Advanced Powder Technology 28 (2017) 1866–1876

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Advanced Powder Technology

journal homepage: www.elsevier.com/locate/apt

Original Research Paper

The synthesis, activation and characterization of charcoal powder for the

removal of methylene blue and cadmium from wastewater
Nicoleta Popa a,b, Maria Visa b,⇑
a
Department of Forest District Teliu, National Admin. State Forests Romsilva, Romania
b
Transilvania University of Brasov, Centre of Renewable Energy Systems and Recycling, Eroilor 29, 500036 Brasov, Romania

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

Article history: Charcoal prepared from biomass, wastes of the local forest (tree branches), activated with NaOH solution
Received 17 January 2017 and with Degussa P25 (TiO2) was used as adsorbent and photocatalyst for the removal of cadmium
Received in revised form 11 April 2017 cations and methylene blue from wastewater. These materials were characterized by using atomic force
Accepted 21 April 2017
microscopy for roughness surface. The energy dispersive X-ray (EDX) spectroscopy and X-ray diffraction
Available online 4 May 2017
(XRD) analysis indicate the existence of nano TiO2 on the charcoal surface. Additionally, the FT-IR spec-
troscopy measurements indicate that the alkali treatment develops hydroxyl groups on charcoal surface
Keywords:
which could adsorb methylene blue, heavy metals and other pollutants via the synergistic effect. The
Charcoal
Pyrolysis
activities of the charcoal (BC), activated charcoal (BCA) and BCA/TiO2 mixture (BCA-D) depend on the con-
Adsorption tact time, adsorbent dosage and pH. The adsorption kinetic data were tested using pseudo-first-order,
Photocatalysis pseudo-second-order and intraparticle diffusion models. The kinetic studies showed that the adsorption
Wastewater is followed by the pseudo-second-order reaction with regard to the intraparticle diffusion rate kinetics.
Ó 2017 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction Methylene blue (MB) is a cationic dye having various applica-

Enhanced industrial activity during recent decades has led to
the discharge of volumes of wastewater which is a serious cause
of environmental degradation. Many industries, such as textile
dyeing and finishing, leather tanning, hair colourings, paper indus-
try, food technology, use the dyes for colouring their products,
which involves large amounts of water. It is estimated that more
than 100,000 commercially available dyes with over 7
105 MT of
dye-stuff are produced annually [1] and are used in the textile
industry. It is estimated that approximately 15% of dye stuff are
discharge in industrial effluents during the manufacturing and pro-
cessing operations [2].
The residual dye discharge in surface water generates a problem
for aquatic life. The wastewaters are loaded with a variety of pol-
lutants such as, dyes, heavy metals and surfactants, and they con-
tain a variety of organic compounds which are harmful and have
carcinogenic properties. All synthetic dyes have complex chemical
structures with one, two or more aromatic rings with chromophore
groups: antrachinone, azo (AN@NA), thiaxine – [3], with heavy
metals, i.e. Pb, Cd, Cu, Co, Cr (metal-complex dyes) [3,4], such as
their complete biodegradation is slow or even impossible.
⇑ Corresponding author. Fax: +40 268 41 05 25.
E-mail address: maria.visa@unitbv.ro (M. Visa).
tions: in dyeing industry (dyeing cotton and silk), in chemistry
and biology. It is not strongly hazardous but can cause harmful
effects: increased heart rate, vomiting, Heinz body formation, cya-
nosis, jaundice, and tissue necrosis in humans. On inhalation, it can
give rise to short periods of rapid or difficult breathing while inges-
tion through the mouth produces a burning sensation and may
cause nausea, vomiting, mental confusion and methemoglobine-
mia [4]. The presence of MB or other dyes in water, even at low
concentration, is highly visible, reduces sunlight penetration, and
inhibits the growth of aquatic biota [5,6]. Many drugs can interact
with methylene blue. A dangerous drug interaction could occur,
leading to serious side effects.
The presence of heavy metals in wastewater is unwanted due to
their solubility in water. Thus, they can be absorbed by living
organisms and they enter in the food chain, start to accumulate
in the human body and can cause serious health disorders.
The conventional methods of removing organic/inorganic
pollutants from wastewaters are: chemical coagulation [7],
electro-flocculation and ozonation [8], biological treatment [8],
electrochemical treatment [9], chemical precipitation, chemical
oxidation [10], nanofiltration membranes [11,12] and adsorption
[13–15]. The adsorption technologies is an effective way for
removing dyes, surfactants and heavy metals from industrial efflu-
ents, in terms of initial cost, easy operation, simplicity of design,

