Colloids and Surfaces A: Physicochem. Eng.

Aspects 490 (2016) 74–83

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Activated carbons produced by pyrolysis of waste potato peels: Cobalt

ions removal by adsorption
George Z. Kyzas, Eleni A. Deliyanni ∗ , Kostas A. Matis
Division of Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Greece

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Removal of cobalt ions by activated

carbons.
• Activation with H3 PO4 at 400, 600,
800 ◦ C.
• SEM, BET, FTIR, DTG, Boehm titrations
as characterization techniques.
• Effect of pH, contact time, tempera-
ture on adsorption.

a r t i c l e i n f o a b s t r a c t

Article history: This study investigates the use of activated carbons after pyrolysis of waste potato peels for the removal
Received 20 July 2015 of cobalt ions from synthetic wastewaters (composed of various Co(II) concentrations in distilled water
Received in revised form 9 November 2015 which adjusted previously at different pH values) without any co-existing ions. The activation agent
Accepted 16 November 2015
was phosphoric acid, while three different carbons were prepared based on the different activation
Available online 19 November 2015
temperatures (400, 600, 800 ◦ C). Characterization techniques used for the study of surface chemistry of
carbons prepared (Boehm and potentiometric titrations, BET analysis, SEM/EDAX, DTG), while the possi-
Keywords:
ble adsorption mechanism between carbons and Co2+ was further investigated using FTIR spectroscopy.
Cobalt ions
Activated carbons
Equilibrium and kinetic experiments were carried out at the optimum pH (6). Free energy, enthalpy, and
Phosphoric acid activation agent entropy were also evaluated.
Adsorption © 2015 Elsevier B.V. All rights reserved.
Kinetics

1. Introduction in many places; hence making it necessary, particularly for devel-

The most widely used carbonaceous materials for the industrial
production of activated carbons are coal, wood and coconut shell.
These types of precursors are quite expensive and often imported,
∗ Corresponding author. Fax: +30 2310 997859.
E-mail addresses: georgekyzas@gmail.com (G.Z. Kyzas), lenadj@chem.auth.gr
(E.A. Deliyanni), kamatis@chem.auth.gr (K.A. Matis).
oping countries, to find a cheap and available feedstock for the
preparation of activated carbon for use in industry, drinking water
purification and wastewater treatment. Biosorption, a biological
method of environmental control was proposed as an alternative
to conventional waste-treatment facilities [1]. Several suitable agri-
cultural by-products (lignocellulosics) – i.e., including olive-waste
cakes [2], cattle-manue compost [3], bamboo materials [4], apple
pulp [5], potato peel [6] – have been investigated in the last years as

