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用于将5-羟甲基糠醛选择性氧化为2,5-呋喃二甲酸的廉价高效钴-锰混合氧化物催化剂

Inexpensive but Highly Efficient Co-Mn Mixed-Oxide Catalysts for Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid.

作者信息

Rao Kasanneni Tirumala Venkateswara, Rogers Jennifer Lorraine, Souzanchi Sadra, Dessbesell Luana, Ray Madhumita Bhowmick, Xu Chunbao Charles

机构信息

Department of Chemical and Biochemical Engineering, Western University, London, Ontario, N6A 5B9, Canada.

出版信息

ChemSusChem. 2018 Sep 21;11(18):3323-3334. doi: 10.1002/cssc.201800989. Epub 2018 Aug 15.

Abstract

A highly active and inexpensive Co-Mn mixed-oxide catalyst was prepared and used for selective oxidation of 5-hydroxymethylfurfural (HMF) into 2, 5-furandicarboxylic acid (FDCA). Co-Mn mixed-oxide catalysts with different Co/Mn molar ratios were prepared through a simple solid-state grinding method-a low-cost and green catalyst preparation method. The activity of these catalysts was evaluated for selective aerobic oxidation of HMF into FDCA in water. Excellent HMF conversion (99 %) and FDCA yield (95 % ) were obtained under the best reaction conditions (i.e., 120 °C, 5 h, Co-Mn mixed-oxide catalyst with a Co/Mn molar ratio of 0.25 calcined at 300 °C (Co-Mn-0.25) and 1 MPa O ). The catalyst could be reused five times without a significant decrease in activity. The results demonstrated that the catalytic activity and selectivity of the Co-Mn mixed-oxide catalysts prepared through solid-state grinding were superior to the same Co-Mn catalyst prepared through a conventional coprecipitation method. The high catalytic activity of the Co-Mn-0.25 catalyst was attributed to its high lattice oxygen mobility and the presence of different valence states of manganese. The high activity and low cost of the Co-Mn mixed-oxide catalysts prepared by solid-state grinding make it promising for industrial application for the manufacturing of polyethylene furanoate, a bioreplacement for polyethylene terephthalate, from sustainable bioresources.

摘要

制备了一种高活性且廉价的钴锰混合氧化物催化剂,并将其用于将5-羟甲基糠醛(HMF)选择性氧化为2,5-呋喃二甲酸(FDCA)。通过简单的固态研磨法(一种低成本的绿色催化剂制备方法)制备了具有不同钴/锰摩尔比的钴锰混合氧化物催化剂。在水中对这些催化剂将HMF选择性好氧氧化为FDCA的活性进行了评估。在最佳反应条件下(即120°C、5小时、钴/锰摩尔比为0.25的钴锰混合氧化物催化剂在300°C下煅烧(Co-Mn-0.25)以及1MPa氧气),获得了优异的HMF转化率(99%)和FDCA产率(95%)。该催化剂可以重复使用五次,活性没有显著降低。结果表明,通过固态研磨制备的钴锰混合氧化物催化剂的催化活性和选择性优于通过传统共沉淀法制备的相同钴锰催化剂。Co-Mn-0.25催化剂的高催化活性归因于其高晶格氧迁移率以及锰不同价态的存在。通过固态研磨制备的钴锰混合氧化物催化剂的高活性和低成本使其在从可持续生物资源制造聚对苯二甲酸乙二酯的生物替代品聚呋喃二甲酸乙二酯的工业应用中具有前景。

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