no - cheric park †, byung-joo kim ... korea research institute of chemical technology, 100,...

HWAHAK KONGHAK Vol. 41, No. 6, December, 2003, pp. 795-801

�� NO ��

��†��Kawasaki, J.*

�� 305-600 �� 100

*�� (2003� 5� 19� ��, 2003� 9� 20� ��)

NO Removal of Electrolessly Copper-plated Activated Carbons

Soo-Jin Park†, Byung-Joo Kim and Junjiro Kawasaki*

Advanced Materials Division, Korea Research Institute of Chemical Technology,100, Jang-dong, Yusong-gu, Daejeon 305-600, Korea

*Department of Chemical Engineering, Tokyo Institute of Technology, Ookayama, Meguroku, Tokyo 152-8852, Japan�Received 19 May 2003; accepted 20 September 2003)

� �

� �� (activated carbons; ACs)� � � �� Cu� �� Cu ��

�� ! Cu" ��# ACs� $%& NO '( )*� +�� ,-�./. Cu" ��# ACs� � ��0 FT-IR

1 scanning electron microscope(SEM)2 $%�� 3-�.�4, N2/77 K 56 78 ��0 BET9, D-R plot, H-K ! BJH

92 $%�� :;�.,, NO '(<=0 ">?�@ABCD� $%�� EF�./. GHI1, �� J$ K"L� M

N ACs � � Cu� O0 PQ K"�.�R, ACs� 78 ��; S� T, ��UV 5� ��W� XY�Z [��

\]2 ^./. ) NO '(<=0 ��# Cu� O$ K"L� MN S_T�� K"�.�4, $`& I1� ACs �

� ��# Cu� �� Cu-ACs � �� NO '( )*$ "abc� de�� fg#/.

Abstract − In this study, the activated carbons (ACs) containing copper metal were prepared by electroless copper plating

technique, in order to remove NO. The surface and structural properties of the ACs were determined by FT-IR and scanningelectron microscope (SEM), respectively. N2/77 K adsorption isotherm characteristics, including the specific surface area and

pore volume, were investigated by BET, D-R plot, H-K, and BJH methods. And NO removal efficiency was confirmed by gas

chromatographic technique. The copper content on ACs increased as the plating time increased. However, a slightly gradual

decrease of adsorption properties, such as BET’s specific surface area and total pore volume, was observed in ACs in the pres-ence of copper metal. NO removal efficiency of all Cu-ACs was higher than that of untreated ACs, and increased with the cop-

per content on ACs. These results indicated that copper metal on Cu-ACs strongly accelerated catalytic reduction of NO on Cu-

ACs surfaces, though it caused the decrease of the adsorption properties of original ACs.

Key words: Activated Carbon, Copper Metal, Adsorption, NO Removal

1. � �

��

�� ! "�, �#$ %& '(� �� )* ++�, -./

0& '1 2/34� �5[1]. �6, �� 1 7834� 9:

;<# �=> ?�, �/� @'�� >A�8=B �#$ C D�

EFG& HI- �J, KL� MNB OPQR� ST U5[2-3].

>A�8=1 �V�/ W� XYZQR� [B \]7 -^�_�

�RJ, - ? `abc1 �de-f, cgh(molecular sieve), i#j

A %� kB lm�n -o�� @p- q_�� 5[4-6]. �_r -

:� lm� ghrR�� G �Vst� �*7 �RJ, -� ue l

m�n vh��9 9: 7_ w C i#- x =>1 Dy�� \]

7 z{�� |5. - ? �}Q~ w- Cu, Ag, Ni, Fe, Co G�� Pt

%-J Cu� G ��& �� u�� st#- ST T��J, �� G

7�- ��9 ��QR� �B 7L7 �5� � � �5 [7-10].

lm� �� i#jA� Cun Dy�� @pB /� \]� u��

U� 47_� �� 5. �}Q~ @pB �mpR�, -� i#

jAn Cu w�� `a 3� C ��R� v� 0 �8�� @

pR� @p.& �6# �� QR� [- to� @p-5. �

_r - @pB �m3� w�- i#jA& K)/�1 �� (.

