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Journal of Electroanalytical Chemistry 658 (2011) 18–24

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Journal of Electroanalytical Chemistry
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Electrodeposition of Co, Sm and SmCo from a Deep Eutectic Solvent
E. Gómez a,⇑, P. Cojocaru b, L. Magagnin b, E. Valles a

Departament de Química Fısica and Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, 08028 Barcelona, Spain
Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘‘Giulio Natta’’, Politecnico di Milano, 20131 Milano, Italy

a r t i c l e

i n f o

Article history:
Received 1 March 2011
Received in revised form 15 April 2011
Accepted 19 April 2011
Available online 28 April 2011
Deep Eutectic Solvent

a b s t r a c t
The suitability of 1 choline chloride:2 urea mixture, Deep Eutectic Solvent (DES) for the electrodeposition
of cobalt, samarium and cobalt–samarium system has been studied. Its electrochemical window permits
deposition analysis to be carried out without interference from parallel reactions. Deposition was studied
at 70 °C in order to stimulate mass transfer and to lower solution viscosity.
Cobalt deposits according to a nucleation and three dimensional growth mechanism, all its characteristic features do appear for all cases studied. Samarium deposition takes place through a more complex
process in which a first potential range is found where the species formed limit the conductive character
of the substrate. When potential becomes more negative, normal behaviour is observed. When both
cobalt and samarium are present in the solution, codeposition occurs, at no potential value, any current
diminution of the current was recorded under stirred conditions. Deposits of SmCo show different morphology and composition depending on applied potential. Nodular cobalt-rich deposits are obtained at
low deposition potentials whereas fine grained samarium-rich ones are obtained at more negative deposition potentials.
Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction
Electrodeposition of some metals has been restricted in aqueous
solutions at moderate temperatures to those presenting a standard
potential less negative than that of water reduction. Some of these
metals could be deposited, albeit expensively, using either organic
solvents or more drastic conditions such as molten salts [1–5].
In the last decade research in ionic liquids (ionic materials with
melting point below 100 °C), with a wide electrochemical window,
has made it possible to deposit metals with very negative standard
potentials and their alloys [6–14]. Metallic coatings that up to then
had been impossible to deposit became obtainable. Different generations of ionic liquids have been developed widening the spectrum of depositable metals [15–19]. However, many of them do
require a complex synthesis and a very accurate electrochemical
work, since the majority of the ionic liquids present high sensibility
to water or degradation by oxygen.
It has been shown recently that it is possible to create an ionic
fluid mixing quaternary ammonium halides with an amide, carboxylic acid or alcohol moiety [20–23]. Such mixtures are not,
strictly speaking, room-temperature ionic liquids (RTIL) since in
general contain an uncharged molecular component, so that, the
term Deep Eutectic Solvent (DES) was coined by Abbott [24].
Unlike the ionic liquids these room-temperature eutectic mixtures
⇑ Corresponding author.
E-mail address: (E. Gómez).
1572-6657/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.

are easy to prepare in pure state. They are not water reactive and
their biodegradability is proven. Moreover, the economic investment involved is much lower than that incurred using roomtemperature ionic liquids. However, little information is available
about their physic–chemical properties [25].
The microelectronic industry employs many kinds of coatings in
specific parts of the devices, magnetic materials being the most popular ones. Important advances has been achieved in the preparation
of soft magnetic materials but the electrodeposition of hard magnetic ones is still restricted to a few ones [26–28]. The challenge
in preparing such alloys by electrodeposition is that these alloys
contain metals that have electrocatalytic character to hydrogen
evolution, very negative standard potential, or both. Then, the use
of water-free solvents with a wide electrochemical window is welcome in this field and its possibilities are worthy of study.
In this work we select to study the cobalt–samarium electrodeposition processing possibilities in DES medium, as this alloy is
potentially a hard magnetic material depending on the metal ratio
[29–31]. Few studies of SmCo electrodeposition have been performed in aqueous medium [32] since samarium has a very
negative standard potential leading to simultaneous hydrogen evolution. A study about the preparation of SmCo by electrodeposition
in urea-acetamide-NaBr-MClx melts has been performed by Liu et
al. [33]. Our interest is to analyse the possible electrodeposition of
cobalt, samarium and cobalt–samarium systems using the eutectic
1 choline chloride:2 urea mixture as solvent due to its easy preparation, good working conditions and non aggressive nature.

Fig. Firstly. A wide electrochemical window in vitreous carbon electrode was observed between the reduction–oxidation processes of the solvent. Cyclic voltammetric scans were recorded at different negative limits. a well defined reduction peak appeared previous to a massive reduction current (Fig. and (B) with potential holds of: (a) t = 0 s. 2A. Cobalt deposition A basic study of cobalt deposition was made using the habitual electrochemical techniques. curve b). 1. Elemental composition was determined with an X-ray analyser incorporated in Leica Stereoscan S-360 equipment and by X-ray fluorescence (XRF). in the molar proportion 1 choline chloride:2 urea. 1 shows the coincidence between voltammetric scans performed immediate after electrode immersion and those made hours after. a single oxidation peak was recorded during the positive scan. were warmed and removed constantly to achieve the liquid state of the deep eutectic solvent (DES).75 lm and 1. and cobalt chloride from Fluka both of analytical grade were used as source of electroactive species. 2.25 V and (c) t = 30 s at . the oxidation charge increase recorded was less important and a widening of the peak to positive potentials was observed (Fig. Experimental Solvent was prepared using choline chloride (from Across Organics) and urea (from Merck) of analytical grade. Gómez et al. curve c). 2. Results Fig. curve b). cleaned ultrasonically for 2 min in water and dried with air prior to be immersed in the solution. Prior to dissolution. Before and during experiments solutions were de-aerated with argon. 3. Only one cycle was run in each voltammetric experiment. (b) t = 30 s at 1. 1) and to ensure reference electrode reproducibility in the DES medium. scanning at first to negative potentials.1. The reference electrode was an Ag|AgCl/NaCl 3 M mounted in a Luggin Cyclic voltammetry was selected to perform the initial electrochemical study of the deposition processes. Working electrodes were vitreous carbon rods (from Metrohm).E. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 19 capillary containing the DES solvent. 2B. and (c) grey: after 50 h of first scan. cobalt salt was maintained in a stove at 110 °C in order to assure maximum dehydration. 3. the electrochemical response of the blank solution (DES solvent) was recorded to establish its electrochemical window (Fig. 2A. A cylindrical three electrode cell of one single compartment was used. By reversing the scan at very low negative overpotential. Holding the scan in the potential range of the first reduction peak.5 V. The counter electrode was a platinum spiral. nucleation loop was observed (Fig. When the hold was made in the potential range of the massive reduction during the same time. For more negative potential limits. Work temperature was kept constant at 70 °C to favour low viscosity and high conductivity of the solvent. The solids. Vitreous carbon electrode was polished to a mirror finish using alumina of different grades (3. Cyclic voltammograms in DES solvent at: (a) black: immediately after desoxigenation. 1. 2B. as corresponds to deposition process. For all the cathodic limits used.113 M solution (A) at different cathodic limits. Samarium nitrate from Aldrich. Voltammetric experiments were carried out at 50 mV s 1. (b) dashed: after two hours of first scan. Magnetic stirrer was used when the agitation effect was tested. Cyclic voltammograms from CoCl2 0. curve a). Fig.87 lm). Stable and reproducible values of the potential were obtained with this reference electrode. Deposits morphology were observed using Hitachi S-2300 scanning electron microscope. Electrochemical experiments were carried out using an Autolab with PGSTAT30 equipment and GPES software. an increase in the oxidation charge was recorded increasing the hold time (Fig. Solutions were prepared using the DES solvent.

3.2 V from different [Co(II)] solutions: (a) 0. a displacement of the maximum to low deposition times and an increase in the recorded current was observed increasing the concentration (Fig. Voltammetric potential holds under stirred conditions from the [Sm(III)] = 0.025 M and (c) 0. For all the solutions tested. 4.34 V during 60 s.113 M.019 M.005 M. By comparing the j–t curves obtained at fixed potential from different cobalt (II) concentrations.78 and 2. All the j–t transients recorded evolved to a maximum from which the current 8 mA cm 2 . (A) Cyclic voltammograms from different Sm(III) solutions: (a) 0. Fig.045 M.036 M solution curves: (b) j = 8 mA cm 2. the only difference observed being the advance in the appearance of the reduction current and the increase of the current recorded as the Co(II) concentration was increased. 3A). This general behaviour was similar using solutions with different Co(II) concentration. and from profile decays to attain a quasi stationary value. (A) j–t transients at 1. For a fixed concentration. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 Fig. .036 M and (c) 0.52 V during 60 s and (C) 1. (c) j = 16 mA cm 2 and (d) j = 32 mA cm 2. Gómez et al. the current decay after the maximum was reduced.025 M solution at: (B) 1. the potentiostatic experiments were made stepping the potential from a potential value at which no current was detected to different potentials values. (quiescent conditions).20 E.113 M at the [Co(II)] = 0. (b) 0. the maximum appeared a short deposition times as the potential applied was made more negative. (B) E–t transients (a) [Co(II)] = 0. (b) 0. Stirring the solutions.

