Comparative Efficacy of Biogenic Silver Nanoparticles
Synthesized by Pseudochrobactrum spp.
C5 and Chemically Synthesized Silver Nanoparticles for Catalytic Degradation of
Methylene Blue and 4-Nitrophenol Dyes
Khadija Siddique1,
Sabir Hussain1*, Muhammad Shahid2, Tanvir Shahzad1,
Faisal Mahmood1, Omer Sadak3, Sundaram Gunasekaran4,
Tahseen Kamal5 and Ikram Ahmad6*
1Department of
Environmental Sciences & Engineering, Government College University
Faisalabad, Faisalabad 38000, Pakistan
2Department of Bioinformatics
& Biotechnology, Government College University Faisalabad, Faisalabad
38000, Pakistan
3Department of
Electrical and Electronics Engineering, Ardahan University, 75000, Turkey
4College of
Agricultural and Life Sciences, University of Wisconsin-Madison, Wisconsin
53706, United States of America
5Department of
Chemistry, King Abdul Aziz University, Jeddah, Saudi Arabia
6Department of
Chemistry, University of Sahiwal, Sahiwal, Pakistan
*For Correspondence: sabirghani@gmail.com;
drikramahmad@uosahiwal.edu.pk
Received 21 August
2020; Accepted 24 September 2020; Published 10 December 2020
Abstract
In this study,
a novel bacterial strain, Pseudochrobactrum
spp. C5, was isolated from a wastewater sample and characterized for synthesis
of the silver nanoparticles (Ag-NPs). The physicochemical and catalytic
properties of biogenic Ag-NPs synthesized by involving the strain C5 were
compared with the Ag-NPs synthesized by a chemical reaction. The both types of
Ag-NPs were characterized for optical properties by UV-visible spectroscopy and
fourier-transform infrared spectroscopy (FT-IR), whereas, the morphological,
structural, chemical and electronic state properties were evaluated by field
emission scanning electron microscope (FESEM), X-ray diffraction (XRD) and
X-ray photoelectron spectroscopy (XPS). These analyses indicated that biogenic
Ag-NPs were nano-rod shaped particles ranging from 100–200 nm in size, whereas
the chemical Ag-NPs were agglomerated flower shaped structures ranging from 120–300
nm in size. Both types of Ag-NPs were observed to have negative zeta potential
values with -27.43 mV and -25.45 mV zeta potential for biogenic and chemically
synthesized Ag-NPs. The comparison of both types of Ag-NPs revealed the
presence of relatively higher metallic silver (Ag°) contents, larger available
surface for pollutant’s contact and larger distribution of particles in
biogenic Ag-NPs as compared to chemically synthesized Ag-NPs, which served for
higher catalytic activity. The biogenic Ag-NPs exhibited significantly higher
photocatalytic activity for degradation of methylene blue and 4-nitrophenol
dyes as compared with that of chemically synthesized Ag-NPs. The findings of
this study suggest that the biological Ag-NPs synthesized by Pseudochrobactrum spp. C5 might serve as
a potential green solution for treatment of dyes loaded textile wastewaters. ©
2021 Friends Science Publishers
Keywords: Microbial synthesis; Pseudochrobactrum spp.; Silver nanoparticles; Photocatalysis;
Methylene blue and 4-nitrophenol
Introduction
Nanotechnology is a vast field dealing with nano sized
particles. The nanoparticles have unique size dependent physicochemical
properties that give them privilege of an exclusive class to be used as
catalyst in numerous products. Shapes and features of surfaces, size,
opto-nanomechanical spectroscopic properties and nanoscale compositional
mapping define the performance of these heterogeneous catalysts (Korhonen et al.
2007; Tasbihi et al. 2007).
Silver nanoparticles (Ag-NPs) are the most commonly synthesized materials being
studied for different applications such as plant disease control, photonics,
electronics, anti-pathogenic and therapeutic activities and catalytic
degradation of synthetic dyes (Hu and Chan 2004;
Habouti et al. 2010; Joseph and
Mathew 2015; Wei et al. 2015).
The Ag-NPs are produced by various methods which might be based on chemical,
physical and biological processes (Abid et al. 2002; Kalimuthu et al. 2008; Nadagouda et al. 2011).
Chemical synthesis normally involves the chemical
reduction of silver salts by using a reducing agent (Bankura et al. 2012).
However, biological synthesis of nanoparticles has nowadays gained a
considerable interest of the scientific community because of being an
eco-friendly approach that gives different sizes and shapes with no or limited use
of harmful solvents (Maurer-Jones et al. 2009; Marquis et al. 2009; Love et al. 2012; Sharifi et al.
2012; Schrofel et al. 2014).
Biological systems are also economic options for nanoparticle fabrication due
to their least requirement of energy (Pearce et al. 2008). For example, bacteria with their unique property of metal
reduction are considered as a potential bio-resource for nanoparticles
synthesis (Shantkriti and Rani 2014; Noman et al. 2020). The resistance of
the bacteria to extreme environmental conditions makes them favourable
candidate for synthesis of such materials (Rouch
et al. 1995; Lee et al. 2019). Pseudomonas stutzeri AG 259 (isolated from silver mines)
was the first bacterial strain reported for the possibility of nanoparticle
synthesis by using microbial machinery (Haefeli et al. 1984). In that study, a
silver nitrate solution added with bacterial strain provided 200 nm sized, equilateral triangles and hexagons nanoparticle that were fixed within the bacterial cells (Joerger et al.
2000). Up till now different bacteria including Streptomyces
atrovirens, Shewanella oneidensis MR-1 strain and Bacillus strain CS
have been reported for synthesis of Ag-NPs (Song and Shi 2017; Subbaiya et al.
