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COMMUNICATION www.rsc.org/ees | Energy & Environmental Science

How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon


fuels
Andrew A. Peterson, Frank Abild-Pedersen, Felix Studt, Jan Rossmeisl and Jens K. Nrskov*
Received 10th May 2010, Accepted 17th June 2010
DOI: 10.1039/c0ee00071j
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Density functional theory calculations explain coppers unique


ability to convert CO2 into hydrocarbons, which may open up
(photo-)electrochemical routes to fuels.

The storage of energy in chemical bonds, as fuels, is attractive for


a number of reasons,1 and a (photo-)electrochemical route to reduce
CO2 to hydrocarbon fuels would provide an ideal storage medium for
intermittent renewable energy sources, resulting in carbon-neutral
fuels. However, no material is known to catalyze the electroreduction
of CO2 to fuels both efficiently and selectively. In fact, only copper
and its alloys have been shown to be capable of producing significant
quantities of hydrocarbons from CO2, but they do so inefficiently
with a large overpotential requirement. In this communication, we
use a computational hydrogen electrode (CHE) model to show how
copper is able to catalyze this reaction, and we outline requirements
for more efficient catalysts to enable artificial photosynthesis.
Numerous researchers210 have studied the electrochemical reduc-
tion of CO2 at metal electrodes, and two excellent reviews have
appeared in the recent literature.11,12 Copper has been found to be
unique among the metals in its ability to produce a high quantity of
hydrocarbon fuels from the electroreduction of CO2.2 A typical
product distribution as a function of potential, as measured by Hori Fig. 1 Experimentally determined current and product distribution at
et al.7 with a Cu electrode, is shown in Fig. 1. The hydrocarbons a copper electrode. Product distribution and total current produced as
methane (CH4) and ethylene (C2H4) are the dominant products at a function of applied potential (versus reversible hydrogen electrode,
sufficiently negative potentials. At less negative potentials, hydrogen RHE) in the electrochemical reduction of CO2 at a copper electrode in
(H2), formic acid (HCOOH), and carbon monoxide (CO) are instead 0.1 M KHCO3 (pH 6.8) at 18.5  C, as measured by Hori et al.7
dominant. It is interesting that methanol (CH3OH) is not among the
products reported since copper catalysts are commonly used to
produce methanol selectively from a mixture of CO2, CO, and H2 in
the methanol synthesis reaction.13
Although copper has been shown to be unique in producing
Center for Atomic-scale Materials Design, Department of Physics,
Technical University of Denmark, DK-2800 Lyngby, Denmark hydrocarbons from CO2, it is remarkably inefficient in doing so.
Electronic supplementary information (ESI) available: Computational Thermodynamically, a potential of +0.17 V vs. RHE is all that is
details. See DOI: 10.1039/c0ee00071j required for the reaction:

Broader context
Hydrocarbon fuels provide unparalleled energy density and are the backbone of our energy infrastructure. However, todays only
sources of hydrocarbons are fossil fuels and biomass. If an efficient electrochemical process could be developed to produce
hydrocarbons from CO2, this could allow processes (known as artificial photosynthesis or solar fuels) to directly produce useful
fuels from CO2 and renewable energy sources, which are often intermittent and will require storage when deployed at large scales. It
was first shown more than 20 years ago that copper can act as an electrocatalyst in reducing CO2 into the hydrocarbons CH4 and
C2H4. Copper is unique in its ability to perform this catalysis, but it does so with a relatively high overpotential (1 V). The
mechanism by which copper performs this catalysis, as well as the reason for the overpotential are unknown. The current
communication outlines a plausible mechanism, based on quantum chemical simulations, that explains the experimental observa-
tions and may help define design principles for improved electrocatalysts.

