Accepted Manuscript

Photocatalytic activity of biogenic silver nanoparticles synthesized using potato

(Solanum tuberosum) infusion

Kaushik Roy, C.K. Sarkar, C.K. Ghosh

PII: S1386-1425(15)00222-X
DOI: http://dx.doi.org/10.1016/j.saa.2015.02.058
Reference: SAA 13360

To appear in: Spectrochimica Acta Part A: Molecular and Biomo-

lecular Spectroscopy

Received Date: 25 September 2014

Revised Date: 6 January 2015
Accepted Date: 16 February 2015

Please cite this article as: K. Roy, C.K. Sarkar, C.K. Ghosh, Photocatalytic activity of biogenic silver nanoparticles
synthesized using potato (Solanum tuberosum) infusion, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy (2015), doi: http://dx.doi.org/10.1016/j.saa.2015.02.058

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Photocatalytic activity of biogenic silver nanoparticles synthesized using
potato (Solanum tuberosum) infusion
Kaushik Roy a, b, C.K. Sarkar a, C.K. Ghosh b *
a
Department of Electronics and Telecommunication Engineering, Jadavpur University, Kolkata-
700032, India
b
School of Material Science and Nanotechnology, Jadavpur University, Kolkata-700032, India
*
Corresponding author’s email id: chandu_ju@yahoo.co.in

Abstract: In this study, we have reported a fast and eco-benign procedure to synthesis silver

nanoparticle at room temperature using potato (Solanum tuberosum) infusion along with the study of

its photocatalytic activity on methyl orange dye. After addition of potato infusion to silver nitrate

solution, the color of the mixture changed indicating formation of silver nanoparticles. Time dependent

UV-Vis spectra were obtained to study the rate of nanoparticle formation with time. Purity and

crystallinity of the biogenic silver nanoparticles were examined by x-ray diffraction (XRD). Average

size and morphology of the nanoparticles were characterized by dynamic light scattering (DLS) and

transmission electron microscopy (TEM). Fourier transform infra-red spectroscopy (FTIR) was

employed to detect functional bio-molecules responsible that contribute to the reduction and capping

of biosynthesized Ag nanoparticles. Further, these synthesized nanoparticles were used to investigate

their ability to degrade methyl orange dye under sunlight irradiation and the results showed effective

photocatalytic property of these biogenic silver nanoparticles.

Keywords: Silver nanoparticles, Potato (Solanum tuberosum) infusion, UV-Vis Spectroscopy, TEM,

Dye degradation, Photocatalytic activity

1
1. Introduction:

Textile, cosmetic and paper industries widely use various dyes which are synthetic organic compounds.

These organic compounds are non-biodegradable and hazardous chemicals that cause serious

environmental pollution. So, it remains a challenge to the research community to degrade these toxic

dyes and save the environment from severe pollution. The conventional methods like electro-

coagulation [1], carbon sorption [2], redox treatment [3], flocculation [4], UV photo degradation [5]

etc. are used frequently for removing toxic dyes from environment. But there is a growing demand for

fast, effective and improved method for degradation and removal of these hazardous organic dyes [6].

In recent times, metallic nanoparticles are found to have impressive photocatalytic property for

degradation of organic compounds under visible light irradiation (at ambient temperature) [7].

Nanoparticles having very high surface to volume ratio possess large fraction of highly active surface

atoms which are exposed to hazardous material [8]. The size, shape and morphology of these

nanoparticles determine this fraction of surface atoms, hence improves the catalytic properties in

comparison to bulk materials [9]. For synthesis of metallic nanoparticles, numerous routes like

physical, chemical and biological green routes are frequently used [10, 11]. Among them, the green

synthesis of metallic nanoparticles has emerged as a potential method as it is a simple, fast and eco-

benign alternative to well-known chemical and physical procedures. In particular, silver nanoparticles

have been reported to be synthesized using numerous microbe-mediated [12 - 14] and plant mediated

methods [15 - 18]. Recently, the synthesis of nanoparticles using plant-mediated procedures are found

to be better and easier than the microbe mediated methods as they don’t involve any maintenance or

preservation of microbe cultures [19]. Leaf and fruit extracts of various plants have already been

reported to have impressive ability for reducing silver ions into Ag metallic nanoparticles [20-24]. But,

very few reports are available on using other parts of a plant for the same purpose [25, 26]. In this

2
paper, silver nanoparticles were prepared from silver salt using infusion of potato (Solanum

tuberosum) tuber that is easily available in common market and cheaper than other vegetables.

