Heteroatom-Based Ligand Engineering of Metal Organic Frameworks for Efficient and Robust Electrochemical Water Oxidation.

Metal-organic frameworks (MOFs) are promising catalysts for the electrochemical oxygen evolution reaction (OER) due to their high surface area, tunable pore structures, and abundant active sites. Ligand engineering is an important strategy to optimize their performance. Here, we report the synthesis of NiFe-MOFs based on three different ligands: 1,4-terephthalic acid (BDC), 2,4-thiophene dicarboxylic acid (TDC), and 2,5-furandicarboxylic acid (FDC), to investigate the effects of heteroatom-based aromatic rings on OER performance. It is revealed that by incorporating electronegative sulfur and oxygen atoms into the ligands, the electron density at the metal sites is reduced, leading to enhanced metal-oxygen covalency and improved charge transfer kinetics. The NiFe-FDC/NF catalyst demonstrates an overpotential of 189 mV at 10 mA⋅cm and stable performance over 1300 hours at 1 A cm. In situ infrared spectroscopy reveal minimal structural reconstruction in NiFe-FDC/NF, contributing to its superior stability. The NiFe-FDC/NF were then subjected to 3600 hours of OER operation and it's metal elution was monitored. These findings offer a novel approach to ligand design for high-performance MOF-based OER catalysts, highlighting the potential of furan-based ligands for MOF ligand engineering.