore size distribution (mainly microporous or mainly meso- the metal particles by enhanced metal–carbon interaction [109].
porous) depends on the choice of the activation agent, the treat- Figueiredo et al. observed different types of oxygen surface
ment time and temperature and the initial textural properties of groups depending on the oxidizing agent. Oxidative treatment
anthracite as carbon source [106]. Wang et al. found that acidic with liquid agents (HNO3 or H2O2) increases the amount of
treatments generally enhance the surface area and porosity of carboxylic groups, while carbonyl and hydroxy surface groups
activated carbons, since the inorganic impurities in the materi- result from modification with O2 or N2O [110].
als were removed. Hydrofluoric acid modification showed the
greatest enhancement of the surface area and porosity [107]. Nitrogen-containing surface groups: Nitrogen-enrichment of
However, the surface area and developed porosity of the acti- activated carbons is possible at the precursor stage or as
vated carbon materials is only one parameter affecting the mate- a modification step after the production of activated
rial application as catalyst support. Another important charac- carbons and results mostly in a basic character of the
teristic is the chemical composition of the activated carbon sur- prepared materials. Typical nitrogen agents are ammonia,
face [2]. urea or amines. Different types of nitrogen-containing func-

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tional groups on activated carbon surfaces are shown in Surface characterization

Figure 2 [10,111]. Scanning electron microscopy (SEM): Surface morphology of
activated carbons is investigated with scanning electron micro-
Ammoxidation of activated carbons is a very effective process graphs. The measurement determines the porosity of a surface
for the introduction of nitrogen surface groups. The simulta- area. Cavities or holes can be observed on activated carbon with
neous oxidation and nitrogenation of the activated carbon sam- higher porosity, while smooth surfaces characterize activated
ples changes the chemical structure significantly and thus the carbon with less porosity [71].
acid–base character of the materials. Pietrzak et al. observed
that the amount of nitrogen in the activated carbons depend on Singh et al. showed SEM pictures of activated carbons pre-
the preparation stage at which the ammoxidation is performed pared from the biomass Arundo donax with different ratios of
and of the different pre-treated carbon precursors used. The KOH as activating reagent. Smooth surfaces were found with-
highest nitrogen content in the samples was found by ammoxi- out KOH, while a high degree of porosity was obtained by the
dation of demineralized coal in the last preparation step after optimum KOH to biomass ratio, resulting in high surface areas
carbonization and activation [10]. Hu and coworkers synthe- [114]. Saka et al. have shown that the external surface of the
sized nitrogen-doped carbon materials from coconut shell by activated carbons prepared from acorn shell by chemical activa-
urea modification and K2CO3 activation. The carbonized pre- tion with ZnCl2 exhibit cracks and holes in different sizes. They
cursor is mixed with urea (1:1 weight ratio), heated and the concluded that a porous structure was formed due to the volati-
unreacted urea is removed by a washing step with hot water. zation of most of the organic compounds during the carboniza-
Subsequently, the urea-treated samples were activated. The tion process and the ruptured surface obtained [46]. SEM
treatment with urea enhanced significantly the nitrogen content micrographs also allow the determination of different types of
in the samples, while the final amount of nitrogen was reduced pores. The group of Okman showed SEM investigations on acti-
by the activation step [63,113]. vated carbons prepared from grape seeds by activation with
KOH. The sponge-like surface of the activated carbon indicates
Activated carbon characterization a microporous structure [56].
Many production methods and possible precursors for activated
carbon preparation are known. Also many characterization Fourier transmission infrared spectroscopy (FTIR): Acti-
methods have been reported. In most cases, several characteri- vated carbon consists mainly of carbon atoms, besides different
zation methods are used to allow a correlation of the heteroatoms such as oxygen, hydrogen, nitrogen and sulfur.
resulting activities and activated carbon properties with the Thus, different functional groups govern the surface of the acti-
preparation and modification methods. In the following, typical vated carbons and FTIR provides information on these chemi-
characterization techniques are introduced and the information cal structures [65]. The spectra are usually recorded between
obtained from the analytical methods is discussed on selected 4000 cm−1 and 400 cm−1. The most characteristic bands of
examples. functional groups on the surface of the activated carbons are

Figure 2: Overview of nitrogen-containing functional groups on the surface of activated carbons. Scheme was drawn according to [10,112].