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CO2 + 8(H+ + e) / CH4 + 2H2O (1) black. Since each successive zone contains the chemical potential of
one extra proton-electron pair, the free energy (DGn) of each inter-
at 18.5  C. However, in experiments, potentials of about 0.8 V are mediate will change as a simple linear function of the applied
required for the onset of CH4 production from CO2, and 1.0 V is potential (U):
required for a decent current (to CH4) of 2 mA cm2.7
The mechanisms by which copper produces this unique product DGn(U) DGn(U 0) + neU
distribution and the reason for the overpotential have remained
elusive. This opens up three main questions to which we propose where n is the number of proton-electron pairs transferred relative to
answers in this work. (1) How does copper catalyse this unique CO2 and e is the elementary (positive) charge. By simulating more
product spectrum, including hydrocarbons, from CO2? (2) Why is negative voltages in the CHE model, the voltage at which different
such a large overpotential required? (3) Why does the pathway chemical pathways become exergonic can be generated. These are
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produce methane, but not methanol, given that methanol is the illustrated by the red pathways in Fig. 2.
dominant product on copper catalysts in industrial processes? These Part (a) of Fig. 2 shows the first pathway to open in this system, in
answers should shed light on the true barriers to making artificial which only H2 is produced; CO2 does not participate in the reaction.
photosynthesis a commercial reality. The adsorption of the first proton from solution (State 1 to 33) is the
It is extremely demanding to provide a detailed theoretical last step to become exergonic as a function of applied potential; this is
description of chemical processes taking place at an electrified solid- the potential-limiting step. The CHE model indicates that this is the
water interface.1425 However, theoretical techniques have recently first pathway to open, consistent with the results in Hori et al.s
been developed that provide an elegant method26 of modeling elec- experimental results reproduced in Fig. 1. This reaction pathway is
trochemical reactions using what we will herein refer to as a compu- predicted by the CHE model to open on the Cu (211) surface at
tational hydrogen electrode (CHE) model; this model is coupled with around 0.03 V, but in experiments, significant current was not
adsorption energies from density functional theory (DFT) calcula- observed until more negative potentials. (In Fig. 1, the first current is
tions. Using these techniques, electrochemical reaction pathways can reported at about 0.4 V, which goes almost entirely to produce H2.)
be elucidated and the voltage requirements at which different This can be understood with the CHE model: oxidation of the Cu
chemical pathways open can be estimated. We will show that by (211) step sites would block the production of H2. According to the
using the simple CHE model as a starting point, the major trends in CHE model, O and OH would bind to the same stepped sites as H
CO2 reduction over Cu surfaces can be elucidated. and a potential of 0.3 V would be necessary to clear adsorbed OH
The CHE model was applied to the electroreduction of CO2 by from these Cu step sites, enabling H2 evolution.
examining a network involving 41 different intermediate steps on the Fig. 2(b) shows the reaction pathway to formic acid (HCOOH)
Cu (211) surface. Full details, including a description of the CHE predicted with the CHE model. Consistent with the experimental
model, are available in the Supplementary Information. From this results, this is the second pathway to open. In this pathway, CO2 and
pathway, numerous routes to the major products CO, H2, HCOOH, a proton-electron pair adsorb as a carboxyl species; the addition of
CH4 and C2H4 are possible and the lowest energy pathways were a second proton-electron pair to this adsorbate results in the
found as a function of applied potential. production of HCOOH. The potential-limiting step is the formation
The least-negative potential at which the pathway to each product of carboxyl, requiring 0.41 V by the CHE model. This potential is
becomes exergonic (downhill in free energy) is referred to as the consistent with the onset in Fig. 1. A second pathway to formic acid
limiting potential, which serves as a first estimate of the onset also exists (not shown in the figure), in which CO2 adsorbs as formate
potential for each species. More exact predictions of onset potentials (OCHO). This may be responsible for some of the formic acid
will require calculations not just of free energies, but of barriers production at more negative potentials; the desorption of formate as
between steps along the pathway. However, each electrochemical step HCOOH is calculated to require 0.61 V to become exergonic.
discussed in this communication involves the transfer of a proton Opening simultaneously with the HCOOH pathway in the
from solution to an adsorbed species on the surface. Barriers for experimental results of Fig. 1 is that to CO, and this is also the next
electrochemical proton transfers have been calculated for the reduc- pathway in the CHE model, opening at 0.41 V, which is illustrated
tion of O2 to OOH on Pt14 and for the reduction of OH to H2O on in Fig. 2(c). This route is also limited by the formation of carboxyl.
Pt.27 In both cases, the proton-transfer reaction barriers were calcu- After this species adsorbs, the free-energy pathway is downhill to
lated to be small (0.15 eV to 0.25 eV) at the potential needed to make remove water and produce adsorbed CO. This CO is weakly bound
the elementary step exergonic, and were found to diminish with at these conditions, leading to the production of CO both as a gas and
higher applied voltages. Similarly, as a first approximation we expect a surface species.
that barriers for electrochemical proton transfers to adsorbed species According to the CHE model, the key step in the formation of the
in this study will be small and easily surmountable at room temper- hydrocarbons CH4 and C2H4 is the hydrogenation of the adsorbed
ature. However, the same assumption cannot be made for reactions CO to form adsorbed CHO at 0.74 V. From this point, the
between two adsorbed species, which will be important in ethylene hydrocarbon-forming reaction pathways open.
formation (which involves the formation of a CC bond) and in The lowest-energy pathway to methane is shown in Fig. 2(d). After
a competing, non-electrochemical pathway to methanol, both of the formation of adsorbed CHO, a second proton-electron pair is
which will be discussed later in this communication. added to form adsorbed formaldehyde (H2CO), which binds weakly
Fig. 2 shows free energy diagrams for the lowest-energy pathways to the Cu (211) step.28 The formaldehyde is protonated to form
for the formation of H2, HCOOH, CO, and CH4 from CO2. In this adsorbed methoxy (OCH3), which stands up in an orientation with its
figure each zone (on the x axis) represents the transfer of one proton- methyl group away from the surface. At this stage, a proton from
electron pair. The free energy pathways at 0 V (vs RHE) are shown in solution takes the methyl group off the methoxy, producing CH4.

