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  • 1
    Online Resource
    Online Resource
    Wiley ; 2019
    In:  Angewandte Chemie International Edition Vol. 58, No. 48 ( 2019-11-25), p. 17433-17441
    In: Angewandte Chemie International Edition, Wiley, Vol. 58, No. 48 ( 2019-11-25), p. 17433-17441
    Abstract: Molten LiCl and related eutectic electrolytes are known to permit direct electrochemical reduction of N 2 to N 3− with high efficiency. It had been proposed that this could be coupled with H 2 oxidation in an electrolytic cell to produce NH 3 at ambient pressure. Here, this proposal is tested in a LiCl–KCl–Li 3 N cell and is found not to be the case, as the previous assumption of the direct electrochemical oxidation of N 3− to NH 3 is grossly over‐simplified. We find that Li 3 N added to the molten electrolyte promotes the spontaneous and simultaneous chemical disproportionation of H 2 (H oxidation state 0) into H − (H oxidation state −1) and H + in the form of NH 2− /NH 2 − /NH 3 (H oxidation state +1) in the absence of applied current, resulting in non‐Faradaic release of NH 3 . It is further observed that NH 2− and NH 2 − possess their own redox chemistry. However, these spontaneous reactions allow us to propose an alternative, truly catalytic cycle. By adding LiH, rather than Li 3 N, N 2 can be reduced to N 3− while stoichiometric amounts of H − are oxidised to H 2 . The H 2 can then react spontaneously with N 3− to form NH 3 , regenerating H − and closing the catalytic cycle. Initial tests show a peak NH 3 synthesis rate of 2.4×10 −8  mol cm −2  s −1 at a maximum current efficiency of 4.2 %. Isotopic labelling with 15 N 2 confirms the resulting NH 3 is from catalytic N 2 reduction.
    Type of Medium: Online Resource
    ISSN: 1433-7851 , 1521-3773
    URL: Issue
    RVK:
    Language: English
    Publisher: Wiley
    Publication Date: 2019
    detail.hit.zdb_id: 2011836-3
    detail.hit.zdb_id: 123227-7
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  • 2
    Online Resource
    Online Resource
    Wiley ; 2019
    In:  Angewandte Chemie Vol. 131, No. 48 ( 2019-11-25), p. 17594-17602
    In: Angewandte Chemie, Wiley, Vol. 131, No. 48 ( 2019-11-25), p. 17594-17602
    Abstract: Molten LiCl and related eutectic electrolytes are known to permit direct electrochemical reduction of N 2 to N 3− with high efficiency. It had been proposed that this could be coupled with H 2 oxidation in an electrolytic cell to produce NH 3 at ambient pressure. Here, this proposal is tested in a LiCl–KCl–Li 3 N cell and is found not to be the case, as the previous assumption of the direct electrochemical oxidation of N 3− to NH 3 is grossly over‐simplified. We find that Li 3 N added to the molten electrolyte promotes the spontaneous and simultaneous chemical disproportionation of H 2 (H oxidation state 0) into H − (H oxidation state −1) and H + in the form of NH 2− /NH 2 − /NH 3 (H oxidation state +1) in the absence of applied current, resulting in non‐Faradaic release of NH 3 . It is further observed that NH 2− and NH 2 − possess their own redox chemistry. However, these spontaneous reactions allow us to propose an alternative, truly catalytic cycle. By adding LiH, rather than Li 3 N, N 2 can be reduced to N 3− while stoichiometric amounts of H − are oxidised to H 2 . The H 2 can then react spontaneously with N 3− to form NH 3 , regenerating H − and closing the catalytic cycle. Initial tests show a peak NH 3 synthesis rate of 2.4×10 −8  mol cm −2  s −1 at a maximum current efficiency of 4.2 %. Isotopic labelling with 15 N 2 confirms the resulting NH 3 is from catalytic N 2 reduction.
    Type of Medium: Online Resource
    ISSN: 0044-8249 , 1521-3757
    URL: Issue
    RVK:
    RVK:
    Language: English
    Publisher: Wiley
    Publication Date: 2019
    detail.hit.zdb_id: 505868-5
    detail.hit.zdb_id: 506609-8
    detail.hit.zdb_id: 514305-6
    detail.hit.zdb_id: 505872-7
    detail.hit.zdb_id: 1479266-7
    detail.hit.zdb_id: 505867-3
    detail.hit.zdb_id: 506259-7
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  • 3
    Online Resource
    Online Resource
    Royal Society of Chemistry (RSC) ; 2019
    In:  Dalton Transactions Vol. 48, No. 5 ( 2019), p. 1562-1568
    In: Dalton Transactions, Royal Society of Chemistry (RSC), Vol. 48, No. 5 ( 2019), p. 1562-1568
    Type of Medium: Online Resource
    ISSN: 1477-9226 , 1477-9234
    Language: English
    Publisher: Royal Society of Chemistry (RSC)
    Publication Date: 2019
    detail.hit.zdb_id: 1472887-4
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  • 4
    In: Angewandte Chemie, Wiley, Vol. 131, No. 48 ( 2019-11-25), p. 17496-17502
    Abstract: There is an exciting possibility to decentralize ammonia synthesis for fertilizer production or energy storage without carbon emission from H 2 obtained from renewables at small units operated at lower pressure. However, no suitable catalyst has yet been developed. Ru catalysts are known to be promoted by heavier alkali dopants. Instead of using heavy alkali metals, Li is herein shown to give the highest rate through surface polarisation despite its poorest electron donating ability. This exceptional promotion rate makes Ru–Li catalysts suitable for ammonia synthesis, which outclasses industrial Fe counterparts by at least 195 fold. Akin to enzyme catalysis, it is for the first time shown that Ru–Li catalysts hydrogenate end‐on adsorbed N 2 stabilized by Li + on Ru terrace sites to ammonia in a stepwise manner, in contrast to typical N 2 dissociation on stepped sites adopted by Ru–Cs counterparts, giving new insights in activating N 2 by metallic catalysts.
