Materials Chemistry and Physics 251 (2020) 123040

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Materials Chemistry and Physics

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

Efficient removal of Congo red from aqueous solutions using phytogenic

aluminum sulfate nano coagulant
Julia Garvasis , Anupama R. Prasad , K.O. Shamsheera , P.K. Jaseela , Abraham Joseph *
Department of Chemistry, University of Calicut, Calicut University P O, Kerala, India

H I G H L I G H T S

� ASNPs of ~13 nm was synthesized using aq. leaf extract of Hemigraphis colorata.
� Most probable mechanism is suggested for the formation of ASNPs.
� ASNPs is an efficient nano coagulant for Congo red dye from aqueous solutions.
� 99.5% efficiency with140 mgL 1 for 100 mgL 1dye solution of pH7 at RT.
� Efficiency of ASNPs remains unaltered with pH, temperature, ionic interferences.

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

Keywords: Aluminum sulfate nanoparticles (ASNPs) were synthesized using Hemigraphis colorata leaf extract with minimal
Hemigraphis colorata use of corrosive solvents. The material was characterized by Fourier Transform-infrared spectroscopy (FT-IR), X-
ASNPs ray diffraction studies (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy
Nano coagulant
(FESEM), energy-dispersive X-ray spectroscopy (EDAX), high resolution transmission electron microscopy (HR-
Congo red
TEM), and zeta potential analysis. We were able to suggest a probable mechanism for the formation of ASNPs.
Coagulation efficiency of ASNPs for Congo red dye solution was explored under various constraints like coag­
ulant dosage, initial concentration, pH, temperature, presence of inorganic ions and settling time. 140 mgL 1 of
ASNPs removed 99.5% of Congo red dye (100 mgL 1) from the solution. The variation in pH of the solution in
the range 3–9 and the increase in temperature from 30 � C to 70 � C did not affect the efficiency of the nano­
coagulant. It was observed that the generated sludge settled within 30 min and SVI was found to be 31 mLg 1.
The nano coagulant can be reused up to five cycles of coagulation. Low dosage, consistent efficiency, easy sludge
management, reusability along with cost-effectiveness makes phytogenic ASNPs a potential coagulant for
removal of Congo red.

1. Introduction human and aquatic life [2,3]. Also, under specific conditions, azo dyes
can be decomposed to produce more than 20 kinds of carcinogenic ar­
With the alarming rate of shrinking resources, water pollution has omatic amines [4,5]. Congo red, the selected dye for the present study is
now become a global concern. A plethora of industries such as the paper, capable to release benzidine which on long term exposure may increase
leather, plastics, cosmetics, food, printing, pharmaceutical and textile the risk of cancer as per reported epidemiological studies [6,7]. Thus,
industries both consume and contaminate gallons of water each day. The the removal of dyes from industrial wastewater before discharging into
effluents from these industries are saturated with toxic components such the hydrosphere is crucial for environmental safety.
as unfixed dyes, organic compounds, and heavy metals, which when left Literature suggests various treatment processes such as adsorption,
untreated pose severe toxicological and aesthetic threats to the coagulation-flocculation, reverse osmosis, photo-catalysis, and ion-
ecosystem [1]. A majority of synthetic dyes used in the textile industry exchange to remove dyes from wastewater [8–13]. Alumina based
contain azo functions often linked to an aromatic ring which makes nanocomposites have been widely used as a catalyst and for the water
them highly toxic, non-biodegradable, carcinogenic, and mutagenic for pollutant treatment [14,15]. The coagulation-flocculation process is

* Corresponding author.
E-mail address: [email protected] (A. Joseph).

