Ionic liquid effects on the redox potential of ferrocene

Angel A.J. Torriero , Patrick C. Howlett

ARC Centre of Excellence for Electromaterials Science, Institute for Technology Research and Innovation, Deakin University, Burwood, Victoria 3125, Australia
a b s t r a c t a r t i c l e i n f o
Article history:
Received 11 November 2011
Received in revised form 6 December 2011
Accepted 6 December 2011
Available online 15 December 2011
Keywords:
Ferrocene
Decamethylferrocene
Ionic liquids
Internal reference systems
The ionic liquid, IL, dependence of the mid-point potential of the ferrocene|ferrocenium, Fc
0/+
, couple versus
the decamethylferrocene|decamethylferrocenium, DmFc
0/+
, couple was studied in eleven ILs and in dichlor-
omethane with added IL as the supporting electrolyte. The difference in mid-point potential between Fc and
DmFc indicates that Fc
0/+
couple is clearly dependent on the IL structure. A variation of about 0.100 V over
the range of ILs studied under neat conditions and by ca. 0.050 V when studied in dichloromethane is
reported. Meanwhile, a variable potential shift ranging from 0.014 to 0.082 V was observed when data was
compared in these two systems (ILs vs. dichloromethane). The effect of water and lithium ion on the Fc
0/+
and DmFc
0/+
redox potential was also evaluated and found to be minimal.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The application of internal reference systems for electrochemical
studies in ILs is of primary importance [1,2]. The establishment of a
solvent independent reference redox system for the comparison of
redox potentials in non-aqueous systems began with the concept of
Rb|Rb
+
or Rb(Hg)|Rb
+
[3], followed by the use of organometallic
redox couples [4]. In order to limit the number of redox systems
used and to simplify comparison, IUPAC arbitrarily selected and
recommended that the systems Ferrocene|Ferrocenium, Fc
0/+
, and
bis(biphenyl)chromium(0)|bis(biphenyl)chromium(I), be used as a
reference redox system in organic solvents and their mixtures [4].
In this recommendation it is assumed that they are solvent indepen-
dent redox systems [4].
Nowadays, it is well understood that the standard redox potential
of Fc is highly dependent on solvation effects by the solvent and sup-
porting electrolyte used [5,6]. This problemis also expected to be pre-
sent in ILs, since both the IL cation and anion might interact with
either member of the Fc
0/+
couple [7,8]. However, information on
the IL dependence of the Fc
0/+
couple is not available. Consequently,
ferrocene is often used as an ideal internal reference systemfor com-
parison of redox processes in different ionic liquids [912].
The electrochemistry of decamethyl-substituted ferrocene, DmFc,
has been studied in organic solvent systems and proven to be a supe-
rior redox standard to ferrocene [1315]. It was concluded that the
methyl substitution on the cyclopentadienyl ring prevents both spe-
cic and nonspecic interaction between DmFc and external mole-
cules by hindering the access of solvent and supporting electrolyte
molecules both to the metal centre and to the ring [1315]. However,
this ferrocene derivative has been scarcely studied in ILs, mainly due
to the limited solubility of this complex in some ILs [10,1618].
The present study reports the effect of IL structure (see Scheme 1 for
structures of anions and cations of ILs used) on the mid-point potentials,
calculated from the average of the oxidation and reduction peak posi-
tions [E
m
=(E
p
ox
+E
p
red
)/2], of the Fc
0/+
and DmFc
0/+
couples obtained
by cyclic voltammetry. To minimize uncertainties related to potential
variation due to changes in liquid junction potentials between the solu-
tion and the reference electrode [19], the E
m
of Fc
0/+
and DmFc
0/+
couples were referenced to the E
m
value of the DmFc
0/+
couple. The
mid-point potential of Fc (vs. DmFc
0/+
) dissolved in dichloromethane,
CH
2
Cl
2
, containing different concentrations of IL as the supporting
electrolyte and its comparison with the E
m
observed in neat ILs is
also discussed. Inaddition, the effect of water and lithiumconcentration
onthe E
m
values is presented. Provisionof this fundamental information
provides a basis for accurate comparison of redox processes in different
ILs and organic solvents systems.
2. Experimental
2.1. Reagents
High purity grade (>99.9%) 1-methyl-3-butylimidazolium
hexauorophosphate, [bmim][PF
6
], 1-methyl-3-butylimidazolium
tetrauoroborate, [bmim][BF
4
], 1-methyl-3-butylimidazolium bis
(triuoromethylsulfonyl)amide, [bmim][NTf
2
], 1-methyl-1-butyl-
pyrrolidinium bis(triuoromethylsulfonyl)amide, [bmpyr][NTf
2
],
1-methyl-1-butylpyrrolidinium dicyanamide, [bmpyr][DCA], 1-
methyl-3-ethylimidazolium tetracyanoborate, [emim][B(CN)
4
], 1-
methyl-3-butylimidazolium triuoromethanesulfonate, [bmim][OTf], 1-
methyl-1-butylpyrrolidinium tris(pentauoroethyl)triuorophosphate,
Electrochemistry Communications 16 (2012) 8487
Corresponding author. Tel.: +61 3 92446897; fax: +61 3 92446868.
E-mail address: angel.torriero@deakin.edu.au (A.A.J. Torriero).
1388-2481/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2011.12.006
Contents lists available at SciVerse ScienceDirect
Electrochemistry Communications
j our nal homepage: www. el sevi er . com/ l ocat e/ el ecom
[bmpyr][FAP], 1-methyl-3-ethylimidazolium tris(pentauoroethyl)tri-
uorophosphate, [emim][FAP], were purchased from Merck. Ferrocene,
Fe(C
5
H
5
)
2
(98%, Aldrich), Decamethylferrocene, Fe(C
5
(CH
3
)
5
)
2
(97%, Al-
drich), tetrabutylammonium hexauorophosphate, [Bu
4
N][PF
6
]
(99.0%, Fluka), and tetraethylammonium tetrauoroborate, [Et
4
N]
[BF
4
] (99.0%, Fluka), were usedas receivedwithout further purication.
Both 1-methyl-3-ethylimidazolium bis(uorosulfonyl)amide, [emim]
[FSI], and 1-methyl-1-propylpyrrolidinium bis(uorosulfonyl)amide,
[pmpyr][FSI], were purchased from Dai-Ichi Kogyu Seiyaku Corpo-
ration and dried under vacuum at 50 C overnight. Lithium bis(tri-
uoromethylsulfonyl)amide, LiNTf
2
(3 M Specialty Chemicals
Division, USA) was dried under vacuum at 80 C for 24 hs before
use. Reagent-grade dichloromethane, CH
2
Cl
2
(Honeywell Burdick
& Jackson), was distilled from appropriate drying agents and
stored over CaH
2
prior to use.
2.2. Apparatus and procedures
Voltammetric experiments were performed with a Biologic VMP3/
Z multi-channel potentiostat. Uncompensated resistance was mea-
sured in a potential region where no Faradaic reaction occurs, using
the RC time constant method available with the instrument. This re-
sistance was 85% compensated by the same instrument; these values
were typically in the range of 0.8 to 3.1 K. The voltammograms of Fc
and DmFc solutions were obtained using a conventional three elec-
trode arrangement, consisting in a 1.0 mm diameter glassy carbon
(GC) working electrode (ALS, Japan), a platinum wire as a counter
electrode and a platinum wire as a quasi-reference electrode, QRE.
In order to minimise errors in the reported potentials related to even-
tual drifts in the QRE potential during the potential scan, all voltam-
mograms were also recorded using a Ag/AgCl,R reference electrode
(where R represent the IL under study). Independently of the refer-
ence electrode used, all potentials quoted are relative to the DmFc
0/+
potential scale. Prior to each experiment, the working electrode was
polished with 0.3 malumina (Buehler, Lake Bluff, IL) on a clean polish-
ing cloth (Buehler), sequentially rinsed with distilled water and ace-
tone, and then dried with lint-free tissue paper.
Typically, IL solutions in the concentration range of 0.5 to 5 mM of
