Green synthesis of violet-blue emitting silver nano ...

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2(5) (2015) 157-168

Green synthesis of violet-blue emitting silver nano particles for applications in UV-LED based phototherapy illuminators by Electrochemical method K. S. Sasireka* [a] , M.Shanthi [a], S Rajendran [b] , S Shanmugapriya[c], D Lakshmi[a] RM Joany[d] and K. Shalabi [e] [a] PG Department of Chemistry, M.V .Muthiah Government Arts College for Women,Dindigul624 001, Tamilnadu,India. Email: [email protected], [email protected] [b]RVS School of Engineering and Technology,Dindigul-624005, Tamil Nadu, India. Email : [email protected], [c]Department of Chemistry , Madha Engineering College, Kundrathur, Chennai, India. Email: [email protected] [d]Sathyabama University, Chennai, India [e] Department of Physical Chemistry ,Faculty of Science ,Mansoura University, Egypt. ABSTRACT Silver nanoparticles find applications in catalysis, optics, electronics and other areas due to their unique size-dependent optical, electrical and magnetic properties. Recently, most of the applications of silver nanoparticles are in antibacterial/antifungal agents in biotechnology and bioengineering, textile engineering, water, and silver-based consumer products. Silver nanoparticles have been incorporated into a wide range of medical devices, including but not limited to cement, surgical instruments, surgical masks and wound dressings. Silver nano Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 157 17th

International Conference on Chemical and Environmental Research (ICCER 2015), December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

particles have been prepared by electrolysis method using silver as anode and graphite as cathode in presence of a reducing agent sodium potassium tartrate (SPT) , in the absence and presence of a capping agent polyvinyl alcohol. The silver nano particles synthesised have been characterized by uv- visible absorption spectroscopy, fluorescence spectroscopy,

SEM and EDAX. The

particle size has also been determined. Since electrochemical method is used , the reaction can be started and stopped at any time. So this method is considered as green method. There is no use of toxic chemicals. Water is used as solvent. Keywords: silver nano particles, uv-fluorescence, SEM, EDAX, sodium potassium tartrate

Electrochemical method ,

INTRODUCTION

Textiles incorporated with nanoparticles have antimicrobial properties. [1, 2]. Metal nanoparticles show unique properties due to their peculiar electronic configuration, very large surface area and high amount of surface atoms [3]. For example, the metal nanoparticles show a broad absorption band in the visible region of the electromagnetic spectrum [4]. Noble metals such as Ag [8], Au [9], and Pd [10, 11] have been used to produce nano composites. Silver nano particles have applications in distinctive industries such as medicine, biochemistry, electrochemistry, and optic and indeed its consumption in textile industry due to obtaining antimicrobial properties is just a case in point [2, 12, 13]. Toxicity of silver ion and its compounds has been confirmed for bacteria and microbes; therefore, they are used in producing the would dressings [14-16] and can be applied for the manufacture of antibacterial food packaging material [17].Magnesium oxide nanoparticles have been characterized by Devi Meenakshi

synthesised and

et al., [ 18 ]. Self assembling of Gold nanoparticles on

modified indium tin oxide substrate has been investigated by

Brindha et al., [19]. Susai

Rajendran et al., have synthesized silver nanoparticles dispersed in water based nanofluid [20]. Inhibition effect of self assembled films formed by Adipic acid molecule on carbon steel surface has been studied by

Rajendran

et al., [21] . Corrosion Resistance Of Nanoparticle -

Incorporated Nano Coatings has been investigated by Joseph Rathish et al., [22]. Corrosion inhibitive property of self assembled Nano Films formed by Adipic Acid molecules on carbon steel surface has been investigated by Rajendran et al., [23]. Self Assembling Monolayers of Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 158 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

