Anal Bioanal Chem (2005) 382: 1912–1918
DOI 10.1007/s00216-005-3334-x
O R I GI N A L P A P E R
N. Cioffi Æ N. Ditaranto Æ L. Torsi Æ R. A. Picca
E. De Giglio Æ L. Sabbatini Æ L. Novello Æ G. Tantillo
T. Bleve-Zacheo Æ P. G. Zambonin
Synthesis, analytical characterization and bioactivity of Ag and Cu
nanoparticles embedded in poly-vinyl-methyl-ketone films
Received: 8 March 2005 / Revised: 10 May 2005 / Accepted: 19 May 2005 / Published online: 20 July 2005

Springer-Verlag 2005
Abstract The electrosynthesis of copper and silver core-
shell nanoparticles (NPs) by the sacrificial anode tech-
nique, employing tetraoctylammonium (TOA) salts as
base electrolyte for the first time, is described. These
surfactants were selected because they combine high NP
stabilizing power with useful disinfecting properties. The
resulting colloids were mixed with a solution of an inert
dispersing polymer and used to prepare nanostructured
composite thin films. The morphologies and chemical
compositions of the nanomaterials were characterized
by Transmission Electron Microscopy (TEM) and X-ray
Photoelectron Spectroscopy (XPS). The TEM reveals
that the average core diameter of the metal NPs ranges
between 1.7 and 6.3 nm, as a function of the nature of
the metal and of the electrosynthesis conditions, and
does not change significantly upon inclusion in the
polymer matrix. An appreciable concentration of the
metal is detected on the nanoparticle surface by XPS.
High-resolution XP spectra indicate that both copper
Electronic Supplementary Material Supplementary material is
available for this article at http://dx.doi.org/10.1007/s00216-005-
3334-x
Dedicated to the memory of Wilhelm Fresenius
N. Cioffi (&) Æ N. Ditaranto Æ L. Torsi Æ R. A. Picca
E. De Giglio Æ L. Sabbatini Æ P. G. Zambonin
Dipartimento di Chimica, Università degli Studi di Bari,
via Orabona 4, 70126 Bari, Italy
E-mail: cioffi@chimica.uniba.it
Tel.: +39-80-5442019
Fax: +39-80-5442026
L. Torsi Æ L. Sabbatini Æ P. G. Zambonin
TIRES, Center of Excellence, Università degli Studi di Bari, Italy
L. Novello Æ G. Tantillo
Dipartimento di Sanità e Benessere degli Animali,
Università degli Studi di Bari,
Strada provinciale per Casamassima Km 3, 70010 Bari,
Valenzano, Italy
T. Bleve-Zacheo
Istituto per la Protezione delle Piante, Sezione di Bari,
C.N.R., 165/A, via Amendola, 70126 Bari, Italy
and silver are present at zero oxidation state in all of the
materials (colloids and composite films). This demon-
strates the high efficiency of the surfactant at controlling
the morphology and the chemical composition of the
nanodispersed metal in both the as-synthesized colloid
and in the polymeric dispersion. The nanocoatings are
shown to exert a marked inhibitory effect on the growth
of eukaryote and prokaryote target microrganisms, and
experimental evidence of a synergic disinfecting effect
due to the surfactant and the nanodispersed metal is
provided. On the basis of these stability and bioactivity
results, it is clear that Cu-NPs and Ag-NPs are suitable
for application in disinfecting or antifouling paint and
coating formulations.
Keywords Nanoparticle Æ Copper Æ Silver Æ
Disinfectant Æ Bioactivity Æ XPS Æ TEM
Introduction
Over the last few years, much effort has been directed
into developing new materials that have specific anti-
microbial activities that can be used to fight infections
and to create sterile conditions [1–7]. The antifouling
properties of copper and silver are well known and their
effectiveness at reducing the growth of various micror-
ganisms has been reported [8–11]. Nanotechnology
could become very important in this research field,
providing the tools needed to synthesize copper-con-
taining and silver-containing nanostructured
films—layers embedding metal nanoparticles (Me-
NPs)—showing an enhanced bioactivity.
