Ultra-thin poly-crystalline TiN films grown by HiPIMS on MgO(100) — In-situ resistance study of the initial stage of growth

Shayestehaminzadeh, S.; Tryggvason, T.K.; Magnus, Fridrik; Ólafsson, S.; Guðmundsson, Jón Tómas

doi:10.1016/j.tsf.2013.07.074

Cited by 11 publications

(8 citation statements)

References 36 publications

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“…[67][68][69] Regarding facet stability, experimental studies show that the growth of films of ZrN, TiN, NbN and CrN results in the texture coefficient for the (100) planes of the synthesized polycrystalline to be one of the major preferential directions. [70][71][72][73][74] For all considered surfaces of WN, ReN, AuN and PtN, significant distortion of the surface atoms is observed during relaxation and thus these nitrides are considered unstable and eliminated from further study. In total, this first consideration reduces the number of potential catalysts from 104 to 21.…”

Section: Stability Of Facetsmentioning

confidence: 99%

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

Abghoui

Garden

Hlynsson

et al. 2015

Phys. Chem. Chem. Phys.

278

272

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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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Section: Stability Of Facetsmentioning

confidence: 99%

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

Abghoui

Garden

Hlynsson

et al. 2015

Phys. Chem. Chem. Phys.

278

272

View full text Add to dashboard Cite

show abstract

“…Only the most stable facet was studied in detail for catalytic activity, which in all cases was either the rocksalt (100) or zinc blende (110) facet. In reality, in the manufacturing of these (electro)catalysts, a multifaceted structure is more probable than a single-crystal catalyst, even for metal nitrides grown with thin film techniques. − Therefore, consideration of other crystallographic textures of these promising nitride catalysts is necessary to gain a realistic insight into the catalytic properties, selectivity, and stability of these metal nitride catalysts.…”

Section: Introductionmentioning

confidence: 99%

Electroreduction of N₂ to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments

et al. 2015

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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.

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“…The most active and selective nitride surfaces that catalyze nitrogen activation to ammonia electrochemically at ambient conditions and relatively small overpotentials turned out to be the RS(100) facets [4,14]. However, the RS(111) facets of earlier TMNs are also one of the most prevalent texture orientations when characterizing the manufactured TMN surfaces [18][19][20][21] and those deserve a detailed theoretical investigation for their NER activity.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical synthesis of ammonia via Mars-van Krevelen mechanism on the (111) facets of group III–VII transition metal mononitrides

2017

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Ultra-thin poly-crystalline TiN films grown by HiPIMS on MgO(100) — In-situ resistance study of the initial stage of growth

Cited by 11 publications

References 36 publications

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

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

Electroreduction of N₂ to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments

Electrochemical synthesis of ammonia via Mars-van Krevelen mechanism on the (111) facets of group III–VII transition metal mononitrides

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Ultra-thin poly-crystalline TiN films grown by HiPIMS on MgO(100) — In-situ resistance study of the initial stage of growth

Cited by 11 publications

References 36 publications

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

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

Electroreduction of N2 to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments

Electrochemical synthesis of ammonia via Mars-van Krevelen mechanism on the (111) facets of group III–VII transition metal mononitrides

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Electroreduction of N₂ to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments