Chemical Physics Letters 748 (2020) 137402

Contents lists available at ScienceDirect

Chemical Physics Letters

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

Research paper

Hydrothermal synthesis of gold nanoparticles using spider cobweb as novel T

biomaterial: Application to photocatalytic
⁎
S.P. Vinaya, Udayabhanub, G. Nagarajub, C.P. Chandrappac, N. Chandrasekhara,
a
Research and Development Center, Department of Chemistry, Shridevi Institute of Engineering and Technology, Tumakuru, Karnataka 572106, India
b
Energy Materials Research Laboratory, Department of Chemistry, Siddaganga Institute of Technology, Tumakuru 572103, Karnataka, India
c
Department of Biotechnology, Shridevi Institute of Engineering and Technology, Tumakuru 572106, India

H I GH L IG H T S

• Gold nanoparticles (Au NPs) have been synthesized using a novel, facile, fast and single step advanced hydrothermal method.
• InAuthe synthesis part, we used novel biomaterial: Spider Cobweb as reducing and stabilizing agent.
• TheyNPshavewerealsonon-toxic to spider cobweb and are environmentally safe.
• shown excellent catalytic activity for the reduction of Rhodamine-B and Methylene blue.

A R T I C LE I N FO A B S T R A C T

Keywords: In the present study, we have followed the hydrothermal path for the synthesis of gold nanoparticles (Au NPs)
Spider cobweb from the novel biomaterial spider cobweb, which is a rapid & non-chemical way. The synthesized nanoparticles
Hydrothermal were thoroughly characterized by XRD, UV–vis, SEM, EDAX and TEM studies used for the photocatalytic dye
Gold nanoparticles degradation studies. Here we have used two dyes namely Rh B and MB, Au NPs has shown the good photo-
Nanocatalyst
catalytic activity, this is due to more sensitive to light and reduces the electron-hole recombination.

1. Introduction
Dye impurities from printing, textiles, production and many other
industries play an important role in the polluting environment. These
wastes enter the aquatic ecosystem and cause huge environmental and
health risks. Different methods like coagulation, adsorption, osmotic
pressure, etc. have been used to remove dyes from the river, but each
method has unique advantages and limitations. The photocatalytic
treatment provides a relatively inexpensive and eco-friendly way to
solve this problem [1]. In recent years, transition metal oxide has been
used most often for the degradation of many organic pollutants [2].
Nanoscale semiconductors have been reported as an effective photo-
catalytic agent, because of its large surface area or the quantum con-
finement effects. The charge carriers on the degradation of organic
pollutants in water under ultraviolet light and sunlight play the major
role to degrade the dyes [3,4]. When the photocatalyst opens to light
with energy that is stronger than its bandgap energy, the electron-hole
pair generated spreads on the surface of the photocatalyst. These free
holes and electrons convert adjacent water and oxygen molecules to
OH% (Hydroxyl radicals) and superoxide radicals (O22−%), these reactive
intermediates can participate in chemical reactions with dyes and this
process is transformed into a powerful oxidizing agent for organic color
degeneration [5–7].
Metal nanoparticles (MNPs) and Graphene, owing to their intriguing
physicochemical properties, have been widely used as the modifiers to
improve the photocatalytic performances of semiconductor photo-
catalysts. The enhanced photocatalytic activity by the decoration with
noble metal NPs is generally ascribed to two mechanisms. First, noble
metal NPs can act as electron sinks to trap photogenerated electrons
from the semiconductor, thus leading to an efficient separation of
electron/hole pairs. Second, noble metal NPs can induce localized
surface plasmon resonance (LSPR) by absorbing visible light with wa-
velengths corresponding to their plasmonic absorption bands. The
electromagnetic field caused by LSPR can facilitate the generation and
separation of electron/ hole pairs in the semiconductor.
Simultaneously, LSPR-induced electron/hole pairs in noble metal NPs
could also participate in the photocatalytic reactions. The two me-
chanisms depend highly on the size of noble metal NPs, that is, smaller-

⁎
Corresponding author.
E-mail address: chandruharshu@gmail.com (N. Chandrasekhar).

https://doi.org/10.1016/j.cplett.2020.137402
Received 11 September 2019; Received in revised form 18 March 2020; Accepted 21 March 2020
Available online 23 March 2020
0009-2614/ © 2020 Elsevier B.V. All rights reserved.
S.P. Vinay, et al. Chemical Physics Letters 748 (2020) 137402

Fig. 1. (a). PXRD pattern of the Au NPs. (b). Rietveld refined pattern.

Table 1 540 nm (a) 00 min

Rietveld refined structural parameters for Au NPs.
3
(f) (b) 240 min
Au NPs Au (JCPDS No.:65-2870) (c) 12 h
Crystal system Cubic
(d) 24 h
Space group Pm-3m (2 2 1) (e) 3 days
(e)
Lattice parameters (Å) Absorbance (a.u.) 2
(d)
(f) 30 days
a=b=c 4.0289
α=β=λ 90O
Unit cell volume (Å3) 67.435 (c)
Atomic coordinates
1
x 0.0000 (b)
y 0.0000
z 0.0000
(a)
Refinement parameters
RP 43.6 0
RWP 45.5 500 600
RExp 32.1
χ2 2.0
Wavelength (nm)
S 1.4826
Fig. 2. UV–vis spectrum: increase the surface plasmon absorption of Au NPs at
RBragg 0.989
different time interval.
RF 0.462
QD 1.7388
field of light emitting diodes, biosensors, diluted and ferromagnetic
materials for spintronics solar cells, photo-catalysis, transistors and also
sized noble metal NPs mainly act as electron sinks, whereas larger-sized acts as anti-oxidants and anti-bacterial agent [18].
noble metal NPs dominantly behave as LSPR effects [8,9]. In general, Au NPs can be synthesized by numerous ways, like
Arthropods form a phylum called Arthropoda, which includes ara- biosynthesis [19–26], combustion route [27], and microwave irradia-
chnids, insects, crustaceans, and myriapods. Arthropods are char- tion [28], chemical, electrochemical [29,30], hydrothermal synthesis
acterized by their attached limbs and cuticles made of calcium carbo- [31], ultrasonic irradiation [32,33].
nate or/and A-chitin [10]. Arthropods are classified into four main Herein, we report the synthesis of gold nanoparticles using novel
categories: 1. Crustacea (lobsters, crabs, shrimps), 2. Chelicerata biomaterial spider cobweb under the hydrothermal synthesis method.
(scorpions and spiders), 3. Tracheata (myriapods and insects), and 4. The spider cobweb act both as a reducing agent and capping agent in
Extinct Trilobites [11]. Spiders have been described as famous silk the reaction, reducing the Chloroauric acid (HAuCl4) to the Au NPs. The
craftsmen in arthropods, known for producing aerial orb webs, used to Au NPs were characterized using XRD, UV–vis, SEM, EDAX and TEM
capture flying insects. The silk threads that are woven into arrays of analysis. Furthermore, the characterized material was examined for
structures are constructed by spiders for a wide range of purposes such Photocatalytic dye degradation of MB & Rh B.
as shelters, protection of egg sacs and webs. Spider cobweb is made-up
of a huge number of glycine, alanine, amino acids and pyrrolidine
[12,13]. Spider cobweb is reported to be valuable in treating wound 2. Experimental
healing because of the presence of vitamin K content and having anti-
microbial properties [14,15]. Therefore, the present experiment seeks 2.1. Preparation of Au nanoparticles
to extend the boundaries of spider nanotechnology applications, parti-
cularly the use of their cobwebs. The synthesis of gold nanoparticles using hydrolyzed spider cob-
Au is an important and distinctive inorganic substance, because of webs under the hydrothermal synthesis method. In this study, we used
its distinctive characteristics and novel applications in various fields of hydrolyzed cobwebs, slightly modified by the method used by Tszydel
scientific and technology [16]. Au has capacity to exhibit piezoelectric, et al. [34]. 100 mg of cobwebs were hydrolyzed with 10 mL of 0.1 mL
pyroelectric, optoelectronic, catalysis and semiconducting properties Sodium hydroxide at 90 °C for 1 h. The hydrolyzed spider cobweb was
[17]. Due to this, Au is a multifunctional compound which is used in the allowed to cool and then centrifuged at 5000 rpm for 20 min. The

