The role of ligands in the electrochemical behaviour and catalytic activity of molybdenum-containing catalyst for dinitrogen fixation under mild conditions

Strelets, V. V.; Gavrilov, A.B.; Pospı́šil, Lubomı́r

doi:10.1016/0022-0728(87)80234-6

Cited by 13 publications

(6 citation statements)

References 3 publications

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“…Indeed, subsequent work by some of the same authors identified two possible catalysts: one containing Mo alone and one containing both Mo and Mg salts. 30 An alternative approach was taken by Sakata and co-workers, who hypothesized that the spontaneous reaction of lithium metal with nitrogen could be exploited to generate lithium nitrides, which could in turn be reacted with proton donors to give ammonia at room temperature (see Figure 5). 31 Hence the authors reduced lithium salts in a mixed THF/ethanol solvent medium at very cathodic potentials (-4 V vs. Ag/AgCl), in the hope that lithium metal species would deposit on the cathode.…”

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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“…Reaction kinetics also play critical roles in determining the selectivity toward NH 3 , which can be tuned by catalysts. For example, N 2 H 4 and/or N 2 H 2 had been detected as major products in some NRR studies …”

Section: Basics Of Electrochemical Nrrsmentioning

confidence: 99%

“…The studies of molecular complexes with a {MP 4 } core, where M = Mo or W, have been inspired by the early discovery of Chatt et al in 1975, reporting the formation of NH 3 via the protolysis of a dinitrogen complex cis -[W(N 2 ) 2 (PMe 2 Ph) 4 ]. NRR was achieved through the cyclic conversion of N 2 to NH 3 using {MP 4 } as a mediator. ,, NH 3 production rates in the range of 1.3 to 35.8% (per mol of the complexes) were reported using Mo/W complexes containing either dinitrogen ([M(N 2 ) 2 (dppe) 2 ], M = Mo or W) or hydrazido(2-) ligands ([M(X)(NNH 2 )(dppe) 2 ]X, M = Mo or W, X = Br, BF 4 or HSO 4 ) . However, this type of complex seldom produces NH 3 exclusively, and N 2 H 4 and N 2 H 2 have been occasionally detected as byproducts over cis - and trans -[M(N 2 ) 2 (PR 3 ) 4 ], trans -[M(N 2 ) 2 (dppe)(PR 3 ) 2 ], trans -[M(N 2 ) 2 (dppe) 2 ], and trans -[M(N 2 ) 2 (triphos)(PPh 3 )] in acidic electrolytes, even though NH 3 would be favored thermodynamically .…”

Section: Progress On Catalysts For Electrochemical Nrrmentioning

confidence: 99%

“…However, this type of complex seldom produces NH 3 exclusively, and N 2 H 4 and N 2 H 2 have been occasionally detected as byproducts over cis - and trans -[M(N 2 ) 2 (PR 3 ) 4 ], trans -[M(N 2 ) 2 (dppe)(PR 3 ) 2 ], trans -[M(N 2 ) 2 (dppe) 2 ], and trans -[M(N 2 ) 2 (triphos)(PPh 3 )] in acidic electrolytes, even though NH 3 would be favored thermodynamically . For example, both NH 3 and hydrazine were formed at the ratio of 1/10 on Mo(III)-Mg 2+ -R 3 P-phospholipid . The ligands coordinated to center metals and the configuration of molecular complexes are speculated to be responsible for the selectivity toward different products.…”

Section: Progress On Catalysts For Electrochemical Nrrmentioning

confidence: 99%

“…62 For example, both NH 3 and hydrazine were formed at the ratio of 1/10 on Mo(III)-Mg 2+ -R 3 Pphospholipid. 63 The ligands coordinated to center metals and the configuration of molecular complexes are speculated to be responsible for the selectivity toward different products.…”

Section: Progress On Catalysts For Electrochemical Nrrmentioning

confidence: 99%

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Homogeneous, Heterogeneous, and Biological Catalysts for Electrochemical N₂ Reduction toward NH₃ under Ambient Conditions

et al. 2019

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Ammonia (NH3) synthesis is an important industrial chemical process. Recently, electrochemically converting the earth-abundant dinitrogen (N2) in the aqueous phase to NH3 at ambient conditions has been proposed as an alternative to the well-established Haber–Bosch process. Catalysts for the electrochemical N2 reduction to NH3 play crucial roles in realizing this NH3 synthesis route. Electrochemical N2 reduction has been studied for decades, and many studies have emerged in the past few years. Herein, we provide a comprehensive review to summarize various catalysts used for achieving electrochemical N2 reduction to NH3, including homogeneous, heterogeneous and biological catalysts, as well as relevant computational studies to understand their reaction mechanisms. We compare the advantages and shortcomings of these catalytic systems. Future research directions for realizing catalysts with low overpotentials, high energy efficiency, good scalability, and stability modularity are also proposed. This review provides an overview of this fast-growing research field and encourages more studies toward the rational design of catalysts for electrochemical N2 reduction to NH3 under ambient conditions.

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Overviews of the Preparation and Reactivity of Transition Metal–Dinitrogen Complexes

Tanabe

Nishibayashi

2019

Transition Metal‐Dinitrogen Complexes

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The role of ligands in the electrochemical behaviour and catalytic activity of molybdenum-containing catalyst for dinitrogen fixation under mild conditions

Cited by 13 publications

References 3 publications

Recent progress towards the electrosynthesis of ammonia from sustainable resources

Recent progress towards the electrosynthesis of ammonia from sustainable resources

Homogeneous, Heterogeneous, and Biological Catalysts for Electrochemical N₂ Reduction toward NH₃ under Ambient Conditions

Overviews of the Preparation and Reactivity of Transition Metal–Dinitrogen Complexes

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The role of ligands in the electrochemical behaviour and catalytic activity of molybdenum-containing catalyst for dinitrogen fixation under mild conditions

Cited by 13 publications

References 3 publications

Recent progress towards the electrosynthesis of ammonia from sustainable resources

Recent progress towards the electrosynthesis of ammonia from sustainable resources

Homogeneous, Heterogeneous, and Biological Catalysts for Electrochemical N2 Reduction toward NH3 under Ambient Conditions

Overviews of the Preparation and Reactivity of Transition Metal–Dinitrogen Complexes

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Product

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Homogeneous, Heterogeneous, and Biological Catalysts for Electrochemical N₂ Reduction toward NH₃ under Ambient Conditions