Journal of

Electroanalytical
Chemistry
Journal of Electroanalytical Chemistry 594 (2006) 1–19
www.elsevier.com/locate/jelechem

Review

A review of the aqueous electrochemical reduction of CO2 to

hydrocarbons at copper
M. Gattrell *, N. Gupta, A. Co
National Research Council, Institute of Chemical Process and Environmental Technology, 1200 Montreal Road, Ottawa, Ont., Canada K1A 0R6

Received 3 February 2006; accepted 16 May 2006

Available online 30 June 2006

Abstract

A review is provided on the aqueous reduction of CO2 to hydrocarbons at copper electrodes, covering the literature since the first report
of the reaction in 1985. This reaction is of interest as a potential component of a carbon energy cycle (i.e. CO2 + energy ! methane !
CO2 + energy). The synthesis of hydrocarbons from CO2 is a complex multistep reaction with adsorbed intermediates, most notably
adsorbed CO. The exact reaction mechanisms leading to the various products are not clear from the literature data to date and likely
change over the range of conditions at which data has been reported. The reaction product distribution is also very sensitive the surface
crystal structure copper electrode. The influences of various reaction conditions (potential, buffer strength and local pH, local CO2 con-
centration, stirring, and CO2 pressure) are discussed and some relationships between reaction conditions and products formed are
presented.
 2006 Elsevier B.V. All rights reserved.

Keywords: Carbon dioxide; Copper; CO2 reduction; Reaction mechanism

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Reaction intermediates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. CO reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4. Single crystal work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.5. The CO2 reaction step . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.6. Other factors – the electrode and electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.7. Other factors – temperature and pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

1. Introduction

*
Corresponding author. Tel.: +1 613 990 3819; fax: +1 613 991 2384. The electrochemical reactions of CO2 are of interest
E-mail address: michael.gattrell@nrc-cnrc.gc.ca (M. Gattrell). for the synthesis of chemicals and for approaches to

0022-0728/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2006.05.013
2 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19
decrease global warming. Work has been done looking at
synthesising specialty chemicals such as formate [1] and
urea [2]. However, a far greater impact on decreasing
atmospheric CO2 levels might be obtained by synthesising
fuels. In these carbon-based energy cycles, energy from
renewable or nuclear power would be used to synthesis
fuels from captured CO2, which, when used, would not
release additional CO2 to the atmosphere (i.e. ‘‘CO2 neu-
tral fuels’’). As such, these processes represent the storage
of these energy sources as chemical energy, which allows
them to be more widely used, particularly for transporta-
tion applications. The main advantages of such carbon
based fuels, vs. storing electricity in batteries or as hydro-
gen, are the ease of use within existing infrastructures and
the higher energy density (see for example [3]). Because
this involves converting electrical energy to chemical
energy, electrochemistry is an important enabling technol-
ogy [4].
In one carbon-based energy cycle concept, electrolytic
hydrogen would be reacted with CO2 to form methanol
and water, which, following distillation, yields liquid meth-
anol [3,5]. Another concept would react electrolytic hydro-
gen and CO2 to form methane (with condensation of water
to shift the equilibrium and achieve good yields) [6]. How-
ever, direct electrochemical reduction of CO2 would allow
for a simpler process and also, by avoiding high tempera-
ture reactors, would enable the process production rate
to be quickly varied to follow the time of day availability
of surplus electricity. A key discovery along the road to this
goal was the direct reduction of CO2 to hydrocarbons
(methane and ethylene) with reasonable current density
(5–10 mA cm2) and current efficiency (up to 69% at
0 C) at a copper foil electrode, reported by the group of
Prof. Hori [7,8]. While this discovery has not, to date, led
to the production of a pure hydrocarbon product, a sur-
prising range of hydrocarbons is formed (including ethanol
and propanol [9,10]). Further, the gaseous products mix
(hydrogen, methane, ethylene and CO), if the selectivity
for hydrocarbons could be improved, would be tantalis-
ingly close in fuel properties to ‘‘hythane’’, a clean burning
hydrogen/natural gas blend that has been promoted as an
alternative fuel for existing vehicles [11]. Thus, these reac-
tions are of interest as one possible tool for combating glo-
bal warming.
Taniguchi wrote a review of electrochemical and pho-
toelectrochemical reduction of carbon dioxide in 1989
[12]. Sullivan, Krist and Guard edited a thorough review
of the general area of electrochemical reduction of CO2 in
1993, with a chapter by Frese that looks specifically at
CO2 electroreduction at solid electrodes [13]. A more
recent overview of CO2 reduction at metal electrodes
has been done by Hori [14]. However, it is aim of this
paper to provide an in depth review focused on specifi-
cally the reduction of CO2 at copper electrodes in aque-
ous electrolytes, and also to try to see how what is
known can lead to a better understanding of the possible
reaction mechanism.
2. Review
2.1. Background
Copper is unique among the metals tried as an electrode
for CO2 reduction in its producing hydrocarbons at signif-
icant current densities. High hydrogen overvoltage elec-
trodes with negligible CO adsorption (such as Hg, Cd,
Pb, Tl, In and Sn) can reduce CO2 with a high current effi-
ciency. However, these metals are poor catalysts in the
sense that the primary product is formate (i.e. there is no
breaking of the carbon–oxygen bond of CO2). At the low
hydrogen overvoltage metals with a high CO adsorption
strength (such as Pt, Ni, Fe and Ti) CO2 is reduced to form
tightly adsorbed CO [15,16]. Because of the low turnover of
the adsorbed CO, when the electrode is pushed to (for
example) 5–10 mA cm2, the principle product is hydro-
gen. The electrode materials with a medium hydrogen over-
voltage and a weak CO adsorption, catalyse the breaking
of the carbon–oxygen bond in CO2, but allow the CO to
desorb. These include Au, Ag, Zn and Cu, with Au, Ag
and Zn producing CO with high current efficiencies, but
with Cu being able to further react CO to more reduced
species in significant amounts [7,14,17,18].
The primary reactions that occur at the copper electrode
during the reduction of CO2 are listed below (with the stan-
dard potentials calculated using formation energies from
[19]):
2Hþ þ 2e ¢ H2 E0 ¼ 0:0 V vs: SHE ð1Þ
þ 
2CO2 þ 12H þ 12e ¢ C2 H4 þ 4H2 O E0 ¼ 0:079 V vs: SHE
ð2Þ
CO2 þ 8Hþ þ 8e ¢ CH4 þ 2H2 O E0 ¼ 0:169 V vs: SHE
ð3Þ
þ 
CO2 þ 2H þ 2e ¢ CO þ H2 O E0 ¼ 0:103 V vs: SHE
ð4Þ
þ
CO2 þ H þ 2e ¢ HCOO  
E0 ¼ 0:225 V vs: SHE ð5Þ
The equilibrium potentials, over the range of pH values
around where the reactions are typically carried out, are
shown in Fig. 1. While, thermodynamically, methane and
ethylene should occur at a less cathodic potential than
hydrogen, kinetically this does not occur.
A set of polarisation curves (from the work of Prof.
Hori’s group [20]), measured at the copper electrode using
different gases and electrolytes is shown in Fig. 2. Curves
(a) and (b) were measured in a 0.1 M KH2PO4 + 0.1 M
K2HPO4 buffer (pH 6.8) under Ar and CO, respectively.
Under Ar, hydrogen evolution begins at around 0.8 V
vs. NHE reaching ca. 2.5 mA cm2 around 1.0 V. Under
a CO atmosphere, the current is greatly suppressed, not
reaching 2.5 mA cm2 until around 1.2 V. For testing
with CO2, a 0.05 M KH2PO4 + 0.15 M K2HPO4 buffer
was used, which equilibrated at pH 6.7 after saturating
with CO2 (curve (c)). The reaction of CO2 starts off near
that of hydrogen, with the current exceeding that of hydro-
 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19 3

-0.1

-0.2

Potential / V vs. SHE CO2/CH4

-0.3 CO2/C2H4
H+/H2
CO2/HCOO -
-0.4

-0.5
CO2/CO

-0.6

-0.7
5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10
pH

Fig. 1. The equilibrium potentials as a function of pH for the principal overall CO2 reduction reactions (at 25 C).

