Top Catal (2014) 57:215221
DOI 10.1007/s11244-013-0171-6
ORIGINAL PAPER
Unifying Solution and Surface Electrochemistry: Limitations
and Opportunities in Surface Electrocatalysis
Venkatasubramanian Viswanathan
Heine Anton Hansen
Published online: 23 October 2013
Springer Science+Business Media New York 2013
Abstract The electrochemical transformations involving
small molecules could play a key role in energy storage and
utilization. In this work, we develop a link between surface
and solution electrochemistry and this is accomplished by
relating the correlated binding of hydrogenated species on
metal surfaces to their formation energy in solution. This
link provides a semi-quantitative treatment of the thermo-
dynamic landscape of multi-electron electrochemical
reactions. Using this simple analysis, we identify some of
the fundamental limits of oxygen, nitrogen and carbon
electrochemistry. This analysis points to new avenues of
electrocatalyst design and two such avenues are discussed
in detail.
Keywords Electrocatalysis  Solar fuels  Volcano
curves
1 Introduction
The use of solar and wind energy represents attractive
sustainable energy options with negligible carbon foot-
print, reasonable energy efficiency and minimal water
consumption. However, if solar and wind are to be used
as a primary energy source, the ability to store and dis-
patch energy on demand to the consumer is necessary [1].
Efficient energy storage represents a major barrier and
one attractive avenue is to utilize natures approach and
store them in the form of chemical bonds. The storage of
sun and wind energy in the form of fuels could, in
V. Viswanathan (&)  H. A. Hansen
Department of Chemical Engineering, Stanford University,
Stanford, CA 94305-3030, USA
e-mail: venkvis@stanford.edu
principle, be enabled by low-temperature electrochemical
transformations.
These electrochemical transformations could be carried
out through the activation of small molecules and con-
verting them into high value fuels. However, it is seen that
the efficiencies of electrochemical reactions involving
small molecules such as O2, N2 and CO2 are low [24].
These transformations involve bond making and bond
breaking processes that require multi-electron and proton
transfer reactions and it is generally seen that the effi-
ciencies become progressively worse with increasing
number of electronproton transfer reactions involved.
Although advances have been made in the theory of
single electron transfer reactions, [5] the theory of multi-
electron electrochemical reactions has not yet reached a
similar level. Recently, the thermodynamic treatment of
multi-electron electrochemical reactions has seen success
in understanding trends for simple reactions such as
hydrogen evolution reaction, oxygen reduction reaction
(ORR) and oxygen evolution reaction (OER) [68]. This
treatment, largely following the principles laid out in the
seminal work by Nrskov et al. [6] attributes the limita-
tions of electrocatalysis to the correlated binding between
certain reaction intermediates. The scaling between these
reaction intermediates immediately imposes fundamental
limits to surface electrocatalysis for multi-electron reac-
tions such as ORR and OER [8, 9]
In this work, we explore the origin of these fundamental
limitations of surface electrochemistry by forming a bridge
between the concepts developed in the thermodynamic
theory of multi-electron reactions on surfaces to aqueous
solution electrochemistry. The establishment of this link
points to certain new avenues which could, in principle,
avoid some of the limits seen in aqueous surface
electrocatalysis.
123
216
2 Surface Electrochemistry
In this section, we introduce the concepts involved in the
thermodynamic theory of multi-electron electrochemical
reactions using ORR as an example. An ideal electrocata-
lyst for the four electron reduction of oxygen to water
should be able to facilitate the reaction just below the
equilibrium potential of 1.23 V. This requires, as a mini-
mum requirement, that the four charge transfer steps
involved have reaction free energies of the same magnitude
equal to the equilibrium potential of 1.23 eV [6].
Considering the associative mechanism shown below [6,
10]:
O2 (g) 4H 4e  ! OOH 3H 3e ; 1a
OOH 3H 3e ! O H2 O(l) 2H 2e ; 1b In a pioneering work, Abild-Pedersen et al. [15] showed
O H2 O(l) 2H 2e ! OH H2 O(l) H e ; energy of hydrogenated species, AHx and the atom A. It
1c
OH H2 O(l) H e !  2H2 O(l); 1d
where * refers to a surface site. In this mechanism, the
electrocatalytic activity for oxygen reduction to water is
governed by the stability of the intermediates, OOH*,
OH* and O*. It is possible that the transfer of a proton and
electron could be decoupled at high pH for weak binding
catalysts and this could lead to additional intermediates that
could affect the electrocatalytic activity [11]. However, in
acidic environment, we expect the concerted pathway
involving the simultaneous transfer of a proton and elec-
tron to be dominant.
