Tp ch Ha hc, T. 42 (1), Tr.

52 - 56, 2004
NGHIN CU POLYME HA ANILIN BNG PHN CUC IN HA
n Ta son 4-3-2003
Hong Th Ngc Quyn
1
, L Xun Qu
2
, ng nh Bch
3
1
ITIMS, Tr"ng i hc Bch khoa H) Ni
2
Vin K thut nhit i, Vin Khoa hc v) Cng ngh Vit Nam
3
Khoa Ha, Tr"ng i hc S" phm H) Ni

Abstract
PANi can be synthesized by electrochemical techniques in an acid solution on metal
electrodes. Tree techniques usually applied are cyclic voltammetry (CV), potentiostatic (PS) and
galvanostatic (GS) polarisation, among them GS method has many advantages.
Using electric current density J = 7 mA/cm
2
, concentration of aniline monomer 5 up to 30 g/l
in H
2
SO
4
1M solution, synthesis of polyaniline was realised continuously during 3 h and 5 h. It has
been found that both polymer product conversion and electric current reaction productivity, H
m
and H
J
respectively, are relatively high. H
J
depends strongly on the monomer concentration.

I - Gii thiu
Polyme dn in ang c quan tm pht
trin nhiu nc cng nghip trn th gii,
trong polyanilin (PANi), mc d c pht
hin t lu, nhng gn y mi c nghin
cu v. ng dng mnh m. Mt trong nhng
lnh vc ng dng in hnh PANi l. to m.ng
bo v chng n mn [1, 2].
PANi c tng hp bng hai phng php:
polyme ha ha hc v. polyme ha in ha. Qu
trnh tng hp PANi bng phng php in ha
c thc hin trn in cc ant, trong dung dch
axit c monome anilin (ANi) ha tan. Cho n nay
c ch tng hp in ha PANi ni ring v.
polyme dn ni chung, vn cha c l gii mt
cch thuyt phc. Tuy nhin v tng th c ch
polyme ha in ha PANi c m t theo s
cc bc chnh nh sau [3]: a) Khuch tn v. hp
ph anilin, b) oxi ha anilin, c) hnh th.nh
polyme trn b mt in cc, d) n nh m.ng
polyme, e) oxi ha - kh bn thn m.ng PANi.
Theo c ch tng hp in ha trn, c hai
giai on lin quan trc tip n phn ng in
cc: giai on khuch tn v. hp ph, ph
thuc trc tip v.o nng monome v. giai
on oxi ha anilin, ph thuc v.o nng
ANi ng thi v.o phn cc in ha.
C nng monome v. mt dng u c
nh hng trc tip n tc v. hiu sut
polyme ha.
Trong thc t c ba phng php phn cc
in ha chnh ch to PANi:
1. Phng php phn cc vng (cyclic
voltammetry, k hiu CV) in th phn cc
c qut tuyn tnh tun ho.n, t in th E1
n in th E2 v. ngc li, theo thi gian vi
vn tc qut khng i, dng in phn hi
c ghi li thit lp ng cong i - E.
2. Phng php phn cc th tnh (potenti-
ostatic, k hiu PS) l. phng php p in th
khng i E v. o dng phn hi theo thi
gian, thit lp ng cong phn cc i t.
3. Phng php phn cc dng tnh (galva-
nostatic, k hiu GS) p dng in khng i
52
ln mu v. o in th in cc E theo thi
gian, thit lp ng cong phn cc E - t.
Chng ti gii thiu di y c im
polyme ha anilin (ANi) trong dung dch axit
bng ba phng php phn cc in ha ni
trn, trong vic ng dng phng php phn
cc dng tnh GS kho st nh hng ca
nng monome n qu trnh tng hp PANi
trong axit sunphuric dc trnh b.y chi tit.
iu kin thc nghim lin quan c gii
thiu cng vi ni dung trong b.i.
II - Polyme ha in ha ANi
1. Phng php phn cc vng CV
iu kin polyme ha ANi bng phn cc
vng a chu k c gii thiu trong [1, 3 - 5].
Phn cc vng c thc hin trong bnh in ha
h ba in cc, nhit phng, khng khuy, vi
my potentiostat Wenking 72 ca CHLB c.
Hnh 1 gii thiu ng cong phn cc
vng a chu k ca thp CT3 trong dung dch
H
2
SO
4
2M, t 350 mV n 750 mV.

