HWAHAK KONGHAK Vol. 38, No. 3, June, 2000, pp (Journal of the Korean Institute of Chemical Engineers) Microemulsion Pd/ZrO 2 Pd ( ,

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1 HWAHAK KONGHAK Vol. 38, No. 3, June, 2000, pp (Journal of the Korean Institute of Chemical Engineers) Microemulsion Pd/ZrO 2 Pd ( , ) Size Control of Pd Particles of Pd/ZrO 2 Catalysts Prepared by A Novel Preparation Method Using w/o Microemulsion Won-Young Kim and Tae-Jin Lee School of Chemical Engineering & Technology, Yeungnam University, Kyongsan , Korea (Received 17 November 1999; accepted 6 January 2000) CO Pd/ZrO 2, Pd waterin-oil microemulsion!" #$ %& # ', Pd ()* +,) -./ 0 12 % 34, micelle% 5, hydrazine% 34 6 Pd ()* 78 9: ;& < Pd ()* microemulsion B 12C7D) EF G HI hydrazine% JA microemulsion% K#L, 12 % 34 MNOP Pd QRS TUV WX Pd ()* 2-12 nm% YZ +F 0[>. Abstract The hydrogenation of carbon monoxide was carried out over zirconia supported palladium catalysts prepared by a novel preparation method using water-in-oil microemulsion composed of organic solvent, surfactant, aqueous palladium salt solution. The catalysts prepared by the microemulsion method were found to exhibit a high activity for the hydrogenation of carbon monoxide. In this study, the effects of the micelle size, the concentration of palladium salts, the concentration of hydrazine were investigated. It was found that the palladium particle size could be controlled from 2 nm to 12 nm by altering the concentration of hydrazine and palladium salts regardless of palladium content. Key words: Metal, Microparticle, Microemulsion 1.,! "# $%&' ( )* +, -./ 0 120( :;<= >?@=. A % B' ( * CD89E F( GHI J KD* L KD8 M=. L KD8 N ( ( OP, ( QR* STU FV QWR XY5 Z * [\8 ]^_ `P[1-3], [abc d e< f HI * g I Qh iyjp[4-6] k89 Vl* m=. <n, o; G'( ( p`q Qr' st microemulsioni k< uv( KD* m w8m=[7-11]. microemulsion G' FV nm _x' FV QW* Z yz. N{0 " FVI y\ wykim@ynucc.yeungnam.ac.kr }' [9z. N= ~HI N!=. A, < u f ' [\ƒ KD =. A %' 2 h f ; ˆh Šƒ= H0, microemulsion G N9' [\ C< ŒRL S * ƒ= HI Ž. N=. c d * OPI kb' ( < KD ƒ, ( FV }' 12 ), ƒ R =. w89e, F +, ƒ T ( :;I 7z. = _ I ], 8M=. < švt œ ž5>( Ÿ I :;h B' FVI [9z C* N=. ;' < c d, [\ N9' ( G( ( ) [9B' (( F VI * [\ƒ GC< ( =. A, ( 9ª< OP N9'R & ƒ4 ( FVR B', FVI «5T [9ƒ * =. 14, KD'( microemulsioni k< [\P[12-16]' 355

2 356 microemulsion G' FV yb', f ; ƒ! &I #ƒ, %ƒ4' FVI [9z. N= >?@=. A, microemulsion G( FV [9 D ƒ =. ±², ( ³* = 4 FV [9 D* B' [9R <=. A µ, microemulsion G' v 8 Pd 7B' *( FV [9* Pd F V :I KDƒ l GCƒ=. }', KD ' y* œ( ¹ºa y S I w Pd/ZrO 2 G»T microemulsion G' v8 Pd u( FV0 [\\ 0( ; I \_$T Pd/ZrO 2 ( Pd FV( [ 9 B KDƒ = Pd/ZrO 2 ( [\ k@ microemulsion¼, cyclohexane/pdcl 2 / polyethyleneglycol-p-nonyl phenyl ether[c 12 H 25 (OC 2 H 4 ) 23 OH, NP-5] _k =. ½.ko ¾ ½.koI _kƒ #ŒR ŽM=. Fig. 1'c d microemulsion G hydrazine(n 2 H 4 )I 3 À9' vá=. A ={, ko f ÂÃ zirconium butoxide[zr(obu) 4 ] Ä I Å*ƒ, i(25 o C)' 1 Æ "Ç *.QB È< É0, $%ƒ ÊËI ÌM=. '( 0o Í³ƒ ½( ŒR ICP(Inductively Coupled Plasma mass spectrometry, Nippon Jahrrell-Ash ICP575II) (B' Q < É0, Å*< ½( 1% ƒî Ïˆ8 ' 7 Q( 89 N= _ I ]. NM=. ={T, A ÊËI ]Ða ÑÒ Ä Â» QÓ ƒ, 80 o C' 12Æ" Ç \< Ô 350 o C' 2Æ"Ç Õ ƒ' Ö ¼4 Fig. 1. Preparation procedure for Pd/ZrO 2 catalysts using w/o microemulsion [ [ =. A Ô, mesh ØÙvB'.Ö jâi < ={ 12 _kƒ =. ƒ, [\P (B' [\@ MEP Ú<=. & Û (1) (B' ¼ =. Å*< ( G& &[wt%] = (1) [ Ì ( G& AÓ, MEP c XYƒ B' _k89ü $ÊP Zirconyl nitrate.ko( ph \Ý (B' ÊË<. ZirconiumI Õ ÖB' Ì Zirconia f PdCl 2 $ÊÁ=. A Ô MEP c "#< \ T.Ö jâþt ÌM= G( ( FV ß, XRD(X-ray diffraction, RIGAKU RINT2500KS) _k =. XRD ß,.ÖjÂ Ô( Q à Ž9' 50 kv, 300 ma( Ë³' á>ƒ Cu-KαŸI 2 o /min Ã \_ƒ, I 6â 1ãB' 5< âýer Dƒ =. Ì9Ü peak œ Scherrer Û[6]I _kƒ ( FVI Dƒ =. AÓ, G( ( 3 äi ƒ, TEM(Transmission electron micrography, # Ë JEM-2000FX)I _k =. å Vk Ã,.Ö jâ Ô( æ, ç ' ºa Q koi è)aó`(typea, éêëì) Ö& 5ƒB' 12Æ Õ G \ ' [\ =. TEM ä œ Ì9Ü íî FV ï 100ð R( F ßB' 45 íî FVT' ˆ = Microemulsion G( FV [9 D ñòe N, ( ³* óer FV [9 D* B' [9 R ô= ]õe N=. }', microemulsion G' v8 7B' * FV [9 * FV :I \_ƒ l GCƒ= z. N=. Microemulsion G' ( >0 microemulsion 9ª< vö ƒ N* B' *( B* N, 9ø ƒ ( microemulsion¼ N9' >?z Vl, microemulsion ( ù á>i Ü<= Bc s 5 ( FVI Ç h úzi <= B* N=. ù á>0 microemulsion ƒ Vl, < ð( micelle û W$89 N ÂÃ i(. (B' ù á>.* ), óü= >?8! ( F ) micelle û( i(. (ü<= >?@ =. ', A i(. micelle( )c micelle û( i ŒR( $.' ýz. N=. <n, microemulsion s 5 FV( Ç ƒ Vl, ( F ) micelle( ) ¼ i erc HR þ( (üƒ T >?@=[17]. Microemulsion G'( ( ) [9$ N9' ù á> 0 microemulsion <= B', microemulsion G( 0 ¼4[( ÿ X(w value) Xƒ micelle ( ), micelle û( i( ŒR, u yz Å*ƒ N hydrazine( ŒR* [9 >?@=. A Ó, s 5 F )( Ç <= B', y( phc i er þ [9 * 8 T KD', < * [9 Ž G' microemulsion ( micelle( ), micelle û( ÂÃ ½.ko( ŒR, hydrazine ( ŒR, ier, ph þ( [\\ FV : 7B' \_ =.

