A rapid
and facile reduction of nitrogen to achieve sustainable
and energy-efficient production of ammonia is critical to its use
as a hydrogen storage medium, chemical feedstock, and especially for
manufacturing inorganic fertilizers. For a decentralization of catalytic
ammonia production, small-scale N2 reduction devices are
required that are equipped with the most stable, selective, and active
catalysts that operate at low temperature and ambient pressure. Here,
we report the development of new and cost-efficient catalysts, transition
metal nitrides, which enable electrochemical reduction of molecular
nitrogen to ammonia in aqueous media at ambient conditions with only
a low applied bias. The most promising catalysts are VN, ZrN, NbN,
and CrN, which are identified among a range of transition metal nitride
surfaces through a comprehensive density functional theory based analysis.
All four nitrides are found to be more active toward nitrogen reduction
than toward the competing hydrogen evolution reaction, in contrast
to pure metal catalysts, which largely evolve hydrogen. Furthermore,
their stability against poisoning and possible decomposition under
operating conditions is also studied. Particular single-crystal surfaces
are needed for ZrN, NbN, and CrN because polycrystalline surfaces
may result in decomposition of the whole catalyst. Polycrystalline
surfaces of VN may, however, be used since the rocksalt (100) facet
is predicted to produce ammonia via a Mars–van Krevelen mechanism
with only a −0.5 V overpotential, thereby avoiding decomposition.
We suggest that this is a promising step toward the development of
a method for synthesizing ammonia cheaply, to prepare high-value-added
nitrogenous compounds directly from air, water, and electricity at
ambient conditions. An additional benefit to the present analysis
is that the method used in this work may be applicable to other aqueous
phase catalytic reactions, where a Mars–van Krevelen mechanism
is operative and product selectivity and activity are key catalytic
criteria.
Commercial design of a sustainable route for on-site production of ammonia represents a potential economic and environmental breakthrough. In an analogous process to the naturally occurring enzymatic mechanism, synthesis of ammonia could be achieved in an electrochemical cell, in which electricity would be used to reduce atmospheric nitrogen and water into ammonia at ambient conditions. To date, such a process has not been realized due to slow kinetics and low faradaic efficiencies. Although progress has been made in this regard, at present there exists no device that can produce ammonia efficiently from air and water at room temperature and ambient pressure. In this work, a scheme is presented in which electronic structure calculations are used to screen for catalysts that are stable, active and selective towards N2 electro-reduction to ammonia, while at the same time suppressing the competing H2 evolution reaction. The scheme is applied to transition metal nitride catalysts. The most promising candidates are the (100) facets of the rocksalt structures of VN and ZrN, which show promise of producing ammonia in high yield at low onset potentials.
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