Journal of Environmental Chemical Engineering 6 (2018) 169–181

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Journal of Environmental Chemical Engineering

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

Multifunctional activated carbon with antimicrobial property derived from T

Delonix regia biomaterial for treatment of wastewater
⁎
Mary R. Louisa, Laxmi Gayatri Sorokhaibama, , Vinay M. Bhandarib, Sunita Bundalec
a
Department of Chemistry, Visvesvaraya National Institute of Technology Nagpur, 440010, India
b
Chemical Engineering & Process Development Division, CSIR-National Chemical Laboratory, Pune, 411008, India
c
School of Biotechnology, Hislop College, Nagpur, 440001, India

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, we report the development of a multifunctional high surface area activated carbon (DRP), from a
Reactive dyes biomaterial, Delonix regia, with antimicrobial potential and demonstrated its applicability towards removal of
Disinfection two reactive dyes, Reactive Red (RR-120) and Reactive Blue (RB-4) with an adsorption capacity of ∼6.36 and
Wastewater treatment 24 mg·g−1 respectively. The newer multifunctional activated carbon was prepared from the deseeded pods of
Adsorbent
Delonix regia through thermo-chemical surface modification and characterized for surface and morphological
characteristics, chemical composition, and thermal stability. DRP exhibited a high surface area of 1577 m2·g−1
with various active functional groups. The decolourisation efficiency achieved was very high, ∼98% for both the
dyes. The effects of various operating parameters like pH, initial dye concentration, adsorbent dosage, surfac-
tant, salt etc. were investigated and the batch adsorption equilibrium data in each dye system was analyzed with
various isotherms-Langmuir, Freundlich, and Tempkin. The kinetics of the adsorption process was best re-
presented by pseudo-second order kinetic model and the adsorption efficiency was also illustrated in the binary
system of varying dye compositions. DRP could successfully reduce the microbial growth of Gram positive B.
subtilis with a higher zone of inhibition.

1. Introduction
Activated carbons are one of the most promising materials used in
the tertiary step of wastewater treatment due to its high surface area,
and high capacity for removal of organic pollutants from water. They
are also employed in water filters [1] and cartridges to treat water of
different uses ranging from potable to indirect use at point sources.
However, due to its extended surface area, well-developed network of
pores (micro, meso and macroporous), they are highly biocompatible
and prone to breed various bacteria, fungi, and other common patho-
gens. The contamination of treated water with these microorganisms is
undesirable and for safe water use, the reduction of only chemical
oxygen demand (COD) or high pollutant removal capacity is not suffi-
cient and there is a need for water available for reuse to be free from
bacteria and pathogens. It has been observed that due to the mixing of
sewage run off or availability of rich nutrients, nitrates, phosphates and
other organic material in effluents or surface waters, wastewater is
often contaminated with different kinds of faecal coliforms and is a
huge problem in the reuse and recycling process of wastewater and are
also known to spread several water borne diseases. They are responsible
for degrading the quality of the water, membrane fouling, pores clog-
ging, fouling of the water where these effluents are released. Even water
for irrigation purpose in certain cases has to be free from microbes. To
make the treated water safe for reuse and other indirect potable ap-
plications, these microorganisms must also be eliminated by processes
which involve low cost and less energy input yielding clean and safe
water [2]. Although disinfection of water is important for various safe
water applications [3,4], the current available disinfection technologies
like UV, ozone or chlorination are either cost intensive or produce
harmful carcinogenic by-products [5]. Hence, if activated carbons are
designed in such a fashion that itself possess biocidal properties, it is
always an added advantage in the treatment process
Among the organic pollutants, dyes and dyestuffs from textile in-
dustry belong to one of the most polluting substance. Their presence in
surface water is a great nuisance as most of them are non-biodegradable
or degrade with the release of harmful carcinogenic [6,7] products or
either themselves are toxic, mutagenic and carcinogenic. Dyes are
usually released from the textile, leather, printing, paper, food, rubber,
plastic and cosmetic industries [8–10], etc. These dyes are classified
into several types, of which reactive dyes belong to the class of anionic

⁎
Corresponding author.
E-mail address: laxmigayatri1@gmail.com (L.G. Sorokhaibam).