http://dx.doi.org/10.1016/j.apt.2017.04.014
0921-8831/Ó 2017 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876
inexpensive equipment, less land area (half to quarter of what is
required in a biological system) superior removal of organic con-
taminants [16] and the adsorbents regeneration.
Utilization of the charcoal (potential substitute for activated
carbon) [17] activated carbon [18,19] obtained from trees, from
bamboo [20,21], wood ash [22] have attracted worldwide attention
in view of the large disposal problem with no detriment to the
environment. The activated carbon derived from agricultural waste
was the most widely used of all the general-purpose industrial
adsorbents [23,24]. They are manufactured from a variety of pre-
cursors, i.e. cheap and available materials such as wood [25], peat
[26], eucalypt bark [27] sawdust [28], rice-husk [29], wheat straw,
corncobs and barley husks [30], pine tree leaves [31]. The reactive
dye was removed from aqueous solutions by adsorption onto acti-
vated carbons prepared from sugarcane bagasse pith [16], etc.
which represent carbonaceous precursors for the removal of dyes
from water and wastewater. The advantage of using agricultural
by-products as raw materials for manufacturing-activated carbon,
charcoal, and fuel is that these raw materials are renewable and
potentially less expensive to manufacture.
The activated carbon is widely used as a support in water reme-
diation because of its good adsorbance, while the supported TiO2
exhibits a synergism that has marked effects on the pollutants dis-
appearance kinetics and each pollutant being more rapidly photo-
degraded [30,31].
To the best of our knowledge, no study has been reported on the
preparation of charcoal from tree branches (forest waste) by pyrol-
ysis process, on the basis of intake limited air and measured in spe-
cially built to facilities called ‘‘Bosha” under limited and controlled
air supply.
Therefore, the main objective of this study was to evaluate the
possibility of using charcoal (BC) to develop new materials with
low cost and its applications for the removal methylene blue
and Cd2+ cations from aqueous solution by adsorption and
photocatalysis.
The adsorbent quality plays a key role and, during the past
years, the use of substrates based on modified wastes received
plenty of attention because two problems are solved simultane-
ously: the wastewater treatment and the forest waste use as raw
materials. In this way new applications for second range raw mate-
rial were identified.
2. Materials and the preparation of substrate
Tree branches were collected from deciduous forests (beech,
hornbeam) were carbonized with an insufficient amount of air
and, then, heated up to temperatures of 400–550 °C through the
channel ignition and flue draft. This process was interrupted when
the smoke coming through the stack turned bluish. Then, the chan-
nel was obturated and is left so few days to cool. The process of
obtaining charcoal from wood waste (BC) can be divided into three
steps:
1. Drying: in this phase water is eliminated from branches, virtu-
ally drying occurs between 0 and 110 °C;
2. Dry distillation: occurs between 150 and 350 °C. At 180 °C
hemicelluloses and 1/3 of cellulose usually begins to decompo-
sition, and the wood resistance drops significantly when the
temperature reaches 260 °C;
3. Charcoal formation: The beginning of this stage is at 350–
400 °C, ending at 400–550 °C, depending on the production
conditions. This stage is characterized by removing large
amounts of incondensable gases resulting from breakdown of
cellulose and lignin [32].
1867
This charcoal and activated charcoal were used for the removal
of dye (MB) and heavy metal (Cd2+) from wastewater.
2.1. The activation of BC with NaOH
The raw charcoal was sieved and the 40–100 lm fractions were
selected for the experiments. The raw charcoal (BC) shows a lim-
ited adsorption affinity for methylene blue and cadmium cations
as a result of high surface charge heterogeneity. The next stage
of the substrates preparation was washing. Previous studies [33]
also proved that an optimum surface charge of the adsorbents is
obtained by washing with using NaOH 1N or KOH as modifiers.
The washed charcoal (BC) was further mixed with NaOH 1N solu-
tion and stirred 48 h at room temperature followed by filtration,
rinsing and drying, at 105–120 °C till constant mass. This substrate
was noted (BCA).
2.2. The activation of BCA with Degussa P25
To improve the adsorbance and photocatalytic properties of the
BCA substrate under UV and VIS radiations, a new substrate noted
as BCA-D was developed by adding the TiO2 (Degussa P25, 80%
anatase and 20% rutile) to the BCA substrate in ratio 1:1. The
new composite BCA-D, with adsorption and photocatalytic proper-
ties for methylene blue and cadmium cations was explored. It is
expected that, due to the synergistic effect of the exposed func-
tional groups (AOH) and TiO2 on the charcoal surface, BCA-D will
exhibit a good adsorption and photocatalytic ability in the wastew-
ater treatment process.
3. The materials characterization
The surface morphology of the substrates were observed using
Scanning Electron Microscopy (SEM, model S-3400N-Hitachi). The
SEM images were obtained at 20–30 kV. The surface elemental
composition was evaluated using Energy dispersive X-ray (EDX)
measurements. The surface roughness and macro-pores size distri-
bution were evaluated using atomic force microscope (AFM Ntegra
Spectra, NT-MDT model BL222RNTE). The images were taken in
semi-contact mode with Si-tips (NSG 10, at constant force
0.15 N/m with 10 nm tip radius). The FT-IR spectra of the samples
were recorded with Spectrum BX Perkin Elmer BX II 75548,
k = 400–4000 nm. The XRD patterns of the samples were recorded
using an X-ray diffractometer (XRD Bruker D8 Discover Diffrac-
tometer) operating at 40 kW and 20 mA, 2h range from 10 to 70°,
scanning step 0.02°, scan speed 2 s/step.) The micro-porosity and
BET specific surface was carried out by N2 adsorption at 77 K using
an Autosorb-IQ-MP, Quantachrome Instruments.
4. Adsorption and photocatalytic experiments
4.1. Methlene blue dye adsorption studies
The synthesized substrates were used to remove the methylene
blue, a cationic dye and Cd2+ cations. The MB was chosen in this
study because of its known strong adsorption onto solids. The
stock-solutions were prepared by dissolving an appropriate quan-
tity of MB, (C16H18N3SCl) (Fluka AG, reagent grade) with
(319.85 g/mol) molecular weight, and CdCl2 2.5H2O (Scharlau Che-
mie S.A., c < 98%), in ultrapure water (Direct-Q3 Water Purification
System). The initial concentration of MB is 0.03125 mMol/L and
Cd2+ in the concentration range of cCd = 500–510 mg/L.
Ultrapure water with resistivity of 18.23 MX cm-1 was used
throughout the whole experiment.
1868 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876

