NO Removal of Electrolessly Copper-plated Activated Carbons

    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)



  ! 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 XYZ [

\]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 scanning electron 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.  

        

 ! ",
#$ %& '(  )* ++, -./

;<# => ?, / @' >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 lmn -o @p- q_ 5[4-6]. _r - : lm ghrR G Vst *7 RJ, - ue l mn vh9 9: 7_ w C i#- x =>1 Dy \]

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

%-J Cu G €& ‚ uƒ„ st#- ST T…J, † G 7‡- ˆ‰9 QR ŠB 7L7 5 ‹ … 5 [7-10].

lm Œ i#jA Cun Dy @pB /Ž \] uƒ„

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 š (.

1 ›‹ … œ5 ž- uŸ5.   ¡¢ @pR i#jAn 

†To whom correspondence should be addressed.

E-mail: psjin@krict.re.kr

 41 6 2003 12

… 5. - @pB st7E­ ®¯ bcr w- Dy

 † .o8˜ i#jAn }„–rR w¥; i#jAn

°‹ … 5 Nž1 7_ s„ Ÿ w c¤n ±/7 ² 5 ž1 7z5. ³_š @pB wDwpR §Dwp ´

§ Dwp- 5. §DwpB bDh~ i#jA §/Q µ1 -o9 ¶® w1 Dy @pR /.¬mp kB Nž1 7_ @p-5. 6 ´§ wDwpB ‘mp §Dwp&

wr1 i#jA Dy @pR, - @pB i#jA& $}

„Q& ¼A7 U_ ½ K)/™ª_ w- ¾ ¿À Nž1 7z5[11-14].

- Á \], Cun ´§ wDw @pR ACs Dy 9 NOV st  G =Â8¹Q lmÃÄ ¯SQ ºÃÄ 1 ÅƂÇRJ, † Cun i#jA Dy3 È i#jA& /

™Œ#1 ÉÊ¥R, ´§ CuDw˜ i#jA& NOVo lm

,& 7Ã# , Ê9 ‚Ç5.

2.  

2-1.


Á !Ë, Oo i#jA(ACs) 5™# lm 8×16 mesh U /& €ÌjA(H), “ ¸1 OoÍ5. !Ë Î, Æ´Ï –

7 _ ½B i#jAn 3q ¬Ð…, 2-3¡ )Ñ 0 80^oC&

”“ Ò, 483’ -. @L3¦ ”“ 0 OoÍ5. Cu& ´§

DwB i#jAn ӈ 10%& HCl oÔ, 30c’ §–  0 ! 3ÍRJ, -— 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 ØØÍ5. i#jA

 Dw˜ Cu& ÌB atomic absorption spectrophotometry(AAS)n O o9 cÙÍ5.

2-2. 

Cu7 Dy˜ ACs& È8˜ }„Œ#1 ÅƂ/ W FT-IR

scanning electron microscope(SEM)n Ú ÉÊÍ5. † Cu Dy 0 i#jA }„&
AÉÃ/& ÌQ~ È8n ÉÊ/ W X-ray photoelectron spectroscope(XPS)n -o9 jA 
A& aÛ Q Ü1 ÝaÍ5. -— source MgKαn -o9 LAB MK-II (VG Scientific Co.) cÙN$n -o9 ÝaÍRJ, chamber Y&

ÞÄB 10⁻⁶-10⁻⁹ torr “ß9 ÝaÍ5.

2-3.   

 3à«B 300^oC, áÐ ÞÄ1 10⁻³ torr- ;_ .â ã 5-6 3’ € ä/3å 0, ASAP 2010(Micromeritics Co.)1 -o9 77 K, .ÞÄ(P/P0) uŸ N2/h& lmÛ1 ÝaÍ5. $}„

2-4. NO  

NO VêB He ëÏE 1,000 ppm ìD& NO 7En Oo9 7 EU³íGî›(DS 6200, Dï~Ef^Óf) st §·0& st=

 ð#=& cÙR ÝaÍRJ, detector thermal conductivity detector(TCD)Í columnB Hayesep A(30 ft, inner dia: 0.085 inch)n -oÍ5. !Ë ? st& D 500^oC ;_ÍRJ, è st 3’B 203’R Í5. st3 ;y˜ NO 7E& ;B M.F.C.

(mass flow controller; GMC1000, MLS)n Oo9 ÚÍRJ, 10 ml ·min⁻¹R ;_3ñ5. cÙ §  3à«B st D, 13’ €

 HeR òó9 …c1 ô§ V9 NO 7E& NLY lm

 & qn õA8  0 OoÍ5.

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⁺ü2^e−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
8R ™ ˜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-  º7 _ ½ æ (3) kB st1 `R4 ˜5.

Table 1. Composition and operating conditions of electroless Cu plating bath

Composition CuSO₄: EDTA Na₂:HCHO 1.0:2.50:1.31

Distilled water 980 ml

Conditions pH 12
0

Temperature 401^oC

Fig. 1. Cu quantification of the electrolessly Cu-plated activated car- bons measured by AAS.

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 

5Ÿ ‚«, _Q - ´§ wDw& T s › Dwh }„& - /™1 w yg7 T„, 3°57 

˜5[20].

3-2. 

´§ Cu DwR È8˜ Cu-ACs& }„Ý#1 FT-IR, XPS C SEMR ÉÊÍ -? IR& Ü1 Fig. 2 ÖY×5. ´§

Cu Dw˜ Cu-ACs& IRÜ1 û — Cu gh& ›Un ‹ …

œ_r 3,450 cm⁻¹b•& ›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⁻¹b•& ›U& ŠB ¬7

−OH ›U& Kã ¬7­  ´/- ù#×/ —R 

˜5. ´§ Cu Dw1 Ú »… Cu r Æ!e `aÛ& CuxO_y 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. 

ÜRbç Dw- z{ ue Cu2p& Ì- x R ¬7

¸1  ‹ … ×RJ,  O1s& ÜD ã’ ¬7 ¸1 É Ê‹ … ×5. 6 C1s& ÜB §sQR ¼AÍ5. DwR ~

 È8˜
A& ¥Û C ]& ¥Û1 ÉÊ/W O1s/C_1sÜ C Cu_2p/C_1sÜ1 ]‚Ç5. & Ü1 û — /ÁQR Dw3’- ¬

7 ue   Ü F  ¬7×RJ, ue, Cu-40, 7N ŠB 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 O_1s (%) C_1s (%) Cu_2p (%) O_1s/C_1s Cu_2p/C_1s

as-received 9.6 89.8 - 0.107 -

Cu-5 10.7 85.6 2.9 0.125 0.034

Cu-15 11.0 84.4 4.2 0.130 0.049

Cu-40 11.6 83.6 5.1 0.138 0.061

Fig. 3. Copper subpeaks in Cu_2p XPS spectra as a function of the plat- ing time.

 41 6 2003 12

& Dw 3 »… CuZ CuxO_yùâD " aD Dy˜5 

J, - Fig. 2 Ö ´/ ›U& ¬7­ .Ú  É Ê˜5.
8˜ ]& Ž#n é~/W XPS& Cu2p›U& sub- peakn *
QR cÍ -n Fig. 3 ÖY×5. ÉÊ , D w3’- ¬7¥ ue Cu metal& .Q~ ̂5 Cu(OH)2& Ì-

žqQR ¬7 ¸1 ‹ … ×5. -:  Î,   Cu7 Dw˜ i#jA&
A¥Û- ¬7 C
8]& Ž#­

$ 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 Éʘ5.

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-  .357 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. Œ ºHù F<, /™&  cg& => s& $7 3- `

—, -: (.B ST U ` J, - ue % lmB º

ž, ‡ .3 Type 1& % lm1 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 Ú9 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 C9 ]ÍRJ, - Ü«B Table 3 ÖY×5.

(4) 9/, W .Þ uŸ 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 &K5.

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

R ]# 5 ¸1 é~‹ … ×RJ, 4 E -& /™U/

n 7_ /™& $ê- ŠF1 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)/™

W

log =logW₀–B T( ⁄β)²log²(P₀⁄P)

Ψ( )2d P P₀ ---

   ln

=

62.38 2d 0.64– ---

– 1.895 10× ^–3 2d 0.32–

( )³

--- 2.7087 10× ^–7 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.

GH& b›7 x R IJ ¸1 Å … ×5. -: ¼AK-

 ´§ Cu Dw1 Ú i#jA& K)/™ GH `b /™ š 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)/™ šµR /~˜ (.-e ˜5.

Fig. 8B Kelvinæ / BJHp1 -o9 ´§ Cu Dw–

§·0& Cu-ACs& ?/™ È8Ü1 @Q/™b› Ü1 Ú9 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 &K5.

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 ¼AÍ ?/™& T G ¼A K-7 $&Q $ QÍ5. _r Cu-40& T /™ s_- 10 Å b•, b›&

¬77 V& œ ¸1 ‹ … ×5. - 5Ÿ 36«, RÆ û … œ (.R ƳD Fig. 4& SEM Oz,D ÉÊ ×-

D Cu Dw & ù#˜ Cu yg« & K)/™ ?/™

O-& GH,  /™ ¶- 10-20 Å b•& /™«& šµ- U `

 ¸R Éʘ5.

Table 3B ACs& ´§ CuDw §·0& $}„Q& È8, è/™b›, /™s_, BET .… C G »lm9(neat heat of adsorption)%1

Ö ¸R -n Ú ]hQ~ /™Œ#& È8n ‹ … 5.

$}„Q& T Cu-5ª_ x ¼A7 Ö_ ½ÇR Cu-40&

T ã 26%& $}„Q ¼A7 ðÍ5. -S x & $}„

Q ¼A Î, _QÍ- Dw & T K)/™ C 10-20 Å U/& /™«& šµ- 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)/™«- šµ- ` §s QR lmÄ& ¼A7 ðÍ/ —R é~×5.

3-4. NO 

Chen %[23]& ‚ uƒ„ NO i#jA­ kB jA* ¯S

&, >A­
A ºJ, -— stð#= N2C COx­ k B b
=1 ð34J, Æî­ kB *!V1 3Í5.