https://doi.org/10.1016/j.jece.2017.11.056
Received 3 August 2017; Received in revised form 3 November 2017; Accepted 17 November 2017
Available online 21 November 2017
2213-3437/ © 2017 Elsevier Ltd. All rights reserved.
M.R. Louis et al.
Table 1
Physico-chemical specification of RB-4 and RR-120.
Dye RB-4
Other name Procion Blue
Class Anthraquinone
Water solubility (g.L−1) 45
Maximum adsorption wavelength (nm) 591
Molecular weight(g.mol−1) 637.43
Molecular structure
polyaromatic structures which are widely applied in the textile in-
dustries due to their industrially beneficial properties like bright col-
ours, wide colour range, high water solubility, tolerance to various
degradation processes, easy and powerful application [11,12]. Reactive
dyes constitute more than 20-40% of the dyes and contain one or more
reactive groups that form covalent bonds with either the hydroxyl or
amino group in fabric materials [13]. They are one of the most re-
calcitrant/persistent dyes due to their higher water solubility, non-
biodegradability and occurrence in higher concentrations than any
other dyes [12]. They may be removed through adsorption process
using activated carbon as adsorbents which are versatile and a widely
applied in industries and is associated with benefits of high efficiency
and ease of operation, over the other processes. However, the high cost
of the conventional commercial adsorbents is a bottleneck in its ap-
plication. It is imperative to identify cheaper sources of activated
carbon. The process can be made economical by involving biomaterial/
bio-waste/agro waste as the raw material source of activated carbon. In
addition, these biomass materials provide a renewable, non-toxic, re-
generating, sustainable, biodegradable source to treat the waste water.
The dyeing process uses various chemicals, acids, alkalis, salts, surfac-
tants and it becomes instructive to study the efficiency of the treatment
process under these different parameters.
The pods of Delonix regia (Gulmohar or Flamboyant) forms one such
sustainable source of adsorbent material as they have limited valuable
use other than the seed dispersal [14,15]. Delonix regia, is a dicotyle-
donous plant belonging to the Fabaceae family which is widely dis-
tributed in countries like India, Taiwan, Caribbean, the United States,
Hawaii, Puerto Rico, the Virgin Islands, the Canary Islands, Hong Kong,
Southern China, South Brazil, Australia [16] etc. These pods are rich in
lignocellulosic material which may provide sites for the binding of the
dye molecules or removal of other organic pollutants and hence a good
precursor for preparation of activated carbons. Delonix regia have been
reported as source of catalyst for the transesterification of the Hevea
brasiliensis oil. There are few reports on the application in the removal
of oil spills, methylene blue and acid dyes like Acid Yellow and Acid
Red [15–17] where different parts of the plant are explored. However,
chemico-thermal modification and activation of Delonix regia using
phosphoric acid has not been reported for removal of reactive dyes.
Further, it is desirable that the activated carbon used for the treatment
of water be imparted with antimicrobial property which may be con-
sidered to be superlative.
The objective of the present study is to develop a multifunctional
activated carbon having high surface area and antimicrobial property
with capability for treating two model pollutants of reactive dyes, viz.,
Reactive Blue (RB-4) and Reactive Red (RR-120). The investigation
involves studying the equilibrium and kinetics of adsorption of the two
reactive dyes (Reactive blue 4 and Reactive red 120), and investigation
of antimicrobial properties of the developed material using two model
microbes, E.coli and B. subtilis. To determine the applicability of the
170
Journal of Environmental Chemical Engineering 6 (2018) 169–181
RR-120
Triazine dye red
Diazo
70
535
1470
prepared adsorbent in real waste water system, the adsorption process
was conducted in presence of various interfering conditions like varying
pH, salt, and surfactant concentrations and also in binary system.
2. Experimental
2.1. Materials and methods
All the chemicals used throughout the experiments were of analy-
tical reagent grade and consisted of Phosphoric acid (98%, BDH),
Cetyltetraammonium bromide, CTAB (98%, LOBA Chemie), Sodium
lauryl sulphate, SDS (CAS No.151-21-3, Fisher Scientific), Sodium hy-
droxide (≥97%, Merck, India), Hydrochloric acid, (35%, Fischer sci-
entific), Sodium chloride (Fisher scientific), Sodium sulphate (99%,
Fischer Scientific),Reactive Blue 4 or Procion Blue (Alfa Aesar), and
Reactive Red-120 (Sigma-Aldrich). Commercial activated carbon (AC)
was procured from Merck (CAS No. 7440-44-0, Methylene blue ad-
sorption ≥180 mg·g−1), India and another AC (Min. Methylene blue
value of 400) was obtained from Sisco Research Laboratories Pvt Ltd,
India. All the chemicals were used without further purification. The
detail chemical specifications of both the dyes are given in Table 1. The
working standard solutions were prepared from the stock solutions of
500 mg·L−1 by subsequent dilution method to the required concentra-
tion. Dye concentrations were then measured using Uv–vis spectro-
photometer at their absorbance maximum.
As seen from the molecular structure in Table 1, RB-4 consisted of
two sulphonyl group, one quinone, two chloro and one amino group
whereas RR-120 consisted of six sulphonyl groups, two azo, one hy-
droxyl and two chloro groups.
2.2. Preparation of adsorbent
The deseeded woody brown pods of Delonix regia were chosen as the
starting material as it is easily and abundantly present and often dis-
carded as waste material. The present study employs phosphoric acid
treated pods of Delonix regia in the preparation of a bio-adsorbent to
target reactive dyes and bacterial pollutants. Dry pods of Delonix regia
(DR) were collected from the local area of Maharashtra region of India.
These pods were washed thoroughly and sun dried, broken down into
small pieces, seeds were separated and finally ground in a blender to
fine dry powder. The clean and dry powder was then mixed with or-
thophosphoric acid (1:1, w/v) for 3 h at 80° C on a hot plate, with in-
termittent stirring. Chemical activation of precursor material has been
reported to increase the adsorbent surface area and porosity, creating
sites available for the adsorption of the pollutant molecule. Many
chemical activating agents like KOH, NaOH, ZnCl2, K2CO3, H2SO4, etc.
have been reported for chemical activation of adsorbent materials.
Phosphoric acid is considered to be a good activating agent for carbo-
nization of biomass material which mainly contains lignocellulosic
M.R. Louis et al.
material. It helps in the development of highly porous carbon structure
with varying degrees of porosity depending on the atmosphere and
heating temperature. Also, phosphoric acid being a good oxidizing
agent induces surface acidic and oxygen functional groups [18] which
are known to enhance the removal of organic pollutants like dye mo-
lecules from aqueous streams. Chemical activation with phosphoric
acid is known to be non-polluting [19] and can be easily removed by
washing, making it a suitable modifying agent. On the other hand,
other modifying agents are either toxic or associated with certain dis-
advantages like low yield in case of KOH [20], toxic on exposure and
narrow applications in case of ZnCl2 or tend to be harsh and corrosive
in nature.
The phosphoric acid treated DR was then placed in a muffle furnace
at 450° C for 1 h at a heating rate of 10° C per min. The obtained ac-
tivated carbon (DRP) was washed thoroughly with deionised water
until the pH of the solution was nearly neutral. The sample was then
placed in an oven at 110 ° C overnight till complete dryness. The dried
DRP was further crushed to finer powder and stored in a desiccator. The
effect of carbonization temperature was also investigated by preparing
three different carbons at 350, 450, and 650 °C.
2.3. Characterization of the adsorbent
The prepared activated carbon was characterized to understand the
surface composition, morphology and thermal stability using FT-IR
(Fourier Transform Infra-red), XRD (X-ray Diffraction), TG-DTA
(Thermo gravimetric and Differential Thermal Analysis, Diamond TG/
DTA PERKIN ELMER USA) and BET (Brunner-Emmet and Teller) sur-
face analysis. FTIR spectra of DRP before and after adsorption were
examined in order to determine the functional groups present on the
surface of the DRP and their possible role in the interaction between the
dye and the adsorbent surface. The spectra were recorded in trans-
mittance mode using Shimadzu- Spectrophotometer with 40 scans and a
resolution rate of 4 cm−1 in the range of 400 to 4000 cm−1. The
samples were prepared using dry FTIR grade KBr powder in a ratio of
1:100. The X-ray diffraction patterns for both the samples were ob-
tained using X-ray Diffractometer (Panalytical’s X’Pert Pro) with wa-
velength 1.54°A (Cμ K-α1), equipped with nickel beta filter and
x’Celerator solid state detector and 2θ range of 5 to 100°. The SEM
images were recorded with a 25000 times magnification by the
Scanning electron microscope (FEI, QUANTA 200-3D). The TEM mi-
crograph was obtained by dripping the DRP dispersed in isopropanol,
followed by ultrasonication for 30 mins and dried on the copper grid
which was then characterized on TEM-EDX (Tecnai T-20) at 200 eV.
Elemental composition of DRP was further checked with CHN analyser
(ThermoFinnigan). The surface area of the prepared adsorbent was
characterized by Quantachrome Sorptometer using the nitrogen ad-
sorption-desorption method where the finely powdered sample was
degassed earlier and then analysed at −196° C. The specific surface
area was calculated by the Brunauer- Emmett-Teller (BET) isotherm
model while the total pore volume and average size was determined by
Barrett-Joyner-Halenda(BJH) method. To determine the thermal sta-
bility of the DRP, TG analysis were performed in the temperature range
of 30 °C to 1100° C under a nitrogen flow of 30 mL per min at the
heating rate of 10° C per minute. To understand the surface charge
properties, pHPZC (point of zero point charge) of DRP was determined
by the pH drift method [21] by contacting 0.15 g of DRP in 50 mL of
0.1 M NaCl solution, whose initial pH was adjusted using a pH-meter
(Systronic, India) in the range of 2–12 (pHi) by using either 0.1 mol·L−1
HCl or NaOH. After a contact time of 48 h, the solutions were filtered
and again their final pH (pHf) was determined. The graph of ΔpH (pHf
− pHi) versus pHi was plotted to determine the pHPZC of the adsorbent.
2.4. Adsorption equilibrium and kinetic studies
Batch adsorption equilibrium was studied using predetermined
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Journal of Environmental Chemical Engineering 6 (2018) 169–181
amount of DRP (0.02 to 0.7 g) in 20 mL of 50 mg·L−1 dye solution for a
contact period of 5 h was shaken with a constant speed in an orbital
shaker (Remi Instruments, India) at 100 rpm. The absorbance of the
residual solution was read spectrophotometrically using UV–vis spec-
trophotometer (Shimadzu Model Uv 1800,) to determine the dye con-
centration at λmax of 591 nm and 535 nm respectively for RB-4 and RR-
120. Effect of dosage of DRP, initial dye concentration (10, 50, 100 and
200 mg L−1), pH range (3 to 12), time of contact and the presence of
other interfering agents like, anions (NaCl, Na2SO4), surfactants (SDS
and CTAB) was also investigated. Approach to equilibrium was ensured
which indicated reaching equilibrium by 3 h and hence the effect of
different parameters was studied using equilibration time of 3 h. The
amount of the dye adsorbed per gram of the adsorbent at equilibrium,
qe (mg·g−1) was obtained by Eq. (1).
q e=(C0 -Ce)V/m (1)
Where C0 and Ce are the initial dye concentrations and equilibrium
concentrations respectively, V is the volume of the solution (L) and m is
the mass of the adsorbent (g).
To understand the competitive nature or selectivity of the adsorbent
material in dye mixtures, the adsorption equilibrium in the binary so-
lution consisting of different ratios of RB-4 and RR-120 was also stu-
died. The batch experiment for binary adsorption study was also per-
formed with 20 mL each of five different compositions (90:10, 70:30,
50:50, 30:70, 10:90 v/v) of RB-4 and RR-120 respectively at room
temperature having an initial concentration of 50 mg·L−1. An opti-
mized dose of 0.5 g of DRP was added and kept in Orbital shaker in-
cubator with shaking speed of 100 rpm at 30 ° C for 5 h and the residual
dye solution was measured using the Eqs. (2) and (3) [22]:
CRB =(k535 591 591 535 535 591
RR .A591-kRR .A535)/(k RB .kRR -kRB .kRR ) (2)
CRR =(k591 535 591 535 535 591
RB .A535-kRB .A591)/(k RB .kRR -kRB .kRR ) (3)
where CRB and CRRare the residual concentrations of RB-4 and RR-120
respectively; k591 535 535 591
RB , kRB , kRR and kRR are the calibrations constants for RB-
4 and RR-120 at 591 nm and 535 nm respectively and A591 and A535 are
the absorbances of RB-4 and RR-120 respectively in the binary system.
To obtain data on the kinetic parameters, the rate of dye removal
was investigated using an optimized dose of 0.5 g of DRP with 20 mL of
RB-4 and RR-120 having initial concentrations of 50 mg L−1. The
mixture was agitated at a speed of 100 rpm in an orbital shaker at
303 K. The adsorption reaction was inhibited at specified time and the
residual solution free of DRP was read spectrophotometrically at the
λmax of the respective dyes to determine the percent removal of the
dyes after elapsed time,‘t’ and the data obtained was fitted to various
rate equations given in Eqs. (9) to (11). All the experiments were car-
ried out in triplicate and reproducibility was found to be satisfactory.
2.5. Antimicrobial assay
The antibacterial property of the DRP was determined by the in-
hibition zone test method [23] using two model representative organ-
isms. E.coli, a Gram negative organism and B. subtilis, a Gram positive
bacterium. The bacterial cultures were obtained from MTCC (Microbial
Type Culture Collection and Gene Bank), CSIR-Institute of Microbial
Technology, Chandigarh. All other reagents for microbial inactivation
study were procured from Hi Media. The bacterial suspension was
prepared by using 10 mL of autoclaved Nutrient broth for 24 h. Further,
2 mL of these cultures with optical densities (0.419 for B.subtilis and
0.424 for E.coli) at 600 nm were used to inoculate 20 mL of prior
sterilized Nutrient Agar. Then the plate was allowed to set for 2 h to
solidify and punctured to form wells of diameter 5 mm. About 0.05 g of
prior autoclaved DRP was placed in the well and 60 μL of sterile dis-
tilled water was added. The plate with uniform agar height of 4 mm was
placed in an incubator at 37° C for 24 h and was later examined for the
occurrence of the zone of inhibition. The appearance of clear zones
M.R. Louis et al. Journal of Environmental Chemical Engineering 6 (2018) 169–181