More series of experimental tests of adsorption and photocatal-
ysis were done:
– Adsorption from bicomponent systems (MB + Cd2+) under
mechanical stirring on BC;
– Adsorption from bicomponent systems (MB + Cd2+) under
mechanical stirring on BCA;
– Adsorption and photocatalysis: MB on BCA-D under UV
irradiation.
In general, the known substrate amounts of (0.1–4 g/L) were
dispersed in a 50 mL (MB + Cd2+) solution and the mixture was stir-
red at 100 rpm at 20–23 °C. In the kinetic studies, aliquots at the
initial concentrations set were taken at fixed moments (10, 15,
30, 45, 60, 90, 120, 150 and 180 min), when stirring was briefly
interrupted and the substrate was removed by centrifugation
(GL-20G, Shanghai, China). The samples were filtered prior to anal-
ysis in order to minimize interference of the charcoal fines with the
analysis. The concentration of (MB) in the supernatant solution
before and after adsorption was analysed by UV–VIS spectrometry
(Perkin Elmer Lambda 25), on the calibration curve registered at
the maximum absorption peaks of MB (k = 665 nm), in order to
evaluate the momentary concentration of dye. The supernatant
was further analysed by AAS (Analytic Jena, ZEEnit 700), at:
kCd = 228.8 nm. Preliminary experiments proved that dye and
Cd2+ losses due to the adsorption onto the flask walls and filter
paper were negligible.
The amount of pollutants uptake by adsorbents (adsorption
capacity), qt, the removal efficiency, g, percentage were calculated
based on the initial ciMB=Cd2þ and equilibrium momentary ceMB=Cd2þ
concentrations of the pollutants using the following Eqs. (1) and
(2).
Following the experimental methodology, adsorption (A) is car-
ried out in systems with two pollutants: MB, Cd2+ and the results
are presented in Fig. 1.
ðciMB=Cd2þ  ctMB=Cd2þ Þ
V
qt ¼
ms
ðciMB=Cd2þ  ceMB=Cd2þ Þ  100
g¼
ciMB=Cd2þ
The high efficiency of MB and Cd2+ on the BCA substrate can be
explained by increased surface area and negative charge of BCA
surface. The initial working pH was 7.85 and it increased to 8.45
after adsorption.
The removal of MB by adsorption on BCA was found to be fast at
the initial period of contact time and, then, turns slow with the
increase of contact time or remains constant until equilibrium.
The change in the rate of adsorption might be due to fact that ini-
tially all adsorbent sites are vacant and the concentration of MB is
high. Later, the lower adsorption rate is due to a decrease in the
number of vacant sites. After the equilibrium, in particular, the
adsorption rate can decrease, which proves the possible monolayer
formation on the adsorbent surface [2,22].
The results indicate that these materials are very good adsor-
bents for simultaneous removal of MB and Cd2+ from aqueous
solutions.
In order to study the effect of adsorbent mass on the adsorption
only of MB, a series of adsorption experiments were carried out
with different adsorbent dosages at 0.03125 mMol/L MB concen-
trations. The MB and cadmium cations hydrated may be removed
by the same mechanism. Along with the adsorbent dosage increase
from 0.1 to 2 g L1, the efficiency of MB adsorbent increased from
44.17 to 99.81% at 60 min stirring time, Fig. 2. The efficiency of MB
removal increases over 80% at using only 0.6 g/L BCA.
In a real industrial process of heavy metals, dyes removing from
wastewaters, adsorption represents an important separate step,
but also, it is the primary step in the photocatalytic degradation.
For the dye degradation to CO2 and H2O or non-toxic compounds,
new materials were prepared starting from BCA and DegussaP25,
noted BCA-D.
Other experimental tests of adsorption and photocatalysis were
done using BCA-D composite under UV irradiation. The obtained
results are presented in Fig. 3. All the results obtained under
adsorption are denoted with (A) while the results obtained under
UV irradiation without stirring have the symbol (F).
In this case, it would be expected that the black charcoal will
block the UV radiations passing through each particle loaded with
ð1Þ MB or Cd2+ after the initial adsorption. The substrate dose is 1 g L1
at irradiation time 60 min.
However, a larger adsorbent amount (black charcoal) can block
ð2Þ the penetration of UV radiation and the higher efficiency is due to
the cumulating adsorption and potodegradation processes. The
removal of dyes by combining the adsorption and photodegrada-
tion processes was studied using nanosized TiO2 and activated car-
bon [34].

100
100
90
90
80 80
70 70
Efficiency [%]

60 60
Efficiency [%]

50 50

40 40

30 2+ 30
MB(MB+Cd )/BCA (A) MB/BCA(0.005g) (A)
20 2+ 2+ 20
Cd (Cd +MB)/BCA (A) MB/BCA(0.01g) (A)
2+
10 MB(MB+Cd )/BC (A) 10 MB/BCA(0.03g) (A)
2+ 2+
Cd (Cd +MB)/BC (A) MB/BCA(0.1g) (A)
0 0
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time [min] Time [min]

Fig. 1. Effect of contact time on the adsorption of MB and Cd2+ by BC and BCA. Fig. 2. Adsorption efficiency of MB with different amounts of adsorbent.
 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876 1869

5. Results and discussions

100

90 5.1. Crystalline structure of substrate

80
The phase composition of raw BC, BCA and of BCA-D was eval-
70 uated with XRD analysis. Fig. 5 presents the XRD patterns of the BC,
60
BCA and BCA-D composite.
Efficiency [%]

The charcoal (BC) and modified charcoal (BCA, BCA-D) composi-

50
tions are confirmed by the XRD analysis and the results are pre-
40 sented in Table 2. The predominant crystalline components of BC
2+
MB(MB+Cd )/BCA-D (F) and BCA are: Sodium Silicate (Na2(Si2O5), Sodium Phosphate
30 2+ 2+
Cd (Cd +MB)/BCA-D (F) Oxide(Na3PO4), Nitratine, syn(NaNO3), while anatase and rutile
20 2+
are prevalent in substrate BCA-D. The XRD data show that the
MB(MB+Cd )/BCA-D (A)
10 2+ 2+
Cd (Cd +MB)/BCA-D (A) new modified biocharcoal has well embedded titanium oxide with
crystallite sizes from 81.4 to 189.6 Å. The crystallites size was cal-
0
0 50 100 150 200 250 300 350 culated using the Scherrer Eq. (3).
Time [min] Kk
s¼ ð3Þ
Fig. 3. MB and Cd 2+
adsorption and photodegradation efficiency vs. time on BCA-D
b cos h
substrate.
where s – is the size of crystallites, K – is the shape factor with a
typical value 0.94, k – is the X-ray wavelength (1.541 Å), b – is
4.2. The repeatability of the experiments and reproducibility of the the line broadening at half the maximum intensity (of a peak), h –
date is the diffraction angle.
Considering the initial Degussa P25 grain dimension (30 . . . 50
Some experiments were repeatability to identify possible errors nm), one may conclude that the ultrasonic treatment also induced
or differences. For example, the influence of the amount of sub- a TiO2 recrystallization process on the micro-size alkaline charcoal
strate, and the results are presented in Fig. 4. (BC), extending the crystallite dimensions. The crystalline percent-
If the amount of substrate is low (0.01 g/L) the reproducibility of age of BC is 51.7%, the rest being represented by amorphous
the data is lower because the probability that MB or Cd2+ cations to phases. The crystalline percentages of BCA decreases (43.1%), by
meet with the active centers of the substrate is reduced. chemical activation, the same dissolution and recrystallization pro-
These differences are presented and in Table 1. cesses occur. The surface area increases after chemical treatment
In the case of the adsorption and of the photocatalysis on BCA-D and decreases when adding TiO2 Degussa with the surface area
the differences from 4.3 to 10.00%) appear on photodegradation of of 50 m2/g, Table 3. This parameter is very important in the adsorp-
MB. These can be explained by difference between particles loaded tion process of methylene blue and Cd2+.
with TiO2.
5.2. Morphology and surface tension of the substrate

