無電鍍銅觸媒應用於一氧化碳氧化反應之研究

(1)

1 CO Oxidation by Electroless Copper Catalyst

: NSC88-2214-E011-006

87/8/1 – 88/7/31

!" (#$% &'()*+

,-,./)

012"3456789:'()

;67&*+/<=,-,./>

?@ABCDEFG;67*+HIJ :KA67LMNOPQR>S;T<

UVWX>YZCT[\]^_A*+

`ab<XRDBETTPRN 2 Oc dSEM_efS;HghiBC,

-,./12+>./RaAjk lm&gnaJo>DEFG;+ip Raq=&gnaJr>'()&*+A

<cd;Rs<JtU>uRvwJ x./Ra>'()&+AVWXyC EDTA z{|ivwJ}~g>&

+A*+8500[\:,-,

./RazrA

Abstract (Keyword: Copper, Electroless catalyst, CO, Oxidation)

The purpose of this study is to investigate the effects of preparation method on the electroless copper catalyst for CO oxidation reaction. The impregnated copper catalysts are also prepared for comparison.

All prepared catalysts were characterized by XRD ƋBETƋTPRƋchemisorption and SEM.

The catalysts were further tested by CO oxidation reaction. Experimental results show that the catalysts prepared by the electroless method has better activities than those prepared by the impregnation method, and the electroless copper catalysts

prepared by EDTA chelating agent were better than those by TEA chelating agent.

Furthermore, the calcined electroless copper catalyst (at 500C) presents highest activities among all the catalysts.

12>

>i

ip">

\ ¡¢£¤¥¦>,-A§

¨,->"S;,->*+

,./A©zª«sz¬<>*+

®C¯u°_±²³A=´

Y±²³¥Uµ¶·¸±iL´ª¹ º12»¼½¾¿ÀÁvCÂÃ´Z±

²³>Ä²³ACÅ>12jklm3 Ä²³C&zªv¾Æ±²³>Â ÃÇAÈÉÊi¹º»12&*+3

,-,./>RaA012Ë12

©ÌÍZÎÏ./Ði'(Ñ;67Á Ê>&*+IÒÓ>FG; ÔÕÖ;¤

67ÁÊ>&*+«kÊwrA0¼

½×<'(Ñ;67&*+B/<=,

-,./ØA Ù12S;

1. *+67

'()&*+>67ÚÛÜPQÝ ÞßÞàiáCuâãRàiäå' ()&âãH'()iæÆàçè

éÆ'()&*+Aêë[\iyCìí

>]^Ùqî[\æÆAFG*+yC

ÒÓ>EïFG;67æÆAðñ<>*

(2)

2 +"gÙZ òZÚ×<'();

¤67Á>'()&+óòZ>+

Ú×<DEFG;¤67Á>+óòÙ Z>+Ú×<EïFG;67wAô : * + Ã õ ö ò Z * + C (1).FE-t-f FE-e-c (2).IE-e-fIE-t-c ÷i F øPQ<cd;RiI øPQ<FG;

R A E ø ' ( ) ; ie øVWX

EDTAit y TEAAf øùú*+ic ø

8[\AòZ*+ IWI DEFG

;AFIWI Ûcd;RPQiáDEF G;AIIWI ÛFG;RPQiàáD EFG;AòÙZ*+ CI ÔFG;A 2. CO,./

Ü 0.5 g *+ûüý=./þi®à

å H ₂ /Ar Wi= 250>]^

¢*+ 8 qîàiË]iá

,-T,>WiB./

H./A

jk5

1. XRDgh

3XRDi&111>`a

&FU>óuFU>

åBªÆ&`a> !i"

8FE-t#'()*+>&100`a

iuFU>i^!iFE-e

#'()*+y$r%.lmu>å

&?@`õ>j'A8[\à>*

+&`a^i=ª[\8>i

í*+8750[\ài©ª(Ý

&>j'Á©is&>`a^)

ADEFG;¤w>+ip&`a

^}='()&*+A 2. BETgh

ø¤ª+>BET+ø,T- }./ABETjklmiDEFG;