The reaction free energies of a step in the mechanism
can be calculated at standard conditions, and a potential, U
= 0 V versus the reversible hydrogen electrode, using the
relation:
DG0 DEw;water DZPE  TDS; 2 rocatalyst having equal free energy difference for reaction
where DEw;water is the reaction energy including the sta-
bilization of water, calculated relative to H2O and
H2 ; DZPE is the difference in zero point energies for the
reaction, and DS is the change in entropy for the reaction
considered. A potential of U = 0 V versus the reversible
hydrogen electrode implies the relation, DGH DGe
aq
1
2 DGH2 g :
This relation provides a computationally tracta-
ble way of calculating the sum of the free energy of a
proton and an electron [6, 12]. The effect of a potential U is
included by shifting the free energy of an electron by
-eU. The reaction free energy is given by DG DG0 eU;
where U is the potential relative to the reversible hydrogen
electrode. This procedure can be used to construct free
energy diagrams and can be used to deduce an important
parameter, the limiting potential, UL, which is defined as
123
Top Catal (2014) 57:215221
the last step that becomes downhill in free energy when the
overpotential is increased [6].
The free energy diagram for the oxygen reduction
reaction on Pt(111) constructed using the approach detailed
above is shown in Fig. 1. On Pt(111), the limiting poten-
tial, UL is given by the free energy change associated with
the reduction of OH* to H2O(l), reaction 1d. This analysis
suggests that directions for better catalysts are those that
bind OH* weaker than Pt(111). This principle has been
used to discover several new catalysts [14]. However, as
we will discuss in the next section, there is a fundamental
limit to how much better these catalysts could be.
2.1 Scaling Relations
the existence of a linear scaling between the adsorption
was further shown using simple bond counting principles
that the slope of the linear scaling between the hydroge-
nated species, AHx and the atom A was only dependent on
the valency and did not depend on the specifics of metal
and the facet. The existence of these linear scaling relations
has an important implication for the oxygen reduction
reaction. This implies that the binding of the oxygen
intermediates, OOH*, OH* and O* cannot be changed
independently and the activity is only governed by a single
parameter [9, 13].
From the analysis in the previous section, it was shown
that a weakening of OH* could lead to better catalysts.
However, a weakening of OH* also weakens O* and OOH*.
The linear scaling between OOH* and OH* adsorbed on fcc
metal (111) and (100) facets is shown in Fig. 1b and this
indicates that beyond a certain weakening of OH*, the
limiting step changes to reaction 1a. This leads to a
Sabatier-type volcano relationship with the optimal elect-
1a and reaction 1d and this is shown in Fig. 1c. This
analysis suggests that the origin of the limitations of oxy-
gen reduction reaction on metals is due to the unfavorable
scaling between OOH* and OH*. On an ideal electrocata-
lyst, the difference in free energy between these two
intermediates, OOH* and OH* should be 2 9 1.23 =
2.46 eV while according to the scaling relation, this dif-
ference is 3.2 eV, indepedent of the metal surface. This
immediately imposes a fundamental limit given by
gORR = 0.37 V, even on the best metal electrocatalyst
[16].
In the next section, we will explore the possibility of
identifying the fundamental limits of electrocatalysis by
making a connection to solution electrochemistry. An
analysis similar in spirit to the one carried out here is
discussed in a recent work [11].
Top Catal (2014) 57:215221 217

Fig. 1 a Free energy diagram (a)

for the oxygen reduction
reaction on Pt(111) plotted at
UL = 0.76 V. The
potential limiting step is the
reduction of OH* to H2O(l). b A
plot of the binding energy of
OOH* versus OH* on fcc metal
(111) and (100) facets. The
scaling line,
DEOOH DEOH 3:2[eV]; is
shown in the figure. The red
dots and blue squares are
binding energies on (111) and
(100) surfaces respectively. c
Activity volcano of the limiting
potential, UL as a function of
DGOH ; the free energy of
adsorbed OH* is shown. The (b) (c)
source of the experimental data
points are listed in ref. [13]

3 Solution Electrochemistry Table 1 The acid dissociation constant, pKa, of different molecules
at 25 C
The free energy diagrams discussed in the context of sur- Name Formula pKa Ref.