Information about the substrate morphology/topography was

100 obtained from the AFM (Fig. 6a) and SEM micrographs. The AFM
90 images (5 lm  5 lm scan area) and pore size distributions shows
80

70
Efficiency [%]

60

50

40 MB/BCA(0.005g) (A)
MB/BCA(0.005g) (A)R
30 MB/BCA(0.01g) (A)
MB/BCA(0.01g) (A)R
20 MB/BCA(0.03g) (A)
MB/BCA(0.03g) (A)R
10 MB/BCA(0.1g) (A)
MB/BCA(0.1g) (A)R
0
0 20 40 60 80 100 120 140 160 180 200 220 240
Time [min]

Fig. 4. Adsorption efficiency of MB with different amounts of adsorbent before and

after repeatability.

Table 1
The differences on efficiency of MB before and after repeatability.

BCA
msubstrate (g) Differences (%)
0.005 7.5–12.00
0.01 2.24–15.2
0.03 0.67–15
0.1 0.04–0.5
Fig. 5. XRD patterns of the samples: (A) BC; (B) BCA; (C) BCA-D.
1870 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876

Table 2
The composition of the crystalline phases.

2H COD/PDF Crystalline phases Structures of the crystallite Crystallite size (Å)

BC
20.865 00-001-1103 Sodium Phosphate Oxide-Na3PO4 – 1624.3
26.64 01-085-2227 Sodium Silicate-Na2(Si2O5) orthorhombic 184.0
28.44 01-086-1316 Sodium Silicate-Na2Si(Si3O9) monoclin 854.5
29.383 01-070-1518 Nitratine, syn-NaNO3 rhombo.H 805.2
50.076 00-004-0333 Tartaric acid-C4H6O6 monoclin 255.5
BCA
20.865 00-001-1103 Sodium phosphate Oxide-Na3PO4 – 1624.3
29.383 01-070-1518 Nitratine, syn-NaNO3 Rhombo.H 805.2
26.64 01-085-2227 Sodium Silicate-Na2(Si2O5) Orthorhombic 184.0
50.076 00-004-0333 Tartaric acid-C4H6O6 monoclin 255.5
54.935 00-002-0839 Sodium Sulfate-Na2SO4 Orthorhombic 184.8
54.930 00-002-0323 Rankinite 3CaO*2SiO2 – 184.1
60.023 01-073-9586 Sodium Aluminium Silicate cubic 567.0
BCA-D
25.322 01-086-1157 Anatase, syn-TiO2 tetragonal 189.6
27.436 03-065-0190 Rutile, syn-TiO2 tetragonal 168.6
36.037 01-072-1148 Rutile, syn-TiO0.95 TiO1.95 Tetragonal 174.1
37.839 01-086-1157 Anatase,syn-TiO2 tetragonal 189.6
41.212 00-011-0217 Titanium Oxide-Ti3O5 monocline 81.7
48.071 00-004-0477 Anatase,syn-TiO2 tetragonal 188.4
53.901 00-021-1272 Anatase,syn-TiO2 tetragonal 191.5
55.101 00-004-0477 Anatase,syn-TiO2 Tetragonal 188.4
56.702 01-089-0554 Rutile,syn-TiO.936 O2 tetragonal 169.5
62.761 00-001-0562 Anatase-TiO2 Tetragonal 152.5
68.991 00-002-0494 Rutile-TiO2 tetragonal 81.4
70.363 03-065-5714 TitaniumOxide-Ti3O5 tetragonal 188.9
75.164 01-086-1157 Anatase,syn-Ti0.72O2 tetragonal 189.6
76.079 00-002-0387 Anatase/-TiO2 tetragonal 181.6

Table 3 tion or photodegradation. After the adsorption, roughness

The characteristics of the surface. increases (55 nm) because the pollutant molecules are adsorbed
on charcoal particles and on TiO2 nanoparticles (Fig. 7).
Sample Crystallinity SBET. Vmicropores (t-plot) D.average pores
degree (%) (m2/g) (cm3/g) (nm) The SEM images of charcoal (BC), charcoals activated with
NaOH (BCA) and of BCA-D are shown in Fig. 8. On the surfaces,
BC 51.7 251.766 0.062 3.558
BCA 43.1 366.769 0.083 3.708 many honeycomb-shape gaps appeared with diameters 10–
BCA-D 78.6 165.716 0.375 3.710 20 lm. These irregular gaps are surrounded by contracted twisted
walls. The walls are thick and smooth without any structure. Based
on the SEM images, we can confirm: when the charcoal particles
are in contact with NaOH, a thin film of NaOH should cover their
Table 4
surface and the interior of chars should be covered with Na+ and
The surface charge dependence on pH for substrates.
HO that are displayed in XRD spectra. However, the watering of
NaOH or KOH to the gap interior favours the micropore develop-
ment that results in an increase of the micropore number
[35,25]. In the pyrolysis process, the lignocelluloses structure
was modified leading to the loss of its cellular structure. The cavi-
ties are very irregular, indicating that, during activation, the alka-
line reagent (NaOH or KOH) caused a higher porosity in the
adsorbent materials.
On the BCA-D surface, one can see the individual TiO2 nanopar-
ticles (2 mm) or agglomerates crystallites with large size
the different granular shape in the size range of 0–200 nm. The (89.9 mm) Fig. 8(c). In this case, charcoal is the active support
AFM images shown in Fig. 6a and b give information about the dis- and they together improve the adsorption and photocatalytic
tribution of TiO2 on charcoal that is very important in photocatal- activity in removing dyes and heavy metals from wastewater.
ysis process. The EDX results demonstrate that elements such as C (44.30%), O
The BCA-D modified charcoal has a rough surface with larger (29.89%), N (1.41%) and Ti (24.32%) are contained in the BCA-D
pores/voids heterogeneously distributed that is confirmed by the sample. The map images (EDX), Fig. 9 of the agglomerate with
pores/voids distribution curve in Fig. 6(c). TiO2 show the distribution of the elements on its surface. The
Thus, during adsorption, photocatalysis BCA-D can host pollu- TiO2 particles are well dispersed on the surface in a honeycomb
tants with large molecules in the active sites/pores, but the effi- shape and even less than on the lamellar structure of charcoal.
ciency depends on the molecule affinity for the surface and
surface charges.
The low roughness value (26nm) obtained for BCA-D displays 5.3. The FTIR analyses of the substrates
a higher number of aggregates differently in shaped (almost round)
and possible stable (AFM image). This surface can be favourable for FT-IR analysis was used to investigate some functional groups
obtaining high efficiency in removal of the pollutants by adsorp- on the surface of charcoal and of modified charcoal [36]. The
 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876 1871