CO produced by the reduction reaction. If the buffer is

Fig. 2. Voltammograms obtained in phosphate solutions with Ar: (a), CO
(b), and CO2 (c) at pH 6.8, and with 0.1 M KHCO3 saturated with CO2 (d)
at pH 6.8. (Reproduced from [20] by permission of the Royal Chemical
Society.)
gen briefly (near 0.9 V), then after a peak current at
1.01 V the reaction current decays to slightly less than
that for CO reduction. As will be discussed later, this sup-
pression of hydrogen evolution during CO2 reduction is
generally agreed to be due to the presence of adsorbed
changed to 0.1 M KHCO3 (pH 6.8 after saturating with
CO2), the results in curve (d) are obtained. The current
starts around the same potential, but only increases slowly
with a slight shoulder near the peak in curve (c). This
shows the sensitivity of the reaction to the electrolyte (in
this example, the anion). Because of these complexities,
and in particular the suppression of hydrogen evolution
(i.e. the reactions are not independent), polarisation curves
need to be combined with other techniques to gain insight
into the CO2 reduction reactions.
The product distribution for CO2 reduction as a func-
tion of potential has been reported by the groups of Frese
[21], Ito [10] and Hori [20]. Frese’s group found that the
onset potential for CH4 was around 1.5 to 1.6 V vs.
SCE (at pH 7.6 and 22 C), with maximum efficiency (of
50% current efficiency) at about 1.95 V. At less negative
potentials (above about 1.6 to 1.7 V), CO production
exceeds CH4 production. The exact point of the change
of the dominant product from CO to CH4 was also influ-
enced by the electrode preparation and by the amount of
mass transport, with higher stirring resulting in more CO.
One suggestion for this was that higher mass transport
removes CO more effectively before it can be further
reduced to CH4. The authors also felt that CO was an
intermediate in the reduction of CO2 to methane, with
the electrochemical dissociation of CO as the slowest step
in the overall reaction. A larger set of products was mea-
sured by Ito’s group, with different products dominating
at different potentials. Starting at 1.35 V vs. Ag/AgCl/
saturated KCl, the main product was formate (at about
30% current efficiency), transitioning to CO at 1.47 V,
then ethylene below 1.54 V, and methane below
1.65 V (peaking at 38% efficiency at 1.70 V before
4 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19

decaying to 10% efficiency at 1.75 V as hydrogen evolu-
tion began to dominate). Solution phase products identi-
fied included ethanol (with 14% efficiency at 1.65 V)
along with propanal, propanol and ethanal (peaking
around 1.58 V with around 5%, 4.5% and 2% efficiencies,
respectively). Similar results were reported by Hori’s group
[20], along with the current densities. From the data of
Hori’s group, partial currents could be calculated for vari-
ous products and are plotted in Fig. 3 along with estimates
of the local pH and CO2 concentrations at the electrode
surface (taken from [22] and discussed in more detail later).
Initially, the current is predominantly for hydrogen evo-
lution. However, the rate of increase of hydrogen evolution
with overpotential begins to decrease around 0.95 V vs.
SHE, where CO begins to form. The hydrogen evolution
reaction eventually begins to recover below 1.26 V but
at a level roughly two orders of magnitude less than that
obtained by extrapolating from the initial data (around
0.9 V). This suggests, as has been indicated elsewhere
[23], that greater than 90% of the electrode surface is
blocked by adsorbed CO. Initially, CO2 reduction produces
CO and formate, until below 1.12 V, where hydrocarbon
products begin to form, with first ethylene, then methane
appearing. These reactions accelerate (with methane pro-
duction showing the stronger potential dependence), dom-
inating over CO and formate at around 1.35 V.
It is important to consider in these reactions the local
concentrations of pH and CO2 at the electrode surface.
The reason for the increased pH at the electrode surface
is the generation of OH ions (or the consumption of
H+) from the various reactions (Eqs. (1)–(5)). This is com-
plicated in this system, because CO2 is both a reactant and
a buffer and because some of the buffer reactions are kinet-
ically limited. In the CO2 and bicarbonate system the key
equilibria are:
CO2 þ H2 O ¢ ðH2 CO3 Þ ¢ Hþ þ HCO
3 pK a ¼ 6:4 ð6Þ
HCO
3 ¢H þ þ
CO2
3 pK a ¼ 10:3 ð7Þ
Eq. (6) results in the CO2 saturated bulk solutions hav-
ing pH values from around pH 6–8 (for bicarbonate con-
centrations of 0.05–2 M, respectively). However, in CO2
saturated bicarbonate solutions, the equilibrium concentra-
tion of H2CO3 is very low and the kinetics of its formation
are slow [24,25].
CO2ðaqÞ þ H2 O ¢ H2 CO3 k f ¼ 6:2  102 s1 ð8Þ