http://dx.doi.org/10.1016/j.colsurfa.2015.11.038
0927-7757/© 2015 Elsevier B.V. All rights reserved.
 G.Z. Kyzas et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 490 (2016) 74–83
activated carbon precursors and are still receiving renewed atten-
tion.
Activated carbons possess large surface area, as mentioned
above and different surface functional groups, which include car-
boxyl, carbonyl, phenol, quinone, lactone and other groups bound
to the edges of the graphite-like layers. Therefore, they are regarded
as good adsorbents for the removal of heavy metal ions and other
inorganic substances, as well as many organic compounds from
liquid and gas phases [7]. Both surface chemistry and texture of
carbons are affected by the nitrogen source and the type of oxygen
functionalities preexisting on the surface [8,9]. Acid–base interac-
tions were found to essentially govern the ammonia removal by
modified activated carbons [10].
A mercury removal method using polymer-coated activated car-
bon was studied for possible use in water treatment [11]; in order
to increase the affinity of activated carbon for mercury, a sulfur-rich
compound, polysulfide-rubber polymer, synthesized by condensa-
tion polymerization, was coated onto the activated carbon. The role
of surface functionality on silica and carbonaceous materials for
adsorption of cadmium ion was also examined using various meso-
porous silica and activated carbon [12]. Introduction of nitrogen
functional groups, such as amine, pyridinic and pyrolic onto the sur-
face of adsorbents and replacing them with oxygen groups is known
as one of the modification methods for producing strong adsor-
bents toward heavy metals, like Cu(II) ion; a new procedure for
nitrogenation of commercial activated carbon was proposed [13].
An activated charcoal, produced from an agricultural waste product
(Lapsi seed), was tested for heavy metal ions removal; according to
the experimental results the kinetics of the sorption process was
found to be pseudo-second order [14].
Cobalt is a strategic metal (usually obtained from different ores),
used widely in the manufacture of catalysts, alloys, steels etc. Var-
ious separation processes were applied for cobalt ions, including
radioactive ones [15]. Especially, adsorption as one of the most
promising techniques [16–26] is applied for Co(II) removal [27–29].
Activated carbon adsorption has been certainly applied; the adsor-
bent was either commercial [30], synthesized from a sugarcane
industry waste [31] or apricot stone [32], among other sources.
The aim of this study is to prepare activated carbons from potato
peels and test them as adsorbents for Co(II) ions. Of course there are
works regarding the use of potato peels for adsorption applications
[33–36], but none with cobalt ions as under-removal pollutant.
Moreover, the effect of activation temperature was evaluated
with characterization techniques (Boehm and potentiometric titra-
tions, BET, SEM/EDAX, FTIR, DTG) and the best adsorbent samples
were further used to adsorption experiments (pH-effect, isotherms,
kinetics, thermodynamics).
2. Materials and methods
2.1. Chemical reagents
H3 PO4 (for potato peels activation) and Co(NO3 )2 ·H2 O were
purchazed from Sigma–Aldrich (St. Louis, MO, USA); they were of
analytical grade (puriss. pa. ≥ 98.5%).
2.2. Preparation of activated carbons
Waste potato peels were washed with distilled water in order
to remove dust and other inorganic impurities. Then, they were
filtered and oven-dried for 24 h at 393 K for achieving the reduction
of moisture content. The dried biomass was ground and sieved to
particles (+0.45–0.15 mm). The latter was denoted as “Po”.
The chemical activation of dry biomass was achieved with
phosphoric acid (H3 PO4 ). 10 g of dry potato peels precursor were
75
impregnated with 125 mL of H3 PO4 (75% w/w) at room temper-
ature and kept under stirring for 24 h. The impregnated biomass
was dried in sand bath at high temperature in order to remove
residual water and then oven-dried for 24 h at 100 ◦ C. A weighed
amount of the dried impregnated samples was placed in a fur-
nace and heated up to (i) 400, (ii) 600, and (iii) 800 ◦ C activation
temperatures. The treatments were carried out with nitrogen flow
(99.999% pure) of 30 STP cm3 /min; the latter was kept at the same
rate during heating and cooling, and at a constant heating rate of
10 K/min. The treatment at the activation temperature lasted 2 h
and after cooling the solid residues were washed in a Soxhlet appa-
ratus for 24 h until neutral pH and then with ethanol. The resulted
activated carbons were dried at 100 ◦ C for 24 h. In order to make
easily understood the abbreviations used for the activated carbons
samples, they were designated as PoP400, PoP600 and PoP800 (the
term “Po” corresponds to potato peels), “P” to phosphoric acid used
for activation, and the numbers “400”, “600”, and “800” to 400, 600,
800 ◦ C activation temperatures, respectively.
2.3. Characterization—instrumentation
Scanning electron microscopy (SEM) images were performed
with electron microscope (model Zeiss Supra 55 VP, Jena, Germany)
equipped with an energy dispersive X-ray (EDX) Oxford ISIS 300
micro-analytical system. The accelerating voltage was 15.00 kV,
while the scanning was performed in situ on a sample powder.
EDAX analysis was done at magnification 10 K and led to the maps
of elements and elemental analysis for the investigation of Co(II)
distribution on carbon surface.
Thermal stability of the samples was measured (6 mg of sample
was used for each measurement) by thermogravimetric analysis
(TGA) using Pyris 1 TGA thermal analyzer (PerkinElmer, Dresden,
Germany) with the following settings: (i) 10 K/min as heating rate,
and (ii) 100 mL/min as flow rate of nitrogen atmosphere.
The FTIR spectra of the samples were taken with a Nicolet 560
(Thermo Fisher Scientific Inc., MA, USA) FTIR spectrometer. The
spectra were recorded in transmission mode using potassium bro-
mate wafers containing 0.5 wt% of carbon. Pellets made of pure
potassium bromate were used as the reference sample for back-
ground measurements. The spectra were recorded from 4000 to
400 cm−1 at a resolution of 4 cm−1 and are baseline corrected.
Nitrogen isotherms were measured using AS1Win (Quan-
tachrome Instruments, FL, USA) at liquid N2 temperature (77 K).
The samples were degassed at 150 ◦ C in a vacuum system at 10−4
Torr before the analysis. The specific surface area (SBET ) was calcu-
lated from the isotherm data using the Brunauer, Emmet and Teller
