Environmental Chemistry Letters

https://doi.org/10.1007/s10311-019-00955-0

REVIEW

Methods for preparation and activation of activated carbon: a review

Zoha Heidarinejad1,2 · Mohammad Hadi Dehghani3,4   · Mohsen Heidari2 · Gholamali Javedan1,5 · Imran Ali6 ·
Mika Sillanpää7

Received: 22 April 2019 / Accepted: 23 November 2019

© Springer Nature Switzerland AG 2020

Abstract
Activated carbon refers to a wide range of carbonised materials of high degree of porosity and high surface area. Activated
carbon has many applications in the environment and industry for the removal, retrieval, separation and modification of
various compounds in liquid and gas phases. Selection of the chemical activator agent is a major step controlling the per-
formance and applicability of activated carbon. Here, we review chemical activators used to produce activated carbon. We
compare the impregnation method with the physical mixing method used in activating with alkali hydroxides. We selected
81 articles from Google Scholar, PubMed, Scopus, Science Direct, Embase and Medlin databases. Eighteen articles report
the activation with potassium hydroxide, 17 with phosphoric acid, 15 with zinc chloride, 11 with potassium carbonate, nine
with sodium hydroxide, and 11 with new activating agents. Activation with phosphoric acid is commonly used for lignocel-
lulosic material and at lower temperatures. Zinc chloride generates more surface area than phosphoric acid but is used less
due to environmental concerns. Potassium carbonate, in comparison with potassium hydroxide, produces higher yields and a
higher surface area for the adsorption of large pollutant molecules such as dyes. Activating with potassium hydroxide in terms
of surface area and efficiency shows better results than sodium hydroxide for various applications. Also, the comparison of
the physical mixing method and the impregnation method in activation with alkali metals indicates that the activated carbon
obtained through physical mixing had a higher porosity than the activated carbon produced by the impregnation method.

Keywords  Activated carbon · Adsorption · Chemical activation · Physical activation

Abbreviations
IR Impregnation rate
MESH Medical subject headings
* Mohammad Hadi Dehghani qmax Maximum adsorption capacity
hdehghani@tums.ac.ir SBET Brunauer, Emmett and Teller surface area
t Adsorption time
1
Food Health Research Center, Hormozgan University T Activation temperature
of Medical Sciences, Bandar ʽAbbas, Iran
Vt Total pore volume
2
Department of Environmental Health Engineering, Faculty FTIR Fourier-transform infrared spectroscopy
of Health, Hormozgan University of Medical Sciences,
Bandar ʽAbbas, Iran
3
Department of Environmental Health Engineering, School
of Public Health, Tehran University of Medical Sciences, Introduction
Tehran, Iran
4
Institute for Environmental Research, Center for Solid Waste
Activated carbon is a porous carbonaceous material with
Research, Tehran University of Medical Sciences, Tehran, continually expanding applications in water treatment and
Iran desalination, wastewater treatment and air purification due
5
Minimally Invasive Surgery Research Center, Iran University to its unique characteristics (Fig. 1) (Kosheleva et al. 2019;
of Medical Sciences, Tehran, Iran Samsuri et al. 2014; Yousefi et al. 2019). Activated carbon
6
Department of Chemistry, Jamia Millia Islamia (Central is a very diverse adsorbent material including a high degree
University), New Delhi, India of porosity and high surface area, while up to 90% of it
7
Department of Green Chemistry, LUT University, may be constituted from carbon (Gopinath and Kadirvelu
Sammonkatu 12, 50190 Mikkeli, Finland

13
Vol.:(0123456789)

Fig. 1  Application of activated
carbon as an adsorbent for envi-
ronmental remediation
Agro-industrial wastes
2018; Morin-Crini et al. 2019; Samsuri et al. 2014). Also,
carbon structures contain the main functional groups such
as carboxyl, carbonyl, phenol, lactone and quinone that are
responsible for adsorbing contaminants. Oxygen, hydro-
gen, sulphur and nitrogen are also present in the form of
functional groups or chemical atoms in the activated carbon
structure. The unique adsorption properties depend on the
existing functional groups of activated carbon, which are
derived mainly from activation processes, precursors and
thermal purification (Bhatnagar et al. 2013; Yousefi et al.
2019).
The advantages of activated carbon for zeolites or
polymer-based adsorbents are high quality in wastewater
treatment, simple process design, easy exploitation of the
process, resistance to corrosive (acid and alkali) and toxic
environments, high adsorption potential in gas and liquid
purification and their use as supportive catalysts (Belala
et al. 2011; Bhatnagar et al. 2013; Rambabu et al. 2015).
Theoretically, all carbon-rich organic materials are com-
monly known as carbonised materials, which can be used
to produce activated carbon. Activated carbon may be pro-
duced from agricultural waste, livestock and industrial by-
products (Huang and Zhao 2016; Khadhri et al. 2019; Njoku
et al. 2014).
The production of activated carbon around the world
is estimated to be around 100,000 tonnes annually (Sam-
suri et al. 2014). The most common sources of activated
carbon on a commercial scale are wood, anthracite and
bitumen charcoal, lignite, peat shells and coconut.
Alternative sources such as olive and almond shells are
also used. The carbon content of these materials ranges
from 40 to 90% (wt.), with a density of 0.4–1.45 g/m 3
(Cui et al. 2011; Huang and Zhao 2016; Khadhri et al.
2019; Mishra et al.2010). Today, much effort has been
devoted to exploiting waste as raw materials in activated
carbon production (Crini et al. 2019). Activated carbon
can also be produced from agricultural residues such as
13
Environmental Chemistry Letters
Activated carbon /Adsorption
Water treatment
Wastewater treatment
Air purification
olive corn, biomass, rice rolls, corn stalks, bagasse, fruit
stones (cherry and apricot stones, grape seeds), hard shells
(pistachio, almond and pecan shell), fruit pulp, bones and
coffee beans (Klasson et al. 2013). The raw material used
for the preparation of activated carbon should be abundant,
cheap and safe (Jolly et al. 2006). The mineral content of
this material and its biodegradability during initial storage
should be minimal (Prauchner et al. 2016; Samsuri et al.
2014; Zhu et al. 2010).
In addition, for the production of activated carbon, the
presence of carbon materials, transportation of raw materi-
als and the availability and seasonal changes in relation to
the quality and availability of raw materials should be con-
sidered (Samsuri et al. 2014; Thitame and Shukla 2016).
Also, to obtain good results, high adsorption of carbon
and oxygen in adsorbents is very necessary. Other features
include high abrasion resistance, high thermal strength and
small pore diameters, which result in an increased expo-
sure surface and thus an increase in adsorption capacity
(Cui et al. 2011; Prauchner et al. 2016; Soleimani and
Kaghazchi 2008). Also, the properties of the prepared acti-
vated carbon mainly depend on the type of activation agent
(Sawant et al. 2017; Uysal et al. 2014).
Considering that the use of different activator sub-
stances culminates in producing different properties in
activated carbon, and in many studies the selection of the
best activated carbon is a priority for many researchers,
a systematic study seems necessary to reach an overall
conclusion. The purpose of this study was therefore to
compare the properties of activated carbon, which were
produced by various chemical activators and in two pre-
cursor/activator mixing modes—impregnation and physi-
cal mixing, through a systematic review of studies. This
study will also mention the advantages and disadvantages
of activating agents in selecting the best activated agent
according to the potential of the activated carbon produced
to adsorb various adsorbates from aqueous solutions.
Environmental Chemistry Letters

Methodology Recovered articles from

internal and external
In order to conduct this study, international databases databases = 201
including Google Scholar, PubMed, Scopus, Science Direct, Re-delete articles
Embase and Medline were searched using the following unrelated= 35
Medical Subject Headings (MESH) keywords: activated
carbon, chemical activation, impregnation, physical mixing, Review of the abstracts of
new activating agents, phosphoric acid, zinc chloride, potas- articles with initial entry
sium carbonate, potassium hydroxide, sodium hydroxide. requirements = 156

In this study, research articles published during

2000–2019 in valid journals in the field of activated carbon Delete articles
unrelated= 35
production from various agricultural bio-wastes through dif-
ferent activation procedures and used for the adsorption of Secondary review Full
various pollutants from aqueous solutions were included. text of related articles =
On the other hand, other literatures including books, lec- 121
articles
Delete = 45 due
some articles
tures, letter to editors, review articles and research articles to lack of adequate
published before 2000 were excluded. The articles with information = 45
the following contents were excluded: i) activated carbon
amended with nanoparticles, organic matters and bases/ All related articles =
76
acids, ii) activated carbon used for application other than
Articles of hand
water and wastewater treatment and iii) accelerated adsorp- searching reference lists
tion onto activated carbon by ultrasound. of articles related = 5