(a) BCA-D (2D) before adsorption (b) BCA-D (3D) before adsorption
Average roughness: 25.639nm
8000

7000
Counts/number of events

6000

5000

4000

3000
BCA-D before (A)
2000

1000

0
0 50 100 150 200 250
Pore diameter [nm]
(c) Pore histogram
Fig. 6. (a, b, c) AFM topography of BCA-D before adsorption (a) BCA-D (2D) before adsorption, (b) BCA-D (3D) before adsorption. Average roughness: 25.639 nm, (c) Pore
histogram.

results are shown in Fig. 10. The peak at 3446 cm1 corresponds to
the OAH stretching vibration of hydroxyl or carboxyl groups, as in
cellulose and lignin, showing the presence of hydroxyl groups on
the adsorbent surface [37]. The peaks around 2323.4–
2372.3 cm1 were assigned to the asymmetric or symmetric defor-
mation of CAH in methyl and methylene [37,38]. The peaks at
1560.3 cm1 can be associated to the stretching C=C vibration in
aromatic rings. The TiAOATi vibration band at 729.4 cm1 is pre-
sent in BCA-D and in TiO2. The other peaks at 2039.2,
2154.2 cm1 correspond to the stretching vibration of C=O groups.
5.4. The PZC analyses of the substrates
The pH level at which the adsorbent surface is neutral is desig-
nated as point of zero charge (PZC). The pHPZC value is an impor-
tant parameter to reach optimal loading surface and maximal
dispersion. The pHPZC of TiO2, BC and BCA-D substrates depends
on the alkali-acid character of surface hydroxyl groups. When pH
in the aqueous solution is lower than pHPZC, the surface is posi-
tively charged Eq. (4). When pH in the aqueous solution is higher
than pHPZC, the forms TiIVAO Eq. (5) exist and the surface is neg-
atively charged (Table 4).
Ti  OH þ Hþ ! Ti  OHþ2
IV IV
ð4Þ
Ti  OH þ HO ! Ti  O þ H2 O
IV IV
ð5Þ
The calculated pHPZC for BC, BCA, and BCA-D are from 7.21 to
8.37 that explains well the high adsorption efficiency of MB on
charcoal modified with NaOH 1N solution.
To test the thermal stability and water bonding of the BCA
material, DSC tests were done (in nitrogen flow) with a scanning
rate: 2 °C/min at 25450 °C. Many transformations appeared over
this temperature range. It should be pointed out that the as holder
peak appeared in the DSC curves for the hemicelluloses at 260 °C
and cellulose appeared at 360 °C, respectively. The BCA-D substrate
is more sable that BCA substrate.
6. Adsorption kinetics modelling
As a chemical reaction occurs, the kinetically data are necessary
to select the optimum conditions for designing the adsorption sys-
tems. The adsorption process depends on the physiochemical char-
acteristics of adsorbent, adsorbent amount, system composition
(type of organic molecules-dyes) and such conditions as concentra-
1872 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876

(a) BCA-D (2D) after adsorption (b) BCA-D (3D) after adsorption

3000 Average roughness: 55.49nm

2500
Counts/number of events

2000

1500

BCA-D after(A)
1000

500

0
0 50 100 150 200 250 300 350 400
Pore diameter [nm]
(c) Pore histogram
Fig. 7. (a, b, c) AFM topography of BCA-D after adsorption (a) BCA-D (2D) after adsorption, (b) BCA-D (3D) after adsorption Average roughness: 55.49 nm, (c) Pore histogram.

tion, pH and temperature (though the adsorption process is an where k2 is the equilibrium rate constant for the pseudo-second
exothermic process). The amount of MB adsorbed, qt (mg/g) at time order adsorption (g mg1 min1). The adsorption capacity (qe),
t was calculated by means the following Eq. (6). (k2) rate constant are determined from the slope and intercept from
a plot of t/qt against t for Eq. (8). This model is based on the assump-
ðciD  ceD Þ  V sol:
qt ¼ ð6Þ tion that the rate limiting step may be chemisorptions involving the
ms valence forces through sharing or exchange of electrons between
The kinetics models are fitted to experimental data by nonlinear the adsorbent and the adsorbate [41,42].
regression analysis. To determine the kinetic mechanisms of dye The intraparticle diffusion model, Eq. (9) [43]
(MB) uptake from systems we investigated:
The pseudo-first order kinetics of Lagergren, generally expressed q ¼ kid t1=2 þ C ð9Þ
as follows [39] Eq. (7) where kid- is the intraparticle diffusion rate constant (mg g - 1