+>+ø,0q='()&*+i- }./!ilmDEFG;1ÆP

Q2q.3>45A&uFUT PQ×<FG;Rîi+ø,L

q.3675)µA89×<TEA

VWX67'()&*+îi+ø,

IEDTAVWX¤w>*+qi:ÚL

TEA>h);<EDTA>20=iL´

H'()&îi&>?@;hÁiª µU>,dAB>©C¥¦A[\8>

+ip+,Ifresh+Ê>qAT 3t][\iBET+ø,!qi- }./!A

3. TPRgh

Fig.1&2>TPRv©ií&u

>FUi&¢ÅD]EFiD EFG;*+y%.is¢3Jt ]>GHÁ©iIî3100dÈªJK

>©C¥¦i">¢LÚDEFG;

*+LMNuN>?>?@¤O Fig.3 ylmCEDTAVWX¤67Á>

'()&*+ªPQKÁ©iTEA

#*+RªQ¢KisJt]

>¢i´jkømEDTA#*+

ªgna>&CTbulk&iEDTA#*

+yRªbulk&A89iTPRjklm í[\]^S350M500îi&>

gnaA8t>[\]^y

T&áUVjéÆ\j>©CA

4. cd

ø&*+&ø,gn^

&W/qAjkwXi'()&*+

>&ø,Tgn^iuFU>

iW/yÚ!qAYømíå Pd

>?àiªZ='()&*+Ø>&²³ gniÆW/!qi&ø,>©

C¦Aø 2 lm'()&*+3 500

[\îªz>&ø,gn^iz q>W/Aí[\]^[8 500îi&

ø,\]iøm*+8t][\

ài*+¥¦\j©CA&FUyC 20^

>*+ip&ø,ztign^zri

(3)

3 W/zqA&FU>)µi&ø

,gn^!>_Ê_qi&W/

!A89C TEA VWX67'()&

*+îi=p:&>Vj¾`=

EDTAiT&>?1=h)=PQØi

Æ&gn^JqiW/JAPQR

9a>"IiB"?@&Vj>jkA : IWI #+ibcde&ø,g n^f¬>qi&W/yÚgg>As Pd 0.012^> IWI +ipgn^&ø

,ihI Pd 0.12^>"Ê>AYøm íNu>Uºi7i&>gni

Æ&Vj>jéggi';}~>g

3PQØA 5. SEMgh

SEMKklmiDEFG;¤6 w>&*+ip&²³>glZmnop

"}~>d=PQØi'();¤w

>*+yJ}~qg=PQØA89 VWX:&²³>glª?@iTEA

#*+ª&²³piVj=PQø

ØiEDTA#*+>&yéÆrs }~qgA

6. *+./Ra

:=,-,./Ra12i Fig.4 lmDEFG;+ip./RaÚ q='()&+A'()*+

&uFU>i./a!>trAD EFG;*+yÚuFU>i.

/a.!>toA'()&*+PQ

8cd;R8ài./RaIFG;R

"Ê>tAFig.5 lm3%IuFUi

&FU:,-H,>?@A vdÁDEFG;*+p3D&FUîu

<%o"iM& 20^îu<vªl

>ØwiRª 8.6^xA'()

&+pu<0&FUØ yAC FE-e-c #+>u<zti FE-t-c #UiIE-t-c #zoAu

<z{vCdÁiFE-e-c #>*+&

FU>iu<gg>|;iu

<z{J}~i FE-t-c T IE-t-c

#>*+ipu<z{yÚJ-A

+8[\i:,-,./R aiI fresh +"Ê>tAFig.5 lm TEA #*+>./RaI EDTA #

+Ê>Di´= TEA #+>&g naI EDTA #+Ê>oAFig.6 FE-e #>+8"I>[\]^:

,-,./>?@AvdÁ

8 500[\>*+Razripu<

72.6^i 450Ui8 750

[\à>*+pu<zDiRª 22.8 ^Al®t][\ÜO&¢?>\

jiT&ø,)µAtt>[\]^

ÜHO(Ý&>j'Á©A

1. Barbier, J. Dumas, J.M. Geron, C. and Kribii, A., Appl. Catal., 47, L9 (1989).

2. Bond G.C Namijo S.N and Wakeman J.S, J. Mol.Catal, 64, 305 (1991).

3. Chang, H.F. and Yung, C.F., IECR., 36, 2080 (1997)ƌ

4. Fabio, B.Noronha and Martin Schmal, Appl.. Catal., 78, 125 (1991).

5. Huang, T.J and Yu, T.C, Appl. Catal., 71, 275 (1991).

6. Laine, J. and Severino, F., J. Catal., 129, 297 (1991).

7. Noronha, Fabio, Schmal and Martin, Appl. Catal., 78, 125 (1991).

8. Rossi, S.D., Ferraris, G. and Mancini, R., Appl. Catal., 38, 359 (1988).

BET

(m ² /g-cat)