(BET) model. The micropore volumes (Vmic ) were obtained with the
accumulative pore volume using density functional theory (DFT)
method. The total pore volumes (Vtot ) were obtained from the vol-
umes of nitrogen adsorbed at a relative pressure of 0.99 cm3 /g. The
mesopore volumes (Vmes ) were calculated by subtracting Vmic from
Vtot . The pore size distribution curves were also obtained using DFT
method.
For the measurement of the surface pH of carbon samples, 0.4 g
of dry carbon sample were added to 20 mL of water, and the sus-
pension was stirred overnight to reach equilibrium. Then the pH
of the solution was measured. This method provided information
about the acidity or basicity of the material’s surface.
The determination of surface functional groups was based on
the Boehm titration method [37]. Aqueous solutions of NaHCO3
(0.05 mol/L), Na2 CO3 (0.05 mol/L), NaOH (0.10 mol/L), and HCl
(0.10 mol/L) were prepared. 25 mL of these solutions were added to
vials containing 0.5 g of adsorbents, let to be shaken (140 rpm) until
equilibrium (24 h), and then filtered. Five blank solution (without
adsorbent) were also prepared. In this way, the number of the basic
sites was calculated from the amount of HCl which reacted with
76 G.Z. Kyzas et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 490 (2016) 74–83
adsorbent. The various free acidic groups were derived using the
assumption that: (i) NaOH neutralized carboxyl, lactonic and phe-
nolic groups; (ii) Na2 CO3 neutralized carboxyl and lactonic groups,
and (iii) NaHCO3 neutralized only carboxyl groups. The excess of
base or acid was then determined by back titration using NaOH
(0.10 mol/L) and HCl (0.10 mol/L) solutions [38].
Potentiometric titration measurements were carried out with
a T50 automatic titrator (Mettler Toledo, Columbia, USA). 0.1 g of
carbon were placed in 50 mL of NaNO3 solution (0.01 mol/L) as sup-
porting electrolyte and stirred overnight. The solution was titrated
with NaOH (0.1 mol/L) under N2 saturation. The titrations were car-
ried out over a wide range of pH. The total surface charge, Qsurf
(mmol/g), was calculated as a function of pH by the following equa-
tion [39]:
CA + CB +[H+ ]+[OH− ]
Qsurf = (1)
W L1/n /g) is the Freundlich constant representing the adsorption
where CA and CB (mol/L) are the acid and base concentrations,
respectively; [H+ ] and [OH− ] are the equilibrium concentrations
of those ions (mol/L), and W (g/L) is the solid concentration.
The analysis of residual concentration of Co(II) was achieved
using flame atomic absorption spectrophotometer (PerkinElmer
1100 B, Shelton, USA). The absorbance was converted to concen-
tration using calibration curve.
2.4. Adsorption experiments
2.4.1. Effect of pH on adsorption
The effect of pH was conducted by mixing 1 g/L of adsorbent
(m = 0.02 g) with 20 mL (V) of ion solution (C0 = 200 mg/L). The pH
value, ranging between 2 and 6, was kept constant throughout
the adsorption process by micro-additions of HNO3 (0.01 mol/L)
or NaOH (0.01 mol/L). The pH adjustment of Co(II) solutions in the
presence of adsorbent was realized in order to study and under-
stand the possible adsorption mechanisms in each particular pH
condition. pH-effect experiments were not carried out at pH > 6,
in order to avoid precipitation phenomena of Co(II). In this pH-
zone, the metal ions get out of the solution due to formation of
colloidal precipitate of Co(OH)2 and not due to the adsorption of
free Co(II) ions [40]. In general the uptake of those metals at pH > 6
is attributed to the formation of metal hydroxide species such as
soluble Co(OH)+ and/or insoluble precipitate of Co(OH)2 . The sus-
pension was shaken for 24 h (agitation rate: N = 140 rpm) into a
water bath to control the temperature at 25 ◦ C (model Grant Instru-
ments OLS Aqua Pro, Cambridge, UK). The optimum pH found (for
performing the equilibrium experiments) was 6.
2.4.2. Effect of contact time
Kinetic experiments were performed by mixing 1 g/L of adsor-
bent with 20 mL of ion solution (C0 = 200 mg/L). The suspensions
were shaken for 24 h at pH 6 (optimum pH found) in water bath
at 25 ◦ C (N = 140 rpm). Samples were collected at fixed intervals
(5 min–24 h). The experimental kinetic data were fitted to two
kinetic models; pseudo-first [41] (Eq. (2)) and -second order [42]
(Eq. (3)) (their selection is based on the fact that they are the two
most widely-used kinetic models in adsorption works [42,43]).
Ct = C0 − (C0 − Ce ) (1 − e−k1 t )
 1
 temperatures of 800 ◦ C was also observed for carbons prepared
Ct = C0 − (C0 − Ce ) 1 −
1 + k2 t
where k1 , k2 (min−1 ) are the rate constants for the pseudo-first,
-second order kinetic equations; C0 , Ct , Ce (mg/L) are the initial,
transient and equilibrium concentrations of Co(II) in the aqueous
solution, respectively.
2.4.3. Effect of initial ion concentration—isotherms
The effect of initial ion concentration on equilibrium was
observed by mixing 1 g/L of adsorbents with 20 mL of ion solutions
of varying initial concentrations (C0 = 10–1000 mg/L). The suspen-
sions were shaken for 180 min (optimum contact time found) at pH
6 in water bath at 25 ◦ C (N = 140 rpm).
The experimental equilibrium data were fitted to the Lang-
muir (Eq. (4)) [44] and Freundlich (Eq. (5)) [45] isotherm equations
expressed by the following equations:
Qm KL Ce
Qe = (4)
1 + KL C e
Qe = KF Ce 1/n (5)
where Qm (mg/g) is the maximum amount of adsorption; KL (L/mg)
is the Langmuir adsorption equilibrium constant; KF (mg1−1/n
capacity; n (dimensionless) is the constant depicting the adsorption
intensity.
The equilibrium amount in the solid phase (Qe , mg/g) was cal-
culated according to the following equation:
(C0 − Ce ) V
Qe = (6)
m
2.4.4. Effect of temperature—thermodynamics
To study the effect of temperature on equilibrium, completely
same experiments as those of 2.4.3 Section, but just varying the
temperature (25, 45, and 65 ◦ C). The scope of the above was also
to investigate the thermodynamic behavior of the carbons-ions
system. For this purpose, three main parameters have been cal-
culated (the change of Gibbs free energy (G0 , kJ/mol), enthalpy
(H0 , kJ/mol) and entropy (S0 , kJ/mol K)) based on the isotherms
resulted at 25, 45, and 65 ◦ C. The system of equations below can
be used for the calculation of the aforementioned thermodynamic
parameters (where Cs (mg/L) is the amount adsorbed on a solid at
equilibrium and R (8.314 J mol−1 K−1 ) is the universal gas constant)
[46]:
Cs
Kc = (7)
Ce
G0 = −RTln (Kc ) (8)
0 0 0
G = H − TS (9)
 
