Yin Ying, Lv Ximeng, Lv Zhuoran, Fang Lei, Fan Tao, Wang Man, Chen Ziyang, Lyu Naixin, Gou Gaozhang, Zhang Lijuan, Zheng Gengfeng, Li Liangchun
Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai, 200092, China.
Laboratory of Advanced Materials, Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200438, China.
ChemSusChem. 2025 Feb 16;18(4):e202401760. doi: 10.1002/cssc.202401760. Epub 2024 Nov 8.
The conversion of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is a promising approach for enhancing biomass utilization. Nevertheless, traditional methods using noble metal catalysts face challenges due to high costs and poor selectivity towards DFF. Herein, we developed a novel catalytic electrode integrating N-hydroxyphthalimide (NHPI) into a metal-organic framework on a hydrophilic carbon cloth. This design significantly enhances the selective adsorption of HMF due to stronger hydrogen-bond interaction between the electrode's hydrophilic surface and the C(sp)-OH group in HMF compared to the C(sp)=O in DFF. Additionally, the electro-driven dissociation of the NHPI-linker generates stabilized N-Oxyl radicals that promote selective semi-oxidation of HMF under neutral conditions. As a result, this approach achieves a high yield rate of 138.2 mol mol h with a selectivity of 96.7 % for the HMF-to-DFF conversion. This work introduces a novel strategy for designing catalytic electrodes with stabilized N-Oxyl radicals, and offers a promising method for electrocatalytic DFF synthesis, leveraging hydrogen-bond interaction between electrode surface and HMF.
将5-羟甲基糠醛（HMF）转化为2,5-二甲基呋喃（DFF）是提高生物质利用率的一种很有前景的方法。然而，使用贵金属催化剂的传统方法面临着成本高和对DFF选择性差的挑战。在此，我们开发了一种新型催化电极，将N-羟基邻苯二甲酰亚胺（NHPI）整合到亲水碳布上的金属有机框架中。与DFF中的C(sp)=O相比，由于电极亲水表面与HMF中的C(sp)-OH基团之间更强的氢键相互作用，这种设计显著增强了HMF的选择性吸附。此外，NHPI连接体的电驱动解离产生稳定的N-氧自由基，促进HMF在中性条件下的选择性半氧化。结果，该方法实现了138.2 mol mol h的高产率，HMF到DFF转化的选择性为96.7%。这项工作引入了一种设计具有稳定N-氧自由基的催化电极的新策略，并提供了一种利用电极表面与HMF之间的氢键相互作用进行电催化合成DFF的有前景的方法。