(Å)

(4)

4 γ-Al ₂ O ₃ 159.9 54.7 Cu 15%-Pd 0.12%

FE-t-f 116.7 60.7 FE-e-f 146.4 62.0 IE-t-f 112.5 66.7 IE-e-f 127.7 69.7 FE-t-c 114.1 64.6 FE-e-c 122.6 66.7 IE-t-c 108.4 70.4 IE-e-c 117.7 71.8

IWI 95.6 74.9

FE-e-c (Pd 0.12

%)

Cu 20 % 112.6 70.3 Cu 15 % 122.6 66.7 Cu 10 % 128.9 63.5 Cu 5 % 147.3 61.9 Cu 15%-Pd

0.012%

FE-t-c 116.8 64.0 FE-e-c 126.2 66.2

IWI 109.6 70.3

(m ² /g)

(%)

(Å) FE-t series (Cu 15%)

Pd 0.24% 148.6 22.0 45.5 Pd 0.12% 143.7 21.2 47.1 Pd 0.012% 94.7 14.5 75.8

FE-e series (Cu 15%)

Pd 0.24% 274.6 40.6 24.6 Pd 0.12% 253.4 37.5 26.7 Pd 0.012% 171.7 25.4 39.4

FE-e series (Pd 0.12%) Cu 20% 290.7 42.7 23.9 Cu 15% 253.4 37.5 26.7 Cu 10% 201.7 29.8 33.5 Cu 5% 145.6 22.5 46.3

IWI series (Cu 15%)

Pd 0.12% 35.6 5.3 190.2 Pd 0.012% 43.5 6.4 155.7

0 10 0 20 0 30 0 40 0

Tem peratur e ( oC )

H ydrogen C o m sumpt ion

Pd 0.012 % calcin P d 0.12 % calci n Pd 0.24 % calcin

α

β

α β

α

Fig. 1

0 1 00 20 0 3 0 0 4 00 50 0

Tem peratur e ( oC )

Hydrogen C o ms u m ption

Pd 0.0 12 % P d 0.12 %

γ

γ δ

δ

Fig. 2

0 1 00 2 00 30 0 40 0

Temp er atur e (0C )

Hydro gen Coms umpt ion

Cu 5 % Cu 10 % Cu 15 % Cu 20 %

α β

α

Fig. 3

(5)

5 0 .00 0 .02 0.0 4 0.0 6 0 .08 0. 10 0.1 2

Pd load in g (w t %)

0 .0 0 .1 0 .2 0 .3 0 .4 0 .5 0 .6

CO convers ion

FE -t- c FE -e-c IE -t- c IE -e-c IWI

Fig. 4

5 10 15 2 0 2 5

Cu lo ading (%)

0. 0 0. 1 0. 2 0. 3 0. 4 0. 5 0. 6

CO convers ion

I WI F E- t-c F E- e- c I E- t-c

Fig. 5

350 40 0 450 50 0 550 60 0 6 50 70 0 7 50 80 0

Temperature ( oC)

0.0 0.2 0.4 0.6 0.8 1.0

CO conve rsi on

Fig. 6

無電鍍銅觸媒應用於一氧化碳氧化反應之研究

1

 

CO Oxidation by Electroless Copper Catalyst

: NSC88-2214-E011-006

 87/8/1 – 88/7/31

  

 !" (#$% &'()*+

,-,./)

012"3456789:'()

;67&*+/<=,-,./>

?@ABCDEFG;67*+HIJ :KA67LMNOPQR>S;T<

UVWX>YZCT[\]^_A*+

`ab<XRDBETTPRN 2 Oc dSEM_efS;HghiBC,

-,./12*+>./RaAjk lm&gnaJo>DEFG;*+ip Raq=&gnaJr>'()&*+A

<cd;Rs<JtU>uRvwJ x./Ra>'()&*+AVWXyC EDTA z{|ivwJ}~g>&*

+A*+8500[\:,-,

./RazrA

Abstract (Keyword: Copper, Electroless catalyst, CO, Oxidation)

The purpose of this study is to investigate the effects of preparation method on the electroless copper catalyst for CO oxidation reaction. The impregnated copper catalysts are also prepared for comparison.