2017).
Industrialization is an important sector which is
playing a vital role in world economy. However, rapid industrialization has led
to introduction of enormous quantities of different types of pollutants
including the synthetic organic dyes into the environment (Imran et al.
2015). For instance, textile industries release massive quantities of
wastewaters which are loaded with different types of contaminants including the
synthetic dyes (Sharma and Anamika 2008; Imran et al. 2015). Some of the studies
reported that 15–50% of the dye stuff used during textile processing is
released in textile wastewaters without any treatment (Bisschops and Spanjers 2003; Carmen and Daniela 2012; Imran et al. 2015). The presence of
dyes in textile wastewaters negatively affects the quality of aquatic and soil
resources as well as the health of various living organisms including the human
beings (Imran et al. 2015, 2019). Hence, untreated dyes loaded wastewaters
are a burning issue that needs to be addressed with immediate actions to save
groundwater quality and different forms of life on earth (Dulkadiroglu et
al. 2002).
The use of nanoparticles for catalytic degradation of
synthetic dyes has nowadays gained a considerable attention worldwide (Jiang et al.
2009; Sheikh et al. 2016).
Nanoscale size and increased band gap are favourable qualities for redox
reactions and, hence, nanoparticles are now in extensive use for dyes removal
from textile wastewaters (Di et al. 2009; Noman et al. 2020). Different types of nanoparticles such as
titanium dioxide, zinc oxide, copper and magnesium oxide nanoparticles have
been reported for degradation of different synthetic dyes (Gozmen et al.
2009; Moussavi and Mahmoudi 2009; Khataee et
al. 2015; Noman et al. 2020).
However, Ag-NPs have gained considerable importance due to its electron relay
effect between donor and acceptor (Mallick et al. 2006; Zhou et al. 2006). The chemically produced Ag-NPs have also been
reported to be used in photocatalytic degradation of synthetic dyes (Edison et al.
2016; Mariselvam et al. 2016).
During the recent years, there is a growing interest in developing the green
strategies for pollution control including the wastewater treatment.
Biosynthesis of the nanomaterials for their application in different functions
including the treatment of wastewaters loaded with synthetic dyes is gaining a
considerable interest as a green approach (Song and Shi 2017; Noman et al. 2020). However, there is little
information about the application of the biogenic Ag-NPs as a catalyst for
degradation of dyes.
The
present study was conducted to isolate and characterize a novel bacterium, Pseudochrobactrum spp. C5, having the
potential for synthesis of silver nanoparticles. This biologically produced
silver nanomaterial was then characterized through FESEM (Field Emission
Scanning Electron Microscopy), FT-IR (Fourier Transform Infrared Spectroscopy),
DLS (Dynamic light scattering) technique, XRD (X-ray Diffraction) and XPS
(X-ray photoelectron spectroscopy). The characteristics of these biologically
synthesized silver nanoparticles were compared with that of the silver
nanoparticles produced by chemical process. Catalytic potential of bacterially
synthesized and chemically synthesized silver nanoparticles was evaluated using
methylene blue and 4-nitrophenol as target synthetic dyes.
Materials and Methods
Isolation of the
strain C5
Isolation of the Ag-NPs synthesizing
bacterial strain was carried out from a textile wastewater sample collected
from Khurrianwala, Faisalabad. Isolation of the bacterial colonies was carried
out following a serial dilution of the wastewater sample in mineral salt medium
as already reported by Hussain et al.
(2020). The purified bacterial isolates were exposed to different
concentrations of silver (50 to 2500 mg L-1), as silver nitrate in
mineral salt agar medium for evaluating their tolerance to silver in terms of
minimum inhibitory concentration (MIC). The isolates having the high values of
MIC of silver were tested for silver reduction in mineral salt medium incubated
under shaking in dark at 28°C. The most efficient silver tolerant bacterial
strain showing the good potential for silver reduction was chosen for the next
studies.
Identification of
the strain C5
Identification of the Ag-NPs producing selected
bacterial isolate was carried out through amplification, sequencing and
analysis of its 16S rDNA gene using 27f and 1492r primers according to the
method already reported by Hussain et al.
(2013). The sequence was analysed through NCBI Blast and by constructing a
phylogenetic tree as already reported by Hussain et al. (2013). The sequence was submitted in GeneBank Database under
accession number MT318655.
Biosynthesis of nanoparticles
The strain C5 was cultured in 50 mL nutrient broth (NB)
medium at 28°C under shaking (150 rpm) overnight. After 24 h incubation, the
culture of C5 was tested for its potential of Ag-NPs synthesis. For this
purpose, 0.003 M silver was used for
50 mL of bacterial growth culture. After adding the silver salt, all the
samples were kept under shaking at 150 rpm at 28°C. At the end of the reaction
time (24 h), the culture was collected and kept at 85°C for drying. The dried
product was collected and kept in muffle furnace at 700°C for 7 h to get it
calcinated.
Chemical
synthesis of nanoparticles
The Ag-NPs were chemically synthesized by reducing the
metal salt. In a typical experiment, 0.5 M
solution of silver nitrate was slowly hydrolyzed by adding 0.5 M NaOH (Qamar
et al. 2015). Solution mixture
was stirred and heated constantly until a brown colour was appeared. A fine
powder of precipitates was collected by calcination as already described above.
