36802-01-4Relevant articles and documents
A High-Performance Base-Metal Approach for the Oxidative Esterification of 5-Hydroxymethylfurfural
Sun, Yuxia,Ma, Hong,Jia, Xiuquan,Ma, Jiping,Luo, Yang,Gao, Jin,Xu, Jie
, p. 2907 - 2911 (2016)
Exploring high-performance base-metal approaches for the sustainable production of chemicals from biomass is presently attracting immense interest and is truly important to promote their industrialized application. Herein, CoOx-N/C and α-MnO2 were combined as a base-metal catalyst that can achieve high yields of furan-2,5-dimethylcarboxylate (FDMC, 95.6 %) for the catalytic oxidative esterification of 5-hydroxymethylfurfural (HMF) without basic additive. The reaction proceeds through fast conversion of HMF to diformylfuran (DFF) with α-MnO2 and subsequent transformation of DFF to FDMC by CoOx-N/C. Quantitative X-ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculations indicated that the pyridinic-N present in doped carbon could behave as a Lewis base to promote the abstraction of hydrogen for the oxidative esterification reaction. Consequently, CoOx-N/C is a high performance catalyst for the synthesis of FDMC from DFF in a neutral medium.
Oxidative Esterification of 5-Hydroxymethylfurfural under Flow Conditions Using a Bimetallic Co/Ru Catalyst
Salazar, Abel,Linke, Alexander,Eckelt, Reinhard,Quade, Antje,Kragl, Udo,Mejía, Esteban
, p. 3504 - 3511 (2020/05/16)
Furanic di-carboxylate derivatives of 5-Hydroxymethylfurfural (HMF) are nowadays important in the polymer industry as they are used as building blocks for bio-based polyesters. The high reactivity of HMF compels to avoid harsh synthetic conditions. Therefore, developing mild catalytic processes for its selective oxidation is a challenging task. Herein, we report the first oxidative esterification of HMF to dimethyl furan-2,5-dicarboxylate (FDCM) under flow conditions using oxygen as oxidant. For that purpose, a new series of nitrogen-doped carbon-supported bimetallic Co/Ru heterogeneous catalysts were prepared and characterized by XRD, XPS and N2 physisorption. These analyses revealed that the porosity of the materials and order of impregnation of the metals to the carbon supports lead to varying catalytic activities. Under optimized conditions the flow reactor showed a 15-fold increase on the production of FDCM compared to batch conditions.
Oxidative Esterification of 5-Hydroxymethylfurfural with an N-doped Carbon-supported CoCu Bimetallic Catalyst
Liu, Huai,Ding, Ning,Wei, Junnan,Tang, Xing,Zeng, Xianhai,Sun, Yong,Lei, Tingzhou,Fang, Huayu,Li, Tianyuan,Lin, Lu
, p. 4151 - 4158 (2020/07/10)
The direct fabrication of furan-2,5-dimethylcarboxylate (FDMC), a promising renewable monomer, from biomass-derived 5-hydroxymethylfurfural (HMF) is a cutting-edge process. In this contribution, an elaborately designed N-doped carbon-supported CoCu bimetallic catalyst (CoxCuy-NC; x/y=9:1, 7:3, 4:6, which represents the designed molar ratio of Co and Cu in the catalyst), which could offer a desirable FDMC yield of 95 percent under mild and base-free conditions (Co7Cu3-NC, 2 bar O2, 80 °C, 4 h) is described for the oxidative esterification of HMF. Notably, an FDMC formation rate of 6.1 molFDMC molCo?1 h?1 was achieved over Co7Cu3-NC, which represents the highest catalytic efficiency so far among Co-based catalytic systems. It has been demonstrated that Cu-doping in Co7Cu3-NC catalyst brings about more active sites (Co-Nx species) with stronger molecular oxygen activation ability. The increase of surface N content of Co7Cu3-NC also improves basicity of the catalyst, which favors the hydrogen abstraction process during the HMF oxidative esterification reaction. These findings may pave an efficient and green way for the synthesis of sustainable bio-based polymer monomers.
SYNTHESIS OF PRECURSORS OF 2,5-FURANDICARBOXYLIC ACID
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Page/Page column 16-18, (2019/10/01)
The present invention relates to a method for the manufacture of stable FDCA precursors from saccharide derived starting materials. More specific the invention relates to the synthesis of FDCA precursors such as alkyl 5-(hydroxymethyl)furan-2-carboxylates or 5-(hydroxymethyl)furan-2-carboxylic acid in an expedient, practical and environmental benign manner from e.g. D-glucono-δ-lactone. These bio-based monomer building blocks hold great potential in the manufacture of polymer materials.