1312 | Energy Environ. Sci., 2010, 3, 13111315 This journal is The Royal Society of Chemistry 2010
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Fig. 2 Calculated free energy diagrams. Free energy diagrams for the lowest energy pathways to (a) H2, (b) HCOOH, (c) CO, and (d) CH4. In each
diagram, the black (higher) pathway represents the free energy at 0 V vs. RHE and the red (lower) pathway the free energy at the indicated potential. The
numbers labeled on the states correspond to the labels in Figure S1 of the Supplementary Information.

The remaining adsorbed oxygen is subsequently cleared as water. Table 1 Calculated reaction free energies for CC bond formation at
After the production of adsorbed CHO, the formation of CHOH on 18.5  C. An asterisk (*) indicates that the species is adsorbed on the
surface
the surface is possible but less thermodynamically stable than the
route highlighted; this is a second potential route to CH4 that will not DGrxn
affect the potential dependence, but will be of importance in future
kinetics studies. 2 CH2O* / 2 O* + C2H4 0.73 eV
CHO* + *OCH3 / 2 O* + C2H4 0.20 eV
The CHE model suggests several pathways to ethylene (C2H4), all CH2O* + CHO* / *OCHCH2 + O* 1.04 eVa
of which proceed through the CHO intermediate. Thus, protonation 2 CHO* / *OCHCHO* 1.12 eVa
of CO to form adsorbed CHO will be the potential-limiting step, a
The subsequent electrochemical proton addition steps to form C2H4
predicting these pathways to open at about 0.74 V. Ethylene from *OCHCH2 and *OCHCHO* are exergonic at 0.74 V.
formation requires the creation of a CC bond, which will occur in
a non-electrochemical step on the surface. Reaction free energies of
these CC bond formation steps are summarized in Table 1; as the surface sites, decreasing the number of active sites available. This
shown, all of the table entries are exergonic. Since these surface results in decreased production of H2 and a decreased overall Fara-
reactions are not simple proton-transfer steps, the CHE model pre- daic current. When the route to protonate the adsorbed CO becomes
sented does not distinguish between them, and a future model that exergonic, the CO clears and total current recovers.
incorporates reaction barriers will be required to determine which We have shown that our analysis is in good agreement with CO2
pathway is dominant for C2H4 formation. electroreduction experiments.7 Other experimental observations
The experimental results show that H2 production decreases as the confirm the feasibility of the pathways presented here. Experiments
production of CO and hydrocarbons is increased, including an starting with HCOOH showed no detectable products,5,7 while
interesting dip in the total current around 0.8 V (see Fig. 1). We can studies employing a CO feedstock have shown CH4 and C2H4
understand these effects as a result of changes in surface coverages. production.3,4,6 This validates the reactions in the early stages of the
As CO production becomes possible, adsorbed CO will start blocking mechanism, in that the hydrocarbon-generating reaction proceeds

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through CO, whereas the formate pathway is a dead end. (According Science, Technology and Innovation. This material is also based
to the present model, adding an additional proton-electron pair to upon work performed as part of the Center on Nanostructuring for
form adsorbed OCH2O from OCHO would require 1.9 V vs. RHE Efficient Energy Conversion (CNEEC) at Stanford University, an
be applied, rendering this pathway unfeasible at the voltages repor- Energy Frontier Research Center funded by the U.S. Department
ted.) Other studies5,6 have shown CH4 formation from a starting of Energy, Office of Science, Office of Basic Energy Sciences under
material of CH2O, which is in agreement with the downstream Award Number DE-SC0001060. The Center for Atomic-scale
pathways shown in Fig. 2(d). Additionally, in experiments starting Materials Design is funded by the Lundbeck Foundation. A.A.P.
with CO, H2 production was suppressed at a less negative potential acknowledges funding from the Hans Christian rsted Postdoc
than when starting with CO2.7 This again is consistent with the CHE Programme.
model, which predicts a barrier for the conversion of CO2 to CO,
resulting from the adsorption of the COOH species. As evidenced in
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