The stirring of the solution minimises the [Co(II)] depletion near the electrode.4 mA cm 2 under stirring. This is a rather unexpected behaviour. The two reduction peaks were advanced. nucleation loop. the reduction process is partially blocked for some reduction products. it seems that in the potential range of the first peak. As the applied current was made more negative.5 mA cm 2 under stirring.E. voltammetric experiments revealed similar features in the negative going sweep: at 21 first a peak-band appeared. (A) j–t transients from the [Sm(III)] = 0. .2.4 mA cm 2 quiescent solution. (C) E–t transients from [Sm(III)] = 0.4 V. In none condition oxidation current was revealed during positive scan. under stirring. (c) j = 6. 3. In general. 4C). more negative potentials were associated (Fig. Fig. increasing the number of consecutive scans favours the onset of deposition process when a previous deposit is present.045 M (a) j = 3. 5. Gómez et al. followed by a second peak developed previous to massive current (Fig.5 V and (d) 1. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 Galvanostatic experiments under stirring conditions revealed that the system initially attained a minimum negative potential value (potential spike) that evolved to less negative values as the deposition time increased (Fig. (b) a polished substrate under agitation and (c) the substrate after experiment b.6 V. Samarium process For all the samarium (III) solutions tested. 4B and C). 4A). and (f) solvent response at j = 3.6 mA cm 2 using: (a) a polished substrate at stationary conditions. By reversing the scan in none condition nucleation loop was recorded. All the experimental results obtained. The shape of both voltammetric and potentiostatic curves and the effect of the stirring over the voltammetric. potentiostatic and galvanostatic responses to the Co deposition process in the eutectic 1 choline chloride:2 urea mixture reveals the transport control of the process. Therefore. 3B. although in this type of solvent vigorous agitation was needed to appreciate the effect of the stirring arising difficult ion transport. 3B. (B) E–t transients from 0. curves b–d).2 mA cm 2 under stirring. maximum in the j–t transient and nucleation spike in the E–t transients evidenced that the characteristic outputs observed in water dissolutions [35–37] continue being valid in the DES solvent demonstrating that nucleation and growth process takes place for cobalt deposition in this eutectic solvent. (b) 1.045 M Sm(III) at j = 1. curve a).5 mA cm 2 quiescent solution. For all Sm(III) concentrations.2 mA cm 2. enhanced and better defined as the Sm(III) concentration increased. (b) j = 6. at stationary conditions. (c) 1. consecutive cyclic voltammetric scans evidenced that as the number of scans increases. During the positive scan no oxidation current was recorded even when very low cathodic limits were used. Whereas when the potential hold was made in the potential range of the second peak predictable behaviour was recorded: a diminution of current was observed under stationary conditions but important current increase occurred under stirring conditions (Fig. the first part of the curves recorded under quiescent conditions and from ⁄ symbol. as in aqueous solutions [34].3 V.025 M solution at different potentials: (a) 1. (e) j = 9. (d) j = 9. the onset of the current appearance occurs at more negative potentials even when the negative potential limit corresponds to low overpotentials. This result was corroborated by a set of voltammetric experiments holding the scan along the potential range of the first peak: both under quiescent and stirred conditions the reduction current decreased during the hold (Fig.