1 �� 5� ��- u�5. ¡¢ @pR�� i#jAn �†To whom correspondence should be addressed.E-mail: [email protected]

795

796 ��Kawasaki, J.

�� K� w c£-� w�1 ¤¥3¦ i#jAn ��

@p- �5. - @pB i#jA7 §hQR� w�� c

¤�5� N�- u�� s� �3� ¨© �� bcª_ w�-

«�7� �� D u�5. ) ¡¢ @pR�� /. ¬mp1 «

� �5. - @pB st7E ®¯�� bc�r w�- Dy�

� �� .o8� i#jAn }��rR� w¥; i#jAn

�°� � �5� N�1 7_� s� �� w c¤n ±/7 �²

5� ��1 7z5. ³_� @pB wDwpR� §�Dwp� ´

§� Dwp- �5. §�DwpB bDh~ i#jA� §/Q µ1

-o�9 ¶® w1 Dy�� @pR� /.¬mp� kB N�1

7_� @p-5. �6 ´§� wDwpB �mp� §�Dwp&

N�r1 ·� ¸R� w1 w� �, 8¹Q �ºpR� »�

wr1 i#jA� Dy�� @pR�, - @pB i#jA& $}

�Q& ¼A7 U_ ½� K)/�ª_ w- ¾� ¿À�� N�1

7z5[11-14].

-� Á \]�,� Cun ´§� wDw @pR� ACs� Dy�

9 NO�V st� �� G =�Â8¹Q lmÃÄ� ¯SQ �ºÃÄ

1 ÅÆ�ÇRJ, �� Cun i#jA� Dy3 È�� i#jA& /

��#1 ÉÊ¥R�, ´§� CuDw� i#jA& NO�Vo lm

��,& 7Ã#� ��, �Ê�9 �Ç5.

2. ��

2-1. ��

Á !Ë�, Oo� i#jA(ACs)� 5�# lm�� 8×16 mesh U

/& �ÌjA(H)�, �� ¸1 Oo�Í5. !Ë� Î, Æ´Ï �

�7 �_ ½B i#jAn 3q ¬Ð��, 2-3¡ )Ñ� 0 80oC&

�� Ò�, 483� -. @L3¦ �� 0 Oo�Í5. Cu& ´§�

DwB i#jAn Ó� 10%& HCl oÔ�, 30c� §�� 0 !

3�ÍRJ, -� Oo� DwÕ C Dw��B Table 1� �ÖY×5.

Dw3�B 5, 15 G�� 40cR� �ÍRJ, K�� 361 ¤¥�9

�� as-received, Cu-5, Cu-15 G�� Cu-40R� ØØ�Í5. i#jA

� Dw� Cu& ÌB atomic absorption spectrophotometry(AAS)n O

o�9 cÙ�Í5.

2-2. ��

Cu7 Dy� ACs& È8� }��#1 ÅÆ�/ W� FT-IR�

scanning electron microscope(SEM)n Ú� ÉÊ�Í5. �� Cu Dy

0 i#jA }�& �AÉÃ/& ÌQ~ È8n ÉÊ�/ W� X-ray

photoelectron spectroscope(XPS)n -o�9 jA� �� A& aÛ

Q Ü1 Ýa�Í5. -� source�� MgKαn -o�9 LAB MK-II

(VG Scientific Co.) cÙN$n -o�9 Ýa�ÍRJ, chamber Y&

ÞÄB 10−6-10−9 torr� �ß�9 Ýa�Í5.