2
S.P. Vinay, et al.
Fig. 3. (a), (b), (c), (d). SEM images. (e). EDAX spectrum of synthesized Au NPs.
supernatant obtained designated as cobweb extract was used to syn-
thesize Au NPs as described in the previous lines [35].
Chloroauric acid (HAuCl4) was used as a precursor and hydrolyzed
spider cobweb was used as a reducing agent for Au NPs synthesis.
33 mL hydrolyzed spider cobweb was taken in a beaker with constant
stirring, with the addition of 330 mg of HAuCl4 then the solution
mixture was stirred for 30 min to obtain a homogeneous solution. This
mixture was taken into a 50 mL Teflon vessel, and sealed in a stainless
steel autoclave and maintained at 180 °C for 3 h. After the reaction was
completed, the autoclave was cooled down to room temperature
naturally. The products were collected by centrifugation and washed
with water and ethanol for five times, respectively. Further, the
3
Chemical Physics Letters 748 (2020) 137402
synthesized Au NPs were dried and stored for further examination [36].
2.2. Characterization
X-ray diffraction (XRD) data were recorded in Rigaku Smart Lab.
The morphology of the synthesized nanoparticles was observed using
Scanning Electron Microscope (Hitachi-7000 Table top). EDAX
(OXFORD XMX N) determines the elemental analysis. Shape and size of
the nanoparticles were determined by Transmission Electron
Microscopy (TEM) (JEOL 3010).
S.P. Vinay, et al. Chemical Physics Letters 748 (2020) 137402

Fig. 4. (a), (b), (c). TEM images. (d). HR-TEM image. (e). SAED pattern and (f). Histogram of Au NPs.

Scheme 1. Schematic mechanism for the dye degradation.

4
S.P. Vinay, et al. Chemical Physics Letters 748 (2020) 137402

(a) 00 min 90 (b)

0.2 1h 663 nm
2h
3h
Absorbance (a.u.)

Degradation (%)
60
290 nm
0.1

30

0.0

0
300 400 500 600 700 0 1 2 3
Wavelength (nm) Time (hr)

No scavenger
(c) 100
TBA
BQ
EDTA
80
% degradation

60

40

20

0
0 10 20 30 40 50 60
Time (min)
Fig. 5. (a). Degradation of Methylene blue dye. (b). Percentage degradation in the presence of Au NPs. (c). Photocatalytic activity of MB in the presence of different
scavengers.

2.3. Photocatalytic degradation of dye 3. Results and discussion

The Photo-catalytic activity of the synthesized Au NPs was assessed
by considering the dye degradation of Rhodamine B (Rh B) and
Methylene blue (MB) in an aqueous solution at ambient temperature
utilizing a 300 W visible light as radiance source. 20 mg of catalyst (Au
NPs) was mixed with 100 mL of 5 ppm Rh B or MB dye and the solution
was unceasingly stimulated in the dark chamber for about 30 min to
attain adsorption-desorption equilibrium. Further, the visible light was
switched on and 2 mL of aliquot withdrawn for every 1 h interval. The
samples were centrifuged using a micro centrifuge for 10 min in order
to segregate Au NPs. Spectrophotometric evaluations were carried out
by utilizing a quartz cell having a path length of 0.3 cm. Absorbance
was recorded at a fixed wavelength using the UV–vis spectro-
photometer.
The degradation percentage of the dye has been determined by the
following equation.
% of degradation = (Ci − C f )/Ci × 100
where Ci and Cf are the initial and final concentration of the dye.
3.1. XRD study
The XRD pattern of Au NPs shown in Fig. 1. The XRD pattern peaks
at 2θ = 38.0°, 44.2°, 64.5°, and 77.4° were indexed with the planes
(1 1 1), (2 0 0), (2 2 0) and (3 1 1) for the resultant particles with cubic
phase (Fig. 1a.). Fig. 1b illustrates the lattice parameter of Au NPs
calculated by utilizing the Rietveld refinement examination. The Re-
fined Parameters, for example, occupancy, atomic functional positions
for Au NPs were summarized in Table 1. The structure of the resultant
data is according to the JCPDS card number 65–2870. No extra peaks
were found in the pattern which indicates the purity of the samples. The
average crystallite size was measured to be 18 nm for Au nanopowder
[37,38].
3.2. UV–Visible study (UV–vis)
(1)
The UV–vis spectrum of the synthesized material is displayed in
Fig. 2. The spectrum shows a strong band in between the wavelength
region 540 nm (confirming the formation of Au nanoparticles) due to
surface plasmon absorption. The synthesized Au nanoparticles was

5
S.P. Vinay, et al. Chemical Physics Letters 748 (2020) 137402

(a) 00 min 90 (b)

553 nm
0.1 1h
2h
3h
Absorbance (a.u.)

