PERGAMON Electrochimica Acta 44 (1999) 2779±2787

Selective electrocatalytic oxidation of

2,5-dihydroxymethylfuran in aqueous medium: a
chromatographic analysis of the reaction products
A. Al Baradii, K.B. Kokoh *, H. Huser, C. Lamy, J.-M. LeÂger
UMR 6503, Equipe Electrocatalyse, CNRS-Universite de Poitiers, 40, Avenue du Recteur Pineau, 86022 Poitiers cedex, France

Received 7 September 1998; received in revised form 23 November 1998

Abstract

The electrocatalytic oxidation of 2,5-dihydroxymethylfuran (DHMF) was carried out on platinum and nickel
electrodes in alkaline medium. Suitable operating conditions of HPLC analyses were found to determine each
reaction product formed during the anodic oxidation. When electrolysis was conducted on a bare Pt electrode or on
a NiOOH anode, DHMF is converted only into 5-hydroxymethylfurfural (HMF). Conversely, the electrooxidation
of DHMF on Pt, modi®ed in situ by lead adatoms, yielded selectively 61% 2,5-furandialdehyde (FDC). In all the
cases, HMF was the primary reaction product. # 1999 Elsevier Science Ltd. All rights reserved.

Keywords: 2,5-Dihydroxymethylfuran; Electrolysis; Electrocatalytic oxidation; HPLC

1. Introduction
2,5-Dihydroxymethylfuran (DHMF) is a compound
which can be produced from the reduction of 5-
hydroxymethylfurfural (HMF). The only work con-
cerning the oxidation of DHMF was reported by
Oleinik and Novitskii [1]. They obtained 2,5-furan-
dialdehyde (FDC) using manganese dioxide. FDC is
used in the synthesis of symmetrical diamines and
Schi€'s bases of the furan series and in various con-
densation reactions. It is also used in the preparation
of annulene oxides, polyenylsubstituted furan or
macrocyclic ligands. Besides HMF, all the other oxi-
dation products of DHMF may serve as starting ma-
terials in several industrial applications [2±5]. For
example, all the oxidation products are potentially
building units for polymers. For this purpose, many
* Corresponding author. Fax: +33-549453580; e-mail: boni-
face.kokoh@campus.univ-poitiers.fr
chemical and catalytic methods were used for the oxi-
dation of HMF [2±11]. This shows that HMF, which
is a raw material easily accessible from biomass,
opens a large research ®eld mainly in the viewpoint
of organic synthesis.
Conversely to several works in organic chemistry,
few investigations of the electrochemical reactivity of
HMF were made. At a platinum anode, FDC was
selectively produced in a biphasic H2O/CH2Cl2
system [12]. At a nickel oxihydroxide electrode, 2,5-fur-
andicarboxylic acid (FDCA) was also obtained with a
71% chemical yield in alkaline medium [13]. As HMF
is considered to be an unstable chemical compound, its
reduction product (DHMF) can be a convenient form
of its storage. Hence, when HMF is needed, it can be
synthetized by the oxidation of DHMF on Au, Pt or,
above all, on Ni electrodes, if the conversion yield can
be improved.
Another aim of this work is to oxidize selectively
DHMF to FDC on platinum electrodes modi®ed by
adatoms.

0013-4686/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 9 9 ) 0 0 0 0 6 - 7
2780 K.B. Kokoh et al. / Electrochimica Acta 44 (1999) 2779±2787
Fig. 1. Potential program used for long-term electrolysis of
2,5-dihydroxymethylfuran.
2. Experimental
2.1. Voltammetry and electrolysis
Cyclic voltammetry was used for investigating the
reactivity of DHMF on Pt, Au and Ni electrodes. The
platinum and gold working electrodes were microbeads
(active surface area of 0.14 cm2 for Pt and of 0.34 cm2
for Au) which were obtained by melting a 0.5 mm di-
ameter wire of the corresponding metal. A nickel
foam, with a geometric area of 2 cm2, was also used as
working electrode. For this, an electrochemical
treatment [14] led to a nickel oxide/hydroxide anode in
alkaline medium. Voltammetry measurements were
performed in a double-wall thermostatted glass cell.
Fig. 2. UV spectra of 2,5-dihydroxymethylfuran (ÐÐÐ) and its derivative products: (- - -) HMF, (± ± ±) FDCA and (


