Tan Hong-Yi, Wang Bing-Hao, Xu Meng-Yi, Peng Zhi-Yong, Wu Wen-Juan, Shen Sheng, Yin Shuang-Feng
College of Chemistry and Chemical Engineering, State Key Laboratory of Chemo/Biosensing and Chemometrics, Ministry of Education of Advanced Engineering Research Center for Catalysis, Hunan University, Changsha, 410082, P. R. China.
College of Chemistry and Chemical Engineering, Central South University of Forestry and Technology, Changsha, 410004, P. R. China.
ChemSusChem. 2025 May 5;18(9):e202402112. doi: 10.1002/cssc.202402112. Epub 2025 Jan 10.
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.
金属有机框架材料（MOFs）因其高比表面积、可调节的孔结构和丰富的活性位点，是电化学析氧反应（OER）中很有前景的催化剂。配体工程是优化其性能的重要策略。在此，我们报告基于三种不同配体合成镍铁金属有机框架材料：1,4-对苯二甲酸（BDC）、2,4-噻吩二甲酸（TDC）和2,5-呋喃二甲酸（FDC），以研究基于杂原子的芳香环对析氧反应性能的影响。结果表明，通过将电负性的硫和氧原子引入配体中，金属位点处的电子密度降低，导致金属-氧共价性增强和电荷转移动力学改善。NiFe-FDC/NF催化剂在10 mA·cm时的过电位为189 mV，在1 A cm下1300小时以上表现出稳定性能。原位红外光谱显示NiFe-FDC/NF中结构重构最小，这有助于其优异的稳定性。然后对NiFe-FDC/NF进行3600小时的析氧反应操作，并监测其金属洗脱情况。这些发现为高性能基于MOF的析氧反应催化剂的配体设计提供了一种新方法，突出了基于呋喃的配体在MOF配体工程中的潜力。