Fig. 1. Surface characteristic of DRP a) SEM image b) TEM image and c) EDX data.

emanating from the plates was monitored and the antimicrobial activity
was inspected by measuring the diameter of the zone of inhibition.

3. Results and discussion

3.1. Characterization results

The surface morphology of DRP surface was obtained from the

Electron microscopic images (SEM and TEM-EDX) given in Fig. 1. The
spongy nature with porous structure of the adsorbent surface is in-
dicated by SEM and TEM images and such structural characteristic may
benefit the uptake of the dyes. SEM reveals that the cavities are nearly
of the same sizes. EDX data shows that the surface of the adsorbent to
be composed of mainly C (88.03 wt%), O (8.92 wt%), P (3.04 wt%) and
traces of other heteroatoms like Si and K. The elemental composition as
obtained from CHN analysis was 65% carbon, 1.7% nitrogen and ∼
1.8% hydrogen confirming the carbonaceous nature of the derived ac-
tivated carbon, DRP. Fig. 2. FTIR Spectra of DRP before adsorption and dye loaded DRP.

The FTIR spectrum of DRP (Fig. 2) showed a large number of

functional groups which can be understood from the peaks at several
specific values. The broad peak at 3359 cm−1 stands for the hydrogen
bonded hydroxyl groups and also a small peak at 1373 cm−1 corre-
sponding to the OeH angular deformation while the peak at 1732 cm−1
shows the presence of carbonyl group on DRP surface. Both these
groups suggest the presence of acidic groups at the surface of DRP. The
carbonyl groups also can be seen from the peaks at 1840 cm−1 which
correspond to the eC]O axial deformation, at 1333 cm−1 which in-
dicate CeO axial deformation [16]. Peaks at 1257 cm−1 stands for the
CeOeC asymmetrical deformation of the ethers or axial/angular de-
formation of CeC(]O)eC in ketones. The presence of ethers is further