https://doi.org/10.1016/j.matchemphys.2020.123040
Received 16 October 2019; Received in revised form 13 March 2020; Accepted 5 April 2020
Available online 21 April 2020
0254-0584/© 2020 Elsevier B.V. All rights reserved.
J. Garvasis et al. Materials Chemistry and Physics 251 (2020) 123040

usually preferred in dye removal due to its ease of operation, high effi­ studies.
ciency and comparatively low cost [16]. The process intends to desta­
bilize the dissolved material instantaneously (coagulation) using
2.3. Characterization
coagulants to form aggregates of small particles (flocculation) which can
be removed by separation processes like sedimentation upon settling
Assorted analytical techniques were performed on the synthesized
[17]. The commonly used chemical coagulants are aluminum sulfate
material for characterization. FTIR spectra were analyzed on a Jasco-
(alum), ferric chloride (FeCl3) and polyaluminum chloride (PACl) [18].
FT/IR- 4100 spectrophotometer. XRD patterns of the material were
The use of these coagulants is now revised due to the high dosage,
examined using a Rigaku diffractometer with Cu-Kα radiation. The zeta
voluminous sludge produced post flocculation, inconsistent perfor­
potential was inferred with a Horiba SZ-100 instrument (version 2.20).
mance with pH, and temperature. Intensive studies to find suitable re­
The morphological characteristics of the samples were examined using
placements are in trend no [19–23]. An optimal coagulant must be
FESEM; Zeiss and HRTEM, Jeol/JEM 2100. The and EDAX system con­
efficient at lower dosages with minimal sludge production and reus­
nected to the aforesaid FESEM instrument was used for elemental
ability [24–27].
analysis. Thermogravimetric studies were performed with a Perkin
There exists a wide arsenal of chemical and biologically assisted
Elmer STA 8000 analyzer.
routines for synthesis of nanomaterials with required morphology and
composition. Among these methods, green, facile and novel synthesis of
nanomaterials have become more attractive area of research in past few 2.4. Coagulation experiment
decades [28–33]. Plant extract solutions such as aloe vera, onion, neem,
tea and coffee extracts, are some of the preferred alternatives for A stock solution of 1000 mgL 1 was prepared in tap water and
chemical reagents in the synthesis of metal and metal oxide nano­ diluted accordingly. The optimum coagulant dosage was determined
particles [34–38]. Use of plant extracts as the reaction medium provides using a 100 mgL 1 dye solution at pH 7. Weighed coagulant was added
a sustainable and cost effective approach in the field of material syn­ to 25 ml of the dye solution at room temperature. The mixture was
thesis [39,40]. initially stirred at 190 rpm and then at 90 rpm for 15 min. After 30 min
In this study we synthesized aluminum sulfate nanoparticles using settling period about 4 ml supernatant solution was meticulously
Hemigraphis colorata leaf extract as the reaction medium. In best of our retrieved at regular intervals and centrifuged to remove any flocs. The
knowledge, this is the first report on aluminum sulfate nanoparticles and clear solution was then screened for residual dye concentration in a
nano coagulant. Also, the synthesis route executed is not yet reported Jasco-v-750 UV–Vis spectrophotometer, λm was set to 498 nm. The
elsewhere. The plant Hemigraphis colorata belongs to the family Acan­ coagulation efficiency of each retrieved dye solution was calculated
thaceae and is believed to possess appreciable wound healing capacity using the given equation.
[41]. The bio-inspired synthetic methods employing plant extracts are
ðC0 CÞ
one of the major recognized routines due to its simple, eco-friendly, % Coagulation Efficiency ¼ x 100 (1)
C0
economical and reliable aspects [42]. The plant extract contains
numerous phytochemicals that are considered to aid the formation of where C0 and C represent the initial and final concentration of the dye
nanoparticles. A probable mechanism for the formation of ASNPs is also solution, respectively. This procedure was followed in determination of
suggested. The synthesized ASNPs were screened for its coagulation coagulation efficiency of the nano coagulant in different conditions. A
properties towards congo red dye. Stemi 508 stereomicroscope attached with axiocam 105 color cam was
employed to attain the optical images of the flocs. The sludge volume
2. Experimental index (SVI) was calculated using the given equation
�
2.1. Materials �
SVI mL ​ g 1 ¼
Settled sludge volume mL L 1
� X 1000 (2)
Suspended solids concentration g L 1
Al2(SO4)3. (14-18 H2O) (98%) was procured from Merk and pure
Settled sludge volume was determined from 30-min settling experi­
Congo red, (C32H22N6Na2O6S2) dye was purchased from Qualigens Pvt.
ment using a graduated container.
Ltd., India. The chemicals were used without further purification. Fresh
Hemigraphis colarata leaves were collected from the agricultural area
2.4.1. Effect of dye concentration and coagulant dosage
near University of Calicut, Malapuram, Kerala.
The change in optimum nanocoagulant dosage with the change in
the dye concentration was verified using 50 mgL 1, 100 mgL 1, 150
2.2. Synthesis of ASNPs mgL 1 and 200 mgL 1 dye solutions. Different weighed fractions of the
coagulant were added to each of the dye solutions at room temperature.
The collected Hemigraphis colarata leaves were washed thoroughly The optimum dosage was determined from the sum of all weighed
and shadow dried. Then finely crushed and 10 g was weighed into 150 fractions required to completely coagulate the dye solution. The pH of
ml of distilled water, vigorously stirred at 80 � C for about 2 h (hot the dye solutions used was 7.
percolation method). The resulting mixture was filtered upon cooling to
obtain a clear dark brown aqueous leaf extract. 20 ml of 0.55 M AS 2.4.2. Effect of temperature and pH
(aluminum sulfate) solution was added dropwise to 25 ml of the leaf Variation of the coagulation efficiency with variables like tempera­
extract kept at room temperature (~28 � C) with constant stirring. The ture and pH were also monitored. Experiments were performed using
reaction mixture was stirred for 3 h and kept overnight for aging. The 100 mgL 1 dye solutions in a temperature ranging from 30 � C to 70 � C at
aged mixture was then dried at 150 � C and calcined at 600 � C for 2 h. pH 7 for studying the effect of temperature on coagulation efficiency.
The obtained matter was ground to a fine powder, repetitively washed Effect of pH on the efficacy of the nano coagulant was investigated on
with deionised water and ethanol to remove any ash content. The pu­ range of pH 3 to pH 9 at room temperature using 100 mgL 1 dye
rified sample was dried at 70 � C for characterization and coagulation solutions.

