From Molecules to Materials: Engineering 2D Catalysts for Efficient Urea Production via C–N Bond Formation

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From Molecules to Materials: Engineering 2D Catalysts for Efficient Urea Production via C–N Bond Formation
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Surface-functionalized two-dimensional materials towards electrocatalytic C−N coupling reaction for urea - Catal

The electrocatalytic C−N coupling of the greenhouse gas carbon dioxide and N2/nitrate presents a promising approach to the conventional Bosch-Meiser method for environmentally friendly urea synthesis. Two-dimensional (2D) materials exhibit significant advantages in electrocatalysis due to their unique ultrathin structure and physicochemical properties as a platform Substrates for atomic modification. Here, this review focuses on the Surface functionalization of 2D electrocatalysts (Oxides, Sulfide, MOFs, Mxene, et al.) through heteroatom doping, defect engineering, and Surface molecule functionalization to enhance the catalyst conductivity, lower the reaction barrier, and improve its cycling stability. Then, we provide a Summary of surface modified 2D electrocatalysts (the single-atom site, synergistic effects of dual-active-sites, et al.) towards C−N coupling reaction of N2 /NOx and CO2 for urea synthesis, analyze the catalysis origins through combination of DFT calculations, which are widely adopted to offer a precise description of the electronic structure of catalysts and the relationship between catalytic activity and catalysts. The reaction mechanisms researches reveals the optimization of reaction pathways by the dynamic evolution of the catalyst surface, providing a new direction for the design of adaptive catalytic materials.Finally, challenges and perspectives in the field are presented.

In this review, we present a comprehensive overview of recent advances in the design and surface functionalization of two-dimensional (2D) materials for electrocatalytic carbon–nitrogen (C–N) coupling reactions, with a particular focus on sustainable urea production. Our work aims to address the limitations of the traditional Haber–Bosch process by exploring ambient-condition electrocatalysis using CO₂ and N₂ or NOₓ as feedstocks.

Key Insights

  • Sustainable Pathway: Electrocatalytic C–N coupling offers a green route for urea synthesis under ambient conditions.
  • 2D Material Platforms: Materials like MoS₂, MXenes, and MOFs provide tunable catalytic properties.
  • Surface Functionalization Strategies: Includes heteroatom doping, defect engineering, and molecular functionalization.
  • Catalyst Innovations: Single-atom and dual-atom catalysts enhance activation and selectivity.
  • Challenges & Future Directions: Addressing low N₂ solubility and complex pathways through reactor and catalyst design.

Significance of the Work

This review underscores the critical role of surface-functionalized 2D materials in advancing electrocatalytic urea synthesis. By integrating theoretical insights with experimental progress, we provide a framework for designing adaptive catalysts capable of operating under mild conditions. Our analysis of reaction mechanisms, intermediate stabilization, and catalyst–substrate interactions offer valuable guidance for future research and industrial translation in the field of green nitrogen–carbon coupling.

Authors & Institutions

  • Yue Shang, Dawei Chen, Chen Chen, Shuangyin Wang

  State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, Changsha, China

  • Yue Shang, Dawei Chen

  College of Material Science and Engineering, Qingdao University of Science and Technology, Qingdao, China

Corresponding Authors & Emails:

  • Dawei Chen – dawechen@qust.edu.cn
  • Chen Chen – chenc@hnu.edu.cn
  • Shuangyin Wang – shuangyinwang@hnu.edu.cn

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