2-3. ��

� 3à«B 300oC�, áÐ ÞÄ1 10−3 torr-�� ;_� .â� ã

5-6 3� �� ä/3å 0, ASAP 2010(Micromeritics Co.)1 -o�9

77 K�, .�ÞÄ(P/P0)� u� N2 /h& lmÛ1 Ýa�Í5. $}�

QB Brunauer-Emmett-Telleræ1 -o�9 % lmR�bç *��ÍR

J[15], è/�b�� D-R plot[16]1 -o�9 é~�Í5. K)/� C

?/�& cÙB �� H-Kp[17]� BJHp[18]1 Ú� ÉÊ�Í5.

2-4. NO ��

NO �VêB He ëÏE 1,000 ppm ìD& NO 7En Oo�9 7

EU�³íGî�(DS 6200, Dï~Ef^Óf)� st § ·0& st=

� ð#=& cÙR� Ýa�ÍRJ, detector� thermal conductivity

detector(TCD)Í� columnB Hayesep A(30 ft, inner dia: 0.085 inch)n

-o�Í5. !Ë ? st�& D� 500oC� ;_�ÍRJ, è st

3�B 203�R� �Í5. st3 ;y� NO 7E& ;B M.F.C.

(mass flow controller; GMC1000, MLS)n Oo�9 Ú��ÍRJ, 10

ml ·min−1R� ;_3ñ5. cÙ § � 3à«B st D�, 13� �

� HeR� òó�9 �c1 ô§� �V�9 NO 7E& NLY lm

� &� qn õA8 � 0 Oo�Í5.

3. � ��

3-1. �� Cu ��

ACs& ´§� Cu DwB `sQR� �º� C /Ö �7�& s

tR� ö÷� st- ;��_r õø ±�_� ̧ B Cu ùâ� - �

�� G .�Q 7L v_pR�,& 7Ln _ú5� û � �RJ,

G st �aB Æî k5[19].

Cu2+ü2e−ýCuþ(Reduction)

E0=ü0.34 V (1)

2HCHOü4OH−ý2HCOO−üH2ü2H2Oü2e− (pH=14)

E0=ÿ1.07 V (2)

HCHOüH2OýHCOOHü2H+ +2e− (pH=0)

E0=ü0.056 V (3)

- k- ACs& }�� Cu(27)n Dy�/ W�,� �& §g

7 ¨©�J, - §g«B ¤�Å��7 ¤��R� �8�R��

�5. -� Table 1�, �Ö� � k- DwÕ& pH7 � Å

�#1 �� st- � �� `��5. -:� -;� Å�# o

Ô�, ¤�Å��& }��8 §W& Ü- Cu2+ - & }��8

§W�5 � °/ �� æ (1), (2) st1 V� Cu2+ - - ¾� Cu

wR� �º�5. �_r s�� #oÔ�,� ¤�Å�-��

º�7 �_ ½� æ (3)� kB st1 `R4� �5.

Table 1. Composition and operating conditions of electroless Cu platingbath

CompositionCuSO4: EDTA Na2:HCHO 1.0:2.50:1.31

Distilled water 980 ml

ConditionspH 12�0

Temperature 40�1 oCFig. 1. Cu quantification of the electrolessly Cu-plated activated car-

bons measured by AAS.

�� 41� �6� 2003� 12�

� �� NO �� 797

Fig. 1B W�, �� ´§� Cu Dwp1 Ú� �� Cu-5, Cu-15

G�� Cu-40& Cu ¥Û& AA cÙÜ1 �Ö� ¸-5. /ÁQR�

Cu& DyÛB Dw3�- ¬7�� ue ¬7�� ¸1 ��

×5. �_r ¬7$, � 3�� DwÛ& $�Q~ É*� ã�&

ôr� ��1 G�� ¸- ��×5. -� ´§� wDw� ��

5� ��«�, _Q�� - ́ §� wDw& �T �s��

Dwh }�& �-� /�1 w yg7 �T�, 3°�57 ��

& �1 ù#� -0�� Dw D7 �� ¼A�/ ��R� �

��5[20].