Hnh 1: Ph phn cc vng thp CT3 trong axit sunfuric, 350 - 750 mV
a: C1 (chu k 1) - C3, b: C4 - C15
nhy n v o dng in: b gp hn 3 ln a
C.ng tng chu k phn cc, dng th ng
c.ng nh. Sau C4, dng th ng t gi tr nh
nht, cc ng phn cc vng trng kht ln
nhau (hnh 1b).
Nu c ANi 2% trong dung dch, dng phn
cc tng ln, xut hin m.ng PANi m.u en trn
b mt in cc (hnh 2). Ba chu k u tin l.
qu trnh th ng in cc v. khi m.o polyme
ha. Bt u t C4 dng polyme ha tng nhanh,
xut hin pic oxi ha v. pic kh PANi [4].
Thc t cho thy, vic xc nh ng hc
polyme ha kh phc tp. Vi hai pic oxi ha
kh m.ng PANi trn y, kh xc nh c
in lng thun ty polyme ha ANi.

a: C1 - C4
b: C5 - C44
c: C45 - C50

Hnh 2: Ph phn cc vng polyme ha ANi to m.ng PANi trn thp CT3
H
2
SO
4
2M + 2% anilin, 300-700mV, 30mV/s,
J
a
b
53
2. Phng php phn cc th tnh PS
i vi polyme ha bng th tnh PS, cn
p mt in th ln ng thi th ng
nn, ng thi oxi ha anilin.
Qu trnh th ng ca thp CT3 v. s khi
m.o polyme ha bng phn cc th tnh (PS)
trong dung dch nghin cu c gii thiu trong
hnh 3.
Khi p th, dng tng cao t ngt do tch
in cho lp kp v. c th do c hin tng oxi
ha trn b mt in cc, t n 500 mA/cm
2
.
Thot kh mnh trn in cc m chng t qu
trnh kh hidro. Sau dng in gim nhanh
do th ng trn b mt in cc l.m vic. Vi
th PS 800 mV, dng nh nht quan st c
l. J
min
nm trong khong 2 - 6 mA/cm
2
(hnh
3), lc n.y cha xut hin kt ta PANi m.u en
trn b mt in cc.
0 10 20 30 40 50 60
0
100
200
300
400
500
1
2
J
(
m
A
/
c
m
2
)
t (s)
15 30 45 60
-20
0
20
40
60
J
(
m
A
/
c
m
2
)
t (s)
Hnh 3: Bin thin dng phn cc theo thi gian
H
2
SO
4
2 M, 2% th tch ANi,
thp CT3, 800 mV/SCE
Hai th nghim cng iu kin
Hnh chn l. phng to th t 10 60 s, dng
polyme ha khng i sau 50 s phn cc
Khi xut hin phn ng polyme ha in ha
anilin, dng in tng ln, v. t n gi tr n
nh (hnh chn trong hnh 3). Dng polyme ha
n nh ph thuc ch yu v.o nng anilin
trong dung dch.
Kt qu thc nghim cho thy cn p th
tnh cao hn 700 mV th ng thp CT3 v.
khi m.o polyme ha. Vi phn cc bng in
th khng i, iu quan trng l. la chn c
gi tr in th ph hp [7].
Tuy nhin trong h nghin cu s dng
phn cc th tnh trn, dng in polyme ha
kh ln, m.ng PANi pht trin nhanh, thng
c xp cao, dng bt, khng u. Phn cc
th tnh PS khng cho php kim sot c tc
phn ng.
III - Ph0ng php phn cc
dng tnh GS
1. Mt s c im ca phn cc dng tnh
to m.ng PANi ng u c r xp
thp trn in cc, thng s dng phn cc
dng tnh GS, vi u im ni bt l. iu chnh
c tc polyme ha.
Vi mt dng phn cc khng i, tc
polyme ha l thuyt c coi l. hng s,
ng thi d d.ng xc nh chnh xc in
lng Faraday ca h. y chnh l. im tri
ni bt ca phng php GS so vi cc phng
php PS v. CV. Tuy nhin cho n nay cha c
kt qu thc nghim gii thiu mt cch h
thng vic nghin cu polyme ha ANi. Sau
y l. mt s kt qu kho st qu trnh tng
hp PANi bng ng dng phng php GS.
Mt dng c la chn l. 7 mA/cm
2
[8], tng ng vi kh nng polyme ha
khong 10
-6
g ANi trong mt giy trn din tch
1 cm
2
. Vi mt dng nh, tc polyme ha
chm nhng PANi thu c mn hn. Vi mt
dng ln, hu ht PANi b oxi ha [9].
Polyme ha ANi c thc hin nhit
phng. in cc l.m vic l. thp khng g c
h.m lng crom gn 18%. iu kin thc
nghim polyme ha ANi { c gii thiu
trc y [4, 5, 6, 8]. Sau khi ch to, PANi sn
phm c ra sch bng nc ct, loi b ht
cht tan. Sau kh nhit phng. Sn
phm c sy kh 95
o
C trong 2 gi, bo
qun trong bnh kn kh c ht m.
Hiu sut khi lng polyme ha H
m
(%)
c tnh theo cng thc :
( ) 00 .1
m
m
% H
0
p
m
= (1)
trong m
0
l. khi lng monome ANi ha tan
trong dung dch trc khi phn ng, m
p
l. khi
J
(
m
A
/
c
m
2
)
t (s)
53
54
lng polyme sy kh thu c, qui theo lng
monome ANi { tham gia phn ng. Khi lng
m
0
ca monome ANi c s dng l. 5, 10, 20
v. 30 g/l, thi gian phn ng l. 3 v. 5 gi.
Hiu sut dng H
J
(%) c tnh theo t l
gia kt qu thc nghim v. tnh l thuyt tnh
theo nh lut Faraay. Lng ANi tham gia
phn ng polyme ha v mt l thuyt c
tnh theo cng thc Faraday { bit:

