Chu Fuhao, Lu Bo, Zhao Guiyi, Zhu Zhiguo, Yang Kaixuan, Su Ting, Zhang Qiaohong, Chen Chen, Lü Hongying
College of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, Shandong, China.
School of Material Science and Chemical Engineering, Ningbo University, 818 Fenghua Road, 315211, Ningbo, China.
ChemSusChem. 2024 Mar 22;17(6):e202301385. doi: 10.1002/cssc.202301385. Epub 2023 Dec 6.
Hydrogen bonding effect exists widely in various chemical and biochemical systems, primarily stabilizing the molecular structure as a positive factor. However, the presence of intermolecular hydrogen bonds among biomass molecules results in a formidable challenge for the efficient utilization of biomass resources. Here in, a novel strategy of "hydrogen bonds reconstruction" was developed by a series of ternary deep eutectic solvent (DESs) as molecular scissors, which disrupting the initial intermolecular hydrogen bonds and reconstructing the new ones to increase the reactivity of the biomass-based compound. The DESs played a crucial role in enhancing the reactivity of 5-hydroxymethylfurfural (HMF) and promoting its oxidation through reconstructing the hydrogen bonds interactions. Furthermore, DESs was also found to activate the Anderson-type catalyst NaIMoO (IMo) through an electron-transfer mechanism, which facilitated the generation of oxygen vacancies and significantly enhances its ability to activate molecular oxygen. With this novel catalytic system, oxidation of HMF exhibited remarkable efficiency as HMF was almost entirely converted into FFCA with an impressive yield of 98 % under the optimized conditions. This finding offers novel insights into the utilization of biomass resources and endows the solvent with new functions in the chemical reaction.
氢键效应广泛存在于各种化学和生化系统中，主要作为一种积极因素稳定分子结构。然而，生物质分子间存在的分子间氢键给生物质资源的高效利用带来了巨大挑战。在此，通过一系列三元低共熔溶剂（DESs）作为分子剪刀，开发了一种“氢键重构”的新策略，该策略破坏初始分子间氢键并重建新的氢键，以提高生物质基化合物的反应活性。DESs在增强5-羟甲基糠醛（HMF）的反应活性以及通过重构氢键相互作用促进其氧化方面发挥了关键作用。此外，还发现DESs通过电子转移机制激活安德森型催化剂NaIMoO（IMo），这促进了氧空位的产生并显著增强了其激活分子氧的能力。在这种新型催化体系下，HMF的氧化表现出显著效率，在优化条件下，HMF几乎完全转化为FFCA，产率高达98%。这一发现为生物质资源的利用提供了新的见解，并赋予了该溶剂在化学反应中的新功能。