10
Total

Partial current density / mA cm -2

1

H2

-
HCOO 0.1

CH4
0.01
CO
C2H4

0.001
-0.8 -0.9 -1 -1.1 -1.2 -1.3 -1.4 -1.5
Potential / V vs SHE

1.0E-08 1.0E-01
[CO2]
CO2 Concentration / M
+ Concentration / M

1.0E-09 [H+] 1.0E-02

1.0E-10 1.0E-03
-0.8 -0.9 -1 -1.1 -1.2 -1.3 -1.4 -1.5
Potential / V vs SHE

Fig. 3. Partial current data from Hori et al. [20]. (Conditions: 0.1 M KHCO3, 19 C, CO2 bubbled, bulk [H+] = 1.55 · 107 M, bulk
[CO2] = 3.41 · 102 M. Estimated local [H+] and [CO2] values for polarisation measurements from [22].)
 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19
Thus, near the electrode surface where hydroxide is
forming, most of the buffer capacity results from reaction
(7) (with a much higher pKa) and from the direct reaction
of CO2 with hydroxide:
CO2 ðaqÞ þ OH ¢ HCO
3 k f ¼ 5:93  103 M1 s1
This can result in a significantly higher local pH. These
equations have been numerically solved by Gupta et al.
[22], and the results of these estimations are included in
Fig. 3. It can be seen that the local pH is predicted to be
around pH 9 for most of the measurements, then increasing
to around pH 10 when the total current exceeds 2 mA cm2.
This likely limits the recovery of hydrogen evolution at
higher overpotentials. The decreased local concentration
of CO2 will slow the formation of formate and CO, with
the more rapid drop in CO product recovery likely due to
the increased rate of its further reaction to CH4 and C2H4.
Other products reported from CO2 reduction at the cop-
per electrode include [9,10,14]: ethanal, ethanol, acetic acid
[26], propanal, 2-propen-1-ol, propanol. Interestingly,
methanol, formaldehyde and ethane are not reported.
2.2. Reaction intermediates
In Fig. 3, CO and formate are initially formed before
hydrocarbons form at more cathodic potentials. Early
work found that the reduction of CO at Cu leads to a sim-
ilar product distribution, suggesting that CO was an inter-
mediate in CO2 reduction [27,21,28]. Tests starting from
formate do not result in any measurable products [20,29]
(though from concentrated formic acid, deposits on the
electrode and trace methane have been reported [28,29]).
It was also found that CO directly suppressed hydrogen
evolution, while CO2 required some charge to be passed
before hydrogen evolution was suppressed. The charge
required at different current densities was found to be con-
sistent with the reduction of CO2 to form an adsorbed CO
layer [23]. In both cases, hydrogen evolution activity could
be recovered if the reaction was interrupted and the solu-
tion bubbled with Ar, suggesting the material blocking
the electrode surface was reversibly adsorbed.
Optical experiments with CO have shown it is adsorbed
on Cu once the potential is sufficiently cathodic to allow
CO to displace adsorbed anions [30]. The observed absorp-
tion peak was found at 2040 cm1 at less cathodic poten-
tials (around 0.6 to 0.7 V vs. NHE), shifting to
2080 cm1 at more negative potentials (around 1.0 V).
This peak corresponds to the vibration of the CO molecule
adsorbed on-top (i.e. at a single copper atom) and is similar
to, though at a slightly lower wavenumber than, typical
results measured for CO adsorption on Cu under
ultra-high vacuum (UHV) conditions (see Table 1). (A dis-
cussion of the different effects of UHV vs. solution environ-
ments on the vibrations of adsorbed CO and NO has been
presented by Weaver et al. [32].) One can also see in Table 1
that the vibration varies with the copper crystal face and
with the degree of coverage.
5
Table 1
Infrared adsorption peak frequencies (cm1) for CO adsorbed on various
copper crystal faces under UHV conditions (approximately 77 K) (from
[31])
Crystal face Low coverage Saturation coverage
ð9Þ 100 2079 2088
111 2080 2070
110 2088, 2104 2094
211 2095, 2109 2110
311 2093, 2109 2104
755 2111 2106
When CO2 is reduced at a copper cathode, it was shown
by the group of Prof. Hori, that the infrared adsorption of
CO is detected (at 2085 cm1 at 0.9 V vs. NHE and
2081 cm1 at 1.0 V) [33]. These results have been con-
firmed by other workers using both infrared and surface
enhanced Raman spectroscopy (SERS). In the work of
Oda et al. [34], CO2 reduction was studied at electrodepos-
ited copper in 0.05 M Na2SO4 at 0.5 and 0.7 V vs. SHE
(using 0.3 V for the reference spectra). CO adsorption
was noted both for the reference and the measured poten-
tials (shifting with potential), but new peaks were noted at
1370 and 1542 cm1 assigned to carbonate (discussed fur-
ther below). SERS measurements were also made using
3.5 M KCl solution. These spectra showed a peak at
283 cm1, characteristic of Cu–Cl stretching at 0.6 and
1.0 V. At 1.4 V this was replaced by a pair of peaks
at 2046 and 1998 cm1, characteristic of CO stretching.
At 1.6 V, these peaks shifted to 2082 and 2037 cm1,
and peaks appeared at 360 cm1 attributed to Cu–CO
stretching and at 1054 cm1 attributed to symmetric
stretching of carbonate. The latter presumably appearing
due to the high overpotential resulting a high local pH,
and hence carbonate from reaction (7).
A SERS study of CO2 reduction was also carried out by
Smith et al. [35]. On polarisation of an electropolished cop-
per electrode to 1.06 V vs. NHE in a CO2 or CO satu-
rated 0.1 M NaHCO3 solution, a number of adsorption
peaks were observed in the spectra. These included the
vibrations for on-top adsorbed CO at 2090 cm1 (CO
stretch), 358 cm1 (Cu–CO stretch) and 280 cm1 (Cu–CO
frustrated rotation). A broad flat band at 2900 cm1 and a
weak band at 1450 cm1 are attributed to CHx stretching
and CHx deformation, respectively, and a peak at
1050 cm1 related to carbonate stretching. Bands were also
found after stepping the electrode anodic (to 1.3 V to clean
the surface and maintain the required roughness for SERS
activity). On the return steps in the cathodic direction at
0.16 and 0.36 V, new peaks were observed at 1580
and 1340 cm1, as well as a large increase in the intensity
of the 1050 cm1 peak. These were assigned to graphitic
carbon. However, the suggested assignments are for crys-
talline graphite vibrations, which appear unlikely, as one
would expect carbon formed under these conditions to
more amorphous. Others have reported similar vibrations
during the oxidation of formate using silver, which they
attributed to adsorbed carboxy species [36]. Adsorbed
6 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19
formate on silver is also reported to give vibrations at
1550 cm1 (O–C–O antisymmetric stretch) and 1350 cm1
(O–C–O symmetric stretch) [37], and at 1560 and
1360 cm1 in UHV [38]. Prof. Hori’s group has recorded
a vibration at 1545 cm1 in 0.2 M K2CO3 solution assigned
to adsorbed carbonate [30]. As discussed above, Oda et al.
assigned vibrations at 1370 and 1542 cm1 measured at
0.5 and 0.7 V vs. SHE in CO2 saturated 0.05 M Na2SO4
to carbonate. However, in both Oda and Smith’s experi-
ments, because they were saturated with CO2, carbonate
would only be expected at high overpotentials where the
local pH becomes high. Therefore, at the low overpoten-
tials involved, the assignment of the peaks around 1560
and 1350 cm1 to carbonate (and also the increased inten-
sity of the 1050 cm1 peak in Smith et al.’s work) is unsat-
isfying. And so, while we feel the assignment of these peaks
to graphite is unlikely, we can at best say they are associ-
ated with some type of adsorbed carboxy species. In the
work of Smith et al., there is also peak (around
525 cm1) that grows with time and is associated with a
slow loss of activity for CO2 reduction (a poisoning
species). However, their solutions were not purified by
pre-electrolysis [39], making any interpretation uncertain
(discussed more in later).
These studies clearly show that the electrode surface is
dominated by adsorbed CO during the CO2 reduction
and that CO is an intermediate in the production of hydro-
carbons. The latter point is especially nicely shown in the
work of Smith et al., where both CO2 and CO saturated
solutions result in similar spectra. Because of the high
implied coverage of CO during the reduction of CO2, it
was felt that the reduction of adsorbed CO was the key rate
determining step for the overall reaction of CO2 to hydro-
pH 6.0-6.3
pH 7.1-7.7
pH 8.0-8.6
pH 8.7-8.9
pH 9.0-9.3
pH 10.5-11.3
pH 12.2
-1.05 -1.1 -1.15
Potential / V vs. SHE
Fig. 4. The partial current densities for ethylene formation from CO in various buffer solutions (data taken from [40]).
carbons [21,20]. Therefore, studies have been done focusing
on the reduction of CO. This has the advantage of having
fewer reaction steps to consider. It also avoids the compli-
cation found with CO2 reduction studies, where the reac-
tant is also part of the buffer, thus simplifying the
estimation of the local CO concentration at the electrode
surface.
2.3. CO reduction
A detailed study of the reduction of CO at copper elec-
trodes was carried out by Prof. Hori’s group [40]. Reac-
tions were carried out at various pHs using phosphate
buffer, borate buffer, or K2HPO4–KOH with a total elec-
trolyte concentration of 0.2 M. The cell was stirred with
a magnetic stirrer and the mass transport characterised
using ferricyanide. Potentiostatic and galvanostatic runs
were carried out for 30 min or more under conditions
below 20% of the estimated limiting current for CO. From
these data, potential and pH dependencies of the CO
reduction could be determined. The results reported for
the partial current for ethylene formation are shown in
Fig. 4. The data show a distinct Tafel slope corresponding
to a transfer coefficient of 0.35 without any apparent effect
of pH. The data found for the partial current for methane
formation, however, did not result in Tafel relationship
unless the results were first corrected for the pH. The best
straight line relationship on a semi-logarithmic plot was
found when the reaction was assumed to be first order in
proton concentration (see Fig. 5). From the corrected data,
a transfer coefficient of 1.33 was determined.
These results raised some interesting questions about the
hydrocarbon formation mechanism. In prior papers, it had
Partial current / mA cm-2
0.1
0.01
-1.2 -1.25 -1.3 -1.35 -1.4
 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19 7

11

pH 6.0-6.3
pH 7.1-7.7 10
pH 8.0-8.6
pH 8.7-8.9
9
pH 9.0-9.3

Log(imethane / mA cm-2) + pH
pH 10.5-11.3
pH 12.2 8

3
-1.05 -1.1 -1.15 -1.2 -1.25 -1.3 -1.35 -1.4
Potential / V vs. SHE

Fig. 5. The partial current densities for methane formation from CO in various buffer solutions assuming a first order reaction with respect to [H+] (data
taken from [40]).

been hypothesised by analogy to Fischer–Tropsch synthe- O

sis and based on the methane and ethylene products, that
carbonyl (Cu@CH2) was a key intermediate leading to
both products [41,28,20]. However, the very different Tafel
slopes found indicate that the pathways to methane and
ethylene are different (also their appearance at different
potentials in Fig. 3). Further, the transfer coefficient of
0.35 for ethylene formation implies that the rate determin-
ing step is the first electron transfer, indicating that the
mechanisms may differ right at the first electron transfer
to CO. As well as the products which are formed, another
important criterion in considering the mechanism is the
lack of formation of methanol. This implies that the car-
bon–oxygen bond of CO is broken early and consistently
in the mechanism.
For the case of methane formation, the transfer coeffi-
cient of greater than 1 suggests that there is an initial elec-
tron transfer in equilibrium before the rate determining
step. This would result in a CO anion radical as shown in
Fig. 6.
The state of the adsorbed CO anion radical on copper
has been evaluated through ab initio calculations by
Watanabe et al. [42]. They estimate a slight decrease of
the Cu–C bond and an increase of the C–O bond to about
1.25 Å, thus predicting a mostly double bond character
(e.g. CO2 1.16 Å, H2C@O 1.21 Å, and H3C–OH 1.42 Å
O
-
O
- -
C e C C
C u Cu Cu Cu C u C u Cu Cu Cu
Fig. 6. The expected resonant structures following an initial electron
transfer to adsorbed CO.
[43]). There is also a proton involved in the reaction, and
this must occur reversibly before the second electron trans-
fer rate determining step (hence an ECE reaction) to yield
the observed transfer coefficient. As the formation of a
C–H bond would not be reversible, this implies an acid–
base reaction at the oxygen. This leads to mechanisms such
as shown in Fig. 7 (with the right hand product similar to
that suggested by Kim et al. [21]).
(Note, for simplicity in this and subsequent examples,
the reaction is written indicating on top bonding to a single
copper. Bridge bonding might also occur.) Another possi-
bility would be the reaction with adsorbed hydrogen (see
Fig. 8). Depending on the potential and pH dependency
of the adsorbed hydrogen coverage, this might also lead
to the observed reaction order and transfer coefficient.
Once the adsorbed CO has been electrochemically split,
the product of this reaction would then go through hydro-
gen additions leading to methane. These hydrogen addi-
tions could occur either through reaction with adsorbed

