Electrocatalytic C–N coupling for urea synthesis: a critical review

Yang, Chuanju; Li, Zhe; Xu, Junpeng; Jiang, Yujing; Zhu, Wenlei

doi:10.1039/d3gc04920e

Cited by 12 publications

(1 citation statement)

References 190 publications

(210 reference statements)

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“…Particularly, NO 3 – widely exists in industrial wastewater along with CO 3 – , which can be successfully used as electrolytes for urea synthesis . The urea synthesis provides a fast and effective way of utilizing NO 3 – and CO 3 – , reducing the amount of pollution that interacts with the environment. , Additionally, this urea production process is clean and cost-effective, consuming less energy and resources. This makes the development of high-performance electrocatalysts and electrolytes with a higher solubility of N 2 and CO 2 highly desirable for the production of urea with high yield.…”

Section: Introductionmentioning

confidence: 99%

Synergistic Bimetallic Sites in 2D-on-2D Heterostructures for Enhanced C–N Coupling in Sustainable Urea Synthesis

Govindan,

Annamalai,

Kumar

et al. 2024

ACS Sustainable Chem. Eng.

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Electrochemical conversion of CO2 and N2 to produce “green urea” using renewable energy represents a promising avenue for CO2 mitigation. A bifunctional electrocatalyst with a desirable composition and structure is highly required for the electrochemical reduction of CO2 and N2 (CO2N2RR) into urea. Herein, Ru–Pd alloyed nanoparticles were successfully incorporated into 2D WO3 and MXene nanosheets, resulting in the formation of Ru–Pd/WO3/MXene heterostructures. The catalyst significantly enhances electrocatalytic C–N coupling in CO2 and N2 reduction, resulting in increased urea yield. The electrochemical reduction initially converts CO2 into *CO, which then undergoes direct coupling with N2 to form urea through continuous protonation. Simultaneously, water molecules are oxidized on the bifunctional Ru–Pd/WO3/MXene electrodes. The mechanism of C–N coupling for urea formation is elucidated through density functional theory (DFT) calculations. The Ru–Pd/WO3/MXene catalyst exhibits a noteworthy urea yield of 227 μgurea mgcat –1h–1 with a faradaic efficiency of 23.7%. The detailed understanding of the CO2N2RR mechanism and the recyclable properties of the electrode emphasizes its suitability for prolonged use. This study not only presents a road map for advancing electrolysis but also provides profound insights into the fundamental chemistry of C–N coupling reactions.

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Section: Introductionmentioning

confidence: 99%

Synergistic Bimetallic Sites in 2D-on-2D Heterostructures for Enhanced C–N Coupling in Sustainable Urea Synthesis

Govindan,

Annamalai,

Kumar

et al. 2024

ACS Sustainable Chem. Eng.

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Multifunctional Strategies of Advanced Electrocatalysts for Efficient Urea Synthesis

Ge,

Huo,

et al. 2024

Advanced Materials

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The electrochemical reduction of nitrogenous species (such as N2, NO, NO2−, and NO3−) for urea synthesis under ambient conditions has been extensively studied due to their potential to realize carbon/nitrogen neutrality and mitigate environmental pollution, as well as provide a means to store renewable electricity generated from intermittent sources such as wind and solar power. However, the sluggish reaction kinetics and the scarcity of active sites on electrocatalysts have significantly hindered the advancement of their practical applications. Multifunctional engineering of electrocatalysts has been rationally designed and investigated to adjust their electronic structures, increase the density of active sites, and optimize the binding energies to enhance electrocatalytic performance. Here, surface engineering, defect engineering, doping engineering, and heterostructure engineering strategies for efficient nitrogen electro‐reduction are comprehensively summarized. The role of each element in engineered electrocatalysts is elucidated at the atomic level, revealing the intrinsic active site, and understanding the relationship between atomic structure and catalytic performance. This review highlights the state‐of‐the‐art progress of electrocatalytic reactions of waste nitrogenous species into urea. Moreover, this review outlines the challenges and opportunities for urea synthesis and aims to facilitate further research into the development of advanced electrocatalysts for a sustainable future.

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Dual Electron Donating Metal‐Boron Reaction Center Boosts Electrocatalytic Urea Synthesis from N₂ and CO₂

Yodsin,

Mano,

Takahashi

et al. 2024

ChemCatChem

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Urea (NH2CONH2) production by electrosynthesis at mild conditions has been hampered due to the lack of systematic evaluation of pathways in effectively activating inert N2 and CO2 molecules and facilitating the formation of C‐N bonds. This work, we evaluated 16 transition metal (M) atoms anchored on a carbon nitride nanosheet with boron (B) doping (M‐B@C2N) for boosting urea production by theoretical calculations. All possible urea synthesis pathways, (i) CO2 pathway, (ii) OCOH pathway, (iii) CO pathway, and (iv) NCON pathway, were comparatively studied on Cu, Fe, Co, Ni‐B@C2N. This systematic calculation identified that the first reduction of *N2 is the key step for urea synthesis. We found that the bond index of *N2 shows a strong correlation with ΔG*N2®*NNH, so they are promising descriptors for screening. Through the screening, we found that Nb‐ and Mo‐B@C2N show a low limiting potential of ‐0.56 and ‐0.53 V. Although previous studies found that spin could promote C‐C bond formation on M‐B@C2N, we found that for C‐N coupling, such effects by spin were only active for Nb‐B@C2N. Combining boron and early transition metal atoms allows for neighboring reaction sites that simultaneously donate electrons to activate inert N2 and CO2 for efficient urea synthesis.

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Electrocatalytic C–N coupling for urea synthesis: a critical review

Abstract: Urea is one of the most important artificial nitrogen fertilizers in the agricultural economy and can provide essential nitrogen for plant growth. However, the industrial production of urea is very...

Cited by 12 publications

References 190 publications

Synergistic Bimetallic Sites in 2D-on-2D Heterostructures for Enhanced C–N Coupling in Sustainable Urea Synthesis

Synergistic Bimetallic Sites in 2D-on-2D Heterostructures for Enhanced C–N Coupling in Sustainable Urea Synthesis

Multifunctional Strategies of Advanced Electrocatalysts for Efficient Urea Synthesis

Dual Electron Donating Metal‐Boron Reaction Center Boosts Electrocatalytic Urea Synthesis from N₂ and CO₂

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Electrocatalytic C–N coupling for urea synthesis: a critical review

Abstract: Urea is one of the most important artificial nitrogen fertilizers in the agricultural economy and can provide essential nitrogen for plant growth. However, the industrial production of urea is very...

Cited by 12 publications

References 190 publications

Synergistic Bimetallic Sites in 2D-on-2D Heterostructures for Enhanced C–N Coupling in Sustainable Urea Synthesis

Synergistic Bimetallic Sites in 2D-on-2D Heterostructures for Enhanced C–N Coupling in Sustainable Urea Synthesis

Multifunctional Strategies of Advanced Electrocatalysts for Efficient Urea Synthesis

Dual Electron Donating Metal‐Boron Reaction Center Boosts Electrocatalytic Urea Synthesis from N2 and CO2

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Product

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Dual Electron Donating Metal‐Boron Reaction Center Boosts Electrocatalytic Urea Synthesis from N₂ and CO₂