Characterizations of nanoparticles
UV-visible spectra of synthesized Ag-NPs were recorded
on Lambda 25, PerkinElmer spectrometer and FT-IR spectroscopy was done with
PerkinElmer Spectrum-100 FT-IR spectrometer (FTIR-Bruker TENSOR-27). The zeta
potential was estimated by a dynamic light scattering technique (Zeta PALS,
Brookhaven Instrument Corp., Holtsville, N.Y., U.S.A.) and particle size
distribution profile was studied using Dynamic light scattering (DLS)
technique, whereas, morphology was evaluated by FESEM (FESEM, LEO 1530-1).
X-ray Diffraction (PANalytical X’PERT PRO) was used to identify phase
transitions by using CuK-alpha radiations (Lambda= 0.1542 nm, 40 kV, 20 mA) and
Elemental composition was determined by X-ray photoelectron spectroscopy
(Thermo scientific K Alpha instrument).
The
catalytic activity of the biogenic and the chemically synthesized Ag-NPs was observed by
testing them for degradation of two selected synthetic dyes viz., methylene blue (MB) and
4-nitrophenol (4-NP). For this purpose, 1 mM
aqueous solutions of each of MB, 4-NP and NaBH4 were prepared. For
catalytic degradation of MB, the treatments consisted of MB added with NaBH4
(Control treatment), MB added with NaBH4 along with biogenic
Ag-NPs (T1) and MB added with NaBH4 along with chemically
synthesized Ag-NPs (T2). The experiment was conducted in three
replicates under completely randomized arrangement. For each treatment of this
experiment, ¾ of 1 mM MB solution was
added with ¼ of 1 mM NaBH4 solution
and distributed in nine cuvettes (Three cuvettes for each treatment). The
control treatment consisted of the three cuvettes containing only the combined
solution of MB and NaBH4. For the treatment T1, 10 mg of
the biogenic Ag-NPs in powdered form were added to each of the three cuvettes
containing the combined solution of MB and NaBH4. For the treatment
T2, 10 mg of the chemically synthesized Ag-NPs in powdered form were
added to each of the three cuvettes containing the combined solution of MB and
NaBH4. All the cuvettes were stirred constantly for 5 min and kept
in natural light to complete the reaction. At different time intervals over the
incubation period, the aliquots were taken, centrifuged (10000 rpm for 5 min)
and the supernatants were scanned at different wavelength from 500 to 800 nm
using the Perkin Elmer UV–Vis spectroscope (U.S.A.) to monitor the degradation
of MB. The similar treatments and procedure were followed for the experiment
carried out for 4-NP degradation in which all the reagents and conditions were
kept the same except that 1 mM 4-NP
solution was used instead of 1 mM MB
solution. The centrifuged solutions of 4-NP were scanned at different
wavelength from 200 to 600 nm using the Perkin Elmer UV–Vis spectroscope (USA)
to monitor the degradation of 4-NP. The incubation and scanning were carried
out until the both solutions were almost completely decolorized.
Over 60 min incubation period, aliquots were taken from all the
replicates of each sample, centrifuged (10000 rpm for 5 min) and analyzed at
668 nm (λmax) for methylene blue and 405 nm (λmax) for 4-Nitrophenol using the
Perkin Elmer UV–Vis spectroscope (U.S.A.). Decolorization was calculated as
below:
Fig. 1: Neighbour
joining phylogenetic tree of Pseudochobactrum
spp. C5
Fig. 2: The comparison of absorption spectra of biosynthesized
(a) and chemically synthesized (b) Ag-NPs
Where X and Y represents the control without any treatment
and the sample with treatment, respectively.
Statistical analysis
One way analysis of variance (ANOVA)
was performed to determine the significance of the treatment effects on
decolorization of methylene blue and 4-Nitrophenol separately. Tukey's HSD test was used for
multiple means comparisons for decolorization (%) for all the treatments. The
statistical analysis was performed using Statistix 8.1.
Results
Screening and
identification of silver nanoparticles producing bacterium
In this study, 28 different types of bacteria having
varying colony types and shapes were isolated and purified from the wastewater.
All the isolated bacteria were separately tested for MIC of silver by letting
them grow at varying concentrations of silver (50–2500 mg L-1) on mineral salt agar media plates. The isolates
showed varying levels of tolerance to the presence of silver in the medium. Out
of these tested 28 bacterial colonies, four bacterial isolates (C3, C5, C17,
C23) were found to resist the presence of even 2500 mg L-1 of silver in the medium. These selected four
silver tolerant bacterial isolates were tested for synthesis of nanoparticle.
On the basis of the silver tolerance and the synthesis of nanoparticles, the
isolate C5 was chosen for next studies. The analysis of 16S rDNA gene of this
strain on BlastN indicated that this strain belonged to genus Pseudochrobactrum. The phylogenetic
analysis also indicated that this strain was grouped with the bacterial strain
belonging to genus Pseudochrobactrum (Fig.
1). Based on BlastN and phylogenetic
analyses, it was designated as Pseudochrobactrum
spp. C5 (GeneBank Accession No. MT318655).
Different concentrations of
silver were tested for synthesis of its nanoparticle by the strain Pseudochrobactrum. The concentration of 800 mg L-1 of
silver was selected for synthesis of nanoparticles because an efficient
synthesis of prominent brown coloured Ag-NPs by Pseudochrobactrum spp.
C5 was detected at this concentration under the set conditions.
Characterization
of silver nanoparticles
Fig. 3: The comparison of zeta-potential profiles of biosynthesized (a)
and chemically synthesized (b) Ag-NPs
Fig. 4: The comparison of FT-IR
spectra of biosynthesized (Ag B)
and chemically synthesized (Ag C) silver nanoparticles. The inset figure is the
exploded view of the same from 500 to 2000 cm-1
Collective oscillations of
free electrons in resonance with light wave were detected by UV analyser.