All prepared catalysts were characterized by XRD ƋBETƋTPRƋchemisorption and SEM.

The catalysts were further tested by CO oxidation reaction. Experimental results show that the catalysts prepared by the electroless method has better activities than those prepared by the impregnation method, and the electroless copper catalysts

prepared by EDTA chelating agent were better than those by TEA chelating agent.

Furthermore, the calcined electroless copper catalyst (at 500C) presents highest activities among all the catalysts.

12 >

>i

ip">

\ ¡¢£¤¥¦>,-A§

¨,->"S;,->*+

,./A©zª«sz¬<>*+­

®C¯u°_±²³A =´

Y±²³¥Uµ¶·¸±iL´ª¹ º12»¼½¾¿ÀÁvCÂÃ´Z±

²³>Ä²³ACÅ>12jklm3 Ä²³C&zªv¾Æ±²³>Â ÃÇAÈÉÊi¹º»12&*+3

,-,./>RaA012Ë12

©ÌÍZÎÏ./Ði'(Ñ;67Á Ê>&*+IÒÓ>FG; ÔÕÖ;¤

67ÁÊ>&*+«kÊwrA0¼

½×<'(Ñ;67&*+B/<=,

-,./ØA Ù12S;

1. *+67

'()&*+>67ÚÛÜPQÝ ÞßÞàiáCuâãRàiäå' ()&âãH'()iæÆàçè

éÆ'()&*+Aêë[\iyCìí

>]^Ùqî[\æÆAFG*+yC

ÒÓ>EïFG;67æÆAðñ<>*

2

+"gÙZ òZÚ×<'();

¤67Á>'()&*+óòZ>*+

Ú×<DEFG;¤67Á>*+óòÙ Z>*+Ú×<EïFG;67wAô : * + Ã õ ö ò  Z * + C (1).FE-t-f FE-e-c (2).IE-e-fIE-t-c ÷i F øPQ<cd;RiI øPQ<FG;

R  A E ø ' ( ) ; ie øVWX

EDTAit y TEAAf øùú*+ic ø

8[\AòZ*+ IWI DEFG

;AFIWI Ûcd;RPQiáDEF G;AIIWI ÛFG;RPQiàáD EFG;AòÙZ*+ CI ÔFG;A 2. CO,./

Ü 0.5 g *+ûüý=./þi®à

å H 2 /Ar Wi= 250>]^

¢*+ 8 qîàiË]iá 

,-T, >WiB­./

H./A

jk5

1. XRDgh

3XRDi&111>`a

&FU>óuFU>

åBªÆ&`a> !i"

8FE-t#'()*+>&100`a

iuFU>i^!iFE-e

#'()*+y$r%.lmu>å

&?@`õ>j'A8[\à>*

+&`a^i=ª[\8>i

í*+8750[\ài©ª(Ý

&>j'Á©is&>`a^)

*ADEFG;¤w>*+ip&`a

^}='()&*+A 2. BETgh

ø¤ª*+>BET+ø,T- }./A BETjklmiDEFG;*

+>+ø,0q='()&*+i- }./!ilmDEFG;1ÆP

Q2q.3>45A&uFUT PQ×<FG;Rîi+ø,L

q.3675)µA89×<TEA

VWX67'()&*+îi+ø,

IEDTAVWX¤w>*+qi:ÚL

TEA>h);<EDTA>20=iL´

H'()&îi&>?@;hÁiª µU>,dAB>©C¥¦A[\8>

*+ip+,Ifresh*+Ê>qAT 3t][\iBET+ø,!qi- }./!A

3. TPRgh

87/8/1 – 88/7/31

!" (#$% &'()*+

,-,./)

