He Yuanqing, Ma Chongyang, Mo Shiheng, Dong Chung-Li, Chen Wei, Chen Shuo, Pang Huan, Ma Renzhi, Wang Shuangyin, Zou Yuqin
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225009, China; State Key Laboratory of Chem/Bio-Sensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, The National Supercomputer Centers in Changsha, Hunan University, Changsha 410082, China.
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, The National Supercomputer Centers in Changsha, Hunan University, Changsha 410082, China.
Sci Bull (Beijing). 2025 Jan 30;70(2):193-202. doi: 10.1016/j.scib.2024.09.013. Epub 2024 Sep 12.
The electrochemical oxidation of 5-hydroxymethylfurfural (HMFOR) in alkaline electrolyte is a promising strategy for producing high-value chemicals from biomass derivatives. However, the disproportionation of aldehyde groups under strong alkaline conditions and the polymerization of HMF to form humic substances can impact the purity of 2,5-furandicarboxylic acid (FDCA) products. The use of neutral electrolytes offers an alternative environment for electrolysis, but the lack of OH ions in the electrolyte often leads to low current density and low yields of FDCA. In this study, a sandwich-structured catalyst, consisting of Ru clusters confined between unilamellar MnO nanosheets (S-Ru/MnO), was used in conjunction with an electrochemical pulse method to realize the electrochemical conversion of 5-hydroxymethylfurfural into FDCA in neutral electrolytes. Pulse electrolysis and the strong electron transfer between Ru clusters and MnO nanosheets help maintain Ru in a low oxidation state, ensuring high activity. The increased *OH generation led to a groundbreaking current density of 47 mA/cm at 1.55 V vs. reversible hydrogen electrode (RHE) and an outstanding yield rate of 98.7% for FDCA in a neutral electrolyte. This work provides a strategy that combines electrocatalyst design with an electrolysis technique to achieve remarkable performance in neutral HMFOR.
在碱性电解质中对5-羟甲基糠醛（HMFOR）进行电化学氧化是一种从生物质衍生物生产高价值化学品的有前景的策略。然而，在强碱性条件下醛基的歧化以及HMF聚合形成腐殖质会影响2,5-呋喃二甲酸（FDCA）产品的纯度。使用中性电解质为电解提供了另一种环境，但电解质中缺乏OH离子通常会导致电流密度低和FDCA产率低。在本研究中，一种由限制在单层MnO纳米片之间的Ru簇组成的夹心结构催化剂（S-Ru/MnO）与电化学脉冲方法结合使用，以实现中性电解质中5-羟甲基糠醛向FDCA的电化学转化。脉冲电解以及Ru簇与MnO纳米片之间的强电子转移有助于将Ru保持在低氧化态，确保高活性。*OH生成的增加导致在相对于可逆氢电极（RHE）为1.55 V时达到了47 mA/cm的突破性电流密度，并且在中性电解质中FDCA的产率高达98.7%。这项工作提供了一种将电催化剂设计与电解技术相结合的策略，以在中性HMFOR中实现卓越性能。
