Conducting polymer-silver composites review

Chemical Papers 67 (8) 814848 (2013)
DOI: 10.2478/s11696-012-0304-6
REVIEW
Conducting polymersilver composites
Jaroslav Stejskal*
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6, Czech Republic
Received 10 July 2012; Revised 22 October 2012; Accepted 25 October 2012
Preparations of hybrid composites composed of two conducting components, a conducting polymer
and silver, are reviewed. They are produced mainly by the oxidation of aniline or pyrrole with
silver ions. In another approach, polyaniline or polypyrrole are used for the reduction of silver
ions to metallic silver. Other synthetic approaches are also reviewed. Products of oxidation of
aniline derivatives, including phenylenediamines, are considered. Morphology of both the conducting
polymers and the silver in composites displays a rich variety. Conductivity of the composites seldom
exceeds 1000 S cm
1
and seems to be controlled by percolation. Interfacial eects are also discussed.
Potential applications of hybrid composites are outlined; they are likely to extend especially to
conducting inks, printed electronics, noble-metal recovery, antimicrobial materials, catalysts, and
sensors.
c 2012 Institute of Chemistry, Slovak Academy of Sciences
Keywords: polyaniline, polypyrrole, poly(o-phenylenediamine), poly(p-phenylenediamine), silver,
silver nanoparticles, hybrid composites, conductivity
Introduction 815
Polyanilinesilver composites 816
Oxidation of aniline with silver
compounds 816
Physical acceleration 817
Chemical acceleration 818
Morphology of composites 818
Reduction of silver ions with PANI 820
Eect of counter-ions 821
Silver complexes 821
Morphology of PANI 821
PANI lms and coatings 821
Preparation of PANI in the presence of
silver particles 822
Reduction of silver ions with external
reductants in the presence of PANI 823
Mixing of PANI and silver particles 823
More complex systems 823
Two reductants of silver ions 823
Two oxidants of aniline 824
Ternary composites 824
Colloids 824
Polypyrrolesilver composites 824
Oxidation of pyrrole with silver
compounds 824
Morphology of composites 825
Reduction of silver ions with PPy 826
Preparation of PPy in the presence
of silver particles 827
Reduction of silver ions with external
reductants in the presence of PPy 827
Mixing of PPy and silver particles 827
More complex systems 827
Multiple reactants 827
Ternary composites 827
Colloids 828
Related polymersilver composites 828
Poly(p-phenylenediamine) 829
Poly(m-phenylenediamine) 829
Poly(o-phenylenediamine) 829
Substituted polyanilines 830
Polymethylanilines 830
Poly(o-methoxyaniline) 830
Poly(2,5-dimethoxyaniline) 830
Poly(4-aminodiphenylamine) 830
Sulfonated polyaniline 830
*Corresponding author, e-mail: stejskal@imc.cas.cz
J. Stejskal/Chemical Papers 67 (8) 814848 (2013) 815
Aniline oligomers 830
Other related systems 831
Conductivity 831
Conductivity of polyanilinesilver
composites 832
Direct preparation 832
Reduction with polyaniline 833
Other syntheses 833
Conductivity of polypyrrolesilver
composites 834
Direct preparation 834
Reduction with polypyrrole 834
Conductivity of other systems 834
Temperature dependence
of conductivity 835
Deprotonation phenomena 835
Applications 835
Antimicrobial activity 835
Bioapplications 836
Catalysis and electrocatalysis 836
Conducting composites 836
Sensors 837
Silver recovery and water-treatment 837
Surface-enhanced Raman scattering 837
Other uses 837
Conclusions 837
References 838
Introduction
Composites of conducting polymers, such as poly-
aniline (PANI) and polypyrrole (PPy), and silver con-
tain two types of electric conductors. Conducting
polymers are organic semiconductors, silver is a metal-
lic conductor. Such composites are called here as hy-
brid because they combine dierent electrical features
of the parent constituents. Both the conducting poly-
mers and silver display a variety of morphologies on
the nanoscale. Their nature, distribution within the
composites, and interfacial phenomena are expected
to control or aect their electrical properties. In addi-
tion to electrical features, many potential applications
rely on chemical, electrochemical, optical, and other
physical properties.
Early studies on polyacetylene have illustrated the
potential of conducting polymers to compete with
metals in the conduction of electric current, and con-
ductivities comparable to those of metals have been
reported. Limited stability of polyacetylene under am-
bient conditions shifted the research interest to other
conducting polymers. Most of the currently-used con-
ducting polymers, such as PANI or PPy, have a typi-
cal conductivity of the order of 1 S cm
1
(Stejskal &
Gilbert, 2002; Blinova et al., 2007b), i.e. at the semi-
conductor level, four to ve orders of magnitude lower
compared with metals such as mercury, copper, sil-
ver, or gold. Various ways to further enhance the con-
ductivity have therefore been sought. Processing of
PANI in m-cresol in the presence of camphorsulfonic
acid leads to the conductivity exceeding 1000 S cm
1
(Cao et al., 1993; Pron & Rannou, 2002). Polyani-
line produced in emulsion polymerization was also re-
ported to reach a room-temperature conductivity ex-
ceeding 1000 S cm
1
(Lee et al., 2006); the follow-up
studies, however, are missing. Mechanical orientation
of conducting-polymer chains is another way demon-
strating the potential of conducting polymers as elec-
tric conductors. Virtually all papers report the con-
ductivity determined in the dry state or at ambient
humidity. It has recently been proposed that, when
immersed in acidic aqueous media, the eective con-
ductivity of PANI may exceed 1000 S cm
1
due to
the contribution of proton conduction (Stejskal et al.,
2009a).
Preparation of composites is an alternative way to
increase the conductivity of these polymers. For that
reason, organic conducting polymers have been com-
bined with inorganic conducting materials, such as
carbon nanotubes, graphene, or graphite (Tchmutin
et al., 2003; Konyushenko et al., 2006; Jimnez, et al.,
2010; Spitalsky et al., 2010). Noble metals, however,
are the most promising candidates for this task. Silver
has received most attention due to its highest conduc-
tivity among metals, 5.6 10
5
S cm
1
at room tem-
perature, and relatively low cost compared to other
noble metals.
Electrical properties of hybrid composites com-
posed of two conducting components are determined:
(i) by composition, i.e. by the mutual proportions of
the organic semiconductor and the metal; (ii) by the
morphology of both components; and (iii) by inter-
facial phenomena, such as the presence of insulat-
ing barriers between both conducting phases (Efros
& Shklovski, 1976; Baibarac et al., 1999; Tchmutin
et al., 2003). Conducting polymers generally pro-
duce globules, nanobres, nanotubes, microspheres,
and various hierarchical nanostructures (Sapurina
& Stejskal, 2008, 2010; Stejskal et al., 2010; Zu-
jovic et al., 2011b). Silver may be present as micro-
spheres, nanocubes, nanobres or nanowires, nanorods
or nanocables, and various two- and three-dimensional
objects (Nadagouda & Varma, 2007; Chang et al.,
2011; Chen & Liu, 2011a). It is of interest to note
that the richness of morphologies displayed is an in-
herent feature of both the conducting polymers and
silver. The size of objects becomes important when it
diminishes to the submicrometre level and the interfa-
cial area increases. Various interfacial phenomena may
then become important.
It has to be stressed, however, that the conduc-
tivity of composites need not be the primary goal
in the potential applications. Conducting polymers
816 J. Stejskal/Chemical Papers 67 (8) 814848 (2013)
Fig. 1. Oxidation of aniline with silver nitrate in an acidic aqueous medium yields a composite of PANI and silver. Nitric acid is
a by-product (Blinova et al., 2009; Bober et al., 2011a).
are stimuli-responsive. They change their electrical
and optical properties depending on external impulses,
such as a change in acidity, humidity, temperature, the
presence of oxidants or reductants, etc. The respon-
sivity of conducting polymers can be improved by the
presence of noble metals and this property may be-
come useful in sensors. Conducting polymers manifest
themselves as oxidants or reductants and can therefore
participate in redox reactions. Corrosion protection
and its improvement may serve as such an example
(Li et al., 2012b) although the cost of such compos-
ites would be rather prohibitive. Widely used catalytic
properties of noble metals can be enhanced by the in-
teraction with conducting polymers (Sapurina & Ste-
jskal, 2009). Optical properties of metal nanoparticles
are well known since the times of Faraday (Kelly et
al., 2003; Stamplecoskie & Scaiano, 2011) and may be
aected by the interaction with conducting polymers.
Synergetic eect of the two components may become
important in pharmacology and medicine.
There are four basic strategies for the prepara-
tion of the composites of conducting polymers and
silver: (i) a single-step preparation, where a corre-
sponding monomer, typically aniline or pyrrole, is ox-
idized with a silver cation to produce a composite of
conducting polymer and silver. This is the most im-
portant approach; (ii) a conducting polymer is pre-
pared by conventional oxidative polymerization and
subsequently used for the reduction of silver salts to
silver; (iii) in another two-step process, the compo-
nents are prepared consecutively. Silver particles are
prepared at rst, and a conducting polymer is syn-
thesized afterwards in their presence. Alternatively,
a conducting polymer is synthesized at rst and sil-
ver nanoparticles subsequently with the help of ex-
ternal reductants; (iv) nally, both components, the
conducting polymer and silver particles, are prepared
separately and simply mixed or blended. Some spe-
cial approaches may combine these four basic synthe-
sis methods.
Polyanilinesilver composites
Oxidation of aniline with silver compounds
Oxidation of aniline with silver salts, such as silver
nitrate, is the most direct way of preparation of PANI
silver composites (Blinova et al., 2009, 2010; Bober et
al., 2011a) (Fig. 1). In this way, the reaction between
two non-conducting chemicals, aniline and silver ni-
trate, yields a mixture of two conductors, PANI and
silver. The standard redox potential (E
) of silver ions
in the conversion to metallic silver, Ag
+
+ e
Ag, is
0.80 V, which is much lower compared with that of the
commonly used ammonium peroxydisulfate (2.00 V).
Nevertheless, this is a suciently high value because
other oxidants such as iron(III) salt, Fe
3+
+ e

Fe
2+
(E
= 0.77 V), are also able to oxidize aniline to

PANI (Li et al., 2007; ednkov et al., 2011; Sapurina
& Stejskal 2012).
There are several requirements on the synthesis by
most potential applications: (i) the products should
have high conductivity; (ii) they should be macroscop-
ically homogenous; (iii) they should not be contami-
nated by other components, such as insoluble silver
salt or aniline oligomers; (iv) or damaged by side re-
actions, such as the nitration of PANI; and (v) they
should be produced within a reasonable time interval.
Simultaneous satisfaction of these conditions is not
trivial.
The success of PANI preparation can be best con-
rmed by UV-VIS spectra, when the PANI base is dis-
solved in N-methylpyrrolidone (Blinova et al., 2009) or
dispersed in dimethylsulfoxide (Li et al., 2012b). The
observation of the absorption maximum at approxi-
mately 630 nm, corresponding to the
transition
of quinoneimine rings, is an unambiguous proof that
PANI was produced (Du et al., 2005; Blinova et al.,
2009; Karim et al., 2009; Bober et al., 2011b; Li et al.,
2012b) (Fig. 2). In its absence (Gao & Xing, 2012), the
formation of aniline oligomers is the most likely ex-
Fig. 2. UV-VIS absorption spectra of PANI base prepared by
the oxidation of aniline with silver nitrate (a) or am-
monium peroxydisulfate (b) (adapted from Blinova et
al., 2009).
planation (Stejskal et al., 2008b; Stejskal & Trchov,
2012). Silver nanoparticles often display a separate ab-
sorption band at 400500 nm caused by plasmon res-
onance (Martins et al., 2006; Dallas et al., 2007), the
position of the absorption band being dependent on
the particle size. Aniline oligomers, however, also ab-
sorb in this region (Stejskal & Trchov, 2012).
pH of the reaction medium decreases in the course
of aniline oxidation. Two hydrogen atoms are ab-
stracted from each aniline molecule that becomes in-
corporated into PANI chains and they are released as
protons (Stejskal et al., 2008b). This applies also to
the oxidation with silver nitrate (AgNO
3
) (Fujii et al.,
2010), where nitric acid is a by-product (Blinova et al.,
2009, 2010) (Fig. 1). pH of the reaction mixture has to
be below pH 23 for the formation of PANI (Stejskal
et al., 2010); otherwise, aniline oligomers are the ex-
clusive product of the oxidation (Stejskal & Trchov,
2012).
In practice, however, the oxidation of aniline with
AgNO
3
in strongly acidic media, such as nitric acid
solutions, is slow and it takes months (Blinova et al.,
2009) to achieve an appreciable yield. Acidic reaction
conditions are satised for the propagation of PANI
chains but, obviously, the initiation of chain growth
is restricted. Some papers reported the formation of
polymer already after 8 h but the yield was not spec-
ied (Neelgund et al., 2008). Physical or chemical ac-
celeration is thus needed, as reviewed below. The ox-
idation of aniline with AgNO
3
at neutral conditions
yielded a composite of brown aniline oligomers and
silver (Gao & Xing, 2012).
The content of silver in the composite as predicted
by the stoichiometry (Fig. 1) is 68.9 mass % of sil-
ver (Blinova et al., 2009). This assumption was con-
rmed experimentally by thermogravimetric analysis.
This method is applicable only if the sample is ho-
mogeneous and a few milligrams are representative of
the whole sample. In case of heterogeneous samples
containing silver particles visible to the naked eye,
standard determination of ash made on larger sam-
ples provides more reliable results. It has to be stressed
that thermogravimetric analysis has to be made in air
(Stejskal et al., 2009d) because when performed in ni-
trogen atmosphere (Khanna et al., 2005; Afzal et al.,
2009; Karim et al., 2009; Wang et al., 2009a; Huang et
al., 2009; Grinou et al., 2012; Jia et al., 2012), PANI
is carbonized leaving about a 40 mass % residue (Tr-
chov et al., 2009; Rozlvkov et al., 2011) in addition
to silver. The residue thus does not correspond to the
silver content in the composite and the results of such
thermogravimetric analyses are dicult to interpret.
Silver nitrate dissolved in solutions of nitric acid
(Blinova et al., 2009), formic acid (Bober et al.,
2010a), or sulfonic acids (Bober et al., 2011a) is typ-
ically used for the oxidation of aniline. These acids
do not precipitate silver ions and they are suciently
strong to provide the high acidity, i.e. low pH, needed
for the formation of PANI. Silver salts of limited sol-
ubility, such as silver acetate (Blinova et al., 2010),
silver chloride (Karim et al., 2009), silver hexacyano-
ferrate (III) (de Azevedo et al., 2008b; Kanwal et al.,
2009), silver nitride (Ag
3
N) (Jia et al., 2010a, 2010b,
2012), or silver vanadate (Mai et al., 2011) have been
used as heterogeneous oxidants. In such cases, insol-
uble silver salts always constitute a part or even the
majority of the product (Blinova et al., 2010).
Interfacial version of the reaction, when aniline is
dissolved in chloroform and silver methanesulfonate in
an aqueous medium, has been reported (Huang et al.,
2009). The oxidation took place at the interface of the
immiscible phases. Nitrobenzene has also been used as
the organic phase (Gniadek et al., 2010a). A similar
experiment has been demonstrated for PPy (Gniadek
et al., 2010b).
An ionic liquid, a 1-methyl-3-butyl-imidazolium
derivative, has recently been used as the reaction
medium for the oxidation of aniline with a silver salt
of this ionic liquid (Correa et al., 2012). A green pre-
cipitate of PANIsilver composite was produced in a
few minutes and the composite had the conductivity
of 100 S cm
1
.
The reaction between the aniline salt and silver
nitrate can proceed in the solid state, even in the ab-
sence of solvents, by mechanical blending of the reac-
tants (ednkov et al., 2011). The product, however,
was composed mainly of aniline oligomers. In another
type of the preparation performed in the solid state,
in frozen reaction mixtures at 24
C (Bober et al.,
2011b), a PANIsilver composite was obtained in high
yield, 74 mass %. The conductivity of such a prod-
uct exceeded 1000 S cm
1
. Acceleration with a small
amount of p-phenylenediamine, which is discussed be-
low, was needed.
Physical acceleration
The slow oxidation of aniline can be accelerated
Fig. 3. Typical morphologies of PANIsilver composites observed by transmission electron microscopy (Blinova et al., 2010).
by either physical or chemical means. It seems that
acceleration is associated with the creation of new ini-
tiation centres of the chain growth rather than by the
increase in the rate of chain propagation. The former
way, a physical acceleration, is represented by irradi-
ation with -rays (Pillalamarri et al., 2005; Kang et
al., 2006; de Barros & de Azevedo, 2008; Karim et al.,
2009; Huang et al., 2010; Kim et al., 2011, 2012) or
UV-light (Khanna et al., 2005; de Barros, et al., 2005,
2010; Li et al., 2007, 2009a, 2009b, 2012a, 2012b; de
Barros & de Azevedo, 2008; de Azevedo et al., 2008a;
Singh et al., 2011; Shukla et al., 2012). Irradiation with
UV-light (de Barros et al., 2005) was also used to en-
hance the oxidation of aniline with silver nitrate after
printing both reactant solutions on paper to develop
the conducting pattern. Daylight alone had no accel-
eration eect on the oxidation of aniline with silver
nitrate (Blinova et al., 2009).
Temperature elevated to 100
C was also used to in-

