Crystals 12 00662
Crystals 12 00662
Crystals 12 00662
Article
Dye Sequestration Using Biosynthesized Silver Nanoparticles
Adsorbent in Aqueous Solutions
Madiha Batool 1 , Walid M. Daoush 2,3, * and Muhammad Khalid Hussain 4
Abstract: Nanomaterials have gained much attention in the field of environmental remediation,
largely due to their high surface area-to-volume ratio and other unique physical, chemical, and
biological characteristics that emerge due to its size effects. Metallic nanoparticles are traditionally
manufactured using wet chemical processes; however, the chemicals utilized are generally hazardous
and combustible. The biosynthesis of nanoparticles using a variety of plant resources is considered a
green technology because it does not use toxic chemicals. This work focuses on the green synthesis of
biogenetic silver nanoparticles and their use in the sequestration of colorants from aqueous solution.
The extract of aquatic macrophyte Salvinia molesta (water hyacinth) has been employed to prepare
silver nanoparticles by chemical reduction reaction. In the UV-visible spectrum of the synthesized
silver nanoparticles, the absorbance peak was detected in the 420–430 nm range. The synthesized
silver nanoparticles were used to sequester methylene blue (MB) dye in aqueous solution. About
Citation: Batool, M.; Daoush, W.M.; 121.04 mg/g was found as the highest adsorption capacity of methylene blue dye on the silver
Hussain, M.K. Dye Sequestration nanoparticles according to the Langmuir isotherm. It was observed that the experimental results
Using Biosynthesized Silver and the pseudo-second order kinetics are in good agreement. As a result, the biosynthesized silver
Nanoparticles Adsorbent in Aqueous nanoparticle might be a potential adsorbent material in the field of environmental rehabilitation
Solutions. Crystals 2022, 12, 662. and cleanup.
https://doi.org/10.3390/
cryst12050662 Keywords: silver nanoparticles; green synthesis; adsorption; colorants; methylene blue dye
Academic Editor: Witold Łojkowski
Nanotechnology allows the creation of nanomaterials that may be used for a variety
of scientific and technical purposes. As a result of nanotechnology, new nanomaterials may
be used for a variety of applications with a measurement of less than 100 nanometers [5].
Research on nanoparticles has received increased attention in recent years, owing to a wide
range of essential uses in health and different environmental issues. As a result of their
tiny size, nanoparticles have a higher surface-to-volume ratio or a greater surface area per
weight than larger particles, making them more reactive to interact with other molecules.
Silver nanoparticles (AgNPs) are more important than other noble metal nanoparticles
due to their specific features, such as excellent optical property, electrical conductivity,
oxidative property, antibacterial activity, and catalytic activity. Silver nanoparticles are
traditionally produced using hazardous chemicals and at a high cost. The utilization of
environmentally friendly resources such as plant leaf extract, microorganisms, and enzymes
may be employed for the biological production of nanoparticles, which offers several
environmental benefits. The green production of nanoparticles is critical for the treatment
of many hazardous compounds that cannot be addressed chemically [6]. The fabrication of
nanoparticles using chemical methods are time-consuming and have a high production
cost. Therefore, scientists were particularly interested in the creation of nanoparticles by
green production methods.
In the literature, researchers fabricated silver nanoparticles and applied for different
applications. Vanaja et al. (2014) prepared silver nanoparticles using Morinda tinctoria leaf
extract under specific pH conditions and further characterized by different spectroscopic
techniques [7]. They concluded that the size as well as the quantity of silver nanoparticles
formed are strongly dependent on the pH, and basic pH supports the biosynthesis of
silver nanoparticles, whereas no silver nanoparticles were detected in the acid medium.
Silver nanoparticles were prepared with sizes ranging from 79 to 90 nm and applied for
photo catalytic activity of MB degradation [8]. Anu Kumar et al. (2016) experimented
with a simple and non-hazardous method for synthesizing silver Nano catalyst by using
Viola serpens leaf extract [9].
The biosynthesis of AgNPs mainly involves three main steps: (1) solvent medium
should be selected, (2) environmentally friendly reducing agents are selected, and
(3) nontoxic substances are chosen for the AgNPs stability. When a substrate of low value is
used by living cells to produce higher-value products, this device is called a bioreactor [10]
Plant parts act as a bioreactor for the expression in tissues remote from the penetration of
ion sites, with the capability to reduce metal ions on the surface. The plant has a strong
hyperaccumulation capacity of metal ions, which is a tool for the bioaccumulation of metal
oxide-NPs. The whole plant can be used for nanoparticle fabrication, whereas size and
shape of NPs mainly depends upon parts of the plant. Biogenic fabrication by plant ex-
tracts have been used in the production of AgNPs and found interesting owing to size,
surface area, structure, and unique properties. There are several disadvantages of physical
and chemical methods of nanometal fabrication, as they need to use biogenic synthesis
methods, which are economically feasible and ecofriendly [11]. The purpose of this work is
to synthesize AgNP using the aquatic weed, Salvinia molesta, as a reducing agent and assess
their effectiveness in sequencing MB dye, which is commonly used in the textile industry.
It was shown that the synthesized AgNPs by plant extracts adsorb and quickly decrease
the concentrations of the MB dye, both in terms of catalysis and kinetics [12].
Crystals 2022, 12, 662 leaves are 0.1–4 cm long, with a bristly surface caused by the hair-like strands and were
3 of 12
collected from riverbanks and ponds in the summer of 2021 (see Figure 1).
2.2. Methods
2.2. Methods
2.2.1. Plant Extraction
2.2.1.The
Plant Extraction
collected S. molesta was washed many times in warm distilled water to remove
any dust
The collected S. molestaAwas
or other impurities. totalwashed S. molesta
of 50 g ofmany timesleaves were distilled
in warm cleaned and finely
water to remove
chopped before being placed in 500 mL beakers containing 200 mL of double-distilled
any dust or other impurities. A total of 50 g of◦ S. molesta leaves were cleaned and finely
water. The mixture was allowed to boil for 1 h at 100 C. The obtained solution mixture was
chopped before being placed in 500 mL beakers containing 200 mL of double-distilled
then cooled to room temperature [14]. The leaf extracts were filtered by using Whatman
water. The mixture was allowed to boil for 1 h at 100 °C. The obtained solution mixture
number 41 filter paper.
was then cooled to room temperature [14]. The leaf extracts were filtered by using What-
man number
2.2.2. 41 filter paper.
Silver Nanoparticle (AgNPs) Synthesis
In order to synthesize AgNPs, an aqueous solution of silver nitrate was prepared using
2.2.2. Silver Nanoparticle
double-distilled water. AgNPs(AgNPs) Synthesis
were made by mixing 1 mM silver nitrate solution with
S. molesta leaf extract
In order and continuous
to synthesize AgNPs,stirring at 300 rpm
an aqueous for 72ofh silver
solution at room temperature
nitrate was prepared
using a magnetic stirrer. The formation of AgNPs is indicated by the appearance of a
using double-distilled water. AgNPs were made by mixing 1 mM silver nitrate solution
yellow-brown color after 8 h of agitation and turns reddish brown after 72 h of agitation in
with
the S. molesta
dark leafresulting
[15,16]. The extract and continuous
suspension stirring
of silver nitrateatand
300S.rpm forextract
molesta 72 h atwere
room tempera-
cen-
ture using a magnetic stirrer. The formation of AgNPs is indicated by the
trifuged at 15,000 rpm for 15 min. To remove silver ions and seed extract residue, the pellet appearance of a
yellow-brown
containing AgNPs color
wasafter 8 h three
washed of agitation and turns
to four times reddish brown
with deionized after 72 h of agitation
water. Biosynthesized
in the dark
AgNPs were [15,16]. Theafter
lyophilized resulting suspension of
being precipitated. To silver
furthernitrate and S.the
characterize, molesta extract were
lyophilized
nanoparticles
centrifuged at were stored
15,000 rpmin afor
cool,
15 dry,
min.andTodark
removeenvironment.
silver ions and seed extract residue, the
pellet containing AgNPs was washed three to four times with deionized water. Biosyn-
2.2.3. Characterization of Biogenic AgNPs
thesized AgNPs were lyophilized after being precipitated. To further characterize, the ly-
The mixture of silver nitrate and S. molesta extract solution were taken in different
ophilized nanoparticles were stored in a cool, dry, and dark environment.
ratios (1:1, 1:2, 1:3, and 1:4), and the UV-visible spectra of AgNPs at different ratios were
obtained using a UV-1800 Shimadzu spectrophotometer. Silver nanoparticle morphology
2.2.3.studied
was Characterization of Biogenic
using a lyophilized sampleAgNPs
of AgNPs using a scanning electron microscope
(SEM)The mixture
operating ofkV.
at 20 silver nitrate and
Transmission S. molesta
electron extract
microscopy solution
(TEM) were
working taken
at an in different
accelera-
tion voltage
ratios of 200
(1:1, 1:2, kVand
1:3, was1:4),
usedand
to determine the morphology
the UV-visible spectra ofand size ofatbiosynthesized
AgNPs different ratios were
AgNPs.
obtainedThe crystalline
using a UV-1800structure of the biogenic
Shimadzu nanoparticlesSilver
spectrophotometer. was determined
nanoparticle using a
morphology
pattern of selected area electron diffraction (SAED).
was studied using a lyophilized sample of AgNPs using a scanning electron microscope
(SEM)Dye
2.2.4. operating at 20
Adsorption kV.
and Transmission
Sequestration electron
Using AgNPsmicroscopy
Adsorbate (TEM) working at an accel-
eration voltage of 200 kV was used to determine the morphology and size of biosynthe-
For the sequestration of MB dye, batch studies were carried out in a 250 mL con-
sized
ical AgNPs.
flask The crystalline
containing structure
50 mL of dye of the
solution. biogenic
The effects nanoparticles was determined us-
of initial dye concentration
ing a pattern of selected area electron diffraction (SAED). ◦
(10–100 mg/L), equilibrium time, pH (2–10), and temperature (30–45 C) were investi-
gated. After adding a desired amount (0.1 g) of AgNPs to MB dye solution, the mixture was
2.2.4. Dye
stirred Adsorption
at 200 rpm with a and Sequestration
magnetic Using
stirrer at an AgNPs
ambient Adsorbate
temperature for equilibrium time.
After equilibrium time, the solution was filtered to separate pellet and supernatant [17–21].