3-2. ��

´§� Cu DwR� È8� Cu-ACs& }�Ý#1 FT-IR, XPS C

SEMR� ÉÊ�Í� -? IR& ��Ü1 Fig. 2� �ÖY×5. ´§�

Cu Dw� Cu-ACs& IR��Ü1 û � Cu gh& �Un ��

�_r 3,450 cm−1 b�& �U7 ́ §� Cu Dw 0 §s§R� x �

R� ¬7� ¸1 �� ×RJ, Dw3�- ¬7�� ue �

w� ¬7�� - ��×5. - �U� K�� ACs & �T −OH

�U7 �Ö�� +-J, �� ´/=- �7�×1 �T ´/�& �

U7 �Ö�� +-5. �� 3,450 cm−1 b�& �U& �B ¬7�

−OH �U& Kã� ¬7 �� ´/�- ù#�×/ ��R� �

��5. ́ §� Cu Dw1 Ú� »�� Cu r Æ!e ̀ aÛ& CuxOy

ùâ& complex7 ù#�×/ ��R� ��5[21].

Table 2� ´§� Cu Dw §0& Cu-ACs }�& C, O C Cu& �

#È8n ÉÊ�/ W� XPS cÙ��& aÛÜ1 �Ö� ¸-5. �

�ÜR�bç Dw- z{�� ue Cu2p& Ì- x �R� ¬7��

¸1 �� ×RJ, �� O1s& ÜD ã�� ¬7�� ¸1 É

Ê� � �×5. �6 C1s& ÜB §sQR� ¼A�Í5. DwR� ~

� È8� �A& ¥Û C ]�& ¥Û1 ÉÊ�/W� O1s/C1sÜ C

Cu2p /C1sÜ1 ]��Ç5. ��& Ü1 û � /ÁQR� Dw3�- ¬

7�� ue Ü F ¬7�×RJ, ue, Cu-40�, 7N �B Ü

~ 0.138 C 0.061n �ÖY×5. -�bç W�, �� k- Cu

Fig. 2. FT-IR results of the electrolessly Cu-plated activated carbons.

Table 2. Chemical composition of electrolessly Cu-plated activated carbons

Sample O1s (%) C1s (%) Cu2p (%) O1s/C1s Cu2p /C1s

as-received 9.6 89.8 - 0.107 -Cu-5 10.7 85.6 2.9 0.125 0.034Cu-15 11.0 84.4 4.2 0.130 0.049Cu-40 11.6 83.6 5.1 0.138 0.061

Fig. 3. Copper subpeaks in Cu2p XPS spectra as a function of the plat-ing time.

HWAHAK KONGHAK Vol. 41, No. 6, December, 2003


& Dw 3 »�� CuZ� CuxOy ùâ�D �" aD Dy�5� ��

�J, -� Fig. 2� �Ö� ´/� �U& ¬7 .Ú�� É

Ê�5. �8� ]�& �#n é~�/W� XPS& Cu2p �U& sub-

peakn *�QR� c��Í� -n Fig. 3� �ÖY×5. ÉÊ ��, D

w3�- ¬7¥� ue Cu metal& .�Q~ Ì�5 Cu(OH)2& Ì-

�qQR� ¬7�� ¸1 �� ×5. -:� �� Î�, �

� Cu7 Dw� i#jA& �A¥Û- ¬7 C �8]�& �#

$ b%�� ¸R� ��5.

Fig. 4� ´§� Cu Dw §0& ACsn ÉÊ� ¸-5. ÉÊ �� }

�- $&Q '(� K�� 36� $� Cu-5 Cu-15& �T ã�&

particle«- ÉÊ �×RJ, Cu-40B )E*� �-� +;ù1 , =

>«- �ð� ¸- ÉÊ�×5. -:� �� ´§� Dw3 �ÛR

� ù#� Cuyg«- ACs }�� ¬m�_ -�� ,� ./ 0� ù

#� ¸R� ÉÊ�5.

