Critical review in electrocatalytic nitrate reduction to ammonia towards a sustainable nitrogen utilization

Zhang, Zhiqiang; Zhang, Nan; Zhang, Jiao; Deng, Beiqi; Cao, Zhiyong; Wang, Zuobin; Wei, Guangfeng; Zhang, Qingbo; Jia, Renyong; Xiang, Pengyu; Xia, Siqing

doi:10.1016/j.cej.2024.148952

Cited by 5 publications

(1 citation statement)

References 122 publications

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“…As is known, NO 3 – has a higher solubility in water compared to N 2 . During the NO 3 RR reaction, it only requires the energy of 204 kJ/mol to break the NO, forming a deoxygenated group from nitrate, remarkably lower than the needed energy to break the NN in N 2 (941 kJ/mol). − Therefore, nitrate is considered an ideal nitrogen source that can replace the more stable N 2 in the NH 3 synthesis processes. Recently, the artificial synthesis of ammonia by electrocatalytic or photocatalytic processes has become a hot research area .…”

Section: Introductionmentioning

confidence: 99%

CuCo₂O₄/CuO Heterostructure with Oxygen Vacancies Induced by Plasma for Electrocatalytic Nitrate Reduction to Ammonia

Liu,

Cheng,

Zhao

et al. 2024

Inorg. Chem.

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Electrochemical nitrate reduction (NO 3 RR) to ammonia production is regarded as one of the potential alternatives for replacing the Haber-Bosch technology for realizing artificial ammonia synthesis. In this study, a CuCo 2 O 4 /CuO−Ar heterostructure in the shape of dandelion nanospheres formed by nanoarrays has been successfully constructed, demonstrating excellent NO 3 RR performance. Experimental results indicate that Ar plasma etching of CuCo 2 O 4 /CuO-Ar significantly increases the content of oxygen vacancies compared to the sample of CuCo 2 O 4 /CuO-Air etched by air plasma, resulting in improved NO 3 RR performance. Density functional theory calculations further confirm that the existence of more oxygen vacancies effectively decreases the energy barrier of nitrate adsorption, which is due to the generation of more oxygen vacancies facilitating nitrate adsorption and weakening the N−O bonds of nitrate after plasma treatment. As a result, CuCo 2 O 4 /CuO-Ar exhibits a high NH 3 yield of 0.55 mmol h −1 cm −2 and a Faraday efficiency of 95.07% at the optimal potential of −0.9 V (vs RHE) in a neutral medium. Importantly, CuCo 2 O 4 /CuO-Ar also showcases excellent electrocatalytic stability. This study presents new views on the design and structure regulation of NO 3 RR electrocatalysts and their potential applications in the future.

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Section: Introductionmentioning

confidence: 99%

CuCo₂O₄/CuO Heterostructure with Oxygen Vacancies Induced by Plasma for Electrocatalytic Nitrate Reduction to Ammonia

Liu,

Cheng,

Zhao

et al. 2024

Inorg. Chem.

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Selective and Efficient Electrocatalytic Synthesis of Ammonia from Nitrate with Copper‐Based Catalysts

Yin,

Guan,

Zhu

et al. 2024

Advanced Sustainable Systems

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The high stability and persistence of nitrates in water poses a serious threat to human health and ecosystems. To effectively reduce the nitrate content in wastewater, the electrochemical nitrate reduction reaction (e‐NO3RR) is widely recognized as an ideal treatment method due to its high reliability and efficiency. The selection of catalyst material plays a decisive role in e‐NO3RR performance. Copper‐based catalysts, with their ease of acquisition, high activity, and selectivity for NH3, have emerged as the most promising candidates for e‐NO3RR applications. In this paper, the mechanism of e‐NO3RR is first introduced. Then the relationship between structural properties and catalytic performance of copper‐based catalysts is analyzed in detail from four aspects: nanomaterials, oxides, monoatomic, and bimetallic materials. Strategies for constructing efficient catalysts are discussed, including surface modulation, defect engineering, heteroatom doping, and coordination effects. Finally, the challenges and prospects of copper‐based catalysts with high e‐NO3RR performance in practical applications are outlined.

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Photoelectrocatalytic Conversion of Nitrates to Ammonia: Effect of Proton Donor

Silveira,

Bericat‐Vadell,

Sá

2024

ChemPhotoChem

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Changes in farming techniques have facilitated the movement of nitrogen‐containing species, making converting nitrate into ammonia (fertilizer) highly desirable. Recently, we introduced a photosystem comprising NiO/Au plasmon/TiO2 that can selectively convert nitrate to ammonia at neutral pH and room temperature using visible light in a photo‐electrochemical approach. The study evaluated the role of adding alcohol to the overall process activity and selectivity. Adding small quantities of alcohol to the electrolyte leads to changes in the catalytic behaviour, which cannot be attributed exclusively to improvement in counter‐electrode reaction kinetics. Analysis of product Faradaic efficiency and photo‐current measurements revealed that alcohols act as proton donors in nitrate/nitrite reduction, possibly through a concerted proton‐couple electron transfer mechanism. These initial findings offer new handles for nitrate reduction to ammonia efficacy at neutral pH. Ultimately, this opens up avenues for agricultural practices that recycle nutrients, improve process circularity, and reduce fertilizer costs, thus contributing to economic sustainability.

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Critical review in electrocatalytic nitrate reduction to ammonia towards a sustainable nitrogen utilization

Cited by 5 publications

References 122 publications

CuCo₂O₄/CuO Heterostructure with Oxygen Vacancies Induced by Plasma for Electrocatalytic Nitrate Reduction to Ammonia

CuCo₂O₄/CuO Heterostructure with Oxygen Vacancies Induced by Plasma for Electrocatalytic Nitrate Reduction to Ammonia

Selective and Efficient Electrocatalytic Synthesis of Ammonia from Nitrate with Copper‐Based Catalysts

Photoelectrocatalytic Conversion of Nitrates to Ammonia: Effect of Proton Donor

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Critical review in electrocatalytic nitrate reduction to ammonia towards a sustainable nitrogen utilization

Cited by 5 publications

References 122 publications

CuCo2O4/CuO Heterostructure with Oxygen Vacancies Induced by Plasma for Electrocatalytic Nitrate Reduction to Ammonia

CuCo2O4/CuO Heterostructure with Oxygen Vacancies Induced by Plasma for Electrocatalytic Nitrate Reduction to Ammonia

Selective and Efficient Electrocatalytic Synthesis of Ammonia from Nitrate with Copper‐Based Catalysts

Photoelectrocatalytic Conversion of Nitrates to Ammonia: Effect of Proton Donor

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CuCo₂O₄/CuO Heterostructure with Oxygen Vacancies Induced by Plasma for Electrocatalytic Nitrate Reduction to Ammonia

CuCo₂O₄/CuO Heterostructure with Oxygen Vacancies Induced by Plasma for Electrocatalytic Nitrate Reduction to Ammonia