Electrochemical oxidation of molecular nitrogen to nitric acid – towards a molecular level understanding of the challenges

Anand, Megha; Abraham, Christina Susan; Nørskov, Jens K.

doi:10.1039/d1sc00752a

Cited by 54 publications

(61 citation statements)

References 48 publications

(53 reference statements)

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“…The other branch is the combination of the electrochemical and chemical redox processes. The electrocatalytic product of NO/NO 2 is first produced and then oxidized to HNO 3 by a chemical reaction [11b, 28] . Specifically, the first step is electrochemical oxidation of inert N 2 into *NO, so the oxygen evolution reaction (OER) is considered a competing reaction that adversely affects the NOR process.…”

Section: Discussion Of the Mechanism Of Electrocatalytic Normentioning

confidence: 99%

“…Unfortunately,t here is still no systematic work in this direction to date.Nørskov et al provided ahelpful discussion on the possible reaction mechanisms of electrochemical NOR at the molecular level and its competition with the OER process. [28] However,t he proposed reaction pathways were limited to specific catalysts.Thus,there is enormous room for systematic theoretical simulations of catalysts for NOR.…”

Section: Discussionmentioning

confidence: 99%

“…Nørskov et al. provided a helpful discussion on the possible reaction mechanisms of electrochemical NOR at the molecular level and its competition with the OER process [28] . However, the proposed reaction pathways were limited to specific catalysts.…”

Section: Discussionmentioning

confidence: 99%

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Electrochemical Synthesis of Nitric Acid from Nitrogen Oxidation

et al. 2022

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Nitric acid is widely applied in agriculture and industry. The present manufacturing process via a combination of the Haber–Bosch process and the Ostwald oxidation process is accompanied by massive energy consumption and greenhouse gas emissions. The direct electrocatalytic nitrogen oxidation reaction (NOR) to nitric acid is a promising alternative, especially when it is driven by renewable energy sources. The standardization of performance evaluation is the prerequisite for the design and synthesis of efficient electrocatalysts for NOR. In this context, this Minireview first discusses the history of the development of HNO3 manufacturing and the possible reaction mechanisms for electrocatalytic NOR. Then, a strict protocol for electrochemical NOR experiments is recommended. Finally, general research targets associated with techno‐economic analysis, challenges, and prospects for NOR are summarized for future studies.

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Section: Discussion Of the Mechanism Of Electrocatalytic Normentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Electrochemical Synthesis of Nitric Acid from Nitrogen Oxidation

et al. 2022

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“…After the first work by Zhang et al, [13,14] the electrochemical N 2 oxidation reaction (NOR), using water and N 2 in the atmosphere (78%), has been demonstrated as a sustainable and promising approach for nitric production. [14][15][16][17][18][19][20][21] Electrochemical NOR is an endothermic and entropy-reducing process, [22,23] involving activation of N 2 , adsorption of OH (*OH), and multielectron transfer at "gas-liquid-solid" three-phase interface. This process is hindered by the slow cleavage of the N≡N bond owing to its high bond energy (941 kJ mol −1 ) and insurmountable first-bond dissociation energy (410 kJ mol −1 ).…”

mentioning

confidence: 99%

“…[24][25][26][27][28] Thus, NOR is featured with sluggish kinetics for its 10-electron transfer process, slower than similar oxygen evolution reaction (OER, 4-electron transfer). [22,23,[29][30][31][32] Parasitic OER at lower potentials results in poor catalytic selectivity of NOR. In previous studies, OER-inactive catalysts and carriers were served to restrain competitive OER, and gained reasonable performance.…”

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confidence: 99%

Catalytic Kinetics Regulation for Enhanced Electrochemical Nitrogen Oxidation by Ru‐Nanoclusters‐Coupled Mn₃O₄ Catalysts Decorated with Atomically Dispersed Ru Atoms