3-3. ��

Fig. 5� ´§� Cu DwpR� �� Cu-ACs& 77K/N2 % lm

��1 �Ö� ¸-5. ��_ ½B 36� �1_ Cun Dy� 3

6« F �/ 2B .�Þ�, lmÛ- �� .3�57 G -

0�� .�Þ1 * d4D � -. ¬7�_ ½� 5ù.â� D�

¥- ÉÊ�×RJ, -� BET cÐ ? K)/�- $ ��

Type 161 é~ � � �×5[15]. - k- K)/�R� -^�z

jA#à& /��,� lm�& 7� lm> cg& ~Ä, � lm

N- ?8�� - *�,& lm9B 8�5. lm9& 8� �¡

lm� cg� äm�/ �4:_J, - �� lm�� cg� $�

äm�� cg& $7 �; °Æ_� �� lm�& lmÄ- 8�

5. �� ºHù F<�, /�& �� cg& => s�& $7 3-� ̀

�, -:� (.B ST U� ̀ �� J, -� ue % lm��B º

��, �� .3�� Type 1& % lm��1 �ÖY� �5[22].

Fig. 6B � 36& K)/�b�n D-R plotR� �Ö� ¸-5. �

h� K)/� ]�n ?� lm�� &� lmB 2B .�ÞÄ��

,� lm>� &� )�t@� &�, -0�� lm� }��,& 5

cgA lm- �ð�� ¸R� �� 5. D-R plot� &� K)

/�& b�*�B Æî& æ (4)n Ú�9 P/P0=0.001-0.05 O-�,

±�z ÜR� ¶�& GîBn ±� Yß6 Ü1 Ôh>A& /hb�

� ��9 ]�Í�, è /�b�� õø lmÛ� È� .�

(0.001547)1 C�9 ]�ÍRJ, - ��Ü«B Table 3� �ÖY×5.

(4)

9/�, W� .�Þ� u� lm� b�, W0� K)/�b�, B�

structural constant, β� affinity coefficient G�� T� D-5.

Fig. 7B Horvath-Kawazoe& slit pore F<& æ (5)� /��9 /�

¶�- 2 nm -�~ K)/�«& @Q/�b�(cumulative pore

volume)n �Ö� GD-5.

(5)

9/�, 2d� /�& ¶�1 &K�5.

Fig. 7�, ACs& K)/�- H� 3-10 E aD U/n 7_� /�

R� ]#�� 5� ¸1 é~� � �×RJ, 4 E -�& /�U/

n 7_� /�& $ê- �F1 Å � �×5. �� Fig. 6& ��Ü1

Ú� Cu-5 36& �T K�� 36� K)/�& b� C /�& c

¤7 V& q-n �-_ ½� s� Cu-15 Cu-40& �T K)/�

Wlog W0log B T β⁄( )2log2 P0 P⁄( )–=

Ψ 2d( ) PP0

----- ln=

62.382d 0.64–---------------------–

1.895 103–×2d 0.32–( )3

---------------------------- 2.7087 107–×2d 0.32–( )9

-------------------------------– 0.05014– 0=

Fig. 4. SEM images of the electrolessly Cu-plated activated carbon sur-faces.

Fig. 5. Adsorption isotherms of N2 at 77 K on the electrolessly Cu-plated activated carbons.

Fig. 6. D-R plots for N2 at 77 K on the electrolessly Cu-plated acti-vated carbons.

�� 41� �6� 2003� 12�

� �� NO �� 799

GH& b�7 x �R� I�J ¸1 Å � �×5. -:� ¼AK-

� ´§� Cu Dw1 Ú� i#jA& K)/� GH� `b /� �

µ- `�L5� ��5. -� Fig. 4& % lm��, �sb&

log scale Ü1 û � lm& 3°�� ÞÄB Dw- z{�� ue 3

6�, �ÞMR� [- LTL� ̧ - ��×�� -� lm9& ¼

A C lmÄ- ¼A� ~¥R� ��z5. �� .�Þ- 10−6

b��, ÉÊ�� ,NK)/�� &� lm- Cu-15 C Cu-40�,

V& �Ö�_ ½B ¸1 ÉÊ � � W�, _Q� �� ´§� Cu D

w� &� K)/� �µR� /~� (.-e� ��5.