Highest absorbance peaks were observed at 430 nm in case of biosynthesized
Ag-NPs (Fig. 2a) and a
sharp peak was observed at 420 nm in case of chemically synthesized Ag-NPs (Fig.
2b). To check the zeta potential,
charge and polarity of Ag-NPs, both the materials were dispersed in distilled
water and sonicated for 5 min to break the bonds between the particles. A
dynamic light scattering analyser characterized the illuminations of
de-aggregated molecules by a laser beam. Both the materials showed negative ZP
values. In case of biologically synthesized Ag-NPs, the average ZP value was
-27.43 mV (Fig. 3a) while
chemically synthesized Ag-NPs showed -25.54 mV ZP value (Fig. 3b).
The
FT-IR analysis provided the idea about interaction between the protein
structures and Ag-NPs. Very
small amount of dried powder of nanoparticles were analysed on Perkin Elmer one
IR spectrophotometer within the range of 500 to 4000 cm−1. The
spectra of biologically produced Ag-NPs
in the range of 500 to 4000 showed many sharp peaks at 3372 cm-1,
2117 cm-1, 1989 cm-1, 1646 cm-1, 1534 cm-1,
1421 cm-1, 1034 cm-1, 869 cm-1 and 553 cm-1
(Fig. 4). The FT-IR
spectra of chemically produced Ag-NPs
(Fig. 4) showed sharp peaks at
3452 cm-1, 3043 cm-1, 2893 cm-1, 2827 cm-1,
1677 cm-1, 1627 cm-1, 1435 cm-1, 1373 cm-1,
1055 cm-1 and 1007 cm-1 respectively.
The
morphology of both chemically and biologically synthesized Ag-NPs was estimated by FESEM. The
results indicated the agglomeration of chemically synthesized Ag-NPs with a flower like shape and
120–300 nm in size (Fig. 5a, b), while the biologically synthesized Ag-NPs were 100–200 nm in size and
nano-rod like shape (Fig. 5c, d). The phase formations
of both Ag-NPs were examined
with the XRD analysis.
Both the chemically produced and biogenic Ag-NPs showed characteristic peaks of Ag-NPs at 2θ= 38.3˚, 44.2˚, 64.5˚,
77.5˚, 33.3˚
and 47.6˚ (Fig. 6a, b).
The XPS analysis was carried out to
compare and investigate the chemical compositions of chemically
and biologically synthesized Ag-NPs.
High resolution 3d spectra in Fig. 7
showed peaks at 374.3 and 368.3 eV for chemically synthesized Ag-NPs while biologically synthesized
Ag-NPs showed a peak shift from
374.3, 368.3 eV to 374.8, 368.8 eV.
Photocatalytic degradation studies
Fig. 5: The comparison
FESEM images of chemically synthesized (a & b) and biosynthesized
(c & d) Ag-NPs at
different magnifications
Fig. 6: The comparison of XRD spectra of chemically synthesized
(a) and biosynthesized (b) Ag-NPs
Absorption
spectra of both the methylene blue and 4-nitrophenol showed a constant decrease
in peaks for both dyes at different time breaks as shown in Fig. 8. There was
an obvious trend of low absorption peaks as exposure time with catalyst
increased. The methylene blue has a broad peak at 666 nm and there was a slight
shift of λmax with addition of NaBH4 that is
considered to be a strong reducing agent (Fig. 8a). The slight shift is observed due to dilution effect and
there was no further decrease in position even after 30 min. The UV-Visible
spectral data of 1 mM methylene blue
solution that was treated against ¼ of NaBH4 and 10 mg of biological
Ag-NPs has been presented in Fig. 8b.
There was a constant decrease in peak intensity after addition of
biosynthesized catalyst and it just took 18 min of duration to fully degrade
the methylene blue (Fig. 8b)
while chemically synthesized Ag-NPs
degraded the same volume of methylene blue in 180 min (Fig. 8c).
In
case of 4-NP, a maximum absorption peak was observed at 400 nm and a slight
shift of λmax was also observed after 150 min due to dilution
effect (Fig. 8d). There was a
constant decrease in peak intensity after addition of biological Ag-NPs catalyst. The formation of 4-AP
was observed in 70 min when treated with biological Ag-NPs catalyst (Fig. 8e)
while chemically synthesized Ag-NPs
catalyst performed the same function in 140 min (Fig. 8f). Absorption kinetics of MB and 4-NP by biosynthesized and chemically synthesized Ag NPs are shown in Fig. 9.
The results clearly indicated that, over a 60 min
incubation period, the catalytic decolourization of both the methylene blue and
4-nitrophenol was significantly higher in the treatments where the biogenic
Ag-NPs were used as a catalyst as compared to the treatments where chemically
synthesized Ag-NPs were used (Fig. 10).
Discussion
In the
present study, the Ag-NPs producing Pseudochrobactrum spp. C5 was isolated
from the textile wastewater. The
bacterial culture was initially light yellow in colour before the addition of
silver salt that eventually started turning to brown with the addition of
silver and the colour was more intense with the passage of time. The specific
brown colour was an indication of silver nanoparticle formation as it has
already been described in a number of previous such studies (Joerger et al.
2000; Kalimuthu et al. 2008;
Manivasagan et al. 2013). Despite that few bacterial strains belonging
to different genera have been reported for synthesis of various nanoparticles (Subbaiya et
al. 2017; Song and Shi 2017; Noman et
al. 2020), to the best of our knowledge, there is not even a single report
regarding the synthesis of nanoparticles from the bacterial strains belonging
to the genus Pseudochrobactrum.