- - -
O OH OH
C H
+
C H
C e
- C O
Cu Cu Cu Cu Cu Cu Cu Cu Cu or C u C u C u C u

Fig. 7. A reaction mechanism that would lead to the observed transfer coefficient and reaction order with pH.
8 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19

- 2.4. Single crystal work

O H -
H C C O
Cu Cu Cu Cu Cu Cu In the review by Frese [13], work is presented that inves-
Fig. 8. A reaction mechanism that might also lead to the observed transfer tigates the influence of the copper surface structure on the
coefficient and reaction order with pH. (Note that the adsorbed oxygen product distribution (in particular the rate and current effi-
might also occur as Cu2O.) ciency for methane production). Methane formation rates
found at 1.85 V vs. SCE in 0.5 M KHCO3 were 0.5 ·
105 mol cm2 h1 on Cu(1 0 0), 1.0 · 105 mol cm2 h1
hydrogen and/or through electron transfer followed by
on Cu(1 1 0) and 5.8 · 105 mol cm2 h1 on Cu(1 1 1).
protonation.
The maximum rates of methane formation, presumably
The reaction to form ethylene begins at a lower potential
due to mass transfer limitations of the CO2, also varied at
(see Fig. 3), without a pH dependence and with the first
each crystal face, indicating different product distributions.
electron transfer being the rate determining step. As the
Variations were also found using electrodeposited copper
first electron transfer begins a reaction pathway that subse-
with different plating baths, deposition current densities
quently results in a two carbon product, it is reasonable to
and substrates. One trend that was noted was a decrease
assume that some type of bond formation occurs in this
in methane production with higher copper deposition cur-
reaction step. A reaction is proposed that involves a ‘‘prior
rent (possibly due to less crystalline deposits). In fact very
association’’ of two adsorbed COs (see Fig. 9). The postu-
low currents, including simply holding a copper foil at open
lation of a starting ‘‘associated pair’’ of adsorbed COs also
circuit, resulted in improved methane yields, attributed to a
would be consistent with the lower activation potential vs.
gentle electropolishing of the copper surface.
the formation of CO (and hence methane). This hypoth-
A detailed study of the effect of copper crystal faces on
esis will be discussed more in the following section.
product distributions, including the influence of step edges,
It can also be shown that the polarisation curves for CO
has been done by the group of Prof. Hori, with a summary
are consistent with those for CO2. From the data shown in
of their results shown in Table 2. It can be seen that the
Fig. 3, one can obtain a transfer coefficient of 0.48 for eth-
product distributions are strongly affected by the copper
ylene production (obtained by excluding the data at
crystal structure. Generally, the crystal faces dominated
1.46 V), similar to the value of 0.35 for CO reduction.
by Cu(1 0 0) tend to result in a significant current efficiency
For methane production a transfer coefficient of 0.86 is
for ethylene at relatively low overpotentials. The crystal
obtained, but assuming the reaction from CO2 is also first
faces dominated by Cu(1 1 1) tend to be polarised to more
order in hydrogen ion, we can correct the partial current
negative potentials and favour methane production.
density by [H+]bulk/[H+]local. This results in a transfer coef-
Finally, the Cu(1 1 0) type surfaces polarise to the most neg-
ficient of 1.19, which is similar to that reported for methane
ative potentials and result in other 2 carbon and 3 carbon
for CO reduction. Thus, the mechanisms appear to be the
products (including acetic acid [26]). Using the Tafel slopes
same with the two different starting reactants. (While we
from the previous section and the data from Table 2, par-
also have estimates for [CO2]local, correcting the partial cur-
tial currents for methane and ethylene can also be norma-
rents would be complicated by needing to be able to relate
lised to a common potential. This is shown in Fig. 10,
this to the coverage of adsorbed CO.)
where one can see that at the chosen relatively low overpo-
In the work of Kim et al. [21], CO2 was reduced in
tential, overall, ethylene production is favoured vs. meth-
0.5 M KHCO3 at a mechanically polished and HCl
ane (consistent with Fig. 3). This formation of ethylene
cleaned copper foil. They obtained a Tafel slope of
at low overpotentials is favoured on Cu(1 0 0) type surfaces,
110 mV decade1 (transfer coefficient of 0.55) for methane
preferably with reasonably wide terraces. If the potential is
and 200 mV decade1 (transfer coefficient of 0.30) for eth-
made more negative, the methane reaction (because of its
ylene. However, they used a higher range of current den-
higher transfer coefficient) rapidly dominates, most notably
sities than those in Fig. 3 and found methane formation to
at the 3 1 1 and 2 1 1 crystal faces. One possible reason for
be mass transport controlled negative of 1.9 V vs. SCE.
the favouring of ethylene formation on Cu(1 0 0) type sur-
Because some of the data was close to the limiting current,
faces might be related to the hypothesised rate determining
and the correction for local pH will likely be large, these
step in Fig. 9. Such a step would require the p orbitals of
results represent minimum possible values for the transfer
the adsorbed CO to interact simultaneously with vibra-
coefficients and so are not conflicting with those taken
tional motions bringing the two oxygens close to copper
from Fig. 3.
surface atoms. Such an intermediate state would be more
likely with a right angle arrangement of surface copper
atoms (see Fig. 11).
O O - The tilting motion of adsorbed CO brings the oxygen
O O
C C C C C C
e- O O closer to the copper surface, which is a likely prerequisite
C u Cu C u C u Cu Cu C u C u Cu C u Cu Cu for CO dissociation. This vibration is described as a frus-
Fig. 9. A reaction mechanism that would lead to the observed transfer trated translational motion or T-mode vibration where
coefficient and produce a two carbon product. most of the motion occurs at the oxygen [45]. The displace-
 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19 9

Table 2
CO2 reduction products at various copper single crystal electrodes (data from [44]) (5 mA cm2, 0.1 M KHCO3)
Test conditions Current efficiency/%
Crystal series n Crystal Potential CH4 C2H4 CO H2 HCOO Other C2+
[n(1 0 0) · (1 1 1)] inf 100 1.40 30.4 40.4 0.9 6.8 3.0 17.4
6 1111 1.37 8.9 50.2 1.8 8.8 3.2 24.2
5 911 1.36 5.7 50.9 0.0 12.7 3.5 28.6
4 711 1.34 5.0 50.0 1.1 15.6 4.6 21.5
3 511 1.36 11.4 39.0 1.9 18.1 8.8 22.3
2 311 1.37 36.0 23.8 2.6 13.3 14.0 9.2
111 1.55 46.3 8.3 6.4 16.3 11.5 7.5
[n(1 0 0) · (1 1 0)] inf 100 1.40 30.4 40.4 0.9 6.8 3.0 17.4
8 810 1.38 6.4 45.1 1.4 8.7 1.5 32.4
6 610 1.37 7.6 44.7 0.9 9.0 1.4 33.6
5 510 1.38 8.1 42.3 2.1 10.5 2.8 37.2
3 310 1.42 17.7 34.6 0.0 12.8 2.7 38.6
2 210 1.52 64.0 13.4 2.2 7.0 5.5 9.5
[n(1 1 1) · (1 0 0)] inf 111 1.55 46.3 8.3 6.4 16.3 11.5 7.5
10 1199 1.48 62.4 10.2 4.9 7.2 7.9 9.0
6 755 1.43 62.9 11.5 4.4 6.9 12.3 8.9
4 533 1.42 62.9 13.0 3.0 4.7 9.7 4.6
3 211 1.38 45.6 17.8 2.1 11.2 13.6 8.2
2 311 1.37 36.0 23.8 2.6 13.3 14.0 9.2
[n(1 1 1) · (1 1 1)] inf 111 1.55 46.3 8.3 6.4 16.3 11.5 7.5
6 332 1.51 39.6 9.9 6.1 10.3 9.4 16.3
3 331 1.55 13.8 16.6 7.7 5.7 9.1 31.1
2 110 1.58 6.9 13.5 13.9 3.1 10.1 52.5
[n(1 1 0) · (1 0 0)] 6 650 1.59 10.5 16.2 14.5 2.5 6.1 48.6
3 320 1.52 52.4 13.7 5.4 5.3 5.8 15.8
2 210 1.52 64.0 13.4 2.2 7.0 5.5 9.5
Other C2+ includes: ethanal, ethanol, acetic acid, propanal, 2-propen-1-ol, propanol.

