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(1)
DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082
Perspective
E0 (V versus RHE)
carbon monoxide, CO
formic acid, HCOOH
formaldehyde, HCHO
methanol, CH3OH
methane, CH4
ethanol, CH3CH2OH
ethylene, C2H4
1
1
1
1
1
2
2
2
2
4
6
8
12
12
1
0
1
1
2
3
4
0.10
0.20 (for pH < 4); 0.20 + 0.059[pH-4] (for pH > 4)
0.07
0.02
0.17
0.09
0.08
The coecients k, n, and m in eq 1 are provided in each case together with the standard equilibrium potentials.
DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082
Perspective
Figure 2. Pathways for the electrochemical production of methane from CO2 on Cu electrodes from (a) a thermodynamic analysis, adapted from ref
4, and (b) a combined thermodynamic and kinetic analysis from ref 5. Species in black are adsorbates, while those in red are reactants or products in
solution. The two mechanisms are identical up to the second protonelectron transfer, that is, until *CO is formed, after which they form (a)
*CHO and (b) *COH.
4075
DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082
Perspective
Figure 3. Possible reaction pathways for the electrocatalytic reduction of CO2 to products on transition metals and molecular catalysts: (a) pathways
from CO2 to CO, CH4 (blue arrows), CH3OH (black arrows), and HCOO (orange arrows); (b) pathways from CO2 to ethylene (gray arrows) and
ethanol (green arrows); (c) pathway of CO2 insertion into a metalH bond yielding formate (purple arrows). Species in black are adsorbates, while
those in red are reactants or products in solution. Potentials are reported versus RHE, while RDS indicates rate-determining steps and (H+ + e)
indicates steps in which either concerted or separated protonelectron transfer takes place.
DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082
Perspective
DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082
Perspective
On p-block metals such as In, Sn, Hg, and Pb, formic acid
and formate are the main products.51,53 The mechanistic
pathway by which formate and formic acid are formed on these
metals has been speculated to proceed via a (weakly adsorbed)
CO2 radical that reacts with water to form formate or formic
acid.53 Formic acid and formate can be formed with high
selectivity on these metals because they are poor catalysts for
the competing HER. However, in order to reach these high
selectivities, high overpotentials are needed as the redox
potential for the formation of the CO2 radical is 1.9 V
(versus NHE).51 It should be noted that recently some
improvements have been reported, showing high selectivities
for CO2 reduction at lower overpotentials on nanostructured
Pb and Sn electrodes.54,55 However, we expect that very low
(near-zero) overpotentials for the reduction of CO2 to
formate/formic acid require the stabilization of an adsorbed
formate intermediate as illustrated in the top part of Figure 3.
As was the case for Cu, some studies have probed the eect
of nanoparticles size on the reduction of CO2 on other
metals.56,57 A decrease in the size of Au nanoparticles caused an
increase in the observed current density and a decrease in the
faradaic eciency toward CO. This is believed to be caused by
an increase of undercoordinated sites, as was also hypothesized
for Cu nanoparticles.56 Tuning the size of Pd nanoparticles
showed that an increase in faradaic eciency toward CO can be
achieved by decreasing the particle size. In this case, the
increase in CO production was ascribed to an increase in corner
and edge sites, which display a higher activity toward CO2
reduction to CO.57
A promising area of research is the design of bimetallic
catalysts for the reduction of CO2. Early work showed that the
selectivity of a metal electrode for CO or formic acid can be
altered by the addition of adatoms on the surface.49 Sakata et al.
studied the eects of alloying Cu with Ni, Sn, Pb, Zn, Cd, and
Ag.58 They showed that alloying can have a (benecial) eect
on the onset potentials for the formation of products from CO2
and that some alloys are able to make products that both metals
separately cannot produce in detectable amounts. A Cu/Ni
alloy, for instance, produces methanol at low overpotentials
with a faradaic eciency of 5%, while Cu and Ni separately
produce methanol only in negligible amounts.58 Moreover,
theoretical studies are also enriching the state of the art in the
design of more energetically ecient and chemically selective
bimetallic catalysts for the reduction of CO2. Approaches based
on copper alloys and the so-called isolated active sites aim at
retaining or mimicking the unique reducing features of Cu
while trying to either hinder the HER or reduce the onset
potential.59,60
CuAu alloys and Cu overlayers on Pt have also been
investigated for the production of CO and hydrocarbons,
respectively.6164 For CuAu alloys, it was shown that the
activity and selectivity toward CO production can be tuned by
controlling the electronic and geometric properties,61,62 while
for Cu overlayers on Pt, dierences in the surface strain allowed
tuning the selectivity toward methane or ethylene.64
The potential of bimetallic catalysts is further illustrated by
our own recent work on a PtPd alloy.65,66 This catalyst was
shown to produce formic acid from CO2 with an onset
potential very close to the corresponding equilibrium potential,
with high faradaic eciencies at high current density and very
moderate overpotentials, and with good stability. Furthermore,
this alloy is able to reversibly reduce CO2 to formic acid and
oxidize formic acid to CO2, as expected for a two-electron4078
DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082
Perspective
DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082
Perspective
Catalysis Society Award 2015 and the EFCATS Best Ph.D. Thesis
Award 2015. Currently, he is working at Avantium.
Federico Calle-Vallejo studied chemical engineering at Colombia
(20022007), received his Ph.D. in Denmark in Nrskovs group
(20072011), and was a postdoc in Kopers group (Leiden, 2011
2013) and Sautets group (Lyon, 20132015). He is currently in
Leiden with a Veni grant for young researchers and is interested in
modeling (electro)catalytic processes using DFT.
Marc Koper has been Professor of Fundamental Surface Science at
Leiden University since 2005. His research interests focus on a
fundamental molecular-level understanding of electrocatalytic reactions by combining electrochemical, spectroscopic, and theoretical
techniques. http://casc.lic.leidenuniv.nl/
ACKNOWLEDGMENTS
This work is supported by NanoNextNL, a micro and
nanotechnology consortium of the Government of The
Netherlands and 130 partners, and the National Research
School Combination Catalysis (NRSC-C). J.S. acknowledges
the award of a grant of the Chinese Scholarship Council
(CSC). F.C.V. acknowledges funding by The Netherlands
Organization for Scientic Research (NWO), Veni Project
Number 722.014.009.
We have discussed some design strategies for the development of ecient and selective catalysts for the electrocatalytic
reduction of CO2. One of these strategies is the alloying of
dierent metals in order to optimize the binding energies of
reaction intermediates like *CO. Alloying might also be good
for breaking scaling relations between similarly adsorbed
intermediates as they cause intrinsic adsorption overpotentials.
Additionally, product selectivity can be inuenced by the pH of
the electrolyte and the use of nonaqueous electrolytes instead
of aqueous electrolytes. Therefore, optimal CO2 reduction
systems require the conjunction of a catalyst with suitable
adsorption properties and an electrolyte with benecial eects
on the catalytic activity and selectivity. We believe that such
delicate catalystelectrolyte interplay can be achieved by means
of a precise, holistic, and consistent understanding of the CO2
reduction mechanism.
REFERENCES
AUTHOR INFORMATION
Corresponding Author
*E-mail: m.koper@chem.leidenuniv.nl.
Notes
DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082
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DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082
Perspective
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DOI: 10.1021/acs.jpclett.5b01559
J. Phys. Chem. Lett. 2015, 6, 40734082