Perspective

pubs.acs.org/JPCL

Activity Descriptors for CO2 Electroreduction to Methane on

Transition-Metal Catalysts
Andrew A. Peterson†,§ and Jens K. Nørskov*,†,‡
†
SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford,
California, United States
‡
SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, California, United States
§
Center for Atomic-scale Materials Design, Department of Physics, Technical University of Denmark, DK-2800 Lyngby, Denmark
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*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: The electrochemical reduction of CO2 into hydrocarbons and alcohols

would allow renewable energy sources to be converted into fuels and chemicals. However,
no electrode catalysts have been developed that can perform this transformation with a low
overpotential at reasonable current densities. In this work, we compare trends in binding
energies for the intermediates in CO2 electrochemical reduction and present an activity
“volcano” based on this analysis. This analysis describes the experimentally observed
variations in transition-metal catalysts, including why copper is the best-known metal
electrocatalyst. The protonation of adsorbed CO is singled out as the most important step
dictating the overpotential. New strategies are presented for the discovery of catalysts that
can operate with a reduced overpotential.

U nlike renewable electricity, which can come from several

sources (hydro, solar, wind, geothermal, and others),
renewable carbon-based fuels are currently only produced from
biomass. The only other possibility to produce such fuels is by
chemically reducing carbon dioxide; if CO2 can be electro-
chemically reduced to hydrocarbons, then any of the renewable
electricity sources can also be used to create fuels, simulta-
neously addressing storage issues for these often intermittent
resources.1 Over the past 3 decades, many heterogeneous and
homogeneous electrocatalysts have been screened for their
effectiveness in this reaction and the related photoelectrochem-
ical process (artificial photosynthesis),2−18 and none have been
found to be more effective than pure metallic copper for its
repeatable demonstration to produce high (>50%) Faradaic
yields of hydrocarbons at reasonable (∼5 mA cm−2) current
densities. The high selectivity of copper for hydrocarbons in
CO2 electroreduction has sparked much interest in uncovering
its mechanism.11−16,19,20 However, the overpotential necessary
to achieve this reaction on copper electrodes is prohibitively
high, on the order of 1 V,2 which dwarfs the overpotential of
the oxygen evolution reaction,21,22 the typical counter electrode
reaction for these systems.
From a purely thermodynamical point of view, CO2 reduc-
tion to the simplest hydrocarbon, CH4, should be possible at a
standard potential of +0.17 V versus the reversible hydro-
gen electrode, or RHE. Because, by definition, hydrogen evolu-
tion becomes thermodynamically possible at 0 V versus RHE
(at any pH), CO2 reduction will be in competition with the
hydrogen evolution reaction (HER)23 at all negative potentials,
and a key criterion for selective catalysts in CO2 reduction will
Beyond the criterion of selectivity
over the hydrogen evolution
reaction, no systematic criteria for
effective CO2 reduction catalysts have
been proposed. It is the purpose of
the present Perspective to develop
such criteria.
be comparatively poor HER activity in the presence of CO2.
However, beyond this criterion of selectivity over the HER, no
systematic criteria for effective CO2 reduction catalysts have
been proposed. It is the purpose of the present Perspective to
develop such criteria.
Many of the trends in CO2 reduction by heterogeneous
electrocatalysts can be observed from the pioneering
experimental work of Hori and co-workers.2,10 In Table 1, we
have highlighted a subset of these electrocatalysts. This table
captures many of the major trends in CO2 reduction, including
selectivity toward hydrocarbons (Cu and, to a lesser extent, Ni
Received: November 4, 2011
Accepted: January 5, 2012
Published: January 5, 2012

© 2012 American Chemical Society 251 dx.doi.org/10.1021/jz201461p | J. Phys. Chem. Lett. 2012, 3, 251−258
The Journal of Physical Chemistry Letters Perspective