H 0 1 S 0
ln (Kc ) = − + (10)
R T R
G0 was given from Eq. (8), while H0 and S0 were given
from the slop and intercept of the chart between ln(Kc ) versus 1/T
(Eq. (10)).
3. Results and discussion
3.1. BET and thermogravimetric analysis—surface properties
The carbonization of potato peels at 400, 600 and 800 ◦ C in
the presence of H3 PO4 resulted in the formation of the activated
carbons PoP400, PoP600, PoP800 in yields of 55, 51, and 49%,
respectively. The increase of carbonization temperature caused
(2)
a progressive decrease of the yield. Similar decrease in yield at
(3) from other carbonaceous precursors, polymers [47] and fruit stones
[48,49]. This can be attributed to thermal degradation of the
phosphor-carbonaceous species and reduction of the phosphates
present to elemental phosphorus having as result the forma-
tion of volatile phosphorous compounds (P4 O10 (phosphorus(V)
oxide) and elemental phosphorus). Elemental phosphorus was
 G.Z. Kyzas et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 490 (2016) 74–83 77

Table 1 0.20
Parameters of the pore structure calculated from nitrogen adsorption isotherms. 1.0 PoP400
Adsorbent 2
SBET cm /g 3
Vmic cm /g Vmes cm /g 3 3
Vtot cm /g PoP600
0.8 Po

Weight loss derivative (%/ C)

PoP400 904.56 0.099 0.357 0.726

o
0.15 0.6
PoP600 1041.43 0.055 0.336 2.960
PoP800 0.91 0.000 0.004 0.004
0.4

0.10 0.2
0.00025
Incremental pore volume (cm /g)

0.04 0.0
0.00020 100 200 300 400 500 600 700 800 900
3

0.00015
0.05
0.03 0.00010

0.00005

0.00000 0.00
0.02 10 100
100 200 300 400 500 600 700 800 900
PoP400
o
PoP600 Temperature ( C)
-in

PoP800
om

0.01 Fig. 2. Differential thermogravimetry (DTG) curves in nitrogen.

zo

0.00
10
Pore width (A)
Fig. 1. Comparison of the pore size distribution (DFT) curves for the PoP400, PoP600
and PoP800 carbons which activated at different temperatures.
also formed after the phosphoric acid activation of phosphorus-
containing phenol resins [50] or Nomex polymer fibers [51].
Volatile phosphorus compounds may be formed according the fol-
lowing reactions [50]:
4H3 PO4 +10C → P4 +10CO+6H2 O
4H3 PO4 +10C → P4 O10 +6H2 O
P4 O10 +10C → P4 +10CO
A useful tool for the characterization of the porosity of acti-
vated carbons, which is an important parameter of adsorption
performance, is nitrogen adsorption measurement; this provides
information about the textural characteristics and the surface area
which is available to the adsorbate [52]. The specific surface areas
and the porosity parameters exhibited by the three activated car-
bons (PoP400, PoP600, PoP800) were calculated and presented in
Table 1.
The surface area of PoP400 (904.56 cm2 /g) is slightly smaller
than this of PoP600 (1041.43 cm2 /g), while the total pore volume is
smaller about 4 times than this of PoP600 (0.726 and 2.960 cm3 /g
for PoP400 and PoP600, respectively). The increase of temperature
from 400 to 600 ◦ C causes a 15% increase of surface area, while fur-
ther increase of the carbonization temperature to 800 ◦ C resulted
in a decrease of the BET surface area, may be due to a collapse of
structure.
Pore size distribution is another important aspect of acti-
vated carbons since it characterizes the structural heterogeneity
of porous materials. According to IUPAC definition, porous car-
bons are classified into microporous (pore size < 2 nm), mesoporous
(pore size = 2–50 nm) and macroporous activated carbons (pore
size >50 nm) [52]. The pore size distributions exhibited by the three
activated carbons (PoP400, PoP600, PoP800) were calculated by the
density functional theory (DFT) method and presented in Fig. 1.
According to Fig. 1, the porous texture of the three carbons is
different. The results confirmed that the activated carbon PoP400
is of micro-mesoporous structure. As it can be observed, the graph
exhibits peaks with a maximum at 1–2 and 3–5 nm. PoP600 pre-
sented a sufficient amount of micro and mesopores, as well as
100 macropores. The measured values of Vmic and Vmeso for all carbons
are presented in Table 1. On the contrary, PoP800 showed a dra-
matic decrease in the amount of pores, which are mainly mesopores
(inset of Fig. 1). This activation temperature (800 ◦ C) caused a col-
lapse in the texture of the activated carbon prepared. Based on the
above, it was decided to not further examine the activated carbon
sample of PoP800.
Similar tendency was also observed for activated carbons pro-
duced from fruit stones activated with phosphoric acid [48] and
was attributed to the contraction of the material [53]. The con-
(11) traction can be due to the catalytic activity of phosphoric acid,
causing the growth of polyaromatic clusters. As a result, a densely
(12) packed structure is formed and causes loss of porosity. Additionally,
by increasing carbonization temperature up to 800 ◦ C, polyphos-
(13)
phates can be progressively formed that can block the pore space
decreasing this way the porosity [50].
The surface chemistry of carbons plays an important role on
in their adsorption performance. Surface chemistry as well as the
changes in the chemistry after the activation are reflected on the
DTG curves for the initial biomass sample (Po) and for the activated
carbons PoP400 and PoP600 (Fig. 2). The DTG curves for the initial
biomass sample as well as for carbon samples showed a continuous
weight loss at about 100 ◦ C related to moisture release.
For the Po sample (inset of Fig. 2), the defined peak in the
temperature range 200–400 ◦ C, represents the decomposition of
cellulose and hemicellulose [54,55]. In this temperature range, the
chemical bonds in potato peels began to break and the lightest
volatile compounds were released [56]. At higher temperatures
than 400 ◦ C, a small, poorly-shaped peak, may be indicative of lignin
weight loss [57]. In the case of PoP400 and PoP600, the effects of
carbon acidity is demonstrated as a significant weight loss between
150 and 600 ◦ C, where the surface functional groups decompose
[58]. An intense peak at 200 ◦ C indicates a high contribution of
strongly acidic carboxylic groups. PoP600 appears to be more acidic
than PoP400. The weight loss at 600 ◦ C is related to the decompo-
sition of phenols and other basic functionalities [8]. Finally, both
carbons showed appreciable mass loss in the range of 850–880 ◦ C.
Since these carbons are phosphoric-activated, the aforementioned
mass loss can be attributed to (i) the evaporation of phosphorus
compounds by thermal decomposition of the C–O–P linkage, and
(ii) phosphate/polyphosphate reduction by carbon [50,51,59]. The
surface areas under all peaks increase with an increase of activation
temperature.
78 G.Z. Kyzas et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 490 (2016) 74–83