172
M.R. Louis et al.
supported by the peak at 1040 cm−1 which corresponds to the angular
deformation of ethers. Also, DRP shows presence of aromatic rings
which can be observed from small peaks near 1515 cm−1 region which
indicates aromatic vibrations while the other peak at 1595 cm−1 may
be ascribed to the C]O stretching vibrations of aromatic rings caused
by lignin like material. Another sharp peak at 1247.57 cm−1 may be
attributed to the C]O stretch of the acetyl group of lignin [15]. The
peaks in the region between 850 and 440 cm−1 represents the vibra-
tions due to alkenes, aromatic nature and the out of plane angular
deformation in benzene. Also the surface of DRP also shows alkanes
(peak at 2922 and 2845 cm−1) corresponding to the CeH stretch of
methyl and methylene groups. The lignocellulosic nature of the DRP
can be well understood by the presence of aromatic moieties along with
carbonyl, hydroxyl, and ethers.
The adsorption of RB-4 and RR-120 is well displayed by the changes
in the intensities of some bands post adsorption in DRP/RR-120 and
DRP/RB-4 surfaces. In the case of DRP/RB-4, the intensity of the bands
has increased with an additional peak at 1714 cm−1 which corresponds
to the carbonyl groups.
Additional peaks on DRP/RB-4 at 1741 and 1254 cm−1 due to C]O
group of esters and shifting of the CeO peak of the acetyl group of
lignin at 1247 to 1254 cm−1 is also observed. The adsorption of RR-120
at the surface of DRP leads to the disappearance of several peaks in-
dicating the interaction between the dye molecule and the adsorbent
surface. Hence it is possible to say that the DRP surface provides various
active sites for the binding of these dye molecules and aids in the re-
moval.
The X-Ray diffraction crystallography studies of DRP (Fig. 3) re-
vealed its carbonaceous composition. This was confirmed by the two
prominent peaks at 2θ values at around 25.12° and 43.15° [24]. The
peak at 25.12° may be due to the amine, hydroxyl, aldehydic and ke-
tonic groups of the hemicellulosic moieties, while the peak at 43.15°
represents the lignin constituent[25].The absence of sharp peaks in-
dicates the amorphous nature of DRP.
The Nitrogen adsorption-desorption isotherm as depicted in Fig. 4
shows the characteristics Type IV hysteresis loop which indicates that
the surface of the DRP contains a large number of mesoporous structure
and a very few micropores. It also indicates the uniform distribution of
the pores on the surface of the adsorbent. The BET surface area of the
adsorbent was found to be quite high, 1577 m2/g (Table 2), which is a
large value, indicating the DRP as a good bio-adsorbent. While the BJH
plot showed homogeneity in the sizes of the pores which was found to
be in the range of 6–9 nm of average diameter.
The surface charge of the adsorbent plays an important role in the
adsorption process. The charge present on the surface of the adsorbent
Fig. 3. X-ray diffraction pattern of DRP.
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Journal of Environmental Chemical Engineering 6 (2018) 169–181
will decide the attractive or repulsive interaction between the ad-
sorbent and the adsorbate. pHpzc indicates the pH where the surface of
the adsorbent will have net zero charge. When the pH of the solution
remains lower than the pHPZC of the adsorbent, the adsorbent surface
remains positively charged which is beneficial in the removal of anionic
dyes whereas for cationic dyes the negatively charged surfaces are
advantageous.
The pH of the solutions before and after adsorption was measured
using Systronics pH-meter which was calibrated using standard buffers
before use. The pH of zero charge for DRP was found to be 2.07 as
indicated in Fig. 5. This result may also be co-related to the work done
by Vargas et al. [16] where the NaOH activated carbon also had pHPZC
at 2.01. It indicates that the surface of the activated carbon form Delonix
regia has a large number of acidic groups which may be exposed by the
activation process. So, it may be understood that at lower pH (< 2.07)
DRP attains a net positive charge and at higher pH (> 2.07) DRP is
present in the anionic form while at pH = 2.07 DRP is present in an
amphoteric form with net zero charge. The plot of ΔpH vs pH has been
shown in Fig. 5
Fig. 6 represents the thermogram of the powdered raw material
(DR) and the activated carbon (DRP) obtained from phosphoric acid
treated DR. The thermogravimetric curve of the raw material (DR) and
the prepared carbon (DRP) indicates that the carbonization of DRP was
successful at 450° C without significant weight loss. The raw material,
DR tends to be less stable at higher temperature. From the thermogram,
it is also evident that at ∼350° C, the biomaterial DR shows maximum
weight loss of 65%, whereas DRP exhibits thermal stability and inert
nature. The initial reduction in weight up to 10% in both the adsorbents
can be attributed to the loss of moisture. The drastic change in the mass
of DR in the temperature range of 260−350° C, can be attributed to
removal of volatile components or likely loss of biomolecules inherently
present in the biomass. Thus, the carbonization temperature of 450° C
appears to be most appropriate where nearly 30% of the initial material
(DR) was present. Additionally, DRP shows a gradual loss in mass in the
temperature range of 500−800° C. So, the thermogram indicates op-
timum carbonization temperature of phosphoric acid treated DRP at
450° C. These observations are in agreement with thermograms of lig-
nocellulosic material[16]
The effect of carbonization temperature was investigated by pre-
paring three different carbons at 350, 450, and 650 °C. It was observed
that the surface area for both low temperature (350 °C) and high tem-
perature (650 °C) was substantially lower than that at 450 °C which also
confirms the earlier discussion pertaining to the selection of carboni-
zation temperature. It is known that the carbonization temperature and
time plays an important role in tuning the structure and determining
application of activated carbons. Other factors like the rate of heating,
atmosphere and nature of the starting material greatly influence the
final product (activated carbon). Higher temperatures of carbonization
are known to yield a highly porous surface on the adsorbent. But this
may not be true in all the cases where higher temperatures have also
resulted in the loss of adsorbent structure due to enlargement, merging
of pores and reduction in surface area[24]. Similar observation during
thermal treatment from 700 to 900 °C in modification of commercial
activated carbon was reported due to increased gasification or thermal
shrinkage of material [26]. Moreover, thermally treated (higher tem-
perature) activated carbons, have lesser oxygen functional groups.
Pereira et al. [26], also observed that heat treatment of carbon samples
above 900 °C also lead to loss of almost all carbonyl functional groups.
3.2. Adsorption equilibrium study
3.2.1. Single dye system
The adsorption data were correlated by applying the linearized form
of Langmuir [27], Freundlich [28] and Tempkin [29] isotherm to un-
derstand the nature of adsorption involved in the removal of RB-4 and
RR-120. The linear equations of all the isotherms are given in Table 3
M.R. Louis et al. Journal of Environmental Chemical Engineering 6 (2018) 169–181

Fig. 4. Specific surface area analysis a) Nitrogen adsorption-deso-

rption isotherm and, b) Pore size distribution using BJH method.

Table 2
Textural and structural properties of DRP.

Surface area Average pore Pore volume Micropore volume

(m2·g−1) diameter (nm) (cm3·g−1) (cm3·g−1)

1577 3.75 1.482 0.017

Fig. 6. TG curve of powdered biomass, DR and activated carbon, DRP.

Table 3
Adsorption constants for removal of RB-4 and RR- 120.

