Technical note

Magnetic nanohydrometallurgy: A promising nanotechnological approach for metal

production and recovery using functionalized superparamagnetic nanoparticles
Ulisses Condomitti, Andre Zuin, Alceu T. Silveira, Koiti Araki, Henrique E. Toma
Instituto de Quimica, Universidade de Sao Paulo, So Paulo, SP, Brazil
a b s t r a c t a r t i c l e i n f o
Article history:
Received 8 May 2012
Received in revised form 1 June 2012
Accepted 7 June 2012
Available online 16 June 2012
Keywords:
Magnetic nanohydrometallurgy
Superparamagnetic nanoparticles
Copper electrodeposition
We report on a new, promising nanotechnological approach for hydrometallurgy based on recyclable, chem-
ically functionalized superparamagnetic nanoparticles. In this process, the metal ions (e.g. Cu
2+
) are cap-
tured by the nanoparticles and conned at the electrode surface by means of an external magnet. Due to
the pre-concentration effect the electrodeposition process is greatly improved, yielding the pure metal in a
much shorter time in comparison with the conventional electrodeposition process. After the electrolysis,
the magnetic nanoparticles are ready to return to the process. The proposed strategy can advantageously
be incorporated in hydrometallurgy, reducing the number of steps associated with complexation, organic sol-
vent extraction, metal release and diffusional electroprocessing, leading to a more sustainable technology.
2012 Elsevier B.V. All rights reserved.
1. Introduction
In the past two decades the global production of strategic metals
such as copper has trended away from pyrometallurgical processes,
in part because of the rich ores depletion and global warming con-
cerns. New initiatives have been directed by legislation towards the
supposedly greener hydrometallurgical technologies. In particular,
heap leaching of oxide copper ores and cathode copper recovery by
solvent extraction (SX) and electrowinning (EW) is well established
as a primary low-cost hydrometallurgical copper recovery method.
Presently, more than 20%of total world production of copper is achieved
through the solvent extraction route (Rotuska and Chmielewski, 2008).
The process involves the lixiviation of the metal ions from the ores
after their treatment with acids or microorganisms (Petersen, 2010),
followed by their complexation with a selective organic reagent, and
by a sequence of extraction steps using organic solvents (Gouvea
and Morais, 2010; Habashi, 2009; Scott et al., 1997; Veit et al., 2006).
The extracted metal complexes are decomposed with acids and trans-
ferred into the aqueous phase. After adjusting the conditions, the
metal ions are deposited electrochemically. The overall process in-
volves a large number of steps. Nowadays, in addition to the metallif-
erous mineral industry, SX-EWhydrometallurgy has also been used in
the recovery of copper from electric/electronic wastes, including the
printed circuits boards (Dudek and Fedkiw, 1999; Dutra et al., 2008;
Fornari and Abbruzzese, 1999; Lemos et al., 2006; Panda and Das,
2001). Considering the increasing world demand of copper, any im-
provement in the production process becomes highly relevant for
the economy and sustainability.
It has already been mentioned that hydrometallurgy has typically
an interdisciplinary nature (Han, 2003). Along this line, in this work,
we are introducing functionalized superparamagnetic nanoparticles in
the hydrometallurgy process, not only for capturing and transporting
metal ions, but also to promote their connement at the electrode sur-
face, and to perform their direct electrochemical deposition, in a single
step. The economy of process, chemicals, energy and solvents are im-
portant green features of this process, here denoted as magnetic
nanohydrometallurgy.
We are employing nanoparticles composed by magnetite. They are
exceptional magnetic carriers exhibiting a very large magnetization re-
sponse as a consequence of the predominance of single magnetic do-
mains, in addition to a very large collective area to interact with the
chemical species in solution. Many interesting bioelectroanalytical and
catalytical applications have already been developed using magnetically
modied enzymes and substrates (Castilho et al., 2011; Hirsch et al.,
2000; Jeong et al., 2007; Katz et al., 2005; Latham and Williams, 2008;
Laurent et al., 2008; Liebana et al., 2009; Netto et al., 2011). By using an
external commercial miniature magnet (e.g. Nd
2
Fe
14
B, 1 cm, 11 kOe,
fromMagTek), the superparamagnetic nanoparticles can be readily con-
centrated at the electrode surface. Normally, by using directly the mag-
netic nanoparticles in electrochemistry, the observed result would be
the blockage of the electrode, since the electrochemical response
would be precluded by the local lmformed by the nanoparticles. How-
ever, we have shown that when the superparamagnetic nanoparticles
incorporate electroactive species, the lms become rather conducting,
exhibiting, in contrast, an enhanced electrochemical response due to
the pre-concentration effect (Condomitti et al., 2011a,b,c). This is one
of the most important aspects associated with the present work.
As a proof of concept, we employed the nanomagnetic hydromet-
allurgy process for the capture and electrodeposition of copper from
Hydrometallurgy 125126 (2012) 148151
Corresponding author. Tel.: +55 11 3091 3887.
E-mail address: henetoma@iq.usp.br (H.E. Toma).
0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2012.06.005
Contents lists available at SciVerse ScienceDirect
Hydrometallurgy
j our nal homepage: www. el sevi er . com/ l ocat e/ hydr omet
aqueous solution. The quantitative recovery of the metal element
was conrmed by parallel energy dispersive X-ray uorescence mea-
surements (EDXRF) from the copper solutions and from the super-
paramagnetic nanoparticles collected at the electrode surface.
2. Methodology
The superparamagnetic nanoparticles of magnetite were obtained
by the aqueous co-precipitation method, and coated with SiO
2
(Kim
et al., 2003; Sen and Bruce, 2005; Yamaura et al., 2004). After this, the
nanoparticles were functionalized with ethylenediaminepropylsilane
or EAPS (PIERCE). Typically, 500 mg sample of silica coated magnetic
nanoparticles were dispersed in 50 mL of tetrahydrofuran and after
5 min of sonication, 500 L of EAPS and 1 mL of water were added.
The system was stirred for 1 day and the material was magnetically
separated and dried under vacuum. The solvent was recycled. This
chemical coating was specially employed because of the well known
facility of ethylenediamine to bind copper(II) ions, forming stable
chelate complexes, as shown in Fig. 1. Suchfunctionalized nanoparticles
were here denoted MagNP/EAPS.
Their superparamagnetic behaviour was conrmed by magnetiza-
tion experiments and related eld cooling (FC) and zero eld cooling
(ZFC) measurements using a Cryogenic Sx600 superconducting quan-
tum interference device (SQUID) based magnetometer. Typically, no
hysteresis was observed above 115 K, corresponding to the blocking
temperature. At room temperature, a saturation magnetization of
49 emu g
1
was determined from the extrapolation to very high
magnetic elds. The starting superparamagnetic nanoparticles were
also monitored by dynamic light scattering and SEM, exhibiting an
average size distribution of 20 nm. The modied nanoparticles were
stored dry, and the solutions were always freshly prepared by
redispersing the solids in water containing the analytes, using an
ultrasonic bath for 30 min. In the dry form, the functionalized
nanoparticles are mainly in the form of aggregates. After mild sonica-
tion, stable colloidal solutions of nanoparticle clusters of about
80100 nm can be obtained. Such colloidal solutions are suited for
chemical purposes, since they respond more rapidly to the applied
magnetic elds, facilitating the transport and deposition of the nano-
particle clusters.
For academic purposes, the electrochemical experiments were
carried out using an AUTOLAB PGSTAT30 potentiostat/galvanostat,
with a rectangular electrochemical cell (Fig. 2) containing, in addition to
a platinum wire counter electrode, a Luggin capillary with the Ag/AgCl
(1 mol dm
3
KCl) reference electrode and a 3 mm diameter gold
disc working electrode. This electrode was placed in contact with the
cell window, using a convenient experimental setup for the application
of an external magnetic eld as shown in Fig. 2. Then, a precise amount
(e.g. 5 mg) of nanoparticles was suspended into 20 mL of 0.1 mol dm
3
KNO
3
solution containing 2.010
3
mol dm
3
of Cu
2+
ions for 5 min
and transferred to the electrochemical cell. By applying an external
magnetic eld at the back side of the gold working electrode, the
superparamagnetic nanoparticles were attracted, forming a visible
coating on the electrode surface. This process was essentially quantita-
tive, since after the transfer there was no evidence of nanoparticles in
solution.
Energy dispersive X-ray uorescence measurements, EDXRF, were
carried out using an EDX720 instrument from Shimadzu, equipped
with a X-ray tube with Rh target and a Si(Li) detector, working at
515 kV.
3. Results and discussion
The superparamagnetic nanoparticles containing the electroactive
species forma redox conducting layer, allowing efcient electrontransfer
to the electrode, as shown by the square wave voltammograms in Fig. 2.
The conditions employed were frequency=20 Hz, amplitude=50 mV,
and E
step
=5 mV. There is a sharp enhancement of the signals at 0.3 V,
due to the high local concentration of the Cu
2+
ions. The intensities
followed a linear with respect to the scan rates. The observed
voltammograms exhibited a prole coherent with a diffusion con-
trolled process for a nanoparticle lm thicker than the diffusion length
of the electroactive species. A similar behaviour has also been observed
for the modied electrodes coated with a layer of magnetic, or den-
drimeric nanoparticles encompassing a large number of ferrocenyl
groups, at the external surface (Qiu et al., 2009; Wang et al., 2009).
The deposition of copper at the electrode was conrmed by magneti-
cally removing the particles from the electrode, and scanning the
potential in the anodic direction, as in a typical stripping analysis
Fig. 2. Square wave voltammograms (150 mV s
1
) of MagNP/EAPS (a) magnetically
conned at the gold disc electrode after their interaction with Cu
2+
ions (2.0
10
3
mol dm
3
) and (b) the corresponding reverse stripping analysis, conrming
the electrodeposition of the metal.
Fig. 1. Representation of MagNP/EAPS interacting with copper(II) ions.
149 U. Condomitti et al. / Hydrometallurgy 125126 (2012) 148151
(Fig. 2B). The observed peak at 0.5 V reects the presence of copper
metal at the electrode surface.
For comparison purposes, the superparamagnetic nanoparticles
containing copper(II) ions were removed from the solution, and the
dry powder analysed using EDXRF, as shown in Fig. 3. Afterwards
they were transferred to the electrochemical cell containing the
supporting electrolyte solution, and the electrolysis was performed
under magnetically conned conditions. After the electrolysis, the
EDXRF analysis of the gold electrode exhibited the characteristic signals
of the copper metal deposited on the surface (Fig. 3), while the initial
copper content from the nanoparticles practically disappeared, cor-
roborating its complete transference fromthe magnetic nanoparticles.
In addition, the agreement between the copper content estimated
from the electroanalytical data and EDXRF was also better than 95%.
3.1. Simulating the hydrometallurgy process in the laboratory
Ina typical laboratory experiment we employed a more concentrated
copper solution, as illustrated in Fig. 4, starting from 200 mL of
2.010
2
mol dm
3
Cu
2+
and treating with 700 mg of MagNP/EAPS,
under stirring, at pH 7. After 10 min the nanoparticles were conned at
the electrode surface with a magnet and the amount of copper in solu-
tion was probed by EDXRF. The amount of MagNP/EAPS was just enough
to form a compact magnetic coating on the copper electrode (12 cm
2
).
The initial amounts of copper in solution were in large excess in relation
to the magnetic nanoparticles. In this way the MagNP/EAPS became
rapidly saturated with copper(II) ions (encompassing about 8% from
the global mass), and were magnetically conned at the electrode in
order to performthe metal electrodeposition. The electrodes were con-
nectedto a source power, and1.2 Vpotential and0.5 Acurrent were ap-
plied for about 3 min (Fig. 4a). According to the voltammograms shown
in Fig. 2, the electrochemical process involved is rather fast and all the
conned metal ions are deposited in a single step, as in a reverse
stripping analysis. After this step, the nanoparticles were released
again from the electrodes, and allowed to interact with the remaining
copper(II) ions in solution. The process is also rather fast and the con-
nement can be repeated several times. The process was carefully mon-
itored after each step by EDXRF (Fig. 4c). We have shown that it is
essentially quantitative, and can proceed, if necessary, up to the com-
plete depletion of copper ions from the solution, as shown in Fig. 4b.
Comparatively, under identical conditions, electrodeposition proceeds
very slowly even under stirring, because of the large volume involved.
On the other hand, in typical copper hydrometallurgy plants the elec-
trodeposition times are measured in days, using extremely concentrat-
ed solutions of copper(II) ions and very large electrodes. Therefore, the
great advantages of our process are associated with the fact that the
nanoparticles are very effective carriers and good electrochemical
mediators. In addition, they can be magnetically manipulated and
recycled, being effective even at highly diluted solutions, where con-
ventional hydrometallurgy is no longer feasible.
These experiments were here reported as a proof of concept. Our
current research is focusing on the process optimization, pursuing
Fig. 4. Starting Cu
2+
solution (2.010
2
mol dm
3
) with the MagNP/EAPS magnetically
conned at the copper electrode at the bottom (a), and after 7 successive capture/
electrolytical cycles (b), as monitored by EDXRF, (c) showing the gradual decay (ag)
and the depletion (h) of the metal ions from the solution.
Fig. 3. EDXRF analysis of copper(II) containing MagNP/EAPS, after removing from the
electrolyte solutions (top) and of the gold electrode surface (bottom) before (a) and
after performing the magnetic conned electrolysis (b).
150 U. Condomitti et al. / Hydrometallurgy 125126 (2012) 148151
new functional groups for many different metals, and a better cell
design.
4. Conclusions
Functionalized superparamagnetic nanoparticles can be employed
for the capture, transport and electrodeposition of copper fromaqueous
solution, leading to a strong enhancement of the electrochemical sig-
nals due the magnetic connement at the electrode surface. Based on
their versatile performance, a promising alternative approach for the
conventional hydrometallurgy process can be devised, allowing metal
production under competitive and sustainable conditions provided by
the possibility of recovering and recycling the superparamagnetic
nanoparticles. Thanks to the pre-concentration effect, another impor-
tant application will be the commercial exploitation of diluted solu-
tions, and the selective metal removal for environmental remediation
purposes.
Acknowledgements
The nancial support fromFAPESP, CNPq and PETROBRAS is grate-
fully acknowledged.
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