Applied Surface Science 280 (2013) 610–618
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Applied Surface Science
jou rn al h omepa g e: www.elsevier.com/locate/apsusc
Novel microwave-synthesis of Cu nanoparticles in the absence of any
stabilizing agent and their antibacterial and antistatic applications
Anna Maria Raspolli Galletti
a,∗
, Claudia Antonetti
a
, Mirko Marracci
b
,
Fabio Piccinelli
c
, Bernardo Tellini
b
a
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy
b
Dipartimento di Ingegneria dell’Energia, dei Sistemi, del Territorio e delle, Costruzioni, Università di Pisa, via Diotisalvi 2, 56125 Pisa, Italy
c
Laboratorio di Chimica dello Stato Solido, DB, Università di Verona, and INSTM, UdR Verona, Strada le Grazie 15, 37134 Verona, Italy
a r t i c l e i n f o
Article history:
Received 12 March 2013
Received in revised form 6 May 2013
Accepted 10 May 2013
Available online 20 May 2013
Keywords:
Copper
Nanoparticles
Microwave
Antibacterial activity
Antistatic behavior
a b s t r a c t
For the first time, copper nanoparticles were synthesized under microwave (MW) irradiation in the
absence of any stabilizing agent. A 2-step synthetic approach was adopted working in basic ethanol
solution and then ascorbic acid was added as a reducing reagent in the second step. The obtained cop-
per nanoparticles were characterized by UV–vis spectroscopy, XRPD and TEM analysis. UV–vis spectra
show an absorption peak at about 580–590 nm, typical of the plasma resonance of copper nanoparticles
and XRPD analysis reveals that the complete reduction to metallic copper was reached at the end of
the second step. Average sizes in the range 7–15 nm were ascertained through TEM microscopy. These
copper nanoparticles are suitable for antibacterial and antistatic applications. The bactericidal effect was
investigated in relation to the diameter of inhibition zone in disk diffusion tests on calf crust leather
sample and an interesting antibacterial activity was verified against both Gram positive and Gram neg-
ative bacteria (Staphylococcus aureus, Escherichia coli, Bacillus subtilis and Candida albicans). Moreover,
this treated leather showed encouraging antistatic behavior: in particular, equivalent circuital parame-
ters were estimated via an impedance spectroscopy technique to have a first evaluation of the charge
dissipation activity by volume conduction.
© 2013 Elsevier B.V. All rights reserved.
1. Introduction
In the recent years, great interest has been devoted to the
synthesis of metal nanoparticles (NPs) in order to explore their
special properties and applications. Differently from expensive
noble metals, copper nanoparticles represent an ideal compro-
mise between their interesting properties and cost, thus becoming
industrially important materials. In fact, they are widely stud-
ied for applications in different fields, such as magnetic storage
media, electronics, solar energy transformations, catalysis and, in
addition, they have shown promising antimicrobial effects [1–10].
During the past few years, different methods have been developed
for the preparation of copper nanoparticles, such as hydrothermal
and solvothermal methods, chemical reduction, electrolytic syn-
thesis, sonochemical methods, sol–gel preparations, vacuum vapor
∗
Corresponding author. Tel.: +39 050 2219290; fax: +39 050 2219260.
E-mail addresses: roxy@dcci.unipi.it (A.M. Raspolli Galletti),
claudia.antonetti@ns.dcci.unipi.it (C. Antonetti), mirko.marracci@ing.unipi.it
(M. Marracci), fabio.piccinelli@univr.it (F. Piccinelli), bernardo.tellini@ing.unipi.it
(B. Tellini).
deposition and so forth [1,7,8,10–38]. However, most of these
methods for the synthesis of Cu NPs are complicated, require
specific and expensive equipments, involve no environmental
sustainable reagents and produce only small amounts of nanomate-
rials. One of the most recent interesting attempts for the synthesis
of stable dispersions of nanosized copper particles is reported in
the paper of Wu et al. where copper NPs were synthesized with an
average size lower than 2 nm working in aqueous medium in the
presence of ascorbic acid as a reducing and stabilizing agent [39]. In
this procedure a relatively high ascorbic acid/Cu molar ratio (from 2
to 5 mol/mol) and traditional heating were employed. In particular,
when the authors studied this reaction using aqueous solutions of
0.2 M CuCl
2
·2H
2
O and 1.0 M ascorbic acid, the characteristic surface
plasmon peak of copper nanoparticles could be observed after 2 h
of reaction time and their synthesis was completed only after 14 h,
a considerable long reaction time. On the other hand, microwave
irradiation has been largely employed for the sustainable prepara-
tion of nanoparticles of different metals, offering more promising
results compared with the thermal heating. The main advantages of
microwave-assisted reactions can be summarized in the increase
of the rate of the reaction by one to two orders of magnitude, in
the rapid initial heating which can lead to save energy and often
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http://dx.doi.org/10.1016/j.apsusc.2013.05.035