    Type of Medium: Online Resource
    ISSN: 0044-8249 , 1521-3757
    URL: Issue
    RVK:
    RVK:
    Language: English
    Publisher: Wiley
    Publication Date: 2019
    detail.hit.zdb_id: 505868-5
    detail.hit.zdb_id: 506609-8
    detail.hit.zdb_id: 514305-6
    detail.hit.zdb_id: 505872-7
    detail.hit.zdb_id: 1479266-7
    detail.hit.zdb_id: 505867-3
    detail.hit.zdb_id: 506259-7
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  • 5
    In: Chemical Science, Royal Society of Chemistry (RSC), Vol. 12, No. 2 ( 2021), p. 688-695
    Abstract: The catalytic synthesis of NH 3 from the thermodynamically challenging N 2 reduction reaction under mild conditions is currently a significant problem for scientists. Accordingly, herein, we report the development of a nitrogenase-inspired inorganic-based chalcogenide system for the efficient electrochemical conversion of N 2 to NH 3 , which is comprised of the basic structure of [Fe–S 2 –Mo]. This material showed high activity of 8.7 mg NH 3 mg Fe −1 h −1 (24 μg NH 3 cm −2 h −1 ) with an excellent faradaic efficiency of 27% for the conversion of N 2 to NH 3 in aqueous medium. It was demonstrated that the Fe 1 single atom on [Fe–S 2 –Mo] under the optimal negative potential favors the reduction of N 2 to NH 3 over the competitive proton reduction to H 2 . Operando X-ray absorption and simulations combined with theoretical DFT calculations provided the first and important insights on the particular electron-mediating and catalytic roles of the [Fe–S 2 –Mo] motifs and Fe 1 , respectively, on this two-dimensional (2D) molecular layer slab.
    Type of Medium: Online Resource
    ISSN: 2041-6520 , 2041-6539
    Language: English
    Publisher: Royal Society of Chemistry (RSC)
    Publication Date: 2021
    detail.hit.zdb_id: 2559110-1
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  • 6
    Online Resource
    Online Resource
    The Electrochemical Society ; 2018
    In:  ECS Meeting Abstracts Vol. MA2018-02, No. 54 ( 2018-07-23), p. 1899-1899
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2018-02, No. 54 ( 2018-07-23), p. 1899-1899
    Abstract: Ammonia is one of the most significant chemical products on the planet due to its central role in agriculture, as well as its use in a wide variety of chemical processes. More recently it has also attracted interest as a carbon-free energy vector, with an energy density similar to that of methanol and immediate compatibility with existing storage and distribution infrastructure. Current ammonia production relies on natural gas for both the hydrogen and the energy required by the high temperature, high pressure Haber-Bosch reaction. This technology consumes over 1% of all global energy and, in Europe, is responsible for 1% of all carbon emissions (1). New processes based on renewable power are therefore urgently required. Electrochemical reduction of nitrogen to ammonia has been demonstrated in a number of systems, although very slow kinetics and competing reduction of protons to hydrogen has severely limited their efficiency, particularly in protic media (2). One promising approach operates in a molten LiCl-KCl eutectic, the unique electrolyte stabilising the unusual nitride anion and enabling direct reduction of nitrogen gas (3). It has been proposed that this ion can then react with hydrogen or even water at an anode to form ammonia in an electrochemically driven process. Despite promising initial rates and current efficiencies, there has been very little development of the proposed cell, particularly in terms of electrocatalyst composition and morphology. Here we setup the proposed cell to investigate the feasibility of this approach. We use various methods to deposit metals (Ni, Co, Mo, Fe) onto carbon felt supports to produce a range of different gas electrodes. These electrodes are tested for ammonia synthesis from nitrogen and hydrogen and compared with the rates at a Ni foam electrode used in initial reports. References 1. Proceedings of the International Fertiliser Society 2008, 639 2. V. Kyriakou, I. Garagounis, E. Vasileiou, A. Vourros, M. Stoukides, Catalysis Today 2017, 286, 2–13. 3. T. Murakami, T. Nishikiori, T. Nohira, Y. Ito, J. Am. Chem. Soc. 2003, 125 (2), 334–335.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2018
    detail.hit.zdb_id: 2438749-6
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  • 7
    In: European Journal of Inorganic Chemistry, Wiley, Vol. 2019, No. 3-4 ( 2019-01-31), p. 502-505
    Abstract: The wheel‐shaped, potassium‐templated 27‐tungsto‐3‐arsenate(III) [K⊂{(β‐As III W 8 O 30 )(WO(H 2 O))} 3 ] 14– ( 1 ) was synthesized by simple one‐pot condensation of the trilacunary [ B ‐α‐As III W 9 O 33 ] 9– precursor in aqueous, acidic KCl solution. Polyanion 1 comprises three β‐{AsW 8 O 30 } units linked via three trans ‐{WO(H 2 O)} groups, forming a cyclic assembly with a potassium ion located in the central cavity. The rubidium‐analogue [Rb⊂{(β‐As III W 8 O 30 )(WO(H 2 O))} 3 ] 14– ( 2 ) could also be prepared, by addition of a small amount of Rb + ions to a solution containing a large excess of K + ions. This indicates that the rigid [{(β‐As III W 8 O 30 )(WO(H 2 O))} 3 ] 15– (As 3 W 27 ) host exhibits high selectivity for Rb + ion guests compared to K + ions. Polyanions 1 and 2 were characterized in the solid state by single‐crystal XRD, FT‐IR, TGA, and elemental analysis.
