COMMENTARY
COMMENTARY
Homogeneous catalysis for the nitrogen fuel cycle
Yanming Liua,b and Thomas J. Meyera,1
The nitrogen cycle is an important biogeochemical
cycle in which nitrogen, a building block of proteins
and nucleic acids, is chemically activated. In the cycle,
atmospheric dinitrogen is converted into ammonia as
our primary source of bioavailable nitrogen. Ammonia
is a carbon-free energy carrier and widely used as
a chemical feedstock. Ammonia oxidation is also a
critical step in global nitrogen cycling. Harnessing the
energy stored in ammonia involves oxidization to
dinitrogen and hydrogen, NH3 → 1/2N2 + 3/2H2, with
the hydrogen produced utilized in hydrogen-based
fuel cells (Fig. 1). Ammonia can be also easily lique-
fied. As a hydrogen carrier, it provides a strategy for
the efficient storage, transport, and utilization of re-
newable hydrogen on large scales, and it is not sur-
prising that ammonia oxidation has attracted great
interest in clean energy and environmental pollution
control. Electrochemical oxidation of ammonia occurs
at room temperature under ambient pressures (1, 2)
with an interest in active electrocatalysts with low
overpotentials and high faradaic efficiencies for its oxi-
dization to hydrogen to dinitrogen.
A study in PNAS by Habibzadeh et al. (3) reports
that ruthenium polypyridyl complexes can be used
as electrocatalysts for the oxidation of ammonia to
Fig. 1. Simplified reaction scheme illustrating an ammonia/N2 fuel cycle in which
NH3 is electrochemically oxidized to N2 and H2, NH3 →1/2N2 + 3/2H2, with H2
utilized in a hydrogen/O2 fuel cell. In a reverse cycle, N2 is electrochemically
reduced to NH3 by nitrogen fixation (1/2N2 +3/2H2O → NH3 + 3/4O2). In a
complete ammonia fuel cycle, both electrochemical ammonia oxidation and
nitrogen fixation would be driven by renewable energy sources.
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a
Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599; and bSchool of Environmental Science and
Technology, Dalian University of Technology, Dalian 116024, China
Author contributions: Y.L. and T.J.M. wrote the paper.
The authors declare no conflict of interest.
Published under the PNAS license.
See companion article on page 2849.
1
To whom correspondence should be addressed. Email: tjmeyer@unc.edu.
Published online February 8, 2019.
2794–2795 | PNAS | February 19, 2019 | vol. 116 | no. 8
dinitrogen and dihydrogen at ambient pressures
and temperature. The results from Habibzadeh et al.
(3) are an important extension of the remarkable high-
oxidation-state chemistry of these complexes with RuII
and OsII. Known examples in this chemistry include cat-
alysts for water oxidation, catalytic organic oxidations,
and a remarkable series of inorganic reactions such as
the oxidation of NH3 to NO3−, all in polypyridyl coordi-
nation environments.
The discovery reported here is an important ex-
tension. It exploits the reactivity of these complexes to
a reaction of potential interest in energy application:
homogenous electrochemical oxidation of ammonia
to N2. Exploitation of the reaction could provide a
basis for efficient molecular catalysis in the oxidation
of ammonia to dinitrogen under mild conditions, as
shown in Fig. 1.
Ammonia oxidation has been extensively studied in
biological systems and in heterogeneous systems based
on thermal conversion, photocatalysis, or electrocatalysis
(4, 5). Biological ammonia oxidation is driven by bacteria
and archaea, and they transform ammonia to dinitrogen
by anaerobic ammonium oxidation, or oxidize ammonia
to nitrite or nitrate by nitrification (5, 6) or, as in Fig. 1, to
dinitrogen as a product.
Electrolysis of ammonia to dinitrogen and dihy-
drogen should be thermodynamically accessible un-
der mild conditions with renewable energy sources.
An ideal electrocatalyst for ammonia oxidation should
have appropriate binding energies for ammonia and
for the key oxidation intermediates that interconvert
the two (7). There are obvious problems, including
stable coordination of ammonia in the first place and
accessing the higher oxidation states at the metal
while avoiding competing decomposition pathways.
Metals such as Pt, Ir, Ru, and Au and their alloys
are active heterogeneous catalysts for electrochem-
ical oxidation of ammonia to dinitrogen (1, 2, 8).
Among these electrocatalysts, Pt and Ir alloys have
been considered as the most effective for ammonia
oxidation, with their low overpotentials and high
www.pnas.org/cgi/doi/10.1073/pnas.1822090116
 current densities (2). The results of experiments on catalyst structure
and composition have been used to lower overpotential and en-
hance the kinetics and efficiency for ammonia electrooxidation. In
heterogeneous catalysis, a major concern for metal heterogeneous
catalysis is electrode-surface poisoning by adsorbed intermediates.
One answer is homogeneous electrocatalysis at inert, conducting
electrodes to overcome activity loss of the catalyst.