Potato (Solanum tuberosum) is one of the world’s primary food crops, whose edible part is its

underground tuber. The plant of potato is herbaceous with spiral leaf arrangement and a swollen end of

stem that is laid underground [27]. This underground stem or tuber is a rich source of bioactive

substances like amino acids, protein, thiamine and ascorbic acid as well [28]. Hence, the infusion of

tuber of potato seemed to be a good choice for preparing Ag nanoparticles from silver nitrate solution.

The aim of this research was to synthesize Ag nanoparticles from AgNO3 solution using potato

(Solanum tuberosum) infusion and study of the photocatalytic degradation of methyl orange dye in the

presence of this biosynthesized nanosilver under solar irradiation.

2. Materials and Methods:

2.1 Preparation of silver nanoparticles

Fresh potatoes (shown in Figure 1) were collected from nearest market for preparation of standard

potato (Solanum tuberosum) infusion. 200 g potatoes were cleaned, peeled and cut into small pieces

and boiled in 1000 ml double distilled water at 90ºC for 15 min. The mixture was then cooled down

and the supernatant was filtered to obtain potato infusion (200g/l). To prepare 20 mM stock solution of

silver nitrate (purchased from Merck India Ltd.), 0.34 g of AgNO3 was dissolved in 100 ml deionized

water. For preparing biogenic silver nanoparticles, 100 ml potato infusion was added dropwise to 100

ml silver nitrate solution (conc. 20 mM) so that the final concentration of the mixture remained 10 mM.

The mixture was kept at room temperature and its color began to change within a few minutes of

addition of potato infusion. After completion of reaction (almost after 24 hours of incubation), the

colloidal nanoparticles were separated from the mixture by centrifuging the mixture at 10000 rpm for

3
30 min. The obtained soup was discarded and the pellet formed at the bottom of the centrifuge tube

was redispersed in 20 ml de-ionized water and centrifuged again at 10000 rpm for 15 min to enhance

the purity of nanosilver. At the end, the precipitate deposited at the bottom of tube was collected

carefully and dried in high vacuum to get dried powder of silver nanoparticles for further study.

2.2 Characterization of Silver nanoparticles

The optical study of the mixture was carries out by measuring UV-Vis spectra of the mixture at

different time using Perkin Elmer spectrometer between 300-800 nm wavelength ranges. The X-ray

diffraction analysis of dried silver nanoparticles was carried out by Rigaku Ultima-III x-ray

diffractometer (operating voltage 40 kV, CuKα radiation with λ = 0.154 nm). FTIR spectrum of the dry

nanoparticles was obtained using IR-Prestige Fourier transform infra-red spectroscope (Shimadzu,

Japan). To prepare sample for TEM and DLS analysis, the dried powder of Ag nanoparticles was

suspended in certain amount of deionized water keeping concentration of 50µg/ml. This suspension of

Ag nanoparticles was scanned using a Malvern dynamic light scattering analyzer (Zetasizer Nano

ZS90, UK) to investigate the average size of biogenic silver nanoparticles. The grid for TEM analysis

was prepared by placing a drop of the suspension on copper grid and drying further the grid in vacuum.

The grid was scanned by JEOL-2010 high resolution TEM (operating voltage 200 kV) to study the

shape and size of these Ag nanoparticles.

2.3 Study of Photocatalytic activity

The photocatalytic activity of the biogenic Ag nanoparticles was evaluated by degradation of methyl

orange dye under solar irradiation. At first, the aqueous stock solution of methyl orange was prepared

by dissolving 10 mg of methyl orange powder (purchased from Merck India Ltd.) in 1000 ml double

4
distilled water maintaining a concentration of 10mg/l. To study the photocatalytic activity of silver

nanoparticles, about 10 mg of Ag nanoparticles was added to 20 ml of methyl orange dye solution. A

control was also kept under the same condition without adding nanoparticles to compare any change in

the coloration. The suspension was stirred for half an hour in dark before exposing to sunlight to

establish equilibrium of silver nanoparticles in the mixture. Then the suspension was put under solar

irradiation with constant stirring. The average temperature during the experiment was measured to be

30ºC with mean shinning duration of 8 hours. At regular interval (2 hrs.), 3-4 ml suspension was taken

from reacting suspension, centrifuged and the obtained soup was scanned by UV-Vis spectrometer

(Perkin Elmer, USA) to observe the degradation of the methyl orange in the solution [7].