mixtures of Fc and DmFc were prepared with stirring. Electrochemi-
cal experiments in ILs with low water content (b100 ppm) were con-
ducted inside an argon-lled glove box. Wet ionic liquid solutions
were made up directly by stirring the IL solution in a water-
saturated atmosphere. The concentration of water in IL and CH
2
Cl
2
media was determined with a Model 756 Karl Fischer Coulometer
(Metrohm) using Hydranal Coulomat AG as the titrant.
3. Results and discussion
Cyclic voltammograms for the oxidation of ferrocene, Fc
0/+
, and
decamethylferrocene, DmFc
0/+
, were reversible at a scan rate of
0.1 Vs
1
in all the systems studied, with a peak-to-peak potential
separation in the range 0.058 to 0.070 V. This variation is attributed
Scheme 1. Structures of the cations and anions employed in this study and the redox species under investigation.
85 A.A.J. Torriero, P.C. Howlett / Electrochemistry Communications 16 (2012) 8487
to both the slower heterogeneous electron transfer rate constant ob-
served in ILs with respect to conventional solvents [20] and the even-
tual presence of uncompensated resistances remaining in the cell. As
expected for reversible processes, E
m
values obtained from the cyclic
voltammograms are independent of the scan rate (0.010.2 V s
1
)
and concentration (0.55 mM) studied. In all solvents used in this
work the Faradaic peak current of the DmFc
0/+
process is smaller
than that of Fc
0/+
under the same experimental conditions due to dif-
ferences in the diffusion coefcients of these redox couples
[12,13,15].
Cyclic voltammograms for the oxidation of DmFc and Fc was ini-
tially studied in CH
2
Cl
2
containing tetraalkylammonium salts as the
supporting electrolyte. The solvent-solute interaction under these
conditions has been shown to be an order of magnitude weaker in
the case of DmFc with respect to Fc [14], making DmFc an important
internal reference to evaluate the solvation effect of ILs on the Fc
redox process.
As presented in Table 1, an E
m
value of 0.549 V vs. DmFc
0/+
was
observed for the Fc
0/+
redox process in CH
2
Cl
2
containing 0.1 M
[Bu
4
N][PF
6
] as the supporting electrolyte, which is consistent with
previously reported values [5,21]. However, this value increases up
to 0.590 V when 0.1 M [emim][FAP] is used as the supporting electro-
lyte. This effect can also be observed in Fig. 1A, where a difference of
ca. 0.050 V is observed when the electrolyte is changed from [Et
4
N]
[BF
4
] to [emim][B(CN)
4
] in CH
2
Cl
2
. A similar situation is observed
over the range of ILs studied under neat conditions (Table 1), where
an increase in the E
m
of Fc of about 0.100 V is observed when chang-
ing the IL from [bmim][OTf] to [emim][FAP]. This appears to be relat-
ed to the nature of the IL anion. For example, subtle variations in the
E
m
of Fc vs. DmFc
0/+
is observed by changing the IL from [emim][FAP]
to [bmpyr][FAP], both in neat ILs and in CH
2
Cl
2
with added [FAP]-con-
taining ILs as supporting electrolyte. Meanwhile, changes of 0.061 V
in neat ILs and 0.021 V in CH
2
Cl
2
with added ILs as the supporting
electrolyte could be observed by keeping the [emim] cation constant
and changing the anion from [FSI] to [FAP]. This result shows that the
E
m
value of the Fc
0/+
process (vs. DmFc
0/+
) is quite sensitive to the
nature of the IL used, similar to what occurs in organic solvents
with added supporting electrolyte.
Further information is obtained from a comparison of E
m
of Fc
obtained for each IL under neat and diluted conditions (0.1 M in
CH
2
Cl
2
). The difference between the E
m
of Fc and DmFc in neat and di-
luted conditions increased from 0.014 for [bmpyr][FAP] to 0.082 V for
[bmim][OTf], and a general trend was determined for the anions,
where the E
m
of Fc
0/+
vs. DmFc
0/+
couple increases in the following
order: [FAP]

