Regulation of the electrocatalytic nitrogen cycle based on sequential proton–electron transfer

He, Daoping; Ooka, Hideshi; Li, Yamei; Kim, Yujeong; Yamaguchi, Akira; Adachi, Kiyohiro; Hashizume, Daisuke; Yoshida, Naohiro; Toyoda, Sakae; Kim, Sun Hee; Nakamura, Ryuhei

doi:10.1038/s41929-022-00833-z

Cited by 35 publications

(25 citation statements)

References 46 publications

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“…Because it was found that the electric field does not affect the activity positively for oxides, we do not study the electric field effect herein. In addition, the sequential proton–electron transfer (SPET) can be a function of pH effects − too, the experimental pH effects are not available over the Cu/Cu 2 O hybrid composite to compare with our modeling, we do not study the pH effect computationally.…”

Section: Computational Sectionmentioning

confidence: 99%

Potential Dependence of Ammonia Selectivity of Electrochemical Nitrate Reduction on Copper Oxide

Yang

Long

et al. 2022

ACS Sustainable Chem. Eng.

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Nitrate electrochemical reduction (eNO 3 RR) has been considered as an alternative strategy for decentralized ammonia production, while there are two critical issues regarding high overpotential and poor selectivity because of nitrite production at low overpotentials. Therefore, it is significant to understand the reaction mechanism of ammonia and nitrite selectivity. In addition, it was found that hydrogen evolution reaction (HER) can become notable and drastically affects the Faradaic efficiency. In this work, taking copper oxide as an example, we have combined density functional theory (DFT) calculations and microkinetic modeling (MKM) to understand the products selectivity and Faradaic efficiency of eNO 3 RR to NH 3 at varying potentials. Our models are consistent qualitatively with the experimental results, describing well the competition of ammonia, nitrite, and hydrogen. As the charge transfer coefficient (β) for *NO 2 protonation (*NO 2 to HNO 2 (g)) is smaller than that of *NO hydrogenation (*NO to *NHO), ammonia production becomes more favorable gradually. As the larger charge transfer coefficient (β) for HER compared to *NO hydrogenation (*NO to *NHO), ammonia production becomes less preferable at high overpotentials. The present mechanistic insights can provide design principles of eNO 3 RR activity and selectivity over ammonia, nitrite, and hydrogen.

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Section: Computational Sectionmentioning

confidence: 99%

Potential Dependence of Ammonia Selectivity of Electrochemical Nitrate Reduction on Copper Oxide

Yang

Long

et al. 2022

ACS Sustainable Chem. Eng.

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“…As the catalyst screening was performed at neutral pH, acid-catalyzed nitrite disproportionation can be excluded as a mechanism of NO formation (3NO2 − + 2H + → 2NO + NO3 − + H2O) (Supplementary Figs. 12−13) [23][24][25] .…”

Section: Resultsmentioning

confidence: 99%

Nonenzymatic anaerobic ammonium oxidation through a hydrazine intermediate

Adachi

Hashizume

et al. 2023

Preprint

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Anaerobic ammonium oxidation (anammox) − the biological process that activates ammonium with nitrite − is responsible for a significant fraction of N2 production in marine environments. Despite decades of biochemical research, however, no synthetic models capable of anammox have been identified. Here, we report that a copper sulfide mineral replicates the entire biological anammox pathway catalyzed by three metalloenzymes. A copper-nitrosonium (Cu+−NO+) complex formed by nitrite reduction was identified as the oxidant for ammonium oxidation, leading to heterolytic N−N bond formation from nitrite and ammonium. Similar to the biological process, N2 production was mediated by the highly reactive intermediate hydrazine, one of the most potent reductants in nature. Another pathway involving N−N bond heterocoupling for the formation of hybrid N2O, a potent greenhouse gas with a unique isotope composition, was also identified. Our study represents the first nonenzymatic anammox reaction that interconnects six redox states in the abiotic nitrogen cycle.

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“…150 Electrocatalysis, stoichiometric electrochemical conversions, and electrochemical separations could enable integrated and distributed manufacturing for numerous products through controlled electron transfers that mimic industrial or biological pathways to common commodities. 151 Tunable electrocatalysis for refining may require producing, stabilizing, and separating intermediates and controlling their delivery to distinct active sites. 152,153 For example, nitrite (formed by NO3RR at Ti) 64 could be isolated and directed in cascading reduction reactions toward inorganic products like ammonium, nitrous oxide, or nitric oxide at MoS2.…”

Section: Subsection 2c: Interfacing Selective Materials With Electroc...mentioning

confidence: 99%

Electrochemical wastewater refining: a vision for circular chemical manufacturing

Miller

Abels

Guo

et al. 2023

Preprint

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Wastewater is an underleveraged resource; it contains pollutants that can be transformed into valuable high-purity products. Innovations in chemistry and chemical engineering will play critical roles in valorizing wastewater to remediate environmental pollution, provide equitable access to chemical resources and services, and secure critical materials from diminishing feedstock availability. This perspective envisions electrochemical wastewater refining—the use of electrochemical processes to tune and recover specific products from wastewaters—as the necessary framework to accelerate wastewater-based electrochemistry to widespread practice. We define and prescribe a use-informed approach that simultaneously serves specific wastewater-pollutant-product triads and uncover mechanistic understanding generalizable to broad use cases. We use this approach to evaluate research needs in specific case studies of electrocatalysis, stoichiometric electrochemical conversions, and electrochemical separations. Finally, we provide rationale and guidance for intentionally expanding the electrochemical wastewater refining product portfolio. Wastewater refining will require a coordinated effort from multiple expertise areas to meet the urgent need of extracting maximal value from complex, variable, diverse, and abundant wastewater resources.

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Regulation of the electrocatalytic nitrogen cycle based on sequential proton–electron transfer

Cited by 35 publications

References 46 publications

Potential Dependence of Ammonia Selectivity of Electrochemical Nitrate Reduction on Copper Oxide

Potential Dependence of Ammonia Selectivity of Electrochemical Nitrate Reduction on Copper Oxide

Nonenzymatic anaerobic ammonium oxidation through a hydrazine intermediate

Electrochemical wastewater refining: a vision for circular chemical manufacturing

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