Shape-Controlled Synthesis of Colloidal Platinum Nanoparticles ‘Temer S. Ahmadi; Zhong L. Wi El-Sayed avis C. Green; Arnim Henglein; Mostafa A. Science, New Series, Vol. 272, No. 5270 (Jun. 28, 1996), 1924-1926. Stable URL htp:/Mlinks jstor.org/siisici=0036-8075% 28 19960628%293%3A272%3A5270%3C 1924%3ASSOCPN%3E2.0.CO%3B2-W Science is currently published by American Association for the Advancement of Science. ‘Your use of the ISTOR archive indicates your acceptance of JSTOR’s Terms and Conditions of Use, available at hup:/www,jstororglabout/terms.hml. ISTOR’s Terms and Conditions of Use provides, in part, that unless you have obtained prior permission, you may not download an entire issue of a journal or multiple copies of articles, and you may use content in the JSTOR archive only for your personal, non-commercial use. Please contact the publisher regarding any further use ofthis work. Publisher contact information may be obtained at hutp:/www jstor.org/joumals/aaas html. Each copy of any part of @ JSTOR transmission must contain the same copyright notice that appears on the sereen or printed page of such transmission. STOR is an independent not-for-profit organization dedicated to creating and preserving a digital archive of scholarly journals. For more information regarding JSTOR, please contact support @jstor.org, upslwww jstor.org/ Fri Oct 8 19:08:13 20048. Olena a i 72, 2251 (1994 JL Kans ‘Bas Meron Pater, Pye 80) 17659 (Toba, Ne hans a afte 375, 76 (1995, tra recreneen rare 4, Qedpachm, i Cimaawsl. RR Seite, C. ha Pe, Po. at 74, 2102 (108), 5. NO lang Pigs Fa 82, 825 1909) OL M Gar, PS. Wes, EK. Setwoanr, NO. eg Fs Re Ltt 6 1189 (195), 7, DML ger and EK. Shar ate 94, S24 (i080, 8, DiM Eg. Lt WY, Rudge 952, 600 feet 9, BLM. Gol aC P. Lute unoubehod ets 10, ie meanred J vers Vand a wore th waproV ampere ner eran 90m 11. We have Ral the vo drop seroes the STM Jmeton costa a we tended the > ped To ‘war the satac. Assets the mod yh ‘ae bocome important hen th rosstance of he ‘tion bocames comparable 10th Tio put resistance 20 keh) of ur lactose. 12, Todetemie ti-sutace sparatn, wa have oom. pore the moaned wrsue Deuce thei” {esto a eaculaton by Lang (3 which mes tre SM jncton as two jalum srtaone wih 3 sng Sstomadecrossen an oft auroces, Tecate ter orewe that an epoca ef 2 = 10 chs for ‘Th uncon corerponss 1 8 tp hah! asowe thosurace of ~7 A. Wo hve fund ang'scaoua ten tote corset wh vert D rasents taken on th same N surface (). We used ts faltation, toga wh the meer changes in tp hogit se to re pocance of cr a to Xo Sma nthe uneton, to dele the ip surace Scorer, 12ND. Lang, Pye. Ay, Let, 98,8179 (987% JK Ciao and R. Mi, ys Ror 98 184 {issn 14, Vefalneor ae PB. Latin, Ps Ro, 26, 805 (997), 15. N-. Lang, So State Phys. 28,225 (1879). 16D. Maran, M. Ser. Chan, Fy: Av Shape-Controlled Synthesis of Colloidal Platinum Nanoparticles Temer S. Ahmadi, Zhong L. Wang, Travis C. Green, Arnim Henglein, Mostafa A. El-Sayed* ‘The shapes and sizes of platinum nanoparticles were controlled by changes in the ratio Cf the concentration ofthe capping polymer material to the concentration of the platinum cations used in the reductive synthesis of colloidal particles in solution at room tem- perature, Tetrahedral, cubi lrregular-prismatic,Icosahedral, and cubo-octahedral par- ticle shapes were observed, whose distribution was dependent on the concentration ratio of the capping polymer material to the platinum cation. Controlling the shape of platinum nanoparticles is potentially important in the field of catalysis. Colloidal metal particles are of interest because of their use as catalysts (1), pho- tocatalysts (2), adsorbents and sensors (3), and ferrofluids (4) and because of the applications in optical (5), electronic (5), and magnetic devices (3). Catalytic reac” tivity depends on the size and the shape of the nanoparticles, and therefore the syn- thesis of well-controlled shapes and sizes of colloidal particles could be critical for these applications. Many studies on colloidal particles have focused on the control of particle sizes and their growth kinetics and have related pat- ticle size and catalytic activity (6). More- ‘over, research has shown that the degree of polymerization (1) and the concentration of the stabilizing polymer (2, 7) influence