Degradation (%)
4h 60
5h
6h
7h
30

0.0
0
500 600 0 1 2 3 4 5 6 7 8

Wavelength (nm) Time (hr)

(c) No scavenger
100
TBA
BQ
EDTA
80
% degradation

60

40

20

0
0 10 20 30 40 50 60
Time (min)
Fig. 6. (a). Degradation of Rhodamine B dye. (b). Percentage degradation in the presence of Au NPs. (c). Photocatalytic activity of Rh B in the presence of different
scavengers.

found to be very stable even after 30 days as compared to Au nano-
particles synthesized by other method which was found to be stable for
10 days [39]. The stability of Au nanoparticles was studied for a period
of 30 days and was assessed by the presence of stable SPR positions at
540 nm. This is an indication that no aggregation of the nanoparticles
took place.
3.3. Scanning electron Microscopy (SEM) and Energy-dispersive X-ray
(EDAX) studies:
Fig. 3a, b, c, d represents SEM images of Au NPs. The particles are
agglomerated crystals with an almost uniform spherical structure [40].
Fig. 3e shows the EDAX spectrum of Au NPs, which describes the ele-
mental analysis of the material, an obtained spectrum exhibits strong
gold peaks.
3.4. Transmission electron Microscopy (TEM) studies
Fig. 4 shows the TEM image, HR-TEM image, SAED pattern, and
Histogram of synthesized Au nanomaterials. These particles are well
dispersed, which acquired the size around 40 nm diameter and these
particles are spherical in shape and some of the particles look like
truncated triangular shape. HR-TEM image gives clear information
about the d-spacing value of Au material. For Au, the d-spacing value is
0.16 nm, which belongs to the (1 1 1) plane. The planes at (1 1 1),
(2 0 0) and (2 2 0) planes having the highest intensity in XRD and which
are matched with bright circular fringes in SAED pattern [41].
4. Photocatalytic degradation
Under visible light radiation, the semiconductor absorbs photons of
energy greater than the band gap of semiconductors and then it creates
electrons and holes in the valence band and conducting band. If the
charge carriers do not recombine, then they can travel on the surface
where the free electrons form the reduction of oxygen and form the
peroxides and superoxide radicals and created holes oxidize the water
and form the OH·; these generated species are highly reactive and un-
stable and ultimately lead to the degradation of organic dyes. Many
factors are influencing the Photocatalytic action on dyes, i.e., phase
composition, crystallinity, particle size, size distribution, morphology,
band gap, surface area, and surface hydroxyl density of the photo-
catalyst [42]. Prepared Au NPs were used as a photocatalyst to test the
degradation of Rh B and MB dyes under in UV source. 2 mm of the
aliquots sample was withdrawn at the regular time period (1 h). The
solution was centrifuged and the absorption of the samples was re-
corded. By measuring the change in intensity, we can calculate the rate
of degradation of dye at 553 and 663 nm (λ max).
Mechanism. Scheme: A schematic representation of the degrada-
tion of Rh B or MB using the Au superstructure is shown below (Scheme
1).

6
S.P. Vinay, et al. Chemical Physics Letters 748 (2020) 137402

−
Au + hv → Au (h+
vb + ecb ) Nanomission (SR/NM/NS1262/2013) for financial support.