Table 1. Faradaic Yields in CO2 Reduction on Face- shown in Figure 1, which is bound by stoichiometry to involve
Centered Cubic (fcc) Metal Electrodes, As Reported by Hori the transfer of eight proton−electron pairs, resulting in seven
et al.,10 for Experiments at 5 mA cm−2 Current Density in a adsorbed intermediates. In both the previous analysis and in the
0.1 M KHCO3 Buffer at 18.5°C current work, we focus on the limiting potential (UL) at which
each elementary step of a reaction becomes exergonic (or
Faradaic yield, %
downhill in free energy) as a simple measure of the potential
V vs hydrocarbons/ dependence of the electrochemical rate. For an example
organicsa
electrode RHE CO HCOOH H2 total
elementary hydrogenation reaction, A* + H+ + e− → B*
Ni −1.09 2.1 0.0 1.4 88.9 92.4 (where A* and B* are generic adsorbed species), the limiting
Cu −1.05 72.3 1.3 9.4 20.5 103.5 potential can be found as a function of the chemical potentials
Pd −0.81 2.9 28.3 2.8 26.2 60.2 (μ) of the bound species
Ag −0.98 0.0 81.5 0.8 12.4 94.6
Pt −0.68 0.0 0.0 0.1 95.7 95.8 μ[B*] − μ[A*] − μ[H+ + e−](U = 0 VRHE)
UL = −
Au −0.75 0.0 87.1 0.7 10.2 98.0 e
a
Predominantly CH4, but also including C2H4, C2H5OH, C3H7OH, C2H6, 0V
−ΔG elem
C3H5OH, CH3CHO, and C2H5CHO. =
e (1)
and Pd), the production of CO (Au and Ag), and the lack of where e is the (positive) charge of an electron and the chemical
strong catalytic activity in CO2 reduction, evolving H2 instead potential of the proton−electron pair at 0 V can be found from
(Pt and Ni). These electrode materials are all late transition the computational hydrogen electrode model.19,24 This is equiv-
metals that can be represented in the face-centered cubic (fcc) alent to the negative Gibbs free-energy change of the elemen-
crystal structure; this uniformity allows us to perform a system- tary reaction divided by the electronic charge. The chemical
atic analysis of the factors determining the electrochemical potentials of the bound species A* and B* can be found from
activity and selectivity toward hydrocarbons. We focus here on standard statistical mechanics treatment of our calculated
the simplest hydrocarbon methane, but the analysis is quite binding energies (EB) of these adsorbed species. It has been
general. Our analysis is based on an extensive set of density found that such an analysis correctly predicts the onset poten-
functional theory (DFT) calculations of the key adsorbates in tial for the formation of different products in CO2 reduction
CO2 reduction on these surfaces, conducted for this study. over Cu surfaces19,20 and that it provides a good description of
In previous work, we proposed19,20 a mechanism by which trends in reactivity of different metals for the oxygen reduction
copper electrocatalysts reduce CO2 to methane; this route is reaction.25

Figure 1. Adsorption energy scaling. The proposed pathway from CO2 to CH4 on copper surfaces is shown at the top of the figure, and the
calculated adsorption energies of the key bound intermediates on fcc (211) facets are shown in the two lower figures. (More tightly bound
adsorbates correspond to more negative binding energies.) The adsorption energies of those adsorbates binding to the surface through carbon can be
correlated and are plotted against the binding energy of CO in the left plot. Similarly, the adsorption energies of those adsorbates binding through
oxygen can be correlated and are plotted versus the binding energy of OH in the right plot. Ir and Rh are included as additional fcc metals to those
shown in Table 1 in order to provide more points for the scaling relations.

252 dx.doi.org/10.1021/jz201461p | J. Phys. Chem. Lett. 2012, 3, 251−258

The Journal of Physical Chemistry Letters Perspective

Figure 2. Limiting potentials (UL) for elementary proton-transfer steps in the mechanism of Figure 1. Each line is the calculated potential at which
the indicated elementary reaction step is neutral with respect to free energy, as a function of the electrocatalysts’ carbon or oxygen affinity, EB[CO]
or EB[OH]. Each elementary reaction involves the addition of a proton−electron pair (H+ + e−) to the reactant. The equilibrium potential for the
overall electrochemical reduction of CO2 to CH4 is +0.17 V versus RHE, which is indicated on the figure. Thermodynamics limits any real catalyst to
operate at potentials more negative than the equilibrium potential; therefore, the theoretical overpotential as a function of EB[CO] or EB[OH] can
be represented by the distance between the equilibrium line and the most-negative limiting potential line (highlighted in gray). The elementary steps
in this figure are limited to the steps in the mechanism of Figure 1 and exclude CH2O* → OCH3*, which has dependence on both EB[CO] and
EB[OH]. The CH2O* → OCH3* transformation can be found in the Supporting Information. The EB[CO] and EB[OH] values for each metal are
shown on the plot, along with their overall predicted value of UL based on these scaling relations.

