纤维素衍生 Co3O4/N 掺杂碳催化剂对生物质基 5-羟甲基糠醛电氧化的协同促进作用

Haixin Sun , Yingying Gao , Mengyuan Chen , Ming Li , Qinqin Xia , Yongzhuang Liu , Juan Meng , Shuo Dou , Haipeng Yu
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摘要

催化剂在通过电化学氧化将 5-hydroxymethylfurfural (HMF) 高效转化为 2,5-呋喃二甲酸 (FDCA) 的过程中发挥着关键作用。本研究报告了一种用于合成生物基羧酸的经济高效的钴基电催化剂。通过将纤维素溶解在含有钴离子的碱性尿素中作为前驱体,得到了一种具有高比表面积和丰富多孔结构的碳包覆 Co3O4(Co3O4@NC)催化剂。在将 HMF 电催化转化为 FDCA 时,该催化剂表现出优异的产率和超过 95% 的法拉第效率。原位拉曼光谱揭示了该催化剂的双通道过程,其中部分 Co3O4 可作为吸附 HMF 的活性位点,而其他 Co3O4 则在反应过程中转化为 CoOOH。这种双途径电催化促进了 HMF 的高效转化。此外,以生物醇/醛为原料,成功合成了八种羧酸,产率从 91.5% 到 99%不等。本研究提出了一种从生物质中提取的高效电催化剂,可以生产多种生物基羧酸,在可持续化学合成方面具有巨大潜力。
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Synergistic boosting the electrooxidation of biomass-based 5-hydroxymethylfurfural on cellulose-derived Co3O4/N-doped carbon catalysts
Catalysts play a pivotal role in the efficient conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) through electrochemical oxidation. In this work, a cost-effective and highly efficient cobalt-based electrocatalyst for the synthesis of bio-based carboxylic acids was reported. By the employment of cellulose, which was dissolved in the alkaline-urea with cobalt ion, as the precursor, it derived a carbon-coated Co3O4 (Co3O4@NC) catalyst with a high specific surface area and rich porous structure. When utilized in the electrocatalytic conversion of HMF to FDCA, the catalyst exhibited exceptional yields and Faradaic efficiency which surpassed 95 %. In-situ Raman spectra unveiled that a dual-pathway process occurred on this catalyst, with part of Co3O4 serving as active sites for HMF adsorption, while other Co3O4 transformed into CoOOH during the reaction. This dual-pathway electrocatalysis facilitated the highly efficient conversion of HMF. Additionally, using bio-based alcohols/aldehydes as the feedstocks, eight carboxylic acids were successfully synthesized with yields ranging from 91.5 % to 99 %. This study presents a highly efficient electrocatalyst derived from biomass, enabling diverse bio-based carboxylic acid production with significant potential for sustainable chemical synthesis.
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