OH−
ads + h+
vb → OH%ads (in basic medium)
References
Rh B or MB + OH%ads → Dye degradation
[1] H. Lachheb, E. Puzenat, A. Houas, M. Ksibi, Appl. Catal. B 39 (2002) 75–90.
The absorbance of Rh B/MB dye solution decreases with an increase [2] C. Gregorio, A review Bioresource Technology. 97 (2006) 1061–1085.
in time of irradiation in the presence of Au NPs photocatalyst. Fig. 5 [3] S. Sreedhar, B. Kotaiah, Iran. J. Environ. Health Sci. Eng. 3 (2006) 239–246.
[4] G.N. Bidhendi, A. Torabian, H. Ehsani, N. Razmkhah, Iran. J. Environ. Health Sci.
shows the dye degradation of MB using the UV–Vis spectrophotometer Eng. 4 (2007) 29–36.
at 663 nm. So, it was observed that MB (5 ppm/100 mL) undergo de- [5] I.W.A. Publishing, UK, 2004, p. 368.
gradation up to 79.32% in a period of 3 h. The absorbance of Rh B [6] John Wiley, 1997, pp. 225–274.
[7] H. Gerixhac, Electrochim. Act. 38 (1993) 39–45.
(5 ppm/100 mL) has been intensely decreased and given 80.64% of [8] X. Zhao, H. Yang, Z. Cui, Z. Yi, H. Yu, J. Mater. Sci.:. Mater. Electron. 30 (2019)
degradation in 7 h (Fig. 6). [43]. 13785–13796.
[9] Y. Yan, H. Yang, Z. Yi, T. Xian, Catalysts 9 (2019) 795.
[10] B. Cutler, Experientia 36 (8) (1980) 953.
4.1. In situ capture experiment:
[11] E.E. Ruppert, R.S. Fox, R.D. Barnes, Invertebrate zoology, 7th ed, Brooks/Cole.
(2004) ISBN:0-03-025982-7.
To examine the possible photocatalysis mechanism, different re- [12] H. Roozbahani, M. Asmar, N. Ghaemi, K. Issazadeh, Int. J. Adv. Biol. Biomed. Res. 2
sponsive species formed during organic pollutant degradation were (7) (2014) 2197–2199.
[13] T.A. Blackledge, M. Kuntner, I. Agnarsson, Adv. Insect. Physiol. 41 (2011) 175–262.
verified by radical and hole trapping experiments. In this study, ben- [14] S. Heimer, Wunderbare Welt der Spinnen, Urania. (1988).
zoquinone (BQ, 1 mM), tert-butyl alcohol (TBA, 1 mM), were and [15] D.S. Chakraborty, Antibacterial activities of cobweb protein, Eur. Congress Clin.
ethylenediamine tetraacetic acid disodium salt (EDTA-2Na, 1 mM), Microbiol. Infect. Dis. (2009).
[16] S.C. Gomes, I.B. Leonor, J.F. Mano, R.L. Reis, D.L. Kaplan, Functionalized silk
were employed as the scavengers for photo-generated superoxide ra- biomaterials for bone regeneration. Semana de Engenharia. Guimaraes, 11 a 15 de
dical (%O2−), hydroxyl radical (%OH), and holes (h+), respectively. Outubro, (2010) 1–2.
As shown in Figs. 5c and 6c, the degradation efficiency of MB and [17] S. Kohtani, M. Koshiko, A. Kudo, K. Tokumura, Y. Ishigaki, A. Toriba, R. Nakagaki,
Appl. Catal. B 46 (2003) 573–586.
Rh B by Au NPs is slightly inhibited upon the addition of TBA. This [18] Z. Zhang, W. Wang, M. Shang, W. Yin, Catal. Commun. 11 (2010) 982–986.
result shows that the presence of the %OH radical plays significant role [19] S.P. Vinay, Udayabhanu, G. Nagaraju, C.P. Chandrappa, N. Chandrashekar, J. Sci.:
during decomposition of MB and Rh B under sun light irradiation. Adv. Mater. Devices (2019), https://doi.org/10.1016/j.jsamd.2019.08.004.
[20] R. Chauhan, A.S. Kumar, R. Chaudhary, J. Optoelectron. Biomed. Mater. 3 (2011)
In constant, the photodegradation rates of MB and Rh B in the
17–23.
presence of BQ and EDTA are majorly suppressed, indicating that %O2− [21] S.P. Vinay, N. Chandrasekhar, C.P. Chandrappa, Int. Res. J. Nat. Appl. Sci. 4 (7)
and h+ are the major active species in the photocatalytic degradation (2017) 9–19.
[22] S.P. Vinay, N. Chandrasekhar, C.P. Chandrappa, Int. J. Pharm. Biol. Sci. (IJPBS). 7
pathways [44].
(2) (2017) 145–152.
[23] S.P. Vinay, N. Chandrasekhar, C.P. Chandrappa, Res. J. Pharm. Biol. Chem. Sci.
5. Conclusion (RJPBCS) 8 (4) (2017) 527–534.
[24] N. Chandrasekhar, S.P. Vinay, Appl. Nanosci. 7 (2017) 851–861.
[25] S.P. Vinay, Udayabhanu, G. Nagaraju, C.P. Chandrappa, N. Chandrashekar, J.