For the sequestration of MB dye, batch studies were carried out in a 250 mL conica
The collected supernatant was analyzed using UV-Vis spectrophotometer at a maximum
flask containing 50 mL of dye solution. The effects of initial dye concentration (10–100
mg/L), equilibrium time, pH (2–10), and temperature (30–45 °C) were investigated. After
adding a desired amount (0.1 g) of AgNPs to MB dye solution, the mixture was stirred at
200 rpm with a magnetic stirrer at an ambient temperature for equilibrium time. After
equilibrium time, the solution was filtered to separate pellet and supernatant [17–21]. The
collected supernatant was analyzed using UV-Vis spectrophotometer at a maximum
Crystals 2022, 12, x FOR PEER REVIEW C0 − C1 4 of 12
Decolorization (%) = ×100%
C0
Crystals 2022, 12, 662 wavelength of 660 nm to measure the MB dye concentration in the residual solution.4 The of 12
where C 0 is the initial concentration of dye and C1 is the concentration of dye afte
efficiency of decolorization (%) has been calculated by using the following Equation (1)
ation in the selected time interval.
[10]:
wavelength of 660 nm to measure the MB dye concentration in the residual solution. The
C − C1
3. Results
efficiency and Discussion
of decolorizationDecolorization (%) = by0 using
(%) has been calculated ×the
100%
following Equation (1) [10]:
(1)
0 C
3.1. Characterization of Biosynthesized AgNPs
C0 − C1
Decolorization(%) = × 100% (1)
C0 is the
whereSilver initial concentration
nanoparticles wereofsynthesized
dye and C1Cis0 by
the the
concentration
additionofofdye after irradi-
Salvinia molesta ex
ation in the selected time interval.
the AgNO
where 3 solution.
C0 is the In the AgNO
initial concentration 3/Salvinia
of dye and C1 is molesta solution,
the concentration silver
of dye nanoparticle
after irradia- sy
is Results
indicated
tion
3. in the and by
selected atime
progressive
Discussion interval. color change from colorless to yellow to reddish br
shown
3.1. in Figure of
Characterization 2.Biosynthesized
Surface plasmon AgNPsvibration, an optical characteristic found only
3. Results and Discussion
metals,
3.1. Silver isnanoparticles
responsible
Characterization for this
were color
synthesized
of Biosynthesized AgNPs change [22]. Further,
by the addition UV-visible
of Salvinia spectroscopy
molesta extract to h
used
the AgNOto confirm
Silver 3 solution. the
nanoparticlesIn theformation
AgNO
were of silver
3/Salvinia
synthesized molesta
by nanoparticles
solution,
the addition silverin
of Salvinia aqueous
nanoparticle
molesta solution.
to the The s
synthesis
extract
is
wasindicated
scanned by a progressive
over a range color
of change
wavelengthfrom colorless
as to
300–800 yellow
nm.
AgNO3 solution. In the AgNO3 /Salvinia molesta solution, silver nanoparticle synthesis to reddish
Biogenic brown,
AgNPs as have a
shown
nent
is in
indicated Figure
peak by 2. Surface
absorbance
a progressive plasmon
at color
430 nm vibration,
[23],
change froman optical
which characteristic
is typical,
colorless to yellow found
astoshown only
reddishin in noble
Figure
brown, as 3. Salv
metals,
shown is responsible
in Figure 2. for this
Surface color change
plasmon [22].an
vibration, Further,
optical UV-visible spectroscopy
characteristic found only has
in been
noble
lesta leaf extract generated highly dense AgNPs, as shown by SEM examination in
used
metals,to isconfirm the formation
responsible for this colorof silver
change nanoparticles
[22]. Further,inUV-visible
aqueous solution. The has
spectroscopy solution
been
4. The
was
usedscanned
acquired
to confirm over morphology
theaformation
range of wavelengthdemonstrated
as 300–800innm.
of silver nanoparticles
that the
Biogenic
aqueous
produced
AgNPs
solution. have
The
AgNPs
a promi-
solution was
were v
spherical.
nent
scannedpeakover The
absorbanceparticles
a range of 430 appear
at wavelength
nm [23], as agglomerated
which is typical,
300–800 because
as shown
nm. Biogenic the
in
AgNPs presence
Figure of several
have3.aSalvinia
prominentmo- sig
lesta leaf
bio-organic
peak extract
absorbance generated
chemicals highly
at 430 nm extruded dense
[23], which from AgNPs, as shown
the leaves appear
is typical, by SEM examination
in Figureas3. aSalvinia
chelatingin Figure
molestaagent
leaf that st
4.
theThe
extract acquired AgNPs
generated
produced morphology
highly dense demonstrated
AgNPs, A
in solution. that by
as shown
similar the produced
SEM AgNPs
examination
phenomenon wasinwere
Figurevirtually
reported 4. The
by Ranjith
spherical. The particlesdemonstrated
acquired morphology appear agglomerated because the
that the produced presence
AgNPs were of virtually
several significant
spherical.
et al. (2018) [24].
bio-organic
The particleschemicals extruded from
appear agglomerated the leaves
because appear asofa several
the presence chelating agent that
significant stabilizes
bio-organic
the produced
chemicals AgNPs
extruded in solution.
from the leavesAappear
similarasphenomenon was that
a chelating agent reported by Ranjith
stabilizes kumar
the produced
et al. (2018)
AgNPs [24]. A similar phenomenon was reported by Ranjith kumar et al. (2018) [24].
in solution.
8h 16 h 24 h 48 h 72 h
8h 16 h 24 h 48 h 72 h
Figure 2. Color change during AgNPs biosynthesis at different time intervals.