Table 2
Surface pH of the carbon samples and Boehm titration results.

Functional groups

Adsorbent Carboxyl Lactonic Phenolic Basic Total acid

pH mmol/g mmol/g mmol/g mmol/g mmol/g

PoP400 2.29 0.0125 0.0115 0.1307 0.0297 0.1608

PoP600 2.85 0.0125 0.0169 0.0316 0.0104 0.0609

0.5 100
PoP400
90 PoP600
0.0 80

70

Removal (%)
-0.5
Qsurf (mmol/g)

60
PoP600
50
-1.0
40

30
-1.5
20

-2.0 10
PoP400
0
2 3 4 5 6
2 3 4 5 6 7 8 9 10 11 12
pH
pH
Fig. 4. Effect of pH on Co(II) adsorption onto PoP400 and PoP600.
Fig. 3. Potentiometric titration curves for PoP400 and PoP600.

200
The acidic and basic surface groups were estimated after Boehm PoP600
PoP400
and potentiometric titration measurements and the results are pre- 175 pseudo-1st
sented in Table 2 and Fig. 3. It is obvious that both carbons are pseudo-2nd
acidic, as was also confirmed by the surface pH measurements 150
(Table 2) with the PoP400 carbon to present more oxygenated sur- 125
Ce (mg/L)

face groups.
100
3.2. Effect of pH 75

The pH of the solution plays an important role on the adsorption 50

of any ion onto materials. It is noteworthy to say that completely
25
reverse results can be found with the change of pH. That is even
more intense when the substrate (adsorbent materials) is full 0
of functional groups with different pKa values and the target- 0 50 100 150 200 250 300 350 400 1200 1500
pollutant is a heavy metal ion. Therefore, the first factor studied t (min)
in the present work is the effect of pH on Co(II) removal. Fig. 4
showed the aforementioned pH-effect. Fig. 5. Effect of contact time on Co(II) adsorption onto PoP400 and PoP600 (fitting
to pseudo-first and -second order equations).
The Co(II) removal at strong acidic pH values was found to be
very small (14 and 24% for PoP400 and PoP600, respectively). How-
ever, with the increase of pH from 2 to 3, 4, and 5, the Co(II) removal
for the observed effect of pH on the adsorption may be the suppres-
sharply increased both for PoP400 (28, 45, 62% at pH 3, 4, and 5,
sion of the complexation. In solutions with a low pH value, some
respectively) and PoP600 (33, 59, 79% at pH 3, 4, and 5, respec-
functional groups are protonated (or difficult to dissociate) and the
tively). At pH 6 was found to be the optimum pH value, in which the
complexation between Co(II) ions and the functional groups on
Co(II) removal was the highest (PoP400, 87.5% and PoP600, 92%).
the surfaces of the activated carbons are suppressed. Earlier work-
The effect of pH can be explained taking into the mind the pH at
ers have reported a similar pattern for the influence of pH on the
zero point of charge (pHzpc) and Co(II) speciation in solution. From
adsorption of heavy metals onto activated carbons [31].
the Co(II) speciation, it is seen that at the pH range 2–6Co(II) is
present as Co2+ . The pH at which the charge of the solid surface is
zero is referred to as the pHzpc. Above pHzpc, the surface charge 3.3. Effect of contact time
of the adsorbent is negative and below the particular pH it will
be positive. The amount of adsorption above the pHzpc was max- To proceed the optimization of adsorption conditions, the next
imum due to the interaction of Co2+ with the negatively charged important parameter is the effect of contact time on adsorption.
carbon surface. At low pH, particularly below pHzpc, the positively The investigation of this parameter can save money and energy in
charged Co2+ species may repel with carbon surface carrying equal the case of industrial-scale adsorption processes. The kinetic results
charge and thereby decreases the Co(II) adsorption. Another reason are presented in Fig. 5, while the kinetic parameters calculated after
 G.Z. Kyzas et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 490 (2016) 74–83 79