Adsorption isotherm Equation Dye system Isotherm constants

number

Langmuir qmax KL R2
Fig. 5. pHPZC determination of DRP by pH drift method. (mg g−1) (L mg−1)
(4) RB-4 40.32 0.03 0.83
RR-120 5.26 0.27 0.91
Ce 1 Ce
(Eqs. 4,5 and 6) along with all the observed values of the various ad- = +
qe qmax KL qmax
sorption constants. Freundlich n KF (mg g−1 R2
Langmuir adsorption isotherm (Eq. (4)) assumes monolayer ad- (L mg)1/n
sorption on homogenous adsorbent surfaces with finite adsorption sites. (5) RB-4 1.27 1.39 0.94
Here qmax is the maximum monolayer adsorption capacity of the ad- RR-120 4.37 1.96 0.82
1
sorbent for a particular adsorbate whereas KL (L−1·mg) is the Langmuir ln(qe ) = ln KF +
n
ln Ce

constant whose value depends upon the feasibility of the adsorption by Temkin bT AT(L g−1) R2
providing information about the affinity of the binding sites for the (6) RB-4 339.19 0.23 0.95
RR-120 3288.70 10.96 0.70
adsorbates. These constants may be determined from the plot of Ce/qe
RT ⎞ RT ⎞
versus Ce. The separation factor RL, obtained with the Langmuir con- qe = ⎛
⎜ ⎟ ln AT + ⎛ ⎜ ln Ce⎟

⎝ bT ⎠ ⎝ bT ⎠
stant is used to investigate whether the adsorption process is favourable

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M.R. Louis et al. Journal of Environmental Chemical Engineering 6 (2018) 169–181

or not favourable and is given by Eq. (7). dye at the DRP surface. The linearization coefficient value, (R2 of 0.91)
in the case of RR-120 and the R2 value of 0.95 in the case of RB-4,
1
RL = showed strong positive evidence that the adsorption process in RB-4 is
(1+K L.C0) (7) explained by Tempkin model and Langmuir isotherm in the case of RR-
120. The maximum monolayer adsorption capacity of DRP for RR-120
when 0 < RL < 1, the adsorption process is considered to be favour-
was found to be 5.26 mg·g−1 from Langmuir adsorption isotherm,
able, while the values of RL = 0 or > 1 indicates irreversible or un-
which is nearly similar to the experimental adsorption qe of
favourable process respectively. The values of RL for RB-4 and RR-120
6.36 mg·g−1. It was observed that DRP has more affinity for RB-4 than
in the present study are 0.290 and 0.053 and hence indicate favourable
RR-120. This may be due to the lower molecular weight of RB-4 in
adsorption under the given experimental conditions.
comparison to RR-120. These interactions may be due to the large
Freundlich isotherm (Eq. (5)) is another widely applied adsorption
molecular size of RR-120 than RB-4 which may have excluded the RR-
isotherm. This model assumes that the surface of adsorbent has binding
120 dye from the pores of the DRP while RB-4 being smaller in size,
sites with different energies and the adsorbate preferentially occupies
could accommodate the pores of the adsorbent. DRP has a high value of
the sites with higher binding energy. The parameters involved in the
surface area and pore volume which is expected to provide increased
preferential binding of the adsorbate are explained by the constant
number of sites for the adsorption of dyes. The surface area and pore
terms ‘KF’, which is the Freundlich constant and ‘n’ is the heterogeneity
volume are significantly higher than many of the biomass derived ac-
factor. These constants relate to the adsorption capacity and the ad-
tivated carbons. Characterization of specific surface area (Fig. 4) in-
sorption intensity of the adsorbent respectively. Again, 1/n values in-
dicated largely mesoporous structure. The uniform pore size distribu-
dicate the type of isotherm to be irreversible (1/n = 0), favorable
tion around 6–9 nm may have also contributed in increasing the
(0 < 1/n < 1) which also indicates a normal Langmuir isotherm,
adsorption capacity. The higher adsorption of RB-4 in comparison to
unfavorable (1/n > 1) [30]. The value of 1/n lies between 0 and 1 in
RR-120 can be attributed to size based exclusion of RR-120.
the present study with 0.79 for RB-4 and 0.24 for RR-120, confirming
The adsorption equilibrium plots and their validation with the three
favourable adsorption.
different isotherms are given in Fig. 7.
Tempkin model (Eq. 6) was also used to understand the interaction
The validity of the three isotherms were determined by calculating
of the adsorbate at the adsorbent surface. This model is an extension of
the qe (cal) using the respective equations and the experimental ad-
the Langmuir model and explains the linear decrease in the heat of
sorption isotherm constants mentioned in Table 3. The fittings of the
adsorption with increasing binding at the adsorbent surface. The linear
theoretical models to the experimental values are shown in Fig. 7. It
equation is given in Table 3, B is a constant in (J·mol−1), whose value is
was observed that the Langmuir qmax (cal) values for RB-4 and RR-120
calculated as, B = RT bT , where R is the molar gas constant, T is the
could be best fitted with the experimental qe values followed by
temperature in Kelvin, bT is a constant associated with the heat of ad-
Tempkin and then Freundlich equilibrium adsorption capacity. The
sorption and AT (L·g−1) is the equilibrium binding constant. The heat of
experimental qmax for RB-4 and RR-120 were 23.5 and 6.36 mg·g−1
adsorption constant, bT are 339 and 3288 for Reactive blue and Re-
respectively which is mostly comparable with the theoretical qe for
active red respectively. These high values are indicative of chemisorp-
Langmuir (26.43 and 4.95 mg·g−1), Tempkin (35.92 and 4.96 mg g−1)
tions mode of adsoprtion. The values of bT yields information about the
and vary hugely from Freundlich isotherm.
process of adsorption. The value of bT may also be used to understand
the thermodynamics of the process. The positive values indicate the
exothermic nature while lower values suggest ionic interaction of the 3.2.2. Dye adsorption in binary system
adsorbate and the adsorbent [31]. In the present study the values of bT The adsorption efficiency of DRP in the multicomponent binary
were large and positive for both the dyes suggesting the exothermic system was investigated using five different ratios of 50 mg·L−1 initial
nature of the adsorptive removal of these dyes. dye solutions (10:90, 30:70, 50:50, 70:30 and 90:10) and designated
Adsorption isotherm curves for RB-4 and RR-120 is given in Fig. 7 hereafter as 1,2,3,4 and 5 respectively for better discussion. The trend
and exhibits Type 1 nature which indicates monolayer deposition of the in variation of qe and removal percentage of both the dyes in the binary

Fig. 7. Single adsorption equilibrium plots and validation for adsorption RB-4 and RR-120. (C0: 50 mg L−1, Agitation speed: 100 rpm).