Surfactant-assisted electrochemical procedures have
been shown to be a powerful tool for preparing stable
NPs composed of a wide range of metals and com-
pounds [12–17]. The most varied and versatile prepara-
tion route appears to be the so-called ‘‘sacrificial anode’’
electrolysis that is usually carried out in the presence of
cationic surfactants such as tetra-alkyl-ammonium salts.
In a seminal paper based on the combined use of

transmission electron and scanning tunnelling micros-
copies, the group of Prof. M. Reetz demonstrated that
these metal NPs possess a core-shell structure in which
the metallic core is stabilized by a monolayer of tetra-
alkyl-ammonium species, and the thickness of this shell
is linearly correlated with the length of the alkyl chains
[18]. Some years later, an X-ray photoelectron spec-
troscopy investigation of the NP surface shed light on
the nature of the anionic species counterbalancing the
positive ammonium charges [19]. In the last decade, the
electrolytic production of nanoparticles and nanocom-
posites containing platinum group elements has been
extensively studied, due to the strong catalytic properties
of these products [12, 19–24]. The electrosynthesis of
copper and silver colloids, on the other hand, has been
the subject of only a few reports [13, 25–27]. In partic-
ular, we have recently studied the electrosynthesis of
copper nanoparticles (Cu-NPs) and proposed their use
in low-cost bioactive nanocomposites spin-deposited on
sterile substrates as thin films [25]. In that paper, it was
shown that Cu-NPs stabilized by biologically-inert tet-
rabutylammonium perchlorate (TBAP) possess biostatic
action against target microorganisms, thanks to the re-
lease of copper ions in the aqueous culture broths. The
TBAP, however, showed only limited stabilizing power
towards NP aggregation and air-oxidation processes.
In this work, we present the electrosynthesis, analyt-
ical characterization and biological properties of newly
synthesized Cu-NPs or Ag-NPs and their related com-
posites. These Me-NPs are stabilized by tetraoctylam-
monium (TOA) salts that show two interesting effects:
first, they guarantee the morphological and chemical
stabilization of metallic clusters; secondly, these surfac-
tants possess significant antimicrobial activity too, as
they belong to the class of disinfectants known as
Quaternary Ammonium Compounds (QACs). Thus,
nanocomposite materials containing TOA-stabilized
NPs are characterized by the synergic action of both
surfactant and metal, which leads to a marked increase
in their efficacy as bioactive coatings.
Experimental
Electrosynthesis of Cu and Ag nanoparticles
The electrosynthesis of Me-NPs was carried out in a
three-electrode cell equipped with copper (or silver) sheet
working electrodes and an Ag/AgNO3 0.1 M in aceto-
nitrile (ACN) reference electrode. The counter electrode
was a platinum sheet. For Ag-NPs preparation, the
base electrolyte was the TOA bromide dissolved at
a concentration of 0.1 M in ACN; Cu-NPs were syn-
thesized in a 0.1 M solution of TOA chloride dissolved in
an ACN/tetrahydrofuran (THF) 1/3 mixture. Two dif-
ferent working electrode potentials (+0.5 and +1.5 V)
were employed for the electrosynthesis of Me-NPs.
The cell was maintained under nitrogen and electro-
chemical syntheses were carried out with an EG & G 263
1913
potentiostat, following procedures that have already
been reported [25]. Tetrabutylammonium perchlorate-
stabilized Cu-NPs used for the comparative XPS char-
acterisation of Fig. 3 were synthesised as reported in [25].
Nanocomposite preparation
Copper and silver nanocomposites (Cu-NPs/PVMK,
Ag-NPs/PVMK) were prepared by mixing the colloid
with a solution of poly-vinyl-methyl-ketone (PVMK) at
a concentration of 25 gL 1 in an ultrasonic bath. The
resulting colloidal mixture could be stored for months
without any significant aggregation and precipitation of
the nanoparticles. The PVMK dispersing matrix was
chosen on the basis of preliminary indications derived
on similar systems [25], demonstrating that this water-
insoluble polymer guarantees high performance in bio-
activity tests.