face electrochemistry are known as LatimerFrost dia-
grams in solution electrochemistry. These diagrams, also Water H2O 15.7 [29]
known as oxidation potential diagrams, were originally Hydrogen peroxide H2O2 11.6 [29]
introduced by Latimer to study the stability of different cis-Diazene N2H2 34.3 [29]
oxidation states of oxides [17]. A refinement of these dia- Hydrazine N2H4 32 [30]
grams was later proposed by Frost, where it was suggested Ammonia NH3 38 [29]
that the use of free energy could be advantageous in better Formic acid HCOOH 3.75 [31]
understanding the reaction landscape [18]. These diagrams Formaldehyde-hydrate H2C(OH)2 13.27 [31]
can be used to study the stable phases of transistion metal Methanol CH3OH 15.5 [31]
oxides, identify stability windows in aqueous solutions and Methane CH4 60 [23]
reaction free energy diagrams. In this section, we explore
these diagrams in the context of small molecule electro-
chemisty namely oxygen, nitrogen and carbon. of oxygen electrochemistry, the 2e- reduction results in
H2O2 and 4e- reduction results in H2O. The free energy
3.1 Procedure of these molecules can be obtained from thermodynamic
tables. The free energy of the corresponding solution
The construction of Frost diagrams involves identifying species can be obtained using the acid dissociation con-
the free energy of intermediate solution species. In a Frost stant, pKa, listed in Table 1. This procedure is used to
diagram, the sequential addition of two protons and construct the Frost diagrams for oxygen, nitrogen and
electrons results in a molecule. For instance, in the case carbon electrochemistry.

123
218
Fig. 2 Frost diagram for oxygen electrochemistry plotted at a
potential of U = 0 VRHE and pH = 0. The stability of OOH-
OH- aq is obtained using the pKa of H2O2 and H2O respectively. The
free energy difference between these two species in solution is 3.4 eV
3.2 Oxygen Electrochemistry
Using the procedure outlined above, we construct the Frost
diagram for oxygen electrochemistry and this is shown in
Fig. 2. The free energy of the two key solution species,
OOH 
aq and OHaq is obtained using the pKa of H2O2 and
H2O respectively, which are listed in Table 1. It is inter-
esting to note that the free energy difference between these
two intermediates is 3.4 eV. This is quite close to the
scaling found on metal surfaces and this is not entirely
surprising as the scaling relations were found to be uni-
versally independent of metal and facet. Thus, we would
expect the solution free energy difference to give a good
first approximation for the free energy difference between
these intermediates on a metal surface. This relation is
given by:
DGOOH  DGOH  DGOOHaq  DGOHaq
This analysis can be used to get a preliminary idea of the
possible energy landscapes of multi-electron electrochem-
ical reactions. In the next section, we will explore this
methodology to nitrogen and carbon chemistry in an
attempt to identify the fundamental limits for these
reactions.
3.3 Nitrogen Electrochemistry
The electrochemical reduction of nitrogen to ammonia has
a reversible potential, U0 & 0.09 VRHE. However, there is a
large barrier to carry out this transformation and typically
high temperature and pressure is required [3]. However, in
biology, this process can be carried out with the help of
nitrogenase enzyme at room temperature [19]. This
enzyme, however, requires the hydrolysis of 16 adenosine
triphosphate (nearly 5 eV) molecules to perform biological
nitrogen fixation.
123
Top Catal (2014) 57:215221
Fig. 3 Frost diagram for nitrogen electrochemistry at a potential of
aq and U = 0 VRHE and pH = 0. The stability of NNH- -
aq and NH2, aq is
obtained using the pKa of N2H2 and NH3 respectively. The free
energy difference between these two species in solution is
2.52 0.24 eV. The error bar is estimated based on 2 units of
uncertainty in the pKa for ammonia and diazene
We explore the origin of this large overpotential by
examining the Frost diagram for nitrogen electrochem-
istry and this is shown in Fig. 3. The reduction of
nitrogen to ammonia proceeds through the addition of
six protons and electrons and thus there are two inter-
mediate molecules involved in the sequential reduction
of N2, namely the 2e- reduction to cis-diazene, N2H2
and the 4e- reduction to hydrazine, N2H4. The origin of
the difficulty associated with nitrogen reduction becomes
immediately apparent by looking at the Frost diagram. In
this analysis, we attribute the limitations in nitrogen
electrochemistry to the large free energy difference
between NNH 
aq and NH2;aq : The free energy differ-
ence between these two species is 2.52 0.24 eV and
3 they are separated by four protons and electrons. In the
ideal case, this difference should only be & 0.22 eV.