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Glycine on Carbon Steel has been reported by Gowri et al., [24]. Maria Joany et al. have used neem extract to reduce silver ions and produce silver nano particles[ 25]. Review of literature on “electrochemical synthesis of silver nanoparticles” reveals that much work has not been done in this field except some works such as “Multifunctional poly(dopamine)-assisted synthesis of silver nano particles/carbon nanotubes nanocomposite: Toward electrochemical sensing of hydrogen peroxide with enhanced sensitivity” by Lin et al [26], “Synthesis of silver nano particles and their applications” by Rajendrachari et al[27], “Synthesis and optical property of one-dimensional Ag-Cu2O heterojunctions” by

Hou et al., and “Synthesis of silver

nanoparticles on carbon papers for electrochemical catalysts” by Hsieh et al.,[28]. The present work is under taken to synthesis silver nano particles by green electrochemical method using silver anode, graphite cathode and sodium potassium tartrate as reducing agent in the absence and presence of a capping agent , polyvinyl alcohol[29]. EXPERIMENTAL The experimental set up used in the present study is shown in Fig. 1.

Fig.1.

The experimental set up .

Very pure chemicals such as sodium potassium tartrate (SPT) [electrolyte] and polyvinyl alcohol were used in the present study. Very pure silver rod was used as anode and very pure graphite rod was used as cathode. An aqueous solution of SPT was used as electrolyte.

Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 159 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

Electrochemical generation of silver nanoparticles Electrolysis was carried out in an undivided cell using silver anode and graphite cathode. 50 ml of double distilled water was taken in the undivided cell. 1 g of SPT was dissolved in 50 ml of water. 0.1 g of PVA was added. The solution was stirred well with magnetic stirrer. Electrolysis in the absence of PVA: A potential difference of 6 volt was applied for 5 minutes. The current density was 30 mA/cm2. The solution turned yellow and then slightly yellowish brown. The power supply was cut off after 5 minutes. Silver nanoparticles were produced. The aqueous solution containing silver nanoparticles was used for further study. Electrolysis in the presence of PVA: A potential difference of 6 volt was applied for 5 minutes. The current density was 30 mA/cm2. The solution turned yellow . The power supply was cut off after 5 minutes. Silver nanoparticles were produced. The aqueous solution containing silver nanoparticles was used for further study. UV-visible absorption spectra

U-visible absorption spectrum of the solution containing silver nanoparticles (AgNPs) was recorded in in a JASCO V-630 spectrophotometer. Fluorescence spectra

Fluorescence spectrum of the solution was recorded in a Agilent Technologie cary Ediose fluorescene spectrophotometer. SEM and EDAX spectra

A few drops of the solution containing AgNPs were dried on a glass plate. The solid mass was used for recording SEM and EDAX. SEM and EDAX were recorded in field Emission Scanning Electron Microscopy (FESEM-SUPRA 5S)-(ARLZEISS,GERMANY). RESULTS AND DISCUSSION Mechanism of formation of AgNPs The solution in the cell contains sodium potassium tartrate which is an electrolyte. So the medium becomes a conductive medium. When a potential difference is applied, there is flow of current through the electrolyte system. Silver anode is immersed in this electrolyte. Silver anode dissolves and releases Ag+ ions slowly. When Ag+ slowly moves towards the cathode, Ag+ is Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 160 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

reduced by the reducing agent SPT. Thus AgNPs are produced in solution. The formation of AgNPs from Ag anode is represented as follows: Ag → Ag+ + eAg+ → Ag

(AgNPs)

U V visible absorption spectroscopy and fluorescence spectroscopy The uv-visible absorption spectra of the solutions containing AgNPs prepared as such by electrolysis are shown in Figs 2 and 3. The uv-visible absorption spectrum of the solution containing AgNPs prepared as such by electrolysis in presence of the reducing agent SPT is shown in Fig 2. A peak appears at 404 nm. This confirms the formation of AgNPs. During electrolysis, first the solution appeared yellow and then turned yellowish brown and remained in the same colour tone even after one weak. This indicates that the AgNPs are stable even after one weak.