CH4
5
C2 H4
-2
Partial current / mA cm

0
inf 6 5 4 3 2 0 inf 8 6 5 3 2 inf 10 6 4 3 2 6 3 2 inf 6 3 2
[n(100)x(111)] [n(100)x(110)] [n(111)x(100)] [n(110)x(100)] [n(111)x(111)]
Crystal face

Fig. 10. Data from Table 2 normalised to 1.39 V vs. SHE using transfer coefficients of 0.4 for ethylene and 1.3 for methane.

ments of the carbon and oxygen within the four main of ±5.14 · 109 V cm1 [46]). The T-mode vibration has
vibrational modes for adsorbed CO have been estimated been studied in the gas phase using He scattering and a
to be relatively independent of electric fields (in the range strong influence of the copper surface structure has been
10 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19

O 2.5. The CO2 reaction step

C O
C The initial stage of the reaction of CO2 to form hydro-
carbons involves the reaction of CO2 to form CO. This
reaction competes with the formation of formate. Refer-
ring to Fig. 3, hydrogen, formate and CO are the dominant
Fig. 11. One explanation for the catalysis of ethylene formation on reactions at less negative potentials. However, the under-
Cu(1 0 0) type copper crystals. standing of the initial reactions of CO2 is complicated by
the blocking of electrode surface by CO and the further
reactions of CO to hydrocarbons. Thus, some clearer
found (see Table 3) [47]. The results show a clear increase in
insight might be gained by examining the literature for
the amplitude of such vibrations as the copper surface
CO2 reduction on similar metals to copper, such as silver
becomes more defective, suggesting that defects and step
and gold, where CO is more easily desorbed and so does
edges should help catalyse the dissociation of CO.
not further react to any significant extent. On these metals
An increase in step edges on the Cu(1 0 0) face does seem
the predominant reaction is CO2 to CO, with a small
to result in increased activity for ethylene (see Fig. 10). How-
amount of formate and hydrogen.
ever, a maximum activity occurs at Cu[4(1 0 0) · (1 1 1)]
At the gold electrode, the reaction has been found to be
(which also corresponds to the lowest overpotential in Table
first order in CO2 with a Tafel slope of around 120 mV
2). As the Cu(1 0 0) terraces become smaller than 4 atoms
decade1, and so the rate determining step is felt to be the ini-
wide, the activity begins to drop. For methane, the highest
tial reduction of CO2 [49,50].
partial current occurs for Cu[2(1 1 1) · (1 0 0)]. It should be
noted, however, that the estimated partial currents in CO2 þ e ¢ CO
2ads ð10Þ
Fig. 10 are for the complete CO2 reduction to hydrocarbons Results using single crystal silver electrodes show that
reaction, and so they include both dissociating CO2 and con- the reaction of CO2 to CO is favoured on Ag(1 1 0) (see
verting CO to hydrocarbons. Thus, the best crystal face for Fig. 12) [51]. The reaction to form formate may also show
the conversion of CO2 to hydrocarbons needs to provide some enhancement at Ag(1 1 0), but the reaction slows
sites for CO2 dissociation and for further reaction of CO. below 1.5 V vs. SHE, likely due to depletion of the local
In some of Prof. Hori’s group’s earlier copper single crystal CO2 concentration by the CO forming reaction.
studies, the product distributions of galvanostatic reactions The adsorption and reaction of CO2 on copper has been
of both CO2 and CO were measured [48]. Because of the studied in the gas phase because of interest in the methanol
lower solubility of CO, experiments were carried out at synthesis reaction (H2 + CO + CO2 ! CH3OH + H2O),
2.5 mA cm2 vs. 5.0 mA cm2 for CO2 reduction. The prod- which is normally carried out on a copper-zinc oxide cata-
uct partial currents for methane and ethylene at polycrystal- lyst. CO2 is found to both physisorb (as a linear molecule)
line copper, Cu(1 0 0), Cu(1 1 0) and Cu(1 1 1) electrodes and chemisorb (as a bent COd 2 molecule) [52]. The activa-
followed generally the same trends. Though, overall, the tion of physisorbed CO2 to chemisorbed form has been
CO2 reduction required a slightly higher overpotential, reported to be promoted by surface defects [53], alkali
and a greater difference in overpotentials was found between metal promoted surfaces [54–56] and possibly through
the different crystal faces. the action of X-rays or photoelectrons during measure-
In any case, the results of the single crystal studies ments [52]. Using SERS the symmetric stretch mode and
clearly show why the electrode preparation can have such deformations modes were reported at 1368 and 650 cm1,
a strong influence on the results obtained. respectively, for physisorbed CO2 and at 1182 and
768 cm1 for chemisorbed CO2 [53]. The dissociative
Table 3 adsorption of CO2 has been reported on stepped copper
The energy related to the frustrated translational vibration of adsorbed
CO on copper (data from [47]) surfaces [57,58], thought to occur through a chemisorbed
COd2 intermediate and leading to CO and adsorbed oxy-
Surface T-modea Relative CO adsorption
energy/meV amplitudeb energy/kJ mol1 gen. The adsorbed COd 2 is also thought to be stabilised
by formation of a T-shaped [OCOCO2] structure with
Cu(1 1 1) 4.07 1.00 47.3
Cu(1 0 0) 3.94 1.03 51.1
neighbouring physisorbed CO2 [52]. As well as dissociation
Cu(1 1 0) parallel 3.75 1.09 54.0 to CO and O, the COd 2 has been reported on alkali metal
to step edge activated copper surfaces to lead to oxalate (thought to be
Cu(1 1 0) perpendicular 3.40 1.20 54.0 via dimerisation of CO 2 ) and CO + carbonate products
to step edge (thought to be via [OCOCO2] or possibly oxalate)
Cu(2 1 1) 3.00 1.36 58.4
Cu(5 1 1) 3.05 1.33 57.7
[52,54]. When COd 2 is co-adsorbed with hydrogen, again
Sputtered on Cu(1 0 0) 3.20–2.52 1.27–1.62 58.2 on alkali metal activate copper surfaces, formate is
a
The frustrated translational vibration of CO parallel to the surface,
reported [55,56].
which results in a tilting vibration. The exact adsorption geometry of COd 2 is not clear,
b
Inversely proportional to the T-mode vibration energy. with the postulated structures shown in Fig. 13 based on
 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19
Fig. 12. Partial current densities on silver single crystals (0.1 M KHCO3, CO2 saturated, from Hori et al. [51]). (Reproduced by permission of the Journal
of Electroanalytical Chemistry.)
Fig. 13. Possible structures for adsorbed COd
2 on metals (adapted from
[52,59] with the metal atom diameter scaled for copper).
the structures of CO2–metal complexes [52,59]. One reason
for the uncertainty is that the expected vibrations could be
affected by surface geometry and, as discussed above, the
COd2 species is most easily produced at surface defects or
in the presence of submonolayer coverage of an alkali
metal. There is also the possibility that the COd2 is stabi-
lised by neighbouring physisorbed CO2 in a [OCOCO2]
structure. On Ni(1 1 0), which has been studied in some
detail [52], it is thought that the predominant form is oxy-
gen coordinated. Though, it is also found that, in the pres-
ence of adsorbed hydrogen, formate is formed, which is
also oxygen coordinated [52]. Note that such a reaction
with the adsorbed hydrogen must involve bringing the car-
bon closer to the metal surface to interact. This might indi-
cate that some interchange of coordinated states is
possible. It was also found that the COd 2 molecular plane,
while perpendicular to the surface, was randomly oriented
in relation to the h1 1 
0i azimuth, while formate was aligned
parallel. This was taken to indicate at least some of the
COd was carbon coordinated allowing free rotation of
2 ium to high overpotential [12]. Formate could also be
the molecule. For the electrochemical case, one would have
additional influences on the preferred orientation from the
electrolyte and the electric field.
The adsorbed state of COd 2 would also be influenced by
the type of metal. As discussed previously, high hydrogen
11
overvoltage electrodes with weak adsorption of hydrogen
also have a high overvoltage for CO2 reduction to CO 2ads
(hence a weak adsorption/stabilisation of CO 2ads ) and pro-
duce predominantly formate (or oxalate in non-aqueous
CO2 electrolysis) (e.g. Hg, Cd, Pb, Tl, In and Sn). Low
hydrogen overvoltage metals also reduce CO2 at low over-
potential to form tightly adsorbed CO (e.g. Pt, Ni, and Fe).
And medium hydrogen overvoltage metals reduce CO2 at
medium overpotential to form more loosely held CO (e.g.
Au, Ag, Zn and Cu) [14,17].
In the electrochemical reduction of CO2 at solid
electrodes it is generally agreed that, at medium to high
overpotentials, the first electron transfer to form a CO 2
anion radical is the rate determining step [12–14]. In aque-
ous solution, this intermediate then reacts further to form
formate or CO with the product distribution being deter-
mined by the relative rates of the different reaction path-
ways. The rates of the different reaction pathways will be
determined by the local rate determining step within that
pathway. Different possible mechanisms have been sug-
gested for the different pathways [12–14].
The reaction to form formate could occur by proton-
ation then reduction.
COO
 þ
ads þ H ! HCOOads

ð11Þ
HCOOads þ e ! HCOO ð12Þ
Such a reaction mechanism, with a proton adding at the
carbon, would appear to be favoured by CO 2 being
adsorbed with oxygen coordination. On high hydrogen
overpotential electrodes, where CO2 is reduced to formate,
the reaction has been reported to have a Tafel slope char-
acteristic of a second electron transfer r.d.s. at low overpo-
tential, shifting to the first electron transfer r.d.s. at
medium to high overpotential. This was suggested to corre-
spond to step 12 at low overpotential and step 10 at med-
formed by reaction with adsorbed hydrogen similar to
the gas phase results. Adsorbed hydrogen would be present
as an intermediate in the hydrogen evolution reaction.