) HFCA.
The experimental set-up consisted of a waveform gen-
erator (Wenking Model VSG72, Bank Electronik), a
Wenking Model LB81 potentiostat (Bank) and a X±Y
recorder (Linseis LY 17100). The counter electrode
was a glassy carbon plate and a saturated mercurymer-
curous sulphate electrode (MSE) served as reference.
A three-electrode glass cell, with two identical com-
partments (volume = 70 cm3 for each compartment)
separated by an ion-exchange membrane (Ionac 3470),
was used to perform long-term electrolysis. The work-
ing electrode consisted of a platinum or a gold grid
(Specpure from Johnson Matthey) having a real sur-
face area of 31 and 24 cm2, respectively. A 90% plati-
num/10% iridium perforated sheet and a saturated
mercurymercurous sulphate electrode (MSE) served as
counter and reference electrodes, respectively. The elec-
trolysis equipment was composed of a potentiostat
(PAR Model 362) monitored by a microcomputer. The
current intensity vs. time was followed on a Kipp and
Zonen BD 40 X±t recorder, whereas the quantity of
electricity was measured directly by a coulometer
(Wenking EVI 80). The electrolyses on a bare platinum
electrode were carried out using an optimized potential
program which was composed of three potential pla-
teaux (Fig. 1). After adsorbing the organic molecule at
low potential (Eads = 0.4 V (RHE)) for 0.1 s, the oxi-
dation reaction was performed at a potential plateau,
chosen at 0.6 V (RHE) for 10 s. The third potential
pulse (Edes), set at 1.9 V (RHE) for 0.1 s, allowed to
reactivate the electrode surface by clearing out the poi-
 K.B. Kokoh et al. / Electrochimica Acta 44 (1999) 2779±2787 2781

Fig. 3. Chromatogram of 2,5-dihydroxymethylfuran (DHMF) and its derivative products: 1 Ð DHMF; 2 Ð HMF; 3 Ð HFCA
and 4 Ð FDCA.

soning species. This sequential unit program was depositing adatoms at the electrode surface was pur-
repeated for several hours throughout the electrolysis. chased from Fluka. Before each experiment, the sol-
In all the electrochemical studies, the electrode po- utions were deaerated with ultra pure nitrogen (U
tentials indicated in the text are given in the reversible Quality from l'Air Liquide) and a nitrogen stream was
hydrogen electrode (RHE) scale. maintained over the solution during the electrolysis.
All the electrolysis experiments were performed at
2.2. Chromatographic analyses room temperature and the glass cell was covered with
an aluminum foil in order to prevent the solution from
Chromatographic analyses were achieved by com- the possible photooxidation of DHMF or HMF.
paring the retention times of the reaction products
with those of references. Some reaction products
(FDC, HFCA and FDCA), which are not available on 3. Results and discussion
the market, were synthesized as described in Ref. [6].
These compounds so prepared were characterized by 3.1. Voltammetric study
IR spectroscopy (Nicolet 10MX), 1 H NMR spec-
trometry (Bruker 300) and by gas chromatography Cyclic voltammetry was used before each electrolysis
(Varian) combined with mass spectrometry (ITS 40 to check the degree of purity of the system and to fol-
Finnigan Matt). low the state of oxidation of the molecule. These pre-
The HPLC equipment consisted of an isocratic liminary studies are also helpful to choose the
pump (Knauer Pump 64), a reversed phase Alltima oxidation potential.
C18 column (2504.6 mm from Alltech), a variable
wavelength UV detector (Knauer) and an integrator± 3.1.1. On a bare platinum electrode
calculator (Merck-Hitachi, D-2000). Several operating The voltammograms of Pt, recorded at 50 mV s ÿ 1
conditions reported in the literature did not allow us and at room temperature in the supporting electrolyte
to separate and to detect DHMF and its derivatives alone (0.1 M NaOH) and in the presence of 50 mM
well. Thus, the suitable mobile phase, which was found DHMF, are given in Fig. 4. A shrinkage of the hydro-
by the approach of the Simplex method consisted of
H2SO4 in ultra pure water (pH 2.19). This acidic water
was added to a mixture of acetonitrile (50 cm3) and
methanol (50 cm3), in order to have 1 L of eluent. The
wavelength of the detector was set at l = 238 nm after
recording the UV-spectra of each reference product
(Fig. 2).
Under the optimum operating conditions, a chroma-
togram of a reference mixture is given in Fig. 3. The
sample loop size was 20 mL and the eluent ¯ow rate
0.6 mL min ÿ 1.