Final articles = 81
Study of article quality

The resources utilised by the researchers were studied. At Fig. 2  Flow diagram of the search and selection of articles
first, the title, abstract and method of work were examined
if needed. Also, for further review of the full text of the
related articles, the final articles were selected and studied. 11 17
Finally, all the articles were studied by an expert group in 11
the field of the adsorption of various pollutants with acti-
vated carbon produced by various activation agents. As 15
shown in Fig. 2, a total of 201 articles were retrieved in
the primary search, from which 156 articles were left after 18
removing repetitive and completely unrelated articles. The 9
focus of research was restricted to studies on the prepara-
tion of activated carbon with chemical activators and using
the obtained adsorbents for the removal of various pollut-
ants from aqueous solutions. After this filtering process, 76 Phosphoric Acid Zinc Chloride
articles were left for further investigation. The initial list of Sodium Hydroxide Potassium Hydroxide
the articles was also manually reviewed, and five additional
Potassium Carbonate New Acvang agents
articles were selected. Finally, 81 articles were approved
for full text review. Among the selected articles, the num-
Fig. 3  Number of articles based on the chemical activator used for
ber of articles based on the chemical activator used for the
the preparation of activated carbon from agricultural residues
preparation of activated carbon from agricultural residues
is presented in Fig. 3.
temperature (T), impregnation rate (IR), Brunauer, Emmett
and Teller surface area (S BET), total pore volume (V t),
Extracting the data adsorption rate and maximum adsorption capacity (Qmax).
The name of the adsorbent and the used precursor was
A checklist of the required information includes the name prepared and completed. Comparison of the performance
of the adsorbent, activation type, activation time, activation and properties of activated carbon with different chemicals

13

showed that among different activation factors used in the
process of the removal of large molecules such as dye, metal
hydroxides produced activated carbon with a higher surface
area than other activating agents, so the capacity adsorption
of the adsorbent is higher with metal hydroxides (Ahmed
and Theydan 2014; Njoku et al. 2013; Tongpoothorn et al.
2011).
In chemical activation, phosphoric acid and zinc chloride
are used to activate lignocellulosic materials that have not
previously been carbonised, while metal compounds such
as potassium hydroxide are used to activate the precursors
of charcoal and char. Phosphoric acid, in comparison with
zinc chloride, has fewer restrictions in environmental and
toxicological contamination and requires a lower activation
temperature than potassium hydroxide (Al Bahri et al. 2012;
de Yuso et al. 2014; Demiral and Şamdan 2016; Nowicki
et al. 2013). The common ranges of activation temperatures
in the process of producing activated carbon with phosphoric
acid, zinc chloride, potassium carbonate, sodium hydroxide
and potassium hydroxide were 450–600 °C, 400–900 °C,
700–1000 °C, 550–850 °C and 450–850 °C, respectively
(Angın et al. 2013; Basta et al. 2009; Ibrahim et al. 2014;
Liu et al. 2010a, 2012; Youssef et al. 2012). In chemical
activation with alkali, in general activation with potassium
hydroxide shows better results than sodium hydroxide in
terms of surface area and performance in different appli-
cations. However, sodium hydroxide is cheaper and more
environmentally friendly and does less harm than potassium
hydroxide, and it is clear that it has more industrial appli-
cations because of its superiority to potassium hydroxide
(Byamba-Ochir et al. 2016; Huang et al. 2014; Yahya et al.
2015). Also, the results of the comparison of the physical
mixing method and the impregnation method in activating
with metal hydroxides in different studies indicated that the
activated carbon obtained through physical mixing had a
higher porosity than the activated carbon produced by the
impregnation method (Alabadi et al. 2015; Byamba-Ochir
et al. 2016; Lee et al. 2015; Nowicki et al. 2013).
Activation of activated carbon methods
Activated carbon could be prepared through the direct acti-
vation of dry raw precursor or through a two-stage process
including initial carbonisation and then activation. In the
two-stage process, the dried raw organic materials such as
walnut hulls, wood, bone and coal should be initially car-
bonised at high temperatures. In the carbonisation process,
the material should be exposed to a red spot (less than
700 °C) temperature in the distillation apparatus in order
to evaporate and remove the hydrocarbons from it in the
absence of oxygen. Overall, the process of carbonisation
is thus a pyrolytic process, and its product is known as
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Environmental Chemistry Letters
carbonised material, char or biochar (Byamba-Ochir et al.
2016; Huang et al. 2014; Yahya et al. 2015). After activating
the activated carbon, various activation methods are used
to further develop porosity and create structures that lead
to the formation of fine solid cavities in activated carbon
(Yahya et al. 2015). The pores created on the surface of acti-
vated carbon could be categorised as macropores > 25 nm,
1 nm < mesopores < 25 nm, micropores < 1 nm (Huang et al.
2014).
In view of the nature of the activation process, acti-
vated carbon could be prepared in two ways: physical and
chemical.
Activated carbon production through physical
activation
Physical activation used commercially is a two-step process
that involves the process of carbonisation (pyrolysis) in a
neutral atmosphere and then activation in atmospheric oxi-
dising gases such as steam, carbon dioxide, carbon dioxide
and nitrogen or air mixtures with increasing temperature
in the range of 800–1100 °C (Bouchelta et al. 2008). This
method has the ability to produce activated carbon of porous
structure and good physical power, which is an inexpensive
method for activated carbon preparation and is considered a
green approach because it is chemical-free (Byamba-Ochir
et al. 2016; Pallarés et al. 2018; Yahya et al. 2015). However,
in the process of the physical activation of activated carbon,
the long activation time and low adsorption capacity of pre-
pared activated carbon and its high energy consumption are
the main disadvantages (Yahya et al. 2015).
Activated carbon production through chemical
activation
Chemical activation, known as wet oxidation, is usually used
for raw materials containing cellulose, such as wood, saw-
dust or fruit pits. These materials are also called biomass
resources. In chemical activation for the preparation of acti-
vated carbon, organic precursors are activated in the pres-
ence of chemicals at high temperatures (Njoku et al. 2014;
Samsuri et al. 2014; Yahya et al. 2015). For chemical acti-
vation, the raw material, in the first stage, is saturated with
oxidising and highly dehydrated chemicals. After impregna-
tion, the suspension is dried and the remaining mixture is
heated for a given time. Depending on the activating mate-
rial and the properties of the final product, activation can
take place at temperatures ranging from 400 to 900 °C, at
which cellulose is degraded. Eventually, activated carbon
is obtained from the repeated washing of the resulting mix-
ture. Another purpose of the final rinse is the recovery of
active substances (Samsuri et al. 2014). Chemical activa-
tion agents are dehydrating agents that influence pyrolytic
Environmental Chemistry Letters
decomposition and, by inhibiting the formation of bitumen,
increase the activated carbon content and, with subsequent
changes in the thermal degradation of precursors, result in
the development of the porous structure of carbon materials
(Gratuito et al. 2008; Molina-Sabio and Rodrıguez-Reinoso
2004). These activating agents with deep penetration into
the carbon structure lead to the development of small pores
in the activated carbon, thereby increasing its surface area
(Gratuito et al. 2008). Unlike thermal physical activation,
the carbonisation and activation phenomena occur simulta-
neously in the chemical activation so, in contrast to physi-
cal activation where carbonisation and activation processes
are typically performed in two different furnaces, chemical
activation can be performed in a single furnace (Samsuri
et al. 2014).
In the process of chemical activation, the variables that
affect the characteristics of the final activated carbon are the
amount of impregnation and the weight ratio of chemical
agents to dry precursor (Gratuito et al. 2008). Compared
to physical activation, this type of activation is more eco-
nomical because it requires a lower activation tempera-
ture, shorter processing time and higher carbon efficiency
(Rambabu et al. 2015). Also, the activated carbon prepared
through chemical activation has a more porous structure than
that of physical activation (Cui et al. 2011). Activated chem-
icals react with carbon matrices and liberate gas products
to form a porous structure (Molina-Sabio and Rodrıguez-
Reinoso 2004). However, the need for a repeated and long
washing step to eliminate the spent activator agent from the
final mixture at the end of activation process is one of the
disadvantages of this method. In addition, toxic wastewater
is produced at the washing step, which causes water pollu-
tion and therefore requires secondary treatment (Wang et al.
2016; Yorgun et al. 2016).
The precise selection of the parameters of the chemical
activation process is important to the quality of activated
carbon production. In addition, in the production of acti-
vated carbon, the efficiency of the process is also considered
an important factor (Molina-Sabio and Rodrıguez-Reinoso
2004; Wang et al. 2016; Yorgun et al. 2016). In the chemi-
cal activation method, the parameters of the chemical agent
effect, impregnation ratio and method, temperature, final
temperature of carbonisation, carbonisation time, activation
space (under atmospheric conditions) and activation method
have been investigated (Cui et al. 2011; Wang et al. 2016;
Yorgun et al. 2016). Different types of chemicals have differ-
ent reactions with precursors and thus affect the adsorption
behaviour. The main chemicals which have been used as
potential activators are alkaline groups such as potassium
hydroxide (KOH), sodium hydroxide (NaOH), calcium
chloride ­(CaCl2) and potassium carbonate (­ K2CO3), acidic
groups such as phosphoric acid ­(H3PO4) and sulphuric acid
­(H2SO4), intermediate metal salts such as Z ­ nCl2 and other
activating agents (Balajii and Niju 2019; Yahya et al. 2015).
Based on the physical nature of the activating agent, the acti-
vator and precursor could be mixed through two approaches:
the physical mixing of the activator and precursor in dry
conditions and impregnation (Nowicki et al. 2013; Yorgun
et al. 2016).
Activated carbon activators
Activated carbon preparation through activation
with phosphoric acid
Among the activating agents, phosphoric acid with the
chemical formula ­H3PO4 is widely used in the activation of
various lignocellulosic materials (Yahya et al. 2015; Yorgun
et al. 2016). In the reaction of phosphoric acid with ligno-
cellulose since cellulose is resistant to hydrolysis of acid,
at the beginning of the mixing of the compounds the acid
first reacts with the cellulose and lignin. Activation with
phosphoric acid is used in the preparation of activated car-
bon from various forms of biomass (Jadhav and Mohanraj
2016; Nowicki et al. 2013). Some studies on activation with
phosphoric acid and related details about activated carbon
prepared with this acid are listed in Table 1.
During the impregnation stage and due to the high polar-
ity of phosphoric acid, controlling the physical and chemi-
cal interactions occurring in the bulk of the solution and
with the substratum is essential. In this regard, the solution
concentration is a primary factor of the activation process
with this acid agent (Yahya et al. 2015; Yakout and El-Deen
2016; Yorgun et al. 2016). In a study by Demiral and Sam-
dan (2016) on the chemical activation of pumpkin skin by
phosphoric acid, it was found that the pores and cavities
formed on the active surface of activated carbon are cre-
ated due to the evaporation of phosphoric acid during the
carbonisation process (Demiral and Şamdan 2016; Yakout
and El-Deen 2016). The main mechanisms of activation with
phosphoric acid are the depolymerisation, dehydration and
redistribution of biopolymers in lignocellulosic materials
(Abdelnaeim et al. 2016; de Yuso et al. 2014). Also, during
the activation process, the reaction of phosphoric acid with
the active carbon-based precursor leads to the formation
of products in the form of particles or volatile substances,
which as a result create pores or increase the number of
pores in the sites previously occupied by this material (de
Yuso et al. 2014; Liu et al. 2010b). In addition, phosphoric
acid leads to the expansion of microporous and mesoporous
pores in activated carbon (Demiral and Şamdan 2016), so
the activated carbon produced from lignocellulose wastes
through activation with phosphoric acid is very porous (de
Yuso et al. 2014; Demiral and Şamdan 2016).
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 Environmental Chemistry Letters

