Electrochemical Nitrogen Reduction to Ammonia at Ambient Condition on the (111) Facets of Transition Metal Carbonitrides.

We conducted Density Functional Theory calculations to investigate a class of materials with the goal of enabling nitrogen activation and electrochemical ammonia production under ambient conditions. The source of protons at the anode could originate from either water splitting or H2, but our specific focus was on the cathode reaction, where nitrogen is reduced into ammonia. We examined the conventional associative mechanism, dissociative mechanism, and Mars-van Krevelen mechanism on the (111) facets of the NaCl-type structure found in early transition metal carbonitrides, including Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Sc, Y, and W. We explored the catalytic activity by calculating the free energy of all intermediates along the reaction pathway and constructing free energy diagrams to identify the steps that determine the reaction's feasibility. Additionally, we closely examined the potential for catalyst poisoning within the electrochemical environment, considering the bias required to drive the reaction. Furthermore, we assessed the likelihood of catalyst decomposition and the potential for catalyst regeneration among the most intriguing carbonitrides. Our findings revealed that the only carbonitride catalyst considered here exhibiting both activity and stability, capable of self-regeneration and nitrogen-to-ammonia activation, is NbCN with a low potential-determining step energy of 0.58 eV. This material can facilitate ammonia formation via a mixed associative-MvK mechanism. In contrast, other carbonitrides of this crystallographic orientation are likely to undergo decomposition, reverting to their parent metals under operational conditions.

Nitrogen Reduction Reaction to Ammonia on Transition Metal Carbide Catalysts.

The development of a low-cost, energy-efficient, and environmentally friendly alternative to the currently utilized Haber-Bosch process to produce ammonia is of great importance. Ammonia is an essential chemical used in fertilizers and a promising high-density fuel source. The nitrogen reduction reaction (NRR) has been explored intensively as a potential avenue for ammonia production using water as proton source, but to this day a catalyst capable of producing this chemical at high Faradaic efficiency (FE) and commercial yield and rates has not been reported. Here, we investigate the activity of transition metal carbide (TMC) surfaces in the (100) facets of the rocksalt (RS) structure as potential catalysts for the NRR. In this study, we use density functional theory (DFT) to model reaction pathways, estimate stability, assess kinetic barriers, and compare adsorbate energies to determine the overall performance of each TMC surface. For pristine TMC surfaces (with no defects) we find that none of the studied TMCs possess both exergonic adsorption of nitrogen and the capability to selectively protonate nitrogen to form ammonia in the desired aqueous solution. ZrC, however, is shown to be a potential catalyst if used in a non-aqueous electrolyte. To circumvent the endergonic adsorption of nitrogen onto the surface, a carbon vacancy was introduced. This provides a well-defined high coordination active site on the surface. In the presence of a vacancy VC, NbC, and WC showed efficient nitrogen adsorption, selectivity towards ammonia, and a low overpotential (OP). NbC did, however, display an unfeasible kinetic barrier to nitrogen dissociation for ambient-condition purposes, and thus it is suggested for high tempearture/pressure ammonia synthesis. Both WC and VC in their RS (100) structure are promising materials for experimental investigations in aqueous electrolytes, and ZrC could potentially be interesting for non-aqueous electrolytic systems.

Biomimetic Nitrogen Fixation Catalyzed by Transition Metal Sulfide Surfaces in an Electrolytic Cell.

The nitrogen reduction reaction was investigated on the surfaces of 18 different stable transition metal sulfides using density functional theory calculations. YS, ScS, and ZrS were modeled in the rocksalt structure with the (1 0 0) facet; TiS, VS, CrS, NbS, NiS, and FeS in NiAs-type structure with the (1 1 1) facet; and MnS2 , CoS2 , IrS2 , CuS2 , OsS2 , FeS2 , RuS2 , RhS2 , and NiS2 in pyrite structure for both the (1 0 0) and (1 1 1) orientations. As the first step towards determination of sulfides that are less prone to hydrogen evolution, the competition between adsorption of NNH and H (for the associative mechanism), and between adsorption of N and H (for the dissociative mechanism) on these surfaces was considered. The catalytic activity through both the associative and dissociative mechanisms was explored and the overpotential required for electrochemical ammonia formation is reported. The scaling relations and volcano plots were constructed with free energy of adsorption of NNH or N on the surface as the descriptor. RuS2 was observed as the most active sulfide that could catalyze nitrogen reduction to ammonia at potentials around -0.3 V through the associative mechanism. NbS, CrS, TiS, and VS are also promising candidates for both the associative and dissociative mechanisms with overpotentials for nitrogen reduction around 0.7-1.1 V.

In silico screening of molecular imprinting prepolymerization systems: oseltamivir selective polymers through full-system molecular dynamics-based studies.

All-component molecular dynamics studies were used to probe a library of oseltamivir molecularly imprinted polymer prepolymerization mixtures. Polymers included one of five functional monomers (acrylamide, hydroxyethylmethacrylate, methacrylic acid, 2-(triflouromethyl)acrylic acid, 4-vinylpyridine) and one of three porogens (acetonitrile, chloroform, methanol) combined with the crosslinking agent ethylene glycol dimethacrylate and initiator 2,2'-azobis(2-methylpropionitrile). Polymers were characterized by nitrogen gas sorption measurements and SEM, and affinity studies performed using radioligand binding in various media. In agreement with the predictions made from the simulations, polymers prepared in acetonitrile using either methacrylic or trifluoromethacrylic acid demonstrated the highest affinities for oseltamivir. Further, the ensemble of interactions observed in the methanol system provided an explanation for the morphology of polymers prepared in this solvent. The materials developed here offer potential for use in solid-phase extraction or for catalysis. The results illustrate the strength of this in silico strategy as a potential prognostic tool in molecularly imprinted polymer design.

Enabling electrochemical reduction of nitrogen to ammonia at ambient conditions through rational catalyst design.

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.