Copper-polymer nanocomposites were prepared
using Cu-NPs electrosynthesized at an anodic dissolu-
tion potential of +1.5 V, while Ag-NPs prepared at
+0.5 V were employed for silver-polymer nanomateri-
als. The resultant solutions were then spin-coated onto
proper substrates, for biological application or analyti-
cal investigations. It is important to note that nano-
structured films with variable amounts of metal-NPs can
be prepared simply by modifying the mixing ratio of
colloidal and polymeric solutions.
Analytical characterization of the nanomaterials
Morphological characterization of the nanostructured
films was performed by Transmission Electron Micros-
copy (TEM) using 400 mesh copper grids. As-synthe-
sized colloids were simply drop-cast onto grids, while
composites were spin-coated on grids tape-fixed on
aluminum substrates. The TEM analysis was performed
only on unstained samples by means of a Philips 400 T
microscope at 100 kV. The size distribution of the metal
clusters was evaluated manually using more than 500
particles.
Fresh colloidal dispersions and nanocomposites were
deposited onto aluminum sheets in order to perform X-
ray Photoelectron Spectroscopy (XPS) characterization,
using a Leybold LHS10 spectrometer equipped with an
unmonochromatized AlKa source. Survey spectra were
recorded in fixed retarding ratio mode with a retarding
ratio of B=30, while high-resolution regions (C1s, O1s,
N1s; Cu2p and Cl2p for copper-based samples, Ag3d
and Br3d for silver based ones) were acquired in fixed
analyzer transmission mode at a pass energy of 30 eV.
Calibration of the Binding Energy (BE) scale was per-
formed by fixing the C-C component at BE values of
284.8±0.1 eV for colloids, while oxygen and carbon
peaks of the PVMK polymer (BE=532.3±0.1 eV,
BE=285.2±0.1 eV) were used for the nanocomposite
samples.
1914

Nanomaterial bioactivity Since the Cu-NPs electrolysis yield was close to 90% in
both cases, the higher dissolution potential was then
Biological tests were performed on three sets of samples chosen for the optimized preparation of Cu-NPs.
deposited on sterile glass: (a) PVMK films, (b) polymeric In the case of silver, two distinct NP size populations
layers containing TOA salts in the same ratio of nano- were obtained. The application of the higher potential
composites; (c) metal nanostructured films (Cu-NPs/ (+1.5 V) to the anode gave two baseline-resolved size
PVMK, Ag-NPs/PVMK). Escherichia coli and Saccha-
romyces cerevisiae were chosen as target microrganisms.
About 1 mg of the lyophilized organism was added to
10 mL Tryptone Soya Broth (TSB) and then this was
incubated for 24 h at 37 C. Different dilutions (10 1–
10 5) were performed with Maximum Recovery Diluent
(MRD) and were then explored in the biological tests in
order to choose the best experimental conditions. About
1 mL of the chosen dilution was let in contact with the
samples (previously placed in sterile Petri dishes) at
22 C for 4 h. In order to assess the microrganisms’
growth into colonies, 20 mL of a Plate Counter Agar
(PCA) culture medium were poured onto the plates and
incubated for 48 h at 37 C. At the end of this period,
the colony’s growth was estimated by counting the
number of Colony Forming Units per plate (CFU/mL).
The broth dilution employed in the tests was different
for the two types of nanomaterials: 10 1 for Cu-NPs/
PVMK films and 10 5 for Ag-NPs/PVMK films. The
use of highly-concentrated broths in the case of copper
was necessary to better distinguish between the biostatic
action of the metal and that of the surfactant. The choice
of different concentrations accounts for a higher CFU
number on the control (bare Petri) and blank (PVMK
film) plates of the copper-based films with respect to the
silver-based ones.

Results and discussion

Electrosynthesis of Cu and Ag nanoparticles

Tetraoctylammonium salts are perfect stabilizing agents

that assist the electrochemical synthesis of Me-NPs with
nanometer-sized diameters and narrow size dispersions.
The high degree of stabilization of these surfactants is
demonstrated by the TEM micrographs of Fig. 1,
showing both copper and silver nanoparticles prepared
under different experimental conditions.
In the simple potentiostatic process used to prepare
the NPs, the working electrode potential is the main
electrochemical parameter, which is tuned to optimize
the NPs morphology, since it affects the rate of sacrificial
anode dissolution and the current density, and thus the
particle nucleation and growth rates [28, 29]. Two ano-
dic dissolution potentials were explored for each metal:
Fig. 1 TEM micrographs and size distribution histograms of
+0.5 and +1.5 V. electrosynthesised Me-NPs. The metal in the colloidal dispersion,
In the case of copper, the average NP diameter the surfactant employed and the working electrode potential
showed no appreciable dependence on the applied po- applied are reported on the left hand side of each panel. In each
tential and was close to 6 nm in both cases. The appli- histogram, the mean NP core diameter (d) is reported in the inset,
along with the relevant standard deviation. Electronic Supplemen-
cation of the lower potential, however, often resulted in tary Material available: Figure 1S: TEM picture of Ag-NPs
a broader NP diameter dispersion and in a less regular (electrosynthesized at +1.5 V) with larger photograph size and
morphology compared to that obtained at +1.5 V. enhanced resolution

histograms centered at 1.7±0.6 and 5.7±0.6 nm, while
for the lower potential, the colloid was less size-dis-
persed, the two populations being closer and centered at
3.8±1.0 and 5.4±1.7 nm, respectively. Moreover, dis-
tinct from the results seen for copper, the electrolysis
yield was appreciably dependent on the anodic potential;
this parameter was 85% at the lower potential and
70% at +1.5 V. On the basis of such considerations,
the lower dissolution potential was chosen for the opti-
mized preparation of the silver nanoparticles.
Finally, it should be noted that to meet the necessary
solubility requirements for ionic metal species, chloride
and bromide counterions of the alkylammonium stabi-
lizer were used to prepare the copper and silver colloids
respectively.
Analytical characterization of the nanomaterials
Figure 2 reports the TEM characterization of the
nanocomposite films. A comparison of Figs. 1 and 2
demonstrates that the pristine morphology of TOA-
stabilized Cu-NPs is almost completely preserved when
they are dispersed in PVMK to form nanocomposite
thin films (see ‘‘Experimental’’ section for details). In
particular, the mean diameter of Cu-NPs embedded in
the polymer is identical (6.1±1.6 nm) to that of the
colloidal sample. The size distribution of supported Ag-
NPs differs slightly from that of the pristine colloid, and
is apparently distributed as a tailed single Gaussian
peak, centered at 6.7±1.9 nm. The disappearance of the
Fig. 2 TEM micrographs and size distribution histograms of Me-
NPs dispersed in PVMK nanostructured films. The mean NP core
diameter (d) is reported in the inset, along with the relevant
standard deviation
1915
smaller Ag-NP population can be attributed to Ostwald
ripening effects that occur in the mixed colloid/polymer
solution employed in the spin-coating deposition of the
nanocomposites.
XPS was employed in order to study the surface
elemental compositions of the surfaces of the nano-
composite coatings employed in the biological experi-
ments. The atomic percentages reported in Table 1
indicate, as expected for an oxygenated polymer matrix
modified with low amounts of Me-NPs, that carbon and
oxygen are the most abundant elements. The elemental
percentages, and the C/O ratio (close to 10), however,
strongly differ from those expected on the basis of the
bare polymer repetition unit: for the standard polymer,
the percentages of carbon and oxygen are 75 and 25%
respectively, while the C/O ratio is 3.
The results in Table 1 can be explained by consider-
ing the presence of the TOA surfactant in the nano-
composites, which is the main source of surface carbon.
As a matter of fact, based on the TOA stoichiometry,
the presence of nitrogen (2%) suggests that the alkyl
ammonium chains provide the main contribution
(64%) to the percentage of carbon. This clearly lowers
all of the other elemental percentages, including the
polymeric contribution to the carbon and oxygen sur-
face concentrations. Despite the high surface carbon
concentration, atomic percentages of 1%(weight/weight)
were measured for the metals nanodispersed in both
composites.
The detailed XPS analysis of the Cu2p3/2 and Ag3d
regions, related both to the colloidal samples and to the
nanocomposite films, has provided useful information
on the chemical speciation of Me-NPs before and after
inclusion in the polymeric matrix.
The Cu2p3/2 spectra of copper colloids and of Cu-
NPs/PVMK nanocomposites are reported in Fig. 3. It is
worth noting that in the case of TOAC-stabilized
nanomaterials (left panels), both spectra show a single
signal falling at BE=933.1±0.2 eV, ascribed to nan-
odispersed copper at zero oxidation state [30, 31]. On the
other hand, spectra recorded on TBAP-stabilized
nanomaterials (right panels) show the presence of a
Cu(II) species, in addition to metallic copper, which is
particularly evident in the nanocomposite film. This
oxidized copper is responsible for both an intense pho-
toelectron peak falling at BE=934.0±0.2 eV and a clear
shake-up feature, fitted by two peaks falling at
BE=941.2±0.2 and BE=943.7±0.2 eV.
Table 1 XPS results for the surface elemental compositions of the
surfaces of the nanocomposite films
C O N Cl Br (%) Cu (%) Ag (%)
(%) (%) (%) (%)
Cu-NPs–PVMK 87.2 8.8 2.1 2.1 – 0.4 –
Ag-NPs–PVMK 89.5 7.1 1.7 – 1.4 – 0.3
The error in the atomic percentages is 0.2% for copper and silver,
0.5% for all the other elements
1916
Fig. 3 Cu2p3/2 XP high
resolution spectra: TOAC-
stabilized Cu nanoparticles (top
left panel) and relevant Cu-
PVMK nanocomposite (bottom
left panel); TBAP-stabilized Cu
nanoparticles (Cu-NPs*, top
right panel) and relevant
nanocomposite (Cu-PVMK*,
bottom right panel)
Ag3d spectra of a silver colloid and an Ag nano-
structured film are presented in the two panels of Fig. 4.
In both cases, the signal can be fitted by a single pho-
toelectron doublet, with the higher component falling at
BE values of 368.3±0.2 eV, which can be assigned to
elemental silver [32].
Experimental evidences derived from the TEM and
XPS characterizations demonstrate that the inclusion of
TOA-stabilized copper or silver NPs in the PVMK
matrix does not significantly affect either the morphol-
ogy or the chemical speciation of the nanoparticles. This
is quite a different result to that observed for tetra-butyl-
ammonium salts, which produced much less stabiliza-
tion. As a matter of fact, the latter species proved to be
unable to prevent a certain amount of aggregation when
the NPs were mixed with the dispersing polymer, or to
stop the complete conversion of nanodispersed Me0 into
metal oxides upon prolonged air-exposure [33] of the
Fig. 4 Ag3d XP high-resolution spectra of Ag nanoparticles (top
panel) and of Ag-PVMK nanocomposite (bottom panel)
nanocomposite. These findings can be interpreted as
evidence and a chain length-dependent stabilizing effect
by the cationic surfactants employed in the present
study. Evidently, long-chain N(C8H15)+ 4 ions preserve
the structure of the pristine NPs, without inhibiting their
catalytic [34] or biological (vide infra) activity.
Nanomaterial bioactivity
The antimicrobial properties of copper- and silver-con-
taining nanomaterials were evaluated on two target
microorganisms: Escherichia coli and Saccharomyces
cerevisiae. Culture broths at suitable dilutions were left
in contact for a limited time (only 4 h) with different
samples to discriminate the biocidal/biostatic effects of
the polymeric matrix, surfactant and nanodispersed
metals. After the contact time, and the PCA incubation
step (see the ‘‘Experimental’’ section for details), the
residual microrganism growth was quantified by count-
ing the number of CFU. The results are reported in
Tables 2 and 3, respectively, for E. coli and S. cerevisiae.
Blank experiments revealed that PVMK does not exert
any biostatic action, whereas TOA halides produce a
strong growth inhibition effect, causing a significant
decrease in the cellular growth.
Table 2 Number of colony forming units (CFU) of E. coli exposed
to different samples
Sample Colony forming units
Control >3·106
PVMK >3·106
TOAC/PVMK 1250
CuNPs/PVMK 21
Control >2400
PVMK >2400
TOAB/PVMK 56
AgNPs/PVMK 0

Table 3 Number of colony forming units (CFU) of S. cerevisiae
exposed to different samples
Sample Colony forming units
Control >3·106
PVMK >3·106
TOAC/PVMK 1100
CuNPs/PVMK 0 greatly acknowledged for useful discussions. Work carried out with
Control >4800
PVMK >4800
TOAB/PVMK 349
AgNPs/PVMK 0
This is a reasonable result, since TOA salts are QAC
(Quaternary Ammonium Compounds) disinfectants.
Interestingly, nanocomposites containing copper or sil-
ver nanoparticles are characterized by an increased
biological activity against both eukaryotes (S. cerevisiae)
and prokaryotes (E. coli), probably due to the simulta-
neous action of the TOA salts and the embedded metal
species.
In a previous paper, on similar copper-based mate-
rials stabilized by a biologically-inactive surfactant, it
was also demonstrated that the nanocomposites produce
a controlled release of copper ions into culture broths
[25]. Moreover, a higher loading of the Cu-NPs was
correlated with a higher concentration of released ions
and increased inhibition of colony growth. Preliminary
results on the materials employed in the present study
confirm these release properties, and support further
studies that take into consideration the influence of air-
storage on the nanomaterials’ bioactivity performances.
Conclusions
Sacrificial-anode electrochemical synthesis of Cu-NPs
and Ag-NPs in the presence of TOA salts allowed us to
prepare copper- and silver-containing coatings simply by
mixing the metal colloid with a polymer dispersing ma-
trix. TEM and XPS analyses demonstrate that the
surfactants employed are capable of stabilizing the Me-
NPs from both the morphological and the chemical
point of view, due to the formation of a protective or-
ganic shell.
Despite the stabilizing effect of TOA, biological tests
show that the nanomaterials proposed in this study also
exert a marked inhibitory effect on the growth of target
microorganisms (E. coli and S. cerevisiae) when they are
employed at very high concentration levels. The peculiar
properties of such nanocomposites are attributed to the
synergic effect of the biocide metal (copper or silver) and
the TOA salts. A comparison between these data and
previous results obtained with shorter chain tetrabuty-
lammonium salts suggests that the stabilizer chain length
is a key parameter in the control of NP chemistry and
stability, which also affects bioactivity. Extension of the
study to other surfactants, like industrially-employed
1917
quaternary ammonium disinfectants, and to pathogen
microorganisms, is in progress.
Acknowledgements Miss C. Caso, Mr. S. Giacummo, and Mr. A.
Tambone are gratefully thanked for their skilled assistance during
biological experiments (C.C.) and XPS analyses (S.G., A.T.).
Professors F. Palmisano and E. Traversa and Dr. L. Ghibelli are
the financial support of Università degli Studi di Bari, and
MIUR—PRIN 2004—Contract No. 2004034021_001.
References
1. Pratten J, Nazhat SN, Blaker JJ, Boccaccini AR (2004) J
Biomater Appl 19:47–57
2. Chohan ZH, Khan KM, Supuran CT (2004) Appl Organomet
Chem 18:305–310
3. Yang MR, Chen KS, Tsai JC, Tseng CC, Lin SF (2002) Mater
Sci Eng C 30:167–173
4. Kasuga T, Hume H, Abe Y (1997) J Am Ceram Soc 80:777–780
5. Kasuga T, Nogami M, Abe Y (1999) J Am Ceram Soc 82:765–
767
6. Newnham RE (1999) Proceedings of the 6th European Ceramic
Society. IOM Communications Ltd, London, pp 3–10
7. Terry RN (2004) US Pat Appl Publ 200411655-6716895
8. Camp DR, Zawacky SR (2004) US Pat Appl Publ 2004197322
9. Chohan ZH, Khan KM, Supuran CT (2004) Appl Organomet
Chem 18:305–310
10. Yamamori N (2004) Jpn Kokai Tokkyo Koho JP 2004002819
11. Acharya V, Prabha CR, Narayanamurthy C (2004) Biomate-
rials 25:4555–4562
12. Reetz MT, Helbig W (1994) J Am Chem Soc 116:7401–7402
13. ten Kortenaar MV, Kolar ZI, Tichelaar FD (1999) J Phys
Chem B 103:2054–2060
14. Chang SS, Shih CW, Chen CD, Lai WC, Chris Wang CR
(1999) Langmuir 15:701–709
15. Mohamed MB, Wang ZL, El-Sayed MA (1999) J Phys Chem A
103:10255–10259
16. Yu YY, Chang SS, Lee CL, Chris Wang CR (1997) J Phys
Chem B 101:6661–6664
17. Kariv-Miller E, Christian PD, Svetličić V (1995) Langmuir
11:1817–1821
18. Reetz MT, Helbig W, Quaiser SA, Stimming U, Breuer N,
Vogel R (1995) Science 267:367–369
19. Cioffi N, Torsi L, Losito I, Sabbatini L, Zambonin PG, Bleve-
Zacheo T (2001) Electrochim Acta 46:4205–4211
20. Reetz MT, Breinbauer R, Wanninger K (1996) Tetrahedron
Lett 37:4499–4502
21. Reetz MT, Quaiser SA, Breibauer R, Tesche B (1995) Angew
Chem Int Edit 23/24:2728–2730
22. Reetz MT, Quaiser SA (1995) Angew Chem Int Edit 34:2240–
2241
23. Calò V, Nacci A, Monopoli A, Fornaro A, Sabbatini L, Cioffi
N, Ditaranto N (2004) Organometallics 23:5154–5158
24. Faticanti M, Cioffi N, De Rossi S, Ditaranto N, Porta P,
Sabbatini L, Bleve-Zacheo T (2005) Appl Catal B–Environ
60:75–84
25. Cioffi N, Torsi L, Ditaranto N, Sabbatini L, Zambonin PG,
Tantillo G, Ghibelli L, D’Alessio M, Bleve-Zacheo T, Traversa
E (2004) Appl Phys Lett 85:2417–2419
26. Rodrı̀guez-Sànchez L, Blanco MC, Lòpez-Quintela MA (2000)
J Phys Chem B 104:9683–9688
27. Dierstein A, Natter H, Meyer F, Stephan HO, Kropf C,
Hempelmann R (2001) Scripta Materialia 44:2209–2212
28. Southampton Electrochemistry Group (1990) In: Instrumental
methods in electrochemistry. Ellis Horwood, Chichester, UK
29. Penner RM (2001) In: Hodes G (ed) Electrochemistry of
nanomaterials. Wiley-VCH, Weinheim
30. Jirka I (1990) Surf Sci 232:307–315
1918

31. Wu Y, Garfunkel E, Madey TE (1996) J Vac Sci Technol A 33. Ditaranto N (2002) Graduate Thesis. University of Bari, Italy
14:1662–1667 34. Reetz MT, Breinbauer R, Wedemann P, Ginger P (1998) Tet-
32. Perkin-Elmer (1992) Handbook of X-ray photoelectron spec- rahedron 54:1233–1240
troscopy. Perkin-Elmer, Ramsey, MN, USA