COO
ads þ Hads ! HCOO

ð13Þ
12 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19

Similar mechanisms are possible for CO formation. One r.d.s. *-

CO2 + e- CO2
pathway might also be protonation then reduction. ads

Though, in this case, with a proton adding at the oxygen, HCOO

- ?
the mechanism would appear to be favoured by CO 2 being
adsorbed with carbon coordination.

COO þ 
ads þ H ¢ COOHads ð14Þ
slow
 
COOHads þ e ! COads þ OH 
ð15Þ CO COads

And, CO could be formed by reaction with adsorbed ?

hydrogen.

COO
ads þ Hads ! COads þ OH

A third alternative for CO formation involves reaction
between two CO2 molecules. As discussed earlier, such for-
mation of a T-shaped structure between the CO2 anion rad-
ical and the neutral form has been estimated to result in a
more stable intermediate species [52].

CO
2ads þ CO2 ¢ ½OCOCO2 ads
½OCOCO2 
ads

þ e ! COads þ CO2
3 ð18Þ
Note that a reaction route involving direct reaction of
two CO 2ads species would have to overcome the repulsion
of the negative charges and so would likely be more
difficult.
A schematic overview of the reaction pathways is shown
in Fig. 14. Following CO2 reduction, two pathways are
shown, one leading to formate and the other to CO and
hydrocarbon products. Both CO2 reduction and hydrogen
evolution occur on unblocked areas of the electrode sur-
face, with CO being the primary cause of surface inhibi-
tion. The possible involvement of adsorbed hydrogen in
the reaction pathways is also indicated. If the reaction
pathways involve hydrogenation, then there will be an
interaction with the hydrogen evolution reaction. In such
hydrocarbons
ð16Þ r.d.s.
H+ + e- Hads
H2
Cu electrode
Fig. 14. The main reaction pathways at the electrode surface, with
adsorbed CO blocking the majority of the surface and hydrocarbon
products being formed by the further reduction of adsorbed CO.
ð17Þ
a case, a full understanding of the mechanism requires an
understanding of hydrogen evolution on copper. (Note

that other the possible interactions such as CO
2 or CO
with hydrocarbon intermediates are not shown here, but
might be expected to be involved in the production of 2
and 3 carbon alcohols and acids.)
Hydrogen evolution on copper over a range of solution
pHs has been studied by Bockris et al. [60]. The results of
their work have been plotted in Fig. 15. One can see that
the reaction kinetics are pH dependent in the acid region
(proton discharge) and pH independent in the alkaline
region (water discharge). Extrapolating from the two data
sets suggests that the shift in mechanisms occurs around
pH 11–12. Thus, for most CO2 reduction work (see, for
example, Fig. 3 where pH < 10), the hydrogen evolution
reaction can be written in terms of protons.

-0.2
Potential / V vs. SHE

-0.4
Erev

-0.6
0.1 mA cm-2

1 mA cm-2
-0.8

-1

-1.2
0 2 4 6 8 10 12 14
pH

Fig. 15. Hydrogen evolution polarisation data at copper with varying solution pHs. Data from [60].
 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19 13

Hþ + e ! Hads
This can be followed by recombination or electrochemical
desorption.
2Hads ! H2
or
Hads + Hþ + e ! H2
The exact mechanism has not been conclusively deter-
mined. A recent impedance study on hydrogen evolution
in acidic solutions (pH 0.7–1.5) has concluded that the
reaction follows steps 19 and 21 [61]. It was also deter-
mined that both steps are irreversible and the steady state
coverage of adsorbed hydrogen is small. Another study
using optical second harmonic generation and closer to
neutral solutions (pH 5.5–6.5) determined the reaction fol-
lows steps 19 and 20, with 19 being rate determining [62].
Steady state polarisation data would be helpful in trying
to determine the mechanism for CO2 reduction at copper.
However, good steady state data requires that the electrode
surface does not change. This in turn requires, because of
the very negative potentials used, that there can be no trace
impurities in the electrolyte that could deposit [39]. Two
published studies, one by Prof. Hori’s group (using electro-
lyte pre-electrolysis) and another by Prof. Ito’s group
(using re-crystallised KHCO3) fulfil the requirements
ð19Þ [20,50]. The results of these studies are shown in Fig. 16.
While, different mass transport intensities were likely used,
the results are qualitatively similar. In both sets of data, as
CO2 reduction begins, formate and CO appear, with for-
ð20Þ mate formation dominating over CO formation. As CO
formation increases, hydrogen evolution becomes sup-
pressed. At around 1.2 V, CO begins to be converted to
ð21Þ hydrocarbons, with first ethylene then methane appearing.
Also around this potential the total current for the path-
way leading to CO plus its products (pathway shown in
Fig. 14) begins to dominate over formate formation.
Finally, at potentials negative of 1.4 V, as the steady state
CO coverage decreases due to its conversion to hydrocar-
bons and the local CO2 concentration decrease (see, for
example, Fig. 3), hydrogen evolution begins to recover.
Thus, the data from these two groups shows similar trends.
The data from Prof. Hori’s group also includes the total
current at each potential, allowing the partial currents for
each species to be estimated (as shown in Fig. 3). This data
can also be converted to reaction rates and so the rates of
the formate and CO + products pathways can be plotted.
This is shown in Fig. 17 along with the estimated condi-
tions at the electrode surface.
At low overpotentials the rates of CO2 reduction and
CO formation have Tafel slopes below 120 mV decade1,
which then increase to above that value. This appears to

45
H2 CH4 40
35

Current Eff. (%)

30
HCOO-
C2H4 25
CO 20
15
10
5
0
-0.8 -0.9 -1 -1.1 -1.2 -1.3 -1.4 -1.5 -1.6
Potential / V vs. SHE A

45
H2
40
35
CH4
Current Eff. (%)

- 30
HCOO
25
20
CO 15
10
C2H4 5
0
-0.8 -0.9 -1 -1.1 -1.2 -1.3 -1.4 -1.5 -1.6
Potential / V vs. SHE B

Fig. 16. Current efficiencies at different potentials (0.1 M KHCO3, CO2 bubbled). A: data from [20] (19 C), B: data from [50] (25 C).
14 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19

1.0E-07

total CO2 reductn.

1.0E-08

Reaction rate / mole cm -2 s-1

H2

1.0E-09

CO
1.0E-10
-
HCOO CO+prod.

1.0E-11

120 mV decade-1

1.0E-12
-0.8 -0.92 -1.04 -1.16 -1.28 -1.4 -1.52
Potential / V vs. SHE

1.0E-08 1.0E-01
[CO2]

CO2 Conc. / M
H+ Conc. / M

1.0E-09 1.0E-02
+
[H ]

1.0E-10 1.0E-03
-0.80 -0.92 -1.04 -1.16 -1.28 -1.40 -1.52
Potential / V vs. SHE

Fig. 17. Data calculated from Hori et al. [20] showing the total CO2 reduction reaction rate and the rates for formate and the total rate for the pathway
leading to CO + hydrocarbon products (using a moles-of-carbon basis) (same data as Fig. 3). (Conditions: 0.1 M KHCO3, 19 C, CO2 bubbled, bulk
[H+] = 1.55 · 107 M, bulk [CO2] = 3.41 · 102 M. Estimated local [H+] and [CO2] values from [22] using a boundary layer of 0.01 cm.)