Hence, Pseudochrobactrum spp. C5
might be a novel potential bioresource for biosynthesis of nanoparticles.
Biosynthesis
of Ag-NPs by the strain C5 was further
confirmed by UV-Visible spectral analysis of the nanoparticles in which
specific peaks were observed at wavelengths of 430 nm (Fig. 2a) and 420 nm
(Fig. 2b) as indicator of specific brown colour as already previously reported
by Sondi and Salopek-Sondi (2004). The stability of the Ag-NPs was
determined by their zeta potential values because a nano-suspension with zeta potential values within the range of ± 30 mV
is supposed to be a stable suspension (Shameli et al. 2012). The zeta potential values of the biogenic and
chemically synthesized Ag-NPs were ranging between -25.54 mV and -27.43 mV
(Fig. 3), respectively, pointing towards a physical stability of both types of
Ag-NPs due to inter-particle repulsions.
Fig. 7: The comparison of High resolution XPS
spectra of Ag 3d for chemically
and biological synthesized Ag-NPs.
AgNPs-C and AgNPs-B represent the chemically and biologically synthesized Ag-NPs, respectively
Fig. 8: The comparison
of degradation of methylene blue in presence of NaBH4 (a),
NaBH4 and biosynthesized Ag-NPs (b) and NaBH4 and
chemically synthesized Ag-NPs (c) as well as the degradation of
4-nitrophenol in the presence of NaBH4 (d), NaBH4
and biosynthesized Ag-NPs (e) and NaBH4 and chemically
synthesized Ag-NPs (f). The absorbance spectra have been prepared on the
basis of mean values having the coefficient of variation values ranging from
1.2 to 9.7 %
The
FT-IR analyses of the Ag-NPs showed different characteristic peaks for both
types of nano-particles which represented different functional groups (Fig. 4).
In case of biogenic Ag-NPs (Fig. 4),
a sharp peak around 3372 cm-1 represented secondary amides (N-H
stretching, H-bond). Another peak at 2117 cm-1 indicated alkyne bond
stretching. The peak at 1989 cm-1 represented C-O stretching, the
peak at 1646 cm-1 represented C=C stretching, the peaks at 1534 cm-1
and 1421 cm-1 represented C-C stretching, the peaks at 1034 cm-1,
869 cm-1 indicated C-O stretching and the peak at 553 cm-1 indicated
=C–H bending (Phanjom and Ahmed
2015). The FT-IR spectra of chemically produced Ag-NPs showed sharp peaks at 3452 cm-1
and 3043 cm-1 which were indication of amino group stretching (Fig. 4). Peaks at 2893 cm-1 and
2827 cm-1 were showing C-H bond stretching, while the peaks at 1677
cm-1 and 1627 cm-1 were related to amine group
stretching. The peaks at 1435 cm-1 and 1373 cm-1 were
showing C=C bond stretching that were specific to aromatic amine group and the
peaks at 1055 cm-1 and 1007 cm-1 were an indication of
C=O bond stretching in proteins. Free amine group serves as bonding agents
between Ag-NPs and proteins. The
FESEM images (Fig. 5) suggested for a relatively smaller particle size of the
biogenic Ag-NPs resulting into a relatively higher surface area which might
result into a relatively better catalytic activity (Cheng et al. 2014). During XRD analysis, the characteristic peaks of Ag-NPs
at 2θ= 38.3˚,
44.2˚, 64.5˚, 77.5˚ (Fig. 6) corresponded to (111), (200), (220), and (311) planes,
respectively, and the data were matching well with those reports
in literature and the joint
committee on powder diffraction standards (JCPDS) file No. 04-0783. In addition
to these characteristic peaks, biological synthesized Ag-NPs showed unpredicted crystalline
structures peaks around 2θ= 33.3˚ and 47.6˚ which
can be due to carbon-based impurities which might be formed after the
calcination at 700˚C (Ahmad et al.
2012; Pasupuleti et al. 2013). As shown in high resolution 3d spectra of Ag-NPs in Fig. 7, the chemically synthesized Ag-NPs showed peaks at 374.3 and 368.3
eV which is corresponding to 3d3/2 and 3d5/2,
respectively, and separated by 6.0 eV. However, when biologically synthesized Ag-NPs were analysed, the peaks at
374.3 and 368.3 eV shifted to 374.8 and 368.8 eV. The shift in the binding
energy is attributed to higher metallic silver (Ag°) in biologically
synthesized Ag-NPs (Gurunathan et al. 2014).
The
photocatalytic degradation of both the methylene blue and 4-nitrophenol as
model dyes was carried out in the presence of sodium borohydride and Ag-NPs to check the catalytic
efficiency of both types of synthesized nanomaterials. As the methylene blue is
stable in almost all types of environment, it is often considered as a probe
pollutant in photocatalytic studies (Kamal et
al. 2016; Kamal 2019). Relatively faster photocatalytic decolourization of
methylene blue in the experiment containing biological Ag-NPs catalyst (Fig. 8) might be due to relatively large surface
area, smaller size and dispersion tendency of
biological Ag-NPs as compared to that
of the
Fig. 9: Plot of ln (At/A0) Vs Time of MB by biosynthesized
(a) and chemically synthesized (b)
Ag-NPs and of 4-NP by biosynthesized
(c) and chemically synthesized (d)
Ag-NPs
Fig. 10: Catalytic decolorization of methylene blue and
4-Nitrophenol in the presence of different treatments using the biogenic and
chemically synthesized Ag-NPs over an incubation period of 60 min
chemically synthesized Ag-NPs catalysts (Kamal
et al. 2016; Ahmad et al. 2017). The degradation rate of
4-nitrophenol was slower as compared to that of the methylene blue in the
presence of both types of Ag-NPs (Fig. 8). This might be due to the formation
of 4-aminophenol as an end product during the reduction of 4-nitrophenol in the
reaction catalysed by Ag-NPs.
