Electrochemical Reduction of N2 under Ambient Conditions for Artificial N2 Fixation and Renewable Energy Storage Using N2/NH3 Cycle

Bao, Di; Zhang, Qi; Meng, Fanlu; Zhong, Haixia; Shi, Ming; Zhang, Yu; Yan, Jun‐Min; Jiang, Qing; Zhang, Xinbo

doi:10.1002/adma.201604799

Cited by 1,038 publications

(690 citation statements)

References 30 publications

(91 reference statements)

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“…24,25 In addition to their catalytic activity and selectivity, we also investigated the durability of commercial Pt/C catalyst for ENRR in both PEMELs and HEMELs. As shown in Figure 5, the amounts of ammonia produced in the first 0.5 h are around 50% of those produced within 1 h, which indicates that the ammonia production rate in 1 h are constant in both PEMELs and HEMELs.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Nitrogen Reduction Reaction on Noble Metal Catalysts in Proton and Hydroxide Exchange Membrane Electrolyzers

Nash

Yang

Anibal

et al. 2017

J. Electrochem. Soc.

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Five noble metal catalysts (Pt/C, Ir/C, Pd/C, Ru/C, and Au/C) are evaluated for electrochemical nitrogen reduction reaction (ENRR) to produce ammonia in both proton exchange membrane (PEM) and hydroxide exchange membrane (HEM) electrolyzers (PEMELs and HEMELs). The competing hydrogen evolution reaction (HER) is found to be the dominant reaction on all catalysts tested in both PEMELS and HEMELs, which is consistent with recent computational predictions that metallic catalysts are unlikely to be selective for ENRR. With the increase of applied potentials, the rate of HER increase significantly, which suppresses the ENRR, leading to significant decreases of faradaic efficiencies. Leaching of quaternary ammonium from HEM is found to interfere with ammonia quantification, which necessitates a pretreatment protocol. Due to the relatively slow kinetics of HER in alkaline solution, faradaic efficiencies in HEMELs are generally higher than those in PEMELs. We believe that these results provide a solid baseline for future research on ENRR in both PEMELs and HEMELs. Ammonia synthesis is one of the foundational chemical processes to the human society, which is estimated to supported approximately 27% of the world's population over the past century.1 The development of the Haber-Bosch process revolutionized modern agriculture, 2 however, the centralized, energy and carbon intensive nature of the Haber-Bosch process 3-5 leaves many aspects to be desired. Distributed and modular ammonia synthesis via the electrochemical nitrogen reduction reaction (ENRR) at or close to ambient conditions, powered by renewable electricity, is an attractive alternative because it allows as-needed production of ammonia, and in turn N-fertilizers, from ubiquitously available resources, i.e., N 2 and water. 4 Widespread adoption of ENRR for ammonia production could drastically reduce the carbon footprint of agricultural activities. In addition, ENRR is compatible with the intermittency of renewable energy sources, e.g., solar and wind, as the ammonia and N-fertilizers can be produced and stored when renewable electricity is available.Electrochemical fixation of atmospheric nitrogen was first attempted in 1908 even before the establishment of the Haber-Bosch process, to make nitric acid via electric discharge. 6 Further studies of ENRR have generally been focused on high temperature proton conductors at 500• C, 7 however, the high operating temperature and the stability of ammonia at such conditions make it unsuitable for distributed deployment. Proton exchange membranes (PEMs) can achieve high proton conductivity (∼100 mS·cm −1 at 25 • C for Nafion) at ambient or slightly elevated temperatures, which opens the possibility for electrochemical ammonia synthesis at those mild conditions. 8 Although Nafion-based low temperature electrochemical ammonia synthesis has been demonstrated in several reports, 9-15 no systematic investigation of noble metal catalysts exists.2 Further, the alkaline environment of hydroxide exchange membranes (HEMs) promises the...