support a mechanism with the rate determining step shift-
ing from a later step, to the first electron transfer with
higher overpotentials. This would be similar to the mecha-
nism discussed above for CO2 reduction to formate at high
hydrogen overpotential electrodes. Around 1 V formate
exceeds that of CO. Then by around 1.2 V the rate of
CO production has reached its maximum rate, most likely
limited by desorption.
rateCO / hCO k desorption
The appearance of a maximum rate for CO production
is therefore indicative of essentially complete coverage of
the electrode surface by adsorbed CO (i.e. hCO  1) (in
agreement with [23]). However, the system shows an inter-
esting feature. While one might expect the hydrogen evolu-
tion to show its most rapid drop in rate as the coverage of
CO nears 1, it actually occurs earlier (from 1.0 to
1.16 V) where one would estimate hCO to be 0.33–0.70.
One possible reason for this would be surface non-homoge-
neities. If the preferred locations for initial CO adsorption
were also the most active sites for hydrogen evolution, one
might see the observed strong inhibition with a hCO below
0.9. This would be consistent with gas phase adsorption of
CO on copper, where adsorption is felt to be initially at
step edges, and only at higher coverage on terraces [63].
Thus, any model of the reactions should consider the pos-
sible effects of surface non-homogeneity.
In the region from 1.12 to 1.26 V there is relatively
little change in the product distribution. The proportion
of CO2 forming formate vs. CO changes from 1.5 times
to 1.3 times and hydrogen evolution decreases by 1.6 times.
In this range, the estimated local concentration of CO2
ð22Þ
remains essentially constant and that of H+ slightly
increases. This is interesting because, if two reaction path-
ways share a common intermediate and one pathway has
an electrochemical controlling step and the other does
not, one would expect to see a large shift in product distri-
bution over this range of 140 mV. Thus for CO 2 , the path-
ways to formate or to CO must (in this potential region)
both have controlling steps that are chemical or both elec-
trochemical (with similar symmetry factors). Similar con-
clusions can be made if adsorbed hydrogen is a key
shared intermediate, however, because in this case steps
13 and 16 are chemical steps, this would imply that hydro-
gen evolution occurred through step 20 (i.e. also a chemical
step).
 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19 15

At potentials negative of 1.3 V, the increase in subse- trode surface pH and CO2 concentrations, with the results
quent reactions of CO causes a decrease in the steady-state of our calculations shown in Fig. 18 along with calculated
surface coverage of CO as can be seen from the decrease in reaction rates from Hori’s data. The estimated decrease in
observed CO production and considering Eq. (22). This local CO2 concentration at higher pH values is driven by a
decrease in the coverage of CO exposes copper surface higher current efficiency for CO2 consuming reactions and
allowing other reactions to proceed. From 1.26 V to a higher rate of reaction (9) as the pH increases.
1.41 V the reduction of CO2 increases 5 times and hydro- Comparing the data in Fig. 18 with Fig. 17, generally
gen evolution increases 2.4 times. However, as the potential similar reaction rates are observed when comparing data
is becoming more negative, CO2 discharge is increasing and at the same potentials and the estimated local pH and
hydrogen evolution is increasing, one can see that the prod- CO2 concentration values are also similar. However, some
uct distribution shifts away from formate towards differences are notable, with the 1.5 M KHCO3 data at
CO + products. The most likely cause of this is the roughly 5 mA cm2 yielding 1.28 V vs. 0.85 mA cm2 at
12 times decrease in estimated proton concentration at the 1.26 V in Fig. 3. A second difference, not shown in the
electrode surface (the estimated [CO2] decrease is 2.1 data plotted here, is that in the 0.03 M, low strength buffer
times). This suggests that reaction steps 11 and 12 play at 1.42 V, the rate of formation of ethylene exceeds that
an important role in formate formation (and conversely of methane (unlike Fig. 3). This is at least partially due
that steps 14 and 15 are less important in CO formations). to the higher local pH slowing the rate of methane produc-
Hori et al. [20] have also carried out a galvanostatic tion according to the postulated mechanisms shown in
experiment using a range of electrolyte strengths from Fig. 7 or 8. (The lower buffer strength, higher pH data also
0.03 M to 1.5 M KHCO3, which resulted in different prod- showed significant fractions of the current producing etha-
uct distributions. The experiment used a single electrode nol and propanol.) Day-to-day variations in the electrode
and exchanged the electrolyte to avoid possible variations preparation can also contribute to differences between the
due to the electrode preparation [64]. In their paper, it is data in Figs. 3 and 17 vs. Fig. 18.
felt that the change in local pH values with the different In considering the trends shown in Fig. 18, as the esti-
buffer strengths plays a key role in the obtained product mated local concentration of protons decreases by 15.1
distributions. We have used our model to estimate the elec- times, the estimated local CO2 concentration decreases

1.0E-07
Reaction rate / mole cm-2 s-1

-1.28 V -1.4 2 V
H2 total CO2 redn.
1.0E-08

HCOO-
1.0E-09 CO + products

CO

1.0E-10
8.8 9 9.2 9.4 9.6 9.8 10 10.2
surface pH

1.0E-08 1.0E-01
[CO2]
CO2 conc. / M
H+ conc. / M

1.0E-09 1.0E-02
1.5 M [H+]
1.0 M
0.5 M 0.3 M
1.0E-10 1.0E-03
0.1 M 0.05 0.03 M
1.0E-11 1.0E-04
8.8 9 9.2 9.4 9.6 9.8 10 10.2
surface pH

Fig. 18. The influence of buffer strength on the product distribution. Data calculated from Hori et al. [20] showing the total CO2 reduction reaction rate
and CO + products rate (using a moles-of-carbon basis). (Conditions: 5 mA cm2, potential 1.28 V vs. SHE at 1.5 M varying to 1.42 V at 0.03 M
KHCO3 buffer (buffer strength indicated on the lower plot), 19 C, CO2 bubbled.) Estimated local [H+] and [CO2] values from [22] using a boundary layer
of 0.01 cm.
16 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19
1.9 times. Thus, if formate was formed by reaction steps 11
and 12 and CO by steps 17 and 18, one would expect the
relative rates of production of CO + products vs. formate
to increase by around 15.1/1.9 or 7.9 times. The actual data
shows an increase in the ratio of CO + products to formate
of 1.8 times. Thus, while the results in Fig. 17 show that
formate production is sensitive to the proton concentra-
tion, other factors must also play a role. The small change
in the ratio is due to the slow increase in CO + products in
comparison to Fig. 17 over the same potential range. One
clear difference between the sets of data is the decrease in
hydrogen evolution with more negative potential in
Fig. 18 vs. Fig. 17. This, along with the previously referred
to shift from methane to ethylene and the greater appear-
ance of ethanol and propanol (less hydrogenated prod-
ucts), hints that adsorbed hydrogen plays a role these
reactions. In other words, a lower availability of adsorbed
hydrogen may result in a slower formation of methane
(possibly because of a reaction such as in Fig. 8). This
may also result in the appearance of partially oxygenated
products, possibly through a higher availability of CO
(i.e. the reaction in Fig. 6 continues but those in Figs. 7
and/or 8 are slower).
In reviewing this data it was found that no simple choice
of rate determining steps from among reactions (10)–(21)
fit the data. It was also found that different relative trends
occur in the data in Figs. 17 and 18. This seems to imply
shifting and/or parallel mechanisms operate and that the
relative balance between these mechanisms might vary
depending on the electrode preparation (not surprising in
light of Figs. 10 and 12) and possibly the electrolyte com-
position (i.e. the concentration and types of anions and cat-
ions present).
2.6. Other factors – the electrode and electrolyte
In the work of Prof. Hori’s group, to obtain a reasonable
degree of reproducibility, the electrodes had to be carefully
prepared. High purity 99.999% copper [8] was used and in
some cases electrochemically deposited foil. Typical elec-
trode preparation involved mechanical polishing followed
by electropolishing in 85% phosphoric acid. The electropol-
ishing involves driving the copper dissolution into its limit-
ing current regime to remove surface irregularities and
produce a mirror-like finish surface (see for example [65]).
For preparing copper single crystals mixtures of phosphoric
and sulphuric acids (which allow a higher limiting current)
and current densities around 2 A cm2 in a pulse or pulses
of around 1 s are preferred to produce a good surface
[66,67]. (Too long a pulse will result in oxygen evolution
and the resulting bubbles can mar the electrode surface
[64].) It is felt that the electropolishing is an important step
in order to remove the stressed surface layer (produced by
polishing) and possible impurities from the electrode surface
[66], with 30 lm thickness or more typically removed [67].
Interesting results have also been reported using in situ
electrodeposited copper on a roughened glassy carbon sub-
strate [41]. In this work the electrolysis was started with
0.5 M KHCO3 and 0.5 mM CuSO4, and run for 15 min
at constant current at 0 C prior to analysis of the cell exit
gas. High Faradaic efficiencies of 73% for CH4 and 25% for
C2H4 (hence 98% for hydrocarbons) were reported using
8.3 mA cm2.
The electrolyte also needs to be carefully prepared
[14,21,39]. As discussed previously, because of the very
cathodic potentials required for CO2 reduction, trace impu-
rities can plate onto the cathode over time changing the
electrode characteristics. Typical impurities in KHCO3 salt,
such as iron or zinc, even at very low concentrations, have
been shown to collect on the cathode surface resulting in a
decrease in the Faradaic efficiency for hydrocarbon forma-
tion [39]. This effect adds uncertainty to the interpretation
of much work in the literature where the problem of elec-
trolyte impurities was not considered.
2.7. Other factors – temperature and pressure
The reaction temperature also influences the product
distribution. In galvanostatic work over the range from 0
to 40 C, lower temperatures resulted in little change in
the current efficiency for formate, decreased efficiencies
for hydrogen evolution and ethylene formation and an
increased efficiency for methane formation (reaching 65%
methane current efficiency at 0 C) [8]. Similar results have
been reported potentiostatically at 2.0 V vs. Ag/AgCl/
saturated KCl in 0.65 M NaHCO3 over the range from
15 C to 2 C [68] and on comparing results at 2.2 V
vs. SCE in 0.05 M KHCO3 at 0 C and at 20 C [18]. In
addition to increased current efficiency for methane, other
workers have also reported a shift in the apparent Tafel
slope for the methane partial current from 93 mV decade1
at 22 C to 520 mV decade1 at 0 C [21]. As well as
changes in reaction rates, lower temperatures would also
influence adsorption equilibria and increase CO2 solubility.
Work has also been carried out where the CO2 solubility
was raised by increasing the CO2 pressure [69]. In this
work, pre-electrolysed solutions were used and the copper
wire cathode was electropolished. The reactions were run
galvanostatically and the IR corrected potential was
recorded. On increasing from 0 to 60 atm of CO2 at a con-
stant current of 163 mA cm2, the predominant reaction
shifted from hydrogen to hydrocarbons, reaching 44% cur-
rent efficiency by around 10 atm of CO2. On further
increasing the CO2 pressure to around 20 atm, hydrocar-
bons decreased to around 12% current efficiency and for-
mate and CO rise to around 30% current efficiency. At
higher pressures formate and CO are the primary products
with formate production having a maximum of 54% cur-
rent efficiency at 30 atm. Thus, as the authors point out,
as increasing amounts of CO2 are fed to the reactor, less
reduced CO2 products are formed. Higher pressure data
also showed a poorer charge balance (as low as 60% of
the applied current accounted for as products at 60 atm),
suggesting the possible formation of new products.
 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19 17

