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Updated: May 20, 2025

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
2D Rhodium-Isocyanide Frameworks
Senhe Huang1, Pu Yan2, Zhiya Han3
1The 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.
This study introduces novel 2D metal-organic frameworks (MOFs) with rhodium-carbon coordination, achieving ultra-narrow bandgaps and high charge mobility. These new MOFs show promise as electrocatalysts for nitrogen reduction, demonstrating a new class of advanced materials.
Area of Science:
- Materials Science
- Nanotechnology
- Coordination Chemistry
Background:
- 2D metal-organic frameworks (MOFs) are versatile organic van der Waals materials with tunable properties.
- Existing 2D MOFs primarily utilize metal-heteroatom coordination, while metal-carbon coordination remains challenging to synthesize.
- Metal-carbon coordination in 2D MOFs is crucial for developing novel materials with unique electronic properties.
Purpose of the Study:
- To report the synthesis and characterization of novel 2D MOFs based on rhodium-carbon (Rh-C) coordination.
- To investigate the optoelectronic properties and charge transport capabilities of these new materials.
- To evaluate the potential of these Rh-C 2D MOFs as electrocatalysts for the nitrogen reduction reaction.
Main Methods:
- Synthesis of 2D MOFs using isocyanide ligands and Rh(I) metal nodes.
- Crystallographic analysis to determine the network structure.
- Terahertz spectroscopy to measure charge carrier mobility.
- Electrocatalytic testing for nitrogen reduction reaction (NRR).
- In situ experiments to elucidate catalytic mechanisms.
Main Results:
- Successfully synthesized crystalline 2D MOFs with quasi-square lattice networks and Rh-C coordination.
- Observed ultra-narrow bandgaps (0.1-0.28 eV) due to Rh(I)-isocyano interactions.
- Achieved exceptional short-range charge mobilities up to 560 ± 46 cm² V⁻¹ s⁻¹.
- Demonstrated excellent electrocatalytic performance for NRR with high NH₃ yield (56.0 ± 1.5 µg h⁻¹ mg_cat⁻¹) and Faradaic efficiency (87.1 ± 1.8%).
- Identified dual catalytic pathways involving Rh(I) via in situ studies.
Conclusions:
- This work pioneers 2D MOFs based on metal-carbon coordination, specifically using Rh-C bonds.
- The synthesized MOFs exhibit promising characteristics for advanced optoelectronic devices due to high carrier mobility.
- These findings open new avenues for reticular chemistry and catalysis, particularly for nitrogen reduction applications.
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