Using the approximation,
DGNNH  DGNH 2  DGNNHaq  DGNH2;aq 4
we immediately identify a fundamental limit for nitrogen
electrocatalysis to ammonia given by g = (2.52 - 0.37
0.24)/4 = 0.54 0.06 V. A similar limit was found in a
recent work using detailed density functional theory cal-
culations of reaction intermediates associated with nitrogen
electrochemistry on stepped metal surfaces [20]. According
to our analysis, the metal surfaces need to have sufficient
binding strength to activate N2 as NNH*. However on these
surfaces, the binding of NH*2 will be so strong that the
limiting step would be the reduction of NH*2 to NH3
forming the strong binding leg of the volcano. At suffi-
cient weakening of NH*2, due to corresponding weaken-
ing of NNH*, the limiting step transitions to the activation
of N2 to NNH* forming the weak binding leg of the vol-
cano. The predictions of our analysis agree well with the
Top Catal (2014) 57:215221
Fig. 4 Frost diagram for carbon electrochemistry at a potential of

U = 0 VRHE and pH = 7. The stability of HCOO aq ; H2 COHOaq ;
-
and CH3Oaq is obtained using the pKa of formic acid, formaldehyde-
hydrate and methanol respectively. The free energy of H2 COH 2;aq
was calculated using an effective Henrys law coefficient of
kH = 3.0 9 103 accounting for hydration [27]. The free energy of
CH3 OHaq was calculated using Henrys law coefficient,
kH = 2 9 102 [28]. The free energy difference between HCOO-
and H2C(OH)O- is 0.52 eV and the free energy difference between
H2 C(OH)O and CH3 O is -0.42 eV
detailed density funcational theory treatment of N2 reduc-
tion [20].
A similar discussion can be made for the oxidation of
ammonia to nitrogen. The overpotential for ammonia oxi-
dation on Pt(100), which is one of the best catalysts for this
reaction, is around 0.50.6 V, close to the fundamental
limit identified [21]. The mechanism suggested for
ammonia oxidation to molecular nitrogen is in good
agreement with the Frost diagram analysis discussed here.
Our simple analysis suggests that electrochemical oxida-
tion of hydrazine could also be difficult, but a more
detailed analysis is necessary to identify the fundamental
limitations associated with this reaction.
3.4 Carbon Electrochemistry
CO2 reduction may result in a wide range of useful products.
However, there are no known metal electrocatalysts that can
catalyze CO2 reduction at low overpotentials [4]. The best
known elemental catalyst that can reduce CO2 to hydrocar-
bons is copper, which requires an overpotential of &1 V. A
particular interesting fuel which may be formed by CO2
reduction is CH3OH. Similar to nitrogen reduction, the
reduction of CO2 to CH3OH occurs at an U0 & 0.03VRHE.
We construct the Frost diagram for carbon electro-
chemistry and this is shown in Fig. 4. The treatment of
carbon electrochemistry is complicated by the fact that the
initial reactant is CO2. Thus, the addition of a proton and an
electron could occur at either the carbon atom or the oxygen
atom. The approach of linking solution intermediates to
surface intermediates relies on similar characteristics of the
metal-adsorbate bond and this does not hold between
219
adsorbates that bind through the carbon end and those that
bind through the oxygen end. [22] These details are crucial
in developing a detailed treatment of surface electrocatal-
ysis of CO2 reduction or methanol oxidation.
In this work, we consider a simplified analysis, consid-
ering bonding primarily through the oxygen atom as the
acid dissociation constants can be experimentally deter-
mined only for the hydrogen attached to the oxygen atom.