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M.R. Louis et al. Journal of Environmental Chemical Engineering 6 (2018) 169–181

Fig. 8. Dye removals in binary dye mixture at various mixing ratios. C0: 50 mg L−1, a) plot of adsorbent capacity against dosage, and b) percent dye removal of RB-4 and RR-120 in dye
mixture; filled legend symbolising RB-4 and corresponding empty legend symbolising RR-120 for the dye mixture.

system with increasing DRP dosage (g·L−1) is shown in Fig. 8. It is 90:10 for RB-4 and 10:90 for RR-120.
observed that qe values of RB-4 and RR-120 vary widely in lower ad- The variation in the selectivity factor with the change in adsorbent
sorbent dosage but the difference in the qe values of RB-4 and RR-120 dosage was also determined which suggested that at lower DRP dosage
decreased at higher adsorbent dosage. This might be due to the fact that the selectivity had a higher value for all the ratio mixture which tend to
the numbers of active sites were surplus and equally available for the decrease further with the increasing DRP dosage. This might be due to
two dyes in the mixture at a higher adsorbent dosage and the numbers the fact that at a lower dosage, the adsorption sites were limited so that
of adsorption sites were limited at the lower adsorbent dose. It was also the dye molecules had to compete for the adsorption sites. But later
evident from the graph that the dye in greater proportion did affect the with the increase in the amount of DRP, all the sites were equally
adsorption of the other dye as it may be seen in cases where 5 g·L−1 of present for both the dyes. It was also observed that the qe of the dye
DRP was used. This effect was prominent when the adsorbent dosage depends upon ratio of the dye in the solution. Dye with higher fraction
had a lower value where the qe values of RR-120 were higher in solu- in the binary solutions had a higher qe value. The β value had a highest
tions 1 and 2 (4.65 and 6.69 mg·g−1 respectively) than the qe values of value in case of solution mixture 1 and 5 for RR-120 and RB-4 re-
RB-4. In the case of solutions 3, 4 and 5 where the proportion of RB-4 spectively (Table 4). The dye removal in the binary mixture is illu-
was higher, the qe values for RR-120 decreased (2.57, ≈0 and strated in Fig. 8.
0.93 mg·g−1 respectively) and those of RB-4 had a higher value. The qe The maximum and the minimum values of the selectivity factor
values for RB-4 in solution 1 to 5 were 0.38, 1.95, 4.00, 6.02 and 7.38 in determined for the present work are listed in Table 4. The larger values
mg.g−1 respectively which clearly indicates the influence of dye pro- of β suggest better selectivity and lower values closer to or below 1,
portion in the binary mixtures. The reason may be due to which par- indicates the absence of selectivity [22]. From Table 4, it can be ob-
ticular dye when present in larger proportion than the other dye, the served that highest selectivity for RR-120 (90.30) was achieved at
chances of the interaction of the dye with the adsorbent becomes re- higher DRP dosage in solution 1 where the RR-120 composition was the
latively higher. But at higher adsorbent dosage due to availability of largest, while for RB-4 the value of selectivity was maximum (5.97) at a
vacant sites increases and the difference in the adsorption capacity higher dosage of adsorbent in solution 5.
values of both the dyes in a binary mixture had diminished. A similar The minimum selectivity factor for RB-4 (0.003) was found to be in
pattern was also seen in case of percent removal at lower DRP dosage. solution 3 at an adsorbent dosage of 35 g L−1 and for RR-120 (0.33) in
But at higher DRP concentration, RR-120 was found to have higher solution 1 at DRP dosage of 5 g L−1. From Table 4, it can be seen that
removal percentage in almost all binary mixtures, 1 to 5. The results of equal proportions of the two dye solution, at lower adsorbent dosage
the experiment revealed that the adsorption value of RR-120 (qRR) was DRP had a higher affinity for RB-4 while RR-120 at a higher dosage.
always higher that of RB-4 (qRB) in all the case of binary solutions. This This reveals the competitive behaviour of the two dyes at the surface of
is in contrast to single adsorption system, where RB-4 had a higher the DRP. The results obtained also support the pattern of qe discussed
value at all dosage. The dye removal capacity of DRP in the binary
system also decreased in comparison to that obtained in the single dye
Table 4
adsorption studies. The decrease was more prominent in the case of RB-
Selectivity Factor for the Reactive dyes on DRP for minimum and maximum dosage and
4 (97 to 25%) whereas RR-120 (98% to 45%) showed a comparatively selected compositions.
lower decrease.
Further, to understand and quantify the interaction of DRP with Solution DRP Dosage βRR/RB
these dyes in the binary system, the selectivity factor or competitive (g·L−1)
βRB/RR
factor, β may be quantified [32] using Eq. (8).
1 5 0.33 3.07
q e(1) /q e(2) 35 0.01 90.30
β1/2 =
C0(1) /C0(2) (8) 3 5 3.33 0.30
35 0.003 350.54
where the subscripts ‘1′ and ‘2′ indicate the two different dyes, RB-4
5 5 3.02 0.33
and RR-120 respectively and other symbols have their usual meaning as 35 5.97 0.17
mentioned earlier. The selectivity was prominent at the mixing ratio of

