pubs.acs.

org/JPCL Letter

Perspectives on the Competition between the Electrochemical

Water and N2 Oxidation on a TiO2(110) Electrode
Ebrahim Tayyebi, Á rni Björn Höskuldsson,⊥ André Wark,⊥ Narges Atrak, Benjamin M. Comer,
Andrew James Medford, and Egill Skúlason*
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ABSTRACT: The electrochemical nitrogen oxidation reaction (NOR) has recently drawn attention due to
promising experimental and theoretical results. It provides an alternative, environmentally friendly route to
directly synthesize nitrate from N2(g). There is to date a limited number of investigations focused on the
electrochemical NOR. Herein, we present a detailed computational study on the kinetics of both the NOR
and the competing oxygen evolution reaction (OER) on the TiO2(110) electrode under ambient
conditions. The use of grand canonical density functional theory in combination with the linearized
Poisson−Boltzmann equation allows a continuous tuning of the explicitly applied electrical potential. We
find that the OER may either promote or suppress the NOR on TiO2(110) depending on reaction
conditions. The detailed atomistic insights provided on the mechanisms of these competing processes make possible further
developments toward a direct electrochemical NOR process.

S ince the early 20th century, ammonia has primarily been

synthesized via the Haber-Bosch process, in which
nitrogen and hydrogen gases are heated to 430 °C, pressurized
NH3 from solvated protons, electrons, and atmospheric
nitrogen:8,9

to 150 atm, and passed over a metal catalyst:1,2 N2(g) + 8(H+ + e−) → 2NH3(g) + H 2(g) (5)

Fe/Ru The ammonia produced in the soil can subsequently be

N2(g) + 3H 2(g) ⎯⎯⎯⎯⎯⎯⎯⎯→ 2NH3(g)
The ammonia can further be converted to nitrate via the
Ostwald process,3 where ammonia is oxidized to nitric oxide at
relatively low pressures (4−10 atm) and high temperatures
(600−800 °C) in the presence of a catalyst, such as platinum
and rhodium in a 9:1 ratio, platinum metal on fused silica
wool, copper, or nickel:
cat
4NH3(g) + 5O2 (g) ⎯⎯⎯→ 4NO(g) + 6H 2O(g)
Then, NO(g) is further oxidized, and nitric acid is produced:
2NO(g) + O2 (g) → 2NO2 (g)
3NO2 (g) + H 2O(l) → 2HNO3(aq) + NO(g)
Recent experimental studies show that nitric acid can be
converted into nitrate via the reaction of NO(g) with a
hydroperoxyl radical at milder conditions (in the pressure and
temperature ranges of 0.10−0.78 atm and −50−50 °C,
respectively).4,5 Together, the industrial conversion of N2 to
ammonia via the Haber-Bosch process and the subsequent
production of NO(g) via the first half of the Ostwald process
account for most of the total energy demand of the nitrogen-
fertilizer industry.6,7
The reaction environments in the Haber-Bosch and Ostwald
processes are far from ambient conditions, under which the
enzyme nitrogenase in bacteria catalyzes the production of
(1) oxidized to nitrate by nitrifying bacteria:
NH3(g) + O2 (g) + H 2O(l) → NO3− + 5(H+ + e−)
(6)
While nitrate is produced from nitrogen fixation via
ammonia, both naturally and artificially, realizing the direct
electro-/photochemical oxidation of N2(g) to nitrate, via the
nitrogen oxidation reaction (NOR), would be of great interest.
Recently, the NOR has been the focus of several experimental
(2)
and theoretical works, wherein a few potential (photo)-
electrocatalysts were identified.10−14 However, some of the
experiments do not include state-of-the-art quantitative
(3) isotopic NMR to quantify the fixed nitrogen in the measured
products (e.g., nitrate or ammonia) to rule out false-positive
(4) results. In the theoretical parts, activation energies and the
presence of solvent are mostly neglected, and no consideration
is given to the competing oxygen evolution reaction
(OER).10−12
The role of TiO2 in (photo)electrocatalytic water splitting
for hydrogen production has been extensively studied.15−35
Received: March 15, 2022
Accepted: June 22, 2022

© XXXX American Chemical Society https://doi.org/10.1021/acs.jpclett.2c00769

6123 J. Phys. Chem. Lett. 2022, 13, 6123−6129
The Journal of Physical Chemistry Letters
The widely accepted OER mechanism in acidic conditions
consists of four proton−electron transfer steps,24,25 as shown
in black in Figure 1. The experimentally determined
equilibrium potential for the overall reaction (7) is 1.23 V vs
the reversible hydrogen electrode (RHE).
2H 2O → O2 (g) + 4(H+ + e−) (7)
Figure 1. The oxygen evolution reaction pathway is shown in black,
while the electrochemical and nonelectrochemical nitrogen oxidation
reactions pathways are shown in red and blue, respectively. Each
catalytic cycle starts from the pristine TiO2 surface.
Anand et al.36 recently looked at the NOR and OER in the
absence of solvent on TiO2(110), IrO2(110), PtO2(110), and
PbO2(110), using the so-called thermochemical model (TCM)
and computational hydrogen electrode (CHE) method, which
relates thermochemical solid−gas phase chemistry with an
electrochemical system. The TCM-CHE method has been
shown to predict fairly accurate onset potentials for a number
of redox reactions.37−46 However, as also demonstrated here,
predicting the selectivity of a catalyst toward different products
in a multistep reaction as a function of potential requires more
complex models.47−52
In this study, grand canonical density functional theory
(GC-DFT) calculations are used to explore the competing
NOR and OER under ambient conditions as a function of
explicitly applied potential on a semiconducting TiO2(110)
photoelectrocatalyst. GC-DFT has recently been developed for
the purpose of simulating electrocatalytic and electrochemical
interfaces with fixed electron and ion chemical potentials in the
grand canonical ensemble.53−55 While GC-DFT was originally
used to compute activation energies for a series of reduction
reactions on transition metal surfaces,56−58 the theoretical
framework has recently been expanded to model the reaction
kinetics on semiconductor materials under applied poten-
tial.59−61
The effects of solvation and applied potential on the
predicted reaction pathways and activation energies are
accounted for with a hybrid implicit/explicit solvent model.
We find that TiO2 may, under certain conditions, catalyze the
electrochemical formation of NO(g) from solvated N2(g). The
overall electrochemical NOR toward NO(g) at acidic
conditions is
N2(g) + 2H 2O(l) → 2NO(g) + 4(H+ + e−) (8)
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where Ueq = 1.68 V vs RHE is the experimentally determined
equilibrium potential.
Two different NOR mechanisms are investigated in this
article. In the first mechanism, shown in red in Figure 1, water
is oxidized to OH*, which then reacts electrochemically with
either N2 or N2O to produce N2O or N2O2, respectively. In the
second, depicted in blue in Figure 1, the O* generated from
OH* oxidation reacts nonelectrochemically with either N2 or
N2O to form N2O or N2O2, respectively. In total, four proton−
electron transfers are required to produce NO, but the further
oxidation of NO toward HNO3 should be facile4,5 compared to
the formation of N2O/N2O2 and is therefore not included
here.
Figure 2 shows free energy diagrams for the OER and the
NOR at 2.43 V vs RHE, which is the predicted onset potential
Figure 2. Free energy diagrams for the competing OER and NOR on
the TiO2(110) surface at 2.43 V. The oxidation of N2 to NO is
divided into two parts: (a) N2 oxidation toward N2O and (b) N2O
oxidation toward NO. In both (a) and (b), the black curve shows the
predicted OER pathway, but for clarity the values of the free energy
barriers are only included in (a). The number of completed proton−
electron transfer steps in the OER is used as a reaction coordinate.
The error bars for the OER barriers represent the maximum (a
symmetry factor of 0.9) and the minimum (a symmetry factor of 0.5)
estimates of the activation free energies for O* and O2(g) formations,
±0.03 eV and ±0.2 eV, respectively. A symmetry factor of 0.7 was
used to estimate the barriers of O* and OOH* formation.
for the OER (Figure S3), in good agreement with the value
previously obtained by Man et al.62 For the remainder of the
text, all reported potentials are referred to the RHE. The
oxidation of N2 to N2O is shown in Figure 2(a), and the
oxidation of N2O to NO is shown in Figure 2(b). The
competing OER is shown in both Figures 2(a) and 2(b). The
calculations were performed using the implicit solvation model
implemented in VASP, VASPsol,63,64 which enables the
application of a tunable explicit potential in the system. Four
water molecules (in addition to the two water molecules
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Figure 3. The blue dots give the calculated activation free energy for the nonelectrochemical reaction of N2 + O* to N2O with only the implicit
solvent model (no explicit water molecules). The cyan colored dots show the calculated activation free energy for the same reaction using the
hybrid implicit/explicit solvent model at 1.2 and 2.43 V. The red dots give the calculated activation free energy for the electrochemical reaction of
N2 + OH* to N2O using the hybrid implicit/explicit solvent model. The black dashed and dotted lines give the estimated activation free energy for
the reaction O* + H2O to O2(g) as a function of the applied potential using the hybrid implicit/explicit solvent model. The dotted and dash-dotted
lines are obtained with a symmetry factor of β = 0.9 (steeper) and β = 0.5 (flatter), respectively, while the dashed line is obtained with a symmetry
factor of β = 0.7. The figure is divided into three regions based on which species are expected to occupy the two CUS sites in the unit cell at a given
applied potential. In the darkest region (U < 2 V), water molecules are expected to be adsorbed on both CUS sites in the unit cell. In the medium
dark region (2 V < U < 2.43 V), one of the adsorbed water molecules has oxidized to OH*, with the other water molecule remaining intact. Finally,
in the light dark region (U > 2.43 V), the OH* species has been further oxidized to O*. The blue and red lines are included for visual guidance.
Filled dots and solid lines denote that the expected surface coverage matches the given reaction step, whereas empty dots and dashed lines signify
that the expected surface coverage at that potential is not the one required for the given reaction step to take place. The insets above the figure
show the relaxed coadsorbed water molecule and the expected adsorbate on the other CUS (H2O*, OH*, and O*) for the three different potential
regions.

