VNU Journl of Siene: Mthemtis Physis, Vol. 30, No. 2 (2014) 18-24 Preprtion of Pltinum Nnoprtiles in Solution of Polyvinyl Pyrrolydone (PVP) y Lser Altion Method Nguyen The Binh*, Nguyen Dinh Thnh, Nguyen Qung Dong, Nguyen Thi Trinh Fulty of Physis, VNU University of Siene, 334 Nguyen Tri, Thnh Xun, Hnoi, Vietnm Reeived 25 April 2014 Revised 20 My 2014; Aepted 18 June 2014 Astrt: Using Nd:YAG lser we studied to produe pltinum nnoprtiles (PtNPs) in solution of polyvinyl pyrrolidone (C 6 H 9 NO) n (PVP) y lser ltion method. The influene of verge lser power, lser irrdition time, lser wve length nd onentrtion of PVP solution in wter on morphology, size distriution of PtNPs ws investigted. The men dimeter of the PtNPs in 1M PVP solution ws of 9 nm. The results on n optimum lser ltion proess for preprtion of PtNPs in PVP solution were disussed in this pper. Keywords: Lser ltion, plsmon resonne, nnoprtile, seond hrmoni. 1. Introdution * Nole metl nnoprtiles in liquid hve eome promising mteril for vriety of pplitions suh s nonliner optil devies, optil reording medi, iosensing nd ioimging pplitions [1-3]. Severl hemil nd physil or eletrohemil methods hve een developed to produe metl nnoprtiles suh s hemil redution [4], gmm irrdition [5], eletron irrdition [6], photohemil method [7], mirowve proessing [8] nd sonoeletrohemil method [9]. In reent yers, pulsed lser ltion method ws employed for preprtion of severl metl nd semiondutor mterils in different medi. One of the dvntges of lser ltion method in omprison with other onventionl methods is the possile esy synthesis of nnoprtiles in ritrry liquids inluding orgni liquids nd iologil-friendly environments without ontmintion y reduing gents [10]. Reently, we develop lser ltion method nd suessfully produed Au, Ag nd Cu nnoprtiles in different solutions nd pure liquids [11-12] In this work, we prepred PtNP in PVP (C 6 H 9 NO) n solution y using lser ltion method. Ftors inluding lser irrdition time, lser wvelength nd PVP onentrtion tht ffet morphology, size distriution of PtNPs were investigted to find out n optiml ltion proedure. The results of the investigtion re lso disussed nd presented. * Corresponding uthor. Tel.: 84-904229007 Emil: theinh@vnu.edu.vn 18
N.T. Binh et l. /VNU Journl of Siene: Mthemtis Physis, Vol. 30, No. 2 (2014) 18-24 19 2. Experimentl The experimentl set-up of lser ltion is shown in Fig 1. Lser em from Nd: YAG lser (Qunt Ry Pro 230-USA) ws foused on pltinum plte (99.9% in purity) pled in glss vessel filed with 10 ml of PVP solution y lens hving fol length of 150 mm. The lser ws set in Q- swith mode to give lser pulse durtion of 8 ns, repetition rte of 10Hz. () () Fig.1. Experiment set-up () nd piture of Nd:YAG lser () 1. Holder 2. Prism 3. Lens 4. Glss vessel 5. Pt plte 6. Rotry system The PVP solution vessel ws pled on support whih exeuted repetitive irulr motions t onstnt speed to prevent gglomertion of prtiles. PVP solutions in distilled wter were prepred in different onentrtions. The solution eomes olored under tion of the lser em. A smll mount of the olored solution ws extrted for sorption mesurement nd TEM oservtion. The sorption spetrum ws mesured on Shimdzu UV-Vis 2450 spetrometer. The TEM mirogrph ws done on JEM 1010-JEOL. The size of nnoprtiles ws determined y ImgieJ 1.37V softwre of Wyne Rsnd (Ntionl institutes of Helth, USA). The size distriution ws otined y mesuring the dimeter of more thn 500 prtiles nd using Origin 7.5 softwre. PVP solutions in distilled wter were prepred in mol onentrtions of 05 M, 10 M, 15 M nd 20 M. The PVP solutions ply the role of the surftnt in the preprtion of PtNPs [13]. The ltion of Pt plte n e rry out y the 1064 nm fundmentl wvelength, 532nm seond hrmoni or 355 nm third hrmoni of Nd:YAG lser. 3. Results nd disussion Using 532 nm wvelength of Nd:YAG lser with verge power of 400mW, irrdition time of 15 min, PtNPs in PVP solution with onentrtions of 10 M. XRD ptterns of the PtNPs re shown in Fig.2.
20 N.T. Binh et l. / VNU Journl of Siene: Mthemtis Physis, Vol. 30, No. 2 (2014) 18-24 111 100 Intensity (.u.) 50 200 220 0 30 35 40 45 50 55 60 65 70 2 θ (deg rees) Fig.2. XRD ptterns of the Pt NPs produed in PVP solution. o o o In the XRD ptterns there re 3 peks t 2θ = 39.8, 46.3 nd 67.4.These peks orrespond to the hrteristi diffrtion peks of the FCC rystlline struture of Pt. The (111) pek is the strongest. The UV-Vis sorption spetr of Pt nnoprtile olloids produed in PVP solution re shown in Fig.3. The hrteristi plsmon resonne sorption pek of Pt nnoprtile olloids ws oserved t 233 nm. 233 Pt - PVP - 1M Fig. 3. UV-Vis sorption spetrum of Pt PNs produed in PVP solutions of 1M. Fig.4 shows TEM imge nd the size distriution of the PtNPs produed in 1M PVP solution using 532nm wvelength with n verge lser power of 400mW nd lser irrdition time of 15 min. From this figure it is seen tht the dimeter of Pt nnoprtiles rnges from 2 to 20 nm. The verge size of Pt nnoprtiles is 9 nm
N.T. Binh et l. /VNU Journl of Siene: Mthemtis Physis, Vol. 30, No. 2 (2014) 18-24 21 () () Fig.4. TEM imge () nd size distriution () of the Pt NPs produed in 1M PVP solution. To study the role of lser influene nd lser irrdition time in the ltion proedure we hve prepred PtNPs with different verge lser powers nd lser irrdition times. The sorption spetr of PtNPs prepred in 1M PVP solution using 1064 nm wvelength with different verge lser powers rnging from 200mW to 550mW nd lser irrdition time of 15 minutes re plotted in Fig.5. 23 23 235 238 242 d e. Pt -PVP - 200mW. Pt -PVP - 250mW. Pt -PVP - 350mW d. Pt -PVP - 450mW e. Pt -PVP - 550mW Fig.5. UV-Vis sorption spetr of Pt NPs prepred y different verge lser powers, From Fig. 5, one n see tht with the inrese of the verge lser power, from 200 mw to 550 mw, the sorptne inreses nd the sorption pek is shifted to the shorter wvelength (lue shift). Aording to the Mie theory for sphere nnoprtiles [14-17], the lue shift of the resonne plsmon sorption pek proves the derese of the nnoprtile size. Fig.6 shows UV-Vis sorption spetr of PtNPs produed in 1M PVP solution y 400 mw verge lser power with different lser exposure time.
