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有序介孔 POMs/SiO-NH 纳米纤维的制备用于从 5-HMF 生产 DFF,以回收纤维素废水资源。

Fabrication of ordered mesoporous POMs/SiO-NH nanofibers for production of DFF from 5-HMF for cellulose wastewater resource recovery.

机构信息

Key Lab of Polyoxometalate Science of Ministry of Education, Northeast Normal University, Changchun, 130024, China; Key Laboratory of Songliao Aquatic Environment, Ministry of Education, Jilin Jianzhu University, Changchun, 130118, China; Science and Technology Innovation Center for Municipal Wastewater Treatment and Water Quality Protection, Northeast Normal University, Changchun, 130117, China.

Key Lab of Polyoxometalate Science of Ministry of Education, Northeast Normal University, Changchun, 130024, China.

出版信息

Chemosphere. 2021 Aug;277:130316. doi: 10.1016/j.chemosphere.2021.130316. Epub 2021 Mar 19.

Abstract

5-hydroxymethylfurfural (5-HMF) is a biomass cellulose platform product that can be transformed into the valuable resource 2,5-diformylfuran (DFF). Polyoxometalates (POMs) have important applications in resource recovery technologies and cellulose wastewater treatment. Ordered mesoporous HPMoVO/SiO-NH (wt%) nanofibers (HPMoV/meso-SiO-NH (wt%)) were synthesized by the combining in-situ fabrication and electrospinning techniques, using HPMoVO (HPMoV) and organic-silica as precursors. Aiming the recovery and transformation of 5-HMF, aerobic oxidation of 5-HMF was explored using these nanofibers as catalysts, while the best yield of DFF (90.0%) was obtained upon HPMoV/meso-SiO-NH (23%) nanofibers after 8 h at 120 °C using oxygen (1.0 MPa). The selectivity to DFF was improved by changing the hydrophilicity of the HPMoV@SiO nanofibers to hydrophobicity by modifying SiO nanofibers with -NHR compared to mesoporous SiO nanofibers, which allowed the formed DFF to be isolated. In the recycling test, HPMoV@SiO-NH showed good performance, and no leaching of active sites from SiO-NH due to the interactions between them occurred after 10 cycles. The production of DFF from the real cellulosic wastewater was obtained with 118% yield based on 5-HMF conversion by HPMoV/meso-SiO-NH (23) and oxygen, which was contributed to the one-pot conversion of sugar, furan and 5-HMF in the wastewater.

摘要

5-羟甲基糠醛(5-HMF)是一种生物质纤维素平台产物,可以转化为有价值的资源 2,5-二糠醛(DFF)。多金属氧酸盐(POMs)在资源回收技术和纤维素废水处理中有重要应用。采用原位合成和静电纺丝技术,以 HPMoVO(HPMoV)和有机硅为前驱体,合成了有序介孔 HPMoVO/SiO-NH(wt%)纳米纤维(HPMoV/meso-SiO-NH(wt%))。为了回收和转化 5-HMF,采用这些纳米纤维作为催化剂,探索了 5-HMF 的有氧氧化反应,在 120°C 下使用氧气(1.0 MPa)反应 8 小时后,得到了最好的 DFF(90.0%)产率,而 HPMoV/meso-SiO-NH(23%)纳米纤维的产率为 90.0%。与介孔 SiO 纳米纤维相比,通过将-SiO 纳米纤维用-NHR 改性来提高 HPMoV@SiO 纳米纤维的亲水性为疏水性,从而提高了 DFF 的选择性,允许形成的 DFF 被分离。在回收测试中,HPMoV@SiO-NH 表现出良好的性能,由于它们之间的相互作用,SiO-NH 中没有活性位点浸出,在 10 次循环后。通过 HPMoV/meso-SiO-NH(23)和氧气,从实际纤维素废水中得到了 118%的 DFF 产率,这得益于废水中糖、呋喃和 5-HMF 的一锅转化。

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