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通过界面工程强化的 Cu-Mn 氧化物空心纳米纤维在水中实现高效有氧 5-羟甲基糠醛氧化为 2,5-呋喃二甲酸。

Enabling Efficient Aerobic 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid in Water by Interfacial Engineering Reinforced Cu-Mn Oxides Hollow Nanofiber.

机构信息

School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, 212003, Jiangsu, P. R. China.

China Petroleum Engineering & Construction Corp., North China Company, Jianshe Road, Renqiu 062552, Hebei, P. R. China.

出版信息

ChemSusChem. 2022 Jul 7;15(13):e202200076. doi: 10.1002/cssc.202200076. Epub 2022 Feb 23.

Abstract

Herein, a one-dimensional hollow nanofiber catalyst composed of tightly packed multiphase metal oxides of Mn O and Cu Mn O was constructed by electrospinning and tailored thermal treatment procedure. The characterization results comprehensively confirmed the special morphology and composition of various comparative catalysts. This strategy endowed the catalyst with abundant interfacial characteristics of components Mn O and Cu Mn O nanocrystal. Impressively, the tuning thermal treatment resulted in tailored Cu sites and surface oxygen species of the catalyst, thus affording optimized oxygen vacancies for reinforced oxygen adsorption, while the concomitant enhanced lattice oxygen activity in the constructed composite catalyst ensured the higher catalytic oxidation ability. More importantly, the regulated proportion of oxygen vacancy and lattice oxygen in the composite catalyst was obtained in the best catalyst, beneficial to accelerate the reaction cycle. Compared to other counterparts obtained by different temperatures, the CMO-500 sample exhibited superior selective aerobic 5-hydroxymethylfurfural (HMF) oxidation to 2,5-furandicarboxylic acid (FDCA, 96 % yield) in alkali-bearing aqueous solution using O at 120 °C, which resulted from the above-mentioned composition optimization and interfacial engineering reinforced surface oxygen consumption and regeneration cycle. The reaction mechanism was further proposed to uncover the lattice oxygen and oxygen vacancy participating HMF conversion process.

摘要

本文通过静电纺丝和定制的热处理工艺,构建了由紧密堆积的多相金属氧化物 MnO 和 CuMnO 组成的一维中空纳米纤维催化剂。表征结果全面证实了各种对比催化剂的特殊形态和组成。该策略赋予了催化剂丰富的组分 MnO 和 CuMnO 纳米晶的界面特性。令人印象深刻的是,调谐热处理导致催化剂中 Cu 位和表面氧物种的调整,从而为增强氧吸附提供了优化的氧空位,同时构建的复合催化剂中晶格氧的活性增强,确保了更高的催化氧化能力。更重要的是,在最佳催化剂中获得了复合催化剂中氧空位和晶格氧的调节比例,有利于加速反应循环。与通过不同温度获得的其他对照物相比,CMO-500 样品在碱性水溶液中使用 O2 在 120°C 下表现出对 5-羟甲基糠醛 (HMF) 到 2,5-呋喃二甲酸 (FDCA,96%收率) 的选择性有氧氧化,这归因于上述组成优化和界面工程增强了表面氧消耗和再生循环。进一步提出了反应机理,以揭示晶格氧和氧空位参与 HMF 转化过程。

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