ChemInform Abstract: Dinitrogen Fixation. Fast Amalgam and Electrochemical Catalytic N2 Reduction at Ambient Temperature and Pressure.

Didenko, L. P.; Gavrilov, A.B.; Shilova, A. K.; Strelets, V. V.; Tsarev, V. N.; Шилов, А. Е.; Makhaev, V. D.; Banerjee, A. K.; Pospı́šil, Lubomı́r

doi:10.1002/chin.198716033

Cited by 6 publications

(13 citation statements)

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“…27 At around the same time as Pickett's study, Shilov, Strelets and co-workers reported a series of molybdenum complexes that mediated the electroreduction of nitrogen to ammonia at a mercury cathode. 28,29 The reactions were conducted in basic methanolic solutions, suggesting that methanol was a sacrificial reagent providing the necessary protons. However, due to the amorphous nature of the catalytic species and a lack of certainty over the optimal composition, firm conclusions on the nature of the most active catalyst from this system could not be obtained.…”

Section: Electrochemical Ammonia Production Using Sacrificial Proton mentioning

confidence: 99%

Recent progress towards the electrosynthesis of ammonia from sustainable resources

2017

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Ammonia (NH 3 ) is a key commodity chemical of vital importance for fertilizers. It is made on an industrial scale via the Haber Bosch process, which requires significant infrastructure to be in place such that ammonia is generally made in large, centralized facilities. If ammonia could be produced under less demanding conditions, then there would be the potential for smaller devices to be used to generate ammonia in a decentralized manner for local consumption. Electrochemistry has been proposed as an enabling technology for this purpose as it is relatively simple to scale electrolytic devices to meet almost any level of demand. Moreover, it is possible to envisage electrosynthetic cells where water could be oxidized to produce protons and electrons at the anode which could then be used to reduce and protonate nitrogen to give ammonia at the cathode. If this nitrogen were sourced from the air, then the only required infrastructure for this process would be supplies of water, air and electricity, the latter of which could be provided by renewables. Hence an electrosynthetic cell for ammonia production could allow NH 3 to be generated sustainably in small, low-cost devices requiring only minimal facilities. In this review, we describe recent progress towards such electrosynthetic ammonia production devices, summarizing also some of the seminal literature in the field. Comparison is made between the various different approaches that have been taken, and the key remaining challenges in the electrosynthesis of ammonia are highlighted.

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Section: Electrochemical Ammonia Production Using Sacrificial Proton mentioning

confidence: 99%

Recent progress towards the electrosynthesis of ammonia from sustainable resources

2017

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“…4 To prepare the active form of the catalyst (designated in the Schemes as [Mg 2 Mo 8 ]), the complex was reduced by sodium amalgam as described previ ously. 1 Acetylene reduction. The experiments were carried out in a specially designed thermostated flat bottom glass vessel with a magnetic stirrer, suitable for working with metal amalgams.…”

Section: Methodsmentioning

confidence: 99%

“…Sodium amalgam, europium amalgam or a cathode with a specified potential equal to the Na/Hg potential can serve as reducing agents. 2 (1), which forms the active site of the system upon reduction, has been determined 3 by X ray diffrac tion (Fig. 1).…”

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Catalytic behavior of a polynuclear Mg-Mo complex and nitrogenase active site (FeMoco) isolated from the enzyme in reactions with C2H2, N2, and CO: A comparative study

et al. 2006

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In order to identify common and distinctive features in the catalytic behavior of natural and artificial nitrogen fixation clusters, the kinetics of the catalytic reduction of C 2 H 2 in the presence of Mg-Mo cluster (1) was investigated and compared with the kinetics of acetylene reduction catalyzed by the cluster FeMoco (2) isolated from the enzyme nitrogenase we studied previously. The reactions were conducted in the presence of Zn/Hg and Eu/Hg as reducing agents and PhSH and C 6 F 5 SH as proton donors, i.e., under the same conditions as had been used in the case of 2. Both polynuclear Mg-Mo complex and the europium amalgam reduced FeMoco have multiple interdependent binding sites for substrates and/or inhibitors. Carbon monoxide inhibits the acetylene reduction much less efficiently in systems with clus ter 1 than in systems with cluster 2, although the type of inhibition is mixed in both systems: CO binds to multiple sites of the cluster and affects both C 2 H 2 complexation to the reduced cluster and decomposition of the catalyst-substrate complex to give the products. Unlike isolated FeMoco, the Mg-Mo cluster efficiently catalyzes the reduction of molecular nitro gen. The reaction is greatly inhibited by acetylene, while no inhibiting effect of N 2 is observed in acetylene reduction, as was found earlier for a system with the natural cluster as the catalyst.Previously, 1 a nitrogen reducing system based on poly nuclear molybdenum complexes was discovered. Cur rently, this is the only known non enzyme system capable of catalytic reduction of N 2 at atmospheric pressure and room temperature at rates comparable with nitro genase. The reaction is carried out in methanol with a minor water additive, which apparently serves as the pro ton donor in ammonia and/or hydrazine formation. Sodium amalgam, europium amalgam or a cathode with a specified potential equal to the Na/Hg potential can serve as reducing agents. 2 The molecular structure of the Mg containing molybdenum anionic cluster {[Mg 2 Mo 8 O 22 (MeO) 6 (MeOH) 4 ] 2-[Mg(MeOH) 6 ] 2+ }• •6MeOH (1), which forms the active site of the system upon reduction, has been determined 3 by X ray diffrac tion (Fig. 1).The available data 1-4 indicate that this compound is reduced with retention of the cluster core, although, strictly speaking, the structure of the complex active with respect to N 2 is unknown. The molecular mechanism of N 2 catalytic reduction with participation of this cluster is also unknown.The active site of the natural nitrogen fixing enzyme nitrogenase incorporates an octanuclear heterobimetallic cluster FeMoco ((µ 6 N)MoFe 7 S 9 •homocitrate (2)) in which nitrogen is bound and then reduced to ammonia. 5 The chemical mechanism of the multielectron reduction of nitrogenase substrates catalyzed by the cluster is un known.In order to elucidate the function of the cofactor and the contribution made by the whole protein matrix and by the amino acids located most closely to FeMoco to the nitrogen reduction under mild conditions, we studied the catalyt...

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“…It also seems to be noteworthy that in the presence of phospholipids the nitrogen reduction catalyzed by an artificial nitrogenase system is very selectively enhanced [45]. Ding et al [46] gave examples of the use of chiral amphiphilic ligands in hydrogenation reactions but directed attention to their application in biphasic systems.…”

Section: Complex-catalyzed Hydrogenation In Micellar Mediamentioning

confidence: 99%

Catalysis in Water as a Special Unit Operation: Sections 4.3–4.5

Hanson

2004

Aqueous‐Phase Organometallic Catalysis

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ChemInform Abstract: Dinitrogen Fixation. Fast Amalgam and Electrochemical Catalytic N2 Reduction at Ambient Temperature and Pressure.

Cited by 6 publications

References 0 publications

Recent progress towards the electrosynthesis of ammonia from sustainable resources

Recent progress towards the electrosynthesis of ammonia from sustainable resources

Catalytic behavior of a polynuclear Mg-Mo complex and nitrogenase active site (FeMoco) isolated from the enzyme in reactions with C2H2, N2, and CO: A comparative study

Catalysis in Water as a Special Unit Operation: Sections 4.3–4.5

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