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ELECTRODEPOSICIN DE
POLIANILINA
1
Cyclic Voltammetry
Reversibility
E = 59/n mV [1]
Beginning
t (s)
Difussion
Ip = k1 x v0.5 [2]
Adsorption:
Ip = k2 x v [3]
2
Electromicrogravimmetry
Counter- Reference
electrode Potentiostat Computer
Work
Frecuency
Oscillator
counter
SENSITIVITY: nanograms
f = - Cfm f frequency change due to mass gain per unit area
m mass gain
Cf sensitivity constant = 1.0707 ng/Hz
20/05/2017 17:24:18 3
Equipment
4
Importance of Intrinsically Conducting Polymers (ICPs)
Macromolecule
Conjugated p bonds
Electrochromism
Conductivity similar to metals
https://www2.warwick.ac.uk/fac/sci/physics/current/postgraduate/regs/mpags/ex5/bandstructure/
5
ICPs: Conductivity
H H H
N N N
N N
H H
Neutral chain, Gap: 1.5 eV
H H H
N N N
N N A
H H Polaron, Gap: 0.5 eV
H H H
N N N
A N N A
H H Bipolaron, Gap: 0.75 eV
6
ICP: Importance
Electrical Electrical
conductivity conductivity in
in oxidised reduced state
Polymer Structure state (Scm-1) Similar to (Scm-1) Similar to
Polyacetilene
Ag, Cu, Si, carbon
n
1x104 Fe, Mg 1x10-7 steel
Polypyrrole
N
H
n 500-7500 Ge 1x10-10
Polythiophene
H
Polyaniline N Diamond,
n 200 In, Sn 1x10-13 glass
Polyfuran
O n 1 1x10-11
http://www.tibtech.com/conductivity.php 7
http://www.electrical4u.com/electrical-conductivity-of-metal-semiconductor-and-insulator/
Important concepts
8
Important concepts
9
Doping/Ionic Dynamics
10
Intermolecular Doping
Mass gain
H E H Anionic
N + x A N
Control
x A
x
11
Intramolecular Doping
Mass loss
H
E H
N N cationic
control
x A x
A H
12
Intramolecular Doping
A- M+
A- M+
A- M+
13
Intramolecular Doping
+ A- M+
+ A- M+
A- M+
+
14
Some applications of conducting polymers
Artificial muscles
W. Takashima, S. S. Pandey, M. Fuchiwaki, K.
Kaneto. Cyclic step-voltammetric analysis of
cation-driven and anion-driven actuation in
polypyrrole films. Jpn. J. Appl. Phys., Part 1 41
(2002) 7532-7536.
15
Some applications of conducting polymers
Rechargeable batteries
16
Some applications of conducting polymers
Rechargeable batteries
OXIDISED REDUCED
17
Some applications of conducting polymers
Thermoelectricity
M. Culebras, C. M. Gmez, A.
Cantarero. Review on polymers for
thermoelectric applications. Materials 7
(2014) 6701-6732.
Importance of PANI
H N
Thermal stability
Applications SO3H
Conductivity at pH < 4
Insoluble in aqueous media
Importance of SPANI H N
Thermal stability SO3H
Conductivity at pH > 7
Soluble in aqueous media
Self-doping
Ionic dynamics different to PANI H N
Increased efficiency
SO3H
19
Influence of sulfonic group
polaron
H H
N N
+
N N N N
H H H H
SPANI: 0.30
1 charge carrier delocalized over 3 phenyl rings 1 SO3H
Max doping 30% sulfonation
20
Electroxidation of o-ASA/PAni
II P(o-ASA)
III
PANI
V
IV
IV
III
I II V
I, III ox parcial
Respuesta caracterstica SPANI II, V ox completa
H6 Jo = 8 Hz
H3
Jm = 2 Hz
Jo = 8.25 Hz H5
Jm = 2.5 Hz Jm = 2.0 Hz
Quinoides-
bencenoides
5 3
Polimerizacin cabeza-cola
4
20/05/2017 17:24:18
Comportamiento como electrodo
HIDROQUINONA/BENZOQUINONA FERRO/FERRICIANURO
P(o-ASA) Au
E = 166 mV E = 110 mV
Au P(o-ASA)
E = 82 mV E = 450 mV
[Hidroquinona] = 0.01 M, [H2SO4] = 0.5 M [K4Fe(CN)6] = 0.01 M, [K3Fe(CN)6] = 0.01 M, [KNO3] = 0.1 M
V = 50 mVs-1. A.G. = 0.1963 cm2 V = 50 mVs-1. A.G. = 0.1963 cm2
No cataliza par HQ/BQ Inhibicin reportada
No permea a travs de P(o-ASA)
Reaccin en superficie
R. Maeikiene, G. Niaura, A. Malinauskas. Voltammetric study of the redox processes of self- R. Maeikiene, G. Niaura, A. Malinauskas. Voltammetric study of the redox processes of
doped sulfonated polyaniline. Synth. Met. 139 (2003) 89-94. self-doped sulfonated polyaniline. Synth. Met. 139 (2003) 89-94.
20/05/2017 17:24:18
Electroactivity of P(o-ASA) as a function of pH
Transicin
p -*
Mayor cristalinidad
20/05/2017 17:24:18
Compensacin de carga en P(o-ASA)
M+ PARTICIPACIN
Totalmente +: no permite salida A-
20/05/2017 17:24:18 [(CH3CH2)4NBF4] = 0.1 M / Acetonitrilo. V = 50 mVs-1. A.G. = 0.1963 cm2
Observaciones
P(o-ASA) es conductor en un amplio intervalo de pH
Dinmica inica:
Control mixto
Proceso (I): predomina control catinico, no es funcin de la masa
del anin
Segundo proceso: predomina control aninico