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Section: Resultsmentioning

confidence: 99%

Electrochemical Nitrogen Reduction Reaction on Noble Metal Catalysts in Proton and Hydroxide Exchange Membrane Electrolyzers

Nash

Yang

Anibal

et al. 2017

J. Electrochem. Soc.

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“…In N 2 -fixing bacteria, nitrogenases biologically can catalyze the reduction of N 2 to NH 3 at ambient conditions. [6,[9][10][11] This traditional process is not only energy-intensive, but the H 2 used as the feeding gas often comes from fossil fuels leading to serious greenhouse gas emission. [6,[9][10][11] This traditional process is not only energy-intensive, but the H 2 used as the feeding gas often comes from fossil fuels leading to serious greenhouse gas emission.…”

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Electrocatalytic Hydrogenation of N₂to NH₃by MnO: Experimental and Theoretical Investigations

et al. 2018

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NH3 is a valuable chemical with a wide range of applications, but the conventional Haber–Bosch process for industrial‐scale NH3 production is highly energy‐intensive with serious greenhouse gas emission. Electrochemical reduction offers an environmentally benign and sustainable route to convert N2 to NH3 at ambient conditions, but its efficiency depends greatly on identifying earth‐abundant catalysts with high activity for the N2 reduction reaction. Here, it is reported that MnO particles act as a highly active catalyst for electrocatalytic hydrogenation of N2 to NH3 with excellent selectivity. In 0.1 m Na2SO4, this catalyst achieves a high Faradaic efficiency up to 8.02% and a NH3 yield of 1.11 × 10−10 mol s−1 cm−2 at −0.39 V versus reversible hydrogen electrode, with great electrochemical and structural stability. On the basis of density functional theory calculations, MnO (200) surface has a smaller adsorption energy toward N than that of H with the *N2 → *N2H transformation being the potential‐determining step in the nitrogen reduction reaction.

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“…[9,[11][12][13] Electrocatalytic N 2 reduction reaction (NRR) is emerging as an alternative technology for N 2 fixation at ambient conditions. [16,17] Until now,e fforts to optimize electrocatalytic NRR mainly center on screening catalysts that can activate dinitrogen with alleviated activation barriers. [16,17] Until now,e fforts to optimize electrocatalytic NRR mainly center on screening catalysts that can activate dinitrogen with alleviated activation barriers.…”

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confidence: 99%

An Amorphous Noble‐Metal‐Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions

et al. 2018

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N 2 fixation by the electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions is regarded as ap otential approach to achieve NH 3 production, which still heavily relies on the Haber-Boschp rocess at the cost of huge energy and massive production of CO 2 .Anoble-metal-free Bi 4 V 2 O 11 /CeO 2 hybrid with an amorphous phase (BVC-A) is used as the cathode for electrocatalytic NRR. The amorphous Bi 4 V 2 O 11 contains significant defects,w hichp lay ar ole as active sites.The CeO 2 not only serves as atrigger to induce the amorphous structure,but also establishes band alignment with Bi 4 V 2 O 11 for rapid interfacial charge transfer.R emarkably, BVC-A shows outstanding electrocatalytic NRR performance with high average yield (NH 3 :2 3.21 mgh À1 mg À1 cat. ,F aradaic efficiency:1 0.16 %) under ambient conditions,w hich is superior to the Bi 4 V 2 O 11 /CeO 2 hybrid with crystalline phase (BVC-C) counterpart.

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Electrochemical Reduction of N₂ under Ambient Conditions for Artificial N₂ Fixation and Renewable Energy Storage Using N₂/NH₃ Cycle

Cited by 1,038 publications

References 30 publications

Electrochemical Nitrogen Reduction Reaction on Noble Metal Catalysts in Proton and Hydroxide Exchange Membrane Electrolyzers

Electrochemical Nitrogen Reduction Reaction on Noble Metal Catalysts in Proton and Hydroxide Exchange Membrane Electrolyzers

Electrocatalytic Hydrogenation of N₂to NH₃by MnO: Experimental and Theoretical Investigations

An Amorphous Noble‐Metal‐Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions

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Electrochemical Reduction of N2 under Ambient Conditions for Artificial N2 Fixation and Renewable Energy Storage Using N2/NH3 Cycle

Cited by 1,038 publications

References 30 publications

Electrochemical Nitrogen Reduction Reaction on Noble Metal Catalysts in Proton and Hydroxide Exchange Membrane Electrolyzers

Electrochemical Nitrogen Reduction Reaction on Noble Metal Catalysts in Proton and Hydroxide Exchange Membrane Electrolyzers

Electrocatalytic Hydrogenation of N2to NH3by MnO: Experimental and Theoretical Investigations

An Amorphous Noble‐Metal‐Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions

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Electrochemical Reduction of N₂ under Ambient Conditions for Artificial N₂ Fixation and Renewable Energy Storage Using N₂/NH₃ Cycle

Electrocatalytic Hydrogenation of N₂to NH₃by MnO: Experimental and Theoretical Investigations