The acidity of the hydrogens on the carbon atom are so
weak that these can not be directly measured and can only
be obtained through extrapolation methods [23]. However,
we expect that this analysis could prove to be useful on
surfaces that have high oxygen affinity. Additionally, the
species considered in our analysis, namely HCOO-,
CH2COO- and CH3O-, form the intermediates in one of
the possible pathways for methanol synthesis on Cu sur-
faces in heterogenous catalysis [24]. It has been shown that
binding energy of the oxygen-bound species, HCOO*,
CH2COO* and CH3O* scale with the binding energy of
OH* with the same slope further validating the link to
solution electrochemistry [25]. In our analysis, we find that
the limiting step is the reduction of CO or HCOO- to
H2C(OH)O- and we estimate a limiting potential of
UL = -0.26 VRHE. However, it is worth pointing out that
this analysis assumes the activation of CO2 through the
oxygen end. The binding of these intermediates through the
carbon end would be competing and the barriers associated
with these processes are expected to play an important role
in determining the exact mechanism on different metals. In
enzyme catalysis, however, it is known that carbon mon-
oxide dehydrogenase enzyme can reversibly catalyze the
transformation of CO2 to CO [26]. Thus, in principle, it
could be possible to find catalysts that mimic the active
centers of these enzymes. The understanding of trends in
electrochemical reduction of CO2 on metal surfaces is still
at its early stages and our present analysis does not rule out
the existence of efficient electrocatalysts for CO2
reduction.
4 Opportunities in Surface Electrocatalysis
In this section, we try to explore possible ways to enhance
the efficiency of electrocatalytic transformations involving
small molecules. We discuss in detail two approaches
which could avoid the limits of electrocatalysis identified
in this work.
4.1 Electrochemistry in Non-aqueous Electrolytes
and Ionic Liquids
We use oxygen reduction reaction as the prototypical
reaction to explore approaches to avoid the fundamental
123
220
Fig. 5 Scaling between OOH* and OH* in different medium and
surfaces. The free energy difference between OOH 
aq and OHaq is
3.4 eV. The free energy difference of adsorbed OOH and OH* on
*
metals and metal oxides is 3.2 and 3.0 eV respectively. The free
energy difference between OOH- - interactions with adsorbates. However, the understanding
(g) and OH(g) is 2.79 eV. The free
energy difference on an ideal electrocatalyst is 2.46 eV
limits of surface electrocatalysis. In the case of the oxygen
reduction reaction, the limit to surface electrocatalysis is
imposed due to the unfavorable scaling of 3.2 eV between
OOH* and OH*. Improvements in surface electrocatalysis
is possible if this scaling is lowered closer to the ideal value
of 2.46 eV. This is possible through the selective stabil-
ization of OOH* relative to OH*. Through detailed density
functional theory calculations of the stabilization of water
on OH* and OOH*, it is known that water stabilizes OH* by
about 0.5 eV and OOH* by only about 0.25 eV [10]. One
approach to change the scaling is through the tuning of
solvent interactions. An instance of this is through loss of
solvation due to water which is typically the case on metal
oxides. On oxide surfaces, the scaling between OOH* and
OH* shifts to about 3 eV [16] and it is not surprising that
this value is closer to the difference between these inter-
mediates in gas phase of 2.79 eV where there is no sol-
vation. The scaling between these two intermediates in
different media and surfaces is shown in Fig. 5. This points
to the opportunity of tuning surface electrochemistry
through suitable catalyst-solvent combinations.
The nature of solvent interactions are characterized based
on donor numbers (DN) and acceptor numbers (AN). The
concept of DN, introduced by Gutmann and Mayer [32]
provides a measure of the donor properties of solvents. This
is defined as the numerical value of the heat of adduct for-
mation between the donor molecule and the reference
acceptor [33]. An analogous definition is used for the
acceptor number and the usefulness of these numbers were
shown by correlating shifts in redox potentials to donor and
acceptor numbers [34]. These can also be used to predict the
thermodynamics of ions in solution which is the key metric in
designing solvents for electrocatalysis. In the case of oxygen
reduction electrocatalysis, as discussed above, the solvent
123
Top Catal (2014) 57:215221
chosen should be such that it has weaker interactions with
OH- than water. Hard anions such as OH- have localized
charge and the solvation of these anions requires hydrogen
bonding. As a result, the solubility of these anions in aprotic
solvents is low. Thus, one approach is to add a mix of aprotic
solvents such as dimethylformamide, dimethyl sulfoxide,
acetonitrile, etc. to tune the nature of solvent interactions.
These solvents show a destabilization of about 0.10.3 eV
relative to water for hard anions [35].
Another approach is to use room-temperature ionic
liquids to tune the solvent interactions. The exponential
growth in the number of synthesized ionic liquids with
wide stability windows makes them attractive candidates as
solvents [36, 37]. With tremendous control over size of
cations and anions, these ionic liquids could be used to tune
of electrodeionic liquid interface is at its infancy and
several efforts have been made to understand the structure
of the double layer of the electrodeionic liquid interface
[3840]. Recently, it has been shown using a linear
response treatment of molten salts that due to correlations,
the phenomenon of overscreening is observed where the
first layer at the electrode has more countercharge than on
the surface with the second layer having a smaller net
charge of the opposite sign, which again overscreens, and
so on, until electroneutrality is achieved [41, 42]. Through
careful choice of cations and anions, it appears to be pos-
sible to tune the adsorbateionic liquid interactions to
enhance electrocatalysis. These ideas have seen pre-
liminary sucess in the work of Freisen and co-workers who
have shown that through suitable tuning of the pKa of the
ionic liquid, control over oxygen electrocatalysis can be
achieved [43]. They have demonstrated that the turn on
potential for oxygen reduction on Pt can be tuned using the
pKa of the aprotic ionic liquid, with the optimal ionic
liquid having a turn-on potential of 1.0 V generating a
current of nearly 1 mA/cm2 [43]. However, a more detailed
understanding is necessary to design catalyst-ionic liquid
combinations and the development of detailed design
principles in this area could be useful in computational
identification of candidate combinations.
4.2 Bifunctional Electrocatalysts
Another approach to avoid the limitations imposed by the
scaling relations is through suitable structural changes at
the electrocatalyst surface. This could be achieved through
alloying with the surface containing two different metals.
The presence of two different metals could help in selective
stabilization of one intermediate relative to another [22].
Another route is through patterning of electrode surfaces
with adsorbates that can subsquently affect the thermody-
namics of reaction intermediates. This strategy has been
Top Catal (2014) 57:215221
used to design cyanide patterned Pt surfaces to enhance
oxygen reduction reaction activity [44]. A detailed under-
standing of the underlying principles for bifunctionality
could aid in the successful development of efficient
electrocatalysts.
5 Summary
In this work, we have established a link between surface
electrochemistry and solution electrochemistry by linking
the correlated binding energies of hydrogenated species to
their formation energies in solution. Using this link, we
have identified some fundamental limits of oxygen, nitro-
gen and carbon electrochemistry. The exact reaction
mechanisms on electrocatalytic surfaces will be more
complex and this analysis could be used to get a pre-
liminary idea of the landscape of some of the reaction
pathways involved.
We would like to emphasize that the principles devel-
oped in understanding small molecule electrochemistry is
expected to play an important role in reactions involving
larger molecules as well. The reactive moieties of the large
molecules are similar to those discussed in the context of
small molecules and we expect the ideas presented in this
work to be generally applicable.
Acknowledgements The authors would like to thank Alan Luntz
for helpful discussions.
References
1. Lewis NS, Nocera DG, Natl P (2006) Acad Sci USA
103(43):15729
2. Markovic NM, Ross PN (2002) Surf Sci Rep 45:117
