Electrochemistry Communications 43 (2014) 67–70

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Short communication

Efficient cathodic carboxylation of graphene

Building a new versatile material
Viatcheslav Jouikov a, Jacques Simonet b,⁎
a
CPM, UMR 6226, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
b
Laboratoire MaSCE, UMR 6226, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: Carbon dioxide is known to be poorly reactive under cathodic conditions. When glassy carbon-graphene elec-
Received 19 February 2014 trodes are put in contact with a saturated solution of CO2 in N,N-dimethylformamide (DMF) containing
Received in revised form 17 March 2014 tetrabutylammonium salts (TBAX) and polarized at potentials b −1.7 V vs. Ag/AgCl (i.e. before own reduction
Accepted 17 March 2014
of CO2), their reduction steps vanish and a large sudden inhibition takes place during further recurrent scans.
Available online 23 March 2014
This suggests that the principal electrode reaction is the cathodic charge of graphene resulting in poly-
Keywords:
nucleophilic species followed by their reaction with electrophilic CO2 in solution. A quite dense poly-
Graphene electrodes carboxylation of the material is chemically confirmed. The grafting of a large panel of reactive electrophiles
Surface carboxylation (eventually carrying a redox group) on these graphene-based carboxylate-covered surfaces was achieved and
Carbon dioxide allowed on the easy building of a wide variety of modified electrodes. The enhanced hydrophilicity of those
Three-dimensional electrodes materials renders possible their use in aqueous media.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction It also appears essential to consider cathodically charged carbons as

Glassy carbon (GC) is a common electrode material for carrying out
analyses and electrolyses, especially in the cathodic domain [1,2]. Thus,
many kinds of electro-organic reactions can be achieved at negatively po-
larized carbon. Development of carbon electrodes at quite negative po-
tentials (E b −1.7 V) brought out the phenomenon of cathodic charge
of this material which is essential for its specific reaction with a large
range of electrophilic species (such as alkyl halides carrying redox groups)
that are present in the vicinity of the surface. This method was used to
anchor — to a large extent — ferrocene [3], tetrathiafulvalenes [4], as
well as a large variety of functionalized alkyl halides [5]. Although con-
sidered for a long time as “inert”, glassy carbon contains ribbons of
graphite-like structures in discontinuity with “crystallite” boundaries
representing all types of unsaturated forms carbons. This provides ex-
traordinary reactive possibilities to glassy carbon due to the presences
of graphite, fullerene, and graphene incorporated in this material during
its preparation (high temperature pyrolysis of phenolic resins [6,7]). In
the same order of ideas, the anodic charge of current GC polarized at
potentials N+2.5 V permits to induce electrophilic zones promising in
specific coverage formations [8] in the presence of appropriate nucleo-
philic agents. Therefore, the use of solid conductive surfaces doped with
graphite or with nano-tubes permits to anticipate a large variety of
modifications of such interfaces under the above conditions where the
recourse to purely radical reactions is quite uncertain.
⁎ Corresponding author.
E-mail address: jacques.simonet@univ-rennes1.fr (J. Simonet).
a material reactive towards a large palette of electrophilic species other
than alkyl halides. Thus, highly oriented pyrolytic graphite (HOPG), nat-
ural graphite from Ceylon, and glassy carbon were reported to react with
organic halides and carbon dioxide under quite simple and efficient
conditions [9,10]. Preliminary experiments on the electrochemical modi-
fication of glassy carbon, owing to the presence of graphite, fullerenes,
and possibly graphene as electroactive impurities, were recently achieved
[11] and demonstrated a global carboxylation of the material. The
growing interest for graphene functionalization, quite obviously rich for
multiple applications [12], prompts us to consider that its charged species
may be of high interest for fixing electrophilic compounds such as CO2
under the conditions previously described with other types of carbons.
Experimentally, cathodic polarization of graphene in non-aqueous
solvents starts at E b − 1.9 V vs. Ag/AgCl to give a series of cathodic
steps described as a globally complex reversible charge rather compara-
ble to that of natural graphite when deposited onto solid conductor like
gold or glassy carbon, while much simpler in its voltammetric re-
sponses. It appears to yield a nucleophilic material capable to induce
both internal and interfacial reactions. It is worth recalling that, when
polar organic solvents are used, highly oriented pyrolytic graphite
(HOPG) under cathodic charge [13] specifically leads to well defined in-
sertion stages [C− +
n ,TAA ] via concomitant insertion of electrons and
tetraalkylammonium salts (TAAX). Exfoliation of natural graphite by
bulky ammonium salts has been reported [14] long before graphene
was experimentally prepared. Similarly, such “graphene salts”, rather
similar to tetraalkylammonium amalgams, could be considered both
as reducing species and as poly-nucleophilic materials.