b[FSI]

[NTf
2
]

[DCA]

b[B(CN)
4
]

b[PF
6
]

[BF
4
]

b[OTf]

.
It is worth noting that data reported in Table 1 represent the dif-
ference in E
m
between the two redox couples and where the
solvent-induced shift in the E
m
of DmFc
0/+
couple is assumed not as
signicant as the Fc
0/+
couple. In addition, it is important to consider
Table 1
Mid-point potential of Fc vs. DmFc
0/+
obtained by cyclic votammetry in different ionic
liquids and dicloromethane solutions containing ionic liquids and alkylammonium
salts as supporting electrolytes.
IL E
m(Fc)
vs. DmFc
0/+
/V
a
H
2
Ob100 ppm Wet conditions
b
0.1 M in DCM
[bmpyr][FAP] 0.575 0.573 (516) 0.589
[emim][FAP] 0.574 0.573 (439) 0.590
[emim][B(CN)
4
] 0.526 0.527 (1343) 0.588
[bmim][NTf
2
] 0.513 0.514 (567) 0.570
[bmpyr][NTf
2
] 0.511 0.512 (676) 0.568
[emim][FSI] 0.512 0.512 (832) 0.569
[pmpyr][FSI] 0.510 0.510 (522) 0.568
[bmpyr][DCA] 0.505 0.504 (736) 0.564
[bmim][PF
6
] 0.478 0.478 (683) 0.556
[bmim][BF
4
] 0.478 0.477 (818) 0.557
[bmim][OTf] 0.474 0.475 (834) 0.556
[Bu
4
N][PF
6
] 0.549
[Et
4
N][BF
4
] 0.541
a
All potentials were obtained with a GC working electrode and calibrated against
that of the DmFc
0/+
process, where midpoint potential of the DmFc
0/+
couple is zero
under all conditions. E
m
values were recorded with an accuracy of 0.003 V (n=5).
Temperature 211 C; scan rate 0.1 Vs
1
.
b
Water content (ppm) is given in parenthesis.
Fig. 1. A) Cyclic voltammograms obtained at a GC electrode for the oxidation of 2 mM
DmFc and 2 mM Fc in CH
2
Cl
2
containing 0.1 M [Et
4
N][BF
4
], [bmpyr][NTf
2
], or [emim]
[B(CN)
4
] as the supporting electrolyte. B) Dependence of the E
m
of Fc
0/+
on the
[bmpyr][DCA] and [pmpyr][FSI] concentration, going from 0.1 M in dichloromethane
to neat conditions. C) Effect of water content on the E
m
of Fc
0/+
in CH
2
Cl
2
containing
[Bu
4
N][PF
6
] and different concentrations of [bmpyr][DCA] as the supporting
electrolyte.
86 A.A.J. Torriero, P.C. Howlett / Electrochemistry Communications 16 (2012) 8487
that the difference between the formal potential of these redox cou-
ples obtained in neat ILs is probably larger than that reported in
Table 1, as the inequality between the diffusion coefcients of the
neutral and charged species of the Fc
0/+
and DmFc
0/+
couples was
not considered [11,22].
In order to obtain more detailed information on the dependence of
the Fc
0/+
redox process with the IL concentration, the E
m
for Fc vs.
DmFc
0/+
over a large [bmpyr][DCA] and [pmpyr][FSI] concentration
range was determined (Fig. 1B). A logarithmic relationship was ob-
served when the concentration was changed from 0.1 to 1.0 M in
CH
2
Cl
2
. However, deviation from that correlation was observed at
higher electrolyte concentration in CH
2
Cl
2
and under neat conditions
(4.5 and 4.35 M for [bmpyr][DCA] and [pmpyr][FSI], respectively),
where a linear relationship between the E
m
and the IL concentration
could be observed.
To support our contention that the potential difference observed
in ILs and CH
2
Cl
2
is primarily due to the IL solvation properties and
not to adventitious water, the E
m
of Fc after the deliberate introduc-
tion of additional water was examined. The results show that the E
m
value was independent of the water content both in neat ILs
(Table 1) and CH
2
Cl
2
with added supporting electrolyte (Fig. 1C).
Specic solvent effects such as Lewis acid/base interactions were
reported to contribute to the variation of the E
m
of Fc in organic sol-
vents [15]. With the aim of determine if this effect is also functional
in ILs, the effect of the presence of lithium ions on the E
m
of Fc was
evaluated. The strong Lewis acid, LiNTf
2
, was added to [bmpyr]
[NTf
2
] containing DmFc and Fc, and a voltammogram was acquired.
Under this condition, no difference between E
m
of Fc and DmFc
was observed by increasing the Li
+
concentration from 0.00 to
0.56 mol kg
1
. It is possible that any inuence of these additions
(e.g., due to changes in viscosity [22]) had a similar effect on the E
m
of both redox couples and hence was not detected. However, the
use of a lithium metal QRE (separated by a porous glass frit from
the test solution) indicated that neither E
m
was shifted to any extent,
within experimental error, relative to one another or the lithium
reference.
4. Conclusion
The present study reports for the rst time the effect of ionic liquid
structure on the mid-point potentials of the Fc
0/+
and DmFc
0/+
redox
processes. The E
m
of Fc vs. DmFc
0/+
varies by about 0.100 V over the
range of ILs studied under neat conditions and by ca. 0.050 V when
studied in dichloromethane with added IL as the supporting electro-
lyte. Between these two systems (neat ILs and CH
2
Cl
2
) a variable
difference that increased from 0.014 to 0.082 V was observed
and followed the order [FAP]

b[FSI]

[NTf
2
]

[DCA]

b[B(CN)
4
]

b[PF
6
]

[BF
4
]

b[OTf]

. The presence of water and lithium ion in

the studied solutions did not affect the E
m
of Fc
0/+
relative to the
DmFc
0/+
couple.
This work provides a platform for the accurate comparison of
redox processes in different ILs and between ILs and organic solvents
with added IL as the supporting electrolyte, where the reported po-
tential values could be used to correct Fc
0/+
E
m
values, either referen-
cing them to the E
m
of DmFc
0/+
or to the E
m
of Fc
0/+
in a specic IL.
Acknowledgements
The authors gratefully acknowledge Deakin University and the
ARC for nancial support, through the ARC Centre of Excellence for
Electromaterials Science. We thank Professors Maria Forsyth and
Douglas R. MacFarlane for their insightful discussions.
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