3. Rosca V, Duca M, de Groot MT, Koper MTM (2009) Chem Rev
109(6):2209
4. Hori Y, Kikuchi K, Suzuki S (1985) Chem Lett 14(11):1695
5. Marcus R (1965) J Chem Phys 43(2):679
6. Nrskov JK, Rossmeisl J, Logadottir A, Lindqvist L, Kitchin JR,
Bligaard T, Jonsson H (2004) J Phys Chem B 108(46):17886
7. Nrskov JK, Bligaard T, Logadottir A, Kitchin JR, Chen J,
Pandelov S, Stimming U (2005) J Electrochem Soc 152(3):J23
8. Man I, Su H, Calle-Vallejo F, Hansen HA, Martnez JI, Inoglu
NG, Kitchin J, Jaramillo TF, Nrskov JK, Rossmeisl J (2011)
ChemCatChem 3:1159
9. Viswanathan V, Hansen HA, Rossmeisl J, Nrskov JK (2012)
ACS Catal 2(8):1654
10. Karlberg GS, Rossmeisl J, Nrskov JK (2007) Phys Chem Chem
Phys 9:5158
11. Koper MTM (2013) Chem Sci. doi:10.1039/c3sc50205h
12. Viswanathan V, Hansen HA, Rossmeisl J, Jaramillo TF, Pitsch H,
Nrskov JK (2012) J Phys Chem C 116(7):4698
221
13. Viswanathan V, Hansen HA, Rossmeisl J, Nrskov JK (2012) J
Phys Chem Lett 3(20):2948
14. Stephens IEL, Bondarenko AS, Perez-Alonso FJ, Calle-Vallejo F,
Bech L, Johansson TP, Jepsen AK, Frydendal R, Knudsen BP,
Rossmeisl J, Chorkendorff I (2011) J Am Chem Soc
133(14):5485
15. Abild-Pedersen F, Greeley J, Studt F, Rossmeisl J, Munter TR,
Moses PG, Skulason E, Bligaard T, Nrskov JK (2007) Phys Rev
Lett 99(1):016105
16. Koper MTM (2011) J Electroanal Chem 660(2):254
17. Latimer WM (1938) Oxidation Potentials. Prentice Hall Inc.,
Englewood Cliffs
18. Frost AA (1951) J Am Chem Soc 73(6):2680
19. Howard J, Rees D (1996) Chem Rev 96(7):2965
20. Skulason E, Bligaard T, Gudmundsdottir S, Studt F, Rossmeisl J,
Abild-Pedersen F, Vegge T, Jonsson H, Nrskov JK (2012) Phys
Chem Chem Phys 14(3):1235
21. Rosca V, Koper MTM (2006) Phys Chem Chem Phys 8(21):2513
22. Peterson AA, Nrskov JK (2012) J Phys Chem Lett 3(2):251
23. Jaun B, Schwarz J, Breslow R (1980) J Am Chem Soc
102(18):5741
24. Behrens M, Studt F, Kasatkin I, Kuhl S, Havecker M, Abild-
Pedersen F, Zander S, Girgsdies F, Kurr P, Kniep BL, Tovar M,
Fischer RW, Nrskov JK, Schlogl R (2012) Science
336(6083):893
25. Tritsaris GA, Rossmeisl J (2012) J Phys Chem C 116(22):11980
26. Armstrong FA, Hirst J (2011) Proc Natl Acad Sci USA
108(34):14049
27. Betterton EA, Hoffmann MR (1988) Environ Sci Technol
22(12):1415
28. Snider JR, Dawson GA (1985) J Geophys Res 90(D2):3797
29. Warren JJ, Tronic TA, Mayer JM (2010) Chem Rev
110(12):6961
30. Bauer N (1960) J Phys Chem 64(7):833
31. Haynes WM (ed) (2012) In: CRC handbook of chemistry and
physics, 93rd edn (Internet Version 2013). CRC Press/Taylor and
Francis, Boca Raton, FL
32. Mayer U, Gutmann V, Gerger W (1975) Monatsh Chem
106(6):1235
33. Mayer U (1979) Pure Appl Chem 51:1697
34. Mayer U (1980) In: Yeager EB, Schumm JB, Blomgren G,
Blankenship DR, Leger V, Akridge J (eds) Proceedings of the
workshop on lithium nonaqueous battery electrochemistry, p. 13
35. Aurbach D, Weissman I (1999) Non-aqueous electrochemistry
chap. 1. Marcel Dekker, New York
36. Welton T (1999) Chem Rev 99:2071
37. Hallett JP, Welton T (2011) Chem Rev 111(5):3508
38. Kornyshev AA (2007) J Phys Chem B 111(20):5545
39. Lockett V, Sedev R, Ralston J, Horne M, Rodopoulos T (2008)
Chem Rev 112(19):7486
40. Islam MM, Alam MT, Ohsaka T (2008) Chem Rev 112(42):
16568
41. Fedorov MV, Kornyshev AA (2008) J Phys Chem B
112(38):11868
42. Bazant MZ, Storey BD, Kornyshev AA (2011) Phys Rev Lett
106(4):046102
43. Zeller RA (2011) Effects of extrinsic and intrinsic proton activity
on the mechanism of oxygen reduction in ionic liquids. Ph.D.
thesis. Arizona State University, Phoenix
44. Strmcnik D, Escudero-Escribano M, Kodama K, Stamenkovic
VR, Cuesta A, Markovic NM (2010) Nat Chem 2(10):880
123