22 N.T. Binh et l. / VNU Journl of Siene: Mthemtis Physis, Vol. 30, No. 2 (2014) 18-24 2.5 234.5 232.5 231. Pt - PVP - 10 min. Pt - PVP - 15 min. Pt - PVP - 20 min Fig.6. UV-Vis sorption spetr of Pt NPs prepred with different lser exposure times. As seen from Fig.6, the undne of Pt PNs inreses nd the sorption pek is shifted to longer wvelength (red shift) with the inrese of lser exposure time from 10 to 20 min. Using 1064 nm fundmentl wvelength nd 532nm, 355nm hrmonis of Nd:YAG lser, we investigted the influene of different lser wvelengths in the proess. The sorption spetr of Pt NPs prepred in 1 PVP solution y verge lser power of 250mW with different lser wvelengths re shown in Fig.7. 0.8 230nm 0.6 0.4 238nm. Pt - PVP - 355nm. Pt - PVP - 532nm. Pt - PVP - 1064nm 0.2 242nm Fig.7. UV-Vis sorption spetr of Pt NPs prepred y different lser wvelengths, verge lser power of 250mW, lser exposure time of 10 min. The otined result in Fig.7 shows tht the sorption pek orresponding to the wvelength of 532 nm is highest, menwhile the one orresponding to the wvelength of 355 nm is lowest. This mens tht the lser ltion effiieny is lowest t the lser wvelength of 355 nm in the experimentl onditions. It is ontrst to the se of ltion in ir where the shorter wvelength (355 nm) or higher photon energy ltes metl more strongly thn the longer wvelength (1064 nm). The low lser ltion effiieny n e explined y the sorption effet of PtNP olloid on lser em of 355 nm wvelength whih is ner the resonne Plsmon sorption pek of Pt NPs. Menwhile, the 1064nm nd 532nm wvelengths re fr from the resonne sorption pek (Fig. 7) nd the shorter
N.T. Binh et l. /VNU Journl of Siene: Mthemtis Physis, Vol. 30, No. 2 (2014) 18-24 23 wvelength (532nm) with higher photon energy ltes metl more strongly thn the longer wvelength (1064 nm). The 532 nm wvelength gives highest lser ltion effiieny in these experimentl onditions. The influene of PVP onentrtion on PtNPs size ws lso investigted. Fig. 8 presents the sorption spetr of PtNPs prepred in different onentrtions of PVP solution y verge lser power of 300mW, lser exposure time of 15 minutes. 233 236 234.5 233.5 23 e d PVP.001M PVP.005M PVP.010M d PVP.015M e PVP.020M 300 400 500 Fig. 8. The UV-Vis sorption spetr of Pt NPs prepred in different onentrtions of PVP solution y 1064nm wvelengths, verge lser power of 400mW, lser exposure time of 15 min. With the inrese of the PVP onentrtion, from 01M to 1M, the sorption profiles eome nrrower nd the hrteristi plsmon resonne sorption peks of PtNPs re shifted from 23 nm to 236 nm. When the PVP onentrtion inreses from 01M to 1M, the plsmon resonne sorption pek is shifted from 23 to 236nm (red shift). When the PVP onentrtion inreses from 1M to 2M, the plsmon resonne sorption pek is shifted from 236 nm to 233 nm respetively (lue shift). The ft tht the sorption spetrum profile is nrrower proves tht the derese of the dispersion of size distriution n e explined y the presene of PVP. Indeed, in the presene of PVP - (C 6 H 9 NO) n, the C=O group of the polymer interts with metl toms on the surfe of nnoprtiles. The oxygen toms of C=O group re tthed to the metl toms nd rete lol surfe stte tht protet metl nnoprtiles ginst growth nd ggregtion [18]. 4. Conlusion With the im to find out n optimum lser ltion proess for preprtion of PtNPs in PVP solution, the ffet of lser power, lser wvelength, lser exposure time nd onentrtion of PVP on morphology, size distriution nd optil properties of Pt NPs ws investigted. Among 3 wvelengths of Nd:YAG lser used (nmely 355, 532 nd 1064 nm), the 532nm wvelength gve the highest lser ltion effiieny. The role of PVP solution s surftnt for Pt NPs ws eluidted. With inrese of the PVP onentrtion, from 01M to 2M, the UV-Vis sorption spetrum profiles eome