Given that there are seven intermediates in the reduction of
CO2 to CH4, such an analysis involves an understanding of the
problem in seven-dimensional space of adsorbate−surface interac-
tion energies. However, as seen in Figure 1, roughly the first half of
the intermediates interact with the catalyst surface through a car-
bon atom, and the second half interact through an oxygen atom.
Scaling relations associated with the d-band theory of adsorption
suggest there may be strong correlations within the carbon-bound
and oxygen-bound species.26 Using this principle, we are able
to successfully correlate the adsorption energies of the carbon-
bound species to EB[CO] and those of the oxygen-bound species
to EB[OH], as shown in Figure 1. For example, the binding
energy of CHO can be found from the linear equation in Figure 1
EB[CHO] = 0.88EB[CO] + 2.03 eV (2)
These scaled affinity relations allow us to reduce the dimen-
sionality of this reaction network from seven to two, thus making
the search for trends within these transition-metal catalysts trac-
table. In this way, the limiting potentials for each of the elemen-
tary steps can be estimated for each surface as a function of that
surface’s affinity for CO and OH. Full mathematical details are
available in the Supporting Information.
The elementary limiting potentials that scale with EB[CO]
are shown in the left pane of Figure 2. Each solid line on this
figure shows the limiting potential (UL) of an elementary proto-
nation reaction for the reaction network of Figure 1. Because
UL is the potential at which the elementary reaction becomes
exergonic, each limiting potential gives a first-order indication
of the electrical potential at which that elementary step begins
to have an appreciable rate. The equilibrium potential is also
plotted in Figure 2. The difference between each UL and the
equilibrium potential gives a first-order estimate of the over-
potential requirement for that elementary step; thus, the most
negative UL line at any CO adsorption energy dictates the
theoretical overpotential. This is indicated as the gray area of
the plot. The two bottom-most UL lines, CO* → CHO* and
253
CO2 → COOH*, are the most negative of the reaction steps
shown in Figure 1; thus, for materials that follow this same
reaction network, they would be expected to dictate the
overpotential requirement of the reaction. Copper is seen to sit
near the top of this “volcano”-type relation.
A similar plot is shown on the right-hand side of Figure 2 for
the steps that involve oxygen-bound intermediates. The ele-
mentary UL lines on this plot are much less negative; it is only for
materials that have very high affinities for OH that the potential of
clearing OH from the surface becomes comparable to the
limitations set by the CO* → CHO* reaction. This does indicate
that for materials that exhibit strong OH binding (more negative
EB[OH]), OH removal will likely limit the catalysts’ effectiveness;
however, for most materials, the potential-limiting step will be set
by the CO* → CHO* transformation discussed above.
A striking feature of Figure 2 is the severity of the limiting
potential needed to protonate CO* to CHO*. This UL is not
only the strongest limitation, it is also the least sensitive
to changes in EB[CO]; that is, the line is nearly horizontal.
The magnitude and insensitivity of
the energetics of this reaction to the
electronic properties of the catalyst
material can explain both the reason
for the large overpotential require-
ment and the dearth of materials that
have been found that can catalyze
this reaction with lower overpoten-
tials than Cu.
dx.doi.org/10.1021/jz201461p | J. Phys. Chem. Lett. 2012, 3, 251−258
The Journal of Physical Chemistry Letters
The magnitude and insensitivity of the energetics of this
reaction to the electronic properties of the catalyst material can
explain both the reason for the large overpotential requirement
and the dearth of materials that have been found that can
catalyze this reaction with lower overpotentials than Cu. The
root cause of this insensitivity can be seen in Figure 1, in which
the CO and CHO binding energies scale with a slope of 0.88,
meaning that a surface that stabilizes CHO will stabilize CO by
a similar amount. Thus, the binding energies are coupled, and
the relative binding energies between the two change only
slightly with catalyst material.
Of course, electrocatalysts are not bound to follow the reac-
tion mechanism shown in Figure 1. Other mechanistic possibi-
lities are included in Figure 3, focusing on the mechanisms that
Figure 3. Limiting potentials (UL), allowing for competitive reaction
mechanisms. Free-energy neutrality lines are plotted as in Figure 1, but
multiple pathways are possible. Competitive pathways are shown as
lines of the same color, and the more favorable route is shown as a
solid line, while the less favorable route is shown dotted. Also shown is
the binding energy at which adsorbed CO is in equilibrium with
gaseous CO (at a partial pressure of 1%); the CO would be predicted
to desorb at binding energies weaker than this line. As in Figure 1, the