6D). Gómez et al. and (D) SEM image of a deposit obtained at 1. The stirring of the solution lead to an increase in the recorded current but was not sufficient to maintain stationary value and especially when the most negative potentials were applied. / Journal of Electroanalytical Chemistry 658 (2011) 18–24 Fig. However when the solution was stirred the potential increased with the increase of deposition time making in evidence the favourable stirring effect over the deposition process.018 M Co(II). At quiescent conditions no clear nucleation spikes were observed. curve c). curves c and d). inset as curve c). 7A. the potential value achieved was more negative than the corresponding one to the polished substrate (Fig. 5C). curves a and b).22 E. SEM images of Samarium deposits obtained during a voltammetric hold potential at 1. 3. 6A). positive difference in the charge recorded under agitation was observed (Fig.045 M of Sm(III) after: (A) 15 min. with the stirring of the solution the charge involved in the reduction process was enlarged (Fig. The j–t transients corresponded. in case that galvanostatic experiment was repeated on a substrate. a smooth current diminution was recorded. 6C).45 V under stirred conditions from the solution 0. curve a) respect to that observed in the free cobalt (II) solution (Fig.9 V during 30 min under stirred conditions in a potentiostatic experiment. Whereas if the potential applied corresponds to more negative potential. Reversing the scan at the current onset a nucleation loop was recorded followed by an oxidation peak (Fig. Samarium–cobalt deposition The effect of cobalt (II) in the samarium (III) deposition process was studied using a solution containing 0. (B) 25 min and (C) 80 min. in all applied potentials. Moreover. more evident when the solution was stirred (Fig. the j–t transients recorded showed a previous current peak followed by a smooth current increase.3. although the shape of the curve remembers the typical nucleation feature and with the time the potential dropped smoothly to more negative values. For currents that evolved to potentials corresponding to the first voltammetric peak. 7A. Nevertheless when the applied currents lead the system to potentials corresponding to the second voltammetric peak. curve b). it was not observed in any case the appearance of nucleation loop. the coating showed different morphology in which flat deposits were observed (Fig. Galvanostatic experiments were made applying currents sufficiently negative to allow codeposition of both metals. 6. stirring of the solution lead the potential to more negative values than that corresponding to quiescent conditions (Fig. In these experiments low current were flowed and the time consuming to achieve sufficient coverage was important. curve f). 5B. in both stationary and stirring conditions and applying wide current densities spectrum. 7B).045 M Sm(III) + 0. Similar results were obtained when deoxygenation of solution was made during 10 h prior to the experiment. Independently of the potential. 8A. The imaging of deposits obtained after a voltammetric hold at potential values corresponding to the first voltammetric peak. Scanning towards negative potential a peak was detected followed by a close peak that did not clearly developed since a current increase was observed. Low or nor oxidation current was detected in the positive scan. revealed that: low deposition times lead to very fine grained deposits (Fig. the observed behaviour corresponds to a mass control transfer: the potential value achieved under stationary conditions was more negative than the corresponding under agitation (Fig. Deposits prepared under agitation at different conditions were analysed by scanning electron microscopy. At long deposition times the deposit was cracked (Fig. which has been maintained into the solution and thus with the deposit already formed present. 6B). 8A). Galvanostatic transients were recorded. The deposits obtained potentiostatically in this zone present similar morphology. The agitation effect was also stated in the potentiostatic curves. . 5C. it seems that this feature corresponds to cobalt deposition. Enlarging the cathodic limit to more negative limits. Increasing deposition time the coverage increased and the deposit showed some cracks and a new growth was observed on the first deposit (Fig. In all conditions the potential value at which the solvent reduction takes place was very negative compared to the values where the metallic cation reduced evidencing that in all cases the main process corresponds to deposit formation (Fig. to a sudden current increase followed by a current decay. 7A. In all potential range where codeposition occurs. 5B. As the potential applied was made more negative the current recorded was greater. thus covering stabilization potentials corresponding to the two reduction peaks. This discards the possible effect of the oxygen presence. Voltammetric scan evidenced a slight advance of the overall deposition process (Fig.

Increasing the deposition time a new growth over the first deposit was developed (Fig. Fig.E.045 M Sm(III) solution containing: (a) [Co(II)] = 0.018 M Co(II) solution under: (a) quiescent and (b) stirred conditions.% of Sm independently of the thickness. This deposit of 27 wt.8 V and (d) 1. or even lower. In order to check the possibilities to deposit on a metallic substrate a Ni/Cu/Au slide was used.% of Sm. (A) j–t transients from 0. . / Journal of Electroanalytical Chemistry 658 (2011) 18–24 23 Fig.018 M. (B) Voltammograms obtained from the 0.045 M Sm(III) + 0.3 V during 3600 s.018 M and (b) [Co(II)] = 0 M. deposition potentials than those over vitreous carbon. When the potential was made more negative. These deposits contain 75 wt. By applying similar. 7. (b) 1. and under stirred conditions at (c) 1.6 V during 900 s and (D) E = 1. (A) Comparison of cyclic voltammograms obtained from 0.018 M Co(II) solution under quiescent conditions at: (a) 1. 8. 8C).8 V.% of Sm shows nodular morphology with rounded grains. the composition of the deposits corresponded always to 80 wt. after one hour of deposition no complete coverage was allowed. fine grained deposits with homogeneous coverage were obtained (Fig.9 V and SEM pictures of deposits obtained over vitreous carbon at: (B) E = 1.9 V. Fig. 8B shows a detail of the morphology of SmCo deposit obtained in a potential near to the minimal necessary to induce codeposition. (C) E = 1.6 V during 2500 s. 8D). Low deposition rate was obtained in this case. Inset of the figure shows the voltammogram recorded reversing the scan at the initio of the deposition and (c) [Co(II)] = 0. Deposits prepared at different potentials under stirred conditions were imaged and their samarium percentage was evaluated.045 M Sm(III) + 0. Gómez et al.

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Gibilaro. when metallic substrate is used or a sufficiently negative potential is applied over vitreous carbon. SmCo deposits with Sm percentages that exceed 70 wt. McKenzie.G. . Chem.