Table 1  Comparison of the functional properties and textural characteristics of activated carbon prepared from various agricultural wastes and
activation with ­H3PO4
Precursor t (h) T (°C) IR (g/g) SBET ­(m2/g) Vt ­(cm3/g) Yield  % qmax (mg/g) Adsorbate References

Date palm pits 1.2 450 3 952 1.380 41 455 Methylene blue Reddy et al. (2012)
Eucalyptus camaldu- 1 500 1 1239 1.109 26 427 Methylene blue Patnukao and Pavasant
lensis Dehn bark (2008)
Vetiver roots 1 600 1 1272 1.190 48 394 Methylene blue Altenor et al. (2009)
Coffee grounds 1 450 1.8 925 0.718 367 Methylene blue Reffas et al. (2010)
Peach stones 2 500 0.4 1393 0.689 41.8 362 Methylene blue Attia et al. (2008)
Cotton cake 1.5 450 2 584 0.298 29.8 250 Methylene blue Ibrahim et al. (2014)
Bamboo 1 600 1.5 1335 0.625 183.3 Methylene blue Liu et al. (2010a)
Rice straw 2 450 1 522 0.550 51.9 109.1 Methylene blue Fierro et al. (2010)
Coffee residue 1 600 1 1003 0.618 46.95 Cadmium Boudrahem et al. (2011)
Pine cone 1 500 3 1094 1.096 55.7 27.53 Lead Momčilović et al. (2011)
Persian mesquite grain 2 600 1 1243 0.651 273 Lead Lemraski and Sharafinia
(2016)
Guava 1 600 1 471.3 0.31 42 11 Lead Brudey et al. (2016)
Lemon peel 1 500 2 1158 52.1 90.91 Lead Mohammadi et al. (2014)
Date pits 1 500 3 502.2 0.72 220 Lead Abdulkarim and Al-Rub
(2004)
Walnut shell 1.12 500 2 789 0.304 80 6.079 Zinc Moreno-Barbosa et al.
(2013)
Pomelo peel 1 450 2.5 1252 1.33 400 Ciprofloxacin Sun et al. (2016)
Waste potato peels 2 600 0.75 1041.43 2.960 51 405 Cobalt Kyzas et al. (2016)

t adsorption time, T activation temperature, IR impregnation rate, SBET BET surface area, Vt total pore volume, qmax maximum adsorption capac-
ity

Generally, acid refinement leads to an increase in acid
groups, eliminates mineral elements and improves the
hydrophilic nature of the surface, so the carbon surface will
have more access to the aqueous phase (Abdelnaeim et al.
2016; de Yuso et al. 2014). Phosphoric acid has two impor-
tant functions: It improves the pyrolytic decomposition of
the starting material and the formation of a grid structure
(net or lattice) (de Yuso et al. 2014; Liu et al. 2010b). How-
ever, the excessive amount of phosphoric acid due to the
formation of an insulating layer on the activated carbon does
not result in the enhancement of porosity on the activated
carbon surface (Zhong et al. 2012). According to a study
conducted by Liu et al. (2010b), at higher phosphoric acid
doses, more potential sites could be created and occupied by
the activating agent, which are beneficial to the subsequent
pore-opening and -widening processes (Liu et al. 2010b).
However, an excessive increase in phosphoric acid leads to
the formation of an insulating layer on the activated carbon
(Liu et al. 2010b; Zhong et al. 2012).
Vicinisvarri et al. (2014) investigated the effects of phos-
phoric acid concentration on the morphology of the acti-
vated carbon derived from the core and shells of nuts. The
results showed that by increasing phosphoric acid (80% by
weight), the highest porosity surface in activated carbon was
observed due to the increase in the velocity of the formation
of cavities. The outer surface of activated carbon has dif-
ferent vents, while the pore size depends on the amount
of carbonisation and impregnation. In this case, the whole
surface of activated carbon is full of holes and irregular
shapes (Vicinisvarri et al. 2014; Yakout and El-Deen 2016).
In a study of activated carbon production from olive stone
through activation by 60, 70 and 80% w/w of phosphoric
acid, Yakout and El-Deen (2016) reported that the surface
area of the activated carbon increased by increasing the con-
centration of the acid. It was found that the activated carbon
prepared with 80% phosphoric acid had the highest surface
area (1218 m2/g) and pore volume (0.63 cm3/g) (Yakout and
El-Deen 2016).
Shamsuddin et al. 2016 carried out a study of the synthe-
sis and characterisation of ­H3PO4-activated carbon prepared
from hemp fibre. The results indicated that the increases
in the surface area and porosity of activated carbon fibre
with acid activation were higher than crude activated car-
bon, and Fourier-transform infrared spectroscopy (FTIR)
showed the significant presence of peaks from different
frequencies before and after activation. The results of BET
analysis indicated an increase in the surface area and poros-
ity of activated carbon after acid activation (Shamsuddin
et al. 2016). It has been shown that the activated carbon
prepared with phosphoric acid has less C = O groups than

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Environmental Chemistry Letters

the raw materials. The reduction of carbonyl groups may be
due to the effect of ­H3PO4 hydrolysis, which decomposes
these groups and other products such as volatile substances
(Baccar et al. 2009). Phosphorus groups are among the most
important substances for the adsorption of heavy metals
from acidic solutions. H­ 3PO4-activated carbon may there-
fore be considered a cation exchanger for the removal of
heavy metal cations from aqueous solutions in the future
(Xu et al. 2014).
Acidic groups are the most derivative of the reaction
between phosphoric acid and activated carbon precursor
(Liu et al. 2010b). Activation with phosphoric acid leads
to the composition of the phosphorus element in the car-
bon structure (Baccar et al. 2009). Phosphoric acid is the
most commonly used chemical activator, can produce high-
porous activated carbon from raw materials and has fewer
environmental and toxicological contaminants than potas-
sium hydroxide and zinc chloride. Moreover, phosphoric
acid requires a lower activation temperature (Al Bahri et al.
2012; de Yuso et al. 2014), is not volatile and can form a
large number of alkaline or acid-soluble phosphates with
elements such as iron, nickel and boron and others that can
be incorporated into carbon precursors (Zou et al. 2016).
Yorgun et al. (2016) and Yorgun and Yildiz (2015) con-
firmed that ­H3PO4 was an effective activator agent, and they
observed via carbon electron micrograph scanning electron
microscope images that the pores created on the surface
of activated carbon are tunnel-shaped and generally have
a honeycomb structure. The honeycomb holes of the acti-
vated carbon have been fully developed as the corners of
the cavities were clearly visible (Yorgun and Yildiz 2015).
Acidic purification of activated carbon leads to an increase
in the adsorption of various pollutants on the surface due
to changes in the chemical surfaces of activated carbon as
observed in various articles (de Yuso et al. 2014; Sham-
suddin et al. 2016; Zhong et al. 2012), so purification can
lead to the removal of hydroxides and the creation of reac-
tive oxygen species groups on activated carbon. Also, the
number of acidic functional groups is strongly associated
with activated carbon capacity to absorb metal compounds
(Bhatnagar et al. 2013; Shamsuddin et al. 2016; Yorgun and
Yıldız 2015).
Activated carbon preparation through activation
with zinc chloride
Among the activating reagents, zinc chloride is widely used
to produce activated carbon, especially lignocellulosic and
cellulosic precursors (Arami-Niya et al. 2010). Table 2 illus-
trates the detailed properties of activated carbon prepared
through activation with zinc chloride (Zou et al. 2016).
Zinc chloride acts as a dampening agent for samples
impregnated with this material during activation. Move-
ment of volatile substances through zinc chloride-saturated

