studies on n-alkylated polyaniline and its application to
TRANSCRIPT
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Studies on N-alkylatedPolyaniline and its
application to measurementof hydrogen peroxyde at
neutral pHDiego L. Raffa1, K. Tong Leung2, Fernando Battaglini1
1 Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires2 Department of Chemistry, University of Waterloo
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Redox and Acid-Base Equilibria of Polyaniline
NH
NH
NH
NH
N
N N
N
NH
NH
N
N
NH
NH
N+
H
N+
H
A-
A-
2A- -2e -2A- -2e
2A- +2H+
Insulating
Insulating
Conducting
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How to use it in Sensors
i
time
C4C3C2C1
C1<C2<C3<C4
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GOxPoly(o-phenylendiamine)
PANI
Carbon Electrodes
HRP
V
POLYMER
CARBON BAND
INSULATOR
Examples
P. N. Bartlett y P. R. Birkin; Synthetic Metals, 61 (1993) 15-21 P. N. Bartlett; P. R. Birkin; J.H Wang; F. Palmisano; G. De
Benedetto; Anal.Chem. 1998, 70, 3685-3694.
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Attempt to improve the problem of pH
•Polymerization in presence of PSS orPVS•A Donnan potential that keeps positiveions in the film is created
Results:•The polymer conductivity is temporarily improved at pHs between 6 and 7•After some minutes, conductivity decreases and is only recovered by immersion in acid
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Our Attempt: Sultonation
NH
NH
NH
NH
n
¨¨
¨¨
OS
OO
+
NH
NH
NH
n
N
SO3-
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XPS Analysisx 102
50
60
70
80
90
100
CPS
410 408 406 404 402 400 398 396 394 392 390Binding Energy (eV)
x 102
40
50
60
70
80
90
CPS
410 408 406 404 402 400 398 396 394 392 390Binding Energy (eV)
Before After
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N1S
190
200
210
220
CPS
N1S
160
165
170
CPS
N1S.DTS
x 102
160
170
180
406 404 402 400 398 396 394Binding Energy (eV)
N1S.DTS
x 102
150
155
406 404 402 400 398 396 394Binding Energy (eV)
3 hs room T overnight room TN1S.DTS
N1S
x 102
140
145
150
155
160
165
170
175
180
185
CPS
406 404 402 400 398 396 394Binding Energy (eV)
N1S.DTS
N1S
x 102
160
165
170
175
180
185
190
195
CPS
406 404 402 400 398 396 394Binding Energy (eV)
3 hs 60ºC overnight 60ºC
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Electrochemistry results
-70
-50
-30
-10
10
30
50
70
90
110
-0.20 -0.10 0.00 0.10 0.20 0.30 0.40 0.50E vs Ag|AgCl/V
i/A
H2SO4 1,8 M, 50 mVs-1
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Electrochemistry results
-70-60-50-40-30-20-10
0102030405060
-0.20 -0.10 0.00 0.10 0.20 0.30 0.40 0.50E vs Ag|AgCl/V
i/A
Buffer acetic 0,1 M; pH 4,7; 50 mVs-1
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Electrochemistry results
-8-7-6-5-4-3-2-1012345678
-0.20 -0.10 0.00 0.10 0.20 0.30 0.40 0.50E vs Ag|AgCl/V
i/A
Buffer PIPES 50 mM; KNO3 0,1 M; pH 7; 50 mVs-1
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Results of Resistance measurements
Resistance of PANI y PSPANI on a switch electrode.
1,3x1041,1x107Buffer PIPES pH 7
1,9x1034,1x104Buffer acetic0,1 M pH 4,7
1,7x1031,7x103H2SO4 1,8 M
R de PSPANI [Ω]
R de PANI [Ω]
Media
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Sensor based on PSPANI and HRP
PSPANICarbon Electrodes
p-phenylendiamine
HRP or MP-11
Works at pH 7!!
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Results for HRP (current curves)
iDrain vs t de switch de PAni sultonada a T amb. con HRP o MP-11 inmovilizada con p-fenilendiamina. HEPES 0,1 M KNO3 0,1 M pH 7
(EDrain=20 mV)(EGate=0 V vs Ag/AgCl) Se agregó a t=~50 s H2O2 hasta llegar a la concentración correspondiente
0
2
4
6
8
10
12
0 100 200 300 400 500 600 700 800
t [s]
i [A]
0,1 mM HRP
0,2 mM HRP
0,3 mM HRP
0,5 mM HRP
1 mM HRP
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Results for MP-11 (current curves)
iDrain vs t de switch de PAni sultonada a T amb. con MP-11 inmovilizada con p-fenilendiamina. HEPES 0,1 M KNO3 0,1 M pH 7
(EDrain=20 mV)(EGate=0 V vs Ag/AgCl) Se agregó a t=~50 s H2O2 hasta llegar a la concentración correspondiente
0
2
4
6
8
0 100 200 300 400 500 600 700 800
t [s]
i [A]
0,025 micro
0,05 micro
0,1 micro
0,2 micro
0,3 micro
0,5 micro
1 micro
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Calibration Curve for: MP-11
Velocidad máxima normalizada de switch de PAni sultonada una noche a T amb. con microperoxidasa MP-11 inmovilizada
con p-fenilendiamina. MOPSs 0,05 M KNO3 0,1 M pH 7 (EDrain=20 mV)(EGate=0 V vs Ag/AgCl) vs Concentración
y = -0.0377xR2 = 0.9776
-4.00E-02
-3.50E-02
-3.00E-02
-2.50E-02
-2.00E-02
-1.50E-02
-1.00E-02
-5.00E-03
0.00E+00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1Concentración [mM]
Velo
cida
d m
áx
norm
aliz
ada[1
/s]
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Calibration Curve for: MP-11
Taking slope of the first seconds as criterion
Pendiente de los 1° segundos de switch de PAni sultonada una noche a T amb. con microperoxidasa MP-11 inmovilizada con p-
fenilendiamina. MOPSs 0,05 M KNO3 0,1 M pH 7 (EDrain=20 mV)(EGate=0 V vs Ag/AgCl) vs Concentración
y = -0.2432x + 0.0066R2 = 0.9893
-2.50E-01
-2.00E-01
-1.50E-01
-1.00E-01
-5.00E-02
0.00E+00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1Concentración [mM]
Pend
ient
e de
los
1°
seg.
[ µA/
s]
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Conclusions:
•Certain independence between conductivity of PANI and pH can be achieved•The procedure can be made simple and fast by changing reaction temperature and time
•A working pH of 7 can be achieved forsensors based on PANI•Analysis time is still too long and must be shortened to optimize the method
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Acknowledgement:
•CONICET•Fundación Antorchas
•DQIA y QF-INQUIMAE•Lab group for making me feel at home