KL
min0.5) and C is the boundary layer thickness. For the given pol-
logðqe  qt Þ ¼ logðqe Þ  t ð7Þ lutant systems, the kinetic parameters are presented in Table 5.
2; 303
The linearization proved that the pseudo-second kinetic order
where KL is the Lagergren constant (min1), qt and qe are the describes fairly well the adsorption mechanism for methylene blue
amount of adsorbed cations (mg g1) by the adsorbent at equilib- (Fig. 11).
rium and at time t (min). The correlation coefficient of the second order kinetic model
The pseudo-second order kinetics given by the equation devel- (0.994) is greater than for the first order kinetic model (0.975),
oped by Ho and M Kay, Eq. (8), [40]: while the MB adsorption on BC proved also to be faster
t 1 t (k2 = 3.525 g mg1 min1) as (k1 = 0.016 min1). This confirms that
¼ þ ð8Þ the rate limiting step is chemisorptions [2,6,44]. The linear portion
qt k2 q2e qe
of the plot in intraparticle diffusion does not pass through by ori-
 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876
Fig. 8. (a) SEM micrographs of BC, (b) SEM micrographs of BCA, (c) SEM micrographs of BCA-D.
gin. This deviation from the origin may be due to the variation of
mass transfer in the initial and final stages of the adsorption. This
confirms that the adsorption on BCA-D was a multi-step process
involving adsorption on the external surface and diffusion into
pores. The adsorption of cadmium on BCA and BCA-D is well
described by second order kinetic model: R2 = 0.992 and qe = 200 -
mg/g.
6.1. Photocatalytic activity of BCA-D
The most active photocatalytic component of the composite
BCA-D is tetragonal anatase with band gaps of 3.2 eV and rutile
3.0 eV which are active under UV radiation. The UV wavelength
used in our photocatalytic experiments was 365 nm, with flux
intensity 3Lx. The photodegradation efficiency on 0.03 g BCA-D
added in 50 mL solution 0.03125 mMol/L is higher that the adsorp-
tion efficiency under the same conditions. The TiO2 particles fixed
on the charcoal surface generates the most active species (HO) by
photo-irradiation and the species attack the MB molecules. In the
BCA-D composite, carbon accepts electrons generated in TiO2 and
produce other species of (O 2 ). In alkaline media under UV irradia-
tion, several other reactions are possible, involving the O2/HO, O2/
HOO and several mechanisms appear [42,43]:
1. RH (organic dye) + HO = R + H2O;
1873
2. Redox reaction: RAOH = RH+ + HO;
3. Addition to the p bonds in the pollutant molecule. The organic
radicals generated in these reactions will form peroxide radicals
(RAOAO) in reaction with oxygen and will initiate chain reac-
tions that can end up in mineralization products (CO2 and H2O)
or in other products [44,45].
The kinetic parameters and the correlation coefficients calcu-
lated from the linear form of the kinetic laws are presented in
Table 5 and the kinetic plots are given in Fig. 12. The kinetics data
were modelled using a first order kinetics derived from the
Langmuir-Hinshelwood model [36], Eq. (10).
lnc=co ¼ kobs t ð10Þ
where c0 and c are initial dye concentration and the concentration
at the moment t and kobs is the overall observed pseudo first-
order degradation rate constant.
The photodegradation results of MB on 1.00 g/L or 0.6 g/L BCA-D
are presented in Fig. 12 and they show that the mechanism follows
the pseudo-first order model with 0.025–0.031 min1 degradation
rate constant, describe the heterogeneous photocatalysis. We
assume that the process of adsorption on substrate is not disturbed
by the decomposition reaction. The possible alternative is to apply
in parallel both mechanisms, when adsorption and photocatalysis
are running independently.
1874 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876

Fig. 9. EDX image of BCA-D on the agglomerate with TiO2.

453.3

24

0.8 MB/BC (A) 22

20
729.4
0.6 18
0.010
16
2154.2
First order Second order
Absorbance [arb.units.]

0.008 2372.3 0.4

Log(qe-qt)

3239.8 2 2 14
1560.3 R =0.975 R =0.994

t/qt
450.5 1023.7
BCA-D 12
0.006 2323.4
0.2
10
0.004 3446
BCA 8
828.9 2327.7
2039.2 0.0
0.002 6
3828
BC 4
0.000 -0.2
0 20 40 60 80 100 120 140 160 180 200
500 1000 1500 2000 2500 3000 3500 4000 Time [min]
-1
Wavelength [cm ]
Fig. 11. The pseudo first order and the second order kinetic plot for MB adsorption
Fig. 10. FTIR spectrum of substrates. on BC.

Table 5
Kinetic parameters of the adsorption processes.