Figure
Figure 2.
2. Color
Color change
change during
during AgNPs
AgNPs biosynthesis
biosynthesis at
at different time intervals.
different time intervals.
Figure 3. UV spectra of the biosynthesized AgNPs using different ratios of silver nitrate to S. molesta
leaves extract.
Figure3.3.UV
Figure UVspectra of the
spectra ofbiosynthesized AgNPs using
the biosynthesized AgNPsdifferent
using ratios of silverratios
different nitrateof S. molesta
tosilver nitrate to S
leaves extract.
leaves extract.
Crystals 2022, 12, x FOR PEER REVIEW 5 of 1
Crystals 2022, 12, 662 5 of 12
Figure5.5.(a–c)
Figure (a–c) TEM
TEM image
image andand (d) SAED
(d) SAED diffraction
diffraction pattern
pattern of the biosynthesized
of the biosynthesized AgNPs. AgNPs.
Figure 6. Effect of time on the decolorization percentage of methylene blue dye adsorbed on the
Figure 6. EffectAgNPs.
biosynthesized of time on the decolorization percentage of methylene blue dye adsorbed on the
Figure 6. Effect of time on the decolorization percentage of methylene blue dye adsorbed on the
biosynthesized AgNPs.
biosynthesized AgNPs.
3.3. Effect of pH on the Adsorption Process
3.3. Effect of pH on the Adsorption Process
3.3. Effect
Each of of pHthe on the Adsorption
adsorbate solutions Process
were prepared at different pH levels (2.0, 4.0, 6.0, 8.0,
Each of the adsorbate solutions were prepared at different pH levels (2.0, 4.0, 6.0, 8.0,
and 10) Eachusing
of either
the 1.0 N HCl
adsorbate or 1.0were
solutions N NaOH.
prepared There were optimum
at different pH amountsamounts
levels (2.0, of 6.0,
adsor-
and 10) using either 1.0 N HCl or 1.0 N NaOH. There were optimum of 4.0,
adsorbents8.0,
bents
and in using
10) dye solutions
either that
1.0 N wereoradded
HCl 1.0 N (0.1
NaOH.g of There
AgNPs), wereand the mixture
optimum was agitated.
amounts of adsor-
in dye solutions that were added (0.1 g of AgNPs), and the mixture was agitated. The
The
bentsamount
inofdye of dye that that was adsorbed was(0.1
measured. From andthe plot of pH versuswas percent-
amount dyesolutions
that was adsorbed were was addedmeasured. g ofFrom
AgNPs), the plot ofthe pHmixture
versus percentage agitated.
of
age
The of dye
amount removal
of dye (Figure
that was 7), it was
adsorbed observed
was that
measured. the optimum
From
dye removal (Figure 7), it was observed that the optimum pH of the process was 4. This is the pH
plot of
of the
pH process
versus was
percent-4.
This
age of
due is dye
to due to the
removal
the fact thatfact
thethat
(Figure the
7), degradation
degradationit wasof MB of
observed dye MB
that
wasdye
the was increased.
optimum
increased. ofThe
the neutralization
pHneutralization
The process wasof the4.
of the
This negative
is due to charges
the fact at
that thethesurface of
degradation AgNPs of will
MB enhance
dye was
negative charges at the surface of AgNPs will enhance the diffusion phenomena to occur, the diffusion
increased. The phenomena
neutralization to
occur,
of the
and and
more morecharges
negative
active active sites
sites willat the
bewill be available
surface
available of for
AgNPs
theforadsorption
the adsorption
will enhance theprocess.
process.diffusion However,
However, phenomena
when when
theto
the pH
occur,
pH is below
and more
is below 4, the
4, theactive dye degradation
sites will beand
dye degradation and
available the number of
for theofadsorption
the number negatively
negativelyprocess. charged
chargedHowever, adsorbent
adsorbentwhen sites
sites
the pH decreases.
decreases. is below The
4, the
The increasing increasing
dye in the number
indegradation
the number and
of theofnumber
positively positively charged
of negatively
charged surface
charged
surface active active
sites sites
adsorbent
enhances
enhances
the the dye-adsorbent
sitesdye-adsorbent
decreases. The increasing
repulsion, repulsion,
whichin the which
number
reduces reduces
the of the efficiency
positively
efficiency charged
of the of the adsorption
surface
adsorption active pro-
process. sites
At a
cess. At
enhances a lower
the pH, the
dye-adsorbent MB adsorption
repulsion, dye
which improved
reduces the
lower pH, the MB adsorption dye improved due to the acidic media. As pH increases, thedue to the
efficiency acidic
of the media.
adsorption As pH
pro-
increases,
cess. At athe
adsorbent loweradsorbent
surface pH, thesurface
acquired MB acquired
adsorption
negatively negatively
dye improved
charges, charges,
and they and they
dueresponsible
are to the areforresponsible
acidic media.
increasingAs for
pH
the
increasing
increases, the
adsorption the adsorption
adsorbent
capacity capacity
due surface due to the
acquired negatively
to the electrostatic electrostatic
interaction. charges, interaction.
However,and they However,
the are the
responsible
adsorption ad-
of MBfor
sorption
was of
increasing
dye MB dyedecreasing
was observed
the adsorption
observed capacity
at highdecreasing
duepH.to theatelectrostatic
high pH. interaction. However, the ad-
sorption of MB dye was observed decreasing at high pH.
