Cao Shihai, Lu Jingyu, Sun Yuntong, Li Yinghao, Hao Zhendong, Lee Jong-Min
Schsool of Environmental Engineering, Nanjing Institute of Technology, Nanjing, 211167, China.
School of New Energy, Nanjing University of Science & Technology, Jiangyin, 214443, China.
Small. 2025 Jul;21(27):e2502708. doi: 10.1002/smll.202502708. Epub 2025 Jun 9.
Electrochemical nitrogen reduction (eNRR) offers a sustainable and energy-efficient alternative to the conventional Haber-Bosch process for ammonia (NH) synthesis, operating under mild conditions with reduced environmental impact. Open framework materials (OFMs), encompassing covalent-organic frameworks (COFs) and metal-organic frameworks (MOFs), have emerged as highly promising candidates due to their modular structures, tunable porosity, and adaptable functionalities. This review summarizes recent advancements in OFMs for eNRR, focusing on strategies for selection and design of active centers, regulation of porous structure, and conductivity enhancement strategy, as well as surface functionalization and interface engineering. Key challenges, including structural instability, low intrinsic conductivity, and the complexity of scalable synthesis, are critically analyzed. Advanced characterization methods, theoretical modeling, and machine learning are proposed as innovative tools to overcome these obstacles. Lastly, the potential for industrial-scale applications of OFMs in sustainable NH production is discussed, highlighting their transformative role in eNRR.
电化学氮还原（eNRR）为传统的哈伯-博施法合成氨提供了一种可持续且节能的替代方法，它在温和条件下运行，对环境的影响较小。包括共价有机框架（COF）和金属有机框架（MOF）在内的开放框架材料（OFM），因其模块化结构、可调孔隙率和可适应的功能，已成为极具潜力的候选材料。本综述总结了OFM用于eNRR的最新进展，重点关注活性中心的选择和设计策略、多孔结构的调控、导电性增强策略以及表面功能化和界面工程。对包括结构不稳定性、固有电导率低以及可扩展合成的复杂性等关键挑战进行了批判性分析。提出了先进的表征方法、理论建模和机器学习作为克服这些障碍的创新工具。最后，讨论了OFM在可持续氨生产中的工业规模应用潜力，突出了它们在eNRR中的变革性作用。