3 Fig. 2. Effect of ph on Pd particle size of Pd/ZrO 2 catalysts prepared by microemulsion method ph hydrazine MEP (B' Pd/ZrO 2 [\z ph* Pd FV : 7B' Ï =. A É0' Ì9Ü FV0 phc( ¼ Fig. 2 ûm=. Fig. 2 œ Pd FV y ( ph ), (üb', ph 8L ph* S g./ F V U ph 8;' FV( (. V:I ÌI. NM=., ph( B' vƒ ( ý4 Ëƒ* B' ( 2 R* < É0 œ Pd/ZrO 2 ¼ N9' ( 2 I [ƒ B' \ ' yi ƒ %Óƒ= _ I ]=. Microemulsion G' yz Å*ƒ hydrazine (N 2 H 4 )( ŒR* Pd FV : 7B' Ï =. Fig. 3 [N 2 H 4 ]/[PdCl 2 ]c Pd FV0( ; I ûm=. Fig. 3T œ Pd FV hydrazine( ŒR ), (üb', [N 2 H 4 ]/[PdCl 2 ] ŒRX* ï 3š Vl *~ + _ I ]=. AÓ, [N 2 H 4 ]/ [PdCl 2 ] ŒRX* 3; A ƒ VlR Pd FV 67ƒ V:I w =., [N 2 H 4 ]/[PdCl 2 ] ŒRX* 3ƒ V ME Pd/ZrO 2 Pd 357 l hydrazine( Pd i XB' 5 % ùi >ƒ < Pd Â* üƒ ù ¼5T 2! >?@=. <n, ŒRX* 3; Vl hydrazine( Pd i XB' m % ph* ;B' ' < c d ( 2 R* E' 2 #9 * >?@=. < É0Ž œ, Pd/ZrO 2 ¼ N9' y( ph Ä hydrazine( }' 2-12 nm Pd F VI «5T [9z. NM= Pd micelle Water-in-oil microemulsion G' v8 u( ) microemulsion( \ þi T ƒ T ]õe N=. AÓ, microemulsion G( ( ù á>rc F>R( (B' FV ÉR <= *( FV É( ¹ [Ç8M=. Ž4, Nagy[8] þ CTAB(cetyl trimethyl ammonium bromide)/1-hexanol¼ microemulsiong' y< NiBc CoB( u( )* microemulsion( ûù.; Ç W$@ Ni(II) Co(II) i(. }' <= ûm=. NiBc CoB( ù á>r* l = I (<=. AÓ Suzuki þ AOT/ iso-octane¼ microemulsion G' y< CdS * Cd 2+ c S 2 ( ;7ŒR }' <= wƒ N, A Â CdS ( ~I [ƒ! <=. A, y< u( )* micelle( ) Ä ÂÃ ½( ŒR (üƒ VlR m=. } ', KD' microemulsion G( micelle( ) Ä ÂÃ Pd ½.ko( ŒR* Pd FV : 7B' Ï =. lÿ, microemulsion G( Pd ½.ko( ŒR* Pd FV : 7B' Ï< É0 Fig. 4 =. ' microemulsion G( 0 ¼4[( ÿ X(w/s value) 4.4 #ƒ, % ' [\ =. Fig. 4 Pd FV TEM ä œ ¼ß< =. A' ]. N Pd FV Pd ½. ko( ŒR* 1.0 mol/l' *~ +, 8, Pd ½.ko( ŒR* Aw=R ) + R 67ƒ V:I w =. AÓ "#< &( $ÊP ( Pd FVR d ûm, \ ' Pd FV 12 nm MEP ( Vl' ± + Pd F* [\@= _ I ]=. Microemulsion G( micelle( )* Pd FV : 7B' Ï< É0 Fig. 5 =. Pd ½.ko( ŒR 0.56 mol/l #ƒ, % ' [\ =. ( Pd FV! Fig. 3. Effect of [N 2 H 4 ]/[PdCl 2 ] molar ratio on Pd particle size of Pd/ ZrO 2 catalysts prepared by microemulsion method. Fig. 4. Effect of PdCl 2 concentrations in water-pool on Pd particle size of Pd/ZrO 2 catalysts prepared by microemulsion method. HWAHAK KONGHAK Vol. 38, No. 3, June, 2000

4 358 Fig. 5. Effect of w value on Pd particle size of Pd/ZrO 2 catalysts prepared by microemulsion method. " N9' ï 3nm ( * M=. }', KD ' k< NP-5/cyclohexane¼' Pd y< Vl, microemulsion Pd F( Ç ƒ T >?@=. < É 0 Rh ( FV (ü( É0[13]c =#$, A % o ; G'( ( ;ö* Pd F 14 Rh jâ[ Å*ƒ hydrazine0 12ƒ %ff v8!# T >?@=. AÓ, Pd ½.ko( ŒR }' Pd ( FV < Pd F 7B' Õüƒ ( }' Pd ( 2 R*! >?@=. 3-3.!" ' '&< c d, NP-5/cyclohexane¼ N9' microemulsion s 5 Pd F( ) Çh úzi <= B' ( F ) micelle( ) ¼ ierc HR þ( (üƒ T >?@=. Pd ½.ko( ŒR ' Pd F( \_< Ž Pd ½.koI Ž _kƒ ½T B' ierc Pd ½.ko( ŒR* d! Pd ½.koŒR( :I \_< É0' Pd F ( )* < < Pd ½.koŒR( : 4 ier( : z. = I ]=. A ', Pd ½.k o( ŒR #ƒ, %hu ier h 0 ie Fig. 7. XRD patterns of Pd/ZrO 2 catalysts prepared by microemulsion method. R #ƒ, %h Pd ½.ko( ŒR ' [ \ƒ Pd F)( \_ =., [\\ "#ƒ, 'M=. [\\ Fig. 6 ûm=. Fig. 6'( (a), (b) ier #ƒ, ƒ, (c), (d) Pd ½.ko( ŒR #ƒ, % ' [\ƒ =. (, [\@ Pd/ZrO 2 ( XRD-patternI Fig. 7 ûm=. Fig. 7' ]. N Pd F( ) Pd ½. ko( ŒR #ƒ, %hu ier Vl ( û T, ier #ƒ, %h Pd ½.k o( ŒR Ž' Pd ½.ko( ŒR* ) g./ Pd F( )* V:I ûm=. < É0 Pd ½.k oœr }# F)( :0( ; I \_ =. A É0, Fig. 8 ' 0 d Pd F( ) ier #ƒ, % h Pd ½.ko( ŒR É0c Fig. 4'( É0* ( # $I ]=. < É0Ž œ MEPT [\< Pd/ZrO 2 '( Pd F)( ier( : (< Pd ½.koŒR( : (< I z. NM=. Fig. 6. Preparation condition of Pd/ZrO 2 catalysts Fig. 8. Pd particle size of Pd/ZrO 2 catalysts prepared by microemulsion method.