3. Result and Discussions

3.1 UV-Vis spectroscopy

It is reported that the tuber of potato (Solanum tuberosum) contains bioactive functional molecules;

hence the infusion may reduce silver ions in the solution. When the infusion of potato (Solanum

tuberosum) was added to the aqueous solution of silver nitrate, the solution initially remained as a

colorless. But after few minutes, the color of the mixture began to turn into dark yellow denoting the

reduction of silver cations and formation of silver nanoparticles in the solution. The solution color

intensified to dark brown after half an hour as shown in Figure 2. The observed change in color of the

mixture arises due to the surface plasmon resonance of silver nanoparticles [29]. The colloidal solution

was scanned under UV-Vis spectroscope and the maximum absorbance at 430 nm verified the

generation of Ag nanoparticles. The UV-Vis spectra of the solution were recorded at different time

intervals (10, 25, 45, 90 min and 24 hrs) to have a perspective of nanoparticles formation rate in the

solution (shown in Figure 3). The peak at 430 nm was found to be increasing with the reaction time

5
and the variance of maximum absorbance with time is depicted in the inset of Figure 3. The inset

figure shows that the absorbance increases almost linearly up to 45 minutes of reaction time suggesting

the formation of more number of nanoparticles in mixture [30]. Beyond 90 minutes of incubation, the

formation tends to saturate leading to the completion of reaction.

3.2 XRD Analysis

Six distinct diffraction peaks at 2θ = 27.78°, 32.04°, 46.12°, 54.86°, 57.28° and 76.78° were observed

in the x-ray diffraction pattern of a typical biosynthesized nanoparticles (represented in Figure 4).

These diffraction peaks can be attributed to the (220), (122), (231), (331), (241) and (311) planes of

silver respectively (JCPDS: File No. 4-783). This indicates the nanoparticles are face centre cubic and

well crystalline by nature.

3.3 DLS and TEM analysis

Figure 5 shows the size distribution profile of these biosynthesized silver nanoparticles. The DLS

study is required to investigate the particle size in colloidal solution and the curve obtained by

scanning suspension of Ag nanoparticles indicates the average size (diameter) of the silver

nanoparticles to be around 10 - 12 nm.

The high resolution TEM images reveal the size, shape and morphology of these biologically

synthesized Ag nanoparticles (shown in Figure 6). It can be observed from TEM images that the

nanoparticles are almost spherical in shape with a diameter nearly 10 - 12 nm. The lattice fringes

indicate highly crystalline structure whereas the interplanar spacing is found to be 0.283 nm that

corresponds to the (122) planes of the biogenic silver nanoparticles.

3.4 FTIR Spectroscopy

6
FTIR spectroscopy of both the extract and the nanoparticles were used (in absorbance mode) to

identify the bioactive molecules responsible for reduction and capping of Ag nanoparticles. The FTIR

spectrum of the potato (Solanum tuberosum) extract shows eight noticeable peaks (shown in Figure 7).

Bands observed at 1653 and 3289 cm-1 may be attributed to the C=O stretching of amides and O-H

stretching of aromatic compounds (like phenol, ascorbic acid etc.) respectively [31]. Bands at 977 and

1394 cm-1 indicate the C-H bending of alkenes and alkanes respectively [32]. The band at 1071 cm-1

denotes the stretching vibration of C-N bond present in amines whereas a band at 1571 cm-1 denotes

the bending of C-H bonds present in hydrocarbons [33]. Two remaining bands at 542 and 651 cm-1

may be assigned to the stretching vibration of halo-alkanes [34, 35]. As presented in Figure 7, the

FTIR spectrum of Ag-based sample appears to be less intensed and broadened. The peaks at 977 and

1571 cm-1 corresponding to C-H bonding of alkenes and hydrocarbons disappeared. On the other hand,

C=O, C-H and C-N vibration of amide and amine groups are shifted. Therefore, we may conclude that

the synthesized Ag nanoparticles are capped by amide and amine group. As observed from the UV-Vis

spectroscopy of the Ag nanoparticles, the plasmon peak position didn’t change significantly indicating

that the size of the synthesized Ag nanoparticles remains unchanged. Such stabilization of particle size

seems to be consequences of capping by amide and amine groups [36]. From this analysis, it is clear

that the aromatic compounds like phenol, ascorbic acid etc. along with the amines present in potato

(Solanum tuberosum) infusion possibly reduce silver ions and stabilize the colloidal particles gradually

in the medium.