2.3. Preparation of solutions

Working solutions were prepared from ultra-pure

water (Millipore Milli-Q System). NaOH, acetonitrile
and methanol were purchased from Merck with the Fig. 4. Voltammograms of platinum at 50 mV s ÿ 1 and at
best purity available. DHMF and HMF were pur- 258C (- - -) in 0.1 M NaOH supporting electrolyte alone (ÐÐ
chased from Sigma. The Pb perchlorate salt used for Ð) in the presence of 50 mM 2,5-dihydroxymethylfuran.
2782 K.B. Kokoh et al. / Electrochimica Acta 44 (1999) 2779±2787
Fig. 5. Voltammograms of gold at 50 mV s ÿ 1 and at 258C
(- - -) in 0.1 M NaOH supporting electrolyte alone (ÐÐÐ)
in the presence of 0.1 M 2,5-dihydroxymethylfuran.
gen region, which is caused by the molecule adsorp-
tion, can be noticed. The oxidation of DHMF begins
only after 0.4 V (RHE). Two oxidation peaks (A and
B) are observed during the positive potential sweep.
Peak A is located in the region where the electrode sur-
face is covered by hydroxyl species, while peak B is
formed in the region of the platinum oxides. During
the negative potential sweep, i.e. after the reduction of
the Pt surface, another oxidation peak (C) takes place.
In all the cases, the current densities of the oxidation
peaks are relatively small ( jmax = 0.12 mA cm2 at 0.8
V (RHE)), showing that DHMF is not very reactive
on a bare platinum surface.
3.1.2. On a gold electrode
The ®rst voltammogram of Au in the presence of 0.1
M DHMF was recorded under the same previous ex-
perimental conditions. The electrode is a grid which
has a surface area of 24 cm2. Two main oxidation
peaks are observed (Fig. 5). During the positive scan,
the ®rst oxidation peak starts with the beginning of the
covering of the electrode surface by hydroxyls and
Table 1
Kinetics parameters of the oxidation of DHMF at noble metal electrodes in alkaline medium
Electrode Plot Slope
peak A
Pt log jp = f(log v) 0.5
log jp = f(1/T) ÿ1.43103
Au log jp = f(log v) 0.6
log jp = f(1/T) ÿ1.33103
jp is the peak current density corrected from double layer and other contributions; v is the potential sweep rate and DH * is the
activation energy.
Fig. 6. Voltammograms of nickel at 50 mV s ÿ 1 and at 258C
(- - -) in 0.1 M NaOH supporting electrolyte alone. (ÐÐÐ)
in the presence of 50 mM 2,5-dihydroxymethylfuran.
reaches its maximum at 1.4 V (RHE) with jmax = 1.5
mA cm ÿ 2. During the negative potential scan, any re-
duction current density can be observed and the sec-
ond oxidation peak shows that DMHF is more
reactive at a gold electrode ( jmax = 2.3 mA cm ÿ 2 at
E = 1.1 V (RHE)) than a platinum electrode.
The e€ect of the potential sweep rate and that of
temperature were investigated by cyclic voltammetry
(with Pt and Au electrodes microspheres) to provide
clear evidences on the kinetics parameters of the
DHMF oxidation. The rate was varied from 5 to 500
mV s ÿ 1, while the temperature was studied from 278
to 343 K. Plots of log jp against log v and against 1/T
allowed us to show that the mechanism of the electro-
oxidation of DHMF on platinum and gold, in alkaline
medium, is di€usion controlled (Table 1).
3.1.3. On a nickel foam electrode
The voltammograms of Ni, recorded under the same
previous conditions, are given in Fig. 6. The voltam-
mogram in the supporting electrolyte (0.1 M NaOH)
does not display a hydrogen adsorption region. The
formation of oxyhydroxide species at the electrode sur-
face (at Emax = 1.44 V (RHE)) occurs after several vol-
tammetric cycles. The stabilization of this layer results
DH * (kJ mol ÿ 1) Kinetics control
peak B peak A peak B
0.5 di€usion
ÿ1.32103 28.5 25.2 di€usion
di€usion
25.4 di€usion
 K.B. Kokoh et al. / Electrochimica Acta 44 (1999) 2779±2787 2783

Fig. 7. (a) Variation with the time of the current density and
the quantity of electricity involved in the electrooxidation of
50 mM DHMF at 0.73 V(RHE) on a Pt electrode. (b)
Evolution of the DHMF concentration and its oxidation pro-
ducts involved in the electrolysis of 50 mM DHMF at 0.73
V(RHE) on a Pt electrode. DHMF (Q), HMF (.). Fig. 8. (a) Variation with the time of the current density and
the quantity of electricity involved in the electrooxidation of
100 mM DHMF at 1.2 V (RHE) on a Au electrode. (b)
Evolution of the DHMF concentration and its oxidation pro-
ducts involved in the electrolysis of 100 mM DHMF at 1.2 V
(RHE) on a Au electrode. DHMF (Q), HMF (.) and HFCA
(R).