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M.R. Louis et al.
earlier. This molecular selectivity of DRP towards RR-120 at higher
dosage can be understood from the higher β values (> 1). This may be
correlated to the higher RR-120 removal of DRP as seen in Fig. 8b. From
Table 4, it can be clearly seen that DRP had selectivity towards a par-
ticular dye, which depends on the adsorbent dosage and the composi-
tion of the binary solution. The competitive nature led to the decrease
in qe and percent removal of both dyes when compared to the values
obtained in the single system. The adsorption capacity of DRP towards
RB-4 decreased to ̴ 7 mg·g−1 in the binary system from qmax of
40.32 mg·g−1 while the qe values of RR-120 (6.68 mg·g−1) remained
nearly same to the that seen in single dye system(qmax = 5.26 mg·g−1).
Thus DRP showed greater selectivity towards RR-120 than RB-4 leading
to competition between the dyes molecules leading to decrease in ef-
ficiency of DRP in the removal of RB-4.
3.3. Kinetic studies
The kinetics of the adsorption of RB-4 and RR-120 was studied using
the data of progress of adsorption with time and the kinetic data was
analyzed by different models,viz., pseudo first order [33], pseudo-
second order [34], and Intraparticle diffusion [35], to understand the
rate controlling step. The linear forms of various rate equations along
with their constants are given in Table 5. The terms in these equations
have their general meanings with qe and qt as the equilibrium con-
centration and at time ‘t’ respectively. The rate constants for the first
order and second order are given by k1 (min−1) and k2 (g·mg−1·min−1)
respectively.
The investigation on the kinetics of removal of RB-4 and RR-120,
showed a faster removal of RB-4 compared to RR-120. The removal
efficiency rapidly increases in the initial stage from ∼93% to 97% for
RB-4 and from 78% to 98% for RR-120 in the time span of 10 mins to
300 mins. This fast kinetics indicates favourable practical application of
DRP for removal of anionic reactive dyes. The pseudo second order
model could describe the kinetics of removal of both RB-4 and RR-120
as observed from the high correlation coefficient value of 0.99 in both
the dye systems and the adsorption process may be favourable con-
trolled by chemisorptions process. The higher rate constants of
0.69 g mg−1. min−1 of RB-4 as compared to 0.17 of RR-120 also in-
dicates the faster removal kinetics of RB-4. However, it is evident that
both the dyes have fast adsorption rate on DRP surface.
The intraparticle diffusion model (Eq. (11)) was applied to under-
stand the contribution of liquid film diffusion, pore diffusion or ad-
sorption at the sites and the rate controlling step in the adsorption
process. In equation 11, kd is the intraparticle diffusion constant and ‘c’
is a parametric constant which defines the layer boundary effect or
thickness. The greater the value of c, the broader is the layer boundary.
The adsorption process usually consists of a) external surface adsorp-
tion, where the dye molecules diffuse through the solution bulk to the
surface of adsorbent, b) intra-particle diffusion and c) pore diffusion
followed by equilibrium stage[36,37]. If the plot of t0.5 versus qe yields
Table 5
Parameters of Kinetic models applied to Experimental data.
Dye system
Pseudo-first order Equation
log(q e-qt)=logq e-(
k1
)t (9) RB-4
2.3030
RR-120
Pseudo-second order
t
=
1
+
1
t (10) RB-4
qt k2qe2 qe
RR-120
Intra-particle diffusion
qt = k dt0.5+c (11) RB-4
RR- 120
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Journal of Environmental Chemical Engineering 6 (2018) 169–181
a single straight line passing through the origin, then intraparticle
diffusion is the only rate limiting step, governing the pollutant uptake
onto the adsorbents surface[21]. But deflection from this condition
point towards the involvement of other steps. The deflection may in-
volve the presence of two or more different stages in the adsorption
process. The plot of qt versus t0.5 in the present study is not a straight
line passing through the origin but consisted of two different steps as
shown in Fig. 9 indicating that more than one kinetic process is in-
volved in the adsorption of the reactive dyes and consisted of two
stages.
The first stage is expressed by the sharper rise in the graph, which
indicates instantaneous adsorptive removal of dyes at the surface of
DRP while the second region, which does not pass through the origin
denotes the time where the process of intraparticle diffusion becomes
the rate controlling process leading to gradual adsorption of the pol-
lutants. About 5 min for RB-4 and ∼6 min for RR-120 is required to
complete the first stage. The positive value of ‘c’ also reveals the pre-
sence of boundary layer in both the cases.
3.4. Dependence on initial concentrations
The dependence of the initial concentration of reactive dyes on the
adsorption capacity of DRP was investigated using different con-
centrations of 10, 50, 100 and 200 mg L−1 under natural pH. The study
of this variable can determine the concentration range that the devel-
oped adsorbent, DRP can actually remove. DRP can remove RB-4 and
RR-120 more successfully at higher concentrations i.e. 99% removal at
200 ppm and 80% removal at 10 ppm initial dye concentrations,
whereas in the case of RR-120, it exhibited an increase in removal ef-
ficiency from 90% to 99% with the increase in initial dye concentra-
tions (Fig. 10). It can be observed from Table 6 that at a higher ad-
sorbent dose above 0.3 g, a higher % removal was achieved in all the
dye concentrations of RR-120 whereas a higher removal was achieved
even at a lower dose for RB-4. Thus DRP can successfully remove even
higher dye concentrations.
3.5. Salt and surfactant effect
The presence of salts, surfactants or ions could affect hydrophobic
and electrostatic interactions between the dye molecules and the DRP
surface. The dyeing process uses salty conditions and various surfac-
tants and herein the present study investigates the adsorption beha-
viour of DRP in presence of different salts and surfactants in varying
concentrations. NaCl and Na2SO4 in the concentration range of 0.1 to
0.5 M. Similarly, the effect of both anionic surfactant, SDS and cationic
surfactant, CTAB was studied in the concentration ranges of 0.1 to
1.0 mM using an optimized dose of 25 g·L−1. The study indicated that
the performance of DRP was not hindered by the presence of NaCl.
Nearly 99% removal was achieved in the case of both the dyes (Fig. 11).
However, the presence of sodium sulfate lowered the percentage
Kinetics constants
k1 (min-1) R2
2.64 0.29
−3
3.06 × 10 0.44
k2 (g·mg-1·min-1) R2
0.69 0.99
0.17 0.99
c(mg·g-1) Kd(mg·g-1 ·min0.5)
1.87 0.01
0.03 0.03
M.R. Louis et al. Journal of Environmental Chemical Engineering 6 (2018) 169–181

Fig. 9. Intra-particle diffusion plot for the progress of

adsorption with time. Initial dye concentration:
50 mg L−1, Dosage: 25 g .L−1.

CTAB.

3.6. pH effect

The effect of initial solution pH is an important parameter in ad-

sorption process as it affects the surface charge of the adsorbent, the
degree of ionization of the dyes and the activity of the functional groups
present on the adsorbent surface. Both the reactive dyes exhibited fa-
vourable range in acidic condition (Fig. 12) with maximum adsorption
at pH 5.3 for RB-4 and nearly neutral pH of 7 for RR-120. There is a
rapid uptake of the reactive dyes upto pH 5.3 and pH 7 for RB-4 and RR-
120 respectively and thereafter it slowly diminishes. At pH above
pHPZC, the surface of the adsorbent remains largely negative. However,
since the uptake of the dyes, increase above pHPZC of 2.07, it may in-
dicate the lesser role of electrostatic attraction between the adsorbent
surface and the dye molecules. Both the dyes showed favourable ad-
sorption in the pH range between 5 to 9 and may be attributed mainly
due to hydrophobic effect and π-π effect[38]. At acidic pH, due to the
protonation of the surface hydroxyl and carboxyl groups of DRP, pos-
Fig. 10. Adsorption performances of DRP under different initial dye concentrations. sible H-bond interactions with the hydroxyl groups of RB-4 and RR-120
are ruled out. However, reactive dyes undergo hydrolysis of sulfonate
Table 6 groups and under the acidic conditions, the protonated functional
Effect of initial dye concentration. groups on DRP, may attract the dye molecule which may explain the
higher uptake in acidic regions. At very high pH above 10, there is a
Dose (g) % Removal decrease in adsorption which may be due to increasing electrostatic
10 ppm 20 ppm 50 ppm 200 ppm
repulsion between the dissociated dye molecules and the negatively
charged surface of DRP.
RR-120 RB-4 RR-120 RB-4 RR-120 RB-4 RR-120 RB-4