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≈3500, 1700, 1610, 1420 and 1140 cm−1 which indicate free or materials, the Dubinin–Radushkevich equation [120] for the
intermolecular bonded OH groups, carbonyl (C=O) stretching calculation of microporosity and the Barrett–Joyner–Halenda
vibrations of carboxyl groups, ketones or aldehydes, C=C model [121] for pore size distribution. In addition, the
double bonds, aromatic rings and ether C–O stretching bonds, hysteresis between the adsorption and desorption gives informa-
respectively [65,82,115]. Changes of the surface properties due tion on mesopores. The absence of a hysteresis indicates that
to the modification of the activated carbon samples can also be there is no or only little mesoporosity [65]. An overview of the
detected by FTIR measurements. pore classification and the concerning pore sizes is shown in
Table 2 [117].
Shafeeyan et al. investigated new N-containing functional
groups on the surface of ammonia treated activated carbon Table 2: Overview of the pore classification in the context of physi-
samples such as bands of N–H stretching vibrations sorption [117,122].
(3376–3294 cm−1), cyclic amides (1665–1641 cm−1), nitriles
(2251–2265 cm−1) and pyridine-like functionalities (1334–1330 Pore type Pore size
cm−1). Simultaneously, a diminished band at about 1700 cm−1
was found due to the decomposition of the oxygen-containing macropores 50 nm
mesopores 2–50 nm
surface groups at higher treatment temperatures [115]. The
micropores <2 nm
group of Moreno-Castilla investigated the treatment with
ultramicropores <0.7 nm
oxidizing agents (H2O2 or HNO3) or activating reagents by
FTIR. They found that the amount of oxygen fixed on the sur-
face of the treated carbons in form of carboxyl groups, ketones,
ether groups and carboxyl-carbonate structures is higher using Sethia et al. investigated the influence of the activation tempera-
nitric acid compared to hydrogen peroxide [116]. ture on the porosity and surface area of nitrogen-containing
activated carbon samples by N2 adsorption measurements. Non-
Nitrogen adsorption–desorption isotherms: The surface area activated carbon samples showed a very low nitrogen uptake in-
and pore size distribution of solid catalyst materials can be de- dicating small surface areas without pores. A sharp increase of
termined by gas adsorption–desorption measurements at 77 K. the isotherms at very low relative pressures with subsequent
To obtain reproducible isotherms from the measurements, a stagnation could be observed with activated carbons prepared
controlled outgassing of the adsorbent with a defined tempera- between 550 and 650 °C due to a narrowly distributed
ture, change in pressure and residual pressure is necessary to ultramicroporous structure. The prepared activated carbon
remove all physisorbed species from the surface. Different sample at 700 °C showed a broader isotherm knee resulting
methods can be used for the measurements. The volumetric from a wider pore distribution [123]. Kalderis et al. prepared
method with determination of the gas removed from the gas activated carbons from bagasse and rice husk by chemical acti-
phase and the gravimetric method, where the uptake of the gas vation with ZnCl2, NaOH and H3PO4. They observed that the
by the adsorbent is determined by the increase in mass. In addi- surface area of the activated carbon depends strongly on
tion, static or dynamic techniques are available for the determi- the activation agent used, the impregnation ratio of the raw ma-
nation of adsorbed gas [117]. terial to activation agent, the activation temperature and activa-
tion time. ZnCl2 showed the best results with surface areas of
As a result, physisorption isotherms are obtained by plotting the 674 and 750 m2 g−1, while the activation with H3PO4 led to sur-
amount of adsorbed gas na in mol g−1 against the equilibrium face areas below 100 m2 g−1 due to a high retention of phos-
relative pressure (p/p0). The resulting isotherms can be grouped phates in the carbon structures forming phosphate esters or po-
in six different types. Type 1 isotherms are concave to the p/p0 lymerization byproducts that bind on the solid carbon matrix
axis and na approaches the limiting value p/p0 → 1. This type is [30].
formed by microporous solids with a relatively small external
surface, for example, activated carbons or molecular sieve Boehm titrations: Boehm titrations are used for the determina-
zeolites [117]. tion of acidic or basic surface oxygen functional groups of solid
materials. The acidic character is caused by carboxyl groups
Numerous methods are available for calculating surface area, (R–COOH), lactones (R–OCO), phenolic groups (R–OH) and
pore size, pore distribution and pore volume by fitting to the carbonyl or quinone groups (R=O). Differentiation is possible
isotherms with different assumptions. For example, the by titration with different basic solutions NaHCO3, Na2CO3,
Brunauer–Emmet–Teller (BET) method [118] or the Langmuir NaOH, NaOC2H5, respectively. Titration of the samples with
method [119] for the determination of the surface area of porous hydrochloric acid determines the basic properties on activated