Fig 2: The uv-visible absorption spectrum of the solution containing AgNPs prepared as such by electrolysis in presence of the reducing agent SPT The uv-visible absorption spectrum of the solution containing AgNPs prepared as such by electrolysis in presence of the reducing agent SPT and the capping agent PVA is shown in Fig 3. A peak appears at 375 nm. This confirms the formation of AgNPs. Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 161 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

During electrolysis, first the solution appeared yellow and remained in the same colour tone even after one weak. This indicates that the AgNPs are stable even after one weak. The shift of the peak from 404 nm to 375 nm speculates that the AgNPs produced in presence of the capping agent PVA are smaller in size when compared with that in its absence. the capping agent PVA controls the growth of the AgNPs.

Fig 3: The uv-visible absorption spectrum of the solution containing AgNPs prepared as such by electrolysis in presence of the reducing agent SPT and the capping agent PVA Fluorescence spectroscopy The solutions containing AgNPs prepared under various conditions were excited at λ ex =404 nm . The corresponding emission spectra are shown in Figures 4 and 5.

Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 162 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

Fig4: Emission spectrum of AgNPs prepared in presence of SPT

Fig5: Emission spectrum of AgNPs prepared in presence of SPT and PVA. In the case of AgNPs prepared in presence of SPT (in the absence of PVA) emission takes place at 409.5 nm with intensity of 2230. When AgNPs are prepared in the presence of a capping agent PVA, and when the same excitation is done, emission occurs at 410 nm with intensity 2993. For both the cases emission takes place at the same wavelength. That is both the emission has the same energy. However the emission intensities are different. The emission intensity increases in presence of the capping agent PVA than in its absence, when SPT is used as the reducing agent. It is well known that the PL intensity is proportional to the absorbed number of the excitation light and luminescent efficiency[30]. Hence it is inferred that in presence of the reducing agent SPT and the capping agent PVA, the AgNPs produced absorbs more photons of light and the luminescence process takes place more efficiently. When we look at the visible spectrum (Fig 6) it is observed that in our present study excitation of AgNPs is done at violet blue region (λ ex =404 nm) and emission takes place at violet blue region (410 nm).

Fig 6: The visible spectrum Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 163 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

Comparison with the work of other researchers It will be quite interesting and useful to compare the outcome of our work with that of the other scientists. Zhendong Hao et al. [ 30 ] have prepared an intense violet–blue emitting (CaCl /SiO ) : Eu2+ phosphor with a composition of 25% CaCl 2and 75% SiO2 by a solid state reaction. The phosphor emits at 427 nm with a narrow bandwidth of 21 nm. It is observed that the PL intensity of (CaCl 2/SiO2) : Eu2+ can be 30% higher than that of commercial Sr2P2O7 : Eu2+ phosphor under 395 nm excitation. They claim that (CaCl 2/SiO2) : Eu2+ would be a promising new phosphor for converting near-ultraviolet radiation to violet–blue emission for a novel phototherapy illuminator using a near-ultraviolet (~395 nm) light emitting diode as the excitation source. 2

2

Thinking in the same line the AgNPs prepared in the present study may find application for converting near-ultraviolet radiation to violet–blue emission for a novel phototherapy illuminator using a near-ultraviolet (404 nm) light emitting diode as the excitation source. It is quite interesting to note that in our study light radiation of low energy (404 nm when compared with 395 nm) is used for excitation and the emission produced is of higher energy (410 nm when compared with 427 nm). SEM and EDAX spectra The SEM image of AgNPs produced in the presence of SPT is shown in Fig. 7. The EDAX spectrum is shown in Fig. 8.

Fig 7: SEM image of AgNPs

Fig 8: The EDAX spectrum Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 164 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