The kinetic barrier between the donor BH4- and accepter
4-NP+ was covered by Ag-NPs
by lowering activation energy. Once the donor BH4- and
accepter 4-NP+ were absorbed on the surface of Ag-NPs, catalytic reduction took place
by transferring the electron from BH4- to
p-nitrophenolate ion (Khan et al.
2016). This conversion might have been achieved by the formation of an
intermediate 4-nitophenolate ion. The faster degradation rate of 4-nitrophenol
in presence of biologically synthesized Ag-NPs,
used as catalyst, can be better explained in terms of its relatively large surface area, smaller
size and dispersion tendency as
compared to chemically synthesized Ag-NPs catalysts (Kamal et al. 2016; Ahmad et al. 2017). Adsorption
kinetics plays a major role in degradation process (Baransi et al. 2012). It has been observed that
photocatalytic particles adsorb organic components of solution coming on
surface from the bulk of material. In the experiment containing biologically
synthesized Ag-NPs as catalyst, a slower degradation was observed at the start
of the experiment which can be better explained by adsorption kinetics for
methylene blue and 4-nitrophenol, respectively (Fig. 9). Once the particles get
settled, the biological Ag-NPs catalyst starts working and a fast degradation
rate is observed (Fig. 9) as
also previously reported by Khan et al.
(2016). However, in case of the experiments containing chemically
synthesized Ag-NPs, a constant pattern
of decolourization of both the dyes was observed as can be found in the
adsorption kinetics calculated for methylene blue and 4-nitrophenol,
respectively. All these findings suggest for higher catalytic efficiency of the
biologically synthesized Ag-NPs as compared to the chemically synthesized
Ag-NPs. The potential of photocatalytic degradation of synthetic dyes by the
biogenic Ag-NPs synthesized by the strain C5 is an important feature which can
be exploited for treatment of the coloured textile wastewaters that can
be a potential threat to the quality of water that ultimately affects all life
forms on earth (Imran et al. 2019; Noman et al.
2020).
Conclusion
Findings of
this study concluded that Pseudochrobactrum
spp. C5 isolated from a textile wastewater might be a potential candidate for
green synthesis of stable Ag-NPs with variable shapes and uniform dispersion.
Moreover, it was concluded that biosynthesized Ag-NPs were catalytically more efficient in decolorizing the model dyes
methylene blue and 4-nitrophenol as compared to chemically synthesized Ag-NPs. Hence, the Ag-NPs synthesized by Pseudochrobactrum spp. C5 might be
effectively used for devising the environment friendly green strategies for
treatment of wastewaters containing the dyes.
Acknowledgement
The authors
acknowledge the ‘Department of Environmental Sciences & Engineering,
Government College University Faisalabad, Pakistan’ and the ‘College of Agricultural and
Life Sciences, University of Wisconsin-Madison, USA for providing
the research facilities for conducting this research. The authors are also
grateful to Higher Education Commission (HEC), Pakistan for providing funding
under Indigenous PhD Fellowships (Phase II, Batch III) No. 315-3044-2SS3-022/HEC/Sch-Ind/2015.
Author Contributions
KS conducted
all the experiments and wrote the first draft of the manuscript. SH and IA were
involved in planning and supervising the experiments as well as final write-up
of the manuscript. MS, TS and FM helped in conducting the experiments and in
improving the write-up of the manuscript. OS, SG and TK supported in
characterization of the nanoparticles as well as in write-up of the manuscript.
References
Abid JP, A Wark, PF Brevet, H Girault (2002). Preparation of silver nanoparticles
in solution from a silver salt by laser irradiation. Chem Commun 7:792–793
Ahmad
I, SB Khan, T Kamal, AM Asiri (2017). Visible light activated degradation of
organic pollutants using zinc–iron selenide.
J Mol Liq 229:429–435
Ahmad
N, S Sharma, R Rai (2012). Rapid green synthesis of silver and gold
nanoparticles using peels of Punica
granatum. Adv Mater Lett 3:376–380
Bankura K, D Maity,
MM Mollick, D Mondal, B Bhowmick, M Bain, A Chakraborty, J Sarkar, K Acharya, D
Chattopadhyay (2012). Synthesis, characterization and antimicrobial activity of
dextran stabilized silver nanoparticles in aqueous medium. Carbohydr Polym 89:1159–1165
Baransi
K, Y Dubowski, I Sabbah (2012). Synergetic effect between photocatalytic
degradation and adsorption processes on the removal of phenolic compounds from olive mill wastewater. Water Res 46:789–798
Bisschops I, H
Spanjers (2003). Literature review on textile wastewater characterisation. Environ Technol 24:1399–1411
Carmen Z, S Daniela
(2012). Textile organic dyes–characteristics,
polluting effects and separation/elimination procedures from industrial
effluents–a critical overview, Vol. 2741,
p:31. Org Pollutants Ten Years After the Stockholm Convention-environ and Anal
Update
Cheng
H, J Wang, Y Zhao, X Han (2014). Effect of phase composition, morphology, and
specific surface area on the photocatalytic activity of TiO2
nanomaterials. RSC Adv 4:47031–47038
Di X, SK Kansal, W
Deng (2009). Preparation, characterization and photocatalytic activity of
flowerlike cadmium sulfide nanostructure. Sep
Purif Technol 68:61–64
Dulkadiroglu H, S
Dogruel, D Okutman, I Kabdaşlı, S Sözen, D Orhon (2002). Effect of
chemical treatment on soluble residual COD in textile wastewaters. Water Sci Technol 45:251–259
Edison TNJI, R
Atchudan, MG Sethuraman, YR Lee (2016). Reductive-degradation of carcinogenic
azo dyes using Anacardium occidentale
testa derived silver nanoparticles. J
Photochem Photobiol B Biol 162:604–610
Gozmen B, M Turabik,
A Hesenov (2009). Photocatalytic degradation of Basic Red 46 and Basic Yellow
28 in single and binary mixture by UV/TiO2/periodate system. J Hazard Mater 164:1487–1495
Gurunathan S, J Raman, SN Malek, P John, S Vikineswary
(2014). Green synthesis of silver
nanoparticles using Ganoderma neo-japonicum Imazeki: A potential
cytotoxic agent against breast cancer cells. Intl J Nanomed 8:4399–4413
Habouti S, CH
Solterbeck, M Es-Souni (2010). Synthesis of silver nano-fir-twigs and
application to single molecules detection. J
Mater Chem 20:5215–5219
Haefeli C, C
Franklin, KE Hardy (1984). Plasmid-determined silver resistance in Pseudomonas stutzeri isolated from a
silver mine. J Bacteriol 158:389–392
Hu X, C Chan (2004).