crease the rate of aniline oxidation (Han et al., 2012).
The oxidation of aniline with silver nitrate in ethanol
and in the absence of acid carried out in an auto-
clave at 250
C yielded micrometre-sized PANI micro-

spheres (Du et al., 2005) decorated by silver nanopar-
ticles. There is always a danger of polymer degrada-
tion under such conditions but the emeraldine struc-
ture of PANI (Stejskal et al., 1996b) was conrmed
by UV-VIS spectra. A similar oxidation of aniline at
90
C (Yang et al., 2011), which took place under alka-

line conditions, produced only silver nanoparticles ac-
companied by aniline oligomers. Ultrasonic radiation
was also used to accelerate the oxidation of aniline
with silver nitrate (Li & Wang, 2010; de Barros & de
Azevedo, 2010) but the associated increase in temper-
ature might have contributed to the acceleration.
Chemical acceleration
The oxidation of aniline with ammonium peroxy-
disulfate is accelerated by the addition of small
amounts of p-phenylenediamine, typically a few per-
cent relative to aniline (Stejskal et al., 1995; Tran
et al., 2008; Shenashen et al., 2010, 2011; Zu-
jovic et al., 2011b). Similar accelerating eect of
p-phenylenediamine has been observed when silver ni-
trate was used as an oxidant (Bober et al., 2010b,
2011b) and the practical and feasible way of the prepa-
ration of PANIsilver composites became available.
Also, small amounts of ammonium peroxydisulfate
eciently accelerate the oxidation of aniline with sil-
ver nitrate (Karim et al., 2009; Bober et al., 2011a).
The introduction of another oxidant, hydrogen perox-
ide, had a similar eect (Li & Wang, 2010). The ad-
dition of a small amount of the second oxidant along
with silver nitrate is thus another way to promote the
oxidation of aniline (Bober et al., 2011a).
Morphology of composites
The resulting composites are produced as powders.
Concerning their morphology (Fig. 3), PANI is ob-
tained as globules (Bedre et al., 2009; Li et al., 2009b;
Blinova et al., 2010), nanobres (Pillalamarri et al.,
2005; Li et al., 2007; de Barros & de Azevedo, 2008;
de Azevedo et al., 2008a; Nadagouda & Varma, 2008;
Zhou et al., 2009; Huang et al., 2009, 2010; Tamboli
et al., 2012; Jia et al., 2012), nanotubes (Gao et al.,
2009; Blinova et al., 2009, 2010; Yin & Yang, 2012),
fused nanospheres (Karim et al., 2007), nanobrushes
(Blinova et al., 2009; Bober et al., 2011c) (Fig. 4), or
sheets (Blinova et al., 2010) depending on the con-
centration of the reactants and the type of acid used
in the reaction medium and other reaction conditions.
Transmission electron microscopy is better suited for
the morphology assessment because of the higher con-
trast between the polymer phase and silver (Fig. 4). A
marble-like texture in the objects is a typical feature
of composites (Blinova et al., 2010; Routh et al., 2010;
Fig. 4. Scanning (a) and transmission electron (b) micrographs of a PANIsilver composite (Blinova et al., 2009).
Li et al., 2012b) (Fig. 3b). This pattern seems to be
associated with PANI because it was observed also in
the absence of silver (Dispenza et al., 2012).
Like PANI, silver also appears in the composites in
various morphologies (Sharma & Imae, 2009). Silver
nanoparticles having a typical size of tens of nanome-
tres are the most common (Kang et al., 2006; Li et
al., 2007, 2009b, 2012b; Karim et al., 2007; Gao et al.,
2009; Blinova et al., 2009; Zhou et al., 2009; Bedre et
al., 2009; Afzal & Akhtar, 2010; Hosseini & Momeni,
2010; Garai et al., 2010; Bober et al., 2011c; Correa
et al., 2012; Jia et al., 2012) (Figs. 3b and 4). Other
morphologies are represented by dendrites (ednkov
et al., 2009; Kovachuk et al., 2010) (Fig. 5), triangu-
lar micrometre-sized plates (Fujii et al., 2010), fused
triangles (Zhang et al., 2011a), hexagons (Kang et
al., 2006), nanorods (Chen et al., 2006; Bober et al.,
2010a; Yin & Yang, 2012) (Fig. 6), microrods (de
Barros & de Azevedo, 2010), nanowires and nano-
bres (Bober et al., 2010a; Xu et al., 2010c, 2010d),
nanosnakes (Mu noz-Rojas et al., 2008a, 2011; Yin &
Yang, 2012), and nanobelts (Xia, 2011). The presence
of whiskers and lamellar morphologies has also been
reported (Gniadek et al., 2010a). Several types of mor-
phologies are usually present simultaneously (Blinova
et al., 2009; Fujii et al., 2010) (Fig. 3a). Macroscopic
silver particles are often visible by the naked eye.
Conducting polymers often produce a coating of
silver objects, i.e. coreshell morphology (Feng et al.,
2007a; Mu noz-Rojas et al., 2008a, 2011; Bober et al.,
2010a; Fujii et al., 2010; Li et al., 2012b), or silver
particles decorate conducting polymer objects (Gao
et al., 2009; Blinova et al., 2009; Li et al., 2012a), or
both components form separate phases.
Occasionally, the size of silver nanoparticles is be-
low 10 nm (Li et al., 2012a). An oxidation of aniline
with silver nitrate under alkaline conditions at 90
C
led to silver nanoparticles of 9 nm size (Yang et al.,
2011). Aniline oligomers have probably been produced
simultaneously under such conditions (Stejskal & Tr-
Fig. 5. Silver dendrites.
chov, 2012), PANI was not detected, as expected.
Small silver nanocrystals of 5 nm in size have been
produced by chronopotentiometric preparation in a
microemulsion (Zhou et al., 2009) and in other cases
(Li et al., 2009b). Morphology of both the conducting
polymer and silver may be aected, rather than con-
trolled, by the addition of surfactants (Thanjam et al.,
2011) or organic acids to the reaction mixture.
The oxidation of aniline with ammonium peroxy-
disulfate in the presence of water-soluble polymers,
such as poly(vinyl alcohol) or poly(N-vinylpyrrolid-
one), yields colloidal PANI dispersions (Stejskal et al.,
1996a; Stejskal, 2001; Dispenza et al., 2012). Aniline
was similarly oxidized with silver nitrate in the pres-
ence of poly(vinyl alcohol). The formation of PANI
was claimed (Fujii et al., 2010) but not proved be-
yond doubt because the green color, typical of the
PANI salt, has not been mentioned. Stable colloidal
Fig. 6. Silver nanorods produced by the oxidation of aniline with silver nitrate in the solutions of formic acid. Two magnications,
scale-bar 500 nm (a) and 200 nm (b), obtained by transmission electron microscopy.
Fig. 7. Polyaniline (emeraldine nitrate) is able to reduce silver nitrate to metallic silver. It is oxidized from the emeraldine to the
pernigraniline oxidation state at the same time (Stejskal et al., 2008c, 2009c).
dispersions having silver core and organic shell were
produced but the particles were accompanied by large
silver crystals.
Reduction of silver ions with PANI
The use of PANI as the reductant of silver ions to
metallic silver is the second method for the prepa-
ration of hybrid composites. Early studies on elec-
trochemically prepared PANI lms demonstrated the
ability of PANI to reduce silver ions (Zhang et al.,
1995). This is called electroless deposition by elec-
trochemists (Ivanov & Tsakova, 2005; Ocypa et al.,
2006; Dimeska et al., 2006; Tsakova, 2008; Wang et
al., 2009a), in contrast to the electrodriven process at
electrodes. The emeraldine form of PANI converts to
pernigraniline at the same time (Stejskal et al., 1996b,
2008b; He et al., 2012b; Patil et al., 2012) (Fig. 7).
Polyaniline can enter the reaction in the protonated
state (Zhang et al., 1995; Wang et al., 2007; Stejskal
et al., 2008c, 2009c; Sim et al., 2009; Ghorbani et al.,
2011; Yan et al., 2012; Qin et al., 2012), i.e. as a PANI
salt in acidic or neutral media, or as a PANI base un-
der neutral or alkaline conditions (Wang et al., 2007;
Stejskal et al., 2009c; Bouazza et al., 2009; Ayad et
al., 2010; Lee et al., 2012). PANI was exceptionally
reduced with hydrazine to leucoemeraldine before the
reaction with silver ions (He et al., 2012b).
Nitric acid is a by-product of this reaction (Fig. 7).
This means that pH drops which can be used to moni-
tor the progress of the reaction (Stejskal et al., 2009d)
(Fig. 8). pH of the reaction medium is very important
(Lyutov & Tsakova, 2011). The increase in the mass
of the PANI lm due to deposited silver in quartz mi-
Fig. 8. Decrease in pH during the reaction of PANI base with
silver nitrate (Stejskal et al., 2009d).
crobalance was also used for this purpose (Ayad et
al., 2010). Progress or the reaction was also followed
by potentiometric determination of the silver-ion con-
centration (Bouazza et al., 2009). The reaction has
usually been completed in minutes (He et al., 2012a)
or tens of minutes (Stejskal et al., 2009d).
Eect of counter-ions
Reduction of silver ions takes place in aqueous
solutions. The reduction has often been performed
with PANI base suspended in water (Bouazza et al.,
2009; Ayad et al., 2010; Trchov & Stejskal, 2010)
or in solutions of nitric acid (Stejskal et al., 2009c,
2009d; Trchov & Stejskal, 2010; Ghorbani et al.,
2011; Yan et al., 2012) to avoid the precipitation of
silver cations. Also, silver ions do not precipitate in
solutions of perchloric acid and sulfonic acids, such
as methanesulfonic, camphorsulfonic, or toluenesul-
fonic acid. For that reason, sulfonate anions belong
to the preferred counter-ions in the studies associated
with hybrid composites (Sim et al., 2009; Bober et al.,
2011b, 2011c; Yan et al., 2012). The reaction can pro-
ceed even in the absence of solvents, in the solid state,
by mechanical blending of reactants (ednkov et al.,
2009).
The role of the counter-ions in PANI salt enter-
ing the reaction has also been analyzed in literature
(Zhang et al., 1995; Dimeska et al., 2006; Stejskal et
al., 2009d; Xu et al., 2010a; Yan et al., 2012). Counter-
ions in the PANI salt often produce insoluble salts
with silver ions. These are especially inorganic anions,
such as chloride, iodide, sulfate, or phosphate (Stejskal
et al., 2009d). Insoluble silver salts are also produced
by most carboxylic acids, such as acetic (Blinova et
al., 2010) or tartaric acid (Stejskal et al., 2009b). In
such cases, the formation of insoluble silver-salt inter-
mediates may aect the reaction. The use of reducing
counter-ions, such as citrate or formate, along with
PANI makes the system even more complex (Xu et
al., 2010a; Bober et al., 2010a).
The reaction between PANI and silver salts has
rarely been performed in solutions because of the
limited solubility of PANI in organic solvents. Only
in a single case has the reduction been made in a
non-aqueous medium, dimethylformamide (Sun et al.,
2012). The electrospinning of mixed solutions of the
emeraldine base in N-methylpyrrolidone and aque-
ous solution of poly(vinyl alcohol) and silver nitrate
yielded composite nanobres (Shahi et al., 2011).
Silver complexes
When ammonia solution is used as an alkaline re-
action medium, it has to be kept in mind that a silver
ion forms a diamosilver complex cation, Ag(NH
3
)
+
2
(Yao et al., 2009; Lee et al., 2012), which has a dif-
ferent redox potential than the simple silver cation,
Ag
+
. A complex anion is produced also with thiosul-
fate, Ag(S
2
O
3
)
3
2
, or ethylenediaminetetraacetic acid
(EDTA), Ag(EDTA)
3
(Ivanov & Tsakova, 2005), or
excess chlorides, AgCl
2
(Vorotyntsev et al., 2011).
The list can be substantially extended.
Morphology of PANI
The reaction between PANI powders and silver
ions has been used for the preparation of PANI
silver composites (Bouazza et al., 2009; Leyva et al.,
2011; Manivel & Anandan, 2011; Ghorbani et al.,
2011; Chang et al., 2012a). Polyaniline in the leu-
coemeraldine oxidation state (Bouazza et al., 2009)
converts to emeraldine, and the emeraldine form of
aniline is oxidized to pernigraniline at the same time
(Stejskal et al., 1996b) (Fig. 7). The reaction was
completed in tens of minutes (Bouazza et al., 2009).
Polyaniline enters the reaction as globules (Stejskal et
al., 2009b, 2009d; Ghorbani et al., 2011), nanobres
(Chang et al., 2012a), or nanotubes (Stejskal et al.,
2009b, 2009c). Silver is produced as globular nanopar-
ticles of 2050 nm in size (Bouazza et al., 2009; Ste-
jskal et al., 2009b; Ghorbani et al., 2011; Chang et al.,
2012a) but it is often accompanied by micrometre-
sized objects (Ivanov & Tsakova, 2005; Bouazza et
al., 2009; Stejskal et al., 2009c). The particles were
smaller at low silver ion concentrations or when stir-
ring or sonication was used (Bouazza et al., 2009).
Silver has been also been occasionally produced in-
side PANI nanotubes (Stejskal et al., 2009c; Trchov
& Stejskal, 2010; Sun et al., 2012) (Fig. 9). This was
explained by the dierent molecular structure of the
nanotube interior (Stejskal et al., 2006), which is rich
in phenazine units, compared with the external sur-
face.
PANI lms and coatings
Polyaniline often entered the reaction as thin lms
deposited chemically or electrochemically on suitable
Fig. 9. When silver nitrate is reduced by PANI nanotubes, sil-
ver is often found inside the nanotubes (Stejskal et al.,
2009c).
Fig. 10. Silver nanoparticles deposited on PANI-coated cellu-
lose bres (Stejskal et al., 2008c).
substrates (Zhang et al., 1995; Wang et al., 2007; Kelly
et al., 2007; Shin & Kim, 2009; Trchov et al., 2012)
or cast from solutions in N-methylpyrrolidone (Xu et
al., 2010a, 2010b, 2010c, 2010d; Yan et al., 2012).
PANI deposited in situ during the oxidation of ani-
line on various fabrics, such as silk, polyamide, lycra,
cotton, linen, acrylic, or polyester was tested with re-
spect to silver recovery (Dimeska et al., 2006). PANI-
coated cellulose bres have been used for the deposi-
tion of silver nanoparticles from a silver nitrate solu-
tion (Kelly et al., 2007; Stejskal et al., 2008c) (Fig. 10),
as well as PANIlignin composite (He et al., 2012b)
or PANI-coated poly(methyl methacrylate) micropar-
ticles (Lee et al., 2012). Finally, PANI-coated carbon
nanotubes have been used for the reduction of silver
nitrate (Gronou et al., 2012).
Silver nitrate has been usually used; silver dode-
canoate solution in xylene was an alternative (Shin &
Kim, 2009). The morphology of silver was aected by
the acid which constituted a salt with PANI (Wang et
al., 2007; Xu et al., 2010a; Yan et al., 2012; He et al.,
2012a, 2012b). Silver particles produced irregular frag-
ments, globules (Shin & Kim, 2009; Xu et al., 2010a),
