Critical Assessment of the Electrocatalytic Activity of Vanadium and Niobium Nitrides toward Dinitrogen Reduction to Ammonia

Du, Hoang-Long; Gengenbach, Thomas R.; Hodgetts, Rebecca Y.; MacFarlane, Douglas R.; Simonov, Alexandr N.

doi:10.1021/acssuschemeng.8b06163

Cited by 113 publications

(107 citation statements)

References 37 publications

(81 reference statements)

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“…Also, the experiment must demonstrate an extended period of testing; obviously even a small continuous net loss of lattice nitride would be destructive to the catalyst in the long run. Some of the present authors have recently described a rigorous examination of nitrides in the vanadium and niobium families and found both to be inactive towards N2 reduction, despite earlier literature reports to the contrary 53 . This lack of the catalytic activity suggests that the theoretically predicted high rates and selectivity for the NRR might be exclusive to particular crystal facets, which are not abundant on the surfaces of polycrystalline nitrides.…”

Section: Nitrides and The Mars-van Krevelen Mechanismcontrasting

confidence: 56%

Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia

et al. 2019

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Ammonia is a widely produced chemical that is the basis of most fertilisers. However, it is currently derived from fossil fuels and there is an urgent need to develop sustainable approaches to its production. Ammonia is also being considered as a renewable energy carrier, allowing efficient storage and transportation of renewables. For these reasons, the electrochemical nitrogen reduction reaction (NRR) is currently being intensely investigated as the basis for future mass production of ammonia from renewables. This Perspective critiques current steps and miss-steps towards this important goal in terms of experimental methodology and catalyst selection, proposing a protocol for rigorous experimentation. We discuss the issue of catalyst selectivity and the approaches to promoting the NRR over H 2 production. Finally, we translate these mechanistic discussions, and the key metrics being pursued in the field, into the bigger picture of ammonia production by other sustainable processes, discussing benchmarks by which NRR progress can be assessed.

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Section: Nitrides and The Mars-van Krevelen Mechanismcontrasting

confidence: 56%

Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia

et al. 2019

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“…For example, in 2019, Hu et al performed the electrochemical experiment on tetragonal Mo 2 N NPs in combination with 15 N‐lableing tests and found Mo 2 N NPs underwent decomposition instead of NRR‐catalytic activities . Similar observations on VN, NbN and Nb 4 N 5 have been reported by Du et al In order to quantitatively compare the tendency of migration against regeneration, Abghoui et al calculated the activation free energy of both processes . Figure b shows the result in the RS (111) case.…”

Section: Computational Insight Into Materials Design For Nrrmentioning

confidence: 66%

Recent Advanced Materials for Electrochemical and Photoelectrochemical Synthesis of Ammonia from Dinitrogen: One Step Closer to a Sustainable Energy Future

Yan

Xia

et al. 2019

Advanced Energy Materials

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Ammonia (NH3), an important raw material for chemical industry and agriculture, is also considered to be an intriguing energy storage and transportation media for chemical conversion schemes. The world's primary NH3 supply is based on the natural nitrogen fixation by diazotrophs through an enzymatic nitrogenase process and the industrial nitrogen fixation through a traditional Haber–Bosch process. The natural synthesis of NH3 can hardly meet the rapidly growing global demand. Meanwhile, the industrial NH3 production is still dominated by the high‐temperature and high‐pressure reaction between nitrogen and hydrogen (N2 + 3H2 → 2NH3), requiring intensive energy input and generating massive CO2. Therefore, seeking a breakthrough in the development of catalysts toward efficient ammonia synthesis has become the frontier of energy and chemical conversion schemes. This review summarizes and discusses the recent progress on developing new strategies to optimize the efficiency of NH3 production coupled with renewable energy sources, with a specific focus on electrocatalytic and photoelectrocatalytic conversion of N2 to NH3. The most recent advances in the development of catalytic materials, the design of the reaction systems, and the computational insights for electrochemical and photoelectrochemical ammonia synthesis are covered.