M
zF
It
m
lt
=
(2)
trong m
lt
(g) l. khi lng cht phn ng l
thuyt. Theo c ch polyme ha in ha ANi
[3] z = 1. Hiu sut dng H
J
(%) c tnh bng
cng thc :

0 .10
m
m
(%) H
lt
J
p
=
(3)
2. Kt qu thc nghim v) tho lun
Hiu sut H
m
vi mt dng J = 7 mA/cm
2
sau 5 gi c gii thiu trong hnh 4. S ph
thuc ca H
j
v.o nng ANi c gii thiu
trong hnh 5.
Hiu sut H
m
t n 56% trong dung dch
lo{ng. Vi dung dch c hn hiu sut ch t
khong 54%. Hiu sut H
J
tng gn nh tuyn
tnh vi nng ANi. Hiu sut dng sau 5 gi
phn ng thp hn so vi 3 gi c th do nng
monome ANi ban u b gim mc
nht nh.
0.00 0.03 0.06 0.09 0.12
52
53
54
55
56
57
5h
H
m
[
%
]
C
ANi
[mol/l]

Hnh 4: Hiu sut khi lng polyme ha H
m
tnh theo nng monome C
ANi

0.00 0.03 0.06 0.09 0.12
20
40
60
80
5h
3h
H
j
,
[
%
]
C
ANi
, [mol/l]

Hnh 5: S ph thuc H
J
v.o nng ANi
trong dung dch
Nh vy vi phng php phn cc dng
tnh, c th kho st d d.ng mt s thng s
ng hc ca polyme ha ANi, gp phn ho.n
thin v. kim sot c qu trnh ch to PANi
in ha.
IV - Kt lun
Phn ng tng hp in ha PANi c th
c thc hin bng phn cc vng a chu k
(CV), phn cc th tnh (PS) v. phn cc dng
tnh (GS). Phng php GS c nhiu u im
ni bt so vi cc phng php CV v. PS, c
s dng ch to PANi.
{ xc nh c hiu sut chuyn ha sn
phm polyme ha bng phng php GS trong
dung dch axit sunphuric 1M, vi mt dng
in 7 mA/cm
2
v. nng monome C = 5 - 30 g/l.
Hiu sut chuyn ha sn phm kh cao, t
54 - 56%. Hiu sut dng c th t n 80%.
Kt qu nghin cu trn l.m r hn hiu qu
polyme ha in ha anilin ch to
polyalinin dn in.
Cng trnh n)y "c ho)n th)nh vi s h
tr kinh ph ca t)i nghin cu c bn mV
s 8530502.
Ti liu tham kho
1. D.W. de Berry. J. Electrochem. Soc., Vol. 132,
No. 3, P. 1022 (1985).
2. Cl. Deslouis et M. Keddam. Lettre des Sciences
Chimiques, CNRS (France), 2 (1999).
H
m
(
%
)
H
J
(
%
)
0 0,03 0,06 0,09 0,12
C
ANi
(mol/l)
0 0,03 0,06 0,09 0,12
C
ANi
(mol/l)
55
3. Junfeng Shou and David O. Wiph. J. Electro-
chem. Soc., Vol. 144, No. 4, P. 1203 (1997).
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Qu. Tp ch Khoa hc v. Cng ngh, Tp
XXXVIII, s 3B, Tr. 87 - 91 (2000).
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ngh chuyn ng.nh in ha v. ng dng,
H. Ni, Tr. 74 - 79 (2001).
6. L Xun Qu, Bi Th Thu H., ng nh
Bch. Tp ch Ha hc, T. 40, s 1, Tr. 49 - 53
(2002).
7. L Xun Qu, Th Hi. Tuyn tp Hi
ngh KH & CN Ha hu c to.n quc ln 2,
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(2002).
9. Trn Kim Oanh. Lun vn thc s, Trng i
hc S phm Thi Nguyn (2000).

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