et al. 2022

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Electrochemical N2 oxidation reaction (NOR), using water and N2 in the atmosphere, represents a sustainable approach for nitric production to replace the conventional industrial synthesis with high energy consumption and greenhouse gas emission. Meanwhile, owing to chemical inertness of N2 and sluggish kinetics for 10‐electron transfer, emerging electrocatalysts remain largely underexplored. Herein, Ru‐nanoclusters‐coupled Mn3O4 catalysts decorated with atomically dispersed Ru atoms (Ru–Mn3O4) are designed and explored as an advanced electrocatalyst for ambient N2 oxidation, with an excellent Faraday efficiency (28.87%) and a remarkable NO3‐ yield (35.34 µg h‐1 mg‐1cat.), respectively. Experiments and density functional theory calculations reveal that the outstanding activity is ascribed to the coexistence of Ru clusters and single‐atom Ru. The synergistic effect between the Ru clusters and Mn3O4 can effectively activate the chemically inert N2, lowering the kinetic barrier for the vital breakage of N≡N. The intensive *OH supply and enhanced conductivity are used to regulate the catalytic kinetics for optimized performance. This work provides brand‐new ideas for the rational design of electrocatalysts in complicated electrocatalytic reactions with multiple dynamics‐different steps.

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Boosting Selective Nitrogen Oxidation to Nitric Acid by Synergizing Cobalt Phthalocyanine on Carbon Nitride Surface

Paul,

Adalder,

Barman

et al. 2024

Adv Funct Materials

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The Ostwald process, which is producing HNO3 for commercial use, involves the catalytic oxidation of NH3 and a series of chemical reactions conducted under severe operating conditions. Due to their energy‐intensive nature, these activities play a major role in greenhouse gas emissions and global energy consumption. In response to the urgent requirements of the global energy and environmental sectors, there is an increasingly critical need to develop novel, highly efficient, and environmentally sustainable methods. Herein, CoPc/C3N4 electrocatalyst, integrating CoPc nanotubes with C3N4 nanosheets, is shown. The CoPc/C3N4 electrocatalyst demonstrates yield rate of 871.8 µmol h−1 gcat−1 at 2.2 V, with corresponding Faradaic efficiency (FE) of 46.4% at 2.1 V, which notably surpasses that of CoPc. Through a combination of experimental investigations and density functional theory (DFT) calculations, this study shows that CoPc anchored on C3N4 effectively simplifies the adsorption and activation of chemically inactive nitrogen molecules. The improved catalytic activity for composite system may be the reason of re‐distribution of charges over the CoPc, tuning the valence orbital of Co center due to the presence of 2D layer of C3N4. This mechanism significantly lowers the energy barrier required for critical breaking of inert N2, ultimately leading to a significant improvement in N2 oxidation efficiency.

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Electrochemical oxidation of molecular nitrogen to nitric acid – towards a molecular level understanding of the challenges

Abstract: Nitric acid is manufactured by oxidizing ammonia where the ammonia comes from an energy demanding and non-eco-friendly, Haber-Bosch process. Electrochemical oxidation of N2 to nitric acid using renewable electricity could...

Cited by 54 publications

References 48 publications

Electrochemical Synthesis of Nitric Acid from Nitrogen Oxidation

Electrochemical Synthesis of Nitric Acid from Nitrogen Oxidation

Catalytic Kinetics Regulation for Enhanced Electrochemical Nitrogen Oxidation by Ru‐Nanoclusters‐Coupled Mn₃O₄ Catalysts Decorated with Atomically Dispersed Ru Atoms

Boosting Selective Nitrogen Oxidation to Nitric Acid by Synergizing Cobalt Phthalocyanine on Carbon Nitride Surface

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Electrochemical oxidation of molecular nitrogen to nitric acid – towards a molecular level understanding of the challenges

Abstract: Nitric acid is manufactured by oxidizing ammonia where the ammonia comes from an energy demanding and non-eco-friendly, Haber-Bosch process. Electrochemical oxidation of N2 to nitric acid using renewable electricity could...

Cited by 54 publications

References 48 publications

Electrochemical Synthesis of Nitric Acid from Nitrogen Oxidation

Electrochemical Synthesis of Nitric Acid from Nitrogen Oxidation

Catalytic Kinetics Regulation for Enhanced Electrochemical Nitrogen Oxidation by Ru‐Nanoclusters‐Coupled Mn3O4 Catalysts Decorated with Atomically Dispersed Ru Atoms

Boosting Selective Nitrogen Oxidation to Nitric Acid by Synergizing Cobalt Phthalocyanine on Carbon Nitride Surface

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Catalytic Kinetics Regulation for Enhanced Electrochemical Nitrogen Oxidation by Ru‐Nanoclusters‐Coupled Mn₃O₄ Catalysts Decorated with Atomically Dispersed Ru Atoms