24 N.T. Binh et l. / VNU Journl of Siene: Mthemtis Physis, Vol. 30, No. 2 (2014) 18-24 nrrower nd hrteristi plsmon resonne sorption pek of PtNPs is shifted. The otined results showed tht the size of PtNPs n e ontrolled y hnging PVP onentrtion nd lser prmeters. Aknowledgments This reserh ws supported y the Projet QGTĐ.11, VNU Hnoi. Referenes [1] Zhng Y J, Hung R, Zhu X F, et l. Synthesis, properties, nd optil pplitions of nole metl nnoprtileiomoleule onjugtes. Chin Si Bull, 57 (2012) 238-246. [2] Hes A J, Chng L, Klein W L, et l. Detetion of iomrker for lzheimer's disese from syntheti nd linil smples using nnosle optil iosensor. J Am Chem So, 127 (2005) 2264 2271. [3] Endo T, Kermn K, Ngtni N, et l. Exittion of lolized surfe plsmon resonne using ore shell strutured nnoprtile lyer sustrte nd its pplition for lel-free detetion of iomoleulr intertions. J Phys: Condens Mtter 19 (2007) 215201. [4] M. G. Guzmn, J. Dille, S. Godet, Synthesis of silver nnoprtiles y hemil redution method nd their ntiteril tivity. Int. J. Chem.Bio. Eng. 2 (2009) 104-111. [5] D. Long, G. Wu, S. Chen, Preprtion of oligohitosn stilized silver nnoprtiles y gmm irrdition, Rd.Phys. Chem 76 (2007) 1126-113. [6] K. A. Bogle, S. D. Dhole, V. N. Bhorskr, Silver nnoprtiles: synthesis nd size ontrol y eletron irrdition, Nnotehnology 17(2006) 3204. [7] K. Mllik, M. J. Witom, M. S. Surrell, Polymer stilized silver nnoprtiles: A photohemil synthesis route, J. Mter. Si. 39 (2004) 4459-4463. [8] H. Yin, T. Ymmoto, Y. Wd, S. Yngid, Lrge sle nd size-ontrolled synthesis of silver nnoprtiles under mirowve iirdition, Mter. Chem. Phys. 83 (2004) 66-70. [9] J. Zhu, S. Liu, O. Plhik, Y. Koltypin, A. Gednken, Shpe-Controlled Synthesis of Silver Nnoprtiles y Pulse Sonoeletrohemil Methods,Lngmuir 16 (2000) 6396-6399. [10] F. Mfune, J. Kohno, Y. Tked, T. Kondow, Struture nd Stility of Silver Nnoprtiles in Aqueous Solution Produed y Lser Altion J. Phys. Chem. B, 104 (2000) 8333-8337. [11] [11] The Binh Nguyen et ll, Preprtion of opper nnoprtiles in wter nd etone y lser ltion, VNU Journl of Siene Mthemtis-Physis 27,No IS (2011) 51-56. [12] The Binh Nguyen et ll, Preprtion of metl nnoprtiles for surfe enhned Rmn sttering y lser ltion method, IOP Siene, Avd. Nt. Si. Nnosi. Nnotehnol. 3 (2012) 025016. [13] Milton J. Rosen (2004), Surftnts nd interfil phenomen, Wiley-Intersiene, United Sttes of Ameri. [14] Cowley A nd Woodwrd, A Helthy Future: Pltinum in Medil Applitions, B 2011 Pltinum Metls Rev. 55 98 10. [15] Athnssiou E K, Grss R N nd Strk W J, Lrge sle prodution of ron oted opper nnoprtiles, Nnotehnolgy, 17 (2006) 1668-1673. [16] Mfune F, Kohno J nd Tked Y Dissoition nd ggregtion of gold nnoprtiles under lser irrdition, 105 (2001) J. Phys. Chem. B 9050 9056 [17] Mfune F, Kohno J, Tked Y nd Kondow T Formtion of stle pltinum nnoprtiles y lser ltion in wter, 107(2003) J. Phys. Chem. B 4218 4223 [18] Tkeshi Tsuji, D.-H. Thng, Yuuki Okzki, Mstk Nknishi, Ysuyuki Tsuoi, Mshru Tsuji Preprtion of silver nnoprtiles y lser ltion in polyvinylpyrrolidone solutions (2008) Applied Surfe Siene 254(16):5224-5230.