Table 3 tural properties of two carbons. The same equilibrium experiments

Kinetic parameters for the adsorption of Co(II) onto PoP400 and PoP600.
were done at 45 and 65 ◦ C. The adsorption behavior was not the
Adsorbent Pseudo-first order Pseudo-second order same for the adsorbents studied. PoP400 increased its Qm from
373 mg/g (25 ◦ C) to 382 and 389 mg/g to 45 and 65 ◦ C, respec-
k1 min-1 R2 k2 min-1 R2
tively (Table 4). This difference was also calculated as percentage
PoP400 0.0272 0.997 0.0479 0.955
increase; 2.4% for the step from 25 to 45 ◦ C and 1.8% for the
PoP600 0.0344 0.997 0.0607 0.952
respective of 45–65 ◦ C. On the contrary, PoP600 showed higher
temperature influence. PoP600 increased its Qm from 405 mg/g
(25 ◦ C) to 447 and 480 mg/g to 45 and 65 ◦ C, respectively. This per-
Langmuir
500 Freundlich centage increase was 10.4% for the step from 25 to 45 ◦ C and 7.4%
for the respective of 45–65 ◦ C. Comparing the two carbons, the tem-
perature influence was approximately 5–8 times higher for PoP600
400
than PoP400 (Table 4).
At this point it is important to make a brief comparison
Qe (mg/g)

300 about the adsorption capacities presented in other recent pub-

200
o
100 25 C
o
45 C
o
65 C
0
0 100 200 300 400
Ce (mg/L)
Fig. 6. Effect of initial concentration and temperature (25, 45, 65 ◦ C) on adsorp-
tion of Co(II) onto PoP400 and PoP600 (fitting to Langmuir and Freundlich isotherm
equations).
fitting to pseudo-first and -second order equations are shown in
Table 3.
The kinetic data were fitted better to pseudo-first order equa-
tion for both carbons (R2 ps1 = 0.997). Moreover, it was found that
the adsorption process was faster for PoP600 (k1 = 0.0284 min−1 )
than PoP400 (k1 = 0.0272 min−1 ), probably due to the more oxygen
content on the surface of PoP600. The end of the adsorption was
at 180 min (for both carbons). An interesting finding was the clear
time kinetic regions for PoP400 and PoP600. During 0–60 min, the
removal of Co(II) was sharp, while for 60–150 more gradual. After
180 min a kinetic plateau was observed, suggesting the end of the
process (Table 3).
3.4. Isotherms—thermodynamics
The effect of initial ion concentration on adsorption was eval-
uated with the isotherms of equilibrium data. Fig. 6 shows the
aforementioned effect at 25, 45, and 65 ◦ C. PoP400 and PoP600
increased their adsorption capacity with increase of the initial
Co(II) concentration from 10 to 1000 mg/L. After fitting to Lang-
muir and Freundlich models (better fitting to Langmuir model
R2 = 0.982–0.998), it was found that PoP600 presented higher max-
imum adsorption capacity (Qm ) than PoP400.
In particular, PoP400 showed 373 mg/g, while PoP600 405 mg/g.
This change of 8% is due to the difference textural and struc-
lished works. Apricot stone activated carbon showed the highest
capacity (111 mg/g) [32], which is by far lowest than the value pre-
sented in the present study for the two activated carbons (PoP400
PoP400 PoP600 and PoP600, 373 and 405 mg/g, respectively). Some other stud-
ies showed even lower adsorption capacities ranged from 0.56 to
80 mg/g for various materials such as pest moss, T. reesei, hectorite
particles, roasted date pits, hezelnut shells, attapulgite, bentonite,
500 600 700 kaolin etc [32].
A brief thermodynamic analysis was also done based on the
change of Gibbs free energy (G0 , kJ/mol), change of enthalpy
(H0 , kJ/mol) and entropy change (S0 , kJ/mol K). These param-
eters (at pH 6), at selected initial Co(II) concentrations (10, 50, 100,
200, 500, 700 mg/L) and all temperatures (25, 45, 65 ◦ C), were given
in Table 5. The negative values of G0 showed the spontaneous
adsorption of Co(II) onto PoP400 and PoP600.
The positive values of H0 indicated the endothermic nature
of the process. These values were reduced with the increase of
Co(II) concentration. The latter could be linked with the fact that
in an endothermic process, the adsorbate species (cobalt ions in
this work) had to displace more than one water molecule for their
adsorption and this resulted in the endothermicity of the adsorp-
tion process; therefore H0 would be positive. The magnitude
of H0 might also give an idea (but not sure) about the type of
adsorption. Moreover, the values of S0 were found to be pos-
itive, which reflected the affinity of the adsorbent towards the
adsorbate species. In addition, the positive value of S0 suggested
increased randomness at the solid/solution interface with some
structural changes in the adsorbate and adsorbent. The adsorbed
solvent molecules, which were displaced by the adsorbate species,
gained more translational entropy than was lost by the adsorbate
species/molecules, thus allowing for the prevalence of random-
ness in the system. The positive S0 value also corresponded to
an increase in the degree of freedom of the adsorbed [60].
The different adsorption capacity of the carbons were also obvi-
ous from scanning electron microscopy (SEM) measurements and
the cobalt distribution onto the surface of cabons (Fig. 7).
The surface morphology of both carbon samples seems to be
as expected; Many pores and cavities without any smooth surface
area. In the case of PoP600, the larger pores than PoP400 is obvi-

Table 4
Equilibrium parameters for the adsorption of Co(II) at 25, 45, 65 ◦ C onto PoP400 and PoP600.