Samples Pseudo-first order Pseudo-second order Intra-particle Diffusion

KL (min1) R2 k2 (g mg1 min1) qe (mg/g) R2 Kid (mg/g) C R2
MB (A)
(MB + Cd2+)/BC 0.016 0.975 3.525 9.901 0.994 0.586 1.111 0.932
(MB + Cd2+)/BCA – 0.271 0.007 3.049 0.999 – – 0.369
(MB + Cd2+)/BCA-D 0.016 0.955 1.302 9.804 0.995 0.375 4.570 0.933
Cd2+(A)
(Cd2+ + MB)/BC – 0.786 0.129 100 0.991 3.223 49.15 0.956
(Cd2+ + MB)/BCA 0.028 0.952 0.053 200 0.992 8.122 87.03 0.96
Cd2+ + MB)/BCA-D 0.013 0.833 0.38 250 0.987 6.567 48.57 0.974
 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876
Pseudo-first order kinecs MB/MRA-D
mMRA-D= 0.6g·L-1
mMRA-D= 1.0g·L-1
2 proposed alteration, Bioresour. Technol. 77 (2001) 247–255.
0 [6] S.B. Wang, Y. Boyjoo, A. Choueib, E. Ng, H.W. Wu, Z.H. Zhu, Role of unburnt
-2 0 50 100 150 200 250 300 350 400
-4
LnC/C0
y = -0.026x + 0.391
-6
R² = 0.993
-8 y = -0.0315x + 0.3063
R² = 0.9955
-10
-12
Time [min]
Fig. 12. Photocatalysis of MB under UV radiation.
7. Conclusions
The BET surface area is the most important property of the
adsorbent materials. The charcoal (BC) with a BET surface area of
251.766 m2/g, which increases to 366.769 m2/g after activated
with NaOH, this partially explain the higher adsorption efficiency
of Cd2+ cations, 58.42%, on activated charcoal (BCA).
The adsorption capacity depends on the chemical nature of the
substrate, pore structure, structure of the crystallite and the crys-
tallite size. The new crystalline phases, Rankinite 3CaO⁄2SiO2
and sodium aluminium silicate from activated charcoal (BCA)
may improves the efficiency.
The BCA-D modified charcoal has a rough surface with larger
pores/voids heterogeneously distributed that is confirmed by the
pores/voids distribution curve in Fig. 6(c).
The adsorption activity of charcoal (BC) can be improved by
increasing the surface area which favours more contacts between
MB, Cd2+ cations and substrate.
The results show that the adsorption mechanism for removing
pollutants from wastewater by means of the above presented com-
posites BC, BCA, BCA-D is a viable, low cost, up-scalable and sus-
tainable technology along with the photodegradation technology.
The operating parameters for the maximal adsorption on BCA
were 60 min, dosage 0.6 g L1, 0.03125 mMol L1 concentration,
8 pH, for BCA-D were 1–2 g L1, 60 min. UV irradiation time. Char-
coal can be a good support for TiO2 to obtain a composite for the
adsorption and photodegradation of organic pollutants and heavy
metals from wastewater.
The rate of adsorption was well described by the pseudo-second
order kinetics and interparticle diffusion model with a good corre-
lation coefficient.
Charcoal is a good support for TiO2 to obtain a composite for the
adsorption and photodegradation of organic pollutants and heavy
metals from wastewater.
Tetragonal anatase is the most active photocatalytic component
of the BCA-D composite.
Acknowledgements
This work was supported by a grant Transylvania University of
Brasov, Doctoral Programme.
References
[1] I.A.W. Tan, B.H. Hameed, A.L. Ahmad, Equilibrium and kinetic studies on basic
dye adsorption by oil paalm fibre activated carbon, Chem. Eng. J. 127 (2007)
111–119.
[2] V.K. Gupta, D. Pathania, S. Sharma, P. Singh, Preparation of bio-based porous
carbon by microwave assisted phosphoric acid activation and its use for
adsorption of Cr(VI), J. Colloid Interface Sci. 401 (2013) 125–132.
[3] M. Visa, F. Pricop, A. Duta, Sustainable treatment of wastewaters resulted in
the textile dyeing industry, Clean Technol. Environ. Policy 13 (2013) 855–861.
1875
[4] M. Malakootian, A. Almasi, H. Hossaini, Sustainable treatment of wastewaters
resulted in the textile dyeing industry, Environ. Sci. Technol. 5 (2008) 217–222.
[5] T. Robinson, G. McMullan, R. Marchant, P. Nigman, Remediation on dyes in
textile effluent: a critical review on current treatment technologies with a
carbon in adsorption of dyes on fly ash, J. Chem. Technol. Biotechnol. 80 (2005)
1204–1209.
[7] J. Sarasa, M.P. Roche, M.P. Ormad, E. Gimeno, A. Puig, J.L. Ovelleiro, Treatment
of a wastewater resulting from dyes manufacturing with ozone and chemical
coagulation, Water Res. 32 (1998) 2721–2727.
[8] A.H. Konsowa, Decolorization of wastewater containing direct dye by
ozonation in a batch bubble column reactor, Desalination 158 (2003) 233–240.
[9] G. Ciardelli, N. Ranieri, The treatment and reuse of wastewater in the textile
industry by means of ozonation and electroflocculation, Water. Res. 35 (2001)
567–572.
[10] L. Fan, Y. Zhou, W. Yang, G. Chen, F. Yang, Electrochemical degradation of
aqueous solution of Amaranth azo dye on ACF under potentiostatic model,
Dyes Pigm. 76 (2008) 440–446.
[11] E. Oguz, B. Keskinler, Comparison among O3, PAC adsorption, O3/HCO 3 , O3/
H2O2 and O3/PAC processes for the removal of Bomaplex Red CR-L dye from
aqueous solution, Dyes Pigm. 74 (2007) 329–334.
[12] T.-H. Kim, C. Park, S. Kim, Water recycling from desalination and purification
process of reactive dye manufacturing industry by combined membrane
filtration, J. Cleaner Prod. 13 (2005) 779–786.
[13] R.W. Bowen, J.S. Welfoot, Modeling of membrane nanofiltration- pore size
distribution effects, Chem. Eng. Sci. 57 (2002) 1393–1407.
[14] T. Robinson, B. Chandran, P. Nigam, Effect of pretreatments of three waste
residues, wheat straw, corncobs and barley husks on dye adsorption,
Bioresour. Technol. 85 (2002) 119–124.
[15] P.K. Singh, D. Mohan, G.S. Tandon, G.S.D. Gupta, Removal of pyridine from
aqueous solution using low cost activated carbons derived from agricultural
