A unique air-assisted DMSO oxidation pathway for the highly efficient synthesis of 2,5-diformylfuran from 5-hydroxymethylfurfural/fructose,Green Chemistry

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A unique air-assisted DMSO oxidation pathway for the highly efficient synthesis of 2,5-diformylfuran from 5-hydroxymethylfurfural/fructose
Green Chemistry ( IF 9.3 ) Pub Date : 2023-09-09 , DOI: 10.1039/d3gc02279j
Yujia Pang ₁ , Ning Chen ₁ , Zhizhou Zhao ₁ , Lei Zhang ₂ , J. O. P. Broekman ₃ , Junnan Wei ₁ , Xiujuan Li ₁ , Lu Lin ₄ , He Huang ₁

Affiliation

The development of safe, economical and highly efficient oxidation systems for the production of chemicals from biomass remains a significant and challenging target. Here, we first found a unique air-assisted reaction mechanism for the non-pressurized oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) using dimethylsulfoxide (DMSO) as an O-donor over CoZrNC-MCM, which affords exceptional productivity among all non-noble catalysts. The combination of control experiments and density functional theory (DFT) calculations reveals that the air-assisted DMSO oxidation pathway is activated by the co-adsorption of DMSO and O₂ on Co-(pyrrolic N–C) pairs of CoNC-MCM. ZrNC species in CoZrNC-MCM will be thermally disintegrated to release ZrO²⁺ and provide the corresponding cation vacancies that might be able to capture Co atoms to form additional Co-(pyrrolic N–C) active pairs, resulting in the increase of catalytic activity. The released ZrO²⁺ is well dispersed over Al-MCM-41 in the form of zirconia, which contributes to the dehydration of fructose to HMF. In this way, a one-step approach for synthesizing DFF from fructose is achieved by the cooperation of zirconia and Co-(pyrrolic N–C) pairs over CoZrNC-MCM.

中文翻译：

独特的空气辅助 DMSO 氧化途径，用于从 5-羟甲基糠醛/果糖高效合成 2,5-二甲酰呋喃

开发用于从生物质生产化学品的安全、经济和高效的氧化系统仍然是一个重要且具有挑战性的目标。在这里，我们首先发现了一种独特的空气辅助反应机制，使用二甲基亚砜（DMSO）作为 O-供体，在 CoZrNC-MCM 上将 5-羟甲基糠醛（HMF）非加压氧化为 2,5-二甲酰呋喃（DFF），其中在所有非贵重催化剂中具有卓越的生产率。控制实验和密度泛函理论（DFT）计算相结合表明，空气辅助DMSO氧化途径是通过CoNC- MCM的Co-（吡咯N-C）对上的DMSO和O _{2的共吸附而激活的。}CoZrNC-MCM 中的 ZrNC 物质将热分解释放 ZrO ²⁺并提供相应的阳离子空位，这些空位可能能够捕获Co原子，形成额外的Co-（吡咯N-C）活性对，从而提高催化活性。释放的ZrO ²⁺以氧化锆的形式很好地分散在Al-MCM-41上，这有助于果糖脱水为HMF。这样，通过氧化锆和Co-(吡咯N-C)对在CoZrNC-MCM上的合作，实现了从果糖合成DFF的一步法。

更新日期：2023-09-09

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