adsorbed on the active sites) were added to the simulation cell
to account for explicit solvation effects (such as hydrogen
bonding interactions) and to enable the simulation of proton−
electron transfer reactions. The model system is shown in
Figure S1(c,d) in the Supporting Information (SI), and the
computational settings used in the simulations are explained in
section S1 of the SI. All OER proton−electron transfer steps
occur spontaneously when a sufficiently high electric potential
is explicitly included in the simulation. Moreover, we introduce
a method to estimate OER activation free energies and
compare the results with those obtained using the climbing-
image nudged elastic band method (CI-NEB)65,66 (section S4,
Figures S6 and S7). Desorbed or physisorbed species are not
specifically marked in Figure 2 or the text. An isolated *
denotes a vacant active site, which for rutile TiO2(110) is the
coordinately unsaturated Ti site (CUS). A chemisorbed
reaction intermediate on the CUS is denoted by a * connected
to a chemical moiety (for instance, *OH).
The OER is found to proceed for only one of the two water
molecules adsorbed on the CUSs in the unit cell. An applied
potential of around 2.2 V is needed to directly oxidize
adsorbed water to OH*, with the proton subsequently
relocating to the bulk of the solution forming a hydronium
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ion (Figure S9-a). A potential of 2.6 V is required for the
subsequent oxidation of OH* to O* to occur spontaneously
(Figure S9-b). The activation free energy for applied potentials
U < 2.6 V is estimated as the potential difference multiplied by
a symmetry factor (β) of 0.7, i.e., 0.7*(2.6 V − U). Using this,
an estimate of 0.12 eV is obtained for the activation free energy
at 2.43 V, as shown in Figure 2. For comparison, similar values
of the activation free energy of OH* oxidation are obtained
using the CI-NEB method at constant charge, with the details
given in section S4 of the SI.
Next, O* is further oxidized to OOH*, with a predicted
reaction free energy of 0.38 eV at 0 V (Figure S3-b), and thus
−2.05 eV at 2.43 V according to the TCM-CHE. However, a
kinetic barrier of around 0.7 eV is predicted when a potential
of 2.43 V is explicitly included in the simulation (Figures 2 and
S11, section S5). The oxidation of O* is thus the predicted
rate-limiting step (RLS) of the OER, while the oxidation of
OH* is potential-limiting according to the TCM. The same
RLS was identified in a recent study of the OER on IrO2(110),
RuO2(110), PtO2(110), and RhO2(110), where explicit
solvent water molecules were included.67 A potential of 3.44
V is required to spontaneously oxidize O* to O2(g) (section
S5 and Figure S11), which is significantly higher than the 2.43
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V predicted by the TCM-CHE. The predicted activation free
energy of 0.71 eV at 2.43 V is again obtained by multiplying
the potential difference by a symmetry factor of 0.7 (Figure 2).
These results reveal that the OOH* is directly oxidized to
O2(g) at such positive potentials (Figure S10), so the second
half of the OER is combined into a single step for the
remainder of this study.
Our results indicate that the N2, N2O, and N2O2 molecules
are all physisorbed on the surface for the duration of the
electrochemical NOR process, with the calculated binding free
energies of the N2, N2O, N2O2, and H2O molecules listed in
Table S1. Hence, the NOR always begins with the adsorption
of water, followed by the oxidation of water to OH*. Then,
OH* is most likely further oxidized to O*, with a predicted
activation free energy of 0.12 eV at 2.43 V. Alternatively, the
OH* can react with N2 to form N2O in a combined
electrochemical process, where the proton is simultaneously
transferred to the solution. However, an activation free energy
of 0.81 eV is obtained for that reaction at 2.43 V (Figures 2(a)
and S12). Likewise, OH* can react with N2O to form N2O2,
with a similarly high activation free energy of 0.87 eV obtained
at 2.43 V (Figures 2(b), S13, and S14). When O* has formed
on the surface, a barrier of around 0.7 eV must be overcome to
form OOH* (using β = 0.7). Alternatively, it can react with
N2/N2O in a nonelectrochemical process to form N2O/N2O2,
with activation free energies of 0.57 and 0.49 eV at 2.43 V,
respectively (Figures 2(a) and 2(b)). The calculated activation
free energies of both N2O and N2O2 formations via the
nonelectrochemical process are slightly smaller than that
predicted for O2 formation, suggesting these reactions will be
competitive. The cleavage of the N−N bond to N2O2 at 2.43 V
is exothermic and has an activation free energy of 0.25 eV