Table 2
Distribution and concentration of the oxidation products formed after long-term electro-
lysis of DHMF in alkaline medium, on Pt, Au and Ni electrodes

Electrode Potential Conversion Oxidation Selectivity

of oxidation V of DHMF products (%)
(RHE) (%)

Pt 0.73 10 HMF (5 mM) 100

Au 1.2 15 HMF (10 mM) 67
HFCA (5 mM) 33
Ni 1.7 29 HMF (12 mM) 81
HFCA (2.7 mM) 19
2 42 HMF (19 mM) 89
HFCA (2.3 mM) 10
2784 K.B. Kokoh et al. / Electrochimica Acta 44 (1999) 2779±2787

Fig. 10. Voltammogram of a Pt±Pb electrode in alkaline med-

ium (0.1 M NaOH), recorded at 50 mV s ÿ 1 and at 258C with
50 mM DHMF.

Fig. 9. Electrocatalytic e€ect of Pb adatoms on the DHMF

oxidation on platinum during the positive potential sweep.

from the oxidation of Ni(OH)2 to oxyhydroxide species

(NiOOH) [14±19]. The oxidation of DHMF on nickel
looks like that of many alcohols. This reaction begins
after the NiOOH layer has been formed (1.44 V
(RHE)) and gives large current intensities.

3.2. Long-term electrolysis of DHMF

3.2.1. On a bare platinum electrode

Despite the small current densities obtained at plati-
num, long-term electrolysis was realized on this elec-
trode using the three-potential program described in
Fig. 1. The potential plateau Eox was set at 0.73 V
(RHE) and the electrolysis was conducted for 8 h on
bare Pt, the active surface area of which was 31 cm2.
HPLC analyses of the bulk solution at regular periods
of time showed that DHMF was oxidized only to
HMF (Fig. 7).

3.2.2. On a gold electrode

Adsorption and oxidation processes take place sim-
ultaneously at a gold electrode. Thus, conversely to the
three-potential pulse program used for platinum, two
potential plateaus were here sucient. The adsorp-
tion±oxidation potential plateau was set at 1.2 V
(RHE) for 10 s and the second one, at 1.7 V (RHE)
for 0.2 s in order to reactivate the surface of the gold
Fig. 11. (a) Variation with the time of the current density and
the quantity of electricity involved in the electrooxidation of
50 mM DHMF at 0.9 V (RHE) on a Pt±Pb electrode. (b)
Evolution of the DHMF concentration and its oxidation pro-
ducts involved in the electrolysis of 50 mM DHMF at 0.9 V
(RHE) on a Pt±Pb electrode. DHMF (Q), HMF (.), FDC
(R) and HFCA (W).
 K.B. Kokoh et al. / Electrochimica Acta 44 (1999) 2779±2787
electrode. The electrooxidation of DHMF was carried
out for 8 h. The current density and the quantity of
electricity involved (Qexp) were recorded. The initial
current density was 0.82 mA cm ÿ 2 and at the end of
the electrolysis, it decreased up to 0.3 mA cm ÿ 2. After
8 h of electrolysis, Qexp reached 270 C, corresponding
to an experimental number of electrons equal to 2.4.
The analysis of the electrolytic solution by HPLC
showed that, with a 15% conversion yield, DHMF
was transformed mainly into 5-hydroxymethylfurfural
(HMF) and 5-hydroxymethylfurancarboxylic acid
(HFCA) (Fig. 8).
3.2.3. On a nickel foam electrode
Under the same conditions, long-term electrolysis
was carried out on a nickel foam but at a ®xed poten-
tial. Two di€erent oxidation potentials were applied
(1.7 V and 2 V (RHE)), i.e. on a Ni anode, the surface
of which was covered with the oxyhydroxide species.
Fig. 12. 1 H NMR spectrum of the lyophilized material obtained from the oxidation of 10 mM DHMF at 0.9 V (RHE) on a Pt±Pb
electrode.
2785
The current intensities increased with the potential.
Oxygen and hydrogen were also evolved in the work-
ing electrode and the counter electrode compartments,
respectively. This leads to a low Faradaic yield com-
pared with the conversion rate of DHMF also trans-
formed into HMF. Table 2 summarizes the results
obtained on bare platinum and gold and on nickel
foam electrodes.
The results of the electrolyses obtained with these
three electrodes show that the oxidation of DHMF
yields mainly HMF. The latter molecule, which is very
reactive but unstable chemically, is obtained selectively
on a Ni electrode, even if the conversion is not total
for a convenient synthetic process.
3.3. Oxidation of DHMF on a Pt±Pb electrode
It is well known that the presence of lead adatoms
at the platinum surface increases its electrocatalytic
2786 K.B. Kokoh et al. / Electrochimica Acta 44 (1999) 2779±2787

