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通过过一硫酸盐引发的木质纤维素生物质温和催化氧化可持续生产2,5-二甲酰基呋喃

Sustainable production of 2,5-diformylfuran via peroxymonosulfate-triggered mild catalytic oxidation of lignocellulosic biomass.

作者信息

Chen Ke-Yu, Yu Lin-Qian, Huang Yun-Xin, Liu Wu-Jun, Huang Bao-Cheng, Jin Ren-Cun, Yu Han-Qing

机构信息

School of Engineering, Hangzhou Normal University, Hangzhou 310018, China.

School of Life and Environmental Sciences, Hangzhou Normal University, Hangzhou 310018, China.

出版信息

PNAS Nexus. 2024 Dec 17;4(1):pgae563. doi: 10.1093/pnasnexus/pgae563. eCollection 2025 Jan.

DOI:10.1093/pnasnexus/pgae563
PMID:39741740
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11686438/
Abstract

The relentless depletion of fossil fuels accentuates the urgent necessity for the sustainable synthesis of chemicals from renewable biomass. 5-Hydroxymethylfurfural (HMF), extracted from lignocellulosic biomass, emerges as a beacon of hope for conversion into value-added chemicals. However, the inherent susceptibility of its unsaturated aldehyde groups to excessive oxidation often culminates in undesired reactions, compromising both the yield and specificity of the desired products. Here, we introduce a holistic methodology for the cost-effective and ecologically responsible generation of 2,5-diformylfuran (DFF), through the heterogeneously catalyzed oxidation of HMF utilizing peroxymonosulfate (PMS) under benign conditions. This strategy, characterized by the meticulous enhancement of surface ketone groups via a mixed-salt-assisted co-pyrolysis technique, achieves an unparalleled selective activation of PMS, engendering singlet oxygen to catalyze the oxidation of HMF into DFF with a selectivity surpassing 80%. Life-cycle assessments underscore a negligible impact on human health, ecosystems, and natural resources, endorsing the holistic utilization of biomass. This integration of pyrolysis for the creation of functional carbonaceous materials within biomass conversion processes significantly enhances sustainability and economic viability, while paving green pathways for selective biomass oxidation and the production of high-value chemicals.

摘要

化石燃料的持续枯竭凸显了从可再生生物质中可持续合成化学品的迫切必要性。从木质纤维素生物质中提取的5-羟甲基糠醛(HMF)成为转化为高附加值化学品的希望之光。然而,其不饱和醛基对过度氧化的固有敏感性常常导致不期望的反应,从而影响所需产物的产率和特异性。在此,我们介绍一种整体方法,通过在温和条件下利用过一硫酸盐(PMS)对HMF进行多相催化氧化,以具有成本效益且对生态负责的方式生成2,5-二甲酰基呋喃(DFF)。该策略通过混合盐辅助共热解技术精心增强表面酮基,实现了对PMS无与伦比的选择性活化,产生单线态氧以催化HMF氧化为DFF,选择性超过80%。生命周期评估强调对人类健康、生态系统和自然资源的影响可忽略不计,支持生物质的整体利用。这种在生物质转化过程中通过热解创建功能性碳质材料的整合显著提高了可持续性和经济可行性,同时为选择性生物质氧化和高价值化学品的生产开辟了绿色途径。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/f33aad56bb92/pgae563f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/539e00585014/pgae563f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/00cd76f75a5f/pgae563f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/d1376066a58f/pgae563f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/5959c3e97441/pgae563f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/f33aad56bb92/pgae563f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/539e00585014/pgae563f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/00cd76f75a5f/pgae563f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/d1376066a58f/pgae563f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/5959c3e97441/pgae563f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd19/11686438/f33aad56bb92/pgae563f5.jpg

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Sunlight-Driven Highly Selective Catalytic Oxidation of 5-Hydroxymethylfurfural Towards Tunable Products.阳光驱动的 5-羟甲基糠醛高选择性催化氧化反应生成可调产物。
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