Measurements were also done at 30 atm CO2 pressure
using varying current densities. The reported potential
and current efficiency data has been used to calculate reac-
tion rates at the various potentials, which are plotted in
Fig. 19. We have also used our boundary layer model
[22] to try to estimate the local pH and CO2 concentrations
at the electrode surface. Because the reactor was stirred and
there is expected to be additional mixing from the high
rates of gas evolution at the current densities used, a smal-
ler boundary layer thickness was used in the calculations.
No correction was made for the curvature of the copper
wire electrode and the CO2 solubility was assumed linear
with pressure. The results of these calculations are also
shown in Fig. 19.
The main product at 30 atm and lower current densities
is formate. As the current density is increased (and the
potential becomes more negative), hydrogen and methane
formation rapidly increase and around 600–700 mA cm2
(1.57 to 1.61 V) CO + products dominates over for-
mate production. The estimated local concentrations show
a much higher pH than Figs. 17 and 18 because of the
much higher current densities used (even with the assumed
thinner boundary layer). The high CO2 pressure results in
a high local concentration of CO2 at the electrode surface.
This is predicted to have only a moderate effect on the
local pH because of the slow kinetics of reaction (9). It
is interesting to note that even with a very high local
CO2 concentration and a relatively negative potential,
for much of the data the rate of formation of CO + prod-
ucts is less than that for formate. This would appear unli-
kely if reaction steps 17 and 18 were the main route to
CO. In fact, the low rate of CO formation appears more
likely to be linked to the low rate of hydrogen evolution
(supporting reaction step 16). Thus, the observation by
the authors of the paper that as the CO2 concentration
is increased, the current needs to be increased to maintain
hydrocarbon production, may be at least partially due to a
need to have sufficient coverage of adsorbed hydrogen. In
spite of a change of 320 mV in Fig. 19, the production of
formate only slightly increases, possibly due to the concur-
rent drop in local proton concentration (consistent with
reaction step 11).

1.0E-05

HCOO - CO+prod.
total CO2 reductn.

Reaction rate / mole cm-2 s-1

1.0E-06

1.0E-07

H2

CO
1.0E-08

CH4

1.0E-09
-1.3 -1.42 -1.54 -1.66 -1.78
Potential / V vs. SHE

1.0E-09 1.0E+01

[CO2]
CO2 Conc. / M
H Conc. / M

1.0E-10 1.0E+00
+

1.0E-11 1.0E-01
[H+]

1.0E-12 1.0E-02
-1.3 -1.42 -1.54 -1.66 -1.78
Potential / V vs. SHE

Fig. 19. Product distribution with potential with 30 atm CO2. Reaction rate data calculated from Hara et al. [69]. (Conditions: galvanostatic from 75 to
900 mA/cm2, 0.1 M KHCO3, 30 atm CO2, stirred, 25 C.) Local [H+] and [CO2] values estimated as described in [22] using a boundary layer thickness of
0.002 cm.
18 M. Gattrell et al. / Journal of Electroanalytical Chemistry 594 (2006) 1–19
It should be noted, however, that simply assuming the
reactions follow step 11 (i.e. the rate of formate dependent
on the local proton concentration), step 16 (i.e. the rate of
CO + products dependent on the adsorbed hydrogen cov-
erage) and step 20 (i.e. the rate of hydrogen evolution
dependent on the adsorbed hydrogen coverage squared)
does not fit all the reported data. The above combination
of reaction pathways should result in the relationship
shown in the following equation:
pffiffiffiffiffiffiffiffiffiffiffiffiffi
rateCOþproducts rateH
/ þ 2 ð23Þ
rateHCOO ½H local
While some regions of data do show such a relationship,
neither this relationship nor other simple relationships that
were tried were able to fit the complete set of reported data
(i.e. Figs. 17–19). One reason for this might be a shifting of
the favoured reaction pathways under different reaction
conditions.
The reactions also show additional complexities. For
example, in Fig. 19, the rate of methane production slows
its increase after about 1.55 V. In this region the CO cov-
erage does not appear to greatly change, hydrogen evolu-
tion continues to increase, and while the local proton
concentration is dropping, the increase in potential and
the reported transfer coefficient of 1.33 should be sufficient
to result in a continuing increase in methane production.
This suggests a new limitation on the reaction at these very
high rates, one possibility being limited turnover at active
sites. Again, issues such as surface heterogeneity should
be considered in trying to understand these reactions.
Indeed, the exact reaction pathways favoured in a given cir-
cumstance may depend on the reaction conditions (poten-
tial, local pH, CO2 concentration, etc.) and on the
availability of different types of active sites. If this is the
case, polarisation measurements using copper single crys-
tals (hopefully with a reduced set of types of active sites)
might yield data that is simpler to interpret mechanistically.
Finally, these results of Hara et al. at high pressures do
clearly show that hydrocarbons can be produced from CO2
at close to 60% current efficiency at 600 mA cm2, which is
important for any practical CO2 conversion reactor.
3. Conclusions
The reduction of CO2 to hydrocarbon products at cop-
per is a complex multi-step reaction involving shared inter-
mediates and multiple reaction pathways. The reaction is
sensitive to the electrode surface structure, local conditions
such as pH and CO2 concentration (which are in turn influ-
enced by buffer strength, the degree of mass transport and
the bulk CO2 concentration/pressure) and temperature.
Other factors, such as the type and amount of other ions
in solution, may also effect the product distribution. Spe-
cific and significant influence has been noted of the local
proton concentration on formate production and of hydro-
gen evolution (presumably through the action of adsorbed
hydrogen intermediate) on CO formation.
Even after 20 years [7] much work is still to be done, but
this ‘‘one-pot’’ electrochemical synthesis of hydrocarbons
directly from CO2 represents an interesting and potentially
useful reaction. One can still say, as was stated in an early
paper of Prof. Hori’s, ‘‘it is remarkable that hydrocarbons
are produced from electrochemical reduction of CO2’’ [8].
Acknowledgements
The authors acknowledge useful discussions with Profs.
Hori and Koga of Chiba Univeristy, Dr. Akio Saito for-
merly of the Kyushu National Industrial Research Institute
and Prof. Colin Oloman and Li Hui of the University of
British Columbia. We also thank Prof. Koji Hashimoto
for discussions on global warming and his infectious enthu-
siasm for finding solutions through green chemistry. Final-
ly, we thank the Canadian Office of Energy Research and
Development’s Innovative Research Initiative for funding
this work.
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