Scheme 1. Distribution of the reaction products resulting from the electrocatalytic oxidation of DHMF on a Pt±
Pb electrode at 0.9 V (RHE) in alkaline medium.

activity [20±22]. Indeed, when depositing underpoten-
tially Pb adatoms at the Pt surface, the current den-
sities of the DHMF oxidation increase up to 90 times
(Fig. 9).
Electrolysis was performed at a Pt±Pb electrode
(obtained with [Pb2+] = 510 ÿ 6 M) using again the
three-potential program of Fig. 1. The oxidation po-
tential plateau was set at 0.9 V (RHE) to take into
account the shape of the voltammogram due to the
presence of lead adatoms (Fig. 10). The current den-
sities were thus more signi®cant than those obtained
on bare Pt. Therefore, the quantity of electricity
recorded at regular periods of time (Fig. 11a) shows
that the oxidation of DHMF on a Pt±Pb electrode is
much important. The chromatographic analysis of the
bulk solution in the working electrode compartment
shows that DHMF is ®rstly oxidized to HMF and
then, HMF is mainly transformed into FDC (Fig. 11b).
Traces of HFCA and FDCA were also detected. The
Faradaic yield reaches 97% while the experimental
 K.B. Kokoh et al. / Electrochimica Acta 44 (1999) 2779±2787
number of electrons (nexp) involved was evaluated close
to 3.7. After 8 h of electrolysis, close to 95% of
DHMF was converted and the selectivity in FDC
became 61%.
3.4. Electrosynthesis of FDC using a Pt±Pb electrode
In the presence of lead adatoms (but obtained with
[Pb2+] = 510 ÿ 6 M), another electrolysis of DHMF
was carried out on platinum and at 0.9 V (RHE).
After 4 h of oxidation, HPLC analysis showed that
DHMF was totally converted. The electrolytic solution
in the compartment of the working electrode was then
neutralized using a cation exchange resin (Amberlite
200 from Sigma), in order to obtain an aqueous sol-
ution of the electrolyzed material free from inorganic
ions. Finally the 1 H NMR spectrum of the lyophilized
material in CD3COCD3 (Fig. 12) allowed us to show
that the main oxidation product of DHMF on Pt±Pb
is 2,5-furandialdehyde (FDC). Some small signals are
present in the spectrum, which are probably due to
presence of traces of the remaining DHMF (d6.31 (s,
.CH±CH.), d4.19 (s, CH2OD)). However the amount
of DHMF is too small to be detected by HPLC.
1
H NMR …CD3 COCD3 †: d7:60…s, .CH±CH.†, d9:89…s, CHO†:
4. Conclusion
The electrooxidation of DHMF was ®rstly carried
out on bare Pt and Au and Ni foam electrodes.
Suitable operating conditions for the liquid chromatog-
raphy analysis, were found to analyze the bulk sol-
ution during prolonged electrolyses. DHMF was
oxidized mainly to HMF on these three electrodes. As
HMF is known to be a very unstable molecule, its re-
duction to the DHMF form may be a convenient
mean for its storage if the conversion yield can be
improved. Thus according to the needs, DHMF can be
oxidized to HMF on Pt or on Ni. Actually, according
the results obtained, with a 42% conversion yield on
Ni, the synthetic process is still far from practical ap-
plications. Otherwise, this work showed that DHMF
can be transformed into another oxidation product
like 2,5-furandialdehyde (FDC) on Pt when the surface
of this electrode was modi®ed in situ by lead adatoms.
Chromatographic analyses showed that HMF
remained in the all cases the primary reaction product.
2787
However, on Pt±Pb the oxidation was completed selec-
tively in FDC as shown in Scheme 1. This work shows
that FDC can be synthetized with an high conversion
yield (close to 100%) when suitable conditions are
found to oxidize DHMF on a Pt±Pb electrode.
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