Photonic crystals with silver nanowires as a near-infrared superlens. Appl Phys Lett 85:1520–1522
Hussain
S, Z Maqbool, M Shahid, T Shahzad, S Muzammil, M Zubair, M Iqbal, I Ahmad, M
Imran, M Ibrahim, F Mahmood (2020). Simultaneous removal of reactive dyes and
hexavalent chromium by a metal tolerant Pseudomonas
spp. WS-D/183 harboring plant growth promoting traits. Intl J Agric
Biol 23:241–252
Hussain S, Z Maqbool, S Ali, T Yasmeen, M Imran, F Mahmood, F Abbas
(2013). Biodecolorization of reactive black-5 by a metal and salt tolerant bacterial strain Pseudomonas spp. RA20 isolated from Paharang drain effluents in Pakistan. Ecotoxicol Environ Saf 98:331–338
Imran M, M Ashraf, S
Hussain, A Mustafa (2019). Microbial biotechnology for detoxification of
azo-dye loaded textile effluents: A critical review. Intl J Agric Biol 22:1138–1154
Imran M, M Arshad, A
Khalid, S Hussain, MW Mumtaz, DE Crowley (2015). Decolorization of Reactive
Black‐5 by Shewanella
spp. in the Presence of Metal Ions and Salts. Water Environ Res 87:579–586
Jiang R, H Zhu, X Li, L Xiao (2009). Visible light
photocatalytic decolourization of CI Acid Red 66 by chitosan capped CdS
composite nanoparticles. Chem Eng J
152:537–542
Joerger R, T Klaus,
CG Granqvist (2000). Biologically produced silver–carbon composite materials
for optically functional thin‐film
coatings. Adv Mater 12:407–409
Joseph S, B Mathew (2015).
Facile synthesis of silver nanoparticles and their application in dye
degradation. Mater Sci Eng B 195:90–97
Kalimuthu K, RS
Babu, D Venkataraman, M Bilal, S Gurunathan (2008). Biosynthesis of silver
nanocrystals by Bacillus licheniformis.
Colloid Surf B Biointerf 65:150–153
Kamal
T (2019). Aminophenols formation from nitrophenols using agar biopolymer
hydrogel supported CuO nanoparticles catalyst. Polym Test 77:105896
Kamal
T, Y Anwar, SB Khan, MTS Chani, AM Asiri (2016). Dye adsorption and
bactericidal properties of TiO2/chitosan coating layer. Carbohydr
Polym 148:153–160
Khan
SB, SA Khan, HM Marwani, EM Bakhsh, Y Anwar, T Kamal, AM Asiri, K Akhtar
(2016). Anti-bacterial PES-cellulose composite spheres: Dual character toward
extraction and catalytic reduction of nitrophenol. Rsc Adv 6:110077–110090
Khataee A, A Karimi,
S Arefi-Oskoui, RDC Soltani, Y Hanifehpour, B Soltani (2015). Sonochemical
synthesis of Pr-doped ZnO nanoparticles for sonocatalytic degradation of Acid
Red 17. Ultrason Sonochem 22:371–381
Korhonen ST, SM
Airaksinen, MA Banares, AOI Krause (2007). Isobutane dehydrogenation on
zirconia-, alumina-, and zirconia/alumina-supported chromia catalysts. Appl Catal A Gen 333:30–41
Lee NY, WC Ko, PR
Hsueh (2019). Nanoparticles in the Treatment of Infections Caused by
Multidrug-Resistant Organisms. Front Pharmacol
10; Article 1153
Love SA, MA
Maurer-Jones, JW Thompson, YS Lin CL Haynes (2012). Assessing nanoparticle
toxicity. Annu Rev Anal Chem 5:181–205
Mallick K, M
Witcomb, M Scurrell (2006). Silver nanoparticle catalysed redox reaction: An
electron relay effect. Mater Chem Phys 97:283–287
Manivasagan P, J Venkatesan, K Senthilkumar, K
Sivakumar, SK Kim (2013). Biosynthesis, antimicrobial and cytotoxic effect of
silver nanoparticles using a novel Nocardiopsis
spp. MBRC-1. Biomed Res Intl 2013; Article 287638
Mariselvam R, A Ranjitsingh, P Mosae Selvakumar, AA
Alarfaj, MA Munusamy (2016). Spectral studies of UV and solar photocatalytic
degradation of AZO dye and textile dye effluents using green synthesized silver
nanoparticles. Bioinorg Chem Appl 2016;
Article 8629178
Marquis BJ, SA Love,
KL Braun, CL Haynes (2009). Analytical methods to assess nanoparticle toxicity.