Figure 7.
Figure Effect of
7. Effect of pH
pH on
on the
the decolorization
decolorization percentage
percentage of
of the
the methylene
methylene blue
blue dye
dye adsorbed
adsorbed on
on the
the
biosynthesized
biosynthesized AgNPs.
Figure 7. EffectAgNPs.
of pH on the decolorization percentage of the methylene blue dye adsorbed on the
biosynthesized AgNPs.
Crystals 2022,
Crystals 2022, 12,
12, 662
x FOR PEER REVIEW 7 7of
of 12
12
Figure 8. Effect
Effect of
of temperature
temperature on
on the
the decolorization
decolorization percentage
percentage of the methylene
methylene blue dye adsorbed
on the biosynthesized AgNPs.
3.5. Adsorption
3.5. Adsorption Isotherms
Isotherms
The interaction
The interactionbetween
betweenadsorbate
adsorbateandand adsorbent
adsorbent is described
is described usingusing adsorption
adsorption iso-
isotherms. Langmuir and Freundlich isotherm models are used to assess experimental
therms. Langmuir and Freundlich isotherm models are used to assess experimental and and
theoretical MB
theoretical MB dye
dye adsorption
adsorption data.
data. According
According to to Langmuir,
Langmuir, adsorption
adsorption occurs
occurs uniformly
uniformly
or homogeneously on the surface of the biosynthesized AgNPs adsorbent.
or homogeneously on the surface of the biosynthesized AgNPs adsorbent. Langmuir’s Langmuir’s
linear expression
linear expression can
can be
be found
found in
in Equation
Equation (2)
(2) [10];
[10];
CC
e 1 1 CC
e
e= + (2)
qe =Qb +Q
e
(2)
qe Qb Q
where Ce is the equilibrium concentration of a dye in solution (mg/L), qe is the amount of
where Ce is theon
dye adsorbed equilibrium concentration
to the Cs (mg/g) MB, Q is of the
a dye in solution
Langmuir (mg/L),
constant qe is the
related amount of
to adsorption
dye adsorbed on to the Cs (mg/g) MB, Q is the Langmuir constant
capacity (mg/g), and b is the Langmuir constant related to sorption energy (L/mg). The related to adsorption
capacity (mg/g),
experimental data and
forbtheis the Langmuir constant
decolorization of MB dye related to sorption
is fitted energy (L/mg).
in the rearranged LangmuirThe
experimental
equation, which datahasforfound
the decolorization of MB dye is
successful applications offitted in the rearranged
monolayer adsorption.Langmuir
The plot
equation,
obtained iswhich
shown hasinfound
Figuresuccessful applications
9. A Freundlich isotherm of monolayer adsorption.
is used to determine theThe plot ob-
adsorption
tained
capacityis of
shown
MB dye in Figure
on the9.biosynthesized
A Freundlich isotherm is used to(3)
AgNPs. Equation determine
is the linearthe form
adsorption
of the
capacity of MB
Freundlich isotherm. dye on the biosynthesized AgNPs. Equation (3) is the linear form of the
Freundlich isotherm. 1
log qe = log k f + log Ce (3)
n
1
where Ce is the equilibrium concentration log q e = oflogthe + inlog
k fdye C e (mg/L), qe is the amount(3)
solution of
dye adsorbed on the adsorbent (mg/g), and Kf and 1/n n are Freundlich constants [27]. The
graph of
where Celog qe isequilibrium
is the plotted against log Ce andof
concentration is the
founddyenotin to be linear
solution as shown
(mg/L), qe is in
theFigure
amount 10.
The 1/n value from the experimental data is greater than 1, which
of dye adsorbed on the adsorbent (mg/g), and Kf and 1/n are Freundlich constants [27]. shows unsatisfactory
adsorption
The graph ofoflog MB qe isdye ontoagainst
plotted the surface
log Ceofandtheis biosynthesized
found not to be linear AgNPs adsorbent.
as shown The
in Figure
parameters of Langmuir and Freundlich constants are given in
10. The 1/n value from the experimental data is greater than 1, which shows unsatisfactoryTable 1. The Langmuir
isotherm was
adsorption of found
MB dye to onto
be thethebest fit in the
surface experimental
of the biosynthesized data—better
AgNPs than the Freundlich
adsorbent. The pa-
Crystals 2022,
Crystals 2022, 12,
12, xx FOR
FOR PEER
PEER REVIEW
REVIEW 88 of
of 12
12
Figure 9.
Figure 9. Decolorization
Decolorization percentage
percentage of
of the
the methylene
methylene blue
blue dye
dye as
as adsorbed
adsorbed on
adsorbed on the
the biosynthesized
the biosynthesized
biosynthesized
AgNPs.
AgNPs. (Fitted
(Fitted with
with the
the Langmuir
Langmuir model).
model).
AgNPs. (Fitted with the Langmuir model).
Figure 10.
Figure 10. Relationship
Relationship between
Relationshipbetween log
logqqeeqwith
betweenlog with loglog
e with
log Cee C
C ofe the
of the adsorbed
of the methylene
adsorbed
adsorbed blueblue
methylene
methylene blue dye dye
dye on the
on the bio-
on bio-
the
synthesized AgNPs.
synthesized AgNPs.
biosynthesized AgNPs.
Table1.