wires (Xu et al., 2010a), hierarchical spheres (Xu et
al., 2010c, 2010d), sheets (He et al., 2012a), or owers
(Song et al., 2007; Xu et al., 2010b; Yan et al., 2012;
He et al., 2012a) of micrometre size. The deposition
of silver was often non-uniform (Xu et al., 2010a) and
concentrated on the most protruding polymer struc-
tures (Lyutov & Tsakova, 2011). The non-uniformity
in the size of silver objects was dependent on the pH of
the reaction medium. The lms cast from PANI pro-
tonated with citric acid, which alone is able to reduce
silver ions, led to silver nanowires (Xu et al., 2010a),
in contrast to other counter-ions.
In producing more complex composites, the PANI
base was exposed to silver nitrate in 1 M nitric acid
(Leyva et al., 2011). The resulting composite was
then dispersed in epoxy resin. Ternary PANIsilver
poly(vinyl alcohol) composite nanobres have been
prepared by electrospinning (Shahi et al., 2011).
Preparation of PANI in the presence of silver
particles
The synthesis of PANI in a medium containing sil-
ver nanoparticles is another way to prepare PANI
silver composites. Silver nanoparticles have been pre-
pared at rst by a variety of methods based on the
reduction of silver salts dissolved in organic or in-
organic media with organic reductants, e.g., citrates,
glucose, hydrazine, etc., or inorganic reductants, such
as sodium borohydride, or electrochemically. It has
to be stressed that both the monomers, such as ani-
line, pyrrole, and their substituted derivatives, and the
corresponding polymers are also organic reductants of
silver ions. These cases, however, are discussed sepa-
rately.
Aniline was oxidized with ammonium peroxydisul-
fate in the presence of silver nanoparticles (Choud-
hury, 2009; Crespilho et al., 2009; Fuke et al., 2009a,
2009b, 2010; Gupta et al., 2010; Alam et al., 2012),
or silver colloids stabilized with dodecylbenzenesul-
fonic acid (Yin & Yang, 2012), mercaptocarboxylic
acid (Jing et al., 2007a), or poly(N-vinylpyrrolidone)
(Kang et al., 2006). In the last two cases, the absorp-
tion band located above 500 nm has not been ob-
served in the visible spectra. This means that, due to
the relatively low acidity of the medium, only aniline
oligomers have probably been produced. Aniline dis-
solved in toluene containing dodecanethiol-stabilized
silver nanoparticles was mixed with an aqueous so-
lution of ammonium peroxydisulfate and composite
nanoparticles were produced (Oliveira et al., 2004,
2006). This approach is somewhat similar to a two-
phase process reported later (Dawn et al., 2007). Sil-
ver nanoparticles have also been combined with 4-
thioaniline which was subsequently polymerized with
ammonium peroxydisulfate to a PANI-like derivative
(Kovachuk et al., 2010).
In another experiment, a polyurethane lm was
immersed in a solution containing silver nanoparti-
cles and aniline, which was subsequently converted to
PANI by the oxidation with peroxydisulfate (Prab-
hakar et al., 2011). Similarly, graphite decorated with
silver nanoparticles was coated with a PANI lm dur-
ing the oxidation of aniline hydrochloride with ammo-
nium peroxydisulfate (Wu et al., 2010, 2012). Multi-
wall carbon nanotubes were similarly decorated with
silver nanoparticles at rst and then coated with a
PANI overlayer during the in-situ oxidation of aniline
(Kim & Park, 2011; Nguyen & Shim, 2011). This is a
well-established method for the surface modication of
carbon nanotubes with a coaxial conducting-polymer
coating (Konyushenko et al., 2006, 2008a).
Reduction of silver ions with external reduc-
tants in the presence of PANI
The preparation of silver nanoparticles using clas-
sical reductants in the presence of PANI has to be
mentioned for the sake of completeness. The fact that
PANI is the second and competitive reductant in the
system makes the overall chemistry rather complex.
Fly-ash microspheres were coated with PANI in
situ during the oxidation of aniline hydrochloride
with ammonium peroxydisulfate and subsequently im-
mersed in an alkaline solution of silver nitrate and
sodium tartarate (Wang et al., 2009a). Tartarate is ex-
pected to reduce silver cations to metallic silver that
deposits on PANI. Similarly, PANI-coated carbon nan-
otubes were immersed in a medium containing silver
nitrate and sodium citrate (Huang et al., 2009).
It should be noted that the presence of aniline can
aect the morphology of silver nanoparticles and pro-
mote the formation of nanorods (Tan et al., 2003).
This was the case when a PANI salt was mixed with
silver nitrate in solutions of formic acid (Bober et al.,
2010b; Garai et al., 2010) (Fig. 6).
The role of the external reductant can be taken
over by the PANI electrode. The electrochemical
preparation of PANI lms followed by the electrode-
position of silver nanoparticles from silver nitrate so-
lutions (Hosseini & Momeni, 2010) belongs to this cat-
egory. A similar approach has also been used in case
of PPy (Vorotyntsev et al., 2011).
Mixing of PANI and silver particles
The most straightforward method of composite
preparation is based on simple mixing of components,
PANI and silver (Afzal et al., 2009; Sezer et al., 2009;
Afzal & Akhtar, 2012). Silver nanoparticles have been
added to a solution of emeraldine base dissolved in
N-methylpyrrolidone. Composite lms were also ob-
tained after evaporation of the solvent (Afzal et al.,
2009) or by other deposition techniques (Sezer et al.,
2009), and their dielectric (Afzal et al., 2009) or non-
linear optical (Sezer et al., 2009) properties were an-
alyzed. The mixtures of PANI camphorsulfonate with
silver powder were tested in electromagnetic interfer-
ence shielding (Lee et al., 1999; Joo & Lee, 2000).
Inkjet printing of silver nanoparticles and PANI in or-
ganic solvents also belongs, formally, to this category
(Ihalainen et al., 2012). The case when PANI was pre-
pared by the oxidation of aniline with ammonium per-
oxydisulfate followed by an addition of silver nanopar-
ticles (Afzal & Akhtar, 2011; Barkade et al., 2011), can
also be regarded as a simple blending of both compo-
nents. In a less typical case, a lm from the PANI base
solution in N-methylpyrrolidone was cast on a rough
silver surface. Interfacial interactions of both compo-
nents were investigated by surface-enhanced Raman
spectroscopy (Baibarac et al., 1999). A more com-
plex composite of silver-coated carbon nanobres and
polypropylenePANI laments has also been reported
(Nasher et al., 2011).
Electrochemical preparations of PANI lms fol-
lowed by electrochemical deposition of silver nanopar-
ticles (Tsakova, 2008), vacuum deposition (Krishna et
al., 2008), or simple adsorption of silver nanoparticles
(Narang et al., 2012) belong to this section. A reverse
process, when silver nanoparticles were deposited on
substrate at rst and PANI subsequently, was also re-
ported (Yi & Song, 2012).
More complex systems
Two reductants of silver ions
In electrochemical preparation, aniline and silver
ions in a nitric acid solution were electrochemically
treated to produce nanobrillar PANI lm and sil-
ver nanoparticles (Zhou et al., 2006). Chemistry of
the process which combines two types of oxidation,
chemical and electrochemical, may be quite com-
plex. In a similar electrochemical preparation using
porous aluminium oxide template, composite PANI
silver nanobres were obtained (Drury et al., 2007).
It should be realized that PANI or PPy produced
during the oxidation of aniline are also able to reduce
silver ions to metallic silver. From this point of view,
two silver reductants, a monomer and a polymer, are
always present in the reaction mixture. The similar re-
duction ability of the reaction intermediates also con-
tributes to the complexity of the system.
A simple redox reaction between PANI and the
silver salt may become complicated when two reduc-
tants of silver ions are present. This is illustrated for
PANI citrate which was used for the reduction of sil-
ver nitrate (Mack et al., 2011). Silver was produced as
micrometre-sized spheres composed of nanobres or
nanosheets. The complexity of this system consists in
the fact that both components constituting the PANI
salt, a PANI base (Ayad et al., 2010; Trchov & Ste-
jskal, 2010) and citric acid (Xu et al., 2010a), are inde-
pendently able to reduce silver ions. The same situa-
tion applies to PANI tartarate (Stejskal et al., 2009d).
Two oxidants of aniline
Another complex system is illustrated by the si-
multaneous use of two aniline oxidants, typically am-
monium peroxydisulfate and silver nitrate (Pillala-
marri et al., 2005; Gao et al., 2009; Karim et al., 2009;
Bedre et al., 2009; Bober et al., 2011a; Tamboli et al.,
2012; Li et al., 2012a). It has been reported that the
presence of ammonium peroxydisulfate, even in small
amounts, accelerates the oxidation of aniline with sil-
ver nitrate (Bober et al., 2011a). The addition of am-
monium peroxydisulfate is thus an ecient way of ac-
celerating the oxidation of aniline with silver nitrate.
In addition, by varying the proportions between the
two oxidants, the silver content in the composite can
be varied (Bober et al., 2011a). Interfacial modica-
tion of the synthesis using a chloroformwater system
has been described (Bedre et al., 2009). Oxidation of
aniline with hydrogen peroxide in combination with
silver nitrate was also reported (Li & Wang, 2010).
An even more complex system is represented by the
simultaneous use of two reductants, aniline and cit-
ric acid and two oxidants, ammonium peroxydisulfate
and silver nitride (Ijeri et al., 2010; Jia et al., 2012).
Ternary composites
Ternary composites composed of three components
constitute a rather special group. In addition to a con-
ducting polymer and silver they also contain: (i) an-
other conducting component, such as graphite (Wu
et al., 2010, 2012; Xu et al., 2010b, 2010d), carbon
nanobres (Nesher et al., 2011), or carbon nanotubes
(Reddy et al., 2009; Xu et al., 2010d; Nguyen & Shim,
2011; Narang et al., 2012; Grinou et al., 2012); (ii) a
non-conducting inorganic ller, such as silica (Kim et
al., 2010b, 2011, 2012; Han et al., 2012) or silver vana-
date (Mai et al., 2011); (iii) an organic component,
such as deoxyribonucleic acid (Dawn & Nandi, 2006),
ribonucleic acid (Route et al., 2010); (iv) polymers
meant to improve mechanical and processing proper-
ties, such as cellulose (Kelly et al., 2007; Stejskal et al.,
2008c), poly(vinyl chloride) (Afzal & Akhtar, 2010),
poly(vinyl alcohol) (Fujii et al., 2010), or epoxy resin
(Leyva et al., 2011). Especially the rst group is im-
portant. The system complexity, however, increases
with the number of components and their contribu-
tion to the composite properties is dicult to assess.
From the scientic point of view, multicomponent sys-
tems should be avoided unless there is a concrete rea-
son for their study or application. A special group of
ternary composites is represented by colloidal disper-
sions.
Colloids
Conducting polymer colloids have been prepared
by oxidation of the respective monomers in the pres-
ence of suitable water-soluble polymers which act as
stabilizers. Probably the rst record can be traced
to 1935, when aniline was oxidized to PANI in the
presence of gelatin (Ptschelin, 1935). Preparations of
colloidal PANI and PPy dispersions have been re-
viewed (Stejskal, 2001) and many interesting novel
approaches have appeared in recent literature (Fujii
et al., 2010; Shi et al., 2010; Chen & Liu, 2011b; Au
et al., 2011; Dispenza et al., 2012). The preparation of
noble-metal colloids is much older and dates to syn-
theses demonstrated by Faraday in 1847.
Polyanilinesilver colloids are potentially useful as
conducting inks. Reports on their preparation, how-
ever, are limited so far. In principle, they can be ob-
tained by the oxidation of aniline with silver nitrate in
the presence of suitable water-soluble polymers. Intro-
ductory experiments performed in acidic media, how-
ever, have always led to colloidally unstable systems.
The preparation of colloidal PANI particles of the
average size of 190 nm has been reported in systems
where the acidity drifted from pH 6.4 to 5.0 during the
oxidation of aniline (Fujii et al., 2010). The pH-drift
conrms that aniline was oxidized, but rather to ani-
line oligomers than to PANI at such a low acidity level;
successful formation of PANI requires a much higher
acidity, pH lower than 2.5 (Stejskal et al., 2008b; Sa-
purina & Stejskal, 2008; Konyushenko et al., 2010).
An alternative way, the reduction of silver salts
with separately prepared PANI colloidal dispersions,
has been reported in a single paper (Li et al., 2006).
Colloidal PANI nanoparticles stabilized with poly-
acrylic acid and of the size of 100150 nm were pre-
pared. Silver was produced as separate nanosheets in
case of non-protonated PANI-base colloids and inside
the particles for the PANI salt.
Polypyrrolesilver composites
Oxidation of pyrrole with silver compounds
Chemistry of aniline and pyrrole oxidations to the
corresponding conducting polymers is similar (Blinova
et al., 2007b) (Fig. 11) but dierent stoichiometry has
also been proposed (Chang et al., 2012b). In contrast
to aniline oxidation, pyrrole is oxidized easily to PPy
in an aqueous medium and no physical or chemical ac-
celeration is needed (Chen et al., 2005a, 2006; Xing &
Zhao, 2007; Dallas et al., 2007; Feng et al., 2008; Chat-
terjee et al., 2011; Zhao & Nan, 2012a, 2012b; Firoz
Babu et al., 2012). An interesting modication of this
experiment is represented by the counter-diusion of
silver nitrate and pyrrole solutions through a polyte-
trauoroethylene membrane (Shi et al., 2012); such an
approach using ammonium peroxydisulfate and ani-
Fig. 11. Oxidation of pyrrole with silver nitrate in an acidic aqueous medium yields a composite of polypyrrole and silver. Nitric
acid is a by-product.
line hydrochloride solution has been reported earlier
(Blinova et al., 2007a).
Nevertheless, UV-irradiation has often been used
(Feng et al., 2007b; Zhao et al., 2007; Martins et al.,
2006; Ijeri et al., 2010; Wei et al., 2010a) to increase
the reaction rate. An increase of the reaction temper-
ature to 95