Table 2  Comparison of the functional properties and textural characteristics of activated carbon prepared from various agricultural wastes and
activation with ­ZnCl2
Precursor t (h) T (°C) IR (g/g) SBET ­(m2/g) Vt ­(cm3/g) Yield  % qmax (mg/g) Adsorbate References

Tea (Camellia sinensis 1 500 1 1530 0.783 44.1 324.7 Methylene blue Gao et al. (2013a)
L.) seed shells
Date stones 1.2 500 2 1045 0.641 40.4 381.7 Methylene blue Ahmed and Theydan
(2012)
Posidonia oceanica 2 600 4.5 1483 1.022 40 285.7 Methylene blue Dural et al. (2011)
(L.) dead leaves
Waste apricot 1 500 1 1060 0.790 136.9 Methylene blue Başar (2006)
Safflower biochar 1 900 4 801 0.393 26 128.2 Methylene blue Angın et al. (2013)
Waste potato residue 1 600 1.5 1357 1.065 29.2 540 Methylene blue Zhang et al. (2015b)
Sugar beet bagasse 1.5 700 3 1826 0.966 27.55 Nitrate Demiral and Gündüzoğlu
(2010)
Coffee residue 1 600 1 889 0.765 63.29 Lead Boudrahem et al. (2011)
Tomato processing 1 600 6 1093 1.569 38.20 385 Metanil yellow  Sayğılı and Güzel (2016)
solid waste
Vine shoots 2 700 1.3 1689 0.842 18.21 746.2 Rifampicine Erdem et al. (2016)
Sea-buckthorn stones 3 550 2 829 33 25.91 Lead Mohammadi et al. (2010)
Fox nutshell 1 600 2 2869 1.96 32.83 75.37 Phenol Kumar and Jena (2016)
Enteromorpha prolifera 1 500 1 1688 1.04 146.85 Lead Li et al. (2010)
Cashew nut shell 2 400 1.5 1100 0.565 59 476 Methylene blue Spagnoli et al. (2017)
Sewage sludge-derived 1 600 2 172 0.193 55.5 Dibenzothiophene Nunthaprechachan et al.
(2013)

13

pores is not disrupted, and after that, during the activation
process, volatile substances are released from the surface of
activated carbon. Increasing the mass ratio of zinc chloride
causes easier release of volatile substances, so the absorption
of nitrogen increases on the activated carbon (Arami-Niya
et al. 2010). Zinc chloride activation induces an electrolytic
action called swelling in the molecular structure of cellulose.
Inflation causes a breaking down of the cellulose molecules
and leads to an increase in different intra- and inter-coated
cavities, which causes a higher surface area in the activated
carbon (Saka 2012). During the activation process, lignocel-
lulosic materials are converted into carbon, and hydrogen
atoms, oxygen, carbon monoxide, carbon dioxide, methane
and aldehydes are liberated, and diatomaceous distillates
are produced (Anisuzzaman et al. 2016). Zinc chloride pre-
vents the formation of bitumen and other fluids that block
the surface of carbon monoxide and prevent the movement
of volatile substances, and volatile substances are subse-
quently released from the surface of activated carbon (Deng
et al. 2009).
In activation with zinc chloride, the yield of activated
carbon increases due to polymerisation by zinc chloride and
the creation of a few large-ring aromatic compounds (Anisu-
zzaman et al. 2016). Since zinc chloride does not react with
carbon, the obtained activated carbon has a higher yield
than activated carbon produced with potassium hydroxide.
Using of zinc chloride leads to the removal of the hydrogen
and oxygen atoms from the activated carbon structure (Gun-
dogdu et al. 2013). The effect of temperature and amount of
zinc chloride on various atoms is that the content of hydro-
gen and oxygen decreases while nitrogen increases (Aloth-
man et al. 2011). Zinc chloride acts as a Lewis acid and
enhances the condensed aromatic reactions by facilitating
molecular hydrogen deformation from the hydro-aromatic
structure of precursors so, through the exclusion of some
of the active sites from the adjacent molecules, polymerisa-
tion reactions occur and are affected (Alothman et al. 2011;
Gundogdu et al. 2013).
By increasing the amount of zinc chloride, more cracks
may occur in the structure of activated carbon, so the pro-
ductivity may decline, resulting in an increase in the mes-
oporosity of the activated carbon structure. It can be said
that by increasing the weight ratio of zinc chloride, the struc-
ture breaks down and the micropores deform and become
mesopores (Donald et al. 2011; Gundogdu et al. 2013).
Increasing the amount of zinc chloride leads to the removal
of volatile compounds from the activated carbon structure,
so the number of acidic groups is reduced. It has also been
reported that by increasing zinc chloride, the phenolic
and carboxylic groups are also affected, while the lactone
groups are not. Then, during activation with zinc chloride,
phenolic and carboxylic groups are reduced, while lactone
groups are increased (Angin 2014; Gundogdu et al. 2013).
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Environmental Chemistry Letters
By increasing the amount of zinc chloride activating agent,
the percentage of carbon and mesopores in the structure of
the prepared activated carbon is increased (Gundogdu et al.
2013). Cavities on the surface of the activated carbon result
from the evaporation of spaces occupied by zinc chloride
during the carbonisation process, so chloride is an active
agent in producing activated carbon with a high surface area
and provides higher adsorption capacity (Angin 2014; Gun-
dogdu et al. 2013).
In a study conducted by Arami-Niya et  al. (2010), it
was observed that the BET surface area and micropore and
mesopore volumes of activated carbon prepared increased by
increasing the amount of zinc chloride in the initial activa-
tor/precursor mixture. Moreover, by increasing the amount
of zinc chloride, the removal of tar from the activated car-
bon structure was increased, as was the release of volatiles
(Arami-Niya et al. 2010). Although zinc chloride is an excel-
lent activating agent in activated carbon preparation, it is
seldom used in the food and pharmaceutical industries due
to its health-related problems (Anisuzzaman et al. 2016;
Saka 2012).
Activated carbon preparation through activation
with potassium carbonate
Potassium carbonate with the chemical formula ­K2CO3 is a
well-known activating agent in the production of activated
carbon (Abbas and Ahmed 2016; Budinova et al. 2008).
Table 3 shows the performance and properties of activated
carbon produced from various agricultural materials and
activated with ­K2CO3. Potassium and sodium hydroxide
have adverse effects, but potassium carbonate is not harmful
if used for food supplements (often used as supplementary
food supplements) (Budinova et al. 2008). Potassium car-
bonate is known to be a better activating agent than potas-
sium hydroxide due to the production of activated carbon
with higher yield, higher surface and pore volume, and
higher capacity for adsorbing large molecules like methyl-
ene blue from aqueous solutions (Abbas and Ahmed 2016).
A study by Tay et al. (2009) showed that the activated
carbon produced by potassium carbonate had higher yields
than the activated carbon produced by potassium hydroxide.
Also, under the same conditions, the specific surface area of
the activated carbon produced from potassium carbonate is
more than the carbon produced from potassium hydroxide.
In addition, the activated carbon produced from potassium
carbonate has lower ash and sulphur content than the acti-
vated carbon produced from potassium hydroxide (Tay et al.
2009). Foo and Hameed (2012c) reported that by increas-
ing the ratio of potassium carbonate to char, the adsorptive
capability of prepared orange peel-based activated carbon
was enhanced (Foo and Hameed 2012c). Moreover, the pres-
ence of potassium carbonate prevents the formation of tar
Environmental Chemistry Letters

Table 3  Comparison of the functional properties and textural characteristics of activated carbon prepared from various agricultural wastes and
activation with ­K2CO3
Precursor t (h) T (°C) IR (g/g) SBET ­(m2/g) Vt ­(cm3/g) Yield  % qmax (mg/g) Adsorbate References