Table
Table 1.Freundlich
1. Freundlich and
Freundlich and Langmuir
and Langmuir isotherm
Langmuir isotherm parameters
isotherm parameters used
parameters used at
used at the
at the adsorption
the adsorption of
adsorption of methylene
of methylene blue
methylene blue
blue
dye onto
dye onto the
onto the surface
the surface of
surface of the
of the biosynthesized
the biosynthesized AgNPs
biosynthesized AgNPs adsorbent.
AgNPs adsorbent.
adsorbent.
dye
Freundlich Parameters
Freundlich Parameters Langmuir Parameters
Langmuir Parameters
Freundlich Parameters Langmuir Parameters
kkff n
n R22
R Qmm (mg/g)
Q (mg/g) b (L/mg)
b (L/mg) R22
R
k n R 2 Qm121.04
(mg/g) b0.2842
(L/mg) R 2
1.0023
1.0023
f 1.100
1.100 0.931
0.931 121.04 0.2842 0.998
0.998
1.0023 1.100 0.931 121.04 0.2842 0.998
3.6. Adsorption Kinetics
3.6. Adsorption Kinetics
For the study of adsorption kinetics, pseudo first order and pseudo second order ki-
neticFor
models are widely used. These
the study of adsorption models
kinetics, are used
pseudo firsttoorder
determine the ratesecond
and pseudo at which ad-
order
sorption occurs or the rate at which solute is absorbed. When it comes
kinetic models are widely used. These models are used to determine the rate at which to designing the
reactors, these models pay more attention. Our study examined the rate at
adsorption occurs or the rate at which solute is absorbed. When it comes to designing the which MB dye
adsorbedthese
reactors, onto models
surfacespayby more
applying pseudoOur
attention. first- andexamined
study second-order equations
the rate in order
at which MB dyeto
determineonto
adsorbed howsurfaces
fast it adsorbed. There
by applying is a strong
pseudo correlation
first- and between
second-order experimental
equations data
in order to
and predicted
determine howvalues
fast it using different
adsorbed. Theremodels (valuecorrelation
is a strong close or equal to 1).experimental data
between
and predicted values using different models (value close or equal to 1).
Crystals 2022, 12, x FOR PEER REVIEW 9 of 12
Crystals 2022, 12, 662 9 of 12
Figure 12.
Figure Pseudo second order
12. Pseudo order Kinetic
Kineticmodel—the
model—theadsorption
adsorptionprocess
processofof
the methylene
the blue
methylene dye
blue on
dye
on
thethe biosynthesized
biosynthesized AgNPs.
AgNPs.
TableAs a resultfirst
2. Pseudo of these findings,
and second orderthe prepared
kinetic nanoparticles mediated by S. molesta could
models.
be used effectively in environmental remediation, and their phenomenal behavior might be
Pseudo First Order Pseudo Second Order
extensively utilized to breakdown hazardous organic colorants from different industrial ef-
qe (mg/g) kad (1/min) R2 q (mg/g) kad (g/mg/min) R2
fluents. The pseudo first order (P.F.O) reaction R2 value was calculated
e
as 0.91 as compared
81.01 0.046 0.916 97.08 0.707 0.99
to pseudo second order (P.S.O) reaction 0.99 and fitted well. Decolorization percentage of
methylene blue dye as adsorbed on the AgNPs was fitted with the Langmuir model.
As a result of these findings, the prepared nanoparticles mediated by S. molesta could
be used effectively in environmental remediation, and their phenomenal behavior might
4. Conclusions
be extensively
This studyutilized to breakdown
highlights hazardous organic
the use of nanotechnology for colorants
methylenefrom bluedifferent indus-
dye adsorption
trial effluents. The pseudo first order (P.F.O) reaction R 2 value was calculated as 0.91 as
on biosynthesized silver nanoparticles with effective results. It was shown that bioactive
compared
components toof pseudo second
the aquatic order (P.S.O)
macrophyte reaction
(S. molesta) 0.99 and
extracts fitted
can be used well.
as a Decolorization
reducing agent
percentage of methylene blue dye as adsorbed on the AgNPs was
to fabricate silver nanoparticles used efficiently in methylene blue dye adsorption.fitted with the Lang-
This
muir model.
is a quick method for the production of well-defined silver nanoparticles, as evidenced
by UV-Vis, TEM, SEM, and SAED methods. The efficient activity of silver nanoparticles
4. Conclusions
enhancing the methylene blue dye degradation was observed. The biosynthesized Ag-NPs
haveThis
highstudy highlights
adsorption theagainst
activity use of the
nanotechnology
decolorizationforof methylene bluedye.
methylene blue dye The
adsorption
present
study
on could be an indication
biosynthesized for furtherwith
silver nanoparticles future research
effective to identify
results. It wasother
shownnanoparticles for
that bioactive
different synthetic dyes for efficient degradation potential.
components of the aquatic macrophyte (S. molesta) extracts can be used as a reducing agent
to fabricate silver nanoparticles used efficiently in methylene blue dye adsorption. This is
aAuthor
quick Contributions:
method for the Conceptualization M.B., W.M.D. silver
production of well-defined and M.K.H.; Methodology,
nanoparticles, M.B., W.M.D.
as evidenced by
and M.K.H.; formal analysis, M.B., W.M.D. and M.K.H.; investigation, M.B.,
UV-Vis, TEM, SEM, and SAED methods. The efficient activity of silver nanoparticlesW.M.D. and M.K.H.;
en-
resources, M.B., W.M.D. and M.K.H.; writing original draft preparation, M.B., W.M.D. and M.K.H.;
hancing the methylene blue dye degradation was observed. The biosynthesized Ag-NPs
writing review and editing, M.B., W.M.D. and M.K.H. All authors have read and agreed to the
have high adsorption activity against the decolorization of methylene blue dye. The pre-
published version of the manuscript.
sent study could be an indication for further future research to identify other nanoparti-
Funding:
cles This research
for different received
synthetic dyesnofor
external funding.
efficient degradation potential.