Anlst 134:425–439
Maurer-Jones MA, KC
Bantz, SA Love, BJ Marquis, CL Haynes (2009). Toxicity of therapeutic
nanoparticles. Nanomed 4:219–241
Moussavi G, M
Mahmoudi (2009). Removal of azo and anthraquinone reactive dyes from industrial
wastewaters using MgO nanoparticles. J
Hazard Mater 168:806–812
Nadagouda MN, TF
Speth, RS Varma (2011). Microwave-assisted green synthesis of silver
nanostructures. Accounts Chem Res
44:469–478
Noman
M, M Shahid, T Ahmed, MBK Niazi, S Hussain, F Song, I Manzoor (2020). Use of
biogenic copper nanoparticles synthesized from a native Escherichia spp. as photocatalysts for azo dye degradation and
treatment of textile effluents. Environ Pollut 257; Article 113514
Pasupuleti
VR, TNVKV Prasad, RA Shiekh, SK Balam, G Narasimhulu, CS Reddy, IA Rahman, SH
Gan (2013). Biogenic silver nanoparticles using Rhinacanthus nasutus leaf extract: Synthesis, spectral analysis,
and antimicrobial studies. Intl J Nanomed 8:3355–3364
Pearce CI, VS Coker,
JM Charnock, RA Pattrick, JFW Mosselmans, N Law, TR Beveridge, JR Lloyd (2008).
Microbial manufacture of chalcogenide-based nanoparticles via the reduction of selenite using Veillonella atypica: An in
situ EXAFS study. Nanotechnol 19:1–13
Phanjom
P, G Ahmed (2015). Biosynthesis of silver
nanoparticles by Aspergillus oryzae (MTCC No. 1846) and its
characterizations. Nanosci Nanotechnol 5:14–21
Qamar MT, M Aslam,
IM Ismail, N Salah, A Hameed (2015). Synthesis, characterization, and sunlight
mediated photocatalytic activity of CuO coated ZnO for the removal of
nitrophenols. ACS Appl Mater Interf
7:8757–8769
Rouch DA, BT Lee, AP
Morby (1995). Understanding cellular responses to toxic agents: A model for
mechanism-choice in bacterial metal resistance. J Ind Microbiol 14:132–141
Schrofel A, G
Kratosova, I Safarik, M Safarikova, I Raska, LM Shor (2014). Applications of
biosynthesized metallic nanoparticles–a review. Acta Biomater 10:4023–4042
Shantkriti S, P Rani (2014).
Biological synthesis of copper nanoparticles using Pseudomonas fluorescens. Intl
J Curr Microbiol Appl Sci 3:374–383
Sharifi S, S
Behzadi, S Laurent, ML Forrest, P Stroeve, M Mahmoudi (2012). Toxicity of
nanomaterials. Chem Soc Rev 41:2323–2343
Sharma A, SJ Anamika
(2008). Screening of microorganisms for azo dye degradation from dye affected
sites of Sanganer, Rajasthan, India. J
Pure Appl Microbiol 2:365–372
Sheikh MUD, GA
Naikoo, M Thomas, M Bano, F Khan (2016). Solar-assisted photocatalytic
reduction of methyl orange azo dye over porous TiO2 nanostructures. New J Chem 40:5483–5494
Shameli K, MB Ahmad,
EA JaffarAlMulla, NA Ibrahim, P Shabanzadeh, A Rustaiyan, Y Abdollahi, S
Bagheri, S Abdolmohammadi, MS Usman, M Zidan (2012). Green biosynthesis of
silver nanoparticles using Callicarpa maingayi
stem
bark extraction. Molecules
17:8506–8517
Sondi I, B
Salopek-Sondi (2004). Silver nanoparticles as antimicrobial agent: A case study
on E. coli as a model for Gram negative bacteria. J Colloid Interf Sci 275:177–182
Song X, X Shi
(2017). Bioreductive deposition of highly dispersed Ag nanoparticles on carbon
nanotubes with enhanced catalytic degradation for 4-nitrophenol assisted by Shewanella oneidensis MR-1. Environ Sci Pollut Res 24:3038–3044
Subbaiya R, M
Saravanan, AR Priya, KR Shankar, M Selvam, M Ovais, R Balajee, H Barabadi
(2017). Biomimetic synthesis of silver nanoparticles from Streptomyces atrovirens and their potential anticancer activity
against human breast cancer cells. IET
Nanobiotechnol 11:965–972
Tasbihi M, F Feyzi,
M Amlashi, A Abdullah, A Mohamed (2007). Effect of the addition of potassium
and lithium in Pt–Sn/Al2O3 catalysts for the
dehydrogenation of isobutane. Fuel Proc
Technol 88:883–889
Wei L, J Lu, H Xu, A
Patel, ZS Chen, G Chen (2015). Silver nanoparticles: Synthesis, properties, and
therapeutic applications. Drug Discov
Today 20:595–601
Zhou WP, A Lewera, R
Larsen, RI Masel, PS Bagus, A Wieckowski (2006). Size effects in electronic and
catalytic properties of unsupported palladium nanoparticles in electrooxidation
of formic acid. J Phys Chem B 110:13393–13398