Yoshiki Ikuto, Takagaki Atsushi, Song Jun Tae, Watanabe Motonori, Ishihara Tatsumi
Department of Applied Chemistry, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
Division of Materials Science and Chemical Engineering, Faculty of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa, 240-8501, Japan.
ChemistryOpen. 2024 Nov;13(11):e202400079. doi: 10.1002/open.202400079. Epub 2024 Oct 7.
Formic acid is considered a promising hydrogen carrier. Biomass-derived formic acid can be obtained by oxidative decomposition of sugars. This study explored the production of formic acid from cellobiose, a disaccharide consisting of d-glucose linked by β-glycosidic bonds using heterogeneous catalysts under mild reaction conditions. The use of alkaline earth metal oxide solid base catalysts like CaO and MgO in the presence of hydrogen peroxide could afford formic acid from cellobiose at 343 K. While CaO gave 14 % yield of formic acid, the oxide itself was converted to a harmful metal peroxide, CaO after the reaction. In contrast, MgO could produce formic acid without the formation of the metal peroxide. The difficulty in selectively synthesizing formic acid from cellobiose using these solid base catalysts was due to the poor conversion of cellobiose to glucose. Using a combination of solid acid and base catalysts, a high formic acid yield of 33 % was obtained under mild reaction conditions due to the quantitative hydrolysis of cellobiose to glucose by a solid acid followed by the selective decomposition of glucose to formic acid by a solid base.
甲酸被认为是一种很有前景的氢载体。生物质衍生的甲酸可通过糖的氧化分解获得。本研究探索了在温和反应条件下，使用多相催化剂由纤维二糖（一种由通过β-糖苷键连接的d-葡萄糖组成的二糖）生产甲酸。在过氧化氢存在的情况下，使用氧化钙和氧化镁等碱土金属氧化物固体碱催化剂，可在343K下由纤维二糖制得甲酸。虽然氧化钙的甲酸产率为14%，但反应后氧化物本身会转化为有害的金属过氧化物CaO₂。相比之下，氧化镁可以生产甲酸而不形成金属过氧化物。使用这些固体碱催化剂从纤维二糖中选择性合成甲酸的困难在于纤维二糖向葡萄糖的转化率较低。通过组合使用固体酸和碱催化剂，在温和的反应条件下获得了33%的高甲酸产率，这是由于固体酸将纤维二糖定量水解为葡萄糖，随后固体碱将葡萄糖选择性分解为甲酸。