0.04 70.4 85.5 14.4 95.0 24.5 72.9 12.7 76.2

3.7. Comparison with commercial activated carbons
0.06 80.1 85.5 18.3 93.7 37.6 99.0 59.8 99.5
0.08 85.7 71.4 27.0 95.1 48.3 98.6 63.0 99.5 Experimental studies under similar operating conditions for dye
0.10 87.4 74.6 35.8 95.5 61.1 99.2 66.3 99.3 removal using two different commercial activated carbons were in-
0.30 90.8 82.3 88.8 97.1 97.5 97.3 91.5 99.4
vestigated and the results for maximum adsorption capacity along with
0.50 92.0 82.6 93.2 99.1 98.5 99.5 99.4 99.3
those reported from literature are given in Table 7.
The adsorbent developed in this work was found to have good ad-
removal value of both the dyes. It was observed that with increasing sorption capacity similar to that reported for many commercial biomass
sodium sulfate concentration, the efficiency of DRP was reduced from derived adsorbents. The color removal efficiency was high and se-
about 97 to 86% for both the dyes. This may be due to the competition paration of the adsorbents was found to be easy. Thus, DRP may prove
between the sulphonyl groups present in the reactive dyes and the su- to be an excellent adsorbent with high dye removal efficiency in ad-
phate ions or due to excessive positive sodium ions generated which dition to its low cost.
might have interacted with the negative surface of the DRP. Also, the
efficiency of DRP in removing RB-4 in presence of both the anionic and 3.8. Antimicrobial activity
cationic surfactant was also not much affected but RR-120 removal
decreased in presence of SDS as well as CTAB. The removal efficiency The highly porous structure of activated carbons promotes the for-
however increased later to some extent with increasing concentration of mation of biofilm, which may affect the water treatment process. Hence

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M.R. Louis et al. Journal of Environmental Chemical Engineering 6 (2018) 169–181

Fig. 11. Removal of reactive dyes in presence of surfactant and salt, a) RB-4 in surfactant medium, b) RR-120 in surfactant medium, c) RB-4 in salt medium, and d) RR-120 in salt
medium. Initial dye concentration = 50 mg·L−1, Adsorbent dosage = 25 g·L−1.

Table 7
Comparison of adsorption capacity with commercial activated carbons.

Activated Carbon Dye Adsorption capacity (mg·g−1) Reference

Norit R1 RR-120 31 [39]

Maxsorb RR-120 35 [39]
WV1050 RR-120 33 [39]
DRP RB-4 23.5 Present study
DRP RR-120 6.36 Present study
AC (Merck) RB-4 22.67 Present study
AC (Merck) RR-120 21.03 Present study
AC (SRL) RB-4 22.71 Present study
AC (SRL) RR-120 22.52 Present study

[30] as it possesses several phytoconstituents like saponins, alkaloids,

Fig. 12. pH effect on adsorption of Reactive dyes; Initial dye concentration: 50 mg·L−1,
Adsorbent dosage = 25 g·L−1.
activated carbon adsorbent with antimicrobial property may help in
removal of both pollutants as well as the microbes for safe water reuse.
DRP was found to have an appreciable antimicrobial activity towards
Gram positive bacteria, B.subtilis than E.coli as seen from Fig. 13 from
the larger clear zone of microbial inhibition (18 mm in Fig. 13 a). This
may be attributed to some extent to the highly negatively charged
surface (pH PZC ∼ 2.07) of the DRP. E.coli may be resistant to the acidic
condition and hence were found to be tolerant to the DRP. There is a
high possibility that B.subtilis may be targeted by acidic groups or
bioactive substances present on DRP surface. The virgin Delonix regia
has been reported to possess many beneficial therapeutic properties like
antifungal, antibacterial, antioxidant and anticarcinogenic potential
flavonoids, tannins, steroids, galactomannon, terpenoids etc. These
constituents may be also responsible for the associated antimicrobial
properties of DRP. The developed multifunctional material has rela-
tively larger zone of inhibition in comparison to other nanocomposites
synthesized using heavy metals and commercial activated carbons
where the reported zone of inhibition are 4 mm(Zn-Ac), 8 mm(Pb-AC)
and 12 mm(Ag-Ac) against Gram positive bacteria[40]. The present
approach also provides a greener protocol for development of the
multifunctional material as it does not make use of heavy metals for
deactivation of microbes.
The antimicrobial effect in B.subtilis may be due disruption of the
bacterial cell permeability or other physico-chemical functions of the
cell including respiration and cellular inactivation or cell death. The
observation of DRP being more active against the B. subtilis species and
tolerant towards E.coli cells is also due to the difference in the com-
position of the cell envelope of the Gram positive and Gram negative
bacterial cells. The variation of diameter of the clear zone around DRP
indicates an apparent difference in microbial activity, suggesting that

179
M.R. Louis et al.
DRP was lesser effective or no activity towards Gram negative species
(Fig. 13b) which may be due to the tough cell membrane and nature of
physiological and biochemical characteristics of bacterial cells of E.coli
interacting with DRP.
The difficulty of inactivating Gram negative bacteria may be due to
the tightly packed lipopolysaccharide membrane which is mainly re-
sponsible for higher resistance of Gram negative bacteria[41,42]. The
presence of outer membrane, consisting of phospholipids and lipopo-
lysacharides acts as a stabilizing/protective layer in Gram negative
bacteria, thereby making it difficult to be easily disintegrated[43]. This
outer membrane is however absent in Gram positive bacteria, B.subtillis
which makes it susceptible to be targeted. In order to compare whether
such bactericidal activities are shown by commercial activated carbon,
the antimicrobial activity was compared with that of a commercial AC.
However, commercial AC showed the absence of any such activity
against both B.subtilis and E.coli as seen in Fig. 13b and d.
4. Conclusions
The results revealed the suitability of activated carbon derived from
Delonix regia biomaterial (DRP) for effective removal of refractory dyes
like RB-4 and RR-120 and its potential for inactivating microorganisms/
pathogens present in wastewater streams, particularly Gram positive
bacteria like B.subtilis. The specific surface area is relatively high
(1577 m2·g−1) and the adsorbent may also be useful for removing other
organic pollutants as well. The adsorbent demonstrated superior per-
formance for the adsorption of Reactive blue with an adsorption ca-
pacity of ∼ 24 mg g−1,and 5 mg·g−1 for Reactive red along with good
decolorizing property and fast removal. The multicomponent binary
adsorption proved the competition for binding sites between RB-4 and
RR-120 which depended on the DRP dosage and the composition of the
multicomponent system. The kinetics was found to obey pseudo second
order kinetics with more than one kinetic process affecting the kinetics
of removal. Thus DRP was found to be effective multifunctional mate-
rial, being capable of not only removing dyes/pollutants but also
showing activity against microbes, Gram positive bacteria in particular.
The present study uses a greener and sustainable methodology for
preparation of the multifunctional material without the fabrication of
metals. DRP may prove to be an efficient adsorbent for treating con-
taminated water bodies.
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Journal of Environmental Chemical Engineering 6 (2018) 169–181
Fig. 13. Antimicrobial activity of DRP a) Clear zone of in-
hibition against B.subtilis by DRP b) No activity against
B.subtilis by commercial AC, c) and d) Negligible or no in-
hibition against E.coli by both DRP and commercial AC. Here
1 indicates sterile water reference and 2 refers to the sample
under examination.
Notes
The authors would like to declare no conflict of interest. This re-
search did not receive any specific grant from funding agencies in the
public, commercial, or not-for-profit sectors.
Acknowledgment
The authors would like to acknowledge Sophisticated Analytical
Instrumentation Facility (SAIF) centre, Panjab University for XRD
characterization and SAIF, IIT Bombay for the CHN and TG analysis.
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