As noted above, given their background redox chemistry,
polypyridyl complexes like [Ru(trpy)(bpy)(NH3)]2+ (trpy = 2,2′:6′,2′′-
terpyridine, bpy = 2,2′-bipyridine) are of particular interest in this
chemistry. Mechanistic studies have shown that they undergo
single-electron oxidation from RuII to RuIII, followed by oxidation
and proton loss to RuIV = NH, with the latter undergoing nucleo-
philic attack on the imido N to give RuII-hydroxylamines (9). There
are related results on the oxidation of coordinated ammonia li-
gands to N2 in dinuclear ruthenium complexes, mononuclear os-
mium complexes, and on a series of molybdenum complexes (10–
12). These observations provide a basis for dinitrogen generation
by oxidation of ammonia in complexes like [Ru(trpy)(bpy)(NH3)]2+,
but E1/2 for the RuIII/RuII couple was 0.15 V more positive than the
onset potential for ammonia oxidation at glassy carbon electrodes.
A key to driving the reaction has come from the results of Habib-
zadeh et al. (3) by exploiting the background synthetic chemistry
to prepare the modified complex [Ru(trpy)(dmabpy)(NH3)]2+ [trpy =
2,2′:6′,2′′-terpyridine, dmabpy = 4,4´-bis(dimethylamino)-2,2′-
bipyridine] (catalyst 1a in ref. 3). They demonstrate 1a to be an
efficient homogenous catalyst for electrochemical oxidation of
ammonia to dinitrogen at room temperature and ambient pres-
sure. The introduction of the dmabpy ligand reduces the RuIII/RuII
oxidation potential from 1.03 to 0.68 V vs. normal hydrogen elec-
trode (NHE), which is ∼0.19 V below the potential for direct oxi-
dation at a glassy carbon electrode.
The reactivity of catalyst 1a toward ammonia oxidation was
first shown by the appearance of a significantly enhanced current
density with added ammonia after oxidation of Ru II to Ru III in
[Ru(trpy)(dmabpy)(NH3)]3+. Compared with uncatalyzed ammonia
oxidation on glassy carbon electrodes, catalyst 1a lowers the over-
potential for ammonia oxidation by ∼0.3 V in THF solution. Of
significant interest here is that dinitrogen and dihydrogen are pro-
duced from ammonia electrolysis in the solvent with high faradaic
efficiencies of 86% and 78% at 0.73 V vs. NHE, showing that the
catalyst converts ammonia to dinitrogen and dihydrogen. The ratio
of dinitrogen to dihydrogen is 1:2.74, close to the stoichiometry for
the reaction of ammonia splitting to dinitrogen and dihydrogen (1:3).
The results of 15NH3 labeling experiments also show that dinitrogen is
generated from ammonia oxidation. There are molybdenum and iron
complex catalysts that are active for fixing dinitrogen to ammonia in
nitrogen fuel cycles (13, 14), but this is a molecular catalyst for the
electrochemical oxidation ammonia to dinitrogen at low overpotential.
A study in PNAS by Habibzadeh et al. reports
that ruthenium polypyridyl complexes can be
used as electrocatalysts for the oxidation of
ammonia to dinitrogen and dihydrogen at
ambient pressures and temperature.
Mechanistic details were also investigated by cyclic voltam-
metry and additional studies in solution. In THF, the rate of
ammonia oxidation was first order in 1a, suggesting that single-
electron oxidation of RuII to RuIII occurs before the rate-limiting
step. Based on the results of previous studies on a series of transition
metal complexes, including examples from ruthenium, osmium, and
molybdenum, the overall reaction presumably proceeds through
hydrazine or nitride pathways (11, 12, 15). In the hydrazine pathway,
deprotonation is followed by N–N bond formation to give the in-
termediate hydrazine complex, RuII(H2N-NH2)2+, with the latter gen-
erated by nucleophilic attack of the amine on a transient imido
intermediate. In the nitride pathway, N–N coupling occurs between
a nitride, RuV(N), and NH3.
Experimental evidence was found for the hydrazine inter-
mediate [(trpy)(dmabpy)RuIII(N2H4)]2+ (5a in ref. 3) by heating
[(trpy)(dmabpy)Ru(Cl)][Cl] in a hydrazine hydrate solution satu-
rated with [NH4][PF6]. The solid was characterized by 1 H NMR
and cyclic voltammetry. 1H NMR spectra of reaction from 1a, 5a,
or [(trpy)(dmabpy)RuIII(N2H4)][PF6]2, with and without added NH3,
are all consistent with N–N bond formation through the hydrazine
complex as an intermediate.
The mechanistic details revealed by Habibzadeh et al. (3) will be
useful for defining conditions for maximizing the oxidation of ammo-
nia to dinitrogen in catalytic systems in the future. The key features
emerging here show that RuII oxidation to RuIII is followed by depro-
tonation and N–N bond formation through a hydrazine intermediate.
The challenge now will be to identify conditions that enhance re-
activity further at larger scales for the design of ammonia fuel cycles.

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