5 4. KD', y* œ( ¹ºay H' ¹ºa y %k< Pd/ZrO 2 G»T microemulsion G' v 8 Pd u( F)c [\\ 0( ; I \_$T Pd/ZrO 2 ( Pd F) [9 =. ;( KD É0 œ = {( É*I ÌM=. (1) Pd F) y ¼'( ph ), (üb', ph* S g./ ( F)* V:I w =. É0 œ Pd/ZrO 2 N9' F( 2 I [ƒ B' ' [\ƒ %Óƒ= I ]. NM=. (2) MEPT [\< Pd/ZrO 2 N9', Pd u y ƒ B' Å*ƒ N hydrazine( Pd F) : 7B' \_< É0, Pd F( ) hydrazine( ), (üb' [N 2 H 4 ]/[PdCl 2 ] ŒRX* ï 3š Vl *~ + Ü= _ I ]=. < É0Ž œ Pd/ZrO 2 ¼ N9' y( ph Ä hydrazine( }' 2-12 nm Pd FVI «5T [9z. NM=. (3) Microemulsion v\ ' Pd ½.ko( ŒR ÞT Pd &I #ƒ, %h4' G( Pd F) 2-12 nm Pd FVI «5T [9z. NM=. <, Pd ½.ko( ŒR* 1.0 mol/l' Pd FV 2nm *~ + Ü= _ I ]=. 1. Yakai, Y., Ueno, A. and Kotera, Y.: Bull. Chem. Soc. Jpn., 56, 2941(1983). 2. Tanabe, S., Ida, T., Suginaga, M., Kotera, Y., Tohiji, K. and Udagawa, ME Pd/ZrO 2 Pd 359 Y.: Chem. Lett., 1567(1984). 3. Tamagawa, H., Oyama, K., Yamaguchi, Y., Tushuiki, H. and Ueno, A.: Chem. Lett., 1189(1986). 4. Furuoya, I. and Shirasaki, T.: Bull. Jpn. Pertol. Inst., 13, 78(1971). 5. Renouprez, A. J. and Imelik, B.: J. Catal., 39, 334(1975). 6. Gallezot, P.: Catal. Rev. Sci. Eng., 20, 121(1979). 7. Boutonnet, M., Kizling, J., Stenius, P. and Maire, G.: Colloids Surfaces, 5, 209(1982). 8. Nagy, J. B.: Colloids Surfaces, 53, 201(1989). 9. Hirai, T., Sato, H. and Komazawa, I.: Ind. Eng. Chem. Res., 32, 3014(1993). 10. Hirai, T., Sato, H. and Komazawa, I.: Ind. Eng. Chem. Res., 33, 3262(1994). 11. Hirai, T., Sato, H. and Komazawa, I.: J. Chem. Eng. Japan, 27, 590(1994). 12. Kim, W. Y., Hanaoka, T., Kishida, M. and Wakabayashi, K.: Applied Catalysis A, 155, 283(1997). 13. Kishida, M., Kim, W. Y., Hanaoka, T. and Wakabayashi, K.: Kagaku Kogaku Ronbunshu, 21, 990(1995). 14. Kim, W. Y., Hayashi, H., Kishida, M. and Wakabayashi, K.: Applied Catalysis A, 169, 157(1998). 15. Hanaoka, T., Kim, W. Y., Kishida, M., Nagata, H. and Wakabayashi, K.: Chemistry Letters, 645(1997). 16. Kishida, M., Kim, W. Y., Nagata, H. and Wakabayashi, K.: Applied Surface Science, 121, 347(1997). 17. Kurihara, K., Kizling, J., Stenius, P. and Fendler, J. H.: J. Am. Chem. Soc., 105, 2574(1983). HWAHAK KONGHAK Vol. 38, No. 3, June, 2000