3.5 Photocatalytic degradation

7
Photocatalytic activity of the biogenic Ag nanoparticles was studied by degradation of methyl orange

under sunlight irradiation. The characteristic peak of absorption for methyl orange dye was observed to

be close to 460 nm. The degradation of the dye in presence of Ag nanoparticles was confirmed by the

gradual decrease of its absorption peak intensity (at 460 nm) within 8 hours of observation (as shown

in Figure 8). The control showed no change of color or peak intensity within the observation period.

Percentage of dye degradation was manipulated by the following formula and its variation with

exposure time is shown in Figure 9.

Dye degradation (%) = [(C0 – Ct) / C0] × 100

Here, C0 is the initial concentration of the methyl orange solution and Ct is the concentration of the dye

solution after t hours of exposure in sunlight. All dye concentrations were measured by the absorbance

value at 460 nm in UV spectra as the absorbance is directly proportional to the concentration here.

Earlier studies reported that, in comparison to other irradiation methods, solar irradiation acts faster for

degrading methyl orange (C14H14N3NaO3S, shown in the inset of Figure 9) in presence of nanosized

metal catalysts [37]. Methyl orange, having azo (-N = N-) and diethylamine group, is an anionic

organic dye that possesses mutagenic properties. Hence, it is harmful for living creatures and should be

degraded before exposure to the environment [38]. Its catalytic degradation process is initiated by the

striking of colloidal Ag nanoparticles by photons of sunlight and the degradation mechanism involves

the excitation of conduction electrons of metallic Ag through surface plasmon resonance effect [39].

The excited surface electrons are captured by dissolved oxygen molecules on its surface and produces

hydroxyl radical as described by Mahmoud et al. [40]. Capture of electrons by oxygen molecules

leaves Ag+ ions that later get attracted towards anionic methyl orange dye [41]. The created hydroxyl

radicals further oxidize methyl orange molecules adsorbed on the surface of the Ag nanoparticles into

8
its degradation by-products [42]. Hence, for degradation of organic dyes under visible light irradiation,

silver nanoparticles may be used as highly stable and effective photocatalysts [43].

4. Conclusion

Now-a-days biological synthesis of metallic nanoparticles has drawn the attention of research

community as it is a clean, non-hazardous and eco-friendly alternative to well-known chemical

procedures. We successfully synthesized silver nanoparticles from silver nitrate solution using potato

(Solanum tuberosum) infusion. The organic molecules present in the infusion reduced the silver ions

leading to the formation and stabilization of Ag nanoparticles. The biogenic nanoparticles were found

to be nearly spherical in shape with an average diameter of 10 - 12 nm. The photocatalytic study

showed that these biosynthesized Ag nanoparticles possess effective photocatalytic property for

degrading methyl orange dye in the presence of sunlight. Hence, they can be used in waste water

treatment and textile effluent technologies as well.

Acknowledgement

One of the authors (Kaushik Roy) thanks CSIR for financial assistance (Senior Research Fellowship).

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All Figures

12
 Figure 1: Fresh potato (Solanum tuberosum)

Figure 2: Color change of the mixture with incubation time

13
Figure 3: UV spectra of the colloidal solution at different time intervals. Inset curve shows variation of
maximum absorbance with reaction time

14
Figure 4: X-ray diffraction pattern of biogenic silver nanoparticles

Figure 5: Particle size distribution of synthesized Ag nanoparticles

15
Figure 6: TEM images of silver nanoparticles at various magnifications

16
 0.40

1653
0.36

1571
1071
542

1394

3289
0.32

977
0.28 651
(a)
Absorbance

0.24
0.20
0.16
0.12
0.08
(b)
0.04
0.00
1000 2000 3000 4000
-1
Wavenumber (cm )

Figure 7: FTIR spectra of (a) potato extract and (b) biogenic Ag nanoparticles

17
 Figure 8: UV spectra indicate photocatalytic degradation of methyl orange

Figure 9: Variation of Dye degradation with exposure time (molecular structure of the
dye shown in inset)

18
 Highlights
• Green synthesis of silver nanoparticles from AgNO3 solution using potato
(Solanum tuberosum) infusion
• Silver nanoparticles were characterized using UV-Vis, XRD and FTIR
• DLS and HRTEM study showed the average particle size (diameter) to be around
10-12 nm with nearly spherical shape
• Photocatalytic activity was studied using methyl orange dye solution under solar
irradiation

19
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