waste materials, Ind. Eng. Chem. Res. 41 (2002) 2480–2486.
[16] N.K. Amin, Removal of reactive dye from aqueous solutions by adsorption onto
activated carbons prepared from sugarcane bagasse pith, J. Desalination 223
(2008) 152–161.
[17] G. Ding, B. Wang, L. Chen, S. Zhao, Simultaneous adsorption of methyl red and
methylene blue onto biochar and an equilibrium modeling at high
concentration, Chemosphere 163 (2016) 283–289.
[18] S. Hajati, M. Ghaedi, S. Yaghoubi, Local, cheep and nontoxic activated carbon as
efficient adsorbent for the simultaneous removal of cadmium ions and
malachite green: optimization by surface response methodology, J. Ind. Eng.
Chem. 21 (2015) 760–767.
[19] A.L. Cazetta, A.M. Vargas, E.M. Nogami, M.H. Kunita, M.R. Guilherme, A.C.
Martins, T.L. Silva, J.C. Moraes, V.C. Almeida, NaOH-activated carbon of high
surface area produced from coconut shell: Kinetics and equilibrium studies
from the methylene blue adsorption, Chem. Eng. J. 174 (2011) 117–125.
[20] B.H. Hameed, A.T.M. Din, A.L. Ahmad, Adsorption of methylene blue onto
bamboo-based activated carbon: kinetics and equilibrium studies, J. Hazard.
Mater. 141 (2007) 819–825.
[21] V.K. Gupta, Application of low-cost adsorbents for dye removal-a review, J.
Environ. Manage. 90 (2009) 2313–2342.
[22] M. Visa, M. Nacu, Comparative heavy metals and dyes removal efficiency on fly
ash and wood ash, Environ. Engine. Manag. J. 9 (2011) 1407–1414.
[23] B.H. Hameed, F.B.M. Daud, Adsorption studies of basic dye on activated carbon
derived from agricultural waste: Hevea brasiliensis seed coat Chem, Eng. J. 139
(2008) 48–55.
[24] W.T. Tsai, C.Y. Chang, M.C. Lin, S.F. Chien, H.F. Sun, M.F. Hsieh, Adsorption of
acid dye onto activated carbons prepared from agricultural waste bagasse by
ZnCl2 activation, Chemosphere 45 (2001) 51–58.
[25] Y.S. Ho, G. McKay, D.A. Wase, C.F. Forster, Study of the sorption of divalent
metal ions on to peat, Adsorpt. Sci. Technol. 18 (2000) 639–650.
[26] P. Patnukao, P. Pavasant, Activated carbon from Eucalyptus camaldulensis
Dehn bark using phosphoric acid activation, Bioresource Technol. 99 (2008)
8540–8543.
[27] P. Pengthamkeerati, T. Satapanajaru, N. Chatsatapattayakul, P.
Chairattanamanokorn, N. Sananwai, Alkaline treatment of biomass fly ash for
reactive dye removal from aqueous solution, Dessalination 261 (2010) 34–40.
[28] E.L. Abd, M.M. Latif, A.M. Ibrahim, Adsorption, kinetic and equilibrium studies
on removal of basic dye from aqueous solutions using hydrolyzed Oak sawdust
Desalin, Water Treat. 6 (2009) 252–268.
[29] P.K. Malik, Use of activated carbons prepared from sawdust and rice-husk for
adsorption of acid dyes: a case study of Acid Yellow 36, Dyes Pigm. 36 (2003)
239–249.
[30] M.T. Yagub, S.T. Kanti, H.M. Ang, Equilibrium, kinetics, and thermodynamics of
methylene blue adsorption by pine tree leaves, Water Air Soil Pollut. 223
(2012) 5267–5282.
[31] S. Li, J. Lyons-Hart, J. Banyasz, K. Shafer, Real-time evolved gas analysis by FTIR
method: an experimental study of cellulose pyrolysis, Fuel 80 (2001) 1809–1817.
[32] M. Visa, A. Duta, Advanced Cd2+ removal on dispersed TiO2 – fly ash, Environ.
Engin. Manag. J. 7 (2008) 373–378.
[33] L. Andronic, A. Enesca, C. Cazan, M. Visa, TiO2-active carbon composites for
wastewater photocatalysis, J. Sol Gel Sci. Technol. 71 (2014) 396–405.
[34] R.-L. Tseng, S.-K. Tseng, Pore structure and adsorption performance of the
KOH-activated carbons prepared from corncob, J. Colloid and Interface Sci. 287
(2005) 428–437.
1876 N. Popa, M. Visa / Advanced Powder Technology 28 (2017) 1866–1876
[35] K. Bilba, A. Ouensanga, Fourier transform infrared spectroscopic study of
thermal degradation of sugar cane bagasse, J. Anal. Appl. Pyrolysis 38 (1996)
61–73.
[36] H. Yang, R. Yan, H. Chen, D.H. Lee, C. Zheng, Characteristics of hemicellulose,
cellulose and lignin pyrolysis, Fuel 86 (2007) 1781–1788.
[37] S. Wang, H. Lin, L. Zhang, G. Dai, Y. Zhao, X. Wang, B. Ru, Structural
characterization and pyrolysis behavior of cellulose and hemicellulose isolated
from softwood pinus armandii Franch, ACS. Energy & Fuels http://dx.doi.org/
10.1021/.6b00650.
[38] M. Arami, N.Y. Limaee, N.M. Mahmoodi, N.S. Tabrizi, Removal of dyes from
colored textile wastewater by orange peel adsorbent: equilibrium kinetic
studies, J. Colloid Interf. Sci. 288 (2005) 371–376.
[39] M. Arami, N.Y. Limaee, N.Y. Limaee, N.M. Mahmoodi, N.S. Tabrizi, Removal of
dyes from colored textile wastewater by orange peel adsorbent: equilibrium
and kinetic studies, in: J. Colloid InterfaceSci. 288 (2005) 371–376.
[40] Y.S. Ho, G. McKay, The kinetic of sorption of basic dyes from aqueous solution
by sphagnum Moss peat, J. Chem. Eng. 76 (1998) 822.
[41] J.M. Coronado, F. Fresno, M.D. Hermandez-Alonso, R. Portela, Design of
advanced photocatalytic. Mater. Energy Environ. Appl., Springer. 12, 13
(2013) ISSN 1865–3537.
[42] M. Visa, C. Bogatu, A. Duta, Simultaneous adsorption of dyes and heavy metals
from multicomponent solutions using fly ash, J. Appl. Surf. Sci. 256 (2010)
5486–5491.
[43] S.J. Allen, G. Mc Kay, Z.H. Khader, Interparticle diffusion of a basic dye during
adsorption onto sphangum peat, J. Environ. Pollut. 56 (1999) 39–50.
[44] L.J. Hsu, L.T. Lee, C.C. Lin, Adsorption and photocatalytic degradation of
polyvinyl alcohol in aqueous solutions using P-25 TiO2, Chem. Eng. J. 173
(2011) 698–705.
[45] A. Duta, M. Visa, Simultaneous removal of two industrial dyes by adsorption
and photocatalysis on a fly-ash-TiO2 composite, J. Photochem. Photobiol. A
Chem. 306 (2015) 21–30.