Fig. 8B Kelvinæ� /�� BJHp1 -o�9 ´§� Cu Dw��

§·0& Cu-ACs& ?/� È8Ü1 @Q/�b� Ü1 Ú�9 ÉÊ�

��Ü-J, ÜB Æî& æ (6), (7) G�� (8)� /��9 ]�Í5.

(6)

(7)

(8)

9/�, rk� Kelvin s_�, rBJH� BJHp� &� /�& s_�, VmB

lm>& Ob�, σ� lm>& }�NÄ, RB /h.�, t� t-plot�

&� P G�� T� Dn &K�5.

W æ«�bç ±B Fig. 8& ��Ü�, K)/�& È8K- $

Q�� Cu Dw3�- ¬7�� ue /�& b�7 ¼A�� 1

�� ×5. �_r K)/�& �T Cu-15 C Cu-40- Cu-5�

$� x �R� ¼A�Í�� ?/�& �T G ¼A K-7 $&Q $

Q�Í5. �_r Cu-40& �T /� s_�- 10 Å b��, b�&

¬77 V& �� ¸1 �� ×5. -� 5� 36«�, RÆ

û � �� (.R� Æ³D Fig. 4& SEM Oz�,D ÉÊ �×�-

�D� Cu Dw� &� ù#� Cu yg«� &� K)/�� ?/�

O-& GH, � /� ¶�- 10-20 Å b�& /�«& �µ- U� `

�� ¸R� ÉÊ�5.

Table 3B ACs& ´§� CuDw §·0& $}�Q& È8, è/�b�,

/�s_�, BET .� C G�� »lm9(neat heat of adsorption)%1

�Ö� ¸R� -n Ú� ]hQ~ /��#& È8n �� 5.

$}�Q& �T Cu-5ª_� x ¼A7 �Ö�_ ½ÇR� Cu-40&

�T� ã 26%& $}�Q ¼A7 �ð�Í5. -S� x �& $}�

Q ¼A� Î�, _Q�Í�- Dw� &� T K)/� C 10-20 Å

U/& /�«& �µ- H� -;� �ð� ¸R�, -:� $}�Q

& ¼A� UK� è/�b� C K)/� b�D $Q� ��R� É

Ê�×5. �6 BET.� CÜ C »lm9& �T Dw3�- ¬7�

� ue ã�� ¼A�� ¸1 �� ×��, -� -K ��

Í�- Dw- z{�� ue ,N K)/�«- �µ- `�� §s

QR� lmÄ& ¼A7 �ð�Í/ ��R� é~�×5.

3-4. NO ��

Chen %[23]& �� u�� NO� i#jA kB jA* ¯S�

&�, >A �A� �º�J, -� stð#=�� N2 C COx k

B b�=1 �ð34J, Æî kB �*!V1 �3�Í5.

NOüC-ACsWCO-ACsü1/2 N2 (9)

COüCO-ACsWCO2üC-ACs (10)

CO-ACsWCO (11)

9/,, C-ACs CO-ACs� �� i#jA+; }�& jA C �AÉ

RTPP0

----- ln 2σ

Vm

rk

-------–=

rk 4.14PP0

----- log=

rBJH rk tPP0

----- +=

Fig. 7. Cumulative micropore volume distribution of the electrolesslyCu-plated activated carbons.

Fig. 8. Cumulative mesopore volume distribution of the electrolesslyCu-plated activated carbons.