It is seen from Fig 7 that the shape of the AgNPs is spherical and the particle size of AgNPs is in the range of 70 to 100 nm.(Absorption peaks appears at 404 nm) The EDAX spectrum confirms the presence of AgNPs. It is expected that the size of the AgNPs is smaller than 70 nm, when a capping agent such as PVA is used and it has been confirmed by uv visible absorption sepectroscopy. The absorption peak appears at 375 nm . The presence of a capping agent controls the size of the AgNPs. CONCLUSIONS  Silver nanoparticles have been synthesized by electrochemical method using Silver anode and graphite cathode.  Sodium potassium tartrate has been used as reducing agent to reduce silver ions (Ag+) into nanosilver.  The yellow / yellowish brown AgNPs produced were characterized by uv-visible absorption spectrum. and uv-fluorescent spectroscopy.  The particle size of the AgNPs has been determined by SEM and EDAX. Application Violet-blue emitting AgNPs may find applications in UV-LED based phototherapy illuminators. Scope for further study  The antimicrobial nature of the AgNPs can be studied in future.  They can be used in making odorless shocks, dressing wounds and preserving vegetables by keeping them on papers impregnated with silver nanoparticles. ACKNOWLEDGEMENT The authors are thankful to their managements for their help and encouragement. REFERENCES [1]. H.J. Lee, S.Y. Yeo, S.H. Jeong, Antribacterial effect of nanosized silver colloidal solution on textile fabrics. J. Master. Sci. 38 (2003) 219-2204. [2]. F. Alimohammadi, Stabilization of silver nanoparticles and antibacterial characterization on the cotton surface against washing. M.Sc Thesis, Islamic Azad University Tehran South Brach, 2009. [3]. J.D. Aiken, R.G. Finke, A. review of modern transition-metal nanoclusters: their synthesis, characterization, and applications in catalysis, J. Mol. Catal, A:Chem. 145 (1999) 1-44. Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 165 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

[4]. R.Liu, H. Chen. S. Hu, Synthesis and characterization of nano metals with coreshell structure, China Particuol. 2 (4) (2004) 160-163. [5]. H.M. Sung-Suh. J.R. Choi, H.J. Hah, S.M. Koo, Y.C. Bae, Comparison of Ag deposition effects on the photocatalytic activity of nanoparticular TiO2, under visible and UV light irradiatioJ.Photochem.Photobiol.A 163 (2004) 37-44. [6]. B. Xin, L. Jing, Z. Ren, B. Wang, H. Fu, Effects of simultaneously doped and deposited Ag on the photocatalytic activity and surface states of TiO2. J.Phys. Chem. B 109 (2005) 28052809. [7]. B. Xu, M. Niu, L. Wei, W.Hou, X. Liu. The structural analysis of biomacromolecule wool fiberswithAg- loading SiO2 nano-antibacterial agent by UV radiation. J. Photochem. Photobiol, A 188 (2007) 98-105. [8]. A. Valentine Rupa, D. Manikandan, D. Divaker, T. Sivakumar. Effect of deposition of Ag on TiO2 nanoparticles on the photodegradation of Reactive Yellow -17. J. Hazard, Mater. 147 (2007) 906-913. [9]. M.J. Uddin, F.Cesano, D. Scarano, F. Bonino, G. Agostini, G. Spoto, S. Bordiga, A. Zecchina,Cotton textile fibers coated by Au/TiO2 films: Synthesis characterization and selfcleaning properties.J.Photochem. Photobiol. A 199 (2008) 64-72. [10].A.Sclafant, J.M. Herrmann, Influence of metallic silver and of platinum-silver bimetallic deposits onthe photocatalytic activity of titania (anatase and rutile) inorganic and aqueous media. J.Photochem.Photobiol.A 113 (1998) 181-188. [11]. A. Wold, Photocatalytic properties of titanium dioxide (TiO2), Chem. Mater. 5 (1993) 280283. [12]. K. Nischala, T.N. Rao, N. Hebalkar, Silica-silver core-shell particles for antibacterial textile application. Colloids Surf. B 82 (2011) 203-208. [13]. M. Rai, A. Yadav, A. Gade, Silver nanoparticles as a new generation of antimicrobials, Biotechnol.Adv.27 (2009) 76-83. [14]. T.Maneerung, S. Tokura, R. Rujiravanit, Impregnation of silver nanoparticles into bacterial cellulosefor antimicrobial wound dressing, Carbohydr. Polym. 72 (2008) 43-51. Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 166 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