Institutional Review Board Statement: Not applicable.
Author Contributions: Conceptualization M.B., W.M.D. and M.K.H.; Methodology, M.B., W.M.D.
Informed
and M.K.H.; Consent
formalStatement: Not W.M.D.
analysis, M.B., applicable.
and M.K.H.; investigation, M.B., W.M.D. and M.K.H.;
resources, M.B., W.M.D. and M.K.H.; writing original
Data Availability Statement: All data are available indraft preparation, M.B., W.M.D. and M.K.H.;
this manuscript.
writing review and editing, M.B., W.M.D. and M.K.H. All authors have read and agreed to the pub-
Acknowledgments:
lished The authors are thankful to the staff of the METS School of Engineering, Thrissur,
version of the manuscript.
India, for their cooperation during conducting this research work.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All data are available in this manuscript.
Crystals 2022, 12, 662 11 of 12
References
1. Aboelfetoh, E.F.; Gemeay, A.H.; El-Sharkawy, R.G. Effective disposal of methylene blue using green immobilized silver nanoparti-
cles on graphene oxide and reduced graphene oxide sheets through one-pot synthesis. Environ. Monit. Assess. 2020, 192, 1–20.
[CrossRef]
2. Hussain, M.K.; Khalid, N.R. Surfactant-assisted synthesis of MoO3 nanorods and its application in photocatalytic degradation of
different dyes in aqueous environment. J. Mol. Liq. 2022, 346, 117871. [CrossRef]
3. Wenjie, Z.; Zhou, C.; Zhou, W.; Lei, A.; Zhang, Q.; Wan, Q.; Zou, B. Fast and considerable adsorption of methylene blue dye onto
graphene oxide. Bull. Environ. Contam. Toxicol. 2011, 87, 86–90.
4. Khalid, N.R.; Hussain, M.K.; Murtaza, G.; Ikram, M.; Ahmad, M.; Hammad, A. A Novel Ag2 O/Fe–TiO2 Photocatalyst for CO2
Conversion into Methane Under Visible Light. J. Inorg. Organomet. Polym. Mater. 2019, 29, 1288–1296. [CrossRef]
5. Ho, Y.S.; Chiang, C.C. Sorption studies of acid dye by mixed sorbents. Adsorption 2001, 7, 139–147. [CrossRef]
6. Bar, H.; Bhui, D.K.; Sahoo, G.P.; Sarkar, P.; De, S.P.; Misra, A. Green synthesis of silver nanoparticles using latex of Jatropha curcas.
Colloids Surf. A Physicochem. Eng. Asp. 2009, 339, 134–139. [CrossRef]
7. Yang, Z.; Zhang, T.; Ren, J.; Li, J.; Ge, J.; Shan, H.; Ji, T.; Xu, M.; Liu, Q. Nano-silver functionalized spherical activated carbon with
enhanced dipropyl sulfide adsorption capacity and antibacterial properties. RSC Adv. 2022, 12, 9933–9943. [CrossRef] [PubMed]
8. Liu, Y.; Shi, T.; Si, Q.; Liu, T. Adsorption and sensing performances of transition metal (Pd, Pt, Ag and Au) doped MoTe2
monolayer upon NO2 : A DFT study. Phys. Lett. A 2021, 391, 127117. [CrossRef]
9. Rezaei, A.; Rezaei, M.R.; Sayadi, M.H. 3D network structure graphene hydrogel-Fe3 O4 @ SnO2 /Ag via an adsorp-
tion/photocatalysis synergy for removal of 2,4 dichlorophenol. J. Taiwan Inst. Chem. Eng. 2021, 121, 154–167. [CrossRef]
10. Ramalingam, B.; Khan, M.M.R.; Mondal, B.; Mandal, A.B.; Das, S.K. Facile synthesis of silver nanoparticles decorated magnetic-
chitosan microsphere for efficient removal of dyes and microbial contaminants. ACS Sustain. Chem. Eng. 2015, 3, 2291–2302.
[CrossRef]
11. Iravani, S.; Korbekandi, H.; Mirmohammadi, S.V.; Zolfaghari, B. Synthesis of silver nanoparticles: Chemical, physical and
biological methods. Res. Pharm. Sci. 2014, 9, 385. [PubMed]
12. Ponarulselvam, S.; Panneerselvam, C.; Murugan, K.; Aarthi, N.; Kalimuthu, K.; Thangamani, S. Synthesis of silver nanoparticles
using leaves of Catharanthus roseus Linn. G. Don and their antiplasmodial activities. Asian Pac. J. Trop. Biomed. 2012, 2, 574–580.
[CrossRef]
13. Sivashankar, R.; Susheeba, O.K.; Sivasubramanian, V. Adsorption of organic dye on to novel magnetic biocomposite: Kinetics and
equilibrium studies. Res. J. Chem. Environ. 2015, 19, 48–57.