Table 3. Textural properties of the electrolessly Cu-plated activatedcarbons

as-received Cu-5 Cu-15 Cu-40

Specific surface area (m2·g−1) 1,162 1,123 954 861Total pore volumea (cm3·g−1) 0.484 0.460 0.398 0.357Micropore volumeb (cm3·g−1) 0.450 0.437 0.376 0.343Micropore volume fraction (%) 93.8 94.3 94.5 96.1Mesopore volumec (cm3·g−1) 0.034 0.023 0.022 0.014Mesopore volume fraction (%) 7.0 5.0 5.5 4.0Micro-/Mesopore ratio 13.2 19.0 17.1 24.5Average pore radiusd (Å) 8.33 8.01 8.39 8.29BET’s constant: C 948 945 940 932Neat heat of adsorptione (kj·mol−1) 4.403 4.401 4.397 4.392

Vaads

molar Volume of liquid N2molar Volume of gaseous N2

----------------------------------------------------------------------×

From D-R plot, b V total ads 0.001547×

Total pore volumec

Micro volume–

2d V total

SBET

------------×

∆eE E0 EL– RT CBET( )ln= =



Ã/n �Ö�5. �6 Park %[24]& \]� u�� Cu7 Dy� ACF�

,& NO �V st& �T Æî& �*!V1 u�� ¸R� XYZ5.

NOüCu-ACFWCu2O-ACFü1/2N2 (12)

2Cu2O-ACFW4Cu-ACFüCO2-ACF (13)

kB [\�, �eû � ´§� Cu Dw� Cu-ACs& �T ACs }

�� »�� Cu C ã�& �8� Cu7 �#�J, NO& =�Q l

m C �ºB �� NO-Cu-ACs, NO-CuxOy-ACs C NO-C-ACs& st

1 Ú� `�� ¸R� ]Ý�5.

Fig. 9� K�� C ´§� CuDw- !3� Cu-ACsn -o�9 ´

�A��, He ëÏE& 1,000 ppm ìD& 7En -o�9 NO �V

!Ë1 !3� ��Ü-5. K�� 36& �T 90c^�, M��-

�ð�9 �� NO& ìD7 53 ¬7�� 1 �Ö� s�

Cu-5� 150c G�� Cu-15� 200c aD�, M��- �ÖLRJ,

Cu-40& �T M��- 93��, �ÖL5.

Fig. 10� 11B �� ']�,& N2 C CO2ìDn �Ö� ̧ -5. Fig. 10

& N2& È8��1 û �, K�� 361 �Z� Cu7 Dy� 36«

& �T �/� 500 ppm� 7ª_ N2ìDn �Í5. -� W�, �

� �*!V� `L�� 2�& NOcg7 c�� & N2

cgn ù#�� ¸R� ��5. st3�- ¬7�� ue K��

36& �T �/� 350 ppm aD& Ü1 �-57 �q �� ¼

A�×5. -� Chen& �� k- i#jA ghD ã�& �ºÄ1

�-/ ��-J, N2ìD& �� ¼A� .�QR� D7 "` �

ºst�5 D7 a� NO& =�Q lmR� ~� a�� M��

55b/ ��R� ��5. s� Cu7 Dy� i#jA«B Cu NO

& 8¹Q~ �º°oR� ~� G N2ìD& ¼A7 K��36�c

�� `��_� ½� ¸- ��×5. Fig. 10& CO2�ðÛ1 ��

K�� 36& �T7 7N �� Ö� s� DwÛ- ¬7�� ue

�qQR� CO2& Ì- ¼A�� - ÉÊ �×5. -� K�� 3

6& �T �/& �º°oR� ã�& CO2n �ð34_r d M��

� -�: G Ì- �� ¼A�� ¸-J, Cun ¤¥�� 36«&

�T i#jA gh& �ºÄ� &� �/�� ã�& CO2n �ð34

_r, Park%- �3� �*!V�c �ð� CO2«- =�QR� i#

jA� lm�� G Ì- U� Q�_� ¸-e ��5. �eQR�

NO �V stB K��<Cu-5<Cu-15<Cu-40 »R� �ÖLRJ, -�

/ÁQR� Dy� ]�& Ì� $�� ¸R� ÉÊ�×5. �_r

Cu-40& �T M��r1 û � 5� 36�5 x �R� G �Vê-

.3�Í�� -:� -;� Æî& OfR� ��z5.