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J. Garvasis et al. Materials Chemistry and Physics 251 (2020) 123040

Fig. 1. X-ary diffraction patterns of AS precursor and synthesized ASNPs. Fig. 2. FTIR spectra of AS and synthesized ASNPs.

2.4.3. Effect of ionic interferences 3016 cm 1 are assigned to the –OH stretching vibrations and –OH
Industrial effluents contain numerous inorganic anions and cations bending vibrations appeared ~1685 cm 1. The sharp intense peak at
which may hinder the coagulation mechanism thus reducing the effi­ 1150 cm 1 and the peak around 978 cm 1 were attributed to SO24
ciency of the nano coagulant. To monitor the ionic interference and to stretching vibrations. The peak observed at around 689 cm 1was iden­
rule out if any, chosen cations and anions were introduced into the dye tified to be SO24 bending vibrations [47–49]. The spectra devoid of any
solution prior to coagulant addition. The efficacy of the nano coagulant other characteristic vibrations imply the removal of binders and the
in the presence of various ions was investigated at room temperature absence of residues from the plant extract.
and neutral pH.
3.2. Morphological and elemental analysis
2.4.4. Separation of nano coagulant and recyclability
The sludge was collected and dried in an air oven at 70 � C for 48 h to The FESEM images of bulk precursor and ASNPs recorded are shown
obtain a thin film of sludge. The film was then collected and ground to in Fig. 3A and Fig. 3B respectively. Morphological changes to the pre­
powder. The powdered sludge was then washed thoroughly with ethanol cursor associated with the Hemigraphis colorata leaf extract treatment
and water repeatedly to separate out the coagulant from the adhered dye were evident from the enhanced hierarchy of NPs. The surface of the
molecules. The white slurry of nano coagulant so obtained was dried at ASNPs was observed to comprise popcorn-like particles, of assorted
100 � C to regenerate ASNPs and weighed. The efficiency of the former sizes. To investigate further the morphology and size of the nano­
was investigated using fresh dye solution of 100 mgL 1. The recycla­ particles HR-TEM analysis was employed. HRTEM micrographs depicted
bility of the coagulant was monitored for multiple cycles following the a collection of relatively spherical particles of average particle size ~13
same procedure. The bulk precursor was also tested for any possible nm. The EDAX profile of ASNPs displaying the elemental composition of
coagulant activity. All the experiments were performed in triplicates. the prepared sample is depicted in Fig. 4. The spectra encounter the
characteristic elemental peak line of Al (Kα1, Kβ1), O (Kα1) and sulfur
3. Results and discussions (Kα, Kβ1, Lα) in 12.46%, 77.89%, and 9.65% atomic weight percentage
respectively. The absence of other elemental peak lines, especially of
3.1. Structure and morphology carbon residues implies the sample purity.