http://dx.doi.org/10.1016/j.elecom.2014.03.013
1388-2481/© 2014 Elsevier B.V. All rights reserved.
68 V. Jouikov, J. Simonet / Electrochemistry Communications 43 (2014) 67–70
Now, the behavior of carbon dioxide (known in organic chemistry as
an “electrophilic” entity) towards negatively charged GC should be con-
sidered both for creating new kind of modified materials/interfaces and
as a new mode of sequestration of this gas in carbons using a very sim-
ple electrochemical reaction. Note that carbon dioxide acts as an elec-
trophilic moiety towards electro-generated anions of π-acceptors as
well as in redox catalysis [15].
We explore here for the first time the capability of graphene species,
electrochemically charged in polar organic solvents, to act as a macro-
nucleophilic substrate towards carbon dioxide for readily building
[carbon poly-carboxylate] materials. With thin layers of graphene de-
posited onto a glassy carbon (deposits onto gold can be achieved as
well) and maintained in contact with a saturated solution of carbon di-
oxide, limited amounts of charge led to a profound chemical modifica-
tion of the material. Several reactions of functionalization of surface
carboxylates are presented here. This process thus should be seen as
an easy way of building a multi-purpose carbon material.
2. Experimental section
Voltammetry was carried out in 0.1 M solutions of Bu4NBF4 in DMF.
All experiments are very simple to set up and need no special treatment
of electrolytic solutions. Salts, CO2(gas), and solvents were purchased
from Aldrich and employed as is. Carbon dioxide was used as saturated
solution in DMF (0.199 mol L−1 at room temperature [16]), with a con-
stant bubbling through the electrolyte.
The potentials are referred to the aqueous Ag/AgCl/KCl(sat). The elec-
trochemical instrumentation has been recently reported [4].
All used carbon electrodes had apparent surface area of 7 mm2.
Glassy carbon samples were purchased from Tokai Carbon Co. (code:
GC Rod) for building GC stationary disk electrodes and from Carbone-
Lorraine (plates of area N.5 cm2) for making larger samples used in
FTIR analysis.
Before using, carbon electrodes were first carefully polished with sil-
icon carbide paper (Struers 500) and then graphene layers were depos-
ited on GC by mechanical rubbing until obtaining a bright and uniform
surface. Graphene was purchased from XG Sciences as XGnP Graphene
Nanoplatelets Grade C typically consisting of submicron platelets (parti-
cle diameter b 2 μm, with thickness of a few nm). The average surface is
of the order of 750 m2/g and TEM images permit to detect almost
Fig. 1. Voltammetry at carbon electrodes. Apparent surface area: 7 × 10−2 cm2. Scan rate: 50 mV s−1. Electrolyte: DMF + TBABF4. (A) Charge and discharge of a graphene layer deposited
at a GC electrode. (B) Recurrent voltammograms of saturated CO2 at a GC electrode. (C) The same experiment with a GC/graphene electrode; the integration between 0 V and −2.3 V
corresponds to 2 × 10−3 C. (D) Electrode prepared according to (C) and treated with 2-(bromomethyl)naphthalene.
transparent platelets. Oxygen content was reported to be b 2 wt.%
while that of carbon N98.0 wt.%.
Graphene carboxylates were marked with a series of organic
electrophiles RX. This preliminary presentation is mainly focused
on benzyl bromides Ar\CH2\Br, purchased (as other chemicals, 2-
aminoanthraquinone and 2-(bromomethyl)anthraquinone) from
Aldrich. A detailed experimental mode is summarized in Fig. 3.
Coulometric measurements and electrolytic grafting were per-
formed using three-electrode cells separated with a fritted glass. Effi-
cient and careful rinsing with water and then with acetone followed
every experiment.
3. Experimental results
Voltammograms (Fig. 1, curve A) of graphene deposited to GC in
DMF containing TBABF4 exhibit a very reproducible behavior of the car-
bon material. At about −1.05 V, a small wave is attributed to the reduc-
tion of graphene oxides. At more negative potentials, a quite specific
“triplet” (peaks at −1.8, − 2.0 and −2.1 V) appears corresponding to
the cathodic charge of graphene. This reduction process leads to the
progressive formation of polyanionic forms distributed on graphene
platelets. On the backward scan, several oxidation steps (very reproduc-
ible) do confirm the reversibility of the overall process.
In the presence of CO2, voltammograms are quite different. As re-
minder, the behavior of GC is exhibited in Fig. 1, curve B. A progressive
shift of peaks towards negative potentials reflects the progressive car-
boxylation of carbon and consecutive loss of its reactivity. Voltammetry
of graphene (curve C) shows a large current during the first scan while
further forward scans progressively become flat. The amount of electric-
