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Urea synthesis through the simultaneous electrocatalytic reduction of N2and CO2molecules under ambient conditions holds great promises as a sustainable alternative to its industrial production, in which the development of stable, highly efficient, and highly selective catalysts to boost the chemisorption, activation, and coupling of inert N2and CO2molecules remains rather challenging. Herein, by means of density functional theory computations, we proposed a new class of two‐dimensional nanomaterials, namely, transition‐metal phosphide monolayers (TM2P, TM = Ti, Fe, Zr, Mo, and W), as the potential electrocatalysts for urea production. Our results showed that these TM2P materials exhibit outstanding stability and excellent metallic properties. Interestingly, the Mo2P monolayer was screened out as the best catalyst for urea synthesis due to its small kinetic energy barrier (0.35 eV) for C–N coupling, low limiting potential (−0.39 V), and significant suppressing effects on the competing side reactions. The outstanding catalytic activity of the Mo2P monolayer can be ascribed to its optimal adsorption strength with the key *NCON species due to its moderate positive charges on the Mo active sites. Our findings not only propose a novel catalyst with high‐efficiency and high‐selectivity for urea production but also further widen the potential applications of metal phosphides in electrocatalysis.
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This content will become publicly available on April 12, 2026
Electrocatalytic CN Coupling: Advances in Urea Synthesis and Opportunities for Alternative Products
Urea is an essential fertilizer produced through the industrial synthesis of ammonia (NH3) via the Haber–Bosch process, which contributes ≈1.2% of global annual CO2emissions. Electrocatalytic urea synthesis under ambient conditions via CN coupling from CO2and nitrogen species such as nitrate (NO3−), nitrite (NO2−), nitric oxide (NO), and nitrogen gas (N2) has gained interest as a more sustainable route. However, challenges remain due to the unclear reaction pathways for urea formation, competing reactions, and the complexity of the resulting product matrix. This review highlights recent advances in catalyst design, urea quantification, and intermediate identification in the CN coupling reaction for electrocatalytic urea synthesis. Furthermore, this review explores future prospects for industrial CN coupling, considering potential nitrogen and carbon sources and examining alternative CN coupling products, such as amides and amines.
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- Award ID(s):
- 2332802
- PAR ID:
- 10586690
- Publisher / Repository:
- Wiley-VCH
- Date Published:
- Journal Name:
- ChemSusChem
- ISSN:
- 1864-5631
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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