EB[CO] values are shown for each metal. The open circles correspond
to surfaces that have an experimental exchange current density in the
hydrogen evolution reaction greater than 10−4 A cm−2;27−29 in these
materials, the hydrogen evolution reaction would be expected to
dominate over CO2 reduction.
proceed through a CO* intermediate. (This is based on the
experimental11,15,30−33 and theoretical19 findings that CO,
rather than HCOOH, is an intermediate in hydrocarbon
production on Cu; however, this does neglect the possibility
that a formate intermediate could produce more reduced
products than formic acid.) A vertical equilibrium line shows
the binding energy at which gas-phase CO (at a partial pressure
of 1%) is more stable than adsorbed CO*; materials to the right
of this line would be expected to liberate any produced CO
rather than further react it to hydrocarbons. CO* can be
protonated to form COH* rather than CHO*, which may
change the reaction pathway for the strongest binding
materials. Lines for both of these reactions are shown in the
same color, with the most favorable reaction at any value of
EB[CO] shown as a solid line and the less favorable shown as a
dotted line. For materials that protonate CO* to form COH*,
the downstream pathway will be different than that for those
254
Perspective
that produce CHO*; the most limiting of these steps is shown,
which is the protonation of CH* to form CH2*. For materials
that form CHO*, other downstream pathways are possible;
these later steps will be important to selectivity15 but should
not affect the overall theoretical overpotential. The most
significant is the subsequent protonation of CHO* to CH2O*
or CHOH*. In both cases, this reaction appears to require less
overpotential than the protonation of CO*.
Over most of the region of the plot, the CHO* route is
favored over the COH* route. However, at low values of
EB[CO], the route to COH* begins to become possible. This
upturn suggests the possibility that materials with a high affinity
for carbon may have reduced overpotentials; however, some
attributes of materials in this region may prevent this from
being realized. Materials that bind carbon strongly will lead to
high coverages when in actual electrochemical operation; this
will weaken the binding strength of each incremental adsorbate,
thus effectively shifting the binding strength of these materials
to the right on the plot. Additionally, many of the materials that
bind carbon strongly also bind oxygen strongly; therefore, remov-
ing OH from the surface may prove to be problematic, as seen for
materials at the left edge of the EB[OH] plot in Figure 2.
The experimentally observed trends in CO2 reduction can be
deduced from Figure 3. Au and Ag sit to the right of the CO
desorption line, agreeing with the experimental observations in
Table 1, as well as numerous studies showing CO formation
from CO2 on Au10,34−41 and Ag10,34,42,43 electrodes.
Copper sits atop the volcano but still requires an extreme
overpotential in order to overcome the CO to CHO hydro-
genation step. The theoretically predicted overpotential is in
agreement with experiment, as shown in earlier studies.19,20
Experimentally, the use of CO as a reactant has been found to
produce a similar product spectrum as CO2, and the potential
requirement to reach a current density of 5 mA cm−2 in 0.1 M
KHCO3 buffer is nearly identical to that of CO2 (although
canceling effects of an increased solution pH and decreased
mass transport likely play a role),10,33 indicating that the
potential-limiting step comes after the adsorption of CO on
the catalyst surface.
The materials in Figure 3 that are known to have significant
activity in hydrogen evolution are marked with open circles; the
HER would be expected to dominate over any CO2 reduction
in these materials. However, in these materials, particularly Pt
and Ni, the onset of H2 evolution is significantly higher than
that in the CO2-free system. This can easily be understood as a
poisoning of the catalyst surface by adsorbed CO. The CO is
bound very tightly to these materials, and the only means of
removing it under these conditions is to react it off, which
requires significant potentials. Some of the CO can be seen to
react off as CH4 in the case of Ni in Table 1, which was brought
to potentials slightly more negative than that of Cu, in
agreement with the more negative potentials needed by the
volcano relation in Figure 3. In the case of Pt, the hydrogen
evolution current density in Table 1 precluded the potential
from being raised more negative than −0.68 V versus RHE;
however, in experiments in which Pt was taken to more
negative potentials, some hydrocarbons were observed.42 This
is in agreement with a large body of experimental evidence, in
which CO has been observed to poison the electrocatalyst
surface in CO2 electroreduction experiments on Pt44−48 and
Ni49,50 surfaces.
Under these highly reducing conditions, Pd would be ex-
pected to form a hydride due to the high effective H fugacity,51
dx.doi.org/10.1021/jz201461p | J. Phys. Chem. Lett. 2012, 3, 251−258
The Journal of Physical Chemistry Letters Perspective