14. Ibrahim, H.M. Green synthesis and characterization of silver nanoparticles using banana peel extract and their antimicrobial
activity against representative microorganisms. J. Radiat. Res. Appl. Sci. 2015, 8, 265–275. [CrossRef]
15. Saha, N.; Trivedi, P.; Gupta, S.D. Surface plasmon resonance (SPR) based optimization of biosynthesis of silver nanoparticles from
rhizome extract of Curculigo orchioides Gaertn. and its antioxidant potential. J. Clust. Sci. 2016, 27, 1893–1912. [CrossRef]
16. Rajamani, R.K.; Kuppusamy, S.; Bellan, C. Biosynthesis, characterization and remedical aspect of silver nanoparticles against
pathogenic bacteria. MOJ Toxicol. 2018, 4, 103–109. [CrossRef]
17. Nam, W.; Kim, J.; Han, G. Photocatalytic oxidation of methyl orange in a three-phase fluidized bed reactor. Chemosphere 2002,
47, 1019–1024. [CrossRef]
18. Banerjee, S.; Chattopadhyaya, M.C. Adsorption characteristics for the removal of a toxic dye, tartrazine from aqueous solutions
by a low-cost agricultural by-product. Arab. J. Chem. 2017, 10, S1629–S1638. [CrossRef]
19. Ünal, G.; Özcan, G.; Gürpınar, G.Ç. Removal of methylene blue from aqueous solution by activated carbon prepared from pea
shells (Pisum sativum). J. Chem. 2013, 2013, 614083.
20. Ghaedi, M.; Ansari, A.; Habibi, M.H.; Asghari, A.R. Removal of malachite green from aqueous solution by zinc oxide nanoparticle
loaded on activated carbon: Kinetics and isotherm study. J. Ind. Eng. Chem. 2014, 20, 17–28. [CrossRef]
21. Khalid, N.R.; Hammad, A.; Tahir, M.B.; Rafique, M.; Iqbal, T.; Nabi, G.; Hussain, M.K. Enhanced photocatalytic activity of Al and
Fe co-doped ZnO nanorods for methylene blue degradation. Ceram. Int. 2019, 45, 21430–21435. [CrossRef]
22. Hussain, M.K.; Khalid, N.R.; Tanveer, M.; Kebaili, I.; Alrobei, H. Fabrication of CuO/MoO3 pn heterojunction for enhanced dyes
degradation and hydrogen production from water splitting. Int. J. Hydrogen Energy 2022, 47, 15491–15504. [CrossRef]
23. Naghizade Asl, M.; Mahmodi, N.M.; Teymouri, P.; Shahmoradi, B.; Rezaee, R.; Maleki, A. Adsorption of organic dyes using
copper oxide nanoparticles: Isotherm and kinetic studies. Desalin. Water Treat. 2016, 57, 25278–25287. [CrossRef]
24. Alver, E.; Ayşegül, Ü.M. Anionic dye removal from aqueous solutions using modified zeolite: Adsorption kinetics and isotherm
studies. Chem. Eng. J. 2012, 200, 59–67. [CrossRef]
25. Khalid, N.R.; Arshad, A.; Tahir, M.B.; Hussain, M.K. Fabrication of p–n heterojunction Ag2 O@ Ce2 O nanocomposites make
enables to improve photocatalytic activity under visible light. Appl. Nanosci. 2021, 11, 199–206. [CrossRef]
26. Agarwal, H.; Shanmugam, V.K. A review on anti-inflammatory activity of green synthesized Zinc Oxide nanoparticle: Mechanism-
based approach. Bioorg. Chem. 2020, 94, 103423. [CrossRef]
27. Yadav, R.K.; Singh, A.K.; Singh, N.B.; Singh, N.; Khare, S.; Pandey, A.K. Green Synthesized Nanoparticle-Mediated Wastewater
Treatment. In Emerging Eco-Friendly Green Technologies for Wastewater Treatment; Springer: Singapore, 2020; pp. 299–309.
28. Das, M.; Samal, A.K.; Mhar, N. Butea monosperma leaf as an adsorbent of methylene blue: Recovery of the dye and reuse of the
adsorbent. Int. J. Environ. Sci. Technol. 2020, 17, 2105–2112. [CrossRef]
Crystals 2022, 12, 662 12 of 12
29. Vizuete, K.S.; Kumar, B.; Vaca, A.V.; Debut, A.; Cumbal, L. Mortiño (Vaccinium floribundum Kunth) berry assisted green synthesis
and photocatalytic performance of Silver–Graphene nanocomposite. J. Photochem. Photobiol. A Chem. 2016, 329, 273–279.
[CrossRef]
30. Vanaja, M.; Paulkumar, K.; Baburaja, M.; Rajeshkumar, S.; Gnanajobitha, G.; Malarkodi, C.; Sivakavinesan, M.; Annadurai, G.
Degradation of Methylene Blue Using Biologically Synthesized Silver Nanoparticles. Bioinorg. Chem. Appl. 2014, 2014, 742346.
[CrossRef]
31. Kumar, A.; Mazumdar, R.S.; Dhewa, T. Biological synthesis of silver nanoparticles by using Viola serpens extract. Asian Pac. J. Trop.
Dis. 2016, 6, 223–226. [CrossRef]