Rice husk ash 1.5 1000 1.5 1713 1.785 210 Methylene blue Liu et al. (2012)
Mangosteen shell 2 900 1 1123 0.560 20.7 100 Methylene blue Chen et al. (2011)
Bamboo 0.5 750 3 2237 1.23 613 Ciprofloxacin Wang et al. (2015)
Pine 2 800 3 1509 0.66 35 434.8 Acetaminophen Galhetas et al. (2014b)
Pine 2 800 1 945 0.40 50 500 Caffeine Galhetas et al. (2014b)
Bean pods 1 700 4 1580 0.809 300 Naphthalene Cabal et al. (2009)
Cork waste 1 700 1 891 0.42 153.2 Ibuprofen Mestre et al. (2007)
Waste apricot 1 900 1 1214 0.703 101.01 Nickel Erdoğan et al. (2005)
Sisal waste 1 700 0.5 1038 0.49 120.5 Paracetamol Mestre et al. (2011)
Peach stones 1 700 1 866 0.385 204 Acetaminophen Cabrita et al. (2010)
Pine gasification residues 1 900 3 1171 0.45 270.3 Acetaminophen Galhetas et al. (2014a)

and other liquids such as acetic acid and methanol during
the process (Adinata et al. 2007). The main reactions that
may occur between the activating agent of potassium car-
bonate and activated carbon under gasification conditions
(during the activation process) are presented in Eqs. (1)–(3)
as follows (Adinata et al. 2007; Foo and Hameed 2012c;
Horikawa et al. 2010):
K2 CO3 + 2C → 2K + 3CO
K2 CO3 → K2 O + CO2
K2 O + 2C → 2K + CO
According to these equations, the development of poros-
ity during activation with K­ 2CO3 is attributed to its reduc-
tion under inert condition to form K, ­K2O, ­CO2 and CO.
The potassium compound formed during the activation stage
penetrates the internal structure of char matrix, expands the
existing pores and creates new pores (Adinata et al. 2007;
Foo and Hameed 2012c; Horikawa et al. 2010). Also, due to
the evaporation of potassium carbonate, the cavities on the
activated carbon surface could be produced from the occu-
pied spaces by the activating agent. These cavities create
channels that provide the adsorbent molecules with access
to the micro- and mesopores of the activated carbon (Abbas
and Ahmed 2016). In K ­ 2CO3-activated carbons, phenolic
groups in the surface area are more specific than the other
groups and, with the increase in the activation temperature,
the number of functional groups decreases (Horikawa et al.
2010). Also, by increasing the concentration of potassium
carbonate, the dehydration effect decreases and leads to the
degradation of mesopores, which reduces the adsorption effi-
ciency. By increasing the carbonisation temperatures from
600 to 800 °C, the microporous pores increase on the surface
of the activated carbon (Tay et al. 2009).
Activated carbon preparation through activation
with sodium hydroxide
Studies show that chemical activation using alkaline materi-
als such as sodium hydroxide and potassium hydroxide pro-
duces large amounts of microspores on the activated carbon
surface (Martins et al. 2015). Sodium hydroxide is widely
known as an effective activating agent for the production
(1) of activated carbon (Table 4) (Pezoti et al. 2016). The pro-
posed reactions during activation by NaOH are presented
(2) in Eqs. (4)–(6) as follows (Martins et al. 2015; Pezoti et al.
2016):
(3)
6NaOH + 2C → 2Na + 2Na2 CO3 + 3H2 (4)
Na2 CO3 → Na2 O + CO2 (5)
2Na + CO2 → Na2 O + CO (6)
The possible reactions between active substances and
the surface of the organic precursor result in the creation
of micropores on the activated carbon surface due to: i)
the release of CO, C­ O2, ­H2 gases [Eqs. (4)–(6)], which are
produced by ­Na2CO3 decomposition at high temperature
and hydroxyl reduction, respectively, and ii) alkali metal
intercalation into the carbon structure (Martins et al. 2015;
Pezoti et al. 2016). As a result, the evaporation of sodium
hydroxide and other compounds derived from activated car-
bon gives rise to a rugged surface with different pore sizes,
indicating that the porous structure is well developed and
that these canals are suitable channels for adsorbent materi-
als to penetrate the surface of the activated carbon (Liou
et al. 2016; Martins et al. 2015; Pezoti et al. 2016).
Through the oxidation reduction process, sodium hydrox-
ide causes the separation and destruction of the graphite
layers and thereby makes the pores expand (Liou et al. 2016;

13
 Environmental Chemistry Letters

Table 4  Comparison of the functional properties and textural characteristics of activated carbon prepared from various agricultural wastes and
activation with NaOH
Precursor t (h) T (°C) IR (g/g) SBET ­(m2/g) Vt ­(cm3/g) Yield  % qmax (mg/g) Adsorbate References

Coconut shell 1.5 700 3 2825 1.498 18.8 916.3 Methylene blue Cazetta et al. (2011)
Rice husk 3 850 2 1958 1.123 492.6 Methylene blue Youssef et al. (2012)
Guava seeds 1.5 750 3 2573.6 1.260 14.94 570.48 Amoxicillin Pezoti et al. (2016)
Plum kernels 1 780 4 1887 1.049 37 277 Phenol Tseng (2007)
Macadamia nut shells 1.5 700 3 1524 0.826 19.79 455.33 Tetracycline Martins et al. (2015)
Factory-rejected tea 1 800 3 368.2 0.21 487.4 Methylene blue Islam et al. (2015)
Rattan (Lacosperma 1 600 3 1135 0.61 359 Methylene blue Islam et al. (2017)
secundiflorum)
Cotton linter fibres 1 550 3 2143 0.948 1340 Oxytetracycline (OTC) Sun et al. (2012)
Date press cake 1.5 650 2 2025.9 0.932 26.2 282.8 Cr(VI) Norouzi et al. (2018)

Pezoti et al. 2016). The production of carbonates and alkali
metals in the carbon matrix leads to the sustainability and
expansion of the spaces between the carbon atomic layers
so, by increasing the sodium hydroxide-to-char ratio in the
activation process, it plays a key role in the development
of pores and increasing the surface area and pore volume
(Foo and Hameed 2012a). However, according to Eq. (7),
excess sodium hydroxide promotes a vigorous gasification
reaction, which destroys the walls between the pores, leading
to a dramatic decrease in accessible area. Moreover, excess
sodium hydroxide molecules deposited in the carbon pore
wall might cause catalytic oxidation and decomposition,
lowering the adsorption capacity and carbon yield (Foo and
Hameed 2012a):
4NaOH + C → 4Na + CO2 + 2H2 O
In chemical activation with alkali, activation with potas-
sium hydroxide generally shows better results than sodium
hydroxide in terms of surface area and performance in dif-
ferent applications. However, sodium hydroxide is cheaper,
more environmentally friendly and less harmful than potas-
sium hydroxide, and it is clear that sodium hydroxide has
industrial applications due to its superiority to potassium
hydroxide (Gratuito et al. 2008). At high temperatures, the
reaction between carbon and sodium hydroxide leads to the
reduction of sodium cation to a sodium metal, the formation
of sodium carbonate and the reduction of hydroxyl anion
to hydrogen gas (Mestre et al. 2007). The results of the
Byamba-Ochir et al. (2016) study showed that the activation
of carbon by sodium hydroxide through physical mixing of
precarbonised precursor and solid sodium hydroxide resulted
in more porous activated carbon than that prepared using the
impregnation procedure (Byamba-Ochir et al. 2016). Also,
Foo and Hameed (2012b) studied the application of different
activating agents in the preparation of activated carbon from
langsat (Lansium domesticum) empty fruit bunch waste. In
that study, sodium hydroxide was selected as the best acti-
vating agent due to its higher adsorption capacity, lower
cost, lower environmental pollution during its life cycle
and lower level of corrosiveness (Foo and Hameed 2012b).
According to a review of various articles, activation with
metal hydroxides such as sodium hydroxide and potassium
can be used for the preparation of activated carbon with a
high surface area in the range of 3500–2300 m2/g (Tong-
poothorn et al. 2011).
Activated carbon preparation through activation
with potassium hydroxide
In recent years, potassium salts such as KOH and ­K2CO3
have been widely used in the production of low-cost acti-
(7) vated carbon (Hui and Zaini 2015). Among the various acti-
vators, potassium hydroxide has been extensively used, due
to its ability to produce activated carbon with a high surface
area, its distribution of fine pore size under the same condi-
tions, low environmental pollution, less corrosiveness and
lower cost (Chayid and Ahmed 2015; Zuo et al. 2016). The
chemical activation of phosphoric acid and zinc chloride
is used to activate lignocellulosic materials that have not
previously been carbonised, while metal compounds such as
potassium hydroxide are used to activate the precursors of
coal (Yakout and El-Deen 2016). Several reports have been
presented on the effectiveness of KOH-activated carbon in
the adsorption of various organic chemicals such as phenol,
dyes, heavy metals and pesticides (Table 5).
Tounsadi et al. (2016) reported that activated carbon with
potassium hydroxide has the highest efficiency in the adsorp-
tion of heavy metals compared to other activators (Toun-
sadi et al. 2016). Cavities formed in activated carbon are
the result of the evaporation of potassium hydroxide from
places previously occupied by this activator (Njoku et al.
2013). KOH activator is an activating agent rapidly saturated
with precursors and does not evaporate completely, so its

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Environmental Chemistry Letters

Table 5  Comparison of the functional properties and textural characteristics of activated carbon prepared from various agricultural wastes and
activation with KOH
Precursor t (h) T (°C) IR (g/g) SBET ­(m2/g) Vt ­(cm3/g) Yield  % qmax (mg/g) Adsorbate References

Cane pith 1 780 5 2207 1.290 8.2 684.5 Methylene blue Tseng and Tseng
(2006)
Rice straw 1 800 4 1554 0.930 13.5 395.3 Methylene blue Basta et al. (2009)
Tyre pyrolysis char 1 750 5 700 1.099 53 316.60 Tetracycline Acosta et al. (2016)
Spartina alterniflora 1.5 450 3 2825 1.374 32 719 p-Nitroaniline Liu et al. (2013)
Bamboo 2 850 1 1896 1.109 454.2 Methylene blue Hameed et al. (2007)
Lignin of papermak- 1 750 3 2943 1.901 41.6 14.02 Nickel Gao et al. (2013b)
ing black liquor
Oil palm empty fruit 1.9 814 2.8 1141 0.6 17.96 168.89 2,4,6-Trichlorophenol Hameed et al. (2009)
bunch
Coconut shell 2 850 1 1026 0.576 205.8 Phenol Din et al. (2009)
Kraft lignin 1 700 3 2920 1.583 213 Phenol Vicinisvarri et al.
(2014)
Wood 2 700 0.75 1255 0.596 180.3 Chromium Khezami and Capart
(2005)
Maize stalks 1 700 0.75 1414 0.725 13.1 347 Lead El-Hendawy (2009)
 Glucose 3 800 3 1612 0.86 24.6 Copper Huang et al. (2014)
Silkworm cocoon 3 800 1 2797 1.735 21.7 519 Congo red Li et al. (2015)
waste
Petroleum coke 1 800 5 2940 1.658 47.95 1121.5 Tetracycline Zhang et al. (2015a, b)
Pomegranate peel 0.5 700 1 941.02 0.470 370.86 Remazol brilliant Ahmad et al. (2014)
blue reactive
Pomelo peel 2.5 800 2 1892.10 1.095 680.2 Methyl orange Li et al. (2016b)
Fir wood 1 780 4 2179 1.24 17.8 69 Phenol Wu et al. (2005)
Date press cake 1.5 750 3 2632.5 1.239 44.5 546.8 Methylene blue Heidarinejad et al.
(2018)

activation temperature is generally lower than the boiling
point of KOH (1327 °C) (Hui and Zaini 2015). KOH-acti-
vated carbon has a higher surface area and pore volume, but
typically has lower yield (10–40%) compared to other activa-
tors such as Z­ nCl2 and H­ 3PO4 (Ahmed and Theydan 2014).
During activated carbon activation with alkali substances,
alkali metals and carbonates are created which, in the carbon
matrix, are responsible for the stability and expansion of
the spaces between the carbon-atom layers and, as a result,
increase the efficiency and adsorption capacity of activated
carbon (Ahmed and Theydan 2014; Njoku et  al. 2013).
Activated carbon produced from potassium hydroxide has
a higher microporous structure than activated carbon pro-
duced from sodium hydroxide (Ahmed and Theydan 2014;
Wu et al. 2010). By increasing the dosage of potassium
hydroxide, microporous pores develop on the surface of the
activated carbon, while the mesoporous pores decrease due
to the characteristics of the potassium hydroxide activators
(Wu et al. 2010).
The results of a study by Jin et al. (2014) showed that
chemical activation for the preparation of activated carbon
from municipal waste with potassium hydroxide (2 M) sig-
nificantly (Jin et al. 2014):
1. Increased the surface area and the total pore volume.
2. Modified the number of functional groups on the
surface.
3. Increased the removal of arsenic in a shorter time.
4. Improved the arsenic adsorption capacity.
The possible reactions that may occur during the acti-
vation process with potassium hydroxide are presented in
Eqs. (8)–(11) as follows (Meng and Park 2010; Jin et al.
2014):
2KOH → K2 O + H2 O (8)
C + H2 O → H2 + CO (9)
CO + H2 O → H2 + CO2 (10)
K2 O + CO2 → K2 CO3 (11)
Activated carbon with potassium hydroxide is oxidised in
alkaline medium with high oxygen content (Huang and Zhao
2016). In strong activation with a high amount of potassium
hydroxide, carbon atoms are eliminated from the internal
structure of carbon, and the BET surface area increases