;67&*+/<=,-,./>

?@ABCDEFG;67*+HIJ :KA67LMNOPQR>S;T<

UVWX>YZCT[\]^_A*+

`ab<XRDBETTPRN 2 Oc dSEM_efS;HghiBC,

-,./12+>./RaAjk lm&gnaJo>DEFG;+ip Raq=&gnaJr>'()&*+A

<cd;Rs<JtU>uRvwJ x./Ra>'()&+AVWXyC EDTA z{|ivwJ}~g>&

+A*+8500[\:,-,

12>

>i

ip">

\ ¡¢£¤¥¦>,-A§

¨,->"S;,->*+

,./A©zª«sz¬<>*+

®C¯u°_±²³A=´

Y±²³¥Uµ¶·¸±iL´ª¹ º12»¼½¾¿ÀÁvCÂÃ´Z±

²³>Ä²³ACÅ>12jklm3 Ä²³C&zªv¾Æ±²³>Â ÃÇAÈÉÊi¹º»12&*+3

,-,./>RaA012Ë12

©ÌÍZÎÏ./Ði'(Ñ;67Á Ê>&*+IÒÓ>FG; ÔÕÖ;¤

½×<'(Ñ;67&*+B/<=,

-,./ØA Ù12S;

'()&*+>67ÚÛÜPQÝ ÞßÞàiáCuâãRàiäå' ()&âãH'()iæÆàçè

>]^Ùqî[\æÆAFG*+yC

+"gÙZ òZÚ×<'();

¤67Á>'()&+óòZ>+

Ú×<DEFG;¤67Á>+óòÙ Z>+Ú×<EïFG;67wAô : * + Ã õ ö ò Z * + C (1).FE-t-f FE-e-c (2).IE-e-fIE-t-c ÷i F øPQ<cd;RiI øPQ<FG;

R A E ø ' ( ) ; ie øVWX

EDTAit y TEAAf øùú*+ic ø

8[\AòZ*+ IWI DEFG

;AFIWI Ûcd;RPQiáDEF G;AIIWI ÛFG;RPQiàáD EFG;AòÙZ*+ CI ÔFG;A 2. CO,./

Ü 0.5 g *+ûüý=./þi®à

å H ₂ /Ar Wi= 250>]^

¢*+ 8 qîàiË]iá

,-T,>WiB./

H./A

jk5

3XRDi&111>`a

&FU>óuFU>

åBªÆ&`a> !i"

8FE-t#'()*+>&100`a

iuFU>i^!iFE-e

#'()*+y$r%.lmu>å

&?@`õ>j'A8[\à>*

+&`a^i=ª[\8>i

í*+8750[\ài©ª(Ý

&>j'Á©is&>`a^)

ADEFG;¤w>+ip&`a

^}='()&*+A 2. BETgh

ø¤ª+>BET+ø,T- }./ABETjklmiDEFG;

+>+ø,0q='()&*+i- }./!ilmDEFG;1ÆP

Q2q.3>45A&uFUT PQ×<FG;Rîi+ø,L

q.3675)µA89×<TEA

VWX67'()&*+îi+ø,

IEDTAVWX¤w>*+qi:ÚL

TEA>h);<EDTA>20=iL´

H'()&îi&>?@;hÁiª µU>,dAB>©C¥¦A[\8>

+ip+,Ifresh+Ê>qAT 3t][\iBET+ø,!qi- }./!A

Fig.1&2>TPRv©ií&u

>FUi&¢ÅD]EFiD EFG;*+y%.is¢3Jt ]>GHÁ©iIî3100dÈªJK

>©C¥¦i">¢LÚDEFG;

*+LMNuN>?>?@¤O Fig.3 ylmCEDTAVWX¤67Á>

'()&*+ªPQKÁ©iTEA

#*+RªQ¢KisJt]

>¢i´jkømEDTA#*+

ªgna>&CTbulk&iEDTA#*

+yRªbulk&A89iTPRjklm í[\]^S350M500îi&>

gnaA8t>[\]^y

T&áUVjéÆ\j>©CA

4. cd

ø&*+&ø,gn^

&W/qAjkwXi'()&*+

>&ø,Tgn^iuFU>

iW/yÚ!qAYømíå Pd

>?àiªZ='()&*+Ø>&²³ gniÆW/!qi&ø,>©

C¦Aø 2 lm'()&*+3 500

[\îªz>&ø,gn^iz q>W/Aí[\]^[8 500îi&

ø,\]iøm*+8t][\

>*+ip&ø,ztign^zri