the size distribution, stability, and catalytic activity of colloidal particles. For example, ‘TS Aimed, 10. Gem LA Sa, Sahoo st Chensty and Becrarisey. Googe nei a Tech flog, Aorta, GA 32, USA, 22. Wang, Sotco of Matta Seieneasand Engrg, Gears tite of Teco, tata, GR 30008 2A Henalon, Hane Meter ine, Abteing Ken tehcertochung, 14108 Gorn, Crary Fig whem coresrondanos sau be saad 1024 a recent study (7) has shown that a higher ratio of capping material to metal produces smaller Au particles, However, shapé con- trol has heen much more ‘difficult to achieve, and the influence of particle shape on catalytic activity has not been reported to date The morphology of colloidal Au has been studied (8, 9), and shape-controlled synthesis of Au particles forming plateike trigons has been explained (10) in terms of the Kossel-Stranski theory of face-selective growth of erystals, Shape-controlled synthe- sis of polymer-protected Cu particles exhib- iting platelike hexagonal morphology has also been reported (11). Recently, the mor- phologies of Pr colloidal particles were stud- ied by means of ultravioletvisible spect photometry and transmission electron mi- croscopy (TEM) (12). A parameter S, de- rived from the optical spectrum, has been suggested as a measure of particulate shape and the degree of dispersion (12). In this report, we describe a method for the synthesis of colloidal Pe nanoparticles with controlled shapes. By changing the ratio of the concentration of the capping ‘material to that of Pe" at room temper: SCIENCE + VOL.272 + 28JUNE 1996 ot. 49, 1494{19795 6,8 Bachokt, DF, Haman, ‘Mer, Py. or. 8 26,4109 (1082, 17, Wesstd= 28K vecquteyimxebindng stance (tah excopt when 2 = 26 A whore wothan sets = 1 anount x he corres al he Ne ae 18, ND Lang Pye Rav Lat 46,842 (08. 18. Son Sr omph Fane, Py Sor 142,110, {to6.! Pye Condor. Matar 009 (1969. ley. vcctor Condensed hat Pryce Natara Voume Honor ot Shang kang he. Girton and G. Mazen, eos. (Word Scie, ‘Sngepore, 1085, po. 101-163, 20. Me Bitar, IBM Fes. Dew 32, 69 (10855 EO. Kano, n Tunneling Phonomenein Sat. Bison fre Ln Ea Param, New Yk 10 21. © seach ot al opty Let. 20,667 1002. 22 Wo tank.) Suertact, R,Landter C.P. Lite, a T Reivers hebhs distor We re also ‘ooo to Pu or toes aston 2b 196; aoe’ 29 A 1996 ture, we were able co change the distrbu- tion of Pr nanoparticle shapes. ‘The Pe nanoparticles were prepared by the method of Rampino and Nord (13) and Henglein etal. (14). A solution of 1 10~* M K,PrCl, was prepared in 250 ml of water, to which we added 0.2 ml of 0.1 M sodium polyacrylate (sample 1). We then bubbled Ar gas through the solution for 20 min. We then reduced the Pe ions by bubbling H, gas ata high flow rate through the solution for 5 min. The reac- tion vessel was then sealed, and the solu- tion was left overnight. After 12 hours, the solution turned lightly golden and the absorption spectrum showed the formation of colloidal Pt. We prepared samples 2 and 3 by adding to the starting solution LO and 0.5 ml of the 0.1 M polyacrylate so- lution, respectively, and following the same procedure, The initial ratios of the concentration of the capping material to that of the metal cation in the solution were therefore 1:1, 5:1, and 2.5:1 in sam= ples 1, 2, and 3, respectively. Because the concentration of the cap- ping polymer was changed in the prepara- tion of samples 1 through 3, the pH values of the searting solutions were also different. ‘The variation of pH in the three solutions ‘was small; it changed from 7.5 to 7.65 when the concentration of the polymer was changed by a factor of 5 (going from sample 1 to sample 2). In our synthesis, we adjusted the initial pH of the solutions to 7.5 in all three solutions. We investigated the structures of the Pe particles using a Hitachi HF-2000 field emission gun TEM (200 kV) with a point- to-point image resolution of better than (0.23 nm and a lattice esolution of 0.1 nm, We recorded the experimental images dig- itally using a charge-coupled device camera, which allows subsequent processing and quantitative modeling, We prepared theFig 1. (A) Low-magrifcation TEM image of sam le 1, showing the Size and shapa csnbtion of the cub parties (B) High recluton late ‘age of acubie Pt rented wth [100] paral othe Ineident boar; the Fourier transform ofthe latioe Image ies the optical tactogyam ofthe part le set, hich expty shows the presence of the {100} facet Fig. 2. (A) Low-magnification TEM image of sam: le 2, indicating the abundance of tetranedta (6) High-resolution mage oa tetranecal parle: the Furor transform ofthe latioe image gives the ‘optical dractogram ofthe parte (net. These panicles ae diferent rom the rounded-oomerW- anguie platlts cbsorved in Au and Aq (76, ‘TEM specimens by dispersing Pr particles ‘on amorphous C films that were less than 20 nm thick Sample 1 predominately contained par- ticles with a square outline (Fig. 1), whereas samples 2 and 3 contained high proportions of particles with a triangular outline (Fig. 2). By tileing the samples in. the TEM, we were able to determine the three-dimensional shapes of the particles. ‘The particles with square outlines were found to be cubic, and those with triangu- lar outlines were tetrahedral We measured the shape and size distri- butions of the partiles from enlarged pho- 100 [Abundanes of structure (3) 8 a8 ‘Sample number Fig. 9. Histogram showing the abundance of t- ferent shapes nahin each sample, Cubes ars pre- 2GaN + 3H) Usually, power samples of hexagonal GaN were synthesized by placing some source materials such as GaCi, or Ga (CHs)y une der flowing aramonia at temperaures fom 600" to 1000°C: (5). Recently, precursors such 6 [H,GaNHigh, of GaCyH15)NIy, which already have a Ga-N bond, could be pyrolysized to produce GaN at relatively low temperatures, but postreatment tem: peratures >500°C are needed (6) ‘(ie andV. Gan, Sromtra Research Laborsioy ard Depariert ot Appod Cromichy. Unie of Sanco ana Tectnateg/ of Che, He, Anu 230028, Pop's Frpubte of ra ‘Wang, Departont ot Applod Chom, Unhersyof ‘Schnen and Teeny of Grn, Hof rh 2026, People's Repub of ina. 5" hang and Zhang, Stuctire Research Labor, ‘eh 20026, Peopl's Rape of Chir, “To whom Sarespondence should be aessod, 1926 Nitrides of lanthanide and transition metals (M) can be synthesized through sol idestate metathesis reactions such as MCI, + LN MN + LiCl in the temperature range fom 600 10 1100°C (7). However, the reaction of Ga, with Li’ through a similar process for the preparation of GaN fled (8). as(coees) Fig. 1. An XRD pattem of nanocrystaline GaN ‘We report on the reaetioi of LisN with ‘GaCl, im benzene at 280°C under pressure in an autoclave. Nanocrystalline GaN was produced through what may be a liquid- solid reaction: GaCl, + LiN "5 GaN + 3LiCl We call chis technique a benzene thermal process, which is similar to a hydrothermal process, except that benzene is substituted for water In order to ensure the quality of the chemical reagent, LisN (9) and anhydrous GaCl, (10) were synthesized according to previously reported methods ‘An appropriate amount of GaCl, solu- tion in benzene and LisN powder was put into a silverliner stainless steel autoclave of 50-ml capacity, and then the autoclave was filled with benzene up co 75% of the total volume. The air dissolved in the solution was driven off by passing argon gas through the solution. The autoclave was maintained ‘at 280°C for 6 co 12 hours and then allowed to cool to room temperature. A dark-gray precipitate was collected that was washed ‘with absolute ethanol to remove LiCl. The final product was dried in vacuum at 100°C for 2 hours The xray powder diflrction (XRD) pattem was recorded on a Japan Rigaku Dina yA seray difractomerer with CuK radiation (X= 1.54178 A). In the XRD pattem (Fig. 1), reflections marked with doxs can be indexed tothe hexagonal cel of GaN with lateice constants a= 3.188 A and c= 5.176 A, which ate near the re ported values (11). However, an unusually Strong (002) peak in the pattern indicates a preferential orientation of [001] in nano- rystalline GaN. Other small reflections (iatked with circles) can be indexed to cic GaN in rocksale structure with a = 4.100 A, which i greater than the reported value of 4006 A at 50 GPa (3). The curve of volume versisprestte (3) shows that the 1 ip Fig. 2 (A) A TEM micrograch of nanocrstaline GaN, (Band ©) HREM images ofnanocrystaine GaN [B)Latice inges of (601) plane in GaN wah a wurtzite structure and (C)/atica ringas of (00) and (110) planes in GaN (marked Aand B, respectively wilt a rocksaf structure SCIENCE * VOL.272 + 28JUNE 1996