C was also used (Chang et al., 2012b).
The catalytic role of silver in the synthesis was con-
sidered (Della Pina et al., 2011; Kate et al., 2011). The
reaction exceptionally took place at elevated temper-
atures (Kate et al., 2011), approximately 100
C, or
in an autoclave at 150
C (Wang & Shi, 2007). The

oxidation of pyrrole has usually been carried out in
aqueous media, exceptionally in methanol (Martins et
al., 2006) or dimethylformamide (Zhao et al., 2007).
Chemical acceleration with sulfonated porphyrin was
also reported (Wei & Lu, 2009).
When the oxidation of pyrrole with silver nitrate
takes place in the presence of silver nanorods, these be-
come coated with a PPy overlayer (Chen et al., 2006).
This trend applies generally and various silver objects
produced during the reaction have been coated in situ
with an overlayer of PPy.
Interfacial polymerization of pyrrole has also been
demonstrated. Pyrrole was dissolved in chloroform
and brought into contact with an aqueous solution of
silver nitrate (Dallas et al., 2007). Tetrachloromethane
(Feng et al., 2007a) or an ionic liquid, 1-butyl-
3-methylimidazolium tetrauoroborate (Wei et al.,
2010a) or hexauorophosphate (Zhou et al., 2009),
have similarly been used as the organic phase immis-
cible with water.
In addition to AgNO
3
, silver nitrite (AgNO
2
) is
another silver salt used for the oxidation of pyrrole
(Chen et al., 2005a). Although the well-soluble silver
nitrate has been the oxidant of the choice, the use of
insoluble silver oxide (Ag
2
O) was also successful in
producing PPysilver nanocomposites (Mu noz-Rojas
et al., 2008a, 2008b, 2011). The reaction has been car-
ried out at elevated temperatures, typically at 120
C.
The silver salt of methyl orange reacted with pyrrole
to PPy nanotubes decorated with silver nanoparticles
on the surface (Feng et al., 2007b).
In more complex experiments, a polyacrylonitrile
solution containing silver nitrate was electrospun at
rst and the resulting nanobres were exposed to pyr-
role in boiling toluene. Polypyrrole nanobres were
thus decorated with silver nanoparticles of 50150 nm
in size (Chen et al., 2008). In another approach, silica
spheres were penetrated with a diamosilver complex,
and subsequently exposed to pyrrole which produced
PPy (Yao et al., 2009).
Morphology of the composites was aected by their
preparation in the presence of cationic surfactants,
such as alkyltrimethylammonium bromides (Dallas et
al., 2007; Chatterjee et al., 2011), an anionic surfac-
tant, sodium dodecylsulfate (Dallas et al., 2007; Mah-
moudian et al., 2012), or their mixtures (Xing & Zhao,
2007). In case of PPy, surfactants play an important
role because the conductivity of the composites was
substantially enhanced when the preparation was car-
ried out in their presence (Omastov et al., 2003; Ste-
jskal et al., 2003).
The oxidation of pyrrole with silver nitrate was
typically carried out in neutral or acidic media. PPy
silver composites were claimed to be produced also
under strongly alkaline conditions (Li et al., 2009d),
and the obtained composites were conducting. Un-
der such conditions, however, the oxidation of aniline
yields only aniline oligomers, not a polymer (Stejskal
& Trchov, 2012). It still has to be checked if the sit-
uation is dierent for pyrrole oxidation.
Morphology of composites
Concerning the composite morphology, PPy was
produced as fused globules (Dallas et al., 2007), hol-
low spheres (Gniadek et al., 2010b), or leaf-like ob-
Fig. 12. Polypyrrole reduces silver nitrate to metallic silver.
jects (Gniadek et al., 2010b). Silver was generated as
globular nanoparticles having the diameter of several
nanometres (Kate et al., 2011) but more often tens of
nanometres (Chen et al., 2005b, 2008; Dallas et al.,
2007; Xing & Zhao, 2007; Feng et al., 2007a; Wang &
Shi, 2007), small and large crystals (Gniadek et al.,
2010b), nanorods (Feng et al., 2007a, Wei & Lu, 2009;
Gniadek et al., 2010b; Chatterjee et al., 2011), nanoca-
bles (Chen et al., 2005b), nanosheets (Chen et al.,
2005b), nanosnakes (Mu noz-Rojas et al., 2008b), or
triangular objects (Chen et al., 2005b; Mu noz-Rojas
et al., 2008b).
Reduction of silver ions with PPy
The ability of PPy to reduce silver ions to metal-
lic silver has been experimentally proved many times.
From the historical point of view, the paper by Pickup
et al. (1998) is quite important. The authors illus-
trated the ability of an electrochemically prepared
PPy lm to reduce silver ions to silver, which was
conrmed by subsequent experiments (Ocypa et al.,
2006; Tian et al., 2008). The course of the reaction,
reduction of silver ions on the PPy lm, was conve-
niently followed by a quartz microbalance (Ayad &
Zaki, 2009).
A formal reaction scheme can be proposed by anal-
ogy with the conversion of the emeraldine form to
the pernigraniline form of PANI (Fig. 12). Some au-
thors proposed also the incorporation of oxygen atoms
during this process (Ansari & Delavar, 2008), as it is
in case of PANI (Stejskal & Trchov, 2012), or other
modications (Pintr et al., 2005). Other studies as-
sume the complexation of silver ions with nitrogen
atoms (Choi & Jang, 2008) rather than a chemical
reaction between both species. The ability of PPy to
reduce a silver cation to metallic silver nanoparticles
has been well documented (Qin et al., 2011). When
the reactants were heated to 90
C, the silver nanopar-

ticles had the size of tens of nanometres. The reaction,
however, typically takes place at room temperature.
Polypyrrole was used in the recovery of silver from
solutions of silver ions (Pickup et al., 1998) and the
counter-ions in PPy demonstrated a signicant eect
on the silver yield (Dimeska et al., 2006). Polypyr-
role was often deposited on supports, such as sawdust
(Ansari & Delavar, 2008) or porous carbon (Choi &
Jang, 2008), in recovery experiments. Polypyrrole was
used as-prepared; only in a single case it was reduced
with sodium borohydride at rst, and subsequently
used for the reduction of silver nitrate to metallic sil-
ver (Kelly et al., 2007).
The morphology of PPy has also been consid-
ered, especially with respect to nanotubes. PPy nano-
tubes were prepared by coating of vanadium(V) oxide
nanowires with PPy and subsequent dissolution of the
template. When exposed to silver nitrate solutions, 4
8 nm silver nanoparticles were produced on their sur-
face and also agglomerated inside the nanotube cav-
ity (Zhang & Manohar, 2005). Nanotubes prepared in
the presence of methyl orange as the structure-guiding
agent were immersed in a silver nitrate solution and
thus decorated with silver nanoparticles (Yang et al.,
2010a, 2010b, 2010c). Polypyrrole nanotubes prepared
by using a hard templete, aluminium oxide, have also
been used for reduction of silver ions (Park et al.,
2012). Analogous experiments have been made with
PANI nanotubes (Stejskal et al., 2009c; Trchov &
Stejskal, 2010).
Depending on the reaction conditions, reduction of
silver ions with PPy yielded silver particles having the
size below 10 nm (Visy et al., 2005; Pintr et al., 2005),
tens of nanometres (Kabir et al., 2008; Mahmoudian et
al., 2012; Park et al., 2012), or micrometres (Pickup et
al., 1998). The occurrence of cubic or triangular silver
crystals (Ayad & Zaki, 2009), nanosheets (Wang &
Zhang, 2009; Wang et al., 2009b), or nanocables (Chen
et al., 2005b; Nadagouda & Varma, 2007) have been
reported. Nanoparticles deposited on PPy microbowls
belong to spectacular composite structures (Wang et
al., 2009b).
Preparation of PPy in the presence of silver
particles
Another strategy consists in the separate forma-
tion of silver nanoparticles followed by the preparation
of PPy in their presence. This approach suers from
the low concentration of silver nanoparticles that can
be incorporated in the composite. Silver nanoparti-
cles have usually been prepared using ethylene gly-
col (Ye & Lu, 2008), citrate (Borthakur et al., 2011),
or formaldehyde (Yang et al., 2012a) for the reduc-
tion of the silver salt and PPy subsequently by the
oxidation of pyrrole with iron(III) chloride. The over-
all chemistry may be complicated by the reaction be-
tween the citrate and the iron(III) ions. Otherwise, sil-
ver particles were prepared electrochemically (Lee &
Liu, 2005). In another approach, silver nanoparticles
were coated with a silica overlayer and, subsequently,
with PPy (Wang et al., 2010c). After the dissolution
of the intermediate layer of silica, yolkshell particles
were obtained. The reduction of silver iodate nanopar-
ticles with sodium borohydride has also served for
the preparation of silver nanoparticles followed by the
oxidation of pyrrole with ammonium peroxydisulfate
(Jing et al., 2007b). Silver nanoparticles were coated
with PPy. A closely related scenario was applied also
to the preparation of a silverPANI composite (Jing
et al., 2007a).
In other experiments, silver nanorods were pre-
pared at rst by the polyol method, i.e. by the re-
duction of silver nitrate in ethylene glycol at elevated
temperatures, and subsequently coated with PPy dur-
ing the oxidation of pyrrole with silver nitrate (Chen
et al., 2006) or copper(II) acetate (Qiu et al., 2011).
Practically identical morphology can also be found
for PANI although under dierent reaction conditions
(Bober et al., 2010a) (Fig. 6). A similar approach, us-
ing iron(III) chloride for the oxidation of pyrrole, has
also been applied to spherical silver particles (Ye et
al., 2009).
Reduction of silver ions with external reduc-
tants in the presence of PPy
Polypyrrole lms were rst prepared electrochemi-
cally, and silver nanoparticles were deposited from the
ammonia solution of complex silver ions with glucose
as the reductant (Wang & Zhang, 2009; Wang et al.,
2010b). The resulting lms were tested as supports for
surface-enhanced Raman scattering. Electrochemical
reduction of silver complex ions to silver nanoparti-
cles inside PPy-based lms belongs to this category
(Vorotyntsev et al., 2011).
In yet another approach, PPy nanotubes were
prepared at rst using metyl orange as a structure-
guiding agent and functionalized with carboxyl groups
(Peng et al., 2012). Silver nitrate was then reduced
with sodium borohydride in their presence and silver
nanoparticles were produced on their surface. Also in
this case, the resulting composites were successfully
tested for surface-enhanced Raman scattering detec-
tion of rhodamine. The fact that PPy alone is able
to reduce silver ions to silver, however, has not been
considered.
Mixing of PPy and silver particles
Silver nanoparticles were deposited on graphene
and PPy was subsequently grown in situ during the
oxidation of pyrrole with ammonium peroxydisulfate
(Kim et al., 2010a). In the electrochemical preparation
process, PPy was prepared at rst on indium tin oxide
(Alqudami et al., 2007) or a glassy carbon electrode
(Atmeh & Alcock-Earley, 2011) and the electrodepo-
sition of silver nanoparticles followed. A ten-fold im-
provement of the PPy lm conductivity after silver
deposition was reported (Alqudami et al., 2007).
More complex systems
Multiple reactants
More complex systems contain an oxidant in ad-
dition to silver nitrate. Silver nitrate was added to
an acetic acid solution at rst, forming insoluble sil-
ver acetate (Yang & Lu, 2005). Similarly, silver bro-
mide particles were produced from calcium bromide
and silver nitrate (Cheng et al., 2006). Silver chloride
particles were prepared by sodium chloride and silver
nitrate (Mo et al., 2007). In all three cases, insolu-
ble silver salts were used as templates for the depo-
sition of PPy. For that purpose, pyrrole and iron(III)
chloride were added to the reaction mixture, i.e. two
oxidants of pyrrole, silver salts and iron(III) chloride,
were present in the system. The template particles
were claimed to be coated with PPy but the possible
reaction of insoluble silver salts with pyrrole to PPy
was not considered. The subsequent dissolution of the
template in thiocyanate or thiosulfate solutions led to
hollow microparticles.
Ternary composites
Many composites reported in literature include
an additional component which is intended to aect
the composite morphology, processing, or mechani-
cal properties as in the case of PANI. Such a com-
ponent has often been a polymer, such as cellulose
Fig. 13. Colloidal PPy nanoparticles prepared by the oxidation of pyrrole with silver nitrate in the presence of a water-soluble
polymer (unpublished results).
(Kelly et al., 2007; Firoz Babu et al., 2012), chitosan
(Cheng et al., 2006; Feng et al., 2008), polyacryloni-
trile (Chen et al., 2008), poly[(4-styrenesulfonic acid)-
co-(maleic acid)] (Jung et al., 2011), poly[styrene-
co-(methyl acrylate)] latex (Borthakur et al., 2011),
poly(N-vinylpyrrolidone) (Chen et al., 2005a; Feng et
al., 2007a; Feng, 2010; Wang & Shi, 2007; Wei & Lu,
2009; Shi et al., 2010; Wei et al., 2010b; Zhang et
al., 2012; Jung et al., 2011; Zhao & Nan, 2012a),
a low-molecular-mass organic component, such as
tripyridin-3-yl-benzene-1,3,5-tricarboxylate (Li et al.,
2011), an ionic liquid (Wei et al., 2010b), or various
surfactants (Dallas et al., 2007; Mo et al., 2007; Zhang
et al., 2012; Zhao & Nan, 2012b). Inorganic compo-
nents, such as iron(III) oxide (Zhang et al., 2012),
magnetite (Zhao & Nan, 2012a), or silica (Yao et al.,
2009), have also been used. Especially electrically ac-
tive components, such as graphite (Mo et al., 2007;
Yang et al., 2012a) and graphene (Kim et al., 2010a),
should be mentioned as interesting but complex ma-
terials.
In other approaches, silver(I)-coordinated organo-
gel produced by (tripyridin-3-yl-benzene-1,3,5-tri-
carboxylate) was exposed to pyrrole (Li et al., 2011).
Composite PPy nanobres with incorporated silver
nanoparticles were produced. Another composite was
obtained by UV-irradiation-initiated polymerization
of substituted dimethacrylate along with pyrrole and
silver nitrate (Ijeri et al., 2010). The silver nanoparti-
cles had 200 nm size.
Colloids
In contrast to PANI, the preparation of compos-
ite PPysilver dispersions was more successful. The
oxidation of pyrrole with silver nitrate in the pres-
ence of suitable water-soluble polymers acting as
steric stabilizers is the rst way of composite PPy
silver colloids preparation (Fig. 13). The prepara-
tion of such colloids has been demonstrated in papers
using poly(N-vinylpyrrolidone) (Feng et al., 2007a;
Feng, 2010; Wang & Shi, 2007; Jung et al., 2011),
poly[4-styrenesulfonic acid-co-(maleic acid)] sodium
salt (Jung et al., 2011), or starch (Chang et al., 2012b)
for stabilization. The colloidal particles had a silver
core of 90300 nm in size and a PPy shell of compa-
rable thickness. Closer inspection suggests that rather
a gemini than a coreshell morphology is often pro-
duced (Change et al., 2012b) (Fig. 13a). This means
that PPy does not wrap silver particles completely,
and both PPy and silver phases are in contact with
the surrounding aqueous medium. In a single case, 10
12 nm silver nanoparticles prepared separately were
used as seeds (Feng, 2010) but it is not clear if they
were needed for the success of the synthesis.
The second approach to the preparation of com-
posite colloids is based in principle on the reduction of
silver cations to silver by colloidal PPy nanoparticles
(Fig. 12). The preparation of template PPy colloids
has been reviewed (Stejskal, 2001). Although such a
synthesis was claimed in literature (Qin et al., 2011),
true colloidal PPy nanoparticles stabilized by water-
soluble polymer have not been used.
Related polymersilver composites
The use of a ring-substituted aniline instead of ani-
line itself is the logical extension of the experiments.
Among substituted anilines, phenylenediamines rep-
resent a special group. The reduction of silver ions
with o- and p-phenylenediamines is of great histor-
ical importance as it constitutes the basis of the
photographic development process. Please note that
m-phenylenediamine has never been used for this pur-
pose. All the important developers have been based
on N,N
-disubstituted phenylenediamines. Reactions

used in the photographic processes, however, have al-
ways taken place under alkaline conditions while the
synthesis of conducting polymers proceeds in acidic
media. The latter type is reviewed below even though
the resulting oxidation products have not always been
conducting. Two main cases: (i) direct synthesis by the
oxidation of the respective monomer with silver salts
and (ii) reduction of silver salts with the respective
polymers, are discussed separately.
Poly(p-phenylenediamine)
Recent studies have demonstrated that, in con-
trast to aniline, p-phenylenediamine is easily oxidized
with silver nitrate to the poly(p-phenylenediamine)
silver composite (Bober et al., 2010b, 2011b;

Ciric-
Marjanovic et al., 2011). The chemistry of p-phenyl-
enediamine oxidation was analyzed in detail on ba-
sis of quantum-chemical calculations and conrmed
by infrared and Raman spectra (
Ciric-Marjanovic et
al., 2011). Molecular weight of the p-phenylenediamine
oxidation product (10
3
10
4
) is somewhat lower than
that of PANI, and the organic component in the com-
posite can be regarded as only oligomeric (Bober et
al., 2011b). The oxidation of p-phenylenediamine pro-
ceeds easily even at 24
C in frozen aqueous reac-

tion mixtures (Bober et al., 2011b). Conductivity of
the composites has often reached impressive values
of the order of 10
3
S cm
1
and even exceeded that
of the PANIsilver analogues. This is unexpected be-
cause poly(p-phenylenediamine) is rated as a non-
conducting polymer (Sulimenko et al., 2001).
p-Phenylenediamine was oxidized with silver ni-
trate and the formation of silver microowers (Song et
al., 2007), dendrites (Sun & Hagner, 2007; Sun, 2010;
Liao et al., 2012), nanowires (Liao et al., 2012), fused
triangles (Zhang et al., 2011a), hexagonal nanoplates
(Wang et al., 2012a), or globular nanoparticles (Bober
et al., 2011b;

Ciric-Marjanovic et al., 2011) was re-
ported. Except for the last two papers, however, the
formation of poly(p-phenylediamine) or other oxi-
dation products has not been considered. Only re-
cently, the possibility that the morphology can be
produced partly by the polymer, rather than exclu-
sively by silver, has been admitted (Bober et al.,
2011b;

Ciric-Marjanovic et al., 2011; Zhang et al.,
2011a).
Composites of this type are of interest because,
rather surprisingly, they are conducting; often even
more than the analogous PANIsilver composites. The
reduction of silver salts with poly(p-phenylenediamine)
has not yet been investigated.
Poly(m-phenylenediamine)
Oxidation of m-phenylenediamine with silver ni-
trate in an aqueous solution led to the forma-
tion of silverpoly(m-phenylenediamine) coreshell
particles (Zhang et al., 2011c). Polymeric charac-
ter of the oxidation product, however, was not
proved.
In another type of experiments, poly(m-phenyl-
enediamine) was prepared by the chemical oxidation
of m-phenylenediamine with ammonium peroxydisul-
fate at rst (Zhang et al., 2011b; Tian et al., 2011).
Then, it was used for the adsorption of silver ions
(Zhang et al., 2011b), and the adsorption capacity of
1.7 g of silver ions per 1 g of polymer was reported.
In this case, however, the chemical reaction, a re-
duction of silver ions with poly(m-phenylenediamine)
to metallic silver (Tian et al., 2011), similar to that
shown in Fig. 7, is more likely than a mere adsorp-
tion.
Poly(o-phenylenediamine)
Silver ions are easily reduced to metallic silver
by o-phenylenediamine. Uniform micrometre-sized sil-
ver spheres were obtained (Sun et al., 2005; Liao et
al., 2011a, 2011b), accompanied by microbelts (Sun
et al., 2005). The fate of o-phenylenediamine oxida-
tion and its potential contribution to the obtained
morphology, however, was not discussed. The for-
mation of a polymer was suggested in the follow-
up studies resulting in ower-like objects (Guo &
Wang, 2008; Liao et al., 2011a, 2011b). The pres-
ence of o-phenylenediamine oligomers has also been
considered as an alternative. Indeed, a similar oxi-
dation of o-phenylenediamine with ammonium per-
oxydisulfate in an aqueous medium at room tem-
perature yielded only dimers or trimers (Sestrem et
al., 2010), orange-colored 2,3-diaminophenazine be-
ing the most important product (Yang & Wang,
2011). The same pathway seems to apply for the ox-
idation with iron(III) chloride (Tian et al., 2010).
Only the oxidation carried out at above 100
C in
glacial acetic acid yielded a black non-conducting
product which was believed to be a polymer (Li et
al., 2009c).
Poly(o-phenylenediamine) particles were used to
reduce silver ions to metallic silver and compos-
ites containing up to 35 mass % of silver were
obtained (Li et al., 2009c). The conductivity in-
creased by four orders of magnitude after the in-
corporation of silver but still did not exceed the
order of 10
8
S cm
1
. Similarly, nanobres pro-
duced from the o-phenylenediamine dimer were dec-
orated with silver nanoparticles when exposed to sil-
ver nitrate (Tian et al., 2010). Whether the oxida-
tion of o-phenylenediamine leads to a polymer or
to oligomers only is still open to discussion. Elec-
trodeposited poly(o-phenylenediamine) lms under-
went subsequent electrodeposition of silver nanopar-
ticles (Wang et al., 2012b).
Substituted polyanilines
Polymethylanilines
Oxidation of N-methylaniline with silver nitrate
was found to produce a silver mirror (Nadagouda &
Varma, 2007) but the formation of the correspond-
ing polymer was not proved. The composite of a con-
ducting polymer was prepared by the oxidation of o-
methylaniline (o-toluidine) with ammonium peroxy-
disulfate in the presence of silver nanoparticles (Reddy
et al., 2008).
Poly(o-methoxyaniline)
Poly(o-methoxyaniline) in chloroform was used to
reduce silver nitrate in aqueous solutions at the inter-
face of immiscible liquids (Dawn et al., 2007; Mukher-
jee & Nandi, 2009). The size of the silver parti-
cles was 922 nm and they were associated with
poly(o-methoxyaniline) and thus transferred to or-
ganic phase. They were, however, non-conducting.
The ability of poly(o-methoxyaniline) to reduce sil-
ver ions to silver has also been demonstrated in aque-
ous media (Dawn & Nandi, 2006; Routh et al., 2010).
Globular silver particles had the size of 516 nm
(Routh et al., 2010), i.e. they were smaller than in
case of PANI. In another type of experiments, poly(o-
methoxyaniline) was deposited electrochemically on
the electrode (Mazur et al., 2007). Hydrogen mi-
crobubbles generated at the same time left circular
holes in the polymer coating which were subsequently
lled with silver.
Poly(2,5-dimethoxyaniline)
Oxidation of 2,5-dimethoxyaniline with silver ni-
trate was claimed to produce a polymer (Huang et
al., 2006a, 2006b; Huang & Wen, 2007; Neelgund et
al., 2008). Brown color of the products and the ab-
sence of the absorption band with a maximum located
above 500 nm in the UV-VIS spectra, however, suggest
that only non-conducting oligomers were produced. In
all these papers, the presence of poly(styrenesulfonic
acid) in the reaction medium prevented the aggrega-
tion of silver nanoparticles having the size below 100
nm. Colloids have probably been produced under such
conditions (Stejskal, 2001) but neither this fact nor the
stability of the colloid were discussed.
Poly(4-aminodiphenylamine)
Oxidation of an aniline dimer, 4-aminodiphenyl-
amine (p-semidine, N-phenyl-p-phenylenediamine),
with silver nitrate led to poly(4-aminodiphenylamine)
silver composites (Paulraj et al., 2011; Thanjam et
al., 2011, 2012a, 2012b). The products were soluble
in the reaction medium and the polymeric charac-
ter of the formed product was not proved. UV-VIS
spectra, however, displayed a polaronic band above
600 nm (Paulraj et al., 2011; Thanjam et al., 2011),
which is typical of PANI salts. A similar oxidation
of 4-aminodiphenylamine with ammonium peroxy-
disulfate led only to semiconducting oligomers (
Ciric-
Marjanovic et al., 2008).
Sulfonated polyaniline
A composite of sulfonated PANI and silver was
prepared by the co-oxidation of aniline and orthanilic
acid (o-aminobenzenesulfonic acid) with silver nitrate
(Karim et al., 2009). Sulfonated PANI was used for the
reduction of silver ions to globular silver nanoparticles
(Krutyakov et al., 2010) or nanobelts (Xia, 2011). In
an earlier case, the emeraldine form of PANI was re-
duced with sodium borohydride at rst. It is not quite
obvious if it was the leucoemeraldine or the borohy-
dride which reduced the silver ions to silver. A statis-
tical copolymer of aniline and 5-sulfo-2-anisidine (5-
sulfo-2-methoxyaniline) was also used as the reductant
of silver ions to metallic silver (Li et al., 2010).
Aniline oligomers
Aniline oligomers are closely related to PANI (Ste-
jskal & Trchov, 2012). They may have various chem-
ical structures, ranging from linear oligomers resem-
bling PANI to phenazine-like heterocyclic molecules
(Wudl et al., 1987; Stejskal et al., 2008b) and
quinoneimine-containing structures (Silva et al., 2011;
K et al., 2011; Stejskal & Trchov, 2012). Their pre-
cise molecular structure has not yet been established
and they are probably represented by complex mix-
tures of molecules. Aniline oligomers are produced at
the early stages of aniline oxidation and especially un-
der low-acidity conditions, where the growth of PANI
chains is not feasible. This includes also oxidations un-
der alkaline conditions but the structure of the aniline
oligomers is then probably dierent from those pro-
duced in acidic media.
Aniline oligomers are non-conducting or their con-
ductivity is low. They are ecient reductants of sil-
ver nitrate (Stejskal et al, 2009b; Trchov & Stejskal,
2010) (Fig. 14). The deposited silver, however, had
no eect on the overall conductivity which remained
negligible at 10
13
S cm
1
(Stejskal et al., 2009b).
In spite of their electrical inactivity, aniline oligomers
and their composites with silver are promising mate-
rials for application due to their chemical properties
(Chao et al., 2009; Stejskal & Trchov, 2012). Aniline
oligomers produce a variety of spectacular morpholo-
gies represented by leaves, owers, and micromats un-
der acidic conditions (Zujovic et al., 2011a; Yang et
al., 2012b; Zhao et al., 2013), and compact or hollow
microspheres in alkaline media (Stejskal et al., 2010;
Luo et al., 2011; Cheng et al., 2011; Stejskal & Tr-
Fig. 14. Polyanilinesilver composites obtained by the reaction
of oligoaniline microspheres with silver nitrate (Tr-
chov & Stejskal, 2010).
chov, 2012). In contrast to PANI, the objects pro-
duced by aniline oligomers are more crystalline and
larger, of micrometre size, due to their better ability
to self-organize.
The oxidation of aniline always results in a prod-
uct which contains some fraction of aniline oligomers.
The content of oligomers is low when the oxidation
is carried out in acidic media. The opposite is true
when the acidity is low and aniline oligomers are
the exclusive products as in an alkaline medium. Ox-
idation potential of the oxidant is also important,
and the fraction of aniline oligomers becomes larger
as the oxidation potential (E
) is reduced (Sapu-
rina & Stejskal, 2012), e.g., when using silver ni-
trate (E
= 0.8 V) instead of ammonium peroxy-

disulfate (E
= 2.0 V). This is reected in the UV-

VIS spectra which do not display the typical ab-
sorption polaron band of a PANI salt at approxi-
mately 810 nm, or that of the
transition of the
quinoneimine rings in the PANI base at 630 nm (Ste-
jskal et al., 1993). The presence of aniline oligomers
is also conrmed by increased absorption in the 300
400 nm region. Aniline oligomers have dierent molec-
ular structure than PANI and they contain quinone
or quinoneimine constitutional units (Stejskal & Tr-
chov, 2012).
Although many papers claim to have prepared
PANI, in fact, only aniline oligomers have been pro-
duced (Kim et al., 2011; Gao & Xing, 2012). The
formation of aniline oligomers, instead of PANI, is
suspected also in the cases when pH of the reaction
medium was higher than 23 (Fujii et al., 2010; Yang
et al., 2011; Gao & Xing, 2012), i.e. it did not reach
the acidity level needed for the formation of PANI (Sa-
purina & Stejskal, 2010; Konyushenko et al., 2010).
Other related systems
Congo red, a dye containing an aniline constitu-
tional moiety, was oxidized with silver nitrate (Sinai
& Avnir, 2011). The formation of a polymer has not
been considered and the authors called the resulting
material as silver doped with Congo red. The reaction
of N-(3-trimethoxysilyl)aniline with silver nitrate was
claimed to produce a corresponding polymer (Manesh
et al., 2010). The silyl moiety was then incorporated
into the silica network.
Electrochemically prepared poly(o-aminophenol)
was used for the reduction of silver ions to sil-
ver (Zhang et al., 1996). Poly(m-aminophenol) was
claimed to have been prepared by the oxidation of
m-aminophenol with ammonium peroxydisulfate in a
strongly alkaline medium (Kar et al., 2011). Under
such conditions, however, the formation of PANI-like
structures is unlikely and indeed, the absorption max-
imum in the red region of the visible spectrum was
missing. Nevertheless, the oxidation products were
able to reduce silver nitrate to metallic silver.
A product of the joint oxidation of sodium di-
phenylamine-4-sulfonate and 1,8-diaminonaphthalene,
probably a copolymer of these two compounds, was
tested for the reactive adsorption of silver ions from
solutions of various acidity (Li et al., 2005). The same
adsorption ability was reported for various polydi-
aminonapththalenes (Huang et al., 2005).
The reaction between benzidine and silver nitrate
was reported to produce a polybenzidinesilver com-
posite (Manivel et al., 2012) and, similarly, electro-
chemically prepared polybenzidine lms were found
to reduce silver ions to silver (DEramo et al., 2000).
Conductivity
Many researchers assume that the introduction of
silver to conducting polymers leads to an increase
in the conductivity. Practical experiments, however,
show that this expectation is usually not fullled. As
it is shown below, most composites do not even reach
the conductivity of the conducting polymers alone but
exceptions to this rule do exist.
In PANIsilver composites, PANI is regarded as
the polymer matrix and silver particles as the ller. In
the classical percolation concept, approximately 16
17 vol. % of the conducting component in the non-
conducting matrix are needed for the formation of
conducting pathways in the three-dimensional com-
posite and for the material to become conducting.
In the present case, the percolation threshold corre-
sponds to at least 60 mass % of silver (Fig. 15). It can
be expected that, above this limit, the conductivity
is controlled by silver and is therefore high, while be-
low this threshold, the control is governed by PANI at
the semiconductor level. Practical experiments seem
to suggest the location of the percolation threshold
Fig. 15. Volume vs. mass fraction of silver in the composites
of silver with PANI. Calculated by assuming the den-
sities of silver and PANI equal to 10.5 g cm
3
and 1.4
g cm
3
, respectively.
Fig. 16. Compilation of the conductivities reported for PANI
silver composites in several recent papers (Blinova et
al., 2009; Bober et al., 2010a, 2010b, 2011a, 2011c).
between 7080 mass % of silver (Fig. 16).
Many results, however, suggest that the conductiv-
ity of composites falls below the conductivity of both
constituents. This implies that additional factors are
in operation. The conductivities reported in literature
are not easy to compare because they refer to widely
diering contents of silver.
For the purpose of discussion, we shall distinguish:
(i) direct synthesis of composites by the oxidation of
aniline or pyrrole with silver salts; and (ii) reduction
of silver salts with PANI and PPy. In the former case,
reaction stoichiometry predicts the content of silver
in the composites to be close to 70 mass % (Blinova
et al., 2009) and, in the latter, to about 37 mass %
(Stejskal et al., 2009d). Thus, the former approach
provides better chances for the preparation of highly
conducting materials; the attractivity of the latter is
in its simplicity.
Conductivity of polyanilinesilver composites
Direct preparation
Oxidation of aniline with silver nitrate in solutions
of nitric acid has led to PANIsilver composites hav-
ing the conductivity of 492250 S cm
1
depending on
the concentrations of aniline and nitric acid (Blinova
et al., 2009). The process, however, was slow and sev-
eral months were needed to obtain reasonable yield
of the composite. The samples were not homogeneous
and contained macroscopic silver particles. Also, un-
desirable nitration of the PANI chains was observed.
Physical acceleration with UV-light yielded a product
having the conductivity of 3050 S cm
1
(Khanna et
al., 2005) or 93 S cm
1
(Li et al., 2012b) within several
days. When using -irradiation for the same purpose,
the achieved conductivity was 0.050.20 S cm
1
(Pil-
lalamarri et al., 2005). Chemical acceleration of aniline
oxidation with p-phenylenediamine made the synthe-
sis feasible from the practical viewpoint (Bober et al.,
2010b) but the homogeneity of the samples still re-
mained a problem. The use of larger proportions of
p-phenylenediamine with respect to aniline led to a
drop in the conductivity due to the loss of regularity
of the PANI chains caused by the copolymerization of
aniline and p-phenylenediamine (Bober et al., 2011b).
Oxidation of aniline in solutions of acetic acid
provided products widely diering in conductivity,
0.0783550 S cm
1
(Blinova et al., 2010). The sam-
ples, however, contained a high fraction of insoluble
silver acetate, which is undesirable. There was also
a notable fraction of aniline oligomers in the sam-
ples, obviously due to the relatively low acidity af-
forded by acetic acid. The problem of the slow re-
action rate persisted and weeks were still needed to
complete the reaction. The reaction was accelerated
by p-phenylenediamine (Bober et al., 2010b) but other
problems remained. Oxidation of aniline in solutions of
hydrochloric acid yielded composites having the con-
ductivity of 5.9 10
3
0.11 S cm
1
(Karim et al.,
2009). Also in this case, the composites probably con-
tained insoluble silver chloride.
Formic acid solutions are better suited as a medium
for the oxidation of aniline (Bober et al., 2010b). The
conductivity of PANIsilver composites was lower and
ranged between 0.8545.00 S cm
1
and the reaction
rate increased so that the products could be isolated
within a few days. Macroscopic homogeneity, however,
was again poor. Chemistry of the reaction is compli-
cated by the fact that silver nitrate is reduced, in ad-
dition to aniline, also by formic acid. This reaction
is fast and exothermic but, surprisingly, it was inhib-
ited after the addition of aniline. Further studies are
needed to understand the course of aniline oxidation
in this medium.
So far, solutions of sulfonic acids seem to be the
most promising, as they do not precipitate silver ions,
yet they provide sucient acidity of the medium for
the preparation of PANI (Bober et al., 2011c). Among
them, methanesulfonic acid performed the best, the
PANIsilver composite reaching the conductivity of
880 S cm
1
. Conductivity of composites prepared in
solutions of camphorsulfonic or toluenesulfonic acids
remained at the level of PANI alone and no contri-
bution of silver to the conductivity was observed. On
the other hand, the reaction yield was high, over 77 %,
and the homogeneity of samples was also good. Accel-
eration with p-phenylenediamine was still necessary.
Conductivity exceeding the value of 10
3
S cm
1
was
also determined for the samples prepared in frozen re-
action mixtures at 24
C (Bober et al, 2011a), when

the polymerization took place in the solid state, in ice
(Konyushenko et al., 2008b).
In most literature sources, conductivity of PANI
silver composites has been mentioned only rarely.
When it was reported, it usually did not exceed that
of the conducting polymer alone, units of S cm
1
.
For example, oxidation of aniline with silver nitrate in
ethanol at 250
C yielded a composite having the con-

ductivity of 0.18 S cm
1
(Du et al., 2005). The pattern
printed by silver nitrate and aniline solution and ex-
posed to UV-irradiation had the conductivity of 0.02
S cm
1
(de Barros et al., 2005); experimental details of
the preparation have not been disclosed. The compos-
ite prepared from PANIsilver nanoparticles stabilized
with poly(vinyl alcohol) had the conductivity of 0.014
S cm
1
(Fujii et al., 2010) but the presence of ani-
line oligomers rather than of PANI is suspected when
noting the low-acidity conditions. Similar composites
prepared in the presence of poly(styrenesulfonic acid)
had the conductivity of 10
3
10
4
S cm
1
(Neelgund
et al., 2008). Oxidation of aniline with a mixture of
oxidants, ammonium peroxydisulfate and silver ni-
tride, in the presence of citric acid yielded composites
having the conductivity of 0.701.62 S cm
1
(Jia et
al., 2010a), and the values of 0.871.56 S cm
1
were
achieved in solutions of nitric acid (Jia et al., 2010b).
The conductivity of PANI prepared in the absence of
a silver salt was 0.13 S cm
1
. The reaction between
aniline and silver salts can proceed even in the absence
of solvents, in the solid state, by mechanical blending
of the reactants (ednkov et al., 2011). The product,
however, had a poor conductivity (1.5 10
3
S cm
1
)
and the organic part was composed mainly of aniline
oligomers.
Reduction with polyaniline
This strategy uses the ability of PANI or PANI
composites to reduce silver salts to silver. Conduc-
tivity of the PANIcellulose composite (6.0 10
4
S cm
1
) was reduced to 3.6 10
9
S cm
1
after the
deposition of silver nanoparticles (Kelly et al., 2007).
It was correctly concluded that the conducting emeral-
dine salt was converted to a non-conducting perni-
graniline base (Kelly et al., 2007; Patil et al., 2012).
The content of silver is too low to aect the overall
conductivity. The same conclusion was made in an-
other study (Stejskal et al., 2008c). The reduction of
silver nitrate by PANI-coated multi-wall carbon nano-
tubes led to an increase in their conductivity from
0.082 S cm
1
to 1.680 S cm
1
with the increasing sil-
ver content (Grinou et al., 2012); however, these values
are still relatively low.
When PANI nanotubes were used as a reductant
of silver nitrate in 1 M nitric acid, the produced com-
posites had the conductivity of 10
4
10
2
S cm
1
de-
pending on the mole ratio of the reactants (Stejskal
et al., 2009c). Preparations using globular PANI in
1 M hydrochloric acid yielded products of the same
conductivity (Patil et al., 2012). A similar reaction
in water, however, yielded a composite with the con-
ductivity of 68 S cm
1
(Stejskal et al., 2009c). The
acidity of the reaction medium thus has an important
role. The composite obtained by the reduction of silver
nitrate with PANI had the conductivity of 35 S cm
1
(Leyva et al., 2011).
Mechanochemical synthesis based on the blending
of reactants, PANI base and silver nitrate, in the solid
state yielded a composite with the conductivity of
10
3
10
2
S cm
1
(ednkov et al., 2009). The pro-
cess is interesting due to the fact that nitric acid is
a by-product. The observed conductivity is thus a re-
sult of the protonation of PANI base to PANI nitrate
rather than the contribution of generated silver.
The most promising direction is represented by
the composites composed of poly(methyl methacry-
late) microparticles coated with PANI and decorated
with silver (Lee et al., 2012). Such a composite does
not obey the simple percolation principle and the per-
colation has to be reached only within the interstitial
space (Proke et al., 1997; Kivka et al., 1999). Un-
der such conditions, even a relatively small fraction of
silver in the composite may lead to high conductivity.
Other syntheses
When PANI was prepared in the presence of silver
nanoparticles, conductivity of the resulting compos-
ites increased from 0.03 S cm
1
for neat PANI to 0.51
S cm
1
for the highest (but unspecied) content of
silver (Gupta, et al., 2010). Similarly, when PANI was
prepared in the presence of carbon nanotubes deco-
rated with silver nanoparticles, conductivity was two
orders of magnitude higher than in the absence of sil-
ver (0.034 S cm
1
) (Kim & Park, 2011), still rela-
tively low. The reverse process in which PANI-coated
carbon nanotubes were decorated with silver nanopar-
ticles obtained by the reduction of silver nitrate with
sodium citrate also led to composites with relatively
low conductivity (2.5 10
3
5.0 S cm
1
).
Mixing of PANI with silver nanoparticles is not
an eective way to increase the conductivity. This is
caused by the low volume fractions of silver which can
be introduced in this way. Conductivity of PANI (0.4
S cm
1
) was found to increase to 2.3 S cm
1
after
the incorporation of silver nanoparticles (Oliveira et
al., 2006) but such an increase is hardly signicant.
After combining PANI methanesulfonate with silver
nanoparticles, the level of conductivity stayed in the
units S cm
1
(Sim et al., 2009). The composite of
PANI with dinonylnaphthalenedisulfonic acid and sil-
ver nanoparticles had the conductivity of 7.10 10
3
1.58 10
2
S cm
1
at approximately 20 mass % of
the silver content (Garai et al., 2010) and it displayed
ohmic behavior.
Conductivity of polypyrrolesilver composites
Direct preparation
Incorporation of silver in PPy led in most cases
to an increase in conductivity. PPy prepared with the
potassium ferricyanide (K
3
[Fe(CN)
6
]) oxidant had the
conductivity of 4 S cm
1
(Feng et al., 2007b). Oxida-
tion of pyrrole with the silver salt of methyl orange
produced PPysilver composite of the 10 S cm
1
con-
ductivity. Conductivity of PPysilver composites con-
taining in addition poly[styrene-co-(methyl acrylate)]
latex varied between 0.11.5 S cm
1
and increased
with the increasing content of silver nearly in a linear
manner (Borthakur et al., 2011). In PPysilver com-
posites prepared by the polymerization at the interface
of water and an ionic liquid, the conductivity increased
from 0.14 S cm
1
for neat PPy to 13.5 S cm
1
for the
composite with the highest silver content (Wei et al.,
2010a). Oxidation of pyrrole with silver nitrate in the
presence of the cationic surfactant tetradecyltrimethy-
lammonium bromide (Chatterjee et al., 2011) led to
products with the conductivity from 25 S cm
1
to 414
S cm
1
. These are exceptionally high values; the pres-
ence of surfactants has also been reported to have a
positive eect on the conductivity of PPy prepared in
the classical way (Omastov et al., 2003).
The presence of a non-conducting polymeric com-
ponent generally reduces the conductivity of the com-
posite. Composites obtained by counter-diusion of
pyrrole and silver nitrate solutions through polyte-
trauoroethylene membranes had the conductivity of
0.050.20 S cm
1
(Shi et al., 2012). The compos-
ite prepared from colloidal PPysilver nanoparticles
stabilized with poly(N-vinylpyrrolidone) had the con-
ductivity of 10
5
S cm
1
which increased to 10
3
S cm
1
when using poly[(4-styrenesulfonic acid)-co-
(maleic acid)] sodium salt as the stabilizer (Jung et
al., 2011). When, in addition, the reaction medium
contained magnetite (Zhao & Nan, 2012a), the re-
sulting composites had the conductivity of 29335
S cm
1
; the product prepared in the absence of mag-
netite, however, was not reported. Similar PPysilver
nanoparticles prepared in the presence of poly(N-
vinylpyrrolidone) had the conductivity of 8 S cm
1
at 65.8 mass % of silver (Feng, 2010). The introduc-
tion of a conducting component, such as graphite, has
not resulted in notable conductivity, which remained
at the 0.4 S cm
1
level (Mo et al., 2007).
Reduction with polypyrrole
Similarly to PANI, PPy also can be used for the
reduction of silver ions to silver. Conductivity of PPy
(2.22.3 S cm
1
) increased only to 2.82.9 S cm
1
af-
ter the reduction of silver ions to silver at the 5 mass %
content (Visy et al., 2005; Pintr et al., 2005). A cer-
tain increase in conductivity is anticipated because
of the incorporated highly conducting silver nanopar-
ticles. Other authors, however, report the opposite
trend when the conductivity of PPy decreased from
2 S cm
1
to 10
2
S cm
1
after the incorporation of sil-
ver nanoparticles (Zhang & Manohar, 2005). This was
explained by the overoxidation of the PPy backbone
(Fig. 12), i.e. similarly to the conversion of emeral-
dine to pernigraniline in PANI. Conductivity of the
PPycellulose composite (0.26 S cm
1
) was similarly
reduced to 3.8 10
4
S cm
1
after the deposition of
silver nanoparticles (Kelly et al., 2007).
Conductivity of other systems
Poly(p-phenylenediamine)silver composite had
the conductivity of 60 S cm
1
(Bober et al., 2010b)
and the order of 10
3
S cm
1
was demonstrated later
(
Ciric-Marjanovic et al., 2011; Bober et al., 2011b)

despite the fact that the polymeric matrix is non-
conducting (Sulimenko et al., 2001) and the conduc-
tivity is aorded only by silver. The highest reported
value was 31700 S cm
1
at 81.4 mass % of the silver
content. Such composites are competitive with PANI
silver or PPysilver composites in which the polymer
matrix is semiconducting. The composite of silver with
any polymer would probably have such high conduc-
tivity at such a high content of silver.
Conductivities of ternary PANIsilvergraphite
composites were 10002000 S cm
1
, i.e. lower than the
conductivity of graphite alone (10
4
S cm
1
) (Wu et al.,
2010). Conductivity of graphite coated with silver was
claimed to be 1.03 10
6
S cm
1
(Wu et al., 2010), i.e.
much higher than that of silver metal. In other cases,
however, the conductivity of composites was found to
be close to that of the polymer matrix. The presence of
silver contributed a little to the conductivity, usually
its eect was negligible due to its low volume fraction
in the composite. The ternary composite of PANI, sil-
ver, and poly(vinyl alcohol) had the conductivity of
0.014 S cm
1
.
The composite of silver nanoparticles and poly(o-
methoxyaniline) was non-conducting; the conductivity
was of the orders of 10
11
10
8
S cm
1
(Dawn et al.,
2007; Routh et al., 2010). Many authors assumed and
indeed reported an increase in the conductivity after
the introduction of silver. The presence of separately
prepared silver nanoparticles in poly(o-methylaniline)
increased its conductivity from 1.09 10
3
S cm
1
to 1.28 S cm
1
(Reddy et al., 2008). The conduc-
tivity of poly(o-phenylenediamine) similarly increased
by four orders of magnitude after the reduction of
the silver ions but it still has not exceeded the value
of 10
8
S cm
1
(Li et al., 2009c). The conductivity
of poly(m-aminophenol) with 26 mass % of silver
was of the order of 10
7
S cm
1
. The conductivity
of poly[aniline-co-(5-sulfo-2-anisidine)] increased ten
times, to 0.41 S cm
1
, after the incorporation of silver
(Li et al., 2010).
Temperature dependence of conductivity
Conducting polymers display conductivity at the
semiconductor level and behave as semiconductors.
For that reason, conductivity of conducting polymers
increases with the increasing temperature while the
opposite trend is observed for metals, such as silver
(Lee et al., 1999, 2002). These two opposite trends
manifest themselves in the conducting polymersilver
composites. When the room-temperature conductiv-
ity of composites was of the order of units S cm
1
or lower, the conductivity was obviously controlled
by PANI. The conductivity thus increased with the
increasing temperature as it is typical of semicon-
ductors (Lee et al., 1999; Sim et al., 2009; Gupta
et al., 2010; Bober et al., 2011a). When the conduc-
tivity was higher than 10 S cm
1
, it was governed
mainly by silver and, consequently, the temperature-
dependence was reversed and became typical of met-
als (Lee et al., 1999; Bober et al., 2011c). When
these two trends compensate each other, dish-like
temperature-dependences of conductivity are found
(Bober et al., 2010b, 2011a) (Fig. 17). As a result, the
conductivity was virtually constant over a broad tem-
perature range. A concave temperature-dependence
of conductivity was also reported for the composite
of silver with poly[aniline-co-(p-phenylenediamine)]
(Bober et al., 2011b). A reverse convex trend, how-
ever, has also been reported in literature (Alam et al.,
2012).
Ageing of a PANIsilver composite led to a de-
crease in its conductivity (Afzal & Akhtar, 2011). This
happened between the temperatures of 100200
C
(Sim et al., 2009). Such behavior is anticipated when
the conductivity of the composite is determined by
that of the PANI matrix and reduced due to the de-
protonation of the conducting PANI salt to the non-
conducting PANI base (Proke & Stejskal, 2004).
Deprotonation phenomena
Silver nanoparticles embedded in the conducting
polymer matrix have been expected to provide ma-
terials with higher conductivity compared with that
of the non-conducting matrix. Rather surprisingly,
conversion of the conducting PANI salt to a non-
conducting PANI base has often resulted in an in-
crease in the composite conductivity (Blinova et al.,
2010; Bober et al., 2011a, 2011b). This also happened
in poly(p-phenylenediamine)silver composites (
Ciric-
Marjanovic et al., 2011).
Two explanations have been oered (Bober et al.,
2011a): (i) the rst is based on the presence of in-
sulating interfacial barriers, such as a silver oxide
overlayer on silver particles (Baibarac et al., 1999).
After its dissolution in ammonium hydroxide, which
is used for the conversion of the PANI salt to the
PANI base, the contact between semiconducting PANI
and metallic silver improves and the conductivity of
the composite increases. The contact between silver
and conducting polymers was reported to have ohmic
character (Liu et al., 2005); (ii) the second expla-
nation is based on the percolation principle. After
the deprotonation of PANI, acid is removed from the
PANI salt and the PANI mass decreases (Stejskal et
al., 2008a). The mass fraction of silver in the com-
posite increases as a consequence and, if it becomes
suciently high (6070 mass % silver), it may ex-
ceed the percolation threshold (Fig. 15). The disso-
lution of water-insoluble silver salts, such as silver
acetate (Blinova et al., 2010), during the deproto-
nation in ammonium hydroxide, has the same eect.
The conductivity thus increases despite the fact that
the semiconducting matrix of the PANI salt is con-
verted to a non-conducting PANI base. Both mecha-
nisms may become operational simultaneously, but the
observation of this eect with non-conducting poly(p-
phenylenediamine) (
Ciric-Marjanovic et al., 2011) fa-

vors the second mechanism.
Applications
Conducting polymers and noble metals are elec-
tric conductors; the former are organic semiconduc-
tors, and the latter are metals. Ionic contribution to
the conductivity aorded by conducting polymers in
aqueous media (Stejskal et al., 2009a; Wolz et al.,
2010; Qaiser et al., 2011) is also of interest. Potential
applications of PANIsilver and PPysilver nanocom-
posites, which exploit conductivity or extend beyond
the conductivity area, are alphabetically listed below.
Antimicrobial activity
Antimicrobial eect of silver is well known and has
also been demonstrated in its composites with con-
ducting polymers (Nesher et al., 2011; Prabhakar et
al., 2011; Jia et al., 2012; Shi et al., 2012; Tamboli et
al., 2012). Cellulose bres coated with PANI or PPy
and decorated with silver nanoparticles (Kelly et al.,
2007; Firoz Babu et al., 2012) can serve as an ex-
ample. It should be noted that PANI alone has been
reported to possess substantial antimicrobial activ-
ity (Gizdavic-Nikolaidis et al., 2011; Jia et al., 2012),
which may be, in some cases, associated with pho-
tocatalytic generation of hydrogen peroxide (Liang et
al., 2012). Synergistic antimicrobial eect of PANI and
silver against Escherichia coli and Staphylococcus au-
reus has recently been demonstrated (Jia et al., 2012;
Park et al., 2012). PPysilver composite deposited on
a polytetrauoroethylene membrane (Shi et al., 2012)
or cotton (Firoz Babu et al., 2012) were also tested
against Escherichia coli and Staphylococcus aureus
with a good result.
Bioapplications
Biocompatibility of PANI has recently been tested
with positive results (Humpolicek et al., 2012a,
2012b). The future role of conducting polymers can
be seen especially in monitoring of vital functions and
in the stimulation of neural or cardiac tissues. The
combination with silver is of obvious benet. Bio-
compatibility of polyurethane modied with PANI
alone or in combination with silver nanoparticles was
improved by comparison with that of polyurethane
alone (Prabhakar et al., 2011). An amperometric
dopamine biosensor based on PPysilver nanoparti-
cles was demonstrated (Feng et al., 2007a).
Catalysis and electrocatalysis
Polyaniline alone has been proved to catalyze var-
ious organic reactions (Zabrodski et al., 2006; Lee
et al., 2009; Zieba et al., 2010) and similar activ-
ity has been reported for PPy (Bashyam & Zelenay,
2006; Zhang et al., 2008). Also, modication of these
properties after the incorporation of silver may be
worthy of investigation. A PANI or its substituted
derivative combined with silver nanoparticles were
used in the catalytic reduction of 4-nitrophenol with
sodium borohydride (Manesh et al., 2010; Chang et
al., 2012a; Han et al., 2012; Thanjam et al., 2012b;
Qin et al., 2012). Electrocatalytic activity of con-
ducting polymers with respect to hydrogen peroxide
reduction has been observed after the introduction
of silver nanoparticles to PANI (Kim et al., 2011;
Manivel & Anandan, 2011; Chang et al., 2012a; Qin
et al., 2012), poly(o-phenylenediamine) (Wang et al.,
2012b), poly(m-phenylenediamine) (Tian et al., 2011),
or PPy (Kim et al., 2010a; Qin et al., 2011). PANI
silver composites improved the electrocatalytic activ-
ity towards the reduction of dopamine compared with
PANI alone (Gao et al., 2009). PANI-modied silver
was investigated in an oxygen reduction reaction (Yi &
Song, 2012). PANIsilver (Hosseini & Momeni, 2010;
Singh et al., 2011) and poly(4-aminodiphenylamine)
silver (Paulraj et al., 2011) composites were tested in
the electrochemical oxidation of hydrazine. Catalysis
of the synthesis of -aminoketones is another example
(Palaniappan & Rajender, 2010).
Similarly, PPysilver nanoparticles deposited on
inorganic substrates have been demonstrated to cat-
alyze the reduction of methylene blue (Yao et al.,
2009) and sodium m-nitrobenzene sulfonate (Zhang
Fig. 17. A weak dish-like dependence of conductivity on tem-
perature (adapted from Bober et al., 2011b).
et al., 2012) with sodium borohydride. They were also
successful in promoting the electrochemical reduction
of nitrates (Zhang et al., 2010). Polypyrrole nanotubes
decorated with silver nanoparticles catalyzed the re-
duction of hydrogen peroxide (Peng et al., 2012).
Conducting composites
The fundamental property of conducting polymer
silver composites is their electrical conductivity. Most
expectations are represented by the design of highly
conducting composites. The composites having the
conductivity of above 1000 S cm
1
, however, can be
prepared only at high silver contents, close to or above
70 mass % (Blinova et al., 2009, 2010; Bober et al.,
2011a, 2011b). Conductivity is also an important fac-
tor in the design of electromagnetic interference shield-
ing (Lee et al., 1999, 2002).
Hybrid composite colloids may nd applications
as conducting inks (Ihalainen et al., 2012) and lm-
forming compositions, including those for corrosion
protection. Inkjet printing of silver nitrate and aniline
solution followed by UV-irradiation yielded a conduct-
ing pattern on paper (de Barros et al., 2005). A PANI
dispersion containing silver nanoparticles was used as
a solderable surface nish (Wessling et al., 2007).
There are electronic conductors, such as met-
als and semiconductors, and ionic conductors. Obvi-
ously, materials that combine various types of con-
duction mechanisms can be expected to have new
properties. Synergetic eect of both components can
be demonstrated on materials with low dependence
of conductivity on temperature (Fig. 17) due to
the compenzation of the semiconductor and metal-
lic types of conduction (Bober et al., 2011b). In
addition, PANI or PPy are mixed electronic and
ionic conductors (Stejskal et al., 2009a; Qaiser et
al., 2011). Separation of electronic and proton con-
tributions to the charge transfer is likely to be-
come important in future applications in aqueous sys-
tems.
Sensors
Responsivity of conducting polymers, i.e. their
ability to respond to various external stimuli by
changes in electrical, electrochemical, or optical prop-
erties constitutes the basis of many sensors. Incorpo-
ration of silver may be a source of modied selectivity
or sensitivity.
Polyanilinesilver composites were tested as sen-
sors for acetone (Choudhury et al., 2009), ethanol
(Choudhury, 2009; Barkade et al., 2011), toluene (Li
et al., 2012a), or trimethylamine vapors and for the
design of hydrogen peroxide/glucose sensors (Chang
et al., 2012a) or hydrogen peroxide sensors (Shukla
et al., 2012). The incorporation of silver nanoparti-
cles into PANI reduced the response time, which still
was too long, to tens of minutes. A ternary system
including carbon nanotubes, in addition, was used as
an amperometric glutathione biosensor (Narang et al.,
2012). Sensors for ammonia, a typical realm of PANI,
have also been demonstrated for PANIsilver compos-
ites (Li et al., 2009a; Yang et al., 2010a, 2010c).
The PPysilver composite was investigated in sens-
ing of gases such as ammonia, hydrogen sulde, or
carbon dioxide (Kate et al., 2011), and as a humidity
sensor (Kabir et al., 2008). An optical waveguide sen-
sor for humidity was also demonstrated (Fuke et al.,
2009a, 2009b, 2010). Silver nanoparticles electrode-
posited on PPy on a glassy carbon electrode were
used as a sensor for nitrate (Atmeh & Alcock-Earley,
2011). Similarly, glassy carbon electrodes coated with
the PPysilver colloid (Qin et al., 2011) or PPy
nanosheets decorated with silver nanoparticles (Mah-
moudian et al., 2012) were tested for hydrogen per-
oxide detection; a similar sensor was reported also for
PANI alone (Kim et al., 2011).
In another type of experiments, changes in the
color of PANI after its exposure to metal ions, such
as silver(I), copper(II), and chromium(III), were pro-
posed for optical ion-sensing (Chi et al., 2010). Ap-
pearance of the plasmon absorption band of silver
nanoparticles in the region between 400500 nm can
also be used in sensing of silver ions.
Poly(m-phenylenediamine)silver nanoparticles
were used as a uorescence sensing platform for nu-
cleic acid detection (Zhang et al., 2011c) and as an
amperometric hydrogen peroxide sensor (Tian et al.,
2011).
Silver recovery and water-treatment
Reactive sorbents converting silver ions to metal-
lic silver have been proposed on one hand for the re-
covery of silver or, on the other, for industrial waste-
water treatment. Although some papers mention only
the adsorption of silver ions, in fact, their reduction
by conducting polymers to metallic silver takes place
(Figs. 7 and 12). In addition to PANI (Dimeska et al.,
2006; Ansari & Delavar, 2008) and PANI composites
with lignin (He et al., 2012b), various PANI deriva-
tives, such as poly[(aniline-co-(5-sulfo-2-anisidine)] (Li
et al., 2010) and poly(o-phenylenediamine) (Li et al.,
2009c), have been proved to be ecient sorbents.
The sorption ability usually extends also to other no-
ble metals and mercury (Choi & Jang, 2008; Li et al.,
2009c).
Polypyrrolesilver composites have similarly been
used for the recovery of silver from exhausted photo-
graphic xers (Pickup et al., 1998) or industrial waste-
waters (Tian et al., 2008). Polypyrrole has been used
as a sorbent for silver ions (Choi & Jang, 2008; Ansari
& Delavar, 2008). A PPy/silicasilver composite was
also tested in this direction (Lim et al., 2012).
Surface-enhanced Raman scattering
Surface-enhanced Raman scattering is an attrac-
tive method of molecular characterization involving
noble metals, such as silver (Trchov et al., 2012;
Yan et al., 2012). Polyaniline base lms cast from
N-methylpyrrolidone solutions and reprotonated with
organic acid were immersed in a silver nitrate solution.
After the deposition of silver, they were successfully
used as a support for surface-enhanced Raman scat-
tering (Xu et al., 2010a, 2010b, 2010d; Yan et al., 2012;
He et al., 2012a).
A similar approach has been demonstrated for PPy
(Wang & Zhang, 2009; Wang et al., 2010a, 2010b),
when silver nanoparticles were deposited on electro-
chemically prepared PPy lms. PPy nanotubes dec-
orated with silver nanoparticles have shown an en-
hancement factor of 6 10
7
in the detection of rho-
damine (Peng et al., 2012).
Other uses
Polyaniline composite with silver (0.9 mass %) was
reported to improve the specic capacitance and in-
crease the conductivity of electrode materials in su-
percapacitors (Patil et al., 2012). Modication of elec-
trode materials in general seems to be a promising
direction in future research. Protective eect of PPy
against electrochemical corrosion of silver (Chang et
al., 2012b) is another result which points to the appli-
cations in corrosion protection of metals, where con-
ducting polymers alone have already been established.
Conclusions
Oxidation of aniline with silver nitrate to poly-
anilinesilver composites is a process in which two
non-conducting reactants generate two conducting
products. The reaction requires chemical or physical
acceleration for its ecient use. The similar oxidation
of pyrrole proceeds much more easily. There are close
similarities between the oxidation of aniline and that
of pyrrole, as well as in the properties of the result-
ing composites. Highly conducting composites, 10
3
10
4
S cm
1
, have been prepared only rarely (Blinova
et al., 2009, 2010; Bober et al., 2011a). They require
the content of silver above the percolation limit, at
7080 mass % of silver. Direct oxidation of aniline
with silver salts seems to be the only way how to
reach this target. The reduction of silver nitrate with
PANI yields composites having the conductivity be-
low 1 S cm
1
of the order of conductivity typical of
PANI salts. This is due to the low content of silver
in the composites, 1020 mass %, generated by this
way. Only in two cases (Stejskal et al., 2009b, 2009c),
conductivity of the order of tens of S cm
1
was found.
The control of the nanostructure of both compo-
nents, PANI and silver, may bring promising results
with respect to their electrical and other properties.
The design of conducting inks applicable in printed
microelectronics seems to be the most important ap-
plication in this respect. The role of interfacial phe-
nomena between the conducting polymer and silver
has still to be analyzed. Electrical properties of hy-
brid composites are of primary interest but the respon-
sivity of conducting polymers, their mixed electronic
and ionic conductivity, and chemical and mechanical
properties are of additional value. This applies also
to the optical properties of silver nanoparticles and
their catalytic and antimicrobial activities. The de-
sign of specic forms, such as bulk materials, colloidal
dispersion, thin lms, and nanobres or nanotubes,
is the next goal. Despite numerous papers reporting
the prepation of hybrid composites, their concrete ap-
plications are scarce so far but they are likely to be
rapidly developed.
Acknowledgements. The author thanks the Technology
Agency of the Czech Republic (TE 1010022) for nancial sup-
port.
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Chemical Papers 67 (8) 814848 (2013)

= 0.77 V), are also able to oxidize aniline to

C was also used to in-

C yielded micrometre-sized PANI micro-

C (Yang et al., 2011), which took place under alka-

C (Wang & Shi, 2007). The

C, the silver nanopar-

-disubstituted phenylenediamines. Reactions

C in frozen aqueous reac-

= 0.8 V) instead of ammonium peroxy-

= 2.0 V). This is reected in the UV-

C (Bober et al, 2011a), when

C yielded a composite having the con-

Ciric-Marjanovic et al., 2011; Bober et al., 2011b)

Ciric-Marjanovic et al., 2011) fa-

Ciric-Marjanovic, G., Trchov, M., Konyushenko, E. N., Holler,

Ciric-Marjanovic, G., Marjanovic, B., Bober, P., Rozlvkov,

Osterbacka, R., & Peltonen, J. (2012). Inuence of surface

C. Polymer Degradation and Stability, 94,

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