This study has led to the synthesis of Au NPs using the extract of Cluster Sci. 30 (2019) 1–20, https://doi.org/10.1007/s10876-019-01598-5.
spider cobweb under hydrothermal synthesis. The prepared Au NPs was [26] S.P. Vinay, N. Chandrasekhar, Mater. Today:. Proc. 9 (2019) 499–505.
confirmed by XRD study. The well-dispersed Au NPs were spherical in [27] S.P. Vinay, Udayabhanu, G. Nagaraju, C.P. Chandrappa, N. Chandrashekar, Int. J.
Biosens. Bioelectron. 5 (4) (2019) 100–105, https://doi.org/10.15406/ijbsbe.2019.
shape with an average size range of 40 nm. The NPs were crystalline in 05.00161.
nature, showing the characteristic FCC (face-centered cubic) structure. [28] S.P. Vinay, Udayabhanu, G. Nagaraju, C.P. Chandrappa, N. Chandrashekar, S N
The Au NPs displayed good photocatalytic degradation of Rh B/MB, Appl. Sci. 1(5) (2019) 477. DOI: http://doi.org/10.1007/s42452-019-0437-0.
[29] K.S. Chou, Y.S. Lai, Mater. Chem. Phys. 83 (2004) 82.
due to its sensitivity to absorb light with wide band gap energy. Hence [30] S. Kapoor, S. Adhikari, C. Gopinathan, J.P. Mittal, Mater. Res. Bull. 34 (1999) 1333.
synthesized material is reported as a potent aspirant for the degradation [31] J.K. Kim, H.D. Lee, S.C. Kim, J. Ind. Eng. Chem. 10 (2004) 850.
of Rh B and MB. Consequently, this work has established the relevance [32] J.S. Park, J.S. Kim, J.H. Han, S.W. Nam, T.H. Lim, J. Ind. Eng. Chem. 11 (2005) 897.
[33] C. Ducamp Sanguesa, R. Herrera Orbina, M. Figlarz, J. Solid. State. Chem. 100
of novel biomaterial spider cobweb in nanotechnology, through the
(1992) 272.
rapid and eco-friendly synthesis of Au NPs. To the best of our knowl- [34] M. Tszydel, S. Sztajnowski, M. Michalak, H. Wrzosek, S. Kowalska, I. Krucinska,
edge, this report represents the first reference to spider cobweb as a B. Lipp-Symonowicz, Fibres. Text. Eastern. Eur. 17 (2009) 7–12.
[35] A. Lateef, I.A. Adelere, E.B. Gueguim-Kana, T.B.L.S. Asafa, Beukes, Int. Nano. Lett. 5
reducing agent for the reduction of HAuCl4 by the hydrothermal
(2015) 29–35..
method. [36] Pramod P. Desai, C. Prabhurajeshwar, Kelmani R. Chandrakanth, J. Nanostruct.
Chem. 6 (2016) 235–246, https://doi.org/10.1007/s40097-016-0197-y.
Declaration of Competing Interest [37] S.P. Vinay, N. Chandrasekhar, Adv. Mater. Lett. 10 (2019) 1–8.
[38] A. Jha, K. Prasad, J. Bionanosci. 7 (3) (2013) 245–250.
[39] A. Lateef, S.A. Ojo, M.A. Azeez, T.B. Asafa, T.A. Yekeen, A. Akinboro, I.C. Oladipo,
The authors declare that they have no known competing financial E.B. Gueguim-Kana, L.S. Beukes, Appl. Nanosci. 6 (6) (2015) 863–874, https://doi.
org/10.1007/s13204-015-0492-9.
interests or personal relationships that could have appeared to influ- [40] Y. Liu, L. Yang, Y. Shen, J. Mater. Res. 33 (2018) 2671–2679, https://doi.org/10.
ence the work reported in this paper. 1557/jmr.2018.274.
[41] L.I. Ying-fen, G.A.N. Wei-ping, Z.H.O.U. Jian, L.U. Zhi-qiang, Y.A.N.G. Chao,
G.E. Tian-tian, Trans. Nonferrous. Met. Soc. China. 25 (2015) 2081–2086.
Acknowledgement [42] D. Suresh, P.C. Nethravathi, H. Rajanaika, H. Nagabhushana, S.C. Sharma, Mater.
Sci. Semicond. Process. 31 (2015) 446–454.
Udayabhanu thanks to CSIR, New Delhi, for Senior Research [43] D. Suresh, P.C. Nethravathi, K. Lingaraju, H. Rajanaika, S.C. Sharma,
H. Nagabhushana, Spectrochim. Acta. Part. A. Mol. Biomol. Spectrosc. 136 (2015)
Fellowship (09/1204(0001)/2018-EMR-1). Dr. Chandrasekhar and
1467–1474.
Vinay thank Dr. M R Hulinaykar, Managing Trustee, Sri Shridevi [44] Tingting Liu, Lei Wang, Lu. Xue, Jiamin Fan, Xinxin Cai, Bo Gao, Rui Miao,
Charitable Trust, and Shridevi Institute of Engineering and Technology Jiaxuan Wang, Yongtao Lv, RSC. Adv. 7 (2017) 12292.
for encouragement and support for research work. Dr. GN Thank DST