NOüC-ACsWCO-ACsü1/2 N2 (9)

COüCO-ACsWCO2üC-ACs (10)

CO-ACsWCO (11)

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

RT P

P₀ ---

  

ln 2σV_m

r_k --- –

=

r_k 4.14 P P₀ ---

   log

=

r_BJH r_k t P P₀ ---

   +

=

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

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

Table 3. Textural properties of the electrolessly Cu-plated activated carbons

as-received Cu-5 Cu-15 Cu-40 Specific surface area (m²·g⁻¹) 1,162 1,123 954 861 Total pore volume^a (cm³·g⁻¹) 0.484 0.460 0.398 0.357 Micropore volume^b (cm³·g⁻¹) 0.450 0.437 0.376 0.343 Micropore volume fraction (%) 93.8 94.3 94.5 96.1 Mesopore volume^c (cm³·g⁻¹) 0.034 0.023 0.022 0.014 Mesopore volume fraction (%) 7.0 5.0 5.5 4.0

Micro-/Mesopore ratio 13.2 19.0 17.1 24.5

Average pore radius^d (Å) 8.33 8.01 8.39 8.29

BET’s constant: C 948 945 940 932

Neat heat of adsorption^e (kj·mol⁻¹) 4.403 4.401 4.397 4.392

aV

ads

molar Volume of liquid N₂ molar Volume of gaseous N₂ ---

× From D-R plot,

b V_{total ads}×0.001547

Total pore volume

c –Micro volume

d2 V_total S_BET ---

×

∆

e E=E₀–E_L=RTln(C_BET)

 41 6 2003 12

Ã/n Ö5. 6 Park %[24]& \] uƒ„ Cu7 Dy˜ ACF

,& NO V st& T Æî& *!V1 uƒ ¸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 Ž#J, NO& =Q l m C ºB  NO-Cu-ACs, NO-CuxO_y-ACs C NO-C-ACs& st 1 Ú ` ¸R ]ݘ5.

Fig. 9 K– C ´§ CuDw- !3˜ Cu-ACsn -o9 ´

A, He ëÏE& 1,000 ppm ìD& 7En -o9 NO V

!Ë1 !3 Ü-5. K– 36& T 90c^, Mž-

ð9  NO& ìD7 53 ¬7 1 Ö s„

Cu-5 150c G Cu-15 200c aD, Mž- ÖLRJ, Cu-40& T Mž- 93’, ÖL5.

Fig. 10 11B  '],& N2C CO2ìDn Ö ¸-5. Fig. 10

& N2& È81 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 žq ‡ ¼ A×5. - Chen& ‚­ k- i#jA ghD ã’& ºÄ1

‚-/ —-J, N2ìD& ‡ ¼A .QR D7 "`  ºst‚5 D7 aŸ NO& =Q lmR ~ aƒ Mž

55b/ —R ˜5. s„ Cu7 Dy˜ i#jA«B Cu­ NO

& 8¹Q~ º°oR ~ G N2ìD& ¼A7 K–36–c

‡ `_ ½ ¸- ×5. Fig. 10& CO2ðÛ1 ‚„

K– 36& T7 7N Š Ö s„ DwÛ- ¬7 ue

žqQR CO2& Ì- ¼A - ÉÊ ×5. - K– 3 6& T /& º°oR ã’& CO2n ð34_r d Mž

 -ƒ: 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 Mžr1 û — 5Ÿ 36‚5 x R G Vê-

.3Í -: -; Æî& OfR z5.

Table 3, micro-/mesopore& $Ü1 û — Cu-40& T G Ü- 24.5 5Ÿ 36 $ % UJ, -n Ú K)/™& cê- .QR ŠB ¸1 Å … 5. NO& lm3 NO gh K)/™

 & lm- bc-_r NO cg7 K)/™ 55ƒ/ W,

 G Ú7  ?/™ C /™& cê- ?©5 ‹ … 5 [22]. - ?/™- /™& cê- g´ Š1 T lm˜ NO c g«- K)/™ª_ -ƒ_ - ?’ lm˜ 0 ¾ äm h 7 Ã#- Ž# ˜5. _r Cu-40& T Dy˜ Cu & K)/

™‚5 ?/™& šµ- U `LRJ - — K)/™& cê - .QR ¬7×5. — lm˜ NO& äm- o-_ ½Ç 1 ¸R ˜5. 6 Î,  Íi ­k- Cu-40& T 5Ÿ 36 $ Cu(OH)2& ¥Û- .QR ŠÇRJ, - —

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, Œ Cu-40& T Mž r1 û

— K– $ G "ê- 400% -. ¬7 ¸- ÉÊ×5. -

¸R ‚Æ i#jA& ´§ DwB ;o }„– @p ?& 

e ˜5. † -: (.& -; /ÁQR Dy Cu

& Ì &ŽJ, b…QR micro-/mesopore& $ G T#Éà / & 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.

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4.  

Á \], ACs ´§ DwpR Cun DyÍRJ, -n -o9 NO lm C ºV€ KL G 9 ÊÍ5.

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, -^_ ¸- õQ-e Éʘ5.

 

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