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“…However, the nitrogen vacancy on TMN would be deactivated during NRR process thus results in poor stability . In addition, researchers claim that some TMNs are inactive toward NRR in aqueous system, which is in contrary to theoretical calculations . To gain insightful understanding of NRR mechanism, it is necessary to design TMNs with simplex structure and stable surface vacancies for the linkage of theoretical models and real‐world catalysts.…”

Section: Exafs Curve‐fitting Results (Error Bounds (Accuracies) Were mentioning

confidence: 99%

Nitrogen Vacancies on 2D Layered W₂N₃: A Stable and Efficient Active Site for Nitrogen Reduction Reaction

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also aggravate the greenhouse effect. [8] Considering the huge energy consumption of this process and the great potential of NH 3 in future energy systems, protonassisted electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is becoming increasingly important in realizing low-cost artificial nitrogen fixation. [10][11][12] More importantly, the NRR system can be easily integrated with renewable solar and wind energy into an environmentally benign process for NH 3 production. [2,7] Even though various materials have shown NRR activity in aqueous system, their performance are still hindered by the sluggish reaction kinetics and competitive hydrogen evolution reaction (HER) resulting in poor activity and unsatisfactory selectivity. [13][14][15] The active site for electrochemical NRR needs twofold properties: for one thing, it can accept the lone-pair electrons for effective N 2 adsorption and for the other thing it can donate electrons to antibonding orbitals of dinitrogen molecules for the NN triple-bond activation. [9,13,[16][17][18][19][20] From this perspective, vacancy-engineering materials are ideal for practical applications. [9,16,20] By virtue of the electron redistribution and special chemical properties, the vacancies can provide unique active sites for nitrogen adsorption and activation. [9,[21][22][23][24] Up to now, the most common vacancy that has been studied for NRR is oxygen vacancy. For example, oxygen vacancies on transition metal oxides are active for NRR by enhancing the dinitrogen molecule adsorption. [9,25] However, oxygen vacancy can also improve the HER performance of the host matrix, which may result in poor NRR selectivity. [26][27][28] Alternatively, nitrogen vacancies on transition metal nitride (TMN) are considered as an ideal active site for NRR because of its unique vacancy properties for dinitrogen molecule adsorption and poor HER activity. [29,30] However, the nitrogen vacancy on TMN would be deactivated during NRR process thus results in poor stability. [29] In addition, researchers claim that some TMNs are inactive toward NRR in aqueous system, which is in contrary to theoretical calculations. [31] To gain insightful understanding of NRR mechanism, it is necessary to design TMNs with simplex structure and stable surface vacancies for the linkage of theoretical models and real-world catalysts. 2D material has onefold and fully exposed crystal surface, which is widely used as platform for both theoretical calculations and Electrochemical nitrogen reduction reaction (NRR) under ambient conditions provides an avenue to produce carbon-free hydrogen carriers. However, the selectivity and activity of NRR are still hindered by the sluggish reaction kinetics. Nitrogen Vacancies on transition metal nitrides are considered as one of the most ideal active sites for NRR by virtue of their unique vacancy properties such as appropriate adsorption energy to dinitrogen molecule. However, their catalytic performance is usually limited by the unstable feature. Herein, a new ...

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Critical Assessment of the Electrocatalytic Activity of Vanadium and Niobium Nitrides toward Dinitrogen Reduction to Ammonia

Cited by 113 publications

References 37 publications

Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia

Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia

Recent Advanced Materials for Electrochemical and Photoelectrochemical Synthesis of Ammonia from Dinitrogen: One Step Closer to a Sustainable Energy Future

Nitrogen Vacancies on 2D Layered W₂N₃: A Stable and Efficient Active Site for Nitrogen Reduction Reaction

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Critical Assessment of the Electrocatalytic Activity of Vanadium and Niobium Nitrides toward Dinitrogen Reduction to Ammonia

Cited by 113 publications

References 37 publications

Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia

Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia

Recent Advanced Materials for Electrochemical and Photoelectrochemical Synthesis of Ammonia from Dinitrogen: One Step Closer to a Sustainable Energy Future

Nitrogen Vacancies on 2D Layered W2N3: A Stable and Efficient Active Site for Nitrogen Reduction Reaction

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Nitrogen Vacancies on 2D Layered W₂N₃: A Stable and Efficient Active Site for Nitrogen Reduction Reaction