(Figures 2(b) and S15), which indicates rapid NO formation
upon the formation of N2O2.
Having calculated all relevant NOR activation free energies
at 2.43 V, the next step is to obtain them at different potentials.
Figure 3 shows the calculated activation free energies of N2O
formation in the absence/presence of water and the estimated
activation free energies of O2 formation, for a range of positive
potentials. A corresponding plot for the formation of N2O2
from N2O is shown in Figure S14.
The potential dependence of the activation free energy of
the nonelectrochemical N2O formation (blue dots) is
explained by the fact that O* is destabilized at more positive
potentials, whereas the transition state remains unchanged (see
Figure S16). While the nonelectrochemical N2O formation can
only occur at potentials where an O* coverage is expected, i.e.
for U > 2.43 V, the activation free energy is also given for U <
2.43 V to show the predicted potential dependency of the
reaction.
An O*−OH2 bond is formed between the adsorbed oxygen
and the oxygen of the nearest solvent water molecule at all
potentials larger than 2.1 V, here defined as the minimum
potential required for O*−OH2 bond formation. The bond
strength increases, and the O*−OH2 distance decreases, as the
potential is increased. The estimated activation free energies
for O2 formation for U < 2.6 V, using β = 0.7, are higher than
the ones obtained for N2O formation. The latter ones are
obtained without accounting for the presence of water (only
implicit solvent). However, the inclusion of explicit water
molecules has insignificant effects on the calculated barriers
(cyan dots), as the O*−OH2 bond breaking is observed upon
the introduction of N2 in the vicinity of the surface, with the
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water molecule diffusing away from the O*. While this suggests
that the O* would rather react with N2 than continuing the
OER, this finding could also originate from the limited number
of explicit water molecules in the simulation. If that is the case,
the presence of the O*−OH2 bond might lead to an increase
in the activation free energy for N2O formation for applied
potentials larger than 2.1 V. Excluding this possibility requires
calculations with, for instance, a full bilayer of water, which is
beyond the scope of this study.
Anand et al.36 calculated the kinetic barriers for the
nonelectrochemical steps of N2 + O* to N2O and N2O +
O* to N2O2 in the absence of a solvent. They concluded the
nonelectrochemical mechanism to be the most likely reaction
pathway of the NOR on TiO2(110) in agreement with our
detailed study here. They obtained an energy barrier of 0.84 eV
when no potential was applied in the simulation for the
reaction of gaseous N2 with O*. A posteriori corrections were
used to account for field effects and entropy loss in the
transition state. From the field effects, they estimate the barrier
to decrease by around 0.5 eV at a potential of 2.13 V, but from
the entropy loss, the free energy barrier is increased to around
1 eV. Our results agree qualitatively with those reported by
Anand et al., as we observe a substantial decrease of the barrier
of N2O formation at more positive potentials (Figure 3).
Contrary to their conclusion that the OER should be favored
over the NOR at all relevant potentials, our detailed analysis of
the competing OER shows that the TiO2(110) might be
selective toward the NOR at potentials of around 2.5 V.
Furthermore, the inclusion of implicit solvent enables us to
predict the changes in surface coverage and local reaction
environment as the electrode potential is continuously tuned.
Such knowledge is essential for those who seek to optimize the
design and performance of the electrochemical cell.
Recently, Kuang et al.10 investigated the NOR on various
Ru-doped TiO2 electrocatalysts in a neutral aqueous solution,
obtaining a Faradaic efficiency of above 25% at 1.8 V and a
nitrate yield exceeding 150 μmol h−1 g−1 at 2.2 V. They also
studied the NOR on the pristine TiO2 surface and observed
only trace amounts of nitrate at 2.2 V, below the limit of
detection. According to our results, OH* is the dominant OER
intermediate on the surface at 2.2 V (Figure 3), though some
O2(g) formation is expected at all potentials above 2 V, as can
be observed from the linear sweep voltammetry curves in ref
10. With the limited availability of O* at 2.2 V, nitrate
formation via the nonelectrochemical NOR pathway could
occur, albeit with a very low efficiency. Thus, the trace
amounts of nitrate reported by Kuang et al. at 2.2 V are
consistent with our predictions of very limited NOR efficiency
