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.

We have calculated frequencies and intensities of fundamental and overtone vibrational transitions in water and water dimer with use of different vibrational methods. We have compared results obtained with correlation-corrected vibrational self-consistent-field theory and vibrational second-order perturbation theory both using normal modes and finally with a harmonically coupled anharmonic oscillator local mode model including OH-stretching and HOH-bending local modes. The coupled cluster with singles, doubles, and perturbative triples ab initio method with augmented correlation-consistent triple-zeta Dunning and atomic natural orbital basis sets has been used to obtain the necessary potential energy and dipole moment surfaces. We identify the strengths and weaknesses of these different vibrational approaches and compare our results to the available experimental results.