13

with the formation of a porous structure (Vukčević et al.
2015). Oxygenated functional groups as active sites are able
to interact with other molecules in adsorption applications
(Bedin et al. 2016). By increasing the activation temperature
of potassium hydroxide, the surface area of activated car-
bon and the number of oxygen groups of activated carbon
increase (Vukčević et al. 2015). Generally, by increasing the
impregnation ratio of potassium hydroxide to char, the sur-
face area of the activated carbon increases, but if the amount
of potassium hydroxide is about eight times greater, the
walls between pores formed on activated carbon are further
degraded so the surface area is reduced (Huang et al. 2015).
Increasing the concentration of potassium hydroxide activa-
tor, the dehydration and degradation of the mesopores and
their conversion to larger pores probably lead to a decrease
in the adsorption capacity of activated carbon (Ahmed and
Theydan 2014). The reactions of carbon with alkali metal
activators are presented in Eqs. (12) and (13) as follows (Cha
et al. 2016):
6NaOH + 2C ↔ 2Na + 3H2 + 2Na2 CO3 (12)
6KOH + 2C ↔ 2K + 3H2 + 2K2 CO3 (13)
Correspondingly, ­K2CO3, along with carbon, is reduced
to K, ­K2O, CO and ­CO2 in accordance with the following
Eqs. (1)–(3).
Potassium metal is thought to be introduced into the inter-
nal structure of the carbon matrix during the gasification
process, leading to the expansion of existing pores and the
creation of new ones (Ahmed and Theydan 2014). There-
fore, increasing the amount of potassium hydroxide plays
a key role in porosity modelling. Porosity expands success-
fully, and micro- and mesopores are formed in the off-centre
walls of the pores, which increases the Brunauer, Emmett
and Teller surface area and pore volume (Chayid and Ahmed
2015).
Activation with potassium hydroxide can also be accom-
plished through direct chemical activation (physical mixing)
or impregnation with activated chemicals. In direct chemical
activation, in the first stage activated carbon precursors get
saturated, moisture is removed and activation occurs at the
desired ratio (KOH weight is greater than precursor weight).
The impregnation is solid and then placed in the furnace at
a specified temperature and time to heat it. Precursor car-
bonisation is often eliminated when the solid impregnation
method is considered (Chayid and Ahmed 2015; Hui and
Zaini 2015). By increasing activation, a large amount of
potassium hydroxide is typically used, and the weight ratio
of KOH to carbon is in the range of 3–7 in most cases. This
not only increases the cost of preparation of materials but
also increases the potential for environmental hazards caused
by potassium hydroxide, the corrosiveness of the process of
13
Environmental Chemistry Letters
washing with acid solutions, which results in using other
appropriate methods (such as potassium induction as an acti-
vation agent by ion exchange) for activation with potassium
hydroxide (Ahmed and Theydan 2014; Chayid and Ahmed
2015; Hui and Zaini 2015; Wang et al. 2016).
Also, in the char impregnation method with KOH, potas-
sium hydroxide molecules are readily in contact with the
surface of the char, thus leading to a higher degree of micro-
and mesoporosity. At the stage of washing the activated car-
bon, a significant amount of potassium hydroxide is intro-
duced into the aquatic media before use. Some studies have
focused on the significant concerns regarding the release
of spent potassium hydroxide residues during activation, in
terms of either environmental risks or their recovery poten-
tial after activation (Chayid and Ahmed 2015; Hui and Zaini
2015; Wang et al. 2016).
The mechanism of the potassium hydroxide reaction is
described by Radovic and Rodriguez-Reinoso. In this mech-
anism (Fig. 4), potassium hydroxide is converted to ­K2O at
the beginning of the dehydration process (step 1), and then
­K2O is converted to metallic potassium (step 2) (Tounsadi
et al. 2016). The free potassium then penetrates the graphene
layers and causes the structural expansion of the graphene
layers. Moreover, after a series of reactions during activation
with potassium hydroxide, oxidation (step 3) and hydration
(step 4), various potassium compounds form. The carbon
produced with chloride acid 0.1 N and water is then washed
to remove K, ­K2O, ­K2CO3 and KOH residues from the gra-
phene layers. However, potassium carbonate will decompose
during the activation process and ­CO2 will be emitted. The
reaction between the activating agent and the precursor of
carbon materials results in the decomposition of volatile
organic compounds, thus creating a porous surface on the
surface of the activated carbon samples (Nur 2015; Tounsadi
et al. 2016).
Among the alkali metals, potassium hydroxide and
sodium hydroxide are effective activators in producing acti-
vated carbon. Among the alkaline metals, KOH is the most
effective factor for producing activated carbon. Researchers
have been able to provide convincing descriptions of the
activated carbon activation process with KOH (Rambabu
et al. 2015). The results showed that sodium hydroxide has
a lower efficiency than potassium hydroxide in the chemi-
cal activation of activated carbon, which is due to the dif-
ferent performances of metal hydroxides in the activation
of activated carbon (Rambabu et al. 2015; Tay et al. 2009;
Tounsadi et al. 2016).
Although potassium hydroxide increases the pore sur-
face, potassium hydroxide-saturated activated carbon is less
efficient than activated carbon saturated with zinc chloride
or phosphoric acid, so activating with potassium hydroxide
requires a high temperature (greater than 650 °C) and car-
bon content is less than constant carbon in the precursor.
Environmental Chemistry Letters
Fig. 4  Mechanisms of KOH
activation. Adapted by kind per-
mission of Noureddine Barka
(Tounsadi et al. 2016)
In this condition, the potassium metal is placed in the car-
bon matrix, with activated carbon efficiency lower than the
carbon content of the raw material (Prauchner et al. 2016;
Rambabu et al. 2015; Thitame and Shukla 2016; Yakout and
El-Deen 2016). The use of KOH as an active agent is to pro-
duce activated carbon with a narrow pore size distribution
and the development of effective porosity. It is believed that
the activation mechanism with alkali metals such as KOH
relies on the fact that alkali metals act as an input catalyst in
the carbon network, an electron donor, during the reaction to
gas (gasification) (Rambabu et al. 2015; Yahya et al. 2015).
Also, using KOH as an activator has been proposed for
environmental compatibility with ­ZnCl2 (Yahya et al. 2015;
Yakout and El-Deen 2016). Generally, chemical activation
with alkaline groups leads to an increase in the positive
charge on activated carbon, which is desirable to absorb
contaminants with a negative charge (Bhatnagar et al. 2013;
Thitame and Shukla 2016).
Activated carbon preparation through activation
with other activating agents
Table 6 shows the performance and properties of prepared
activated carbon from various agricultural materials and
activated with various uncommon activating materials.
Phytic acid with the chemical formula ­C 6H 18O 24P 6
(Fig. 5) is one of the new activator materials. Phytic acid
is a strong type of acid with the ability to chemically react
with proteins in the form of a partial depolymerisation. In
addition, phytic acid can easily enter into the spaces of raw
material and cause dehydration on hemicelluloses and cel-
lulose (Cheng et al. 2016).
Phytic acid decomposition can simultaneously lead to
the release of some of the radicals that can accelerate oxi-
dative decomposition and the process of carbonisation at
lower temperatures. As a result, some cracks and pores are
generated on the activated carbon surface after activation.
By increasing the amount of impregnation, the pores on the
activated carbon surface are reduced because they are fur-
ther degraded by increasing the amount of impregnation,
and more organic matter is produced, so it is deposited on
the activated carbon surface and the pores are blocked (Al-
Qodah and Shawabkah 2009; Cheng et al. 2016). In other
studies, it was found that, by increasing the impregnation of
activated carbon created with phytic acid, the acid decom-
poses into di-ester or monoester and eventually turns into
phosphorus oxoacids, which can create organic materials
with high amounts of free radicals, as well as increasing
the efficiency. Sulphuric acid is a chemical activating agent
that is able to dissolve many minerals and impurities from
activated carbon precursor (Al-Qodah and Shawabkah 2009;
Cheng et al. 2016; Olivares-Marín et al. 2012). An alterna-
tive method is chemical purification of dry carbonisation
with concentrated sulphuric acid. Sulphuric acid is a highly
reactive material that can be combined with organic com-
pounds (such as carbohydrates and other organic materials)
to remove water and break down organic precursors into
carbon elements according to Eq. (14) (Olivares-Marín et al.
2012):
Cn H2n On + H2 SO4 → nC + H2 SO4 ⋅ nH2 O (14)
In addition, sulphuric acid reacts with the mineral com-
pounds of lignocellulosic material. In fact, sulphuric acid is
used as a cleaning and de-ashing agent from activated carbon
precursors, so using H­ 2SO4 for carbonisation has some advan-
tages in addition to low cost (Olivares-Marín et al. 2012). Acti-
vation with sulphuric acid has been used for various porous
structures, in which the sulphuric acid activation process enters
into the material and leads to large and medium porosity on
13
 Environmental Chemistry Letters

the surface of the activated carbon (Al-Qodah and Shawabkah

Ahmed and Theydan (2012)

Theydan and Ahmed (2012)

Auta and Hameed (2011b)

2009; Cheng et al. 2016; Olivares-Marín et al. 2012).
Di-ammonium hydrogen with a molecular formula

Karagöz et al. (2008)

Oliveira et al. (2009)

Mouni et al. (2011)

of ­( NH 4) 2HPO 4 obtained from ammonium phosphate

Chen et al. (2013)

Tang et al. (2012)
Gao et al. (2011)
Table 6  Comparison of the functional properties and textural characteristics of activated carbon prepared from various agricultural wastes and activation with others activating agents

Liu et al. (2016)

((NH4)3PO4) decomposition at temperatures above 155 °C
is one of the activating agents for the production of acti-
References

vated carbons with various pore distribution and surface area

(Benaddi et al. 2000). In a study by Li et al. (2016a) con-
ducted on activated carbon preparation with different ammo-
nium phosphate groups, it was found that the activated carbon
Methylene blue
Methylene blue
Methylene blue
Methylene blue
Methylene blue

Methylene blue
prepared with (­ NH4)3PO4 (activated carbon –(NH4)3PO4) had

Acid Blue 25
much higher surface area and pore volume than those pre-
Adsorbate

Phenol

pared with ­(NH4)2HPO4 (activated carbon –(NH4)2HPO4) and

Dyes

Lead
­NH4H2PO4 (activated carbon –NH4H2PO4), while activated
carbon –(NH4)2HPO4 had the largest micropore volume ratio.
Activated carbon –NH4H2PO4 had a lower specific surface
qmax (mg/g)

area. The different micropore sizes distribution in the car-

181.03

259.25

203.34

bons was attributed to the different molecular sizes of these

314.1
129.5

359.9

21.38
16.4
330

75

­(NH4)x ­HyPO4. In this regard, activated carbon –(NH4)3PO4

had the highest pore volume because (­ NH4)3PO4 can be con-
verted to lower-sized N ­ H4H2PO4. Overall, activated carbon
Yield  %

–(NH4)2HPO4 had higher nickel adsorption capacity than other

47.08

47.08
26.5
41.1

42.6

37.9

adsorbents (Li et al. 2016a). The results of the study obtained

by Benaddi et al. (2000) showed that the maximum obtained
surface area in activated carbon prepared by phosphoric acid
Vt ­(cm3/g)

was 1800 m2/g (Benaddi et al. 2000), while in the results of the

0.680
0.568
0.670
0.510
0.116
0.573
1.493
0.573
0.192
0.219

study Liodakis et al. (2009), the highest surface area obtained

in activated carbon prepared by ­(NH4)2HPO4 was about
1350 m2/g, but the pore structure of (­ NH4)2HPO4-activated
SBET ­(m2/g)

carbon was mainly composed of micropores (Liodakis et al.

2009).
393.2
1258
1061
1154

1924
956
240
780

780

820

Ferric chloride is an activating agent that has rarely been

used as such. The small size of iron cations enables ferric chlo-
ride to produce activated carbon of small pore size. Various
IR (g/g)

reports indicate that impregnation with ferric chloride has a

0.7
0.5

0.9
1.5

1.5
0.5

significant effect on increasing the specific surface area and

5
1

development of micropores (Theydan and Ahmed 2012).

During the activation process of potassium hydroxide with
T (°C)

800
800
700
550
600
700
500
700
650
800

activated carbon, potassium acetate (­ C2H3O2K) is produced,

which is known as a good activator (Auta and Hameed 2011a).
Potassium acetate is converted to potassium and acetate ions
1.25

1.33
t (h)

2.5

1.5

0.5

when dissolved in deionised water. Under optimal conditions,

2
1
3
1

the adsorption of opposite charges in the solution of both

potassium acetate and water leads to the formation of new
C2H3O2K
N2H9PO4
N2H9PO4
Activator

K2C2O4

compounds such as KOH from the hydrolysis of metal ions

H2SO4

H2SO4
CuCl2
FeCl3

FeCl3

FeCl3

(Auta and Hameed 2011b).