which will likely weaken its affinity for carbon52 and shift it to
the right (weaker CO binding) in Figure 3. Experimental
evidence of this occurring can be seen in Table 1, in which a
Faradaic balance was not closed. This behavior has been
observed and exploited numerous times in electrochemical CO2
reduction.54−59 Nevertheless, this study captures the trends that
Pd weakly produces CH4 but is in major competition with the
hydrogen evolution reaction and the formation of a hydride.

Crucially, effective catalysts must be

capable of efficiently catalyzing the
protonation of adsorbed CO to
adsorbed CHO or COH and exhibit
simultaneous poor activity for the
competitive hydrogen evolution
reaction.

Crucially, effective catalysts must be capable of efficiently

catalyzing the protonation of adsorbed CO to adsorbed CHO or
COH and exhibit simultaneous poor activity for the competitive
hydrogen evolution reaction. Regardless of the downstream
pathway after the formation of CHO or COH, products that are
more reduced than CO, such as hydrocarbons and alcohols, will be
produced as long as the subsequent products desorb from the
electrocatalyst surface. We observe that Cu exhibits a slightly better-
than-average ability to perform the hydrogenation of adsorbed CO,
but this is only in conjunction with its relatively poor activity at the
hydrogen evolution reaction that this works, as exhibited by it
having among the most negative potentials in Table 1.
For an electrocatalytic system to be more effective at reduc-
ing CO2 to CH4, a means to protonate CO at a less negative
potential must be found; in other words, the binding energy
EB[CHO] must be strengthened (made more negative) relative
to EB[CO]. For materials at the right side of the volcano of
Figure 3, a possible strategy is to increase the CO(g) partial
pressure, either by letting product gases build up or by
employing a series of electrochemical reactors. However, for
materials over the broadest range of carbon-binding energies,
CO and CHO will both be bound to the surface, and their
binding energies must be decoupled. We can use our under-
standing of surface reactivity to suggest general means in which
the binding energetics of CO and CHO may be decoupled,
possibly leading to electrocatalysts with substantially improved
overpotentials relative to that of Cu. Several strategies are listed
below and shown in Figure 4.
• Alloying with metals with higher oxygen af f inity. CO tends
to bind to surfaces in an upright geometry with respect to
the carbon atom. In contrast, CHO tends to bind in a
planar geometry with respect to the carbon atom, with
the oxygen not extending directly away from the surface
as is the case with CO*. (See also Figure 1.) Catalyst
materials have varying degrees of affinity for oxygen and
for carbon; alloying an element that has high oxygen
affinity into an electrocatalyst may allow CHO* to bind
to the surface through both the carbon and oxygen atoms,
thus increasing its stability without affecting the stability of
255
Figure 4. Suggested decoupling strategies exploiting the geometric
differences between adsorbed CHO and adsorbed CO.
CO*. However, the element with high oxygen affinity may
change the potential-determining step, such that clearing of
OH* from those sites may limit UL. Thus, a balance must
be found between these two effects.
• Ligand stabilization. In an analogous concept to alloying,
an electrophilic chemical ligand can be applied in homo-
geneous catalysis, in which a ligand can be constructed
that is geometrically capable of interacting with the
planar geometry of CHO* but not that of the linear CO*.
This partial bond formation with CHO* will act to