The XRD profiles of the ASNPs and its precursor are shown in Fig. 1.
3.3. Thermogravimetric analysis
The crystalline diffraction patterns obtained exactly similar to the bulk
precursor, confirms the sample formed to be aluminum sulfate. More­
Thermogravimetric profile of AS and ASNPs are given in Fig. 5. It can
over, the absence of remarkable diffractions other than the precursor
be observed that the nature of thermogravimetric degradation for both
reveals the formation of pure particles free from extract residues/
the samples follows a similar trend. Two distinctive weight loss were
binders (see Fig. 2).
observed; the first one around ~100 � C pertains to dehydration and
Phytoconstituents in Hemigraphis coloratata leaves include flavo­
dehydroxylation while the second one around ~800 � C is due to
noids, polyphenols, tannin, alkaloids, steroids, xanthoprotein, carbo­
desulfurization reaction. The sharp endothermic peaks appeared around
hydrates and carboxylic acids [43–46]. They are believed to act as
~100 � C and ~800 � C in the DTA curve correspond to dehydration/
binders to facilitate the formation of ASNPs. FTIR studies were con­
dehydroxylation and desulfurization processes respectively [49,50].
ducted to identify the composition and purity of the synthesized Nano
The characterization studies confirmed that the obtained product
coagulant. FTIR spectra of the ASNPs and the bulk precursor displayed
was ASNPs. Phytochemicals in the leaf extract are incapable of facili­
good correlation. The vibrational bands obtained around 3440 and
tating the formation of aluminium oxide from the sulfate precursor at

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J. Garvasis et al. Materials Chemistry and Physics 251 (2020) 123040

Fig. 3. FESEM micrographs of A) AS, B) ASNPs, C&D) HRTEM images of ASNPs.

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J. Garvasis et al. Materials Chemistry and Physics 251 (2020) 123040

Fig. 4. EDAX profile of synthesized ASNPs.

Fig. 5. TGA degradation curves of AS and synthesized ASNPs.

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J. Garvasis et al. Materials Chemistry and Physics 251 (2020) 123040

Table 1 which in turn promotes destabilization through charge neutralization

Effect of initial concentration on optimum dosage and coagulation efficiency of [54]. The effect of initial concentration on coagulation efficiency was
ASNPs. monitored. The study revealed that there exists an ideal dosage for the
Initial Concentration Coagulant Dosage (mg Coagulation Efficiency coagulant corresponding to the concentration of the dye solution, below
(ppm) L 1) % which the coagulation is incomplete. The coagulation of congo red dye
50 60 92.4634 solution attained 99.5% efficiency at a dose of 140 mgL 1 for 100 mgL 1
80 97.3739 dye solution of pH 7 at room temperature. These findings were set as
100 99.5934 standards for a further set of experiments. The details of the study are
120 99.5906
tabulated in Table 1. Samples calcined at 400 � C and 700 � C did not
100 100 94.3261
120 97.4705 exhibit any coagulant activity towards congo red dye. The sample ob­
140 99.5085 tained at 500 � C displayed incomplete coagulation towards the dye even
160 99.5421 at higher dosages.
150 240 95.3585
260 97.1078
280 99.5219
3.4.2. Effect of pH and temperature
300 99.6082 The pH of the dye solution is a major factor in determining the ef­
200 340 94.1526 ficacy of a coagulant [55–58]. The efficiency of the nano coagulant
360 95.9387 under different pH was hence estimated. 0.25molL-1 HCl and 0.25
380 99.6718
molL-1 NaOH was used to adjust the pH accordingly. The λm red shifted
400 99.7942

the given temperature. This can be attributed to the mild reducing na­
ture of phytochemicals in general towards a hard metal ion like Al3þ.
Therefore, the probable mechanism of formation of ASNPs is through
the recrystallisation of solvated bulk aluminium sulfate precursor in the
phytochemical medium. In contrary to similar reports of green synthesis
[51–53] where the phytoconstituents act as both reducing and capping
agents in this study the phytochemicals solely act as capping agents. This
in turn resulted in efficient size reduction of the particles instigating the
formation of ASNPs.