    Type of Medium: Online Resource
    ISSN: 1434-1948 , 1099-0682
    URL: Issue
    RVK:
    Language: English
    Publisher: Wiley
    Publication Date: 2019
    detail.hit.zdb_id: 1475009-0
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  • 8
    In: Faraday Discussions, Royal Society of Chemistry (RSC), Vol. 190 ( 2016), p. 399-419
    Type of Medium: Online Resource
    ISSN: 1359-6640 , 1364-5498
    Language: English
    Publisher: Royal Society of Chemistry (RSC)
    Publication Date: 2016
    detail.hit.zdb_id: 1472891-6
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  • 9
    In: Faraday Discussions, Royal Society of Chemistry (RSC), Vol. 190 ( 2016), p. 291-306
    Type of Medium: Online Resource
    ISSN: 1359-6640 , 1364-5498
    Language: English
    Publisher: Royal Society of Chemistry (RSC)
    Publication Date: 2016
    detail.hit.zdb_id: 1472891-6
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  • 10
    Online Resource
    Online Resource
    The Electrochemical Society ; 2018
    In:  ECS Meeting Abstracts Vol. MA2018-02, No. 54 ( 2018-07-23), p. 1945-1945
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2018-02, No. 54 ( 2018-07-23), p. 1945-1945
    Abstract: Ammonia is one of the most important base chemicals in the world being a quintessential ingredient in most fertilizers. It is produced on the mega ton per year scale by the Haber-Bosch process from hydrogen and nitrogen at temperatures of around 400-500°C and pressures of up to 200 atmospheres contributing approximately 2% to global CO 2 emissions. 1 A promising alternative for small scale applications is electrochemical ammonia production utilizing molten salts as electrolytes. 2 Such systems work at ambient pressure, moderate temperature and use renewable hydrogen sources like water enabling small local production of ammonia for energy storage and as building block chemical for fertilizer synthesis. 2 Few materials have been evaluated as electrocatalysts for ammonia synthesis in molten salts, mainly transition metals. 2 Metal nitrides, especially Co 3 Mo 3 N, are highly active in classical ammonia synthesis with a Mars-van-Krevelen-type mechanism being suggested as the mechanism at play. 3 Recently, computational studies have suggested using metal nitrides as electrocatalysts for ammonia formation assuming a similar mechanism. 4 In this work, we explore the possibilities of using more complex gas electrode materials in alkali chloride melt to increase the rate and current efficiency of electrochemical ammonia synthesis. Furthermore, we hope to gain a deeper understanding of the mechanism of nitrogen reduction and more generally ammonia formation in molten salts. We synthesized several ternary metal nitrides using temperature-programmed nitridation of oxide precursor and characterized them by powder XRD, BET, XPS, UV-Vis, SEM, TEM and SQUID. Furthermore, the stability of the nitride phase in the chloride melt was tested and the necessary conditions to inhibit decomposition were optimized. A range of electrochemical tests (CV, amperometry, etc.) were carried out and XPS, as well as SEM were used to monitor compositional and structural changes on the surface. Finally, metal nitride electrodes were used for nitrogen reduction. Lan, R.; Irvine, J. T. S.; Tao, S. Sci. Rep. 2013 , 3 . Giddey, S.; Badwal, S. P. S.; Kulkarni, A. Int. J. Hydrogen Energy 2013 , 38 (34), 14576. Abghoui, Y.; Skúlasson, E. Procedia Computer Science 2015 , 51 , 1897. Howalt, J. G.; Vegge, T. Phys. Chem. Chem. Phys. 2013 , 15 (48), 20957.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2018
    detail.hit.zdb_id: 2438749-6
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