stabilize the complex, thus lowering the energy of CHO*
relative to that of CO*. Many other homogeneous
catalysis techniques may prove beneficial in performing
this reaction more effectively.60−62
• Tethering. Homogeneous and heterogeneous approaches
can be combined through tethering of a ligand to an
electrode surface, such that the adsorbates (CO* and
CHO*) bind to the electrode surface, but only the planar
CHO* can interact with the tethered ligand. The reverse
is also possible, in which the adsorbates bind to the
ligand and the CHO* interacts with the surface.
• Addition of promoters. Promoters can change the relative
binding strength of adsorbates through electronic effects
dx.doi.org/10.1021/jz201461p | J. Phys. Chem. Lett. 2012, 3, 251−258
The Journal of Physical Chemistry Letters
(ligand effects, induced fields) and through structural effects
(geometry disruption, binding through promoter atoms) or
through combinations of these effects. It is likely that many
promoted catalysts will not follow the same correlation of
binding energies of CO and CHO, as is observed on the
pure transition metals in this study. The addition of pro-
moters that are resistant to electrochemical reduction may
lead to new possibilities, and one such possibility for geo-
metrical stabilization is shown in Figure 4, in which the
promoter atom acts to make the adsorbed promoter−
adsorbate complex adsorb in a bidentate manner.
• Hydrogen bond stabilization/solvent ef fects. Due to the
differences in binding geometries, hydrogen bond donors
near the surface may interact with CO* and CHO* in
different fashions. Also, a hydrogen bond acceptor may
work to preferentially stabilize COH* (with a strong
hydrogen-bonding group, OH) over CO*. The hydrogen
binding difference may be achieved by changes in the
electrolyte or by the presence of hydrogen-bonding ligands
attached to the catalyst surface.
■ METHODS
Electronic structure calculations were undertaken using the
DACAPO plane wave implementation of density functional theory,
using the (211) facet of a periodic fcc crystal and the RPBE
exchange−correlation functional.63 Full details are available in the
Supporting Information.
■
ASSOCIATED CONTENT
*
S Supporting Information
The computational methodolgy, the additional scaling relations
necessary to create Figure 3, a comparison to direct
hydrogenation reactions, and a two-dimensional volcano plot
illustrating transformation of CH2O* to OCH3*. This material
is available free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Biographies
Andrew A. Peterson is an Assistant Professor at Brown University. He
conducted this work while a postdoctoral scholar at Stanford. Andrew
also worked with Jens Nørskov as a postdoc at the Technical
University of Denmark and received his Ph.D. and bachelors from
MIT and the University of Minnesota, respectively.
Jens K. Nørskov is the Leland T. Edwards Professor in Chemical
Engineering at Stanford University and is the Director of the
SUNCAT Center for Interface Science and Catalysis at Stanford and
the SLAC National Accelerator Laboratory. Previously, Jens directed
the Center for Atomic-scale Materials Design at the Technical
University of Denmark.
■
ACKNOWLEDGMENTS
We appreciate insights from Professor Clifford Kubiak and
Dr. Kyle A. Grice of the University of California at San Diego.
This material is based on work supported by the Air Force
Office of Scientific Research through the MURI program under
AFOSR Award No. FA9550-10-1-0572. The authors also
acknowledge support from the Catalysis for Sustainable Energy
(CASE) initiative, which is funded by the Danish Ministry of
Science, Technology, and Innovation.
256
■
Perspective
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