3.4. Coagulation efficiency

3.4.1. Effect of coagulant dosage and initial concentration

The bulk precursor and the sample dried at 150 � C was devoid of any
visible coagulation ability. But the coagulation of congo red dye solution
by ASNPs was instantaneous. Initially, the efficiency of dye removal
increased with the addition of ASNPs. The solution encircling the flocs
appeared clear on introducing the nano coagulant of the optimum dose.
The addition of the nano coagulant past the optimum dosage did not
result in any significant changes in the coagulation efficiency. This Fig. 7. Effect of interfering anions on the coagulation efficiency of ASNPs.
behaviour may be attributed to the increase in the number of cationic
active sites in the solution with an increase in the coagulant dosage

Fig. 6. (A) Effect of pH on coagulation efficiency of ASNPs and turbidity, (B) Effect of temperature on coagulation efficiency of ASNPs.

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Fig. 8. The optical microscopic images of Pre-flocculation at (A) pH 3, (B) pH 7 and (C) pH 9.

Fig. 9. Schematic representation of coagulation flocculation process by ASNPs.

to 511 nm on the addition of HCl while it was stable on the addition of 3.4.3. Effect of interfering anions
NaOH. Fig. 6A shows that within the investigated range the influence of All the experiments were conducted using tap water which may
pH on the efficiency of the nano coagulant is negligible. The plot also contain several inorganic ions and organic matter. But to rule out any
depicts the trend of residual turbidity of the dye solution with a change type of coagulation intervention by inorganic ions, the effect of sulfate,
in pH. Zeta potential analysis detected a surface charge of 7 mV on the sulfite, nitrate, nitrite, chloride, and bromide ions on the efficiency of
nano coagulant. This cationic surface is believed to cause the instant the nano coagulant were investigated. Equimolar solutions of the chosen
coagulation of anionic dye, congo red, through charge neutralization. anions were prepared for the purpose, coagulant dosage and other
The introduction of hydrogen and hydroxyl ions probably do not experimental conditions were kept the same. Fig. 7 concludes that these
interfere with the interaction between cationic nano coagulant and ions have no significant influence on coagulation efficiency of the nano
anionic congo red dye. The effect of temperature on the efficiency of the coagulant. Therefore, it can be proposed that Naþ and Kþ cations and
nano coagulant was investigated. Fig. 6B suggests that temperature SO24 , SO23 , NO3 , NO2 , Cl and Br anions do not interfere with the
variations do not influence the coagulation efficiency of ASNPs. It was coagulation of congo red dye solution by ASNPs.
inferred that the synthesized nano coagulant does not undergo any
compositional changes during temperature rise. 3.4.4. Effect of settling time and sludge characteristics
The effect of settling time on the coagulation efficiency of ASNPs was

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neutralizes the less charged dye species. Initial coagulation results in

formation of mesh like frames around the coagulant particle. The nano
coagulant particles entrapped in these frames cause more coagulation of
the dye molecules producing larger aggregates similar to sweep flocs.
The process continues, and more dye molecules get neutralized in this
enmeshment. The nanometer size of the coagulant induces self-assembly
to form larger aggregates that facilitate bridging among molecules. As
the bridging progresses, larger molecules cumulate at each active site
causing complete and instantaneous coagulation of the dye solution. The
negligible variations in the coagulation efficiency of the nano coagulant
under different conditions suggest that the coagulation properties are
results of surface to surface physical interactions. Rapid flocculation and
settling behaviour of ASNPs without any flocculant aids confirm high
aggregation capacity of the nano coagulant.
To evaluate the reusability of the nano coagulant for practical ap­
plications the recycled ASNPs were tested using fresh congo red dye
solutions. The coagulation experiments were repeated for five cycles
using the recycled coagulant. Fig. 10 shows that the coagulation effi­
ciency of the synthesized nano coagulant was retained even after five
cycles. A trivial reduction in the efficiency may be correlated to the loss
Fig. 10. Coagulation efficiency of recycled ASNPs.
of coagulant during the repeated washing and drying processes. Table 2
compares ASNPs with a few alternatives for removal of Congo red dye
monitored. It was observed that under optimum conditions the flocs
from effluents. Though there are similar reports offering comparable dye
formed were considerably thick and consequently, settled faster. The
removal efficiency [61] cost effectiveness, consistent performance under
microscopic images of flocs, Fig. 8, under different pH displaying a
different environments, high settling ability, low SVI, and recyclability
comparable floc population also support the inference. The period after
makes ASNPs a suitable alternative.
which the sludge volume and coagulation efficiency remained constant
was taken as the optimum settling period, which in this case was 30 min.
4. Conclusions
At this point, the separation between the treated dye solution zone and
the settled sludge zone becomes evident. The increased surface area
Phytogenic ASNPs were synthesized with an average dimension of
attained through size reduction may have resulted in the exposure of
~13 nm employing Hemigraphis colorata leaf extract. The prepared
more cationic active sites forcing the anionic dye in the solution to
sample can be employed as a nano coagulant for the removal of haz­
coagulate.
ardous Congo red dye from aqueous solutions. The coagulation effi­
An SVI less than 80 mLg 1represent a good sludge and a value
ciency was found to be consistent with the changes in pH and
around 50 mLg 1indicates a very good sludge. An SVI greater than 120
temperature. The presence of various ions (Naþ and Kþ cations and
mg/g indicates poor settling characteristics [59]. The low dosage of the
SO24 , SO23 , NO3 , NO2 , Cl and Br anions) does not interfere the
nano coagulant used, aided in the significant reduction of sludge gen­
coagulation efficiency of the material. The ASNPs also displayed high
eration. The sludge volume index (SVI) was found to be 31 mLg 1.
coagulation efficiency and rapid settling ability. The sludge produced is
Lower SVI values indicate appreciable settling ability of the sludge. It
less and thermally decomposable. The coagulant can be reused up to five
was found that with increasing initial concentration, SVI value also
number of cycles without remarkable compromise in efficiency. Thus,
increased. Coagulants with low SVI values are preferred for industrial
the synthesized ASNPs is a promising candidate for the removal of
applications as they offer easy sludge management.
Congo red in terms of cost efficiency, low dose, high coagulation effi­
ciency, sludge management, and shelf life.
3.4.5. Coagulation mechanism and recyclability
For practical applications, the efficiency of a chemical substance to
Declaration of competing interest
destabilize and coagulate targeted particles is the result of a combina­
tion of several mechanisms [56–60]. Fig. 9 shows a schematic repre­
None.
sentation of the coagulation/flocculation process by ASNPs. On addition
to the aqueous dye solution the nano coagulant slightly swells to form a
CRediT authorship contribution statement
gel like consistency. The coagulation is assumed to be triggered by
adsorption of anionic dye molecules on the cationic surface of ASNPs
Julia Garvasis: Conceptualization, Data curation, Formal analysis.
followed by charge neutralization. The swelling of the nano coagulant
Anupama R. Prasad: Conceptualization, Data curation, Formal anal­
helps in holding the complex structure of Congo red dye molecules thus
ysis. K.O. Shamsheera: Software, Validation, Writing - original draft. P.
making it available for the charge neutralization process. The surface of
K. Jaseela: Software, Validation, Writing - original draft. Abraham
the nano coagulant abundant with cationic active sites sufficiently
Joseph: Supervision, Writing - review & editing.

Table 2
Comparison of coagulation properties of ASNPs with similar reports.
Coagulant Concentration of dye solution (mgL 1) Coagulant dosage (mg) Coagulation Efficiency % pH Reference

Alum 100 20 99 7 [27]

Ferrous sulfate and calcium hydroxide 100 350 90 7 [27]
Algal alginate and Calcium 250 60 and 6000 96 4 [20]
HOC-100Aa 1000 1500 99 7 [61]
FeCl3a 1000 2000 97 5 [61]
ASNPs 100 140 99.5 3 to 9 (Present study)
a
With the use of one/more coagulant aids.

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