[15]. R. Dastjerdi, M. Montazer, A. review on the application of inorganic nano-structured material inthe modification of textiles: focus on anti-microbial properties, Colloids Surf. B 79 (2010) 5-18. [16]. M.Ip, S.L. Lui, V.K.M. Poon, I. Lung, A. Burd, Antimicrobial activities of silver dressings: an in vitro comparison, J. Med. Microbiol. 55 (2006) 59-63. [17]. R. Tankhiwale, S.K. Bajpai, Graft copolymerization onto celluslose-based filter paper and its further development as silver nanoparticles loaded antibacterial food-packaging material, ColloidsSurf.B 69(2009) 164-168. [18]. S. Devi Meenakshi, M. Rajarajan, Susai Rajendran, Z. Robert Kennedy and G. Brindha, Elixir Nanotechnology 50 (2012) 10618-10620. [19]. G. Brindha, A.Suganthi, S.Rajendran, P.Satyabama and Z. Robert Kennedy, Elixir Nanotechnology 50 (2012) 10585-10587. [20]. Susai Rajendran, V. Sribarathy, P. Nithya devi, J.Angelin Thangakani, Z. Robert Kennedy, N.Nazeera Banu, P. Satyabama and G. Brindha 50(2012)10552-10555. [21]. S.Rajendran,V. Sri Bharathy, A. Krishnaveni, J.SathiyaBama ,T.S. Muthumegala, M. Manivannan, Zastita Materijala,52,( 2011)broj3, pp.163-172. [22]. R.Joseph Rathish, R. Dorothy, R. M. Joany, M. Pandiarajan and Susai Rajendran, Eur. Chem.,Bull., 2(12)(2013) 965-970. [23] S.Rajendran, V. Sribharathy , A. Krishnaveni , J. Sathiyabama , Z.Robert Kennedy , V.R.Nazeera ,Banu and G.Brintha, Elixir Thin Film Tech. 50 (2012) 10509-10513 [24] S.Gowri, J. Sathiyabama S. Rajendran and J. Angelin Thangakani, Eur. Chem. Bull. 2(4) (2013) 214-219. [25] R .Maria Joany , P.Shanthy , A.Christy Catherine Mary, J.Jeyasundari, Jasmine and S.Rajendran Synthesis Of Silver Nanoparticles Using Neem Extract,Int J Nano Corr Sci and Engg. 2(2)(2015) 1 - 6 [26].Y.Lin, L. Li, L. Hu, K. Liu, Y. Xu. Sensors and Actuators, B: Chemical, 202 (2014) 527535. [27]. S.Rajendrachari, B.E. Kumara Swamy, S. Reddy, D. Chaira. Analytical and Bioanalytical Electrochemistry, 5(4) (2013) 455-466. Int J Nano Corr Sci and Engg 2(5) (2015) 157-168 167 International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India

Sasireka et al.,

[28].C.T.Hsieh, C. Pan, W.Y. Chen, Journal of Power Sources, 196(15) (2011) 60-61. [29] Mandeep kaur ,L. Singh, Praveen Kumar, Effect of PVA Capping on the Optical and Structural Properties of hydrothermally synthesized ZnS , Nanocrystals International Journal of IT, Engineering and Applied Sciences Research , 2(1)January(2013)20-24 [30] Zhendong Hao, Jiahua Zhang, Xia Zhang, Xinguang Ren, Yongshi Luo, Shaozhe Lu and Xiaojun Wang , Intense violet-blue emitting (CaCl2/SiO2) : Eu2+ phosphor powders for applications in UV-LED based phototherapy illuminators, J. Phys. D: Appl. Phys. 41 (2008) 182001-182004 .

Received: 10-11-2015 Int J Nano Corr Sci and Engg 2(5) (2015) 157-168

Accepted: 25-11-2015 168

International Conference on Chemical and Environmental Research (ICCER 2015), 17th December 2015, PG and Research Department of Chemistry JAMAL MOHAMED COLLEGE (Autonomous), Tiruchirapalli, Tamilnadu, India