Tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) is a bio-based cyclic dicarboxylic acid with greater flexibility and biosafety than the renowned 2,5-furandicarboxylic acid (FDCA), but its synthesis is limited to thermochemical methods with only several reports. This study pioneers an electrocatalytic strategy for the efficient synthesis of THFDCA via the oxidation of tetrahydrofuran dimethanol (THFDM). By constructing NiCo bimetallic oxides micron sheets on nickel foam (NiCoMS/NF) through controlled pyrolysis of a metal-organic framework (MOF)-like precursor, we achieved a remarkable THFDM conversion of 99.0% and THFDCA yield up to 98.2%, surpassing all reports on thermocatalytic oxidation as we know. In-depth analysis revealed that the synergistic effect between NiO and Co 3 O 4 contributes to the high catalytic performance. In-situ Raman and rotating ring-disk electrode (RRDE) techniques were employed to discuss the reaction mechanism and the inhibitory effect on oxygen evolution reaction (OER). This study not only provides a paradigm-shifting, groundbreaking strategy for the synthesis of the flexible cyclic dicarboxylic acid derived from furanic biomass but also offers deep insights into the synergistic effects of electrocatalysts.
Jiali Zheng,Zhihui Li,Dongsheng Zhang,Xinqiang Zhao,Qian Zhao,Yanji Wang
Bio-based route for preparing adipic acid (AA) from 5-hydroxymethylfurfural is the direction for achieving green and sustainable AA production. In light of the challenges, such as corrosion and difficulties in recycling of I - containing homogeneous catalyst, large amount, high cost, and significant mass transfer resistance of ionic liquid (IL) catalyst, encountered in the current hydrodeoxygenation of 2,5-tetrahydrofurandicarboxylic acid (THFDCA) to AA process. Herein, 1-sulfobutyl-3-methylimidazolium iodide IL ([HSO 3 -b-mim]·I) was used to functionalize MIL-101-NH 2 through acid-base self-assembly approach, hence, a heterogeneous catalyst, IL/MIL-101-NH 2 was designed and applied in the hydrodeoxygenation of THFDCA to bio-based AA for the first time. When reacted at 180 °C for 2 h, the THFDCA conversion and AA yield were 100 % and 99.9 %, respectively. Moreover, IL/MIL-101-NH 2 exhibited remarkable stability and could be reused multiple times with minimal loss in activity. XRD, SEM, FT-IR, BET, XPS, and TG results revealed that the functionalization process involved the reaction between HSO 3 in the IL and NH 2 in MIL-101-NH 2 , forming a salt that chemically bonded the IL to MIL-101-NH 2 , thereby enhancing stability. The excellent hydrodeoxygenation activity was attributed to the synergistic effect of the Lewis acid site (Cr 3+ ) and the Lewis base nucleophilic site (I - ) within IL/MIL-101-NH 2 .
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