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carbon surface in form of pyrone or chromene-like structures iodine number to investigate the surface area and porosity of the
and aromatic π electrons [108,124,125]. AC prepared from corncob by physical (steam) and chemical
(KOH) activation with different carbonization and activation
Nowicki et al. showed different acidic and basic conditions on conditions. Chemical activation showed obviously higher sur-
the surface of the activated carbon materials resulting from dif- face areas compared to steam activation [71].
ferent activation methods of cherry stones-based carbons. Acti-
vation by carbon dioxide led to basic surface character, while Temperature-programmed desorption (TPD): TPD is used
using the chemical activation with KOH results in weakly for the study of surface oxides due to the thermal stability of the
acidic surface properties of the materials. The temperature used surface groups. The samples were heated in an inert gas atmo-
for the activation showed less influence compared to the activa- sphere or in vacuum with a constant heating rate and the
tion method [52]. Comparison of the amounts of acidic and evolved gases were determined by mass spectrometry. In
basic surface groups on treated and untreated activated carbon general, each type of surface group decomposes to a defined
from bituminous coal investigated Pietrzak. He found that the product such as CO2 from carboxylic acid or lactones and CO
carbonization process reduced slightly the amount of acidic sur- from carbonyl, hydroxide, phenol, ether or quinone groups and
face groups, while the amount of basic surface groups remains thus, information on the amounts of oxygen-containing surface
constant. Nitrogen introduction to the materials led to an groups are obtained. Nevertheless, the decomposition products
obvious decrease of acidic surface groups and simultaneously are not always clearly assignable, since two adjacent carboxyl
increase of basic properties [10]. groups form primarily the anhydride followed by decomposi-
tion to CO and CO2 [15,110,124].
Phenol, methylene blue and iodine adsorption: Adsorption
capacity and amount of pores of activated carbon materials are Capart and co-workers investigated the activated carbons pro-
determined by using different adsorbates (phenol, methylene duced from wood and the basic wood components lignin, cellu-
blue and iodine). The activated carbons are added to defined lose and xylan by KOH activation with TPD. The different pre-
methylene blue or phenol solutions and are shaken for a certain pared materials showed no significant difference of the surface
time. The concentration of the adsorbates methylene blue and functionalities. All TPD spectra show a water peak at about
phenol is spectrophotometrically determined at defined absor- 500 K according to dehydration of carboxylic acid during for-
bance wavelengths. The iodine number is determined by mation of anhydrides, a CO peak at 900 K due to decomposi-
titration with sodium thiosulfate. Generally, the iodine number tion of carboxylic anhydrides and a CO2 peak at about 500 K
represents the surface area resulting from the amount of micro- resulting from carboxylic acids [15]. Figueiredo et al. exam-
pores (<1 nm). Mesopores (<1.5 nm) are denoted by methylene ined the influence of oxidative treatments on activated carbon
blue adsorption, which is also used as model substrate for the by TPD studies. Enhanced CO and CO2 peaks found by TPD
adsorption of organic pollutants [51,126]. Phenol adsorption indicate an increasing amount of oxygen-containing surface
takes place in ultramicropores and micropores with diameters groups on the activated carbon materials. They could observe
between 0.7 nm and 2 nm and thus, determination of specific that gas phase oxidation led to a higher amount of mainly
surface areas is possible. In addition, phenol is the primarily hydroxy and carbonyl groups, whereas liquid phase treatment
used liquid-phase reference for adsorption studies. The with nitric acid results in an increase of carboxylic acid groups
adsorption capacity of phenol is influenced by oxygen- [110]. Lillo-Ródenas et al. used TPD for the determination of
containing functional groups: basic properties promote the the released gases during the activation process of anthracite
adsorption of phenol by oxidative coupling reactions and acidic with sodium or potassium hydroxide and thus for clarification
functional groups decrease the amount of adsorbed phenol of the activation mechanism with hydroxides. The reaction of
[51,127,128]. carbon precursor and metal hydroxide at lower temperatures
(Na: 570 °C and K: 400 °C) lead to the formation of hydrogen
Duman and co-workers studied different pyrolysis tempera- and metal carbonates as well as metallic metal or M2O (M = Na
tures and activation times with ZnCl2 for the preparation of or K). The absence of carbon dioxide at these temperatures sug-
highly porous activated carbon from fruit stones and nutshells. gests that the carbonates are not formed by reaction of hydrox-
They found that both conditions influence strongly the adsorp- ides with CO 2 . At higher temperatures, CO and CO 2 were
tion of phenol and methylene blue on the nutshell-based found due to the decomposition of the metal carbonates. More-
carbons. It is essential to find the optimum activation time, over, they found that no porosity of the resulting materials was
since shorter treatments (6 h) do not lead to a porous structure formed by using a metal carbonate instead of hydroxide as acti-
and longer activation times (24 h) causes a collapsing of the vation reagent [8,14]. Pis and co-workers used the TPD method
structure [51]. Song et al. used methylene blue adsorption and for evaluation of the thermal stability of introduced nitrogen

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functionalities by modification with ammonia due to the evolu- XPS method, the carbon 1s electron binding energy was refer-
tion of NH3 and HCN. Depending on the modification tempera- enced at 284.6 eV [10,124,131,132].
ture, nitrogen is incorporated mainly to aromatic rings at higher
temperatures, while less temperature-stable amide-like function- Pietrzak investigated with XPS different methods for the
alities were formed at lower temperatures [129]. enrichment of bituminous coal by ammoxidation. The greatest
enrichment of nitrogen occurs by using the ammoxidation as
Composition of activated carbon last step after carbonization and activation of the bituminous
Elemental composition by CHNS/O: The elemental composi- coal. The measurements showed that nitrogen is introduced in
tion is determined for starting materials as well as for the result- the activated carbon as amines, imines, amides, pyridine
ing activated carbon materials. Thereby, the influence of the nitrogen and pyrrole nitrogen or as oxidized nitrogen species,
different preparation, activation and modification methods on e.g., pyridine-N-oxides [10]. Díaz-Terán et al. examined the
the carbon or heteroatom content can be compared. surface of the samples (surface groups, chemical state of the el-
ements, metal content and distribution) during the activation
Nowicki et al. found that physical activation of cherry stones process of lignocellulosic precursor with KOH by XPS. They
results in higher carbon contents and simultaneously lower observed that the oxygen on the surface of the material is
hydrogen and oxygen amounts, while chemical activation show associated with potassium as carbonates or oxides [131].
only smaller changes of the elemental composition with excep- Cordero and co-workers observed by XPS that different
tion of a significant decrease of the nitrogen content [52]. amounts and species of nitrogen-containing surface groups are
Pietrzak examined the different elemental compositions of the obtained by HNO3 treatment of olive stones-based activated
bituminous coal based materials after carbonization, activation carbon depending on the activation method. Chemical
and ammoxidation for the enrichment of nitrogen. He found that activation by H3PO4 form a higher amount of N-containing sur-
the carbonization step causes an increase of the carbon content, face groups, mainly as nitro groups, compared to physical acti-
a decrease of oxygen and hydrogen and the nitrogen amount vation with CO2, whereby only less oxidized nitrogen species
stays almost constant. The activation process leads to an were formed. They concluded that the phosphorous species in
increase of oxygen, while all other elements decrease. Thus, the the carbons could be responsible for the examined difference
activation reagent (KOH) oxidizes the initial material during [130].
this step. As expected, the ammoxidation results in an enrich-
ment of nitrogen [10]. X-ray diffraction (XRD): X-ray diffraction gives information
on the crystallinity or amorphicity of activated carbons.
Scanning electron microscopy with energy-dispersive X-ray Comparison of resulting XRD patterns with the crystallo-
(SEM-EDX): An energy-dispersive X-ray detector allows the graphic databases clarify that partially graphitic structures
investigation of the composition of the materials and of the dis- are available in the activated carbon materials. In addition,
tribution of elements on the investigated materials by EDX XRD can be used for investigations of the activation
mapping. process by detecting crystalline intermediates of the activation
reagents.
Ternero-Hidalgo et al. found by SEM-EDX investigations that
the treatment of olive stones-based carbons with H3PO4 during Liang and co-workers found in the activated carbon prepared by
chemical activation or modification with HNO 3 occurs microwave-induced ZnCl2 activation of wood broad peaks at
uniformly on the entire surface, since the heteroatoms (nitrogen about 23° and 44° due to the (002) and (100) reflexes of graph-
and phosphorous) are quite homogeneously distributed on the ite. Thus, they concluded the formation of a carbon structure
surface of the activated carbons [130]. with randomly orientated graphitic carbon layers. Calculation of
d values by the Bragg equation allows the comparison of the
X-ray photoelectron spectroscopy (XPS or ESCA): X-ray layer distances found in the activated carbon samples with the
photoelectron spectroscopy determines the chemical state of el- values of graphite (0.335 nm). The prepared wood-based acti-
ements and the composition of the sample on the upper surface vated carbon show higher d values between 0.365 nm and
layer (only few atomic layers). X-ray irradiation (Mg Kα or 0.375 nm [104]. Singh et al. received very similar results by
Al Kα) excite core electrons to leave the atoms and their kinetic KOH activation of biomass Arundo donax with broad peaks at
energies are measured. The characteristic binding energies are 23° and 43°. Moreover, they found that the intensities of the
calculated from the measured kinetic energies. After baseline reflections are enhanced by an increasing KOH to biomass
subtraction, the curves are fitted to Gaussian and Lorenztian ratio, indicating that KOH promotes the graphitization of the
peak shapes with different proportions. For calibration of the prepared activated carbons [114]. Díaz-Terán et al. used XRD

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to detect the development of crystalline compounds during the Using these methods for the preparation of supported metal
activation of a lignocellulosic precursor with KOH. They found catalysts, the interaction between the precursor and supporting
the formation of K2CO3 during this step, which increases with material and its pore systems shows the greatest influence on
the pyrolysis temperature and is responsible for the pore devel- the dispersion of the metal on the support and thereby limits
opment [131]. the metal loading [134]. Various factors play also a role in
the distribution of the metal precursor on the support: type
Thermogravimetric analysis (TGA): TGA provides informa- of metal compound, solvent used and pH of the solution
tion on the weight loss of the starting materials during the [135,136].
heating process due to, e.g., decomposition.
For the wet impregnation, the supporting material is added to a
Kumar et al. found by using TGA that the activation process of large excess of solution with the metal precursor. Thereby,
the used nutshells by ZnCl 2 proceeds in three steps. In the larger catalyst particles with an egg-shell distribution of the
beginning, the organic matter decomposes, followed by a metal are formed due to the deposition of the metal precursor on
further decomposition of the obtained intermediates and the the outside of the support without using the pore system. To use
activating reagent. At least, the char reacts with ZnCl2 and the the pore system of the supporting materials and obtain smaller
pores open [133]. Kalderis and co-workers observed also catalyst particles with a uniform metal loading, the incipient-
three steps in the study of the thermal behavior of rise wetness impregnation method was developed. The metal pre-
husk and bagasse. The first step (≈100 °C) shows a weight cursor is dissolved in exactly that amount of solvent, which is
loss due to the moisture of the samples. Further heating necessary to fill the pores of the supporting material, whereby a
to about 370 °C led to decomposition of the main components closer contact of the metal precursor and the support is guaran-
cellulose, hemicellulose and lignin and the loss of the volatile teed [134]. After the impregnation, the solvent is removed by a
matter is responsible for the decrease in weight. Higher temper- drying step and reduction of the metal precursor is necessary to
atures result in carbonization of the residues and gaseous form the active metal on carbon catalysts by adding a reducing
products or tars are formed associated with another weight loss agent, such as hydrogen, formaldehyde or sodium borohydride
[30]. [1]. Is the drying step replaced by filtration of the large
excess of solution, the method is called ionic adsorption
Ash content: The total ash content is determined by using [134,137].
ASTM standards. A defined amount of sample is weighed in a
porcelain basin, heated in a muffle furnace to a given final tem- Deposition
perature and for a certain time. After cooling to room tempera- The deposition of a precursor of an active component from an
ture in a desiccator, the sample is reweighed. The ash content is excess of solution onto a support by a chemical reaction is
calculated using the following equation [30,50]: called deposition precipitation. It is necessary to have enough
carboxylic acid groups available on the support to obtain a high
dispersion of the metal.

(4) The increase of pH, the change of valency of the metal ion
(electroless plating) or the removal of a stabilizing ligand of the
metal ion allow the deposition precipitation from a suspension.
Compared to the impregnation/adsorption method, several
advantages can be obtained by this method: reproducibility,
Metal loading methods high metal loadings, high metal dispersion at high metal load-
The macroscopic distribution of a metal on the support, the size ings and uniform distribution of the metal over the support
of the metal crystallites on the support surface and the oxida- [1,134,137].
tion state of the metal species determine the catalytic perfor-
mance of a supported metal catalyst [1]. Summary – Influence of the preparation
parameters on the material properties
Impregnation und adsorption Each step in the preparation of a carbon-supported catalyst
The impregnation method is comparatively simple and influences its final properties such as the surface area, the pore
thus widely used in the preparation of supported catalysts. size distribution, the attrition resistance, the ash content and the
Three different methods are available: wet impregnation, surface chemistry of the carbon materials and thus the perfor-
incipient-wetness impregnation and ionic adsorption. mance of the catalyst [1].

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The choice of starting material influence the particle size ORCID® iDs
distribution, morphology and the attrition resistance of the car- Burkhard König - https://orcid.org/0000-0002-6131-4850
bon material. These properties determine the filterability and ac-
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