Table 3�, micro-/mesopore& $Ü1 û � Cu-40& �T G Ü-

24.5� 5� 36� $� %�� UJ, -n Ú� K)/�& cê-

.�QR� �B ¸1 Å � �5. NO& lm3 NO gh� K)/�

� &� lm- �bc-_r NO cg7 K)/�� 55�/ W�,

� G Ú�7 �� ?/� C �/�& cê- ?©�5� � � �5

[22]. -� ?/�-� �/�& cê- g´ �1 �T lm� NO c

g«- K)/�ª_ -�_ -�� ?�� lm� 0 ¾� äm h 7

Ã#- �#�� 5. �_r Cu-40& �T Dy� Cu� &� K)/

��5 ?/�& �µ- U� `�LRJ - �� K)/�& cê

- .�QR� ¬7�×5. �� lm� NO& äm- o-�_ ½Ç

1 ¸R� ��5. �6 Î�, ��Íi �k- Cu-40& �T

5� 36� $� Cu(OH)2& ¥Û- .�QR� �ÇRJ, - ��

T#ÉÃ/ NO& =�Q~ interaction- 8�×1 ¸R� ]Ý

�J, -7 Cu-40& NO �Vst�, � ©~R� °oj1 ¸R� �

��5[25].

-.R�, ACs& ´§� CuDwB ��_ ½B 36� $� NO�

V "ê- §sQR� ¬7�×RJ, �� Cu-40& �T M�� r1 û

� K�� $� G "ê- 400% -. ¬7�� ¸- ÉÊ�×5. -

¸R� �Æ i#jA& ´§� DwB ;o� }�� @p ?& �

�e� ��5. �� -:� (.& -;� /ÁQR� Dy�� Cu

& Ì� &��J, b�QR� micro-/mesopore& $ G�� T#ÉÃ

/� &� NO& ~Ä %� Ék- �� ¸R� ÉÊ�×5. �_r

Fig. 9. Outlet concentration of NO as a function of plating time.

Fig. 10. Outlet concentration of N2 as a function of plating time.

Fig. 11. Outlet concentration of CO2 as a function of plating time.

�� 41� �6� 2003� 12�

� �� NO �� 801

ath

n 50

o,

i-

re-

p-

s,”

ng,

er

per

,”

in

f

c-

of

I.

tile

by

,”

ur

-

.

ata-

i-

Cu& Dy� ue ACsgh& lmÃ, � $}�Q� K)/�b� %

B ¼A�Í5. NO& �V st- NO-C-ACs NO-Cu-ACs�, �3

� ̀ �� ̧ 1 ¼�� 5Û& Cu DyD �l¶�_r lm� g

h& lmÃ1 U� ¼A34_ ½� IW Y�, Cu& Dy- -^�

_� ¸- 7N -.Q` ¸R� ÉÊ�5.

4. � �

Á \]�,� ACs� ´§� DwpR� Cun Dy�ÍRJ, -n

-o�9 NO lm C �ºV�� KL� G�� 9 �Ê�Í5.

Dw 3�- ¬7¥� ue ACs }�� Dy�� Cu& ÌB ¬7��,

s�� ACs& $}�Q, /� b� %& lm#>- ¼A�� ¸- É

Ê�×5. �� -n -o�9 NO �V !Ë1 � ��, Cu7 Dy�

FJ 36«B Dy�_ ½B ¸� $� �B NO �Vê1 �ÍRJ,

�� Cu-40 36& �T K�� 36� $� G "ê- 400% m� �

ÖL5. �_r NO& �V7 lm� gh�,D �ð�� ¸1 ¼��

� Cu& DyB lm� gh& lmÃ1 U� ¼A�_ ½� IW Y

�, -^�_� ¸- õQ-e� ÉÊ�5.

� �

Á \]� �¹/nb& �¹/nX�8O� (M1-0105-00-0059)&

_º� &�9 �{�ÍRJ, -� ¼O�o!5.

��

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