Sunflower oil cake
Ramulus mori

Apricot stone
Coffee husks

Date stones
Kenaf core

Rice straw

Rice husk

Waste tea
Precursor

Date pits

13
Environmental Chemistry Letters
Fig. 5  Structure of phytic acid
The effect of physical mixing
and impregnation methods on chemical
activation
In the chemical activation process, the initial mixing
of dry precursor and alkali hydroxides (such as sodium
hydroxide and potassium hydroxide) could be performed
in two ways (Lillo-Ródenas et al. 2007):
1. Impregnation In this method, precursors are mixed with
suitable volumes of hydroxide solutions and then the
samples are filtered and dried at 110 °C.
2. Physical mixing In this method, the precursors are mixed
directly with solid hydroxide lentils at room temperature
and other activation steps are performed (it should be
emphasised that this process is done in the absence of
water).
These two simple processes are useful for activating
with sodium hydroxide and potassium hydroxide. In addi-
tion, it has been proven that the method of physical mixing
is much more efficient in the case of sodium hydroxide
(Lillo-Ródenas et al. 2007). A study by Ros et al. (2006)
on the preparation of activated carbon from sewage sludge
showed that activation with sodium hydroxide through
physical mixing, compared to impregnation, led to a
higher Brunauer, Emmett and Teller surface area in the
final activated carbon. This finding was attributed to bet-
ter physical contact between the precursor and the sodium
hydroxide powder in the physical mixing method (Ros
et al. 2006). Overall, the physical mixing method is good
for the development of porosity in activated carbon (Lillo-
Ródenas et al. 2007; Ros et al. 2006). The behaviour of
NaOH and KOH is very similar, although activation with
KOH produces a slightly higher porosity (Lillo-Ródenas
et al. 2007; Ros et al. 2006). The general reaction of metal
hydroxides during the activation stage of activated carbon
production is according to Eq. (15) (Lillo-Ródenas et al.
2007; Ros et al. 2006):
6MOH + 2C → 2M + 3H2 + 2M2 CO3 (15)
M = Na; K
Activation after physical mixing is rarely studied (Lillo-
Ródenas et al. 2001). In a study by Lillo-Ródenas et al.
(2001) to compare the impregnation and physical mixing
methods of the sodium hydroxide activator, the results
indicated that the activated carbon produced by the physi-
cal mixing had a higher porosity than the activated carbon
produced by impregnation (Lillo-Ródenas et al. 2001).
Also, the activated carbon obtained from physical mixing
has a higher surface area and greater pore volume than
the activated carbon obtained by impregnation. Moreover,
since the physical mixing method requires less time and
work than the impregnation method, physical mixing is
appropriate to produce activated carbon on an industrial
scale (Alabadi et al. 2015; Lillo-Ródenas et al. 2001).
In a study by Byamba-Ochir et al. (2016) on the activa-
tion of activated carbon induced by anthracite with NaOH,
both activation methods (physical mixing and impregna-
tion) were used. The results indicated that the activation
process under the same conditions by physical mixing
resulted in higher Brunauer, Emmett and Teller surface
area and pore volume than by impregnation, so the surface
areas of the activated carbon obtained by physical mix-
ing and impregnation were reported to be 2063–1357 and
1763–816 m2/g, respectively. In this regard, the adsorption
capacity of activated carbon prepared through physical
mixing was higher than that prepared through impregna-
tion (Byamba-Ochir et al. 2016). Studies showed that the
activation process by the impregnation method creates
both micro- and mesopores, while in the physical mixing
method, mesopores were formed on activated carbon. Acti-
vated carbon derived from impregnation resulted in more
oxygenated functional groups and less carbon bonds than
that produced by physical mixing (Alabadi et al. 2015;
Byamba-Ochir et al. 2016; Lillo-Ródenas et al. 2001).
13
 Environmental Chemistry Letters

Other studies also reported that, through impregnation,
more micropores are created on the activated carbon surface
and a small fraction of the pores are mesopores. It seems
that, in the impregnation method, small micropores are
developed during the activation process, because the chemi-
cal activating agent is better distributed into the pores of raw
material than by the physical mixing method (Byamba-Ochir
et al. 2016; Lee et al. 2015; Lillo-Ródenas et al. 2001).
Basically, the two approaches mentioned in the process of
activation of carbon precursors using alkali metal hydroxides
depend on the physical state of the activating agent (Alabadi
et al. 2015). In the mechanism of pore formation by physical
mixing, a solid activating agent such as KOH pellet is mixed
with activated carbon precursor and it seems that, during the
carbon oxidation process, KOH is converted into potassium
metal and carbonate. In the impregnation method, where the
activating agent is the liquid phase and precursor in solid
form such as KOH in the first step, KOH is broken down as
Eq. (16) (Alabadi et al. 2015; Nur 2015):
KOH(s) → K+(aq) + OH−(aq) (16)
The alkali metal ions have the power to bind to differ-
ent materials. In aqueous solutions, potassium ions are ran-
domly distributed and free to move. During activation of
these ions, this leads to the formation of pores in the struc-
ture of the activated carbon. Then, in the washing stage, the
potassium ions are removed from the activated carbon (Nur
2015; Tounsadi et al. 2016). The pore formation processes
at lower and higher KOH concentrations are presented in
Figs. 6 and 7.
In the study of Nowicki et al. (2013), comparing the acti-
vating methods of activated carbon with sodium hydrox-
ide by physical mixing and impregnation shows that the
activated carbon produced by physical mixing is of more
porosity and larger pore volume than that of activated car-
bon produced by impregnation. Also, oxygenated functional
groups on activated carbon produced by physical mixing
are greater in number and have higher adsorption capacity
(Nowicki et al. 2013).
Conclusion
Activated carbon contains a wide range of carbonised mate-
rials that have a high degree of porosity and surface area.
Due to its unique characteristics, it has various applications
in water purification, domestic and industrial wastewater
treatment, desalination, refining and separating gases, odour
and pollutant removal and medical applications in many
parts of the world. Today, various industrial wastes are used
to produce activated carbon. The activation of activated car-
bon is done both physically and chemically. Compared with
physical activation, chemical activation is more economi-
cal because it requires lower activation temperature, shorter
processing time and higher carbon efficiency. Also, in the
chemical activation method, the development of porous
structures in activated carbon is greater.

Fig. 6  Pore formation processes

at lower KOH concentrations
(< 2.0M): carbon sphere (CS)
surrounded by free ­K+ in aque-
ous solution (a), penetration
of energised potassium ion,
*K + into the carbon sphere (b),
removal of the ions to produce
porous carbon sphere (c).
Adapted by kind permission of
Sanagi (Nur, et al. 2015)

13
Environmental Chemistry Letters

Fig. 7  Pore formation and struc-

tural collapse of carbon spheres
(CS) at higher KOH concentra-
tions (above 2.5 M): penetra-
tion/intercalation of *K + into
the carbon sphere (a); formation
of through and blind pores
(b); distortion of the sphere
structure by the interconnecting
through pores (c). Adapted by
kind permission of Sanagi (Nur
2015)

Various chemicals used as potential activators include
alkaline groups such as potassium hydroxide (KOH),
sodium hydroxide (NaOH), calcium chloride (­ CaCl 2),
potassium carbonate (­ K2CO3), acidic groups such as phos-
phoric acid ­(H3PO4) and sulphuric acid ­(H 2SO4), inter-
mediate metal salts such as Z ­ nCl 2 and other activating
agents. In this study, the role of different activation factors
was studied in the performance and efficiency of activated
carbon produced from various precursors. Utilising acti-
vated carbon in developed countries is very important due
to the production cost and adsorption capacity of various
pollutants, so the selection of the best activating agents in
activated carbon production is of particular importance.
The discussion of the present study showed that some acti-
vating chemicals create more adsorption capacity in the
activated carbon.
Activation with phosphoric acid has less environmental
and toxicological contamination than with zinc chloride and
also requires a lower activation temperature than potassium
hydroxide. Generally, in chemical activation with alkali
materials, activation with potassium hydroxide gives a bet-
ter result than sodium hydroxide in terms of surface area
and performance in different applications. However, sodium
hydroxide is cheaper, more environmentally friendly and is
less harmful than potassium hydroxide, and it is clear that
sodium hydroxide has industrial applications due to its supe-
riority to potassium hydroxide. Also, activated carbon with
potassium hydroxide is more efficient in adsorption than
other activators.
On the other hand, the salts of alkali metals are used on the
basis of the two methods of physical mixing and impregnation
method for the activation of activated carbon. Comparison of
these two approaches has shown that activated carbon pro-
duced by physical mixing is of a more porous structure and
larger pore volume than activated carbon produced through
impregnation. Despite the fact that a large number of articles
have been written on the removal of various pollutants using
activated carbon, few have compared the performance of dif-
ferent activation factors in the production of activated carbon
using various primary precursors. As noted, several factors
affect the activation of activated carbon, so lots of studies are
necessary to better understand the adsorption mechanism and
improve the adsorption of pollutants using activated carbon
produced on various scales worldwide.
Acknowledgements  This research has been supported by the Hor-
mozgan University of Medical Sciences (Code # 980071) and Tehran
University of Medical Sciences, Iran.
Compliance with ethical standards 
Conflict of interest  The authors of this article declare that they have no
conflict of interests.
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