Li Hu, Liu Xiaofang, Yang Tingting, Zhao Wenfeng, Saravanamurugan Shunmugavel, Yang Song
State-Local Joint Engineering Lab for Comprehensive Utilization of Biomass, State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering (Ministry of Education), Center for R&D of Fine Chemicals, Guizhou University, Guiyang, Guizhou, 550025, P.R. China.
Center of Innovative and Applied Bioprocessing (CIAB), Mohali, 160 071, Punjab, India.
ChemSusChem. 2017 Apr 22;10(8):1761-1770. doi: 10.1002/cssc.201601898. Epub 2017 Feb 28.
Biofuranic compounds, typically derived from C and C carbohydrates, have been extensively studied as promising alternatives to chemicals based on fossil resources. The present work reports the simple assembly of biobased 2,5-furandicarboxylic acid (FDCA) with different metal ions to prepare a range of metal-FDCA hybrids under hydrothermal conditions. The hybrid materials were demonstrated to have porous structure and acid-base bifunctionality. Zr-FDCA-T, in particular, showed a microspheric structure, high thermostability (ca. 400 °C), average pore diameters of approximately 4.7 nm, large density, moderate strength of Lewis-base/acid centers (ca. 1.4 mmol g ), and a small number of Brønsted-acid sites. This material afforded almost quantitative yields of biofuranic alcohols from the corresponding aldehydes under mild conditions through catalytic transfer hydrogenation (CTH). Isotopic H NMR spectroscopy and kinetic studies verified that direct hydride transfer was the dominant pathway and rate-determining step of the CTH. Importantly, the Zr-FDCA-T microspheres could be recycled with no decrease in catalytic performance and little leaching of active sites. Moreover, good yields of C (i.e., furfural) or C products [i.e., maleic acid and 2(5H)-furanone] could be obtained from furfuryl alcohol without oxidation of the furan ring over these metal-FDCA hybrids. The content and ratio of Lewis-acid/base sites were demonstrated to dominantly affect the catalytic performance of these redox reactions.
生物呋喃类化合物通常源自碳和碳水化合物，作为基于化石资源的化学品的有前景的替代品，已得到广泛研究。本工作报道了在水热条件下，将生物基2,5-呋喃二甲酸（FDCA）与不同金属离子简单组装，制备一系列金属-FDCA杂化物。这些杂化材料被证明具有多孔结构和酸碱双功能性。特别是Zr-FDCA-T呈现出微球结构、高热稳定性（约400℃）、平均孔径约4.7 nm、大密度、中等强度的路易斯酸碱中心（约1.4 mmol g）以及少量的布朗斯特酸位点。该材料在温和条件下通过催化转移氢化（CTH）从相应醛中几乎定量地得到生物呋喃醇。同位素 1H NMR光谱和动力学研究证实，直接氢化物转移是CTH的主要途径和速率决定步骤。重要的是，Zr-FDCA-T微球可以循环使用，催化性能不降低且活性位点几乎不浸出。此外，在这些金属-FDCA杂化物上，糠醇可在不氧化呋喃环的情况下得到高产率的C（即糠醛）或C产物[即马来酸和2(5H)-呋喃酮]。路易斯酸碱位点的含量和比例被证明主要影响这些氧化还原反应的催化性能。