ity necessary to deplete the first scan signal (from 0 V to −2.2 V) could
be estimated as 2 × 10−3 C. We expect that this charge is roughly nec-
essary to modify the graphene layer. The carboxylated layer turns out
to be almost inert within this potential range. The reaction of this
layer with 2-(bromomethyl)naphthalene (see process in Fig. 3) led to
a flat response until the peak at −2.4 V that corresponds to the reduc-
tion of graphene-immobilized naphthalene.
A series of experiments relative to the carboxylation of graphene
(reduction in the saturated solution of CO2) followed, after a first work-
up (rinsing with water and acetone), by addition of a redox marker.
Such a tagging of the grafted carboxylates with a number of redox-
 V. Jouikov, J. Simonet / Electrochemistry Communications 43 (2014) 67–70
Fig. 2. Redox responses (in DMF/TBABF4, scan rate: 50 mV s−1) of carboxylated graphene obtained by electrolysis of GC-graphene electrode in the presence of CO2 at −1.9 V (electricity
amount: 10−2 C) and redox-tagged according to the process described in Fig. 3 A.
active groups was achieved as shown in Fig. 2. For instance, curves A
account for the addition of para-nitrobenzyl bromide when a large re-
versible reduction signal of the immobilized nitrophenyl group was ob-
tained. Its integration (first run), reported to the area of glassy carbon,
gives an overall mass concentration of (1.3 ± 0.2) × 10−8 mol cm−2
(from three runs). Let us note that the reversible (minor) pre-peak
could be assigned to nitroso form generated by chemical reduction of
nitro group by remnant partially charged graphene. After several
scans, the total reduction into hydroxylamine could be well visualized
due to the presence of acidic impurities. Then, curve B corresponds to
the generation of amide from 2-aminoanthraquinone whereas curve C
reflects the efficient addition of benzyl bromides (phenyl substituted
by Br or I). The irreversible step on the first scan accounts for the
two-electron scission of the C\I bond. The level of grafting was
found to be (1.0 ± 0.3) × 10− 8 mol cm− 2. Lastly, curve D exhibits
two one-electron steps of the reduction of anthraquinone (electrophile
used: 2-(bromomethyl)anthraquinone) immobilized in (1.5 ± 0.3) ×
10−8 mol cm−2 apparent concentration. The results with various re-
agents (esters or amide formation) are quite coherent. It is not yet
established whether carboxylation is uniform within the layer or it oc-
curs in depth with a concentration gradient.
Additionally, FTIR spectra of the concerned interfaces (Fig. 3)
support the results of voltammetry described above. Moreover,
69
the wetting ability of the carboxylated layer (its face) is also well
shown.
4. Conclusion
The cathodic charge of graphene, deposited as a thin layer onto a
conducting support such as GC, achieved in the presence of carbon diox-
ide (in a form of saturated solution in a non-aqueous polar solvent like
DMF) provides an easy way for carboxylation of this material to a quite
large extent. The present study therefore reveals the capacity of
graphene deposited onto GC to react with CO2. A similar behavior
could be observed with Au/graphene system. Under the conditions pro-
posed in this preliminary note, the fixation of CO2 by such materials
might reach very high levels equivalent to up to 100 layers (compared
to the compact carboxy-monolayer at a flat GC surface). The reactivity
of CO2 was confirmed by FTIR spectroscopy and by the ensuing
functionalization of graphene-incorporated carboxylate groups with
suitable redox markers (nitrobenzene, anthraquinone) that allow one
to quantify the level of carboxylation. Chemical versatility of this poly-
carboxylic graphene material and its technological promise are obvious:
even preliminary macro-electrolyses of graphene under CO2 atmo-
sphere in a conventional electrochemical cell presently permit to pre-
pare the graphene-carboxylate in a quite large scale (several hundred
70 V. Jouikov, J. Simonet / Electrochemistry Communications 43 (2014) 67–70

Fig. 3. (A) Carboxylation (phase 1) of a GC–GR interface followed (phase 2) by functionalization. A drop of water on (a) GC–GR surface and (b) GC–GR–COOH surface underlining enhanced
wetting ability of the surface after carboxylation. (B) Bottom: FTIR (reflectance mode) of Carbone-Lorraine GC plates covered with graphene after the carboxylation: (a) — graphene on GC.
(b) — GC–GR–COOH. A: 3400 cm−1 v(O\H); B: 2350 cm−1 CO2; (C) 1720 cm−1 v(C = O); D: 1220 cm−1 v(C\O); E: 900 cm−1 δ(O\H). (c) — GC–GR–COOCH2C6H4NO2. A: 3100–
2900 cm−1 v(CPh\H) + v(CH2); B: 1720 cm−1 v(C = O); C: 1560, 1400 cm−1 v(C\N); D: 1200 cm−1 v(C\O); E: 850 cm−1 δ(C\N).

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