Huang Senhe, Yan Pu, Han Zhiya, Wu Hongyu, Wang Youcheng, Zhang Jichao, Yuan Lei, Fu Shuai, Wen Guanzhao, Zhu Jinhui, Bonn Mischa, Wang Hai I, Cao Kecheng, Zhuang Xiaodong
The Soft2D Lab, State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
School of Physical Science and Technology, Shanghai Key Laboratory of High-resolution Electron Microscopy, ShanghaiTech University, Shanghai, 201210, China.
Adv Mater. 2025 May;37(19):e2502192. doi: 10.1002/adma.202502192. Epub 2025 Mar 25.
2D metal-organic frameworks (2D MOFs) are emerging organic van der Waals materials with great potential in various applications owing to their structural diversity, and tunable optoelectronic properties. So far, most reported 2D MOFs rely on metal-heteroatom coordination (e.g., metal-nitrogen, metal-oxygen, and metal-sulfur); synthesis of metal-carbon coordination based 2D MOFs remains a formidable challenge. This study reports the rhodium-carbon (Rh-C) coordination-based 2D MOFs, using isocyanide as the ligand and Rh(I) as metal node. The synthesized MOFs show excellent crystallinity with quasi-square lattice networks. These MOFs show ultra-narrow bandgaps (0.1-0.28 eV) resulting from the interaction between Rh(I) and isocyano groups. Terahertz spectroscopy demonstrates exceptional short-range charge mobilities up to 560 ± 46 cm V s in the as-synthesized MOFs. Moreover, these MOFs are used as electrocatalysts for nitrogen reduction reaction and show an excellent NH yield rate of 56.0 ± 1.5 µg h mg and a record Faradaic efficiency of 87.1 ± 1.8%. In situ experiments reveal dual pathways involving Rh(I) during the catalytic process. This work represents a pioneering step toward 2D MOFs based on metal-carbon coordination and paves the way for novel reticular materials with ultra-high carrier mobility and for versatile optoelectronic devices.