Adsorbent Langmuir equation Freundlich equation

◦ 2
T C Qm mg/g KL R KF mg1−1/n L1/n g-1 n R2

PoP400 25 373 0.035 0.998 57.68 3.31 0.937

45 382 0.041 0.998 63.55 3.42 0.936
65 389 0.047 0.997 69.52 3.53 0.934
PoP600 25 405 0.050 0.995 72.40 3.50 0.947
45 447 0.057 0.988 82.27 3.49 0.959
65 480 0.076 0.982 95.64 3.57 0.966
80 G.Z. Kyzas et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 490 (2016) 74–83

Table 5
Thermodynamic parameters for the adsorption of Co(II) onto PoP400 and PoP600.

PoP400 PoP600

C0 T Qe Kc G0 H0 S0 Qe Kc G0 H0 S0

mg/L K mg/g kJ/mol kJ/mol kJ/mol K mg/g kJ/mol kJ/mol kJ/mol K

10 298 9.90 99.00 −11.19 26.50 0.128 9.96 249.00 −13.44

318 9.92 124.00 −12.14 9.98 499.00 −15.65 52.94 0.226
338 9.95 199.00 −13.78 9.99 999.00 −17.98
50 298 45.98 11.44 −5.94 16.38 0.072 47.48 18.84 −7.15
318 46.78 14.53 −6.74 48.46 31.47 −8.69 43.37 0.170
338 46.99 15.61 −7.15 48.78 39.98 −9.60
100 298 90.96 10.06 −5.62 11.85 0.061 93.96 15.56 −6.69
318 91.98 11.47 −6.15 95.8 22.81 −7.88 28.78 0.123
338 93 13.29 −6.73 97.99 48.75 −10.12
200 298 174.89 6.96 −4.73 10.39 0.055 184.79 12.15 −6.08
318 178.87 8.47 −5.38 187.91 15.54 −6.91 25.52 0.108
338 182.68 10.55 −6.13 191.93 23.78 −8.25
500 298 314.68 1.70 −1.29 6.70 0.027 344.79 2.22 −1.94
318 324.16 1.84 −1.54 374.57 2.99 −2.76 19.83 0.074
338 334.57 2.02 −1.83 394.4 3.73 −3.43
700 298 354.98 1.03 −0.07 4.36 0.015 384.35 1.22 −0.48
318 364.91 1.09 −0.21 424.68 1.54 −1.09 15.92 0.056
338 374.58 1.15 −0.37 454.24 1.85 −1.60

Fig. 7. SEM images of (a) PoP400 and (c) PoP600; Cobalt distribution map after Co(II) onto (b) PoP400 and (d) PoP600.

ous. Figs. 7b, 7d show the cobalt distribution onto the surface of
carbons. It seems that PoP600 has more in number white dots sug-
gesting that the adsorption of Co(II) onto PoP600 is greater than
the respective onto PoP400. The latter can be concluded after the
adsorption evaluation (see Section 3.4).
3.5. Adsorption mechanism
In order to understand the adsorption mechanism of Co(II) onto
carbon surface, FTIR spectra were obtained for the PoP400 and
PoP600 carbons before and after cobalt adsorption (Fig. 8).
The FTIR spectrum of the potato peel sample (Po) presented
a wide band at about 1100 cm−1 that indicates the presence of
secondary hydroxyl groups. Three more vibrational bands were
recorded at: (i) 1750 cm−1 attributed to the C O stretching vibra-
tion, of acetyl and uronic ester groups of hemicelluloses, as well as
the ester linkage of the carboxyl group in lignin and (ii) 1514 cm−1
and 1456 cm−1 assigned to the skeletal C C vibration of aromatic
rings. The stretching vibrations of –CH3 at 1387 cm−1 is related
to methyl structures. The adsorption bands between 1000 and
1350 cm−1 may be assigned to C O vibrations.
In the case of PoP400, the main characteristic absorption peaks
are presented at: (i) 3100–3400 cm−1 attributed to O H stretching
vibration which originated from chemisorbed water and phenolic
groups (band not shown in figure), (ii) 1740 cm−1 assigned to car-
boxylic acid vibrational frequencies, (iii) 1615 cm−1 related to C C
 G.Z. Kyzas et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 490 (2016) 74–83 81

Po Co2+ Co2+
O
Co2+
O

*
O

II)

*
o(
Co2+ Co2+

-C
00
O

P4
Po
Transmittance

00
Co2+

P4
Po
O
H

II)
o(
C
C

0-
C

0
HO

P6
O HO O
Po

00
P6
Po Co2+ Co2+

* represents an "in-plane sigma-pair"

2000 1800 1600 1400 1200 1000 800
-1
Wavenumber (cm )
Fig. 8. FTIR spectra of the studied carbon samples before and after Co(II) adsorption.
stretching vibration of the aromatic ring or highly conjugated C O
group, (iv) 1150 cm−1 attributed to OH stretching and bending
vibrations in C OH bonds, respectively, such as phenols, and (v)
980 cm−1 that could be related to epoxy groups.
In the case of PoP600, besides the peaks at 1740 cm−1 due to the
stretching vibrations of C + O moieties in aromatic carboxyl groups
and at 1150 cm−1 attributed to OH stretching and bending vibra-
tions in C OH bonds, a new peak at 1050 cm−1 appeared, which
can also be assigned to the C O bonds in phenols. On the other
hand, some new peaks at 1380 and 1660 cm−1 appeared. It has been
demonstrated that the appearance of these peak was an indication
of carboxylate group [61].
Moreover, since these carbons were phosphoric acid-activated,
the FTIR spectra of phosphoric acid-activated carbons presented
absorption bands at about 1150, 1060 and 990 cm−1 . Those bands
are characteristic of phosphorus and phosphor-carbonaceous com-
pounds present in these carbons [62,63]. The peak at 990 cm−1
may be attributed to P O C aliphatic or aromatic stretching, P O
stretching in >P OOH or P OH bending or P O P asymmetric
stretching in polyphosphates. The peak at 1060 cm−1 could be
due to a combination of the P+ O− bond in acid phosphate esters
and the symmetrical vibration of the polyphosphate chain P O P,
while the band at 1150 cm−1 can be assigned to the stretch-
ing vibration of O C in the P O C aromatic groups or hydrogen
bonded P O groups of phosphates or polyphosphates [50,64–66].
After Co(II) adsorption onto PoP400 and PoP600 carbons, the
band at 1740 cm−1 due to the stretching vibration of C O attributed
to carboxyl groups and the band at 980 cm−1 related to epoxy
groups were no longer visible, indicating that those groups have
reacted with the adsorbate/metal species. Additionally, the band
at 1150 cm−1 due to phenolic O H bending mode was eliminated
may be due to the dissociation of H+ , showing that these groups
were also involved in adsorption.
FTIR results for the samples after cobalt adsorption also
presented a decreased vibration intensity of O H due to the disso-
ciation of H+ as well as an eliminated absorption intensity of C O
groups. This can lead to a conclusion that Co(II) interacted with the
C O moieties in phenolic and carboxylic groups during the adsorp-
tion. It has also been measured that the final pH of the solution was
less than the initial pH due to the exchange of Co2+ species with
H+ ions of the carbon. The presence of large amounts of surface
with * being a localized pi-electron
Fig. 9. Possible adsorption interactions between activated carbon samples and
Co(II).
groups as measured from Boehm titration (Table 2) is expected to
be beneficial for the binding of metal ions.
The reactions that are reported to take place during the adsorp-
tion of Co(II) on activated carbon [31]:
2(COH)+Co2+ (CO− )2 Co2+ +2H+ (14)
− 2+
2CO +Co (CO )2 Co − 2+
(15)
where C represents solid surface.
The interactions may proceed through a non-covalent combi-
nation and not a chemical covalent bonding. Co2+ ions probably
replaced the H+ of the phenol and carboxyl groups, and electrova-
lently attached on the C O groups.
In addition, the band at 1615 cm−1 was shifted to 1630 cm−1 ,
which was mainly attributed to the dispersive interactions between
the ␲-electrons of the electron rich region in the aromatic ring
of PoP400 and Co(II). An increased adsorption was achieved may
be due to an ion-exchange reaction between the metal ion and
the delocalized protonated ␲-electrons of the graphene layer (-Cp-
H3 O+ ) [67]. The latter has been also noticed for the adsorption of
Cd(II), Hg(II) and Cr(III) on activated carbons [50].
Based on the above results, it is concluded that H3 PO4 activa-
tion introduced oxygen functional groups, especially aliphatic ones,
which provided complexation sites for cobalt. Cation exchange,
electrostatic interaction, and surface complexation were consid-
ered as major mechanisms for the adsorption. Some possible
adsorption interactions can be illustrated in Fig. 9. The above pre-
sented results suggest that activated carbon from potato peels,
activated with phosphoric acid have a considerable promise for
heavy metal ion removal and as a consequence the water purifi-
cation.
4. Conclusions
Three samples of activated carbons (PoP400, PoP600, PoP800)
were prepared after pyrolysis of waste potato peels in order to
remove Co(II) from synthetic wastewaters. BET analysis showed
that the surface area of PoP400 (904.56 cm2 /g) was slightly smaller
than this of PoP600 (1041.43 cm2 /g). . The adsorption properties
of PoP400 and PoP600 were studied, because PoP800 presented
nearly zero specific surface area. FTIR spectroscopy confirmed
the proposed adsorption mechanism which is based on interac-
tions between oxygen-containing groups of carbons and Co(II).
The maximum theoretical adsorption capacity (Qm ) for PoP400
82 G.Z. Kyzas et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 490 (2016) 74–83
was 373 mg/g, while PoP600 even larger (405 mg/g). With the
increase of temperature, the adsorption capacity was improved,
but (comparing the two carbons) the temperature influence was
approximately 5–8 times higher for PoP600 than PoP400. The
adsorption experiments were carried out at pH 6 as it was found
that it was the optimum pH value. Kinetic experiments showed that
the adsorption process was faster for PoP600 (k1 = 0.0284 min−1 )
than PoP400 (k1 = 0.0272 min−1 ).
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