in this potential range. Below, we propose some strategies to
increase the NOR efficiency of pristine TiO2 and similar
materials to achieve appreciable yields.
Based on the results, we conclude that a close competition
exists between the NOR and OER on TiO2. The conclusion of
which reaction prevails will depend on the details of the
reaction environment, the specific facet or active site
investigated, and the level of theory and simulation techniques
employed. The findings suggest that further theoretical
advances are needed to elucidate the precise potential-
dependent barriers for the OER on TiO2 due to the instability
of the final OOH* transition state and that it may be necessary
to use hybrid functionals or even higher levels of theory to
conclusively determine the prevailing reaction on a given active
site under typical reaction conditions. The NOR is always at a
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disadvantage compared to the OER due to the limited
solubility of N2 in the solution. However, we suggest here
several strategies which may be fruitful for promoting NOR
selectivity. One possibility is tuning the relative chemical
potentials of N2 and H2O to limit the availability of reactants
for the OER. Alternatively, increasing the concentration of O2
may cause the OER to become equilibrium limited and
simultaneously promote O*-covered surfaces, leading to
enhanced NOR activity. Finally, utilizing potential pulsing,
where the potenital is varied between higher values, which
promote O* coverage, and lower values, which promote NOR
selectivity, may offer a viable strategy.68−70 Furthermore, our
detailed study indicates that N2O(g) may be formed during the
NOR process. Thus, quantifying N2O(g) yield will be a critical
experimental contribution that will provide additional insight
into the reaction mechanism.
To summarize, we explore whether N2 can be directly
oxidized to nitric oxide through an electrochemical process on
rutile TiO2(110). We use GC-DFT calculations to elucidate
the NOR mechanism toward several NOR products, N2O,
N2O2, and NO, and propose ways in which the selectivity of
the NOR in an electrochemical reaction cell can be enhanced.
We predict that the NOR can occur on TiO2(110) under
certain conditions at relatively high potentials (around 2.5 V),
albeit likely with a relatively low efficiency as reported in a
recent experiment.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpclett.2c00769.
Section S1, computational and methodological details
and model system; section S2, potential referencing
scheme; section S3, oxygen evolution reaction pathway
for different xc-functionals; section S4, comparison of
explicit and explicit/implicit solvation models; section
S5, effects of explicitly applied potential on OER; section
S6, binding free energies of relevant molecules; section
S7, effects of explicitly applied potential on N2O and
N2O2; section S8, stabilizing/destabilizing effects of
potential on transition state of N2O formation; and
section S9, alternative version of Figure 1 showing NOR
pathway toward NO (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Egill Skúlason − Science Institute, University of Iceland, 107
Reykjavík, Iceland; Faculty of Industrial Engineering,
Mechanical Engineering and Computer Science, University of
Iceland, 107 Reykjavík, Iceland; orcid.org/0000-0002-
0724-680X; Email: egillsk@hi.is
Authors
Ebrahim Tayyebi − Science Institute, University of Iceland,
107 Reykjavík, Iceland; orcid.org/0000-0002-9461-0410
Á rni Björn Höskuldsson − Science Institute, University of
Iceland, 107 Reykjavík, Iceland
André Wark − Science Institute, University of Iceland, 107
Reykjavík, Iceland
Narges Atrak − Science Institute, University of Iceland, 107
Reykjavík, Iceland
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pubs.acs.org/JPCL Letter
Benjamin M. Comer − School of Chemical and Biomolecular
Engineering, Georgia Institute of Technology, Atlanta,
Georgia 30318, United States; SUNCAT Center for Interface
Science and Catalysis, Department of Chemical Engineering,
Stanford University, Stanford, California 94305, United
States
Andrew James Medford − School of Chemical and
Biomolecular Engineering, Georgia Institute of Technology,
Atlanta, Georgia 30318, United States; orcid.org/0000-
0001-8311-9581
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpclett.2c00769
Author Contributions
⊥
A.B.H. and A.W. contributed equally.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the Icelandic Research Fund
(Grant no. 196437-051) and the Doctoral Fund of the
University of Iceland.
■
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