Russian Chemical Bulletin, International Edition, Vol. 66, No.11, pp. 2035—2043, November, 2017 2035
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2035—2043, November, 2017.
10665285/17/66112035 © 2017 Springer Science+Business Media, Inc.
Mediated electrochemical synthesis of copper nanoparticles in solution
V. A. Kokorekin,
A. V. Gamayunova,
V. V. Yanilkin,
and V. A. Petrosyan
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Email: firstname.lastname@example.org
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences,
8 ul. Arbuzova, 420088 Kazan, Russian Federation.
Environmentally friendly mediated electrochemical synthesis of copper nanoparticles in
the solution using a copper anode as a source of copper ions has been realized for the first
time. It is shown that at the potential of the redox pair MV
able to mediate a reduction of Cu
ions in 60% aqueous DMF/0.1 M Bu
nanoparticles build large aggregates (200—250 nm) in the absence of a stabilizer. The use of
polyvinylpyrrolidone as a stabilizer makes it possible to obtain smaller copper nanoparticles
(20—50 nm) of spherical and oval shape and to characterize them by physicochemical methods.
Key words: electrochemical reduction, nanoparticles, copper, mediator, methylviologen.
An interest to metal nanoparticles (MNPs) is due to
their unusual properties, which are actively studied in
chemistry, medicine, electronics, and other important
fields of science and technology. The main route of the
MNPs synthesis is chemical reduction of ions (com
plexes) of metals in the bulk of solution.
At the same time, more attention should be paid to
the ecologically attractive electrochemical synthesis of
where electric current replaces chemical reduc
ing agents, as a rule, unrecyclable. Since synthesized
MNPs can be deposited on the surface of the working
electrode, it becomes necessary to transfer these particles
into the bulk of the solution. To a certain extent, this
problem can be solved by combining the shortterm elec
trosynthesis of MNPs with the electrode sonication
) or by realizing
electrosynthesis in a presence of salts of surfactant
tetraalkylammonium or phosphonium cations, which pre
vent the precipitation of MNPs.
Recently, a new efficient approach to the electrochem
ical synthesis of MNPs, based on the use of various red
oxmediating systems, has been proposed.
case, the mediator (and not the metal ion) undergoes
reduction at the cathode, afterwards, the reduced form of
mediator diffuses into solution and reduces the metal ion
(complex) with the formation of MNPs already in the
bulk of the solution (Scheme 1). Thus, the deposition of
metal on the electrode is almost completely eliminated.
The efficiency of this method was demonstrated using
as an example of the electrosynthesis of Pd,
NPs. Undoubted interest is the de
velopment of methods for the mediated electrosynthesis
of nanoparticles of other metals. Our attention was at
tracted to the copper nanoparticles (CuNP), which pos
sess a wide range of practically useful properties (high
properties, the possibility of
using in the glucose level sensors,
etc.). The results of
the previously undescribed electrochemical synthesis of
uNPs using methylviologen (MV
) as a redox media
tor are presented in this paper.
Methods of cyclic voltammetry (CV), microelectrolysis,
preparative electrolysis, UVVis spectroscopy, Xray powder
diffraction (XRD), scanning and transmission electron micro
scopy (SEM and TEM) were used in this work.
Cyclic voltammograms (CV) were recorded in a thermo
C) cell using an Elins P30JM potentiostate (Russia)
(without IR compensation) at a potential scan rate of
= 0.1 V s
(Tables 1 and 2, experiments 1, 2, 6, 7). The working electrodes
Cathode: m Med
+ n ze
Solution: m Med
+ n M
+